Ion exchanged glass-ceramic article

Abstract

The present application relates to ion exchanged glass-ceramic articles. The glass-ceramic articles disclosed herein have a first surface; a second surface opposite the first surface; a first region extending from the first surface to a first depth dl; and a second region extending from a depth greater than or equal to dl to a second depth d2, wherein the second region comprises a crystalline phase and a glass phase, and wherein the area percent of crystals in the first region is less than the area percent of crystals in the second region. In some embodiments, a compressive stress layer extends from the first surface to a depth of compression (DOC), wherein the DOC is greater than or equal to 0.05 mm, and the average compressive stress in the first region is greater than or equal to 50 MPa. In some embodiments, the DOC is greater than dl; the reduced modulus of the first region is less than the reduced modulus of the second region; and / or the hardness of the first region is less than the hardness of the second region.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Application Serial No. 62 / 649863, filed March 29, 2018, pursuant to 35 USC § 119, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to ion-exchanged glass-ceramic articles, and more specifically, to ion-exchanged glass-ceramic articles in which the outer region has fewer crystals than the inner region. Background Technology

[0004] Glass-ceramic products can be chemically strengthened, for example, through ion exchange, thereby improving mechanical properties such as resistance to crack penetration and chipping. Glass-ceramics are multiphase materials with one or more crystalline phases and a residual glassy phase, and the ion exchange process within them can be complex. In addition to affecting the residual glassy phase, ion exchange can also influence one or more of the crystalline phases. This phenomenon leads to new improvements in the mechanical properties of glass-ceramic products, which is desirable for covering substrates and housings used in mobile electronic devices. Summary of the Invention

[0005] In a first aspect, a glass-ceramic article includes: a first surface; a second surface opposite to the first surface; a first region extending from the first surface to a first depth d1; a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase; and a compressive stress layer extending from the first surface to a depth of compression (DOC), wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, wherein the DOC is greater than or equal to 0.05 mm, and wherein the average compressive stress in the first region is greater than or equal to 50 MPa.

[0006] In a second aspect, the glass-ceramic article includes: a first surface; a second surface opposite to the first surface; a first region extending from the first surface to a first depth d1; a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase; and a compressive stress layer extending from the first surface to a depth of compression (DOC), wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, and wherein the DOC is greater than d1.

[0007] In a third aspect, the glass-ceramic article includes: a first surface; a second surface opposite to the first surface; a first region extending from the first surface to a first depth d1; and a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, and wherein the reduced modulus of the first region is less than the reduced modulus of the second region.

[0008] In a fourth aspect, the glass-ceramic article includes: a first surface; a second surface opposite to the first surface; a first region extending from the first surface to a first depth d1; and a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, and wherein the hardness of the first region is less than the hardness of the second region.

[0009] In a fifth aspect, the glass-ceramic article includes: a first surface having an average maximum scratch width of less than 155 micrometers when subjected to a scratch test with a 5 N load based on an average of 15 measurements; a second surface opposite to the first surface; a first region extending from the first surface to a first depth d1; and a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0010] In a sixth aspect, the glass-ceramic article includes: a first surface having an average maximum scratch width of less than 100 micrometers when subjected to a scratch test with a 1 N load based on an average of 15 measurements; a second surface opposite to the first surface; a first region extending from the first surface to a first depth d1; and a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0011] In the seventh aspect, the consumer electronic product includes: a housing comprising a front surface, a back surface, and a side surface; an electronic component at least partially located within the housing, the electronic component including at least a controller, a memory, and a display, the display being located on or adjacent to the front surface of the housing; and a cover substrate disposed above the display, wherein at least one of the housing or a portion of the cover substrate comprises a glass-ceramic article of any of the foregoing aspects.

[0012] In an eighth aspect, a method for ion-exchanging a glass-ceramic article includes: contacting at least a first surface of the glass-ceramic article with an ion-exchange medium comprising one or more lithium-containing salts in total less than 0.03% by weight; and during the contact process, forming a first region in the glass-ceramic article extending from the first surface to a first depth d1, wherein a compressive stress layer extends from the first surface to a depth of compression (DOC), wherein after the formation of the first region, the glass-ceramic article includes a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0013] In a ninth aspect, a method for ion-exchanging a glass-ceramic article includes: contacting the surface of the glass-ceramic article with a first ion-exchange medium, the first ion-exchange medium comprising a total of at least 0.03% by weight of one or more lithium-containing salts; after contacting with the first ion-exchange medium, contacting the surface of the glass-ceramic article with a second ion-exchange medium, wherein the total weight percentage of lithium-containing salts contained in the second ion-exchange medium is less than the total weight percentage of lithium-containing salts contained in the first ion-exchange medium; and during the contact with the second ion-exchange medium, forming in the glass-ceramic a first region extending from the first surface to a first depth d1, and a compressive stress layer extending from the first surface to a depth of compression (DOC), wherein after forming the first region, the glass-ceramic article comprises a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0014] Other features and advantages of this document are set forth in the following detailed description, some of which will be readily apparent to those skilled in the art from the description, or will be recognized by practicing the various embodiments described herein, including the following detailed description, the claims, and the accompanying drawings.

[0015] It should be understood that the general description above and the detailed description below are merely exemplary, intended to provide a general overview or framework for understanding the nature and features of the claims. The accompanying drawings, which are incorporated in and form part of this specification, provide further understanding. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operation of various embodiments. Attached Figure Description

[0016] Figure 1 This is an exemplary cross-sectional view of a reinforced glass-ceramic article; Figure 2 This is an exemplary stress distribution of a reinforced glass-ceramic article; Figure 3 This is an exemplary cross-sectional view of a reinforced glass-ceramic article according to an embodiment having a transition region therein; Figure 4A It is a plan view of an exemplary electronic device incorporating any of the reinforced articles disclosed herein; Figure 4B yes Figure 4A A perspective view of an exemplary electronic device; Figure 5 The concentration distribution of Na2O and K2O (in mole %) was obtained by microscopic measurement of various samples after ion exchange as described in Example 1. Figure 6 The X-ray diffraction traces are those of the ion-exchanged glass-ceramic product of Example 1. Figure 7 This shows the stress distribution of various samples after ion exchange in Example 1; Figure 8 This is a graph showing the reduced modulus (y-axis) and glass layer thickness (x-axis) of various samples after ion exchange in Example 2; Figure 9 This is a graph showing the relationship between the total area of ​​the sample with vitrified region (per kg of bath salt) and lithium poisoning at the end of the run in Example 4; Figure 10 The thickness of the vitreous region is shown for each group of samples subjected to ion exchange under different conditions in Example 4. Figure 11 The graph shows the relationship between the effective diffusion coefficient and the weight % of LiNO3 at the start of various ion exchange operations in Example 4; and Figure 12 The average compressive stress in the vitreous region of each group of samples from various ion exchange operations in Example 4 is shown. Detailed Implementation

[0017] Definition and measurement techniques

[0018] As used herein, the term “glass-ceramic” refers to a solid obtained by controlled crystallization of a precursor glass, having one or more crystalline phases as well as a residual glass phase.

[0019] As used herein, a “glassy” region or layer refers to a surface region having a lower percentage of crystals than the inner regions. Glassy regions or layers can be formed by: (i) decrystallization of one or more crystalline phases in a glass-ceramic article during an ion exchange process; (ii) laminating or fusing glass onto a glass-ceramic; or (iii) other methods known in the art, such as forming them simultaneously with the glass-ceramization of a precursor into a glass-ceramic.

[0020] As used herein, “compression depth” or “DOC” refers to the depth of the compressive stress (CS) layer, and is the depth within a glass-ceramic article where the stress changes from compressive stress to tensile stress and the stress value is zero. According to common practice in the art, compressive stress is expressed as negative stress (<0) and tensile stress as positive stress (>0). However, throughout this specification, unless otherwise stated, CS is expressed as a positive or absolute value; that is, CS = ... CS .

[0021] The depth / thickness of the vitreous region can be measured by identifying the depth of abrupt changes in the relative area of ​​crystalline and amorphous sub-regions in a scanning electron microscope (SEM) image of a polished cross-section of the sample, including the polished cross-section and the edges formed by the original sample surface.

[0022] Nanoindentation can be used to measure reduced modulus, hardness, and penetration depth. Specifically, a Bruker Hysitron TI980 instrument with a 1D 3-plate capacitive transducer and a Brinell geometry tip is used to perform quasi-static indentation to obtain load-depth curves. Then, as described by Oliver, WC, and GMPharr in “An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments,” J. Mater. Res., Vol. 7, No. 6, June 1992, the reduced modulus (Er), hardness (H), and penetration depth (h_f) are calculated, the full text of which is incorporated herein by reference. Penetration depth is the final depth of the nanoindentation after the indenter tip has been unloaded.

[0023] The maximum scratch width of glass-ceramic artifacts was measured according to the following procedure (referred to herein as the “scratch test”). Scratches were generated in the samples using a Bruker Universal Mechanical Tester (UMT) with a Knoop tip, employing the following load function: (1) starting with a load of 0.25 N and increasing the load to the maximum load at a rate of 0.14 N / s; (2) then scratching the sample for 10 mm at a scratching speed of 5 mm / min; and (3) then unloading to a load of 0.25 N at a rate of 0.14 N / s, at which point the tip was removed. Maximum loads of 1 N, 3 N, and 5 N were used for each sample. After scratching, the samples were left to stand for at least 12 hours to prevent any delayed failure. Images of the scratched samples were then taken at 300x magnification using a Keyence VHX-5000 digital microscope. Three points were measured for each scratch. The first measurement is taken at the top 50% of the scratch at its widest lateral position (0-5 mm); the second at the exact middle of the scratch (5 mm); and the third at the bottom 50% of the scratch at its widest lateral position (5-10 mm). The first and third measurements vary for each scratch based on the location of its widest lateral portion. Imaging software was used to obtain these measurements, and for each scratch, the average maximum width value (in µm) was calculated based on these three measurement locations.

[0024] The CS of the glassy region was obtained by birefringence measurement of the first transmission (coupled) resonance in the glassy region in prism coupling measurement, and the layer depth of the glassy region was measured by the spacing between the first and second transmission resonances or the width of the first transmission resonance.

[0025] The DOC value and maximum center tension (CT) value were measured using a Scattered Light Polarizer (SCALP) (model SCALP-04) purchased from Glassstress Ltd., located in Tallinn, Estonia.

[0026] The near-field refraction (RNF) method described in U.S. Patent No. 8,854,623, entitled "Systems and methods for measuring a profile characteristic of a glass sample," is incorporated herein by reference in its entirety. The RNF measurement is force-balanced and calibrated using a maximum CT value provided by SCALP measurement. Specifically, the RNF method includes placing the glass article close to a reference block, generating a polarization-switched beam (which switches between orthogonal polarizations at a rate from 1 Hz to 50 Hz), measuring the power in the polarization-switched beam, and generating a polarization-switched reference signal, wherein the power measured in each orthogonal polarization is within 50% of each other. The method also includes passing the polarization-switched beam through the glass sample and the reference block to different depths in the glass sample, and then using a delay optics system to delay the passing polarization-switched beam to a signal photodetector, which generates a polarization-switched detector signal. The method further includes dividing the detector signal by the reference signal to form a normalized detector signal, and determining the distribution characteristics of the glass sample from the normalized detector signal.

[0027] Stress distribution can be measured by the following combination: (i) for CS in the vitreous region, birefringence measurement of the first transmission (coupling) resonance of the vitreous region in prism coupling measurement; (ii) for CS in the inner region, RNF is used; and (iii) for CT region, SCALP is used.

[0028] The amount of crystals in a region of a specimen can be measured by examining the percentage of area in a high-resolution scanning electron microscope (SEM) image.

[0029] Based on X-ray diffraction (XRD), Rietveld analysis was used to determine the crystal phase set (before ion exchange).

[0030] Overview of the properties of glass and ceramic products

[0031] The preferred embodiments described herein are described in detail below, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals are used in all drawings to denote the same or similar components.

[0032] The properties of strengthened glass-ceramic articles can be designed or controlled by chemical strengthening (e.g., through ion exchange). As disclosed herein, when a glass-ceramic article is subjected to certain ion exchange conditions, one or more of the crystalline phases are "de-crystallized," forming a surface region or layer with a lower percentage of crystalline area than the inner region of the glass article. During this de-crystallization process, one or more of the crystalline phases fracture via the ion exchange process. This surface region with a lower percentage of crystalline area exhibits properties different from the inner region of the glass-ceramic article, such as different reduced modulus and / or hardness, which in turn results in better scratch resistance on the surface of the glass-ceramic article than on an ion-exchanged glass-ceramic article without this lower percentage of crystalline area. The formation of this surface region also results in unique stress distribution characteristics, wherein the surface region and a portion of the inner region are simultaneously under compressive stress, and the compressive layer depth extends into the inner region. In other embodiments, these same properties can be achieved in a laminate of glass articles stacked onto a glass-ceramic article.

[0033] Figure 1 An exemplary cross-sectional side view of a reinforced glass-ceramic article 100 is shown, having a first surface 102 and an opposing second surface 104 separated by thickness (t). In some embodiments, the reinforced glass-ceramic article 100 is ion-exchanged and has a vitreous outer region 106 (or first region) extending from the first surface 102 to a first depth d1. An inner region 108 (or second region) extends from a second depth d2 greater than or equal to the first depth d1. In some embodiments, the reinforced glass-ceramic article 100 also has a vitreous outer region 110 (or third region) extending from the second surface 104 to a third depth d1'. In embodiments where the reinforced glass-ceramic article 100 has vitreous outer regions 106 and 110, the inner region 108 extends from the second depth d2 to a fourth depth d2', wherein the fourth depth d2' is measured from the second surface 104 and is greater than or equal to the third depth d1'. The first depth d1 of the outer vitreous region 106 and the third depth d1' of the outer vitreous region 110 may be equal or different. Similarly, the second depth d2 and the fourth depth d2' may be equal or different. In some embodiments, the reinforced glass-ceramic article has only a single outer vitreous region 106, and in such cases, the inner region 108 extends from the second depth d2 to the second surface 104. Figure 1 This illustration shows an implementation where d1 equals d2 and d1' equals d2', but this is merely exemplary. Other implementations are described below. Figure 3 As discussed, d2 is greater than d1 and / or d2' is greater than d1'.

[0034] In some embodiments, the crystal area percentage of the outer vitreous regions 106 and / or 110 may be lower than that of the inner region 108 of the glass-ceramic article 100, as determined by SEM imaging as described above. For example, the crystal area percentage of the outer vitreous regions may be within the following ranges: 0% to 15%, 0% to 12%, 0% to 10%, 0% to 8%, 0% to 5%, 0% to 2%, 2% to 15%, 2% to 12%, 2% to 10%, 2% to 8%, 2% to 5%, 5% to 15%, 5% to 12%, 5% to 10%, 5% to 8%, 8% to 15%, 8% to 12%, 8% to 10%, 10% to 15%, 10% to 12%, 12% to 15%, and all ranges and subranges thereof. In some embodiments, the outer vitreous regions may have a crystal area percentage less than or equal to 15%, 10%, or 5%.

[0035] The reinforced glass-ceramic article 100 also has a compressive stress (CS) layer 112 extending from the first surface 102 to the depth of compression (DOC). In some embodiments, such as Figure 1 As shown, DOC is greater than the first depth d1 of the outer vitreous region 106, thereby subjecting the outer vitreous region 106 and a portion of the inner region 108 to compressive stress, and causing DOC to be located in the inner region 108. In other embodiments, DOC may be less than or equal to the first depth d1 of the outer vitreous region 106. In some embodiments, such as Figure 1 As shown, the glass-ceramic article 100 also has a compressive stress (CS) layer 114 extending from the second surface 104 to the compression depth DOC'. A central tension region 116 under tensile stress also exists between DOC and DOC'. In some embodiments, such as Figure 1 As shown, DOC' is greater than the third depth d1' of the outer vitreous region 110, thereby subjecting the outer vitreous region 110 and a portion of the inner region 108 to compressive stress, and causing DOC' to be located in the inner region 108. In other embodiments, DOC' may be less than or equal to the third depth d1' of the outer vitreous region 110.

[0036] Figure 2 The thickness of the upper half of the glass-ceramic product 100 is shown to be 0.5 mm. An exemplary stress distribution is shown for t). The x-axis represents the stress value (compressive stress for positive stress and tensile stress for negative stress) and the x-axis represents the depth within the glass-ceramic article measured from the first surface 102. Figure 2As can be seen, in some embodiments, the stress distribution may have an embedded CS (maximum CS) lower than that of the first and / or second surfaces 102, 104, and the stress distribution from embedded peak to embedded peak may be described as a semi-parabola.

[0037] In some implementations, such as Figure 2As shown, the maximum CS may be below the first surface 102 and / or the second surface 104. However, in other embodiments, the maximum CS may be located on the first surface and / or the second surface 104. In some embodiments, the maximum CS and / or average CS in the first CS layer 112 may differ from the maximum CS and / or average CS in the second CS layer 114. In other embodiments, the maximum CS may be located below the first surface 102 and / or the second surface 104. In some embodiments, the location of the maximum CS of the first CS layer 112 and / or the second CS layer 114 can be any range or subrange thereof from the corresponding first and second surfaces 102, 104, consisting of: 0.1 to 25 micrometers, 0.1 to 20 micrometers, 0.1 to 15 micrometers, 0.1 to 10 micrometers, 0.1 to 5 micrometers, 0.5 to 25 micrometers, 0.5 to 20 micrometers, 0.5 to 15 micrometers, 0.5 to 10 micrometers, 0.5 to 5 micrometers, 1 to 25 micrometers, 1 to 20 micrometers, 1 to 15 micrometers, 1 to 10 micrometers, 1 to 5 micrometers, 5 to 25 micrometers, 5 to 20 micrometers, 5 to 15 micrometers, 5 to 10 micrometers, and so on. In some embodiments, the maximum CS of the first CS layer 112 and / or the second CS layer 114 can be located in the corresponding outer vitreous region 106 / 110.In some embodiments, the average CS in the outer vitreous regions 106, 110 can be in the following ranges: 50 MPa to 1500 MPa, 50 MPa to 1250 MPa, 50 MPa to 1000 MPa, 50 MPa to 900 MPa, 50 MPa to 800 MPa, 50 MPa to 700 MPa, 50 MPa to 600 MPa, 50 MPa to 500 MPa, 50 MPa to 400 MPa, 50 MPa to 300 MPa, 50 MPa to 200 MPa, 100 MPa to 1500 MPa, 100 MPa to 1250 MPa, 100 MPa to 1000 MPa, 100 MPa to 900 MPa, 100 MPa to 800 MPa, 100 MPa to 700 MPa, 100 MPa to 600 MPa, 100 MPa to 500 MPa. MPa, 100 MPa to 400 MPa, 100 MPa to 300 MPa, 100 MPa to 200MPa, 200 MPa to 1500 MPa, 200 MPa to 1250 MPa, 200 MPa to 1000 MPa, 200 MPa to 900 MPa, 200 MPa to 800 MPa, 200 MPa to 700 MPa, 200 MPa to 600 MPa, 200 MPa to 500 MPa, 200 MPa to 400 MPa, 300 MPa to 1500 MPa, 300 MPa to 1250 MPa, 300 MPa to 1000 MPa, 300 MPa to 900MPa, 300 MPa to 800 MPa, 300 MPa to 700 MPa, 300 MPa to 600 MPa, 400 The ranges are 400 MPa to 1500 MPa, 400 MPa to 1250 MPa, 400 MPa to 1000 MPa, 400 MPa to 900 MPa, 400 MPa to 800 MPa, 400 MPa to 700 MPa, and all ranges and subranges therebetween. In some embodiments, the average CS in the outer region of the vitreous is greater than or equal to 50 MPa, 100 MPa, 200 MPa, 300 MPa, 400 MPa, 500 MPa, 600 MPa, 700 MPa, 800 MPa, 900 MPa, 1000 MPa, 1250 MPa, or 1500 MPa.

[0038] As described above, DOC and / or DOC' may be present in the inner region 108 (in other words, the first and / or second CS layers 112, 114 may extend into the inner region 108). In such embodiments, the maximum compressive stress in the inner region 108 may be greater than or equal to 10 MPa, 20 MPa, or 30 MPa, extending into the inner region by at least 5 micrometers. In some embodiments, the first and / or second CS layers 112, 114 may extend through the vitreous regions 106, 110 and into the inner region 108 to a range greater than 0. t to 0.3 t、0 t to 0.25 t、0 t to 0.2 t、0 t to 0.15 t、0 t to 0.1 t. 0 t to 0.05 t. 0.05 t to 0.3 t, 0.05 t to 0.25 t, 0.05 t to 0.2 t, 0.05 t to 0.15 t, 0.05 t to 0.1 t, 0.1 t to 0.3 t, 0.1 t to 0.25 t, 0.1 t to 0.2 t, 0.1 t to 0.15 t, and all ranges and subranges therein, where t is the thickness of the glass-ceramic article 100.

[0039] In some embodiments, the maximum CT ranges from 10 MPa to 170 / √t, where t is the thickness of the glass-ceramic article in millimeters. In some embodiments, the maximum CT is greater than or equal to 10 MPa, 20 MPa, 30 MPa, 40 MPa, 50 MPa, 60 MPa, 70 MPa, 80 MPa, 90 MPa, 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, or 150 MPa. In some implementations, the maximum CT can be in the following ranges: 10 MPa to 150 MPa, 10 MPa to 100 MPa, 10 MPa to 90 MPa, 10 MPa to 80 MPa, 10 MPa to 70 MPa, 20 MPa to 150 MPa, 20 MPa to 100 MPa, 20 MPa to 90 MPa, 20 MPa to 80 MPa, 20 MPa to 70 MPa, 30 MPa to 150 MPa, 30 MPa to 100 MPa, 30 MPa to 90 MPa, 30 MPa to 80 MPa, 30 MPa to 70 MPa, 40 MPa to 150 MPa, 40 MPa to 100 MPa, 40 MPa to 90 MPa, 40 MPa to 80 MPa, 40 MPa to 70 MPa, 50 MPa to 150 MPa, 50 MPa to 100 MPa, 50 MPa to 100 MPa, 50 MPa to 15 ...50 MPa, 50 MPa to 100 MPa, 50 MPa to 150 MPa, 50 MPa to 150 MPa, 50 MPa to 150 MPa, 50 MPa to 150 MPa, 50 MPa to 150 MPa MPa to 90 MPa, 50 MPa to 80 MPa, 50 MPa to 70 MPa, or any range and subrange thereof.

[0040] In some embodiments, the depth of the compressive stress layer (e.g., DOC and / or DOC') is greater than the depth d1, d1' of the outer vitreous region. In some embodiments, the depth of the compressive stress layer (e.g., DOC and / or DOC') is in the range of 0.05. t to 0.3 t, 0.05 t to 0.25 t, 0.05 t to 0.2 t, 0.05 t to 0.15 t, 0.05 t to 0.1 t, 0.1 t to 0.3 t, 0.1 t to 0.25 t, 0.1 t to 0.2 t, 0.1 t to 0.15 t, 0.15 t to 0.3 t, 0.15 t to 0.25 t, 0.15 t to 0.2 t, and all ranges and subranges thereof, where t is the thickness of the glass-ceramic article. For example, the depth of the compressive stress layer can be greater than 0.05. t, 0.06 t, 0.07 t, 0.08 t, 0.09 t, 0.1 t, 0.11 t, 0.12 t, 0.13 t, 0.14 t, 0.15 t, 0.16 t, 0.17 t, 0.18 t, 0.19 t, 0.2 t, 0.21 t, 0.22 t, 0.23 t, 0.24 t, 0.25 t, 0.26 t, 0.27 t, 0.28 t, 0.29 t or 0.3 In other embodiments, the depth of the compressive stress layer is in the following ranges: 0.05 mm to 0.6 mm, 0.05 mm to 0.5 mm, 0.05 mm to 0.4 mm, 0.05 mm to 0.3 mm, 0.05 mm to 0.2 mm, 0.05 mm to 0.1 mm, 0.1 mm to 0.6 mm, 0.1 mm to 0.5 mm, 0.1 mm to 0.4 mm, 0.1 mm to 0.3 mm, 0.2 mm to 0.6 mm, 0.2 mm to 0.5 mm, 0.2 mm to 0.4 mm, and all ranges and subranges therein. In some embodiments, the depth of the compressive stress layer is greater than or equal to 0.05 mm, 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm, 0.45 mm, 0.5 mm, 0.55 mm, or 0.6 mm.

[0041] In some embodiments, the outer vitreous region (e.g., 106, 110) may have a thickness of approximately: 100 nm to 25 µm, 100 nm to 20 µm, 100 nm to 15 µm, 100 nm to 10 µm, 100 nm to 5 µm, 500 nm to 25 µm, 500 nm to 20 µm, 500 nm to 15 µm, 500 nm to 10 µm, 500 nm to 5 µm, 1 µm to 25 µm, 1 µm to 20 µm, 1 µm to 15 µm, 1 µm to 10 µm, 1 µm to 5 µm, 1 µm to 4 µm, 1 µm to 3 µm, 2 µm to 25 µm, 2 µm to 20 µm, 2 µm to 15 µm, 2 µm to 10 µm, 2 µm to 5 µm, 2 µm to 4 µm, 3 µm to 25 µm. The vitreous outer region may have a thickness greater than or equal to 100 nm, 200 nm, 3 µm to 20 µm, 3 µm to 15 µm, 3 µm to 10 µm, 3 µm to 5 µm, 5 µm to 25 µm, 5 µm to 20 µm, 5 µm to 15 µm, 5 µm to 10 µm, and all ranges and subranges therebetween. In some embodiments, the outer vitreous region may have a thickness greater than or equal to 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 µm, 1.5 µm, 2 µm, 2.5 µm, 3 µm, 3.5 µm, 4 µm, 4.5 µm, 5 µm, 10 µm, 15 µm, or 20 µm.

[0042] In some embodiments, the outer region of the glassy material can transition to the inner region. For example, the outer region of the glassy material can be characterized by having: (i) a substantially uniform percentage of crystal area and / or a substantially uniform lithium-ion concentration; and (ii) a gradient of crystal and / or lithium-ion concentration with increasing average slope as depth from the surface increases. The transition region can be characterized by having a gradient of crystal area percentage and / or lithium-ion concentration, wherein the percentage of crystal area and / or lithium-ion concentration increases from the outer region of the glassy material to the inner region with a second average slope, the absolute value of which is greater than the absolute value of the first average slope of the outer region of the glassy material. The inner region can be characterized by having: (i) at least a portion having a substantially uniform percentage of crystal area and / or lithium-ion concentration; and / or (ii) a portion having a gradient of crystal and / or lithium-ion concentration with increasing average slope as depth from the surface increases, wherein the absolute value of the second average slope of the transition region is greater than the absolute value of the third average slope of the inner region. In some embodiments, the absolute value of the average second slope of the transition region is at least three times the absolute value of the average first slope of the vitreous region and / or the absolute value of the average third slope of the inner region. In some embodiments, the transition region may be formed when the outer vitreous region is formed by decrystallization of one or more crystalline phases of a glass-ceramic article during an ion exchange process. In some implementations, the transition region may have depths of: greater than 0 µm to 40 µm, greater than 0 µm to 35 µm, greater than 0 µm to 30 µm, greater than 0 µm to 25 µm, greater than 0 µm to 20 µm, greater than 0 µm to 15 µm, greater than 0 µm to 10 µm, 5 µm to 40 µm, 5 µm to 35 µm, 5 µm to 30 µm, 5 µm to 25 µm, 5 µm to 20 µm, 5 µm to 15 µm, 5 µm to 10 µm, 10 µm to 40 µm, 10 µm to 35 µm, 10 µm to 30 µm, 10 µm to 25 µm, 10 µm to 20 µm, and all ranges and subranges therein.

[0043] Figure 3 This is an exemplary diagram of a reinforced glass-ceramic article 100, which has a transition region 320 between the outer vitreous region 106 and the inner vitreous region 108, and a transition region 322 between the outer vitreous region 1110 and the inner vitreous region 108. Figure 3As shown, in some embodiments where transition regions 320 and 322 exist, the inner region is defined as the thickness between d2 and d2', where d2 is greater than d1 and d2' is greater than d1', transition region 320 is defined as the thickness between d1 and d2, and transition region 322 is defined as the thickness between d1' and d2'. Figure 3 This is merely an example, and as described above, there may be cases with only a single outer vitreous region, and transition regions between the single outer and inner vitreous regions. In other embodiments, there may be... Figure 3 The first and second outer vitreous regions are shown, but only a single transition region (either of 320 or 322) exists. In some embodiments, such as when the outer vitreous layer is formed by stacking or fusing glass layers onto a glass ceramic, the transition between the outer and inner vitreous regions may be a transition point rather than a transition region.

[0044] In some embodiments, the reduced modulus of the outer region of the vitreous is less than that of the inner region. In some embodiments, the reduced modulus of the outer region of the vitreous is less than that of the inner region by: 5% to 30%, 5% to 25%, 5% to 20%, 5% to 15%, 5% to 10%, 10% to 30%, 10% to 25%, 10% to 20%, 10% to 15%, 15% to 30%, 15% to 25%, 15% to 20%, and any range and subranges therebetween. In some embodiments, the reduced modulus of the outer region of the vitreous is less than that of the inner region by 5%, 10%, 15%, 20%, 25%, or 30%. It is believed that the lower reduced modulus of the outer region of the vitreous improves the scratch resistance of the glass-ceramic article, as shown in more detail in Example 2 below. The reduced modulus was measured according to the nanoindentation scheme described above. The reduced modulus is related to Young's modulus, and the reduced modulus can be converted to Young's modulus based on the following relationship: 1 / E r = [(1-v 2 ) / E] + [(1-v i 2 ) / E i ], where E r E is the reduced modulus, E is Young's modulus, and v is Poisson's ratio. i It is the Young's modulus of the nanoindentation meter, and v i It is the Poisson's ratio of the nanoindentation meter.

[0045] In some embodiments, the hardness of the outer region of the vitreous material is less than that of the inner region. In some embodiments, the hardness of the outer region of the vitreous material is less than that of the inner region by: 5% to 30%, 5% to 25%, 5% to 20%, 5% to 15%, 5% to 10%, 10% to 30%, 10% to 25%, 10% to 20%, 10% to 15%, 15% to 30%, 15% to 25%, 15% to 20%, and any range and subranges therebetween. In some embodiments, the hardness of the outer region of the vitreous material is less than that of the inner region by 5%, 10%, 15%, 20%, 25%, or 30%. It is believed that the lower hardness of the outer region of the vitreous material improves the scratch resistance of the glass-ceramic article, as shown in more detail in Example 2 below. Hardness was measured according to the nanoindentation scheme described above.

[0046] In some embodiments, the average maximum scratch width of the glass-ceramic article is less than or equal to 155 µm, 150 µm, 145 µm, 140 µm, 135 µm, 130 µm, 125 µm, 120 µm, 115 µm, 110 µm, 105 µm, 100 µm, 95 µm, or 90 µm, based on the average of 15 scratches under a 5 N load. In some embodiments, the average maximum scratch width of the glass-ceramic article is less than or equal to 150 µm, 145 µm, 140 µm, 135 µm, 130 µm, 125 µm, 120 µm, 115 µm, 110 µm, 105 µm, 100 µm, 95 µm, 90 µm, 85 µm, or 80 µm, based on an average of 15 scratches, measured by a scratch test with a 1 N load. In some embodiments, the average maximum scratch width of the glass-ceramic article is less than or equal to 100 µm, 90 µm, 80 µm, 70 µm, 60 µm, 50 µm, 45 µm, 40 µm, 35 µm, 30 µm, 25 µm, or 20 µm, measured by a scratch test with a 1 N load. As described above, it is believed that the lower hardness and / or lower reduced modulus of the outer region of the vitreous material compared to the inner region contributes to the improvement in scratch resistance in terms of the average maximum scratch width of the glass-ceramic article, as shown in Example 2 below. In some embodiments, the average maximum scratch width increases by no more than 3 times or no more than 2 times as the scratch test load increases.

[0047] In some embodiments, for a glass-ceramic article with a thickness of 1 mm, the glass-ceramic article is transparent for light in the wavelength range of 450 nm to 600 nm, and has an average transmittance (including surface reflection losses) of 85% or greater, 86% or greater, 87% or greater, 88% or greater, 89% or greater, 90% or greater, 91% or greater, 92% or greater, or 93% or greater. In other embodiments, the glass-ceramic may be translucent in the wavelength range of 450 nm to 600 nm. In some embodiments, for a glass-ceramic article with a thickness of 1 mm, the translucent glass-ceramic may have an average transmittance of about 20% to less than about 85% for light in the wavelength range of about 450 nm to about 600 nm. In some embodiments, the refractive index of the outer regions 106 and 110 of the glass is lower than that of the inner region 108.

[0048] In some embodiments, one or more of the above properties may be different for the first and second surfaces 102, 104. For example, the stress distribution of the glass-ceramic article may be asymmetrical, for example: (i) the compressive stresses at the first and second surfaces 102, 104 may differ from each other by 5%, 10%, 15%, 20%, or 25%; (ii) the depths of the compressive stress layers measured from the first and second surfaces 102, 104 may differ from each other by 5%, 10%, 15%, 20%, or 25%; (iii) the average compressive stresses in each outer region of the vitreous may differ from each other by 5%, 10%, 15%, 20%, or 25%; and / or (iv) the thicknesses in the outer regions of the vitreous may differ from each other by 5%, 10%, 15%, 20%, or 25%. As a complement or alternative to having an asymmetric stress distribution, the reduced modulus, hardness and / or maximum scratch width of the first and second surfaces 102, 104 under loads of 1 N, 3 N and / or 5 N may differ by 5%, 10%, 15%, 20% or 25%, respectively.

[0049] In some embodiments, the thickness t of the glass-ceramic article is in the following ranges: 0.2 mm to 4 mm, 0.2 mm to 3 mm, 0.2 mm to 2 mm, 0.2 mm to 1.5 mm, 0.2 mm to 1 mm, 0.2 mm to 0.9 mm, 0.2 mm to 0.8 mm, 0.2 mm to 0.7 mm, 0.2 mm to 0.6 mm, 0.2 mm to 0.5 mm, 0.3 mm to 4 mm, 0.3 mm to 3 mm, 0.3 mm to 2 mm, 0.3 mm to 1.5 mm, 0.3 mm to 1 mm, 0.3 mm to 0.9 mm, 0.3 mm to 0.8 mm, 0.3 mm to 0.7 mm, 0.3 mm to 0.6 mm, 0.3 mm to 0.5 mm, 0.4 mm to 4 mm, 0.4 mm to 3 mm, 0.4 mm to 2 mm, 0.4 mm to 1.5 mm, 0.4 mm to 1 mm, 0.4 mm to 1 mm, 0.4 mm to 4 mm, 0.4 mm to 3 mm, 0.4 mm to 2 mm, 0.4 mm to 1.5 ...4 mm, 0.4 mm to 3 mm, 0.4 mm to 2 mm, 0.4 mm to 1 mm, 0.4 mm to 1 mm, 0.4 mm to 4 mm, 0.4 mm to 4 mm, 0.4 mm to 4 mm, 0.4 mm to 3 The thickness ranges from 0.5 mm to 0.9 mm, 0.4 mm to 0.8 mm, 0.4 mm to 0.7 mm, 0.4 mm to 0.6 mm, 0.5 mm to 4 mm, 0.5 mm to 3 mm, 0.5 mm to 2 mm, 0.5 mm to 1.5 mm, 0.5 mm to 1 mm, 0.5 mm to 0.9 mm, 0.5 mm to 0.8 mm, 0.5 mm to 0.7 mm, 0.8 mm to 4 mm, 0.8 mm to 3 mm, 0.8 mm to 2 mm, 0.8 mm to 1.5 mm, 0.8 mm to 1 mm, 1 mm to 2 mm, 1 mm to 1.5 mm, and all ranges and subranges therebetween. In some embodiments, the glass-ceramic article may be substantially planar and flat. In other embodiments, the glass-ceramic article may be shaped, for example, it may have a 2.5D or 3D shape. In some embodiments, the glass-ceramic article may have a uniform thickness, while in other embodiments, the glass-ceramic article may not have a uniform thickness.

[0050] In some embodiments, the glass-ceramic articles disclosed herein may be laminates. In such embodiments, the vitreous region may be a glass layer, while the inner region may be glass-ceramic. The glass may be any suitable ion-exchangeable glass, such as glass containing alkali metal ions. In such embodiments, the vitreous region has a zero (0) crystal area percentage. The glass and glass-ceramic layers can be laminated together in a conventional manner. In some embodiments, lamination may include fusing the layers together. In other embodiments, lamination excludes fusing the layers together. In some embodiments, the layers may be ion-exchanged before lamination. In other embodiments, ion exchange may be performed after lamination.

[0051] composition

[0052] The precursor glass and glass-ceramic described herein can generally be described as lithium-containing aluminosilicate glass or glass-ceramic, and contain SiO2, Al2O3, and Li2O. In addition to SiO2, Al2O3, and Li2O, the glass and glass-ceramic practiced herein may also contain basic salts (e.g., Na2O, K2O, Rb2O, or Cs2O), as well as P2O5 and ZrO2, and many other components described below. In some embodiments, the precursor glass (before ceramization) and / or glass-ceramic (after ceramization), by weight percentage of oxides, may have the following composition: SiO2: 55-80%; Al2O3: 2-20%; Li2O: 5-20%; B2O3: 0-10%; Na2O: 0-5%; ZnO: 0-10%; P2O5: 0.5-6%; and ZrO2: 0.2-15%.

[0053] In some embodiments, the precursor glass and / or glass-ceramic, by weight percentage of the oxide, have a composition that also optionally includes the following additional components: K2O: 0-4%; MgO: 0-8%; TiO2: 0-5%; CeO2: 0-0.4%; and SnO2: 0.05-0.5%.

[0054] Table 1 below lists exemplary precursor glass and glass-ceramic compositions in wt% of metal oxides.

[0055]

[0056] Table 1 (continued)

[0057] Table 1 (continued)

[0058] SiO2, an oxide related to glass forming, can stabilize the network structure of glass and glass-ceramic materials. In some embodiments, the glass or glass-ceramic composition contains about 55 to about 80% by weight of SiO2. In some embodiments, the glass or glass-ceramic composition contains about 69 to about 80% by weight of SiO2. In some embodiments, the glass or glass-ceramic composition may contain SiO2 of the following ranges and subranges: about 55 to about 80 wt%, about 55 to about 77 wt%, about 55 to about 75 wt%, about 55 to about 73 wt%, 60 to about 80 wt%, about 60 to about 77 wt%, about 60 to about 75 wt%, about 60 to about 73 wt%, 65 to about 80 wt%, about 65 to about 77 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, 69 to about 80 wt%, about 69 to about 77 wt%, about 69 to about 75 wt%, about 69 to about 73 wt%, about 70 to about 80 wt%, about 70 to about 77 wt%, about 70 to about 75 wt%, about 70 to about 73 wt%, about 73 to about 80 wt%, about 73 to about 77 wt%, about 73 to about 75 wt%, about 75 to about 80 wt%, about 75 to about 77 wt%, about 77 to about 80 wt%, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition contains about 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80% by weight of SiO2.

[0059] Regarding viscosity and mechanical properties, these are influenced by the glass composition. In glasses and glass-ceramics, SiO2 acts as the primary glass-forming oxide for the precursor glass and also functions to stabilize the network structure of the glass and glass-ceramics. The amount of SiO2 can be limited to control the melting temperature (200 poise temperature), as the melting temperature of pure SiO2 or high-SiO2 glasses is undesirably high.

[0060] Al₂O₃ can also provide network stabilization, as well as improved mechanical properties and chemical durability. However, if the amount of Al₂O₃ is too high, the proportion of lithium silicate crystals may decrease, possibly to the point where interlocking structures cannot be formed. The amount of Al₂O₃ can be adjusted to control viscosity. Furthermore, if the amount of Al₂O₃ is too high, the viscosity of the melt generally also increases. In some embodiments, the glass or glass-ceramic composition may contain about 2 to about 20 wt% Al₂O₃. In some embodiments, the glass or glass-ceramic composition may contain about 6 to about 9 wt% Al₂O₃. In some embodiments, the glass or glass-ceramic composition may contain Al2O3 as follows: about 2 to about 20%, about 2 to about 18% by weight, about 2 to about 15% by weight, about 2 to about 12% by weight, about 2 to about 10% by weight, about 2 to about 9% by weight, about 2 to about 8% by weight, about 2 to about 5% by weight, about 5 to about 20%, about 5 to about 18% by weight, about 5 to about 15% by weight, about 5 to about 12% by weight, about 5 to about 10% by weight, about 5 to about 9% by weight, about 5 to about 8% by weight, about 6 to about 20%, about 6% by weight. From about 18% by weight, about 6% to about 15% by weight, about 6% to about 12% by weight, about 6% to about 10% by weight, about 6% to about 9% by weight, about 8% to about 20%, about 8% to about 18% by weight, about 8% to about 15% by weight, about 8% to about 12% by weight, about 8% to about 10% by weight, about 10% to about 20%, about 10% to about 18% by weight, about 10% to about 15% by weight, about 10% to about 12% by weight, about 12% to about 20%, about 12% to about 18% by weight, about 12% to about 15% by weight, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% by weight Al2O3.

[0061] In the glasses and glass-ceramics described herein, Li₂O contributes to the formation of crystalline phases. In some practical compositions, the glass or glass-ceramic may contain about 5% to about 20% by weight of Li₂O. In other embodiments, the glass or glass-ceramic may contain about 10% to about 14% by weight of Li₂O. In some embodiments, the glass or glass-ceramic composition may contain Li2O as follows: about 5 to about 20 wt%, about 5 to about 18 wt%, about 5 to about 16 wt%, about 5 to about 14 wt%, about 5 to about 12 wt%, about 5 to about 10 wt%, about 5 to about 8 wt%, 7 to about 20 wt%, about 7 to about 18 wt%, about 7 to about 16 wt%, about 7 to about 14 wt%, about 7 to about 12 wt%, about 7 to about 10 wt%, 10 to about 20 wt%, about 10 to about 18 wt%, about 10 to about 16 wt%, about 10 to about 14 wt%, about 10 to about 12 wt%, 12 to about 20 wt%, about 12 to about 18 wt%, about 12 to about 16 wt%, about 12 to about 14 wt%, 14 to about 20 wt%, about 14 to about 18 wt%, about 14 to about 16 wt%, about 16 to about 20 wt%, about 16 to about 18 wt%, about 18 to about 20 wt%, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% by weight of Li2O.

[0062] As mentioned above, Li₂O is generally used to form the glass-ceramics in practice, but other basic oxides tend to reduce the formation of glass-ceramics and the formation of aluminosilicate residual glass within them. It has been found that amounts exceeding about 5% by weight of Na₂O or K₂O (or combinations thereof) result in undesirable amounts of residual glass, leading to deformation during crystallization and undesirable microstructures from a mechanical property perspective. The composition of the residual glass can be tuned to: control the viscosity during crystallization to minimize deformation or undesirable thermal expansion, or control microstructure properties. Therefore, the compositions described herein generally have low amounts of non-lithium basic oxides. In some embodiments, the glass or glass-ceramic composition may contain about 0 to about 5% by weight of R₂O, wherein R is one or more of the basic cations Na and K. In some embodiments, the glass or glass-ceramic composition may contain about 1 to about 3% by weight of R₂O, wherein R is one or more of the basic cations Na and K. In some embodiments, the glass or glass-ceramic composition may contain Na₂O or K₂O (or combinations thereof) in the ranges of: 0 to about 5 wt%, 0 to 4 wt%, 0 to 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, >0 to about 5 wt%, >0 to about 4 wt%, >0 to about 3 wt%, >0 to about 2 wt%, >0 to about 1 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 3 wt%, about 1 to about 2 wt%, about 2 to about 5 wt%, about 2 to about 4 wt%, about 2 to about 3 wt%, about 3 to about 5 wt%, about 3 to about 4 wt%, about 4 to about 5 wt%, and all ranges and subranges therebetween. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 1, 2, 3, 4, or 5 wt% R₂O.

[0063] Glass and glass-ceramic compositions may contain P2O5. P2O5 can function as a nucleating agent to produce bulk nucleation. If the concentration of P2O5 is too low, the precursor glass does crystallize, but only at higher temperatures (due to lower viscosity), and a weak and often deformable bulk is formed from the surface inward; however, if the concentration of P2O5 is too high, it becomes difficult to control devitrification after cooling during precursor glass formation. Embodiments may contain >0 to about 6 wt% P2O5. Other embodiments may contain about 2 to about 4 wt% P2O5. Still other embodiments may contain about 1.5 to about 2.5 wt% P2O5.The composition of practice may comprise P2O5 as follows: 0 to about 6 wt%, 0 to about 5.5 wt%, 0 to about 5 wt%, 0 to about 4.5 wt%, 0 to about 4 wt%, 0 to about 3.5 wt%, 0 to about 3 wt%, 0 to about 2.5 wt%, 0 to about 2 wt%, 0 to about 1.5 wt%, 0 to about 1 wt%, >0 to about 6 wt%, >0 to about 5.5 wt%, >0 to about 5 wt%, >0 to about 4.5 wt%, >0 to about 4 wt%, >0 to about 3.5 wt%, >0 to about 3 wt%, >0 to about 2.5 wt%, >0 to about 2 wt%, >0 to about 1.5 wt%, >0 to about 1 wt%, about 0.5 to about 6 wt%, about 0.5 to About 5.5% by weight, about 0.5% to about 5% by weight, about 0.5% to about 4.5% by weight, about 0.5% to about 4% by weight, about 0.5% to about 3.5% by weight, about 0.5% to about 3% by weight, about 0.5% to about 2.5% by weight, about 0.5% to about 2% by weight, about 0.5% to about 1.5% by weight, about 0.5% to about 1% by weight, about 1% to about 6% by weight, about 1% to about 5.5% by weight, about 1% to about 5% by weight, about 1% to about 4.5% by weight, about 1% to about 4% by weight, about 1% to about 3.5% by weight, about 1% to about 3% by weight, about 1% to about 2.5% by weight, about 1% to about 2% by weight, about 1% to about 1.5% by weight, about 1.5% to about 6% by weight, about 1.5% to about 5.5% by weight, about 1%. 5 to 5% by weight, about 1.5 to 4.5% by weight, about 1.5 to 4% by weight, about 1.5 to 3.5% by weight, about 1.5 to 3% by weight, about 1.5 to 2.5% by weight, about 1.5 to 2% by weight, about 2 to 6% by weight, about 2 to 5.5% by weight, about 2 to 5% by weight, about 2 to 4.5% by weight, about 2 to 4% by weight, about 2 to 3.5% by weight, about 2 to 3% by weight, about 2 to 2.5% by weight, about 2.5 to 6% by weight, about 2.5 to 5.5% by weight, about 2.5 to 5% by weight, about 2.5 to 4.5% by weight, about 2.5 to 4% by weight, about 2.5 to 3.5% by weight. %, about 3 to about 6 wt%, about 3 to about 5.5 wt%, about 3 to about 5 wt%, about 3 to about 4.5 wt%, about 3 to about 4 wt%, about 3 to about 3.5 wt%, about 3.5 to about 6 wt%, about 3.5 to about 5.5 wt%, about 3.5 to about 5 wt%, about 3.5 to about 4.5 wt%, about 3.5 to about 4 wt%, about 4 to about 6 wt%, about 4 to about 5.5 wt%, about 4 to about 5 wt%, about 4 to about 4.5 wt%, about 4.5 to about 6 wt%, about 4.5 to about 5.5 wt%, about 4.5 to about 5 wt%, about 5 to about 6 wt%, about 5 to about 5.5 wt%, about 5.5 to about 6 wt%, and all ranges and subranges therein.In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6% by weight of P2O5.

[0064] In the glasses and glass-ceramics discussed herein, ZrO2 is generally found to improve the stability of Li2O-Al2O3-SiO2-P2O5 glasses by significantly reducing glass devitrification during forming and lowering the liquidus temperature. At concentrations above 8 wt%, ZrSiO4 forms the main liquidus phase at high temperatures, which significantly reduces the liquidus viscosity. When the glass contains more than 2 wt% ZrO2, a transparent glass-ceramic is formed. The addition of ZrO2 also helps reduce the crystal grain size, which contributes to the formation of transparent glass-ceramics. In some embodiments, the glass or glass-ceramic composition may contain about 0.2 to about 15 wt% ZrO2. In some embodiments, the glass or glass-ceramic composition may contain about 2 to about 4 wt% ZrO2. In some embodiments, the glass or glass-ceramic composition may contain ZrO2 in the following proportions: about 0.2 to about 15 wt%, about 0.2 to about 12 wt%, about 0.2 to about 10 wt%, about 0.2 to about 8 wt%, about 0.2 to 6 wt%, about 0.2 to about 4 wt%, 0.5 to about 15 wt%, about 0.5 to about 12 wt%, about 0.5 to about 10 wt%, about 0.5 to about 8 wt%, about 0.5 to 6 wt%, about 0.5 to about 4 wt%, 1 to about 15 wt%, about 1 to about 12 wt%, about 1 to about 10 wt%, about 1 to about 8 wt%, about 1 to 6 wt%, about 1 to about 4 wt%, and 2 to about 15 wt%. %, about 2 to about 12 wt%, about 2 to about 10 wt%, about 2 to about 8 wt%, about 2 to 6 wt%, about 2 to about 4 wt%, about 3 to about 15 wt%, about 3 to about 12 wt%, about 3 to about 10 wt%, about 3 to about 8 wt%, about 3 to 6 wt%, about 3 to about 4 wt%, about 4 to about 15 wt%, about 4 to about 10 wt%, about 4 to about 8 wt%, about 4 to 6 wt%, about 8 to about 15 wt%, about 8 to about 12 wt%, about 8 to about 10 wt%, about 10 to about 12 wt%, about 12 to about 15 wt%, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt% ZrO2.

[0065] B₂O₃ is beneficial for improving precursor glasses with low melting solubility. Furthermore, the addition of B₂O₃ to the precursor glass (and consequently to glass-ceramics) helps achieve an interlocked crystal microstructure and can also improve the glass-ceramics' resistance to breakage. When boron in the residual glass is not charged by basic oxides or divalent cation oxides, it is in a trigonal coordination state (or, tricoordinated boron), which opens up the glass's structure. The network around these tricoordinated borons is not as rigid as tetrahedral (or tetracoordinated) boron. It is believed, without being bound by theory, that precursor glasses and glass-ceramics containing tricoordinated boron can tolerate a certain degree of deformation before crack formation. This tolerance of deformation increases the Vickers indentation crack initiation value. It can also increase the fracture toughness of precursor glasses and glass-ceramics containing tricoordinated boron. It is believed, without being bound by theory, that the presence of boron in the residual glass (and precursor glass) of glass-ceramics reduces the viscosity of the residual glass (or precursor glass), which facilitates the growth of lithium silicate crystals, especially large crystals with high aspect ratios. It is believed that a larger amount of tricoordinated boron (as opposed to tetracoordinated boron) results in a greater Vickers indentation crack initiation load on the glass-ceramic. In some embodiments, the amount of tricoordinated boron (as a percentage of all B₂O₃) can be about 40% or more, 50% or more, 75% or more, about 85% or more, or even about 95% or more. In general, the amount of boron should be controlled to maintain the chemical durability and mechanical strength of the ceramized bulk glass-ceramic.

[0066] In one or more embodiments, the glass and glass-ceramic described herein may contain 0 to about 10 wt% or 0 to about 2 wt% B2O3. In some embodiments, the glass or glass-ceramic composition may contain B2O3 as follows: 0 to about 10 wt%, 0 to about 9 wt%, 0 to about 8 wt%, 0 to about 7 wt%, 0 to about 6 wt%, 0 to about 5 wt%, 0 to about 4 wt%, 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, >0 to about 10 wt%, >0 to about 9 wt%, >0 to about 8 wt%, >0 to about 7 wt%, >0 to about 6 wt%, >0 to about 5 wt%, >0 to about 4 wt%, >0 to about 3 wt%, >0 to about 2 wt%, >0 to about 1 wt%, about From 1 to 10 wt%, from 1 to 8 wt%, from 1 to 6 wt%, from 1 to 5 wt%, from 1 to 4 wt%, from 1 to 2 wt%, from 2 to 10 wt%, from 2 to 8 wt%, from 2 to 6 wt%, from 2 to 4 wt%, from 3 to 10 wt%, from 3 to 8 wt%, from 3 to 6 wt%, from 3 to 4 wt%, from 4 to 5 wt%, from 5 wt% to 8 wt%, from 5 wt% to 7.5 wt%, from 5 wt% to 6 wt%, from 5 wt% to 5.5 wt%, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% B2O3.

[0067] MgO can be incorporated into lithium aluminosilicate crystals. In one or more embodiments, the glass and glass-ceramics described herein may contain 0 to about 8% by weight of MgO. In some embodiments, the glass or glass-ceramic composition may contain MgO in the following ranges and subranges: 0 to 8 wt%, 0 to 7 wt%, 0 to 6 wt%, 0 to 5 wt%, 0 to 4 wt%, 0 to 3 wt%, 0 to 2 wt%, 0 to 1 wt%, about 1 to 8 wt%, about 1 to 7 wt%, about 1 to 6 wt%, about 1 to 5 wt%, about 1 to 4 wt%, about 1 to 3 wt%, about 1 to 2 wt%, about 2 to 8 wt%, about 2 to 7 wt%, about 2 to 6 wt%, about 2 to 5 wt%, about 2 to 4 wt%, about 2 to 3 wt%, about 3 to 8 wt%, about 3 to 7 wt%, about 3 to 6 wt%, about 3 to 5 wt%, about 3 to 4 wt%, about 4 to 8 wt%, about 4 to 7 wt%, about 4 to 6 wt%, about 4 to 5 wt%, about 5 to 8 wt%, about 5 to 7 wt%, about 5 to 6 wt%, about 6 to 8 wt%, about 6 to 7 wt%, about 7 wt% to 8 wt%, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 1, 2, 3, 4, 5, 6, 7, or 8% by weight of MgO.

[0068] ZnO will be incorporated into lithium aluminosilicate. In one or more embodiments, the glass and glass-ceramic described herein may contain 0 to 10 wt% ZnO. In some embodiments, the glass or glass-ceramic composition may contain ZnO as follows: 0 to 10 wt%, 0 to 9 wt%, 0 to 8 wt%, 0 to 7 wt%, 0 to 6 wt%, 0 to 5 wt%, 0 to 4 wt%, 0 to 3 wt%, 0 to 2 wt%, 0 to 1 wt%, about 1 to 10 wt%, about 1 to 9 wt%, about 1 to 8 wt%, about 1 to 7 wt%, about 1 to 6 wt%, about 1 to 5 wt%, about 1 to 4 wt%, about 1 to 3 wt%, about 1 to 2 wt%, about 2 to 10 wt%, about 2 to 9 wt%, about 2 to 8 wt%, about 2 to 7 wt%, about 2 to 6 wt%, about 2 to 5 wt%, about 2 to 4 wt%, about 2 to 3 wt%, about 3 to 1 wt%. 0% by weight, about 3 to 9% by weight, about 3 to 8% by weight, about 3 to 7% by weight, about 3 to 6% by weight, about 3 to 5% by weight, about 3 to 4% by weight, about 4 to 10% by weight, about 4 to 9% by weight, about 4 to 8% by weight, about 4 to 7% by weight, about 4 to 6% by weight, about 4 to 5% by weight, about 5 to 10% by weight, about 5 to 9% by weight, about 5 to 8% by weight, about 5 to 7% by weight, about 5 to 6% by weight, about 6 to 10% by weight, about 6 to 9% by weight, about 6 to 8% by weight, about 6 to 7% by weight, about 7 to 10% by weight, about 7 to 9% by weight, about 7% by weight to 8% by weight, about 8 to 10% by weight, about 8 to 9% by weight, about 9 to 10% by weight, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight of ZnO.

[0069] In one or more embodiments, the glass and glass-ceramic described herein may contain 0 to about 5 wt% TiO2. In some embodiments, the glass or glass-ceramic composition may contain TiO2 in the following ranges and subranges: 0 to about 5 wt%, 0 to about 4 wt%, 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 3 wt%, about 1 to about 2 wt%, about 2 to about 5 wt%, about 2 to about 4 wt%, about 2 to about 3 wt%, about 3 to about 5 wt%, about 3 to about 4 wt%, about 4 to about 5 wt%, and all ranges and subranges therebetween. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 1, 2, 3, 4, or 5 wt% TiO2.

[0070] In one or more embodiments, the glass and glass-ceramic described herein may contain 0 to about 0.4 wt% CeO2. In some embodiments, the glass or glass-ceramic composition may contain CeO2 in the following ranges and subranges: 0 to about 0.4 wt%, 0 to about 0.3 wt%, 0 to about 0.2 wt%, 0 to about 0.1 wt%, about 0.1 to about 0.4 wt%, about 1 to about 0.3 wt%, about 1 to about 0.2 wt%, about 0.2 to about 0.4 wt%, about 0.2 to about 0.3 wt%, about 0.3 to about 0.4 wt%, and all ranges and subranges therebetween. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 0.1, 0.2, 0.3, or 0.4 wt% CeO2.

[0071] In one or more embodiments, the glass and glass-ceramic described herein may contain 0 to about 0.5 wt% SnO2. In some embodiments, the glass or glass-ceramic composition may contain SnO2 in the following ranges and subranges: 0 to about 0.5 wt%, 0 to about 0.4 wt%, 0 to about 0.3 wt%, 0 to about 0.2 wt%, 0 to about 0.1 wt%, about 0.05 to about 0.5 wt%, 0.05 to about 0.4 wt%, 0.05 to about 0.3 wt%, 0.05 to about 0.2 wt%, 0.05 to about 0.1 wt%, about 0.1 to about 0.5 wt%, about 0.1 to about 0.4 wt%, about 0.1 to about 0.3 wt%, about 0.1 to about 0.2 wt%, about 0.2 to about 0.5 wt%, about 0.2 to about 0.4 wt%, about 0.2 to about 0.3 wt%, about 0.3 to about 0.5 wt%, about 0.3 to about 0.4 wt%, about 0.4 to about 0.5 wt%, and all ranges and subranges therein. In some embodiments, the glass or glass-ceramic composition may contain about 0, >0, 0.05, 0.1, 0.2, 0.3, 0.4, or 0.5 mol% SnO2.

[0072] Heat treatment for crystallization / ceramization

[0073] In one or more embodiments, the process for manufacturing glass-ceramics includes: heat-treating a precursor glass at one or more predetermined temperatures for one or more predetermined periods of time to induce glass homogenization and crystallization (i.e., nucleation and growth) of one or more crystalline phases (e.g., having one or more compositions, amounts, geometries, sizes, or size distributions). In some embodiments, the heat treatment may include: (i) at 1-10 (ii) Heating the precursor glass to the glass nucleation temperature at a rate of C / min; (iii) Maintaining the crystallizable glass at the glass nucleation temperature for about 1 / 4 hour to about 4 hours to produce a pre-nucleation crystallizable glass; (iv) Heating the pre-nucleation crystallizable glass to the nucleation temperature (Tn) at a rate of C / min; (v) Maintaining the crystallizable glass at the nucleation temperature for approximately 1 / 4 hour to approximately 4 hours to produce nucleated crystallizable glass; C / minute to approximately 10 (vi) The nucleated crystallizable glass is heated to the crystallization temperature (Tc) at a rate of C / min; (vi) the nucleated crystallizable glass is maintained at the crystallization temperature for about 1 / 4 hour to about 4 hours to produce the glass-ceramic described herein; and (vii) the formed glass-ceramic is cooled to room temperature. The term crystallization temperature, as used herein, may be used interchangeably with ceramization temperature or ceramization process. Furthermore, the terms "ceramization" or "ceramization" in these embodiments may be used together to denote steps (v), (vi), and optionally (vii). In some embodiments, the temperature before glass nucleation may be 500 °C. C to 600 C (for example, 500) C, 510 C, 520 C, 530 C, 540 C, 550 C, 560 C, 570 C, 580 C, 590 C, or 600 C); the nucleation temperature can be 530. C to 650 C (for example, 530) C, 540 C, 550 C, 560 C, 570 C, 580 C, 590 C, 600 C, 610 C, 620 C, 630 C, 640 C, or 650 C); and / or the crystallization temperature can be 630°C. C to 850 C (e.g., 630) C, 640 C, 650 C, 660 C, 670 C, 680 C, 690 C, 700 C, 710 C, 720 C, 730 C, 740 C, 750 C, 760 C, 770 C, 780 C, 790 C, 800 C, 810 C, 820 C, 830 C, 840 C, or 850 C). In some embodiments, the crystallization temperature depends on whether a transparent or translucent / opaque glass-ceramic is required. In some embodiments, approximately 750°C. Crystallization temperatures of C or lower result in transparent glass-ceramics, while those above approximately 750°C lead to transparent glass-ceramics. The crystallization temperature of C results in translucent / opaque glass-ceramics. In some embodiments, the glass can be heated to 540°C. The pre-nucleation temperature of C was maintained at the pre-nucleation temperature for 4 hours, and then heated to 600°C. The nucleation temperature of C was maintained at the nucleation temperature for 4 hours, then heated to 730°C. The crystallization temperature of C, and the time to maintain the crystallization temperature for 4 hours.

[0074] In other embodiments, the heat treatment does not include maintaining the crystallizable glass at a pre-nucleation temperature. Therefore, the heat treatment may include: (i) at 1-10 (ii) Heating the precursor glass to the nucleation temperature (Tn) at a rate of C / min; (iii) Maintaining the crystallizable glass at the nucleation temperature for about 1 / 4 hour to about 4 hours to produce nucleated crystallizable glass; C / minute to approximately 10 (iv) The nucleated crystallizable glass is heated to the crystallization temperature (Tc) at a rate of C / min; the nucleated crystallizable glass is maintained at the crystallization temperature for about 1 / 4 hour to about 4 hours to produce the glass-ceramic described herein; and (v) the formed glass-ceramic is cooled to room temperature. In the foregoing embodiments, the term "ceramization" or "ceramization" may be used to refer to steps (iii), (iv), and optionally (v) collectively. In some embodiments, the nucleation temperature may be 500 °C. C to 650 C (for example, 500) C, 510 C, 520 C, 530 C, 540 C, 550 C, 560 C, 570 C, 580 C, 590 C, 600 C, 610 C, 620 C, 630 C, 640 C, or 650 C); and / or the crystallization temperature can be 600°C. C to 850 C (for example, 600) C, 610 C, 620 C, 630 C, 640 C, 650 C, 660 C, 670 C, 680 C, 690 C, 700 C, 710 C, 720 C, 730 C, 740 C, 750 C, 760 C, 770 C, 780 C, 790 C, 800 C, 810 C, 820 C, 830 C, 840 C, or 850 C, 740 C, 750 C, 760 C, 770 C, 780 C, 790 C, 800 C, 810 C, 820 C, 830 C, 840 C, or 850 C). In some embodiments, the crystallization temperature depends on whether a transparent or translucent / opaque glass-ceramic is required. In some embodiments, approximately 750°C. Crystallization temperatures of C or lower result in transparent glass-ceramics, while those above approximately 750°C lead to transparent glass-ceramics. The crystallization temperature of C results in translucent / opaque glass-ceramics. In some embodiments, the glass can be heated to 560°C. The nucleation temperature of C was maintained at the nucleation temperature for 4 hours, then heated to 720°C. The crystallization temperature of C, and the time to maintain the crystallization temperature for 1 hour.

[0075] In addition to the composition of the precursor glass, the temperature-time profiles of the heat treatment steps, which involve heating to the crystallization temperature and maintaining the temperature at the crystallization temperature, are carefully selected to produce one or more of the following desired properties: the crystalline phase of the glass-ceramic, the ratio of one or more primary crystalline phases and / or one or more secondary crystalline phases to the residual glass, the crystalline phase set of one or more primary crystalline phases and / or one or more secondary crystalline phases to the residual glass, and the grain size or grain size distribution among one or more primary crystalline phases and / or one or more secondary crystalline phases, which in turn can affect the final integrity, quality, color, and / or opacity of the resulting glass-ceramic.

[0076] After the precursor glass undergoes the aforementioned heat treatment, the resulting glass-ceramic has one or more crystalline phases and a residual glassy phase. In some embodiments, the glass-ceramic contains the following exemplary crystalline phases: lithium disilicate, spodumene, β-spodumene solid solution, β-quartz solid solution, and any combination thereof. In some embodiments, a mixture of lithium disilicate, spodumene, and β-quartz solid solution crystalline phases may be present. In other embodiments, a mixture of lithium disilicate and spodumene crystalline phases may be present. In other embodiments, a mixture of lithium disilicate and β-quartz solid solution crystalline phases may be present. In other embodiments, a mixture of lithium disilicate, β-spodumene solid solution, and β-quartz solid solution crystalline phases may be present. In some embodiments, lithium disilicate is the crystalline phase with the highest weight percentage. In some embodiments, spodumene is the crystalline phase with the highest weight percentage. In some embodiments, β-spodumene is the crystalline phase with the highest weight percentage. In some embodiments, β-quartz is the crystalline phase with the highest weight percentage. In some embodiments, the residual glass content of the glass-ceramic is: about 5 to about 30 wt%, about 5 to about 25 wt%, about 5 to about 20 wt%, about 5 to about 15 wt%, about 5 to about 10 wt%, about 10 to about 30 wt%, about 10 to about 25 wt%, about 10 to about 20 wt%, about 10 to about 15 wt%, about 15 to about 30 wt%, about 15 to about 25 wt%, about 15 to about 20 wt%, about 20 to about 30 wt%, about 20 to about 25 wt%, about 25 to about 30 wt%, and all ranges and subranges therebetween. In some embodiments, the residual glass content can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%. In some embodiments, the inner region may have the following crystal weight percentages: greater than 20 wt% to 100 wt%, greater than 20 wt% to 90 wt%, greater than 20 wt% to 80 wt%, greater than 20 wt% to 70 wt%, 30 wt% to 100 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 30 wt% to 70 wt%, 40 wt% to 100 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 50 wt% to 100 wt%, 50 wt% to 90 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, and all ranges and subranges therein.In some embodiments, the inner region may have the following crystal weight percentages: greater than 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%.

[0077] Ion exchange

[0078] In some embodiments, glass-ceramic articles can be chemically strengthened using one or more ion exchange techniques. In these embodiments, a compressive stress layer can be formed on one or more surfaces of such glass-ceramic articles by subjecting them to one or more ion exchange media (e.g., a molten salt bath) with a specific composition and temperature for a specific time period. In some embodiments, the ion exchange medium is a molten bath containing ions (e.g., alkali metal ions) larger than those present in the glass-ceramic article, wherein the larger ions from the molten bath exchange with the smaller ions in the glass-ceramic article, imparting compressive stress in the glass-ceramic article and thereby increasing its strength. As described above, in some embodiments, when the glass-ceramic article is subjected to the ion exchange conditions described below, the residual glass phase undergoes ion exchange, and one or more crystalline phases are "decrystallized" to form surface regions or layers having a lower weight percentage of crystals than the inner regions of the glass-ceramic article. During this decrystallization process, one or more crystalline phases may fracture via the ion exchange process.

[0079] In some embodiments, a single-step ion exchange process can be used, while in others, a multi-step ion exchange process can be used. In some embodiments, for both single-step and multi-step ion exchange processes, the ion exchange medium (e.g., a molten bath) may contain 100% by weight of a sodium-containing salt (e.g., NaNO3) or may contain a mixed salt bath (e.g., a combination of a sodium-containing salt (e.g., NaNO3) and a potassium-containing salt (e.g., KNO3)). In some embodiments, the molten salt bath contains a sodium-containing salt (e.g., NaNO3) in the following ranges: 3% to 100% by weight, 3% to 95% by weight, 3% to 90% by weight, 3% to 85% by weight, 3% to 80% by weight, 3% to 75% by weight, 5% to 100% by weight, 5% to 95% by weight, 5% to 90% by weight, 5% to 85% by weight, 5% to 80% by weight, 5% to 75% by weight. 10% to 100% by weight, 10% to 95% by weight, 10% to 90% by weight, 10% to 85% by weight, 10% to 80% by weight, 10% to 75% by weight, 20% to 100% by weight, 20% to 95% by weight, 20% to 90% by weight, 20% to 85% by weight, 20% to 80% by weight, 20% to 75% by weight, 30% to 100% by weight, 30% to 95% by weight, 30% to 90% by weight, 30% to 85% by weight, 30% to 80% by weight, 30% to 75% by weight, and all ranges and subranges therein. In some embodiments, the molten salt bath contains sodium salts (e.g., NaNO3) of 3% to 95% by weight, 5% to 10% by weight, 15% to 20% by weight, 25% to 30% by weight, 35% to 40% by weight, 45% to 50% by weight, 55% to 60% by weight, 65% to 70% by weight, 75% to 80% by weight, 85% to 90% by weight, or 95% by weight. In some embodiments, the molten salt bath may also contain up to 1% by weight of NaNO2 (e.g., 0.25% to 0.5% by weight, 0.75% by weight, or 1% by weight), as its interaction with alkaline earth metals reduces impurities in the molten salt bath.

[0080] In some implementations, for a single-step ion exchange process, ion exchange is performed in a fresh bath, wherein the bath is considered fresh if it contains a total of less than 0.03 wt%, less than 0.02 wt%, less than 0.01 wt%, less than 0.009 wt%, less than 0.008 wt%, less than 0.007 wt%, less than 0.006 wt%, less than 0.005 wt%, or less than 0.0004 wt% of lithium-poisoned salts (including but not limited to LiNO3 and LiNO2). A fresh melt bath contributes to faster forming times and greater final vitreous outer region depth, as illustrated in the examples below.

[0081] In some embodiments, a multi-step ion exchange process (e.g., a two-step ion exchange process) may include a first ion exchange step in which the ion exchange medium (e.g., a molten salt bath) is poisoned with lithium salts, and a second ion exchange step is performed in an ion exchange medium (e.g., a molten salt bath) having a lower total content of lithium-poisoned salts. The molten salt bath in the first ion exchange step is intentionally poisoned to a level that prevents the formation of a vitreous outer region during the first step. In some embodiments, the molten salt bath in the first ion exchange step contains a total of the following lithium-containing salts (e.g., LiNO3 and / or LiNO2): 0.03 wt% to 0.5 wt%, 0.03 wt% to 0.4 wt%, 0.03 wt% to 0.3 wt%, 0.03 wt% to 0.2 wt%, 0.03 wt% to 0.1 wt%, 0.05 wt% to 0.5 wt%, 0.05 wt% to 0.4 wt%, 0.05 wt% to 0.3 wt%, 0.05 wt% to 0.2 wt%, 0. 0.05 wt% to 0.1 wt%, 0.07 wt% to 0.5 wt%, 0.07 wt% to 0.4 wt%, 0.07 wt% to 0.3 wt%, 0.07 wt% to 0.2 wt%, 0.07 wt% to 0.1 wt%, 0.1 wt% to 0.5 wt%, 0.1 wt% to 0.4 wt%, 0.1 wt% to 0.3 wt%, 0.1 wt% to 0.2 wt%, 0.2 wt% to 0.5 wt%, 0.2 wt% to 0.4 wt%, and all ranges and subranges therein. In the first ion exchange step, a deep compressive stress layer is formed, and then in the second ion exchange step, a vitreous outer region is formed. In some embodiments, the total lithium salt content (e.g., LiNO3 and / or LiNO2) in the ion exchange medium (e.g., molten salt bath) of the first ion exchange step is at least 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, or 0.05 wt% higher than that in the ion exchange medium (e.g., molten salt bath) of the second ion exchange step. In some embodiments, the poisoning level preventing the formation of a vitreous outer region in the second step of a two-step ion exchange is higher than the poisoning level preventing the formation of a vitreous outer region in the same bath but used in a single-step ion exchange. For example, the permissible poisoning level in the second step of a two-step ion exchange process may be at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% higher than the permissible poisoning level in the same bath but used in a single-step ion exchange. In some embodiments, this two-step process results in a thicker vitreous outer region than a single-step ion exchange process. These trends are illustrated in the embodiments below.

[0082] In some embodiments, the first ion exchange medium is maintained at a higher temperature than the second ion exchange medium, and / or the glass-ceramic article is in contact with the first ion exchange medium for a longer period than it is in contact with the second ion exchange medium. In some embodiments, multi-step ion exchange may include a third ion exchange.

[0083] Final product

[0084] The reinforced glass-ceramic articles disclosed herein can be integrated into another article, such as articles with displays (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and wearable devices (e.g., watches)), building articles, transportation articles (e.g., vehicles, trains, aircraft, ships, etc., used as interior display covers, windows, or windbreaks), electrical articles, or any article requiring partial transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles incorporating any of the reinforced glass-ceramic articles disclosed herein include... Figure 4A and 4B As shown. Specifically, Figure 4A and 4B Display consumer electronic device 400 includes: a housing 402 having a front surface 404, a rear surface 406, and a side surface 408; electronic components (not shown) at least partially or entirely located within the housing and including at least a controller, memory, and a display 410 located on or adjacent to the front surface of the housing; and a cover substrate 412 located on or above the front surface of the housing, thereby positioning it above the display. In some embodiments, at least one of the cover substrate 412 or a portion of the housing 402 may include any reinforced glass-ceramic article as disclosed herein.

[0085] Example

[0086] The various implementation methods are further illustrated by the following examples.

[0087] Example 1

[0088] The resulting 800-micrometer-thick precursor glass sample had the following composition by weight of oxides: 73.47% SiO2, 7.51% Al2O3, 2.14% P2O5, 11.10% Li2O, 1.63% Na2O, 3.55% ZrO2, and 0.22% SnO2. The precursor glass sample was then subjected to a ceramization process, with the glass uniformly held at 540°C for 4 hours, followed by nucleation at 600°C for 4 hours, and then crystallization at 730°C for 4 hours, thereby forming a glass-ceramic. The glass-ceramic possessed lithium disilicate and lithium feldspar crystalline phases, as well as a residual glassy phase.

[0089] Then, the sample was subjected to ion exchange under the conditions listed in Table 2 below.

[0090] Table 2

[0091] Figure 5 The concentration distribution of Na₂O and K₂O (in mol%) was measured using a microprobe. For all three samples, the Na₂O concentration at the surface ranged from 18 to 20 mol%. This was confirmed by ion exchange occurring in some crystalline portions of the glass-ceramic. X-ray diffraction traces of the samples were taken before and after ion exchange under the conditions of Sample 1, as shown in the diagram. Figure 6 As shown, the X-ray diffraction traces of the ion-exchanged glass-ceramic show a decrease in crystal content (lithium disilicate and lithium feldspar phase). Without being bound by theory, it is believed that ion exchange occurs in the crystals of the glass-ceramic, resulting in a glassy region approximately 5 micrometers thick when lithium is extracted from the crystal. This destabilizes the sodium counterpart of the crystal due to the incoming ions.

[0092] Figure 7 The stress distribution of samples 1-3 after ion exchange, measured using a combination of techniques described above, shows a different pattern than... Figure 2 The typical configuration shows compressive stress as negative and tensile stress as positive. The stress distribution exhibits a distinct parabolic shape. The maximum tensile stress exceeds 50 MPa.

[0093] Example 2

[0094] Union-exchanged glass-ceramic samples with a thickness of 800 micrometers were formed according to the scheme in Example 1. Ion exchange was performed on the samples according to the conditions in Table 3 below, and the reduced modulus, hardness, and penetration depth were measured using the nanoindentation technique described above. The depth of the glassy region formed during the ion exchange process was also measured using GDEOS (glow discharge emission spectroscopy) based on changes in alkali metal ion concentration. Note that GDEOS is an alternative technique to the SEM measurement technique described above for measuring the depth of the glassy region. The average maximum scratch width was also measured according to the scratch test described above, with 1 N, 3 N, and 5 N loads for each sample, and the average of 15 measurements was used.

[0095] Table 3

[0096] As the data above shows, a glassy region was formed in both ion exchange processes, but the sample ion-exchanged in a 95 wt% NaNO3 salt bath exhibited a thicker glassy region. Using the two-step ion exchange as a control to minimize glassy region formation reveals how a thicker glassy region leads to lower reduced modulus, lower hardness, and a lower average maximum scratch width. For example, Figure 8 (Where, the y-axis represents the reduced modulus (GPa) and the x-axis represents the thickness of the glassy region (µm)). This shows that the thicker the glassy region, the smaller the reduced modulus. Extrapolating the data points yields the line equation 7 = -5.7267x + 100.3, R0 2 The value is 0.97.

[0097] Table 3 also shows that samples with a large glassy region thickness and ion exchanged in a 95 wt% NaNO3 salt bath exhibited the best scratch performance (lowest average maximum scratch width). Two sets of scratch tests were performed on samples ion-exchanged in a 95 wt% NaNO3 salt bath. The results for 3 N and 5 N loads were similar; however, the results for 1 N load changed. It is believed that the change in the 1 N load result is due to the increased likelihood of transverse cracking during scratching at 1 N load, which increases the width measurement.

[0098] Example 3

[0099] An union-exchanged glass-ceramic sample with a thickness of 800 micrometers was formed according to the scheme of Example 1. The first sample underwent ion exchange in a molten salt bath for 4.5 hours. The molten salt bath contained 95 wt% NaNO3 and 5 wt% KNO3, and 0.5 wt% NaNO2 additive. The bath was fresh and contained less than about 0.01 wt% LiNO3 and LiNO2. The first sample had a region at the surface with a thickness of about 5 micrometers where the crystalline phase had been consumed (in this region, there was more amorphous phase compared to before ion exchange). The average compressive stress in this region was about 200 MPa. This region had a reduced modulus of about 84 GPa, compared to about 100 GPa for the glass-ceramic before ion exchange. A Na2O concentration gradient existed from the surface to a depth exceeding 30% of the thickness. The compressibility depth, measured by SCALP, was between 13% and 20% of the thickness, and the maximum central tension was about 65 MPa.

[0100] The second sample underwent ion exchange in a molten salt bath at 470°C for 4 hours. This bath contained 95 wt% NaNO3 and 5 wt% KNO3, along with 0.5 wt% NaNO2 additive, and was poisoned due to the presence of more than approximately 0.03 wt% LiNO3 and LiNO2. It is believed that the lithium poisoning of the bath prevented the formation of a glass transition layer. Compared to the first sample, the second sample exhibited similar or slightly lower central tension, and through scratch testing with loads of 1 N, 3 N, and 5 N as described above, the maximum scratch width obtained on the second sample (approximately 200 μm at 5 N load) was approximately twice that of the first sample (approximately 100 μm at 5 N load).

[0101] Example 4

[0102] Thirty glass-ceramic samples with dimensions of 50 mm x 50 mm x 0.8 mm were prepared as in Example 1. These 30 samples underwent a first ion exchange for 4 hours in a NaNO3 molten salt bath at 460°C, the bath containing 0.5% NaNO2 additive by weight. The molten salt bath was intentionally poisoned to contain 0.04 to 0.05% LiNO3 by weight. It is believed that bath poisoning prevented the formation of vitrified regions as a result of the first ion exchange. The samples were then subsequently subjected to a second ion exchange in six groups under the conditions listed in Table 4 below, starting with a fresh molten salt bath containing 2.6 kg NaNO3 and 0.5% NaNO2 additive by weight.

[0103] Table 4

[0104] Figure 9 This graph shows the relationship between the total area of ​​the sample with vitrified region (per kg of bath salt) and lithium poisoning (wt% LiNO3) at the end of each run. Figure 9 The results showed that after the 6th run, the samples in group 6 had approximately 6 times more vitrified area than the samples in group 1 after the 1st run. Figure 10 The thickness (DOL) of each vitreous region in each sample group is displayed. Samples are immersed in the ion exchange bath in a vertical orientation, and the surface points located at the top of the ion exchange bath are marked by GDEOS. Figure 10 (referred to as "DOL top") and the point located at the center of the surface ( Figure 10 The DOL (Deck of Oxide) is used to measure the glassy region (referred to as the "DOL center" in the text). The measurement at the top of the DOL is greater than that at the center, indicating a decreasing thickness gradient of the glassy region on the surface of the glass-ceramic sample from the edge at the top of the ion exchange bath to the edge at the bottom. It is believed that this phenomenon can be prevented by agitating the ion exchange bath.

[0105] The effective diffusion coefficient (Deff) was measured for each group of samples, and Figure 11 The graph shows the relationship between Deff and the weight percentage of LiNO3 at the start of each run. The relationship between Deff and DOL in the glassy region is as follows: DOL = 2 √(Deff The formula is given by t), where t is time. It can be seen that Deff decreases with increasing lithium poisoning, and remains above 0 even when poisoning exceeds 0.02 wt% LiNO3. Figure 11 The top and center of the Deff were recorded, calculated based on the Deff from the top to the center of the DOL. This level of poisoning exceeds that of restricted poisoning, which forms the vitrified region in a single IOX step by at least 50%.

[0106] Figure 12 The average compressive stress in the vitrified region of each sample group is shown, and it is shown that after run 3, the average compressive stress in the vitrified region begins to decrease.

[0107] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope or spirit of the invention. For example, various features can be combined according to the following embodiments.

[0108] Implementation Method 1: A glass-ceramic product comprising: First surface; The second surface opposite to the first surface; A first region extending from the first surface to a first depth d1; A second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region contains both crystalline and glassy phases; and A compressive stress layer extending from the first surface to the depth of compression (DOC); Wherein, the percentage of crystal area in the first region is less than the percentage of crystal area in the second region. Wherein, the DOC is greater than or equal to 0.05 mm, and The average compressive stress in the first region is greater than or equal to 50 MPa.

[0109] Embodiment 2: The glass-ceramic product as described in Embodiment 1, wherein the DOC is greater than or equal to 0.1 mm.

[0110] Embodiment 3: A glass-ceramic product comprising: First surface; The second surface opposite to the first surface; A first region extending from the first surface to a first depth d1; A second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region contains both crystalline and glassy phases; and A compressive stress layer extending from the first surface to the depth of compression (DOC); Wherein, the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, and Wherein, the DOC is greater than d1.

[0111] Implementation Method 4: The glass-ceramic product as described in Implementation Method 3, wherein the DOC is greater than or equal to 0.05. t, where t is the thickness of the glass-ceramic product.

[0112] Implementation Method 5: The glass-ceramic product as described in Implementation Method 3, wherein the DOC is greater than or equal to 0.1. t, where t is the thickness of the glass-ceramic product.

[0113] Embodiment 6: A glass-ceramic article as described in any of the preceding embodiments, wherein the reduced modulus of the first region is less than the reduced modulus of the second region.

[0114] Embodiment 7: A glass-ceramic article as described in any of the preceding embodiments, wherein the hardness of the first region is less than the hardness of the second region.

[0115] Embodiment 8: A glass-ceramic article as described in any of the preceding embodiments, wherein, when a scratch test is performed with a 5 N load, the average maximum scratch width of the first surface is less than 155 micrometers based on the average of 15 measurements.

[0116] Embodiment 9: A glass-ceramic article comprising: First surface; The second surface opposite to the first surface; A first region extending from the first surface to a first depth d1; and A second region extending from a depth greater than or equal to d1 to a second depth, wherein the second region contains both crystalline and glassy phases; Wherein, the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, and The reduction modulus of the first region is less than that of the second region.

[0117] Embodiment 10: The glass-ceramic article as described in Embodiment 9, wherein the reduced modulus of the first region is at least 5% smaller than the reduced modulus of the second region.

[0118] Embodiment 11: A glass-ceramic article comprising: First surface; The second surface opposite to the first surface; A first region extending from the first surface to a first depth d1; and A second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region contains both crystalline and glassy phases; Wherein, the area percentage of crystals in the first region is less than the area percentage of crystals in the second region, and The hardness of the first region is less than that of the second region.

[0119] Embodiment 12: The glass-ceramic article as described in Embodiment 11, wherein the hardness of the first region is at least 5% less than the hardness of the second region.

[0120] Embodiment 13: A glass-ceramic article as described in Embodiment 11 or 12, wherein the reduced modulus of the first region is less than the reduced modulus of the second region.

[0121] Embodiment 14: A glass-ceramic article comprising: The first surface, when subjected to a scratch test with a 5 N load, has an average maximum scratch width of less than 155 micrometers based on the average of 15 measurements. The second surface opposite to the first surface; A first region extending from the first surface to a first depth d1; and A second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0122] Embodiment 15: The glass-ceramic article as described in Embodiment 14, wherein, when a scratch test is performed with a 3 N load, the average maximum scratch width of the first surface is less than 150 micrometers based on the average of 15 measurements.

[0123] Embodiment 16: A glass-ceramic article as described in Embodiment 14 or 15, wherein, when a scratch test is performed with a 1 N load, the average maximum scratch width of the first surface is less than 100 micrometers based on the average of 15 measurements.

[0124] Embodiment 17: A glass-ceramic article comprising: The first surface, when subjected to a scratch test with a 1 N load, has an average maximum scratch width of less than 100 micrometers based on the average of 15 measurements. The second surface opposite to the first surface; A first region extending from the first surface to a first depth d1; and A second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0125] Embodiment 18: The glass-ceramic article as described in Embodiment 14, wherein, when a scratch test is performed with a 3 N load, the average maximum scratch width of the first surface is less than 150 micrometers based on the average of 15 measurements.

[0126] Embodiment 19: A glass-ceramic article as described in any one of Embodiments 14-18, wherein the reduced modulus of the first region is less than the reduced modulus of the second region.

[0127] Embodiment 20: A glass-ceramic article as described in any one of Embodiments 14-19, wherein the hardness of the first region is less than the hardness of the second region.

[0128] Embodiment 21: A glass-ceramic article as described in any of the preceding embodiments, wherein the glass-ceramic article contains lithium.

[0129] Embodiment 22: A glass-ceramic article as described in Embodiment 21, wherein the crystalline phase comprises lithium disilicate.

[0130] Embodiment 23: A glass-ceramic article as described in Embodiment 21 or 22, wherein the crystal phase includes one or more of the following: lepidolite, β-spodumene solid solution, or β-quartz solid solution.

[0131] Embodiment 24: A glass-ceramic article as described in any of the preceding embodiments, wherein the depth d1 is at least 100 nm.

[0132] Embodiment 25: A glass-ceramic article as described in any of the preceding embodiments, wherein d1 is 100 nm to 25 µm.

[0133] Embodiment 26: A glass-ceramic article as described in any of the preceding embodiments, wherein d1 is 1 µm to 4 µm.

[0134] Embodiment 27: A glass-ceramic article as described in any of the preceding embodiments, wherein the refractive index of the first region is lower than that of the second region.

[0135] Embodiment 28: A glass-ceramic article as described in any of the preceding embodiments, wherein the compression depth is 0.05. t to 0.3 t, where t is the thickness of the glass-ceramic product.

[0136] Embodiment 29: A glass-ceramic article as described in any of the preceding embodiments, wherein the average compressive stress in the first region of the glass-ceramic article is 50 MPa to 1500 MPa.

[0137] Embodiment 30: A glass-ceramic article as described in any of the preceding embodiments, wherein the inner region has a compressive stress of at least 10 MPa extending at least 5 micrometers into the inner region.

[0138] Embodiment 31: A glass-ceramic article as described in any of the preceding embodiments, wherein the inner region has a compressive stress of at least 30 MPa extending at least 5 micrometers into the inner region.

[0139] Embodiment 32: A glass-ceramic article as described in any of the preceding embodiments, wherein the unit of the maximum central tension is MPa and the range is 10 to 170 / √t, where t is the thickness of the glass-ceramic article in millimeters.

[0140] Embodiment 33: A glass-ceramic article as described in any of the preceding embodiments, wherein the maximum center tension is 40 MPa to 150 MPa.

[0141] Embodiment 34: A glass-ceramic article as described in any of the preceding embodiments, wherein the glass-ceramic article is transparent and has a transmittance of at least 85% for light in the wavelength range of 450 nm to 600 nm for a thickness of 1 mm.

[0142] Embodiment 35: The glass-ceramic article as described in any of the preceding embodiments further includes a third region extending from the second surface to a third depth d1', wherein the third depth d1' is measured starting from the second surface, and the area percentage of crystals in the third region is less than the area percentage of crystals in the second region.

[0143] Embodiment 36: The glass-ceramic article as described in Embodiment 35, wherein the first depth d1 is greater than the third depth d1'.

[0144] Embodiment 37: A glass-ceramic article as described in Embodiment 36, wherein the first depth d1 is at least 5% greater than the third depth d1'.

[0145] Embodiment 38: A glass-ceramic article as described in any one of Embodiments 35-37, wherein the compressive stress at the first surface is greater than the compressive stress at the second surface.

[0146] Embodiment 39: A glass-ceramic article as described in any one of Embodiments 35-38, wherein the reduced modulus of the third region is less than the reduced modulus of the second region.

[0147] Embodiment 40: A glass-ceramic article as described in any one of Embodiments 35-39, wherein the hardness of the third region is less than the hardness of the second region.

[0148] Embodiment 41: A glass-ceramic article as described in any one of Embodiments 35-40, wherein, when a scratch test is performed with a 5 N load, the average maximum scratch width of the second surface is less than 155 micrometers based on the average of 15 measurements.

[0149] Embodiment 42: A glass-ceramic article as described in any one of Embodiments 35-41, wherein the compressive stress at the first surface is at least 5% greater than the compressive stress at the second surface.

[0150] Embodiment 43: A glass-ceramic article as described in any of the preceding embodiments, wherein the thickness t of the glass-ceramic article is 4 mm or less.

[0151] Embodiment 44: A glass-ceramic article as described in Embodiment 43, wherein the thickness of the glass-ceramic article is 1 mm or less.

[0152] Embodiment 45: A glass-ceramic article as described in any of the preceding embodiments, wherein the area percentage of crystals in the first region is 0.

[0153] Embodiment 46: The glass-ceramic article as described in any of the preceding embodiments further includes a transition region between the first region and the inner region.

[0154] Embodiment 47: A glass-ceramic article as described in any one of Embodiments 1-46, wherein the glass-ceramic article is not a laminate.

[0155] Embodiment 48: A glass-ceramic article as described in any one of Embodiments 1-45, wherein the glass-ceramic article is a laminate, the second region is glass-ceramic and the first region is glass.

[0156] Implementation method 49: A consumer electronics product comprising: An outer shell comprising a front surface, a back surface, and side surfaces; Electronic components, at least partially located within the housing, including at least a controller, memory, and a display, wherein the display is located on or adjacent to the front surface of the housing; and The cover substrate arranged above the display, At least one of the outer shell or covering substrates includes a glass-ceramic article as described in any of the foregoing embodiments.

[0157] Implementation Method 50: A method for ion exchange of glass-ceramic articles, the method comprising: At least such that the first surface of the glass-ceramic article is in contact with an ion exchange medium containing one or more lithium salts in total less than 0.03% by weight; and During the contact process, a first region is formed in the glass-ceramic article extending from the first surface to a first depth d1, wherein a compressive stress layer extends from the first surface to the depth of compression (DOC). Wherein, after the first region is formed, the glass-ceramic article includes a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0158] Embodiment 51: The method as described in Embodiment 50, wherein the ion exchange medium comprises at least 3% by weight of one or more sodium-containing salts.

[0159] Implementation method 52: The method as described in implementation method 51, wherein the sodium salt includes NaNO3.

[0160] Embodiment 53: The method as described in any one of Embodiments 51 or 52, wherein the ion exchange medium comprises a potassium salt.

[0161] Implementation method 54: The method as described in implementation method 53, wherein the potassium salt includes KNO3.

[0162] Embodiment 55: The method as described in any one of Embodiments 51-54, wherein the ion exchange medium contains up to 1% by weight of NaNO2.

[0163] Embodiment 56: The method of any one of Embodiments 51-55, wherein the ion exchange medium comprises one or more lithium-containing salts in total less than 0.02% by weight.

[0164] Embodiment 57: The method as described in Embodiment 56, wherein the ion exchange medium comprises one or more lithium-containing salts in total less than 0.01% by weight.

[0165] Implementation Method 58: A method for ion exchange of glass-ceramic articles, the method comprising: The surface of the glass-ceramic article is brought into contact with a first ion exchange medium containing at least 0.03% by weight of one or more lithium salts in total; After contact with the first ion exchange medium, the surface of the glass-ceramic article is brought into contact with a second ion exchange medium, wherein the total weight percentage of lithium salt contained in the second ion exchange medium is less than the total weight percentage of lithium salt contained in the first ion exchange medium; and During the contact process with the second ion exchange contact, a first region extending from the first surface to a first depth d1 and a compressive stress layer extending from the first surface to the depth of compression (DOC) are formed in the glass-ceramic article. Wherein, after the first region is formed, the glass-ceramic article includes a second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region comprises a crystalline phase and a glassy phase, and wherein the area percentage of crystals in the first region is less than the area percentage of crystals in the second region.

[0166] Embodiment 59: The method as described in Embodiment 58, wherein at least one of the first and second ion exchange media contains at least 3% by weight of one or more sodium-containing salts.

[0167] Implementation method 60: The method as described in implementation method 59, wherein the sodium salt includes NaNO3.

[0168] Embodiment 61: The method as described in any one of Embodiments 58-60, wherein at least one of the first and second ion exchange media contains a potassium salt.

[0169] Implementation method 62: The method as described in implementation method 61, wherein the potassium salt includes KNO3.

[0170] Embodiment 63: The method as described in any one of Embodiments 58-62, wherein at least one of the first and second ion exchange media contains up to 1% by weight of NaNO2.

[0171] Embodiment 64: The method of any one of Embodiments 58-63, wherein the first ion exchange medium comprises at least 0.05% by weight of one or more lithium-containing salts.

[0172] Embodiment 65: The method of any one of Embodiments 58-64, wherein the second ion exchange medium comprises a total of less than 0.5% by weight of one or more lithium-containing salts.

[0173] Implementation 66: The method as described in Implementation 65, wherein the second ion exchange medium comprises one or more lithium-containing salts in total less than 0.2% by weight.

[0174] Embodiment 67: The method of any one of Embodiments 58-66, wherein the temperature of the first ion exchange medium is maintained higher than that of the second ion exchange medium.

[0175] Embodiment 68: The method as described in any one of Embodiments 58-67, wherein the glass-ceramic article is in contact with the first ion exchange medium for a longer period than it is in contact with the second ion exchange medium.

[0176] Implementation method 69: The method of any one of implementation methods 58-68, wherein the total amount of one or more lithium salts in the first ion exchange medium is at least 0.01 by weight more than the total amount of one or more lithium salts in the second ion exchange medium.

[0177] Implementation method 70: The method as described in any one of implementation methods 50-69, wherein the reduced modulus of the first region is less than the reduced modulus of the second region.

[0178] Embodiment 71: The method as described in any one of Embodiments 50-70, wherein the hardness of the first region is less than the hardness of the second region.

[0179] Implementation 72: The method as described in any one of Implementations 50-71, wherein, when a scratch test is performed with a 5 N load, the average maximum scratch width of the first surface is less than 155 micrometers based on the average of 15 measurements.

[0180] Implementation method 73: The method as described in any one of implementation methods 50-72, wherein the DOC is greater than d1.

[0181] Embodiment 74: The method as described in any one of Embodiments 50-71, wherein the DOC is greater than or equal to 0.05 mm, and wherein the maximum compressive stress in the first region is greater than or equal to 50 MPa.

Claims

1. A glass-ceramic product comprising: First surface; The second surface opposite to the first surface; A glassy region extending from the first surface to a first depth d1, wherein d1 is greater than 5 µm and not greater than 25 µm; A second region extending from a depth greater than or equal to d1 to a second depth d2, wherein the second region contains both a crystalline phase and a glassy phase; and A compressive stress layer extending from the first surface to the depth of compression (DOC). In this region, the percentage of crystal area in the glassy region is smaller than the percentage of crystal area in the second region. In this region, the area percentage of crystals in the glassy region is 0. Specifically, at a location at least 5 µm from the interface between the glassy region and the second region, the second region has a compressive stress of at least 10 MPa, and Among them, the crystalline phase with the highest weight percentage in glass-ceramic products is lithium disilicate or lepidolite.

2. The glass-ceramic product as described in claim 1, wherein, DOC is greater than d1.

3. The glass-ceramic product as described in claim 1, wherein, The hardness of the vitreous region is less than that of the second region.

4. The glass-ceramic product as described in claim 1, wherein, The refractive index of the glassy region is lower than that of the second region.

5. The glass-ceramic product as described in claim 1, wherein, When a scratch test is performed with a 5 N load, based on the average of 15 measurements, the average maximum scratch width on the first surface is less than 155 micrometers.

6. The glass-ceramic article as described in claim 1, wherein, When a scratch test is performed with a 1 N load, based on the average of 15 measurements, the average maximum scratch width on the first surface is less than 100 micrometers.

7. The glass-ceramic article as described in claim 1, wherein, The compression depth is 0.05·t to 0.3·t, where t is the thickness of the glass-ceramic product.

8. The glass-ceramic article as described in claim 1, wherein, The average compressive stress in the glassy region ranges from 50 MPa to 1500 MPa.

9. The glass-ceramic article as described in claim 1, wherein, The maximum center tension ranges from 10 MPa to 170 / √t MPa, where t is the thickness of the glass-ceramic product in millimeters.

10. The glass-ceramic article as described in claim 1, wherein, Glass-ceramic products are transparent and have a transmittance of at least 85% for light in the wavelength range of 450 nm to 600 nm for a thickness of 1 mm.

11. The glass-ceramic article as described in claim 1, wherein, The thickness t of the glass-ceramic product is 4 mm or less.

12. The glass-ceramic article of claim 1, further comprising a third region extending from the second surface to a third depth d1', wherein the third depth d1' is measured from the second surface, wherein, The area percentage of crystals in the third region is less than the area percentage of crystals in the second region.

13. The glass-ceramic article as described in claim 12, wherein, The first depth d1 is greater than the third depth d1'.

14. The glass-ceramic article as described in claim 12, wherein, The compressive stress at the first surface is greater than the compressive stress at the second surface.

15. The glass-ceramic article as described in claim 12, wherein, The reduced modulus of the third region is less than that of the second region.

16. The glass-ceramic article as described in claim 12, wherein, The hardness of the third region is less than that of the second region.

17. A consumer electronics product comprising: An outer shell comprising a front surface, a back surface, and side surfaces; Electronic components arranged at least partially within the housing, the electronic components including at least a controller, a memory, and a display, the display being located on or adjacent to the front surface of the housing; as well as The cover substrate arranged above the display, Wherein, at least a portion of the outer shell or covering substrate comprises the glass-ceramic article as described in claim 1.

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