Glass articles coated with silica-based release agents and their ceramicizing methods

Abstract

Coated glass articles used in the ceramicization process for glass ceramics include a release agent coated on the surface of the glass article. The release agent coating may contain an aqueous dispersion comprising amorphous silica agglomerate particles and a dispersant. The release agent coating may be dried to form a release layer of the glass articles in a glass stack during the ceramicization process for transforming the glass articles into glass ceramic articles.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 033944, filed June 3, 2020, pursuant to 35 USC §119, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to release agent materials and release layers used in the ceramicization process for ceramicizing glass articles into glass-ceramic articles. Specifically, the embodiments described in this disclosure relate to release agent materials and release layers for use in the manufacture of glass-ceramic articles used in various industries (e.g., optical displays and electromagnetic charging devices). Background Technology

[0004] There is a demand for high-strength glass for consumer devices, such as portable electronic devices. Several materials are currently used in the market, including glass, zirconium oxide, plastics, metals, and glass ceramics. The advantages of using glass ceramics lie in their strength properties and high transparency, making them a viable option for a variety of applications, including optical displays and electromagnetic charging applications.

[0005] Therefore, there is a continuous demand for methods and products suitable for the efficient production of high-quality glass and ceramic products. Summary of the Invention

[0006] This disclosure relates to release agent materials and release layers for physically and chemically separating adjacent glass articles in a glass stack during the ceramization process. The release agent materials and release layers help prevent adhesion and sticking between adjacent articles during ceramization cycles, which can reduce or eliminate undesirable article warping during the cycles. The release agent materials and release layers are also non-reactive to the glass composition of the glass articles, so that the release agent materials and layers do not cause undesirable phase transitions at the surface of the glass articles during ceramization cycles. These properties of the release agent materials and release layers described in this disclosure, among others, facilitate the efficient manufacture of high-quality glass-ceramic articles.

[0007] The first aspect (1) of this application relates to a coated glass article comprising: a glass article having a first surface, a second surface opposite to the first surface, and a release agent coated on the first surface of the glass article, said release agent comprising an aqueous dispersion comprising amorphous silica agglomerate particles and a dispersant.

[0008] In the second aspect (2), the dispersant according to the first aspect (1) may include hydroxides or acids.

[0009] In the third aspect (3), the dispersant may include hydroxides.

[0010] In the fourth aspect (4), the hydroxide according to the third aspect (3) is sodium hydroxide.

[0011] In the fifth aspect (5), the release agent according to any one of aspects (1) to (4) may contain 0.25% by weight to 1% by weight of dispersant.

[0012] In the sixth aspect (6), the amorphous silica agglomerate particles according to any one of aspects (1) to (5) may contain an average (mean) particle size range of 100 nanometers to 20 micrometers.

[0013] In the seventh aspect (7), the release agent according to any one of aspects (1) to (6) may contain 10% to 30% by weight of amorphous silica agglomerate particles.

[0014] In the eighth aspect (8), the release agent according to any one of aspects (1) to (7) may contain a colloidal inorganic binder.

[0015] In the 9th aspect (9), the colloidal inorganic binder according to the 8th aspect (8) may contain colloidal silica.

[0016] In the 10th aspect (10), the release agent according to any one of aspects (1) to (9) may include a pH range of 8.5 to 11.

[0017] In the 11th aspect (11), the release agent according to any one of aspects (1) to (10) may have a viscosity range of 5 cP to 160 cP.

[0018] In the 12th aspect (12), the release agent according to any one of aspects (1) to (10) may have a viscosity range of 5 cP to 50 cP.

[0019] In the 13th aspect (13), the release agent according to any one of aspects (1) to (12) is not applied to the second surface of the glass article.

[0020] In aspect 14 (14), the amorphous silica agglomerate particles according to any one of aspects (1) to (13) are not colloidal particles.

[0021] In the 15th aspect (15), the dispersant according to any one of aspects (1) to (14) can cause amorphous silica agglomerate particles to adhere to the first surface of the glass article.

[0022] In the 16th aspect (16), the release agent according to the 1st aspect (1) is a dry release agent, and the coated glass article includes 0% to 50% haze.

[0023] The 17th aspect (17) of this application relates to a stack of glass articles comprising: a first glass article having a first surface and a second surface opposite to the first surface; a second glass article disposed above the first surface of the first glass article and having a first surface and a second surface opposite to the first surface; and a release layer disposed between the first surface of the first glass article and the second surface of the second glass article, wherein the release layer is either directly adhered to the first surface of the first glass article and in direct contact with the second surface of the second glass article, but not adhered to the second surface of the second glass article; or directly adhered to the second surface of the second glass article and in direct contact with the first surface of the first glass article, but not adhered to the first surface of the first glass article.

[0024] In the 18th aspect (18), the release layer according to the 17th aspect (17) may contain silicon dioxide.

[0025] In the 19th aspect (19), the release layer according to the 17th aspect (17) may contain amorphous silica agglomerate particles.

[0026] In aspect 20 (20), the silica agglomerate particles according to aspect (19) may contain an average (mean) agglomerate particle size range of 100 nanometers to 20 micrometers.

[0027] In aspect 21 (21), the release layer according to any one of aspects (17) to (20) may include an average (mean) coating thickness of 1 micrometer to 5 micrometers.

[0028] In aspect 22 (22), the release layer according to any one of aspects (17) to (21) may include an average (mean) dry cover of 0.5 gsm to 1.5 gsm.

[0029] In aspect 23 (23), the release layer according to any one of aspects (17) to (22) may include a thickness uniformity of + / -0.5 gsm.

[0030] The 24th aspect (24) of this disclosure relates to a method for ceramizing a plurality of glass articles, the method comprising: coating a first surface of a first glass article with a release agent comprising an aqueous dispersion comprising amorphous silica agglomerate particles and a dispersant; drying the release agent on the first surface of the first glass article; placing a second glass article in direct contact with the dried release agent to form a glass stack comprising the first glass article, the second glass article and the dried release agent; and exposing the glass stack to a ceramization cycle sufficient to ceramize the first glass article and the second glass article into glass-ceramic articles.

[0031] In the 25th aspect (25), applying a release agent to a first surface of a first glass article according to the 24th aspect (24) may include a coating process in which the release agent is not applied to a second surface of the first glass article opposite to the first surface.

[0032] In the 26th aspect (26), the release agent according to the 24th aspect (24) or the 25th aspect (25) may contain 0.25% to 1% by weight of a dispersant and 10% to 30% by weight of amorphous silica agglomerate particles.

[0033] In aspect 27 (27), the dry release layer according to any one of aspects (24) to (26) is directly adhered to the first surface of the first glass article, and the dry release layer is in direct contact with the second surface of the second glass article but is not adhered to the second surface of the second glass article. Attached Figure Description

[0034] The accompanying drawings, incorporated herein by reference, form part of the specification and illustrate embodiments of the present disclosure. In conjunction with the specification, the drawings further serve to explain the principles of the disclosed embodiments and to enable those skilled in the art to perform and use them. These drawings are intended to be illustrative and not restrictive. While the present disclosure is described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the present disclosure to these specific embodiments. In the drawings, the same reference numerals denote the same or functionally similar elements.

[0035] Figure 1 Displaying coated glass articles according to some embodiments.

[0036] Figure 2 This illustrates a ceramicized stack according to some implementation methods.

[0037] Figure 3 This illustrates a ceramicized stack including an intermediate layer pad according to some embodiments.

[0038] Figure 4 This is a particle size distribution diagram of amorphous silica agglomerates compared to two other commercially available silica particles, based on some implementation methods.

[0039] Figure 5A These are scanning electron microscope (SEM) images of the release layer on a glass-ceramic product according to some embodiments. Figure 5B These are scanning electron microscope (SEM) images of the release layer on a glass-ceramic product according to some embodiments.

[0040] Figure 6A This is the energy dispersive X-ray (EDX) analysis of the release layer in Figure 5. Figure 6B This is the energy dispersive X-ray (EDX) analysis of the glass-ceramic product in Figure 5.

[0041] Figure 7 X-ray diffraction (XRD) and Ritwald analysis show the phase assemblies in the glass-ceramic artifacts in Figure 5.

[0042] Figure 8 The surface grazing incident X-ray diffraction (GIXRD) analysis is performed at a grazing angle, and the surface interactions are only shown in the phase assemblies of the glass-ceramic artifacts in Figure 5.

[0043] Figure 9 It is a comparison of images of two coated glass-ceramic products.

[0044] Figure 10 It is a graph comparing the percentage haze of two types of coated glass products.

[0045] Figure 11 This illustrates a method according to some implementations. Detailed Implementation

[0046] The following examples of this disclosure are illustrative and not limiting. Other suitable modifications and adjustments will be apparent to those skilled in the art, depending on various conditions and parameters, and are within the spirit and scope of this disclosure.

[0047] To achieve high throughput in glass-ceramic manufacturing, conventional ceramization processes involve stacking multiple glass sheets on a backing plate and ceramizing them to form glass-ceramics. However, warping of the glass sheets can occur in conventional ceramization processes. In some cases, warping may stem from adhesion between the stacked glass sheets and adjacent glass sheets and / or the backing plate during the process. Warping can affect the strength and optical properties of glass-ceramics, among other things.

[0048] The embodiments described in this disclosure relate to release agent materials for glass-ceramic manufacturing. The release agent materials are designed to reduce or prevent adhesion between the article and adjacent articles and / or backing plates in a glass stack during ceramization cycles. By reducing or preventing adhesion, the release agent materials can help reduce or eliminate warpage (undesired shape changes) of the article during ceramization cycles. And by reducing or eliminating warpage, the yield of high-quality glass-ceramic articles can be improved.

[0049] Accordingly, the release agent material is designed to prevent adhesion between the articles and adjacent articles and / or backing plates in the glass stack during ceramization cycles. During ceramization cycles, the articles in the glass stack shrink during phase transformation and crystal growth. The release agent material described in this disclosure promotes free movement (expansion and / or shrinkage) of the articles in the glass stack during ceramization. By reducing or preventing adhesion, the release agent material can help reduce or eliminate warping of the articles during ceramization cycles. And by reducing or eliminating adhesion, the yield of high-quality glass-ceramic articles can be improved.

[0050] Furthermore, the release agent described in this disclosure has the ability to survive high-temperature ceramization cycles (e.g., ceramization temperatures exceeding 750°C) without undergoing undesirable decomposition. The material can survive these high-temperature ceramization cycles while also preventing adhesion and / or sticking between articles and / or between articles and the backing plate during the ceramization cycle.

[0051] The release agent slurry described in this disclosure can be a water-based release agent slurry. The water-based nature of the release agent slurry can reduce or eliminate contamination from waste streams. This water-based nature also provides release agent materials that do not release volatile organic compounds (VOCs) during the glass-ceramic manufacturing process.

[0052] The release agent materials described in this disclosure may be non-reactive with the glass articles on which they are coated. In other words, the release agent material may be non-reactive with the glass material composition of the glass article. Similarly, the release agent materials described in this disclosure may be non-reactive with the material of one or more backing plates used to hold the glass article during ceramization cycles. A release agent material that is “non-reactive” with the glass article means that the release agent material does not have a tendency to cause changes in the phase composition of the glass article during ceramization cycles. Similarly, a release agent material that is “non-reactive” with the material of one or more backing plates means that the release agent material does not have a tendency to cause undesirable oxide aggregation and surface roughening on the backing plate surface (which would lead to undesirable surface texturing in the glass-ceramic article). Furthermore, a “non-reactive” material is thermally stable during ceramization cycles, meaning that the material does not undergo phase or oxidation state changes during ceramization cycles. Some release agent materials (e.g., boron nitride) oxidize at high ceramization temperatures, which reduces the liquidus phase and leads to glass and boron oxide deposition on the backing plate surface. This will cause the pad material to fail.

[0053] The non-reactive properties of release agent materials can reduce or eliminate the formation of a "skin" on glass articles or backings during ceramization cycles. The "skin" formed during ceramization cycles is a phase transition of an undesirable glass composition at the surface of the glass article during the ceramization cycle, resulting from the reaction between the release agent and the glass article or backing during the ceramization process. By reducing or eliminating the formation of the "skin," the release agent material can reduce or eliminate the additional material removal steps required to remove the skin during the finishing process. In some embodiments, the release agent materials described herein can prevent the formation of a "skin" with a depth of 5 micrometers or more on the surface of the glass article or backing.

[0054] The embodiments described in this disclosure also relate to a coating process for release agent materials. The coating methods described herein facilitate the coating of a release layer with desired properties. The coating methods can deposit a release layer with desired thickness, thickness uniformity, and coverage uniformity. These properties can help reduce or prevent adhesion and sticking in glass stacks, help reduce or prevent warping in glass stacks, and / or help or eliminate skin formation during ceramization cycles. Furthermore, these properties can help reduce waste generation in glass-ceramic manufacturing processes, which can reduce process costs. In some embodiments, the coating method may include atomization of the release agent slurry.

[0055] In addition to eliminating or preventing adhesion between adjacent articles, release agent materials can also be capable of adhering to and bonding to the surface of coated glass articles. By properly adhering to and bonding to the surface of the glass article, the release agent material can reduce or eliminate the presence of loose release agent material during the manufacturing process, thereby reducing or eliminating any cleaning steps associated with removing loose material. This can reduce costs associated with glass-ceramic manufacturing processes. In some embodiments, hydroxides or acids in the release agent material can promote direct adhesion and bonding of solids in the material to the surface of the glass article.

[0056] When dry, the release agent material can directly adhere to and bond to the surface of the coated glass article. The dried release agent can also physically and chemically separate the surface of the glass article from the surfaces of adjacent glass articles or backing plates. In a specific embodiment, the dried release agent material can directly adhere to and bond to the coated glass surface. The dried release agent material described herein resists adhesion to adjacent glass article or backing plate surfaces during the ceramization cycle. This lack of adhesion promotes de-stacking of the glass-ceramic articles after the ceramization cycle.

[0057] In some embodiments, the release agent material may contain only the same atomic elements present in the glass composition of the glass articles in the glass stack. In such embodiments, the release agent material may not add atomic elements to the finishing waste stream during the polishing process of preparing glass-ceramic articles for use in the final product.

[0058] Conventional mold release agents on the market are typically classified according to the following characteristics. The mold release agent materials described in this article avoid or reduce the harmful properties of these conventional mold release agents.

[0059] Category 1: Powders, which may be organic or inorganic. Organic powders include organic materials that burn off during thermal processing and cause adhesion and / or VOC generation. Inorganic powders typically leave powder residues that must be removed from the product after a ceramicization cycle. An exemplary powder is hexagonal boron nitride powder, which leaves powder residues. Gordon's U.S. Patent No. 4,855,000 describes an exemplary hexagonal nitride powder.

[0060] Category 2: Greases and oils. These materials are not effective at the high temperatures required for glass-ceramic manufacturing methods. Exemplary greases are described in U.S. Patent No. 9,334,461 to Wirtensohn et al.

[0061] Category 3: Ceramic sheets, fiber sheets, foils, and paper. Foil materials are typically burned, releasing VOCs. The thickness variations of these materials are also difficult to control, leading to unacceptable warping in stacked glass-ceramic articles. U.S. Patent No. 5,053,107 to Barber, Jr. describes an exemplary inorganic paper comprising glass and ceramic fibers. U.S. Patent No. 5,145,811 to Lintz et al. describes an exemplary inorganic ceramic paper.

[0062] Category 4: Insert layers. These materials are not effective at the high temperatures required for glass-ceramic manufacturing processes. An exemplary insert layer is described in Bohland's U.S. Patent No. 7,108,889.

[0063] Category 5: Boron nitride-containing and boron-containing slurries. These slurries undergo oxidation during the ceramization process. They also lower the liquidus temperature of the glass article at its surface (where more free silicon atoms are present). This can lead to roughening and / or adhesion between the glass article and adjacent glass articles or pads during high-temperature ceramization cycles (e.g., ceramization temperatures above 750°C). U.S. Patent No. 7,598,210 to Olliges describes an exemplary lubricant slurry containing boron nitride.

[0064] The release agent material described in this disclosure may have one or more of the following properties: (1) The surface chemistry of the slurry allows it to interact and adhere directly to the surface it is coated with, thereby enabling it to function as an intercalation layer while facilitating slurry application processes (e.g., spray coating processes). (2) The particle size range of the agglomerates is tuned to produce physical separation between adjacent articles in a glass stack without promoting defect formation during the ceramization cycle. (3) The coating properties are ultra-thin and uniform, achieving cost advantages and improved glass-ceramic article properties. (4) Suitable anti-stick properties, which reduce or eliminate warping of articles in a glass stack, thus improving yield. (5) An environmentally friendly composition that reduces hazardous material waste streams and lowers costs. (6) The composition contains only atomic elements present in the glass composition of the glass articles in the glass stack, thus not introducing foreign substances into the finishing waste stream of the glass-ceramic manufacturing process. (7) The material adheres directly to and bonds to the surface of the glass articles on which it is coated, forming a coating that is easily removed during finishing and avoiding or reducing cleaning steps after ceramization.

[0065] Figure 1This illustrates a coated glass article 100 according to some embodiments. The coated glass article 100 includes a glass article 110 having a first surface 112 and a second surface 114 opposite to the first surface 112. In some embodiments, the first surface 112 of the glass article 110 may be the “top surface” of the glass article 110, while the second surface 114 of the glass article 110 may be the “bottom surface” of the glass article 110. In some embodiments, the first surface 112 of the glass article 110 may be the “bottom surface” of the glass article 110, while the second surface 114 of the glass article 110 may be the “top surface” of the glass article 110. As used herein, “top” and “bottom” are top and bottom features of the glass article when they are oriented in a glass stack during a ceramicization cycle.

[0066] Release agent 120 is applied to one or more surfaces of the glass article 110. In some embodiments, release agent 120 may be applied to a first surface 112 of the glass article 110. In some embodiments, release agent 120 may be applied to a second surface 114 of the glass article 110. In some embodiments, release agent 120 may be applied to both the first surface 112 and the second surface 114 of the glass article 110. In some embodiments, release agent 120 may be applied to the first surface 112 of the glass article 110 but not to the second surface 114. In some embodiments, release agent 120 may be applied only to the first surface 112 of the glass article 110. In some embodiments, release agent 120 may be applied to the second surface 114 of the glass article 110 but not to the first surface 112. In some embodiments, release agent 120 may be applied only to the second surface 114 of the glass article 110.

[0067] To coat one or more surfaces of the glass article 110 with release agent 120, a release agent slurry is formed and applied to said one or more surfaces of the glass article 110. Prior to drying, the composition of the release agent 120 coated on one or more surfaces of the glass article 110 is the same as the composition of the release agent slurry. In other words, release agent 120 is a release agent slurry coated on one or more surfaces of the glass article. After drying, release agent 120 defines a dried release agent layer (e.g., release layer 220), as described herein.

[0068] Release agent 120 (or a release agent slurry for coating release agent 120) comprises an aqueous dispersion containing silica (silica). In some embodiments, release agent 120 (or release agent slurry) may comprise an aqueous dispersion containing silica particles. In some embodiments, release agent 120 (or release agent slurry) may comprise an aqueous dispersion containing silica agglomerated particles. In some embodiments, release agent 120 (or release agent slurry) may comprise an aqueous dispersion containing amorphous silica agglomerated particles. In some embodiments, release agent 120 (or release agent slurry) may comprise an aqueous dispersion containing two or more of silica particles, silica agglomerated particles, and amorphous silica agglomerated particles. In some embodiments, the amorphous silica agglomerated particles may be pyrolytic silica soot formed by a flame hydrolysis process. An exemplary pyrolytic silica soot is AEROSIL-OX-50 pyrolytic silica, with a typical specific surface area (BET) of 35-65 square meters per gram, purchased from Evonik.

[0069] In some embodiments, the silica particles or silica agglomerates in the aqueous dispersion may have an average particle size range from 100 nanometers (nm) to 20 micrometers, including sub-ranges. For example, in some embodiments, the silica particles or silica agglomerates may have the following average particle size ranges: 100 nm to 20 micrometers, 100 nm to 10 micrometers, 100 nm to 5 micrometers, 100 nm to 1 micrometer, 100 nm to 0.9 micrometers, 100 nm to 0.8 micrometers, 100 nm to 0.7 micrometers, 100 nm to 0.6 micrometers, 100 nm to 0.5 micrometers, 100 nm to 0.4 micrometers, 100 nm to 0.3 micrometers, 100 nm to 0.2 micrometers, 0.2 micrometers to 20 micrometers, 0.3 micrometers to 20 micrometers, 0.4 micrometers to 20 micrometers, 0.5 micrometers to 20 micrometers, 0.6 micrometers to 20 micrometers, 0.7 micrometers to 20 micrometers, 0.8 micrometers to 20 micrometers, 0.9 micrometers to 20 micrometers, 1 micrometer to 20 micrometers, 5 micrometers to 20 micrometers, or 10 micrometers to 20 micrometers, or a range including any two of these values ​​as endpoints.

[0070] In some embodiments, the amorphous silica agglomerate particles of the aqueous dispersion can have an average particle size range of 100 nm to 20 micrometers, including sub-ranges. For example, in some embodiments, the amorphous silica agglomerate particles may have the following average particle size ranges: 100 nm to 20 μm, 100 nm to 10 μm, 100 nm to 5 μm, 100 nm to 1 μm, 100 nm to 0.9 μm, 100 nm to 0.8 μm, 100 nm to 0.7 μm, 100 nm to 0.6 μm, 100 nm to 0.5 μm, 100 nm to 0.4 μm, 100 nm to 0.3 μm, 100 nm to 0.2 μm, 0.2 μm to 20 μm, 0.3 μm to 20 μm, 0.4 μm to 20 μm, 0.5 μm to 20 μm, 0.6 μm to 20 μm, 0.7 μm to 20 μm, 0.8 μm to 20 μm, 0.9 μm to 20 μm, 1 μm to 20 μm, 5 μm to 20 μm, or 10 μm to 20 μm, or a range including any two of these values ​​as endpoints.

[0071] Figure 4 Figure 400 in the figure shows the particle size distribution of amorphous silica agglomerate particles (“SL56 solid”) according to some embodiments. Unless otherwise stated, the “mean particle size” values ​​described herein are obtained according to ASTM-D4464-15 (“Standard Test Method for Particle Size Distribution of Catalytic Materials by Laser Light Scattering”).

[0072] The average particle size described herein can reduce the surface roughness of the release layer and promote the formation of a thin and uniform release layer. It was found that an average particle size smaller than 100 nm is insufficient to prevent adhesion between adjacent glass articles in a glass stack. An average particle size larger than 20 micrometers was found to be difficult to apply uniformly. For example, an average particle size larger than 20 micrometers is difficult to apply by spraying processes and contributes to increasing the roughness of the release layer and / or indentations on the glass articles.

[0073] In some embodiments, the release agent 120 (or release agent slurry) may contain 10% by weight or more silica particles or silica agglomerates. In some embodiments, the percentage by weight of silica particles or silica agglomerates in the release agent 120 (or release agent slurry) may range from 10% by weight to 30% by weight, including subranges. For example, in some embodiments, the weight percentage of silica particles or silica agglomerates in the release agent 120 (or release agent slurry) may be in the following ranges: 10 wt% to 30 wt%, 10 wt% to 27.5 wt%, 10 wt% to 25 wt%, 10 wt% to 22.5 wt%, 10 wt% to 20 wt%, 10 wt% to 17.5 wt%, 10 wt% to 15 wt%, 10 wt% to 12.5 wt%, 12.5 wt% to 30 wt%, 15 wt% to 30 wt%, 17.5 wt% to 30 wt%, 20 wt% to 30 wt%, 22.5 wt% to 30 wt%, 25 wt% to 30 wt%, or 27.5 wt% to 30 wt%, or any two of these values ​​as endpoints, including the endpoints. In some embodiments, the weight percentage of silica particles or silica agglomerates in the release agent 120 (or release agent slurry) can range from 15% to 25% by weight. In some embodiments, the weight percentage of silica particles or silica agglomerates in the release agent 120 (or release agent slurry) can range from 1% to 30% by weight. The weight percentage of silica particles or silica agglomerates is the weight percentage of particles in the release agent 120 or release agent slurry, based on the total weight of the release agent 120 or release agent slurry.

[0074] In some embodiments, the release agent 120 (or release agent slurry) may contain 10% by weight or more of amorphous silica agglomerates. In some embodiments, the percentage by weight of amorphous silica agglomerates in the release agent 120 (or release agent slurry) may range from 10% by weight to 30% by weight, including subranges. For example, in some embodiments, the weight percentage of amorphous silica agglomerates in release agent 120 (or release agent slurry) may be in the following ranges: 10 wt% to 30 wt%, 10 wt% to 27.5 wt%, 10 wt% to 25 wt%, 10 wt% to 22.5 wt%, 10 wt% to 20 wt%, 10 wt% to 17.5 wt%, 10 wt% to 15 wt%, 10 wt% to 12.5 wt%, 12.5 wt% to 30 wt%, 15 wt% to 30 wt%, 17.5 wt% to 30 wt%, 20 wt% to 30 wt%, 22.5 wt% to 30 wt%, 25 wt% to 30 wt%, or 27.5 wt% to 30 wt%, or any two of these values ​​as endpoints, including the endpoints. In some embodiments, the weight percentage of amorphous silica agglomerates in release agent 120 (or release agent slurry) may be in the range of 15 wt% to 25 wt%. In some embodiments, the weight percentage of amorphous silica agglomerates in release agent 120 (or release agent slurry) can range from 1 wt% to 30 wt%. The weight percentage of amorphous silica agglomerates is the weight percentage of particles in release agent 120 or release agent slurry, based on the total weight of release agent 120 or release agent slurry.

[0075] In some embodiments, the release agent 120 (or release agent slurry) may contain a dispersant. In some embodiments, the dispersant includes one or more hydroxides, one or more acids, or combinations thereof. In some embodiments, the hydroxide may be, but is not limited to, sodium hydroxide, ammonium hydroxide, potassium hydroxide, lithium hydroxide, or alkaline earth hydroxides. Exemplary alkaline earth hydroxides include calcium hydroxide (Ca(OH)2) and magnesium hydroxide (Mg(OH)2). In some embodiments, the acid may be, but is not limited to, inorganic acids (e.g., nitric acid or phosphoric acid), organic acids (e.g., citric acid).

[0076] In some embodiments, the release agent 120 (or release agent slurry) may contain 0.25 wt% to 2 wt% of a dispersant, including sub-ranges. For example, in some embodiments, the release agent 120 (or release agent slurry) may contain the following amounts of dispersant: 0.25 wt% to 2 wt%, 0.25 wt% to 1.75 wt%, 0.25 wt% to 1.5 wt%, 0.25 wt% to 1 wt%, 0.25 wt% to 0.75 wt%, 0.25 wt% to 0.5 wt%, 0.5 wt% to 2 wt%, 0.75 wt% to 2 wt%, 1 wt% to 2 wt%, 1.25 wt% to 2 wt%, 1.5 wt% to 2 wt%, or 1.75 wt% to 2 wt%, or a range including any two of these values ​​as endpoints. In some embodiments, the release agent 120 (or release agent slurry) may contain 0.25 wt% to 1 wt% of a dispersant.

[0077] The weight percentage of the dispersant in the release agent 120 (or release agent slurry) on the glass article 110 is calculated based on the weight percentage of the dispersant compound (e.g., NaOH in release agent 120 or release agent slurry, based on the total weight of release agent 120 or release agent slurry). As a non-limiting example, for a release agent having 0.15 g NaOH, 30 g silica soot, and 118 g water, the weight percentage of NaOH is 0.1 wt%. In some embodiments, the dispersant may be present in the colloidal inorganic binder added to the release agent slurry.

[0078] In some embodiments, the total amount of water, dispersant, and silica, silica agglomerates, and / or amorphous silica agglomerate particles in the release agent 120 (or release agent slurry) may be 90% by weight or higher. For example, in some embodiments, the range of the total amount of water, dispersant, and silica, silica agglomerates, and / or amorphous silica agglomerate particles may be 90% to 100% by weight, 92% to 100% by weight, 94% to 100% by weight, 96% to 100% by weight, or 98% to 100% by weight.

[0079] In embodiments containing a dispersant, the dispersant can adhere silica particles, silica agglomerates, and / or amorphous silica agglomerates from the release agent 120 to one or more surfaces of the glass article 110 coated with the release agent 120. In some embodiments, the dispersant can promote the formation of direct bond between the particles and one or more surfaces of the glass article 100. In such embodiments, direct bond can be generated during a ceramicization cycle. In some embodiments, direct bond can be a covalent bond. In such embodiments, covalent bonds can be generated by forming Si-O-Si or Si-O-Al bonds during a ceramicization cycle.

[0080] In some embodiments, release agent 120 (or release agent slurry) may comprise a colloidal inorganic binder. In some embodiments, the colloidal inorganic binder may comprise colloidal oxides. As used herein, "colloidal oxide" (e.g., colloidal silica) refers to a solution of charged oxide particles dispersed in and insoluble in the solution. The degree of agglomeration of oxide particles in a "colloidal" solution is sensitive to changes in the pH of the solution. Non-colloidal oxide particles do not possess the same intrinsic charge as colloidal oxide particles. The agglomeration of particles in a solution of non-colloidal oxide particles is insensitive to changes in the pH of the solution. The silica particles, silica agglomerates, and / or amorphous silica particles of release agent 120 (or release agent slurry) may not be colloidal particles.

[0081] In some embodiments, the colloidal oxide may be colloidal silica, colloidal alumina, colloidal zirconium oxide, colloidal titanium oxide, colloidal tin oxide, or a combination thereof, but is not limited thereto. In some embodiments, the colloidal oxide may be acid-dispersed. In some embodiments, the colloidal oxide may be alkali-dispersed.

[0082] In some embodiments, the colloidal oxide may be colloidal silica particles. For example, the colloidal silica particles may be NexSil manufactured by Nyacol Nanotechnology Co., Ltd. TM 8. Colloidal silica. In some embodiments, colloidal alumina may be colloidal alumina particles. In some embodiments, the colloidal alumina particles may be manufactured by Nyacol Nanotechnology Co., Ltd. Colloidal alumina, for example AL20. In some embodiments, the colloidal oxide may be colloidal zirconia particles. In some embodiments, the colloidal zirconia particles may be manufactured by Nyacol Nanotechnology Co., Ltd. Colloidal zirconium oxide. In some embodiments, the colloidal oxide may be colloidal titanium oxide particles. In some embodiments, the colloidal titanium oxide particles may be manufactured by Nyacol Nanotechnology Co., Ltd. Colloidal titanium dioxide. In some embodiments, the colloidal oxide may be colloidal tin oxide particles. In some embodiments, the colloidal tin oxide particles may be manufactured by Nyacol Nanotechnology Co., Ltd. Colloidal tin oxide.

[0083] In some embodiments, release agent 120 (or release agent slurry) may contain 1% to 10% by weight of colloidal inorganic binder, including sub-ranges. For example, in some embodiments, release agent 120 (or release agent slurry) may contain the following amounts of colloidal inorganic binder: 1% to 10% by weight, 1% to 8% by weight, 1% to 6% by weight, 1% to 4% by weight, 1% to 2% by weight, 2% to 10% by weight, 4% to 10% by weight, 6% to 10% by weight, or 8% to 10% by weight, or within any two of these values ​​as endpoints, including endpoints. In some embodiments, release agent 120 (or release agent slurry) may contain 4% to 6% by weight of colloidal inorganic binder. The weight percentage of colloidal inorganic binder is the solid weight of the colloidal inorganic binder solution of release agent 120 or release agent slurry, based on the total weight of release agent 120 or release agent slurry. As a non-limiting example, for Nexsil containing 22 grams TM A release agent slurry consisting of 8g of colloidal silica solution, 20g of AEROSIL-OX-50 (amorphous silica soot powder), 0.15g of NaOH, and 91g of deionized water, with the colloidal silica solution comprising 5% by weight (Nexsil). TM 8 represents 30% by weight solids. In this example, the total solids content of the release agent slurry is 20% by weight (15% by weight silica soot powder and 5% by weight solids from colloidal silica solution).

[0084] In some embodiments, the release agent 120 (or release agent slurry) may contain 10 wt% to 40 wt% of total solids, including sub-ranges. For example, in some embodiments, the total solids content range may be: 10 wt% to 40 wt%, 10 wt% to 35 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 10 wt% to 15 wt%, 15 wt% to 40 wt%, 20 wt% to 40 wt%, 25 wt% to 40 wt%, 30 wt% to 40 wt%, or 35 wt% to 40 wt%, or a range with any two of these values ​​as endpoints, including endpoints.

[0085] In embodiments comprising a colloidal inorganic binder, the colloidal inorganic binder can adhere silica particles, silica agglomerates, and / or amorphous silica agglomerates in the release agent 120 to one or more surfaces of the glass article 110 coated thereon with the release agent 120. In such embodiments, after the release agent 120 dries to form the release layer 220, the colloidal inorganic oxide of the colloidal inorganic binder can maintain the positions between the particles and allow the particles to adhere to one or more surfaces of the glass article 110. In some embodiments, the colloidal inorganic binder can promote the formation of direct adhesion between the particles and one or more surfaces of the glass article 100. In such embodiments, direct adhesion can occur during a ceramicizing cycle. After the ceramicizing cycle, the colloidal inorganic oxide of the colloidal inorganic binder can form oxygen-bridged adhesions with one or more surfaces of the glass article 110, and thus firmly bond the release layer 220 to one or more surfaces. In some embodiments, the acid or alkali of the colloidal inorganic binder can promote adhesion and / or bonding.

[0086] In some embodiments, the total amount of water, dispersant, colloidal inorganic binder, and silica, silica agglomerates, and / or amorphous silica agglomerate particles in the release agent 120 (or release agent slurry) may be 90% by weight or higher. For example, in some embodiments, the total amount of water, dispersant, colloidal inorganic binder, and silica, silica agglomerates, and / or amorphous silica agglomerate particles may range from 90% to 100% by weight, 92% to 100% by weight, 94% to 100% by weight, 96% to 100% by weight, or 98% to 100% by weight. In embodiments containing a colloidal inorganic binder, the water present in the release agent 120 or release agent slurry is the water added to the release agent slurry and the water added to the colloidal inorganic binder solution of the slurry.

[0087] In some embodiments, the release agent 120 (or release agent slurry) may include a pH greater than 7. In some embodiments, the release agent 120 (or release agent slurry) may include a pH range of 8.5 to 11, including sub-ranges. For example, in some embodiments, the release agent 120 (or release agent slurry) may include pH ranges of 8.5 to 11, 8.5 to 10.5, 8.5 to 10, 8.5 to 9.5, 8.5 to 9, 9 to 11, 9.5 to 11, 10 to 11, or 10.5 to 11, or a range with any two of these values ​​as endpoints, including endpoints. Any pH within these ranges may reduce or prevent pitting or etching on the surface of glass articles coated with the release agent 120. Furthermore, any pH within these ranges may enable the use of coating processes (e.g., spraying processes) that would be sensitive to corrosive slurries.

[0088] In some embodiments, the release agent 120 (or release agent slurry) may include a viscosity range of 5 cP (centipoise) to 160 cP, including sub-ranges. For example, in some embodiments, the release agent 120 (or release agent slurry) may include the following viscosity ranges: 5 cP to 160 cP, 5 cP to 150 cP, 5 cP to 125 cP, 5 cP to 100 cP, 5 cP to 75 cP, 5 cP to 50 cP, 5 cP to 25 cP, 25 cP to 160 cP, 50 cP to 160 cP, 75 cP to 160 cP, 100 cP to 160 cP, 125 cP to 160 cP, or 150 cP to 160 cP, or a range including any two of these values ​​as endpoints. In some embodiments, the release agent 120 (or release agent slurry) may include a viscosity range of 5 cP to 50 cP. Any viscosity within these ranges can promote the formation of a uniform release agent coating. Furthermore, any viscosity within these ranges allows for the use of certain coating processes (e.g., spraying).

[0089] After applying release agent 120 to one or more surfaces of the glass article 110, the release agent can dry to form a release layer on one or more surfaces of the glass article 110 (e.g., as shown in the image). Figure 2 The release layer 220 is shown. After the release agent 120 is applied and dried, the release agent 220 can adhere directly to the surface of the glass article 110 (e.g., the first surface 112 or the second surface 114). As used herein, the term "direct adhesion" means that the release agent 220 is in direct contact with the surface of the glass article 110, and that at the surface, there is a direct attachment between the material of the release layer 220 and the glass composition of the glass article 110. Direct attachment can be, for example, a hydrophilic bond between the material of the release layer 220 at the surface and the glass composition of the glass article 110.

[0090] After drying, the release layer 220, which adheres directly to the surface of the glass article 110, may not directly adhere to another glass article disposed on the dried release layer 220. Drying the release agent 120 to form the release layer 220 can create a direct adhesion between the first surface of the release agent 220 (e.g., surface 222) and the surface of the glass article 110, leaving the second surface of the release layer 220 (e.g., surface 224) not directly adhered to the surface of the glass article 110. When a second glass article is disposed on the second surface of the dried release layer 220, no direct adhesion is formed between the second glass article and the second surface of the dried release layer 220. In other words, once dried on the first glass article, the release layer 220 does not form a direct adhesion to the second glass article disposed on the dried release layer 220. Because no direct adhesion is formed between the second glass article and the dried release layer 220, no direct bond is formed between the second glass article and the dried release layer 220 during the ceramization process.

[0091] During the ceramization process, the release layer 220 can become directly bonded to the surface of the glass article (e.g., the first surface 112 or the second surface 114). As used herein, the term "direct bond" means that the release layer 220 is in direct contact with the surface of the glass article 110, and that at the surface, there is a direct bond between the material of the release layer 220 and the glass composition of the glass article 110. Direct bond can be, for example, a covalent bond. Direct bond can replace the direct attachment between the material of the release layer 220 and the glass composition of the glass article 110. In other words, the ceramization process can transform the direct attachment between the material of the release layer 220 and the glass composition of the glass article 110 into a direct bond between the material of the release layer 220 and the glass composition of the glass article 110. As a non-limiting example, a dispersant such as sodium hydroxide can form covalent bonds between the particles of the release agent and the surface of the glass article. Sodium in sodium hydroxide can help dissolve surface silicon from 2SiOH at the surface of the glass product, forming SiO-Si bonds at the surface, and releasing H2O to form a direct bond between the release agent material particles and the glass composition of the glass product. Silica alone does not have enough OH groups to produce such a bond. In this embodiment, the hydrophilic bonds generated by sodium hydroxide during the ceramization process can be transformed into Si-O-Si covalent bonds between the release agent material particles and the glass composition of the glass product.

[0092] Prior to the ceramization cycle, release layer 220 may contain the same solid components as release agent 120 (or release agent slurry). For example, release layer 220 may contain silica particles, silica agglomerates, and / or amorphous silica agglomerates having the average particle size described above for release agent 120 and release agent slurry. In embodiments containing a colloidal inorganic binder, release layer 220 may contain the colloidal inorganic binder described above for release agent 120 and release agent slurry.

[0093] In some embodiments, the release layer 220 may include an average coating thickness 226 of 1 micrometer to 5 micrometers, measured from a first surface 222 to a second surface 224 of the release layer 220, including sub-ranges. For example, in some embodiments, the range of the average coating thickness 226 may be: 1 micrometer to 5 micrometers, 1 micrometer to 4.5 micrometers, 1 micrometer to 4 micrometers, 1 micrometer to 3.5 micrometers, 1 micrometer to 3 micrometers, 1 micrometer to 2.5 micrometers, 1 micrometer to 2 micrometers, 1 micrometer to 1.5 micrometers, 1.5 micrometers to 5 micrometers, 2 micrometers to 5 micrometers, 2.5 micrometers to 5 micrometers, 3 micrometers to 5 micrometers, 3.5 micrometers to 5 micrometers, 4 micrometers to 5 micrometers, or 4.5 micrometers to 5 micrometers, or a range including any two of these values ​​as endpoints. In some embodiments, the range of the average coating thickness 226 may be 1 micrometer to 3 micrometers.

[0094] Figure 5A Image 500 shows a release layer 220 on a glass-ceramic article 510 according to some embodiments. A slurry is used to... Figure 5A The release layer 220 is sprayed onto the glass article 110, and the slurry has the following composition: 22 grams of Nexsil. TM 8g (colloidal silica solution), 20g AEROSIL-OX-50 (amorphous silica soot powder), 0.15g NaOH (from Nexsil) TM 8) and 91 grams of deionized water (i.e., composition “SL56” in Table 1). The slurry has a total solids content of 20% by weight (5% colloidal silica solution and 15% silica soot), 0.1% by weight NaOH, a pH of 9, and an emulsion consistency. The coated glass article 110 was subjected to the following ceramicization cycle. First, nucleation phase at 580°C for 2.5 hours. Second, crystalline phase at 755°C for 0.75 hours. Figure 5A As shown, after the ceramization cycle, the release layer 220 on the glass-ceramic article 510 has an average coating thickness of less than 3 micrometers.

[0095] Figure 5BImage 550 shows a release layer 220 on a glass-ceramic article 510 according to some embodiments. A slurry is used to... Figure 5B A release layer 220 was sprayed onto the glass article 110. The slurry had the following composition: 20 wt% AEROSIL-OX-50, 0.1 wt% NaOH, and the balance deionized water (i.e., composition "SL63" in Table 1). The coated glass article 110 underwent the following ceramization cycles: First, nucleation phase at 580°C for 2.5 hours. Second, crystalline phase at 755°C for 0.75 hours. After the ceramization cycles, the release layer 220 on the glass-ceramic article 510 had an average coating thickness of less than 3 micrometers.

[0096] In some embodiments, the release layer 220 may contain only the same atomic elements present in the glass composition of the glass article in the glass stack (and thus in the ceramized glass ceramic article). Figure 6A and 6B Figures 600 and 650 in Figure 5 show the elemental similarity between the glass-ceramic composition of the glass-ceramic article 510 and the release layer 220. Figure 600 shows the energy-dispersive X-ray (EDX) analysis results of the release layer 220. Figure 650 shows the EDX analysis results of the glass-ceramic article 510. The similarity between the peaks in Figures 600 and 650 demonstrates the compositional similarity between the glass-ceramic article 510 and the release layer 220.

[0097] Figure 7 and 8 Figures 700 and 800 in Figure 5 show a lack of reactivity between the glass-ceramic composition of the glass-ceramic article 510 and the release layer 220. Figure 700 shows the X-ray diffraction (XRD) and Rietwald analysis results, revealing the phase composition in the glass-ceramic article 510. Figure 800 shows the surface grazing angle incident X-ray diffraction (GIXRD) results, revealing the phase composition in the release layer 220 and the glass-ceramic article 510. Figures 700 and 800 show that the phase composition of the glass-ceramic article 510 remains relatively unchanged in the presence of the release layer 220.

[0098] In some embodiments, the release layer 220 may include an average dry coverage of 0.5 gsm (grams per square meter) to 1.5 gsm on the surface of the glass article 110, including sub-ranges. For example, in some embodiments, the release layer 220 may include an average dry coverage of 0.5 gsm to 1.5 gsm, 0.5 gsm to 1.25 gsm, 0.5 gsm to 1 gsm, 0.5 gsm to 0.75 gsm, 0.75 gsm to 1.5 gsm, 1 gsm to 1.5 gsm, or 1.25 gsm to 1.5 gsm, or a range of any two of these values ​​as endpoints, including endpoints.

[0099] In some embodiments, the release layer 220 may include a thickness uniformity of + / - 0.5 gsm. As used herein, “thickness uniformity” of a coating or layer refers to a variation in the dry weight (measured in grams per square meter (gsm)) of the coating or layer per unit area not exceeding + / - X gsm. “Thickness uniformity” is calculated by measuring the dry weight of the coating or layer at six or more distinct locations on the glass surface. These six locations should be distributed across the glass surface to provide accurate representativeness of the coating or layer thickness across the entire glass surface. In some embodiments, the release layer 220 may include a thickness uniformity of + / - 0.4 gsm. In some embodiments, the release layer 220 may include a thickness uniformity of + / - 0.3 gsm.

[0100] The average coating thickness, average dry coverage, and thickness uniformity range described herein are characteristics of the release layer 220 that prevent or reduce adhesion between adjacent ceramized glass articles 110 or between the glass article 110 and the backing plate, which could cause warping of the glass article 110 during the ceramization cycle. Relatedly, these characteristics can prevent or reduce adhesion between adjacent ceramized glass articles or between the ceramized glass article and the backing plate, which could cause warping of the glass article 110 during the ceramization cycle. Relatedly, these characteristics can prevent or reduce adhesion between adjacent ceramized glass articles or between the ceramized glass article and the backing plate, which could cause warping of the glass article 110 during the ceramization cycle.

[0101] In some embodiments, the uniformity of the release layer 220 can be characterized by the percentage haze of the coated glass article containing the release layer 220. Unless otherwise specified, the percentage haze is measured using suitable equipment (e.g., the BYK Haze-Gard Plus instrument from Paul N. Gardner, Ltd.) according to ASTM D 1044. The Haze-Gard Plus instrument uses an Illuminant C light source representing average daylight and is calibrated for a color temperature of 6774 K. In some embodiments, the glass article 110 coated with the release layer 220 may include a percentage haze of 50% or less. For example, in some embodiments, the glass article 110 coated with the release layer 220 includes percentage hazes of: 0% to 50%, 1% to 50%, 5% to 50%, 10% to 50%, 20% to 50%, 30% to 50%, or 40% to 50%.

[0102] Figure 9 and 10 The uniformity of the release layer 220 (referred to as "SL56") according to some embodiments is shown to be improved compared to the boron-containing release layer (referred to as "INX"). Table 1 below shows the composition of the SL56 release layer and the INX release layer.

[0103] Table 1: Composition of Exemplary Release Agent Slurry

[0104]

[0105]

[0106] Figure 9 Image 900 shows a comparison of a glass article 910 with an INX release layer and a glass article 920 with an SL56 release layer after a ceramicization cycle. The patterned background behind glass article 920 is significantly clearer than that behind glass article 910, indicating that the percentage haze value of glass article 920 is significantly lower than that of glass article 910.

[0107] Figure 10 Graph 1000 shows the percentage haze measurements of glass articles 910 and 920 after the release agent has dried but before the ceramization cycle. Glass article 910 has a percentage haze of approximately 48%. Glass article 920 has a percentage haze of approximately 27%.

[0108] As shown, for example in Figure 2 In this process, multiple glass products 110 coated with release layer 220 can be placed in a glass stack for ceramicization cycle to ceramicize the glass products 110. Figure 2This illustrates a ceramicized stack 200 comprising a glass stack 210 and a backing plate 204 according to some embodiments. The backing plate 204 may be placed on the opposite side of the glass stack 210 and serves to support the glass stack 210 during the ceramicization cycle.

[0109] The glass stack 210 includes a plurality of glass articles 110. In some embodiments, the glass stack 210 may include three or more glass articles 110, for example: 3 to 24 glass articles, 6 to 24 glass articles, 10 to 20 glass articles, 5 to 15 glass articles, or 6 to 10 glass articles. In some embodiments, the glass articles 110 may be glass sheets. In some embodiments, the glass composition may be manufactured into glass sheets by processes including, but not limited to, slot drawing, float glass processing, roll forming, and other glass sheet forming processes known to those skilled in the art.

[0110] Each glass article 110 in a stack 210 can be separated from its adjacent glass article 110 by a release layer 220 disposed between adjacent glass articles 110. For example, the glass stack 210 may include a first glass article 110 and a second glass article 110 disposed above a first surface 112 of the first glass article 110. In such an embodiment, the release layer 220 may be disposed between the first surface 112 of the first glass article 110 and the second surface 114 of the second glass article 110. And in such an embodiment, the release layer 220 disposed between the first and second glass articles 110 may be either: (i) directly adhered to the first surface 112 of the first glass article 110 and in direct contact with the second surface 114 of the second glass article 110, but not adhered to the second surface 114 of the second glass article 110; or (ii) directly adhered to the second surface 114 of the second glass article 110 and in direct contact with the first surface 112 of the first glass article 110, but not adhered to the first surface 112 of the first glass article 110.

[0111] For example, the glass stack 210 may include a first glass article 110, a second glass article 110 disposed above a first surface 112 of the first glass article 110, and a third glass article 110 disposed above the first surface 112 of the second glass article 110. In such embodiments, a first release layer 220 may be disposed between the first surface 112 of the first glass article 110 and the second surface 114 of the second glass article 110, and a second release layer 220 may be disposed between the first surface 112 of the second glass article 110 and the second surface 114 of the third glass article 110. In such embodiments, the first release layer 220 may be either (i) directly adhered to the first surface 112 of the first glass article 110 and in direct contact with the second surface 114 of the second glass article 110, but not adhered to the second surface 114 of the second glass article 110; or (ii) directly adhered to the second surface 114 of the second glass article 110 and in direct contact with the first surface 112 of the first glass article 110, but not adhered to the first surface 112 of the first glass article 110. Similarly, in such embodiments, the second release layer 220 may be either (i) directly adhered to the first surface 112 of the second glass article 110 and in direct contact with the second surface 114 of the third glass article 110, but not adhered to the second surface 114 of the third glass article 110; or (ii) directly adhered to the second surface 114 of the third glass article 110 and in direct contact with the first surface 112 of the second glass article 110, but not adhered to the first surface 112 of the second glass article 110. A glass stack 210 having more than three glass articles 110 may include an additional release layer arranged in a similar manner between the additional glass articles 110.

[0112] After ceramization, each glass ceramic in the stack 210 can be separated from its adjacent glass articles by a release layer 220 disposed between them. For example, the glass stack 210 may include a first glass ceramic article and a second glass ceramic article disposed above a first surface 112 of the first glass ceramic article. In such an embodiment, the release layer 220 may be disposed between the first surface 112 of the first glass ceramic article and the second surface 114 of the second glass ceramic article. And in such an embodiment, the release layer 220 disposed between the first and second glass ceramic articles 110 may be either (i) directly to the first surface 112 of the first glass ceramic article and in direct contact with the second surface 114 of the second glass ceramic article, but not bonded to the second surface 114 of the second glass ceramic article; or (ii) directly bonded to the second surface 114 of the second glass ceramic article and in direct contact with the first surface 112 of the first glass ceramic article, but not bonded to the first surface 112 of the first glass ceramic article.

[0113] For example, after ceramization, the glass stack 210 may include a first glass-ceramic article, a second glass-ceramic article disposed above a first surface 112 of the first glass-ceramic article, and a third glass-ceramic article disposed above the first surface 112 of the second glass-ceramic article. In such embodiments, a first release layer 220 may be disposed between the first surface 112 of the first glass-ceramic article and the second surface 114 of the second glass-ceramic article, and a second release layer 220 may be disposed between the first surface 112 of the second glass-ceramic article and the second surface 114 of the third glass-ceramic article. In such embodiments, the first release layer 220 may be either (i) directly bonded to the first surface 112 of the first glass-ceramic article and in direct contact with the second surface 114 of the second glass-ceramic article, but not bonded to the second surface 114 of the second glass-ceramic article; or (ii) directly bonded to the second surface 114 of the second glass-ceramic article and in direct contact with the first surface 112 of the first glass-ceramic article, but not bonded to the first surface 112 of the first glass-ceramic article. Furthermore, in such embodiments, the second release layer 220 may be either (i) directly bonded to the first surface 112 of the second glass-ceramic article and in direct contact with the second surface 114 of the third glass-ceramic article, but not bonded to the second surface 114 of the third glass-ceramic article; or (ii) directly bonded to the second surface 114 of the third glass-ceramic article and in direct contact with the first surface 112 of the second glass-ceramic article, but not bonded to the first surface 112 of the second glass-ceramic article. A glass stack 210 having more than three glass-ceramic articles may include additional release layers arranged in a similar manner between the additional glass-ceramic articles.

[0114] In some embodiments, the glass stack 210 may include a release layer 220 located between the bottom glass article 110 and the bottom pad 204. In some embodiments, the glass stack 210 may include a release layer 220 located between the top glass article 110 and the top pad 204. In some embodiments, the release layer 220 may be applied to the surface of the pad 204 and disposed between the surface of the pad and the glass article 110. If adhesion occurs during ceramization cycles, a mismatch in the coefficient of thermal expansion (CTE) between the glass composition of the glass article 110 and the pad material can lead to scratches. Using a release layer 220 disposed between the surface of the pad 204 and the glass article 110 can prevent scratch defects. In embodiments where the surface of the pad 204 is coated with a release layer 220, the release agent material can not only reduce CTE mismatch but also extend the life of the pad 204 by reducing wear on the pad 204.

[0115] In some embodiments, the backing plate 204 may be made of a material that does not react with the glass composition of the glass article 110. In such embodiments, the release layer 220 may not be located between the top glass article 110 and the top backing plate 204 of the glass stack 210 and / or between the bottom glass article 110 and the bottom backing plate 204 of the glass stack 210.

[0116] In some embodiments, the ceramicized stack 200 may include a carrier plate 202 supporting one or more glass stacks 210 and one or more pads 204. The structure and material of the carrier plate 202 may be selected to control the thermal uniformity of the glass articles 110 in the one or more glass stacks 210. In some embodiments, the carrier plate 202 may contain about 17% solid metal (e.g., steel). In some embodiments, the carrier plate 202 may be a hollow plate made of reaction-bonded silicon carbide beams having about 45% solid metal. Other suitable carrier plates known in the art may also be used.

[0117] In some implementations, for example, Figure 3 As shown, the ceramicized stack 200 may include intervening spacers 206 and multiple different glass stacks 210. In such embodiments, the intervening spacers 206 are arranged between the glass stacks 210. In such embodiments, each glass stack 210 may have one or more spacers 206 located between the glass stack 210 and adjacent glass stacks 210.

[0118] Generally, to form a glass-ceramic article, one or more glass stacks 210 are heated to a temperature above the annealing point of the glass composition (multiple glass compositions) of the glass article 110 in the stacks (multiple stacks) 210, for a sufficient time to establish crystal nucleation (also called nucleating phase) in the glass article 110. After being heated above the annealing point, the glass article 110 is then further heated, typically to a higher temperature between the glass annealing point and the glass softening point, thereby establishing a crystalline phase (also called a crystallizing phase). The nucleating phase and the crystalline phase can be carried out, for example, in a toughening furnace or a furnace. After the crystalline phase, the glass article 110 is cooled. The nucleation and crystallization steps serve to ceramize the glass article 110, resulting in a glass-ceramic article. In this document, the combination of the nucleating phase, the crystalline phase, and the cooling of the glass article 110 is referred to as the "ceramization cycle".

[0119] Figure 11 This illustrates a ceramization method 1100 for a plurality of glass articles 110 according to some embodiments. Unless otherwise stated, the steps of method 1100 are not necessarily performed in the order described herein.

[0120] In step 1102, the release agent 120 is applied to the first surface 112 and / or the second surface 114 of the first glass article 110. In some embodiments, the release agent 120 may be applied using a spraying technique. In some embodiments, the release agent 120 may be applied using a spraying technique that includes atomizing the release agent slurry. Exemplary spray atomization coating facilities include, but are not limited to, rotary atomizers or air atomizers, or ultrasonic spraying processes. Other exemplary coating techniques for step 1102 include, but are not limited to, high-pressure spraying or inkjet coating.

[0121] In some embodiments, step 1102 may include applying a release agent 120 to a first surface 112 of the first glass article 110 using a coating process, wherein the release agent 120 is not applied to a second surface 114 of the first glass article 110. In some embodiments, step 1102 may include applying a release agent 120 to a second surface 114 of the first glass article 110 using a coating process, wherein the release agent 120 is not applied to the first surface 112 of the first glass article 110. In some embodiments, the first glass article 110 may be placed on a pad (e.g., pad 204) prior to step 1102. In such embodiments, the first glass article 110 may be coated with the release agent 120 on the pad.

[0122] In step 1104, the release agent 120 dries on the first surface 112 and / or the second surface 114 of the first glass article 110, thereby forming a release layer 220. The drying step 1104 can employ suitable drying techniques, including but not limited to convection dryers and infrared (IR) dryers. Drying conditions can be adjusted to minimize facility footprint and drying time without inducing drying defects (e.g., bubbles or meshes).

[0123] In step 1106, following step 1104, the second glass article 110 is placed in direct contact with the dried release agent (i.e., release layer 22), thereby forming a glass stack 210 comprising the first glass article 110, the second glass article 110, and the dried release agent (i.e., release layer 22). Placing the second glass article 110 in direct contact with the dried release agent may include placing the second glass article 110 on top of the first glass article 110, or placing the first glass article 110 on top of the second glass article 110. For example, in some embodiments, the second surface 114 of the second glass article 110 may be placed in direct contact with the dried release agent in step 1106. In some embodiments, step 1106 may include placing more than two glass articles 110 in the same manner as described with respect to the second glass article, each article stacked sequentially adjacent to the previous one.

[0124] In step 1108, the glass stack 210 is exposed to a ceramicizing cycle sufficient to ceramicize the first glass article 110 and the second glass article 110 into glass ceramic articles.

[0125] In specific embodiments, the ceramization cycle may include: heating the glass stack 210 to a nucleation temperature, maintaining the nucleation temperature for a predetermined period of time, heating the glass stack 210 to a crystallization temperature, and maintaining the crystallization temperature for a predetermined period of time. In some embodiments, the step of heating the glass stack 210 to the nucleation temperature may include heating the glass stack 210 to a nucleation temperature of about 700°C at a rate of 1-10°C / min. The glass stack 210 may be maintained at the nucleation temperature for about 0.25 hours to about 4 hours. In some embodiments, the step of heating the glass stack 210 to the crystallization temperature may include heating the glass stack 210 to a crystallization temperature of about 800°C at a rate of 1-10°C / min. The glass stack 210 may be maintained at the crystallization temperature for about 0.25 hours to about 4 hours.

[0126] The nucleation and crystallization steps described above are exemplary; depending on the specific implementation, other heat treatment methods (including different times and / or temperatures) may be used. The temperature-time profiles of the heat treatment steps can be selected to produce one or more of the following properties: the crystalline phase of the glass-ceramic article, 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. These properties affect the final integrity, quality, color, and / or opacity of the resulting glass-ceramic article.

[0127] Following the nucleation and crystallization steps, the glass stack 210 is cooled back to room temperature. In some embodiments, the cooling rate is controlled to descend to a temperature of approximately 450°C, after which the glass-ceramic article can be quenched. Thus, in some embodiments, the ceramization process may include: controlled cooling from a maximum temperature to a temperature of approximately 4°C / min at a rate of approximately 4°C, followed by a quenching step to bring the temperature to approximately room temperature.

[0128] After completing the ceramization cycle in step 118, the glass-ceramic products can be destacking in step 1110.

[0129] Glass composition

[0130] Glass article 110 can be manufactured from any glass composition suitable for forming glass-ceramic articles. The glass composition of glass article 110 affects the mechanical and optical properties of the glass-ceramic article made using glass article 110. In some embodiments, the glass composition can be selected such that the resulting glass-ceramic article has a lithium feldspar crystalline phase and a lithium silicate salt crystalline phase. In some embodiments, the weight percentage of the lithium feldspar crystalline phase and the lithium silicate salt crystalline phase is greater than that of other crystalline phases present in the glass-ceramic article.

[0131] For example, in some embodiments, the glass article 110 may be formed from a glass composition comprising: about 55 wt% to about 80 wt% SiO2, about 2 wt% to about 20 wt% Al2O3, about 5 wt% to about 20 wt% Li2O, about 0 wt% to about 10 wt% B2O3, about 0 wt% to about 5 wt% Na2O, about 0 wt% to about 10 wt% ZnO, about 0.5 wt% to about 6 wt% P2O5, and about 0.2 wt% to about 15 wt% ZrO2, but is not limited thereto.

[0132] SiO2, an oxide involved in glass forming, can stabilize the network structure of glasses and glass-ceramics. In some embodiments, the concentration of SiO2 can be sufficiently high to form a lithium feldspar crystalline phase when the glass article is ceramicized. The amount of SiO2 can be limited to control the melting temperature of the glass, as the melting temperature of pure SiO2 or high-SiO2 glasses is undesirably high. In some embodiments, the glass or glass-ceramic composition contains about 55 wt% to about 80 wt% SiO2. In some embodiments, the glass or glass-ceramic composition contains about 69 wt% to about 80 wt% SiO2. In some embodiments, the glass or glass-ceramic composition may contain SiO2 of the following percentages: about 55% to about 80% by weight, about 55% to about 77% by weight, about 55% to about 75% by weight, about 55% to about 73% by weight, about 60% to about 80% by weight, about 60% to about 77% by weight, about 60% to about 75% by weight, about 60% to about 73% by weight, about 69% to about 80% by weight, about 69% to about 77% by weight, about 69% to about 75% by weight, about 69% to about 73% by weight, about 70% to about 80% by weight, about 70% to about 77% by weight, about 70% to about 75% by weight, about 70% to about 73% by weight, about 73% to about 80% by weight, about 73% to about 77% by weight, about 73% to about 75% by weight, about 75% to about 80% by weight, or about 77% to about 80% by weight SiO2.

[0133] Al₂O₃ in glass or glass-ceramic compositions can also provide network stabilization and improved mechanical properties and chemical durability. However, if the amount of Al₂O₃ is too high, the proportion of lithium silicate salt crystals may decrease, possibly to the point where interlocking structures cannot be formed. The amount of Al₂O₃ can also be adjusted to control viscosity. 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% by weight to about 20% by weight of Al₂O₃. In some embodiments, the glass or glass-ceramic composition may contain about 6% by weight to about 9% by weight of Al₂O₃. In some embodiments, the glass or glass-ceramic composition may contain Al2O3 as follows: about 2 wt% to about 20 wt%, about 2 wt% to about 18 wt%, about 2 wt% to about 15 wt%, about 2 wt% to about 12 wt%, about 2 wt% to about 10 wt%, about 2 wt% to about 9 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 5 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 18 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 12 wt%, about 5 wt% to about 10 wt%, about 5 wt% to about 9 wt%, about 5 wt% to about 8 wt%, 6 wt% to about 20 wt%. Weight%, about 6% to 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% by weight, 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% by weight, 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% by weight, about 12% to about 18% by weight, or about 12% to about 15% by weight.

[0134] In some embodiments, the glass or glass-ceramic composition may contain Li₂O, which can facilitate the formation of both crystalline phases of lithium feldspar and lithium silicate. To obtain lithium feldspar and lithium silicate as the main crystalline phases, it may be desirable to have at least about 7 wt% Li₂O in the composition. Furthermore, it has been found that once the Li₂O content becomes too high (greater than about 15 wt%), the composition becomes very fluid. Therefore, in some embodiments, the glass or glass-ceramic composition may contain about 5 wt% to about 20 wt% Li₂O. In some embodiments, the glass or glass-ceramic composition may contain about 10 wt% to about 14 wt% Li₂O. In some embodiments, the glass or glass-ceramic composition may contain Li2O as follows: about 5 wt% to about 20 wt%, about 5 wt% to about 18 wt%, about 5 wt% to about 16 wt%, about 5 wt% to about 14 wt%, about 5 wt% to about 12 wt%, about 5 wt% to about 10 wt%, about 5 wt% to about 8 wt%, about 7 wt% to about 20 wt%, about 7 wt% to about 18 wt%, about 7 wt% to about 16 wt%, about 7 wt% to about 14 wt%, about 7 wt% to about 12 wt%, about 7 wt% to about 10 wt%, about 10 wt% to About 20 wt%, about 10 wt% to about 18 wt%, about 10 wt% to about 16 wt%, about 10 wt% to about 14 wt%, about 10 wt% to about 12 wt%, about 12 wt% to about 20 wt%, about 12 wt% to about 18 wt%, about 12 wt% to about 16 wt%, about 12 wt% to about 14 wt%, about 14 wt% to about 20 wt%, about 14 wt% to about 18 wt%, about 14 wt% to about 16 wt%, about 16 wt% to about 20 wt%, about 16 wt% to about 18 wt%, or about 18 wt% to about 20 wt%.

[0135] As mentioned above, Li₂O is generally used to form various glass ceramics, 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 residual glass amounts, 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, in some embodiments, the glass or glass ceramic composition contains a small amount of non-lithium basic oxides. In some embodiments, the glass or glass ceramic composition may contain about 0% by weight 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% by weight 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, K2O, or combinations thereof as follows: 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, >0 wt% to about 5 wt%, >0 wt% to about 4 wt%, >0 wt% to about 3 wt%, >0 wt% to about 2 wt%, >0 wt% to about 1 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4 wt%, or about 4 wt% to about 5 wt%.

[0136] In some embodiments, the glass or glass-ceramic composition 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 crystallizes, but (due to its lower viscosity) only at higher temperatures, resulting in a weak and generally deformable bulk from the surface inwards. However, if the concentration of P2O5 is too high, it may be difficult to control devitrification after cooling during the forming of the glass article. In some embodiments, the glass or glass-ceramic composition may contain >0 wt% to about 6 wt% P2O5. In some embodiments, the glass or glass-ceramic composition may contain about 2 wt% to about 4 wt% P2O5. In some embodiments, the glass or glass-ceramic composition may contain about 1.5 wt% to about 2.5 wt% P2O5. In some embodiments, the glass or glass-ceramic composition may contain P2O5 as follows: 0 wt% to about 6 wt%, 0 wt% to about 5.5 wt%, 0 wt% to 5 wt%, 0 wt% to about 4.5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3.5 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2.5 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1.5 wt%, 0 wt% to about 1 wt%, >0 wt% to about 6 wt%, >0 wt% to about 5.5 wt%, >0 wt% to 5 wt%, >0 wt% to about 4.5 wt%, >0 wt% to about 4 wt%, >0 wt% to about 3.5 wt%, >0 wt% to about 3 wt%, >0 wt% to about >2.5 wt%, 0 wt% to about 2 wt%, >0 wt% to about 1.5 wt%, >0 wt% to about 1 wt%, about 0.5 wt% to about 6 wt%, about 0.5 wt% to about 5.5 wt%, about 0.5 wt% to 5 wt%, about 0.5 wt% to about 4.5 wt%. Weight%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 3.5 wt%, about 0.5 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5.5 wt%, about 1 wt% to 5 wt%, about 1 wt% to about 4.5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%. 5 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2.5 wt%, about 1 wt% to about 2 wt%, about 1 wt% to about 1.5 wt%, about 1.5 wt% to about 6 wt%, about 1.5 wt% to about 5.5 wt%, about 1.5 wt% to 5 wt%, about 1.5 wt% to about 4.5 wt%, about 1.5 wt% to about 4 wt%, about 1.5 wt% to about 3.5 wt%, about 1.5 wt% to about 3 wt%, about 1.5 wt% to about 2.5 wt%, about 1.5 wt% to about 2 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 5.5 wt%, about 2 wt% to 5 wt%, about 2 wt% to about 4.5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3.5 wt%, about 2 wt% to about 3 wt%, about 2 wt% to about 2.5 wt%, about 2.5 wt% to about 6 wt%, about 2.5 wt% to about 5.5 wt%, about 2.5 wt% to about 5 wt%, about 2.5 wt% to about 4.5 wt%, about 2.5 wt% to about 4 wt%, about 2.5 wt% to about 3.5 wt%, about 2.5 wt% to about 3 wt%, about 3 wt% to about 6 wt%, about 3 wt% to about 5.5 wt%, about 3 wt% to 5 wt% %, about 3% by weight to about 4.5% by weight, about 3% by weight to about 4% by weight, about 3% by weight to about 3.5% by weight, about 3.5% by weight to about 6% by weight, about 3.5% by weight to about 5.5% by weight, about 3.5% by weight to 5% by weight, about 3.5% by weight to about 4.5% by weight, about 3.5% by weight to about 4% by weight, about 4% by weight to about 6% by weight, about 4% by weight to about 5.5% by weight, about 4% by weight to about 5.5% by weight, about 4% by weight to about 6% by weight, or about 5.5% by weight to about 6% by weight.

[0137] In some embodiments, the glass or glass-ceramic composition may contain ZrO2. 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 clear glass is formed. The addition of ZrO2 also helps reduce the grain size of the transparent lithium feldspar, which contributes to the formation of a clear glass-ceramic. In some embodiments, the glass or glass-ceramic composition may contain about 0.2 wt% to about 15 wt% ZrO2. In some embodiments, the glass or glass-ceramic composition may contain about 2 wt% to about 4 wt% ZrO2. In some embodiments, the glass or glass-ceramic composition may contain ZrO2 in the following proportions: about 0.2 wt% to about 15 wt%, about 0.2 wt% to about 12 wt%, about 0.2 wt% to about 10 wt%, about 0.2 wt% to about 8 wt%, about 0.2 wt% to about 6 wt%, about 0.2 wt% to about 4 wt%, about 0.5 wt% to about 15 wt%, about 0.5 wt% to about 12 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 8 wt%, about 0.5 wt% to about 6 wt%, about 0.5 wt% to about 4 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 4 wt%, about 2 wt% to about 1 wt%. 5% by weight, about 2% by weight to about 12% by weight, about 2% by weight to about 10% by weight, about 2% by weight to about 8% by weight, about 2% by weight to about 6% by weight, about 2% by weight to about 4% by weight, about 3% by weight to about 15% by weight, about 3% by weight to about 12% by weight, about 3% by weight to about 10% by weight, about 3% by weight to about 8% by weight, about 3% by weight to about 6% by weight, about 3% by weight to about 4% by weight, about 4% by weight to about 15% by weight, about 4% by weight to about 12% by weight, about 4% by weight to about 10% by weight, about 4% by weight to about 8% by weight, about 4% by weight to about 6% by weight, about 8% by weight to about 15% by weight, about 8% by weight to about 12% by weight, about 8% by weight to about 10% by weight, about 10% by weight to about 15% by weight, about 10% by weight to about 12% by weight, or about 12% by weight to about 15% by weight.

[0138] In some embodiments, the glass or glass-ceramic composition may contain B₂O₃. B₂O₃ is advantageous for providing glass articles with low melting temperatures. Furthermore, adding B₂O₃ to glass articles can help achieve interlocked crystalline microstructures and can also improve the destructive resistance of glass-ceramic articles. When boron in the residual glass is not charged-balanced by basic oxides or divalent cation oxides, it is in a trigonal coordination state (or, tricoordinated boron), which opens up the glass structure. The network around these tricoordinated borons is not as rigid as tetrahedral (or tetracoordinated) boron. It is believed, without being limited by theory, that glass and glass-ceramic articles containing tricoordinated boron can tolerate a certain degree of deformation before crack formation. This tolerance of deformation increases the Vickers indentation crack initiation value. The fracture toughness of glass or glass-ceramic articles containing tricoordinated boron can also be increased. It is believed, without being limited by theory, that the presence of boron in the residual glass of glass-ceramics reduces the viscosity of the residual 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, 85% or more, or even 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.

[0139] In some embodiments, the glass or glass-ceramic composition 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 wt% to about 10 wt%, 0 wt% to about 9 wt%, 0 wt% to about 8 wt%, 0 wt% to about 7 wt%, 0 wt% to about 6 wt%, 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, >0 wt% to about 10 wt%, >0 wt% to about 9 wt%, >0 wt% to about 8 wt%, >0 wt% to about 7 wt%, >0 wt% to about 6 wt%, >0 wt% to about 5 wt%, >0 wt% to about 4 wt%, >0 wt% to about 3 wt%, >0 wt% to about 2 wt%. >0 wt% to about 1 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 4 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 8 wt%, about 3 wt% to about 6 wt%, about 3 wt% to about 4 wt%, about 4 wt% to about 5 wt%, about 5 wt% to about 8 wt%, about 5 wt% to about 7.5 wt%, about 5 wt% to about 6 wt%, or about 5 wt% to about 5.5 wt%.

[0140] In some embodiments, the glass or glass-ceramic composition may contain MgO. MgO may be incorporated into the petalite crystals in a partial solid solution. In some embodiments, the glass or glass-ceramic composition may contain 0 wt% to about 8 wt% MgO. In some embodiments, the glass or glass-ceramic composition may contain MgO as follows: 0 wt% to about 8 wt%, 0 wt% to about 7 wt%, 0 wt% to about 6 wt%, 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 7 wt%, about 2 From % by weight to 6% by weight, from 2% by weight to 5% by weight, from 2% by weight to 4% by weight, from 2% by weight to 3% by weight, from 3% by weight to 8% by weight, from 3% by weight to 7% by weight, from 3% by weight to 6% by weight, from 3% by weight to 5% by weight, from 3% by weight to 4% by weight, from 4% by weight to 8% by weight, from 4% by weight to 7% by weight, from 4% by weight to 6% by weight, from 4% by weight to 5% by weight, from 5% by weight to 8% by weight, from 5% by weight to 7% by weight, from 5% by weight to 6% by weight, from 6% by weight to 8% by weight, or from 7% by weight to 8% by weight.

[0141] In some embodiments, the glass or glass-ceramic composition may contain ZnO. ZnO may be incorporated into the petalite crystals within a partial solid solution. In some embodiments, the glass or glass-ceramic composition may contain 0% to about 10% ZnO. In some embodiments, the glass or glass-ceramic composition may contain ZnO as follows: 0 wt% to about 10 wt%, 0 wt% to about 9 wt%, 0 wt% to about 8 wt%, 0 wt% to about 7 wt%, 0 wt% to about 6 wt%, 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 9 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 10 wt%, about 2 wt% to about 9 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 7 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3 wt%. About 3% to about 10% by weight, about 3% to about 9% by weight, about 3% to about 8% by weight, about 3% to about 7% by weight, about 3% to about 6% by weight, about 3% to about 5% by weight, about 3% to about 4% by weight, about 4% to about 10% by weight, about 4% to about 9% by weight, about 4% to about 8% by weight, about 4% to about 7% by weight, about 4% to about 6% by weight, about 4% to about 5% by weight, about 5% to about 10% by weight, about 5% to about 9% by weight, about 5% to about 8% by weight, about 5% to about 7% by weight, about 5% to about 6% by weight, about 6% to about 10% by weight, about 6% to about 9% by weight, about 6% to about 8% by weight, about 6% to about 7% by weight, about 7% to about 10% by weight, about 7% to about 9% by weight, about 7% to about 8% by weight, about 8% to about 10% by weight, or about 9% to about 10% by weight.

[0142] In some embodiments, the glass or glass-ceramic composition may further comprise one or more components, such as, but not limited to, TiO2, CeO2, and SnO2. As a supplement or alternative, an antimicrobial component may be added to the glass or glass-ceramic composition. Antimicrobial components that may be added to the glass or glass-ceramic may include, but are not limited to, Ag, AgO, Cu, CuO, and Cu2O. In some embodiments, the glass or glass-ceramic composition may further comprise a chemical clarifying agent. Such clarifying agents include, but are not limited to, SnO2, As2O3, Sb2O3, F, Cl, and Br. Further details regarding the glass and / or glass-ceramic compositions applicable to various embodiments can be found, for example, in U.S. Patent Application Publication No. 2016 / 0102010, filed October 8, 2015, entitled “HighStrength Glass-Ceramics Having Petalite and Lithium Silicate Structures,” the entire contents of which are incorporated herein by reference.

[0143] Example

[0144] Table 2 below shows the evaluation of various water-based release agent slurry compositions (Examples 1-15) to determine their suitability for use as release agent layers in glass-ceramic manufacturing processes as described herein. The hexagonal boron nitride in Example 8 was purchased from Zyp Coatings. AL20), various samples of components within this range of weight percent were tested. The slurry of Example No. 5 was mixed by a blending process to promote better mixing of silica soot and dispersant and to help break up agglomerated particles.

[0145] Table 2

[0146]

[0147]

[0148]

[0149] Each embodiment's release agent was sprayed onto different glass samples, dried, stacked with other glass samples, and subjected to ceramization cycles. The ceramization cycles differed between the embodiments, but each cycle included a nucleating phase at 500-600°C for 1.5-4 hours and a crystalline phase at 750-800°C for 0.25-4 hours. The release agent slurries of Examples 1, 4, 6, 10, 12, 13, and 15 exhibited good dispersibility, good coating thickness and uniformity, and good adhesion and bonding to the surfaces of the glass samples. These embodiments also showed little to no adhesion to adjacent samples in the ceramization stack. The release agent slurries of Examples 2 and 3 exhibited adequate dispersibility. The release agent slurries of Examples 5, 7, 11, and 14 did not adhere well to the surfaces of the glass samples and resulted in loose powder on the glass sample surfaces. The release agent slurry of Example 8 was too viscous to be properly sprayed. The release agent slurry in Example No. 9 produced adhesion between adjacent samples in a stack of ceramicized articles.

[0150] Although various embodiments have been described herein, they are given by way of example and are not intended to be limiting. It should be noted that, based on the teachings and guidance set forth herein, the aim is to include adjustments and modifications within the meaning and equivalence of the disclosed embodiments. Therefore, it will be apparent to those skilled in the art that various modifications and variations in form and detail can be made to the embodiments disclosed herein without departing from the spirit and scope of this disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive, but can be interchanged to satisfy various situations, as will be understood by those skilled in the art.

[0151] Embodiments of this disclosure are described in detail with reference to the accompanying drawings, wherein the same reference numerals are used to denote the same or similar functional elements. References to "one embodiment," "an embodiment," "some embodiments," "in some embodiments," etc., indicate that the described embodiment may include specific features, structures, or characteristics, but not every embodiment necessarily includes that specific feature, structure, or characteristic. Furthermore, such expressions do not necessarily refer to the same embodiment. In addition, when a specific feature, structure, or characteristic is described in connection with an embodiment, it means that those skilled in the art are capable of incorporating other embodiments to affect such feature, structure, or characteristic, whether or not it is explicitly described.

[0152] The examples in this disclosure are illustrative and not limiting. Other suitable modifications and adjustments are typically made based on various conditions and parameters, as will be apparent to those skilled in the art, and fall within the spirit and scope of this disclosure.

[0153] The indefinite articles “a” and “a kind” used to describe elements or components indicate the presence of one or more of these elements or components. Although these articles are generally used to indicate that the noun they modify is singular, the articles “a” and “a kind” as used herein also include plural nouns unless otherwise stated. Similarly, the definite article “the” as used herein also indicates that the noun it modifies may be singular or plural, unless otherwise stated.

[0154] The directional terms used in this article, such as up, down, left, right, front, back, top, bottom, inside, and outside, are only for reference to the accompanying drawings and are not used to indicate absolute orientation.

[0155] As used in the claims, "comprising" is an open-ended transitional phrase. The series of elements following the transitional phrase "comprising" are non-exclusive examples, and thus elements other than those specifically listed may also exist. As used in the claims, the phrase "essentially composed of" or "essentially made of" limits the composition of the material to the specified material and those that do not significantly affect the material's essential and novel characteristics. As used in the claims, "made of" or "entirely composed of" limits the composition of the material to the specific material and excludes any unspecified material.

[0156] Unless otherwise specified in the specific context, the numerical ranges stated herein include upper and lower limits, and are intended to include their endpoints and all integers and fractions within the range. When a range is defined, it is not intended to limit the scope of the claims to the specific values ​​stated. Furthermore, when a quantity, concentration, or other value or parameter is expressed as a range, one or more preferred ranges, or a preferred upper and lower limit, it should be understood that this is equivalent to specifically disclosing any range by combining any pair of upper or preferred values ​​with any lower or preferred value, regardless of whether such pairing is specifically disclosed. Finally, when the term “about” is used to describe the value or endpoint of a range, it should be understood that this disclosure includes the specific value or endpoint referred to. Regardless of whether the endpoint of a numerical value or range is stated as “about,” the endpoint is intended to include two implementations: one modified with “about” and one not modified with “about.”

[0157] As used herein, the term “about” refers to a value within ±10% of the stated value. For example, about 3 MPa can include any number between 2.7 MPa and 3.3 MPa.

[0158] The terms “substantially,” “basically,” and their variations, as used herein, are intended to indicate that the described feature is equivalent to or approximately the same as the numerical value or description. For example, a “substantially flat” surface is intended to indicate a flat or approximately flat surface. Furthermore, “substantially” is intended to indicate that two values ​​are equal or approximately equal. In some embodiments, “substantially” may mean that the values ​​are within approximately 10% of each other, for example, within approximately 5% of each other, or within approximately 2% of each other.

[0159] The implementation described above has been illustrated using functional building blocks that explicitly perform specific functions and their relationships. For ease of description, the boundaries of these functional building blocks have been arbitrarily defined. Alternative boundaries can be defined, as long as the specified functions and their relationships are performed appropriately.

[0160] It should be understood that the phrases and terms used herein are for descriptive purposes and not for limitation. The breadth and scope of this disclosure should not be limited to any of the exemplary embodiments described above, but only to the following claims and their equivalents.

Claims

1. A coated glass article comprising: Glass articles, the glass articles comprising: First surface; A second surface opposite to the first surface; and A release agent coated on the first surface of a glass article, the release agent comprising an aqueous dispersion containing amorphous silica agglomerate particles and a dispersant. The release agent includes a pH range of 9.5 to 11, and The dispersant contains hydroxides.

2. The coated glass article as claimed in claim 1, wherein, The hydroxide is sodium hydroxide.

3. The coated glass article as described in claim 2, wherein, The release agent contains 0.25% to 1% by weight of dispersant.

4. The coated glass article as claimed in claim 1, wherein, Amorphous silica agglomerates include average particle sizes ranging from 100 nanometers to 20 micrometers.

5. The coated glass article as claimed in claim 1, wherein, The release agent contains 10% to 30% by weight of amorphous silica agglomerate particles.

6. The coated glass article as claimed in claim 1, wherein, Release agents also contain colloidal inorganic binders.

7. The coated glass article as claimed in claim 6, wherein, Colloidal inorganic binders include colloidal silica.

8. The coated glass article according to any one of claims 1-7, wherein, Release agents include pH ranges from 10 to 11.

9. The coated glass article according to any one of claims 1-7, wherein, Release agents range in viscosity from 5 cP to 160 cP.

10. The coated glass article according to any one of claims 1-7, wherein, Release agents range in viscosity from 5 cP to 50 cP.

11. The coated glass article according to any one of claims 1-7, wherein, The release agent was not applied to the second surface of the glass product.

12. The coated glass article according to any one of claims 1-7, wherein, Amorphous silica agglomerates are not colloidal particles.

13. The coated glass article according to any one of claims 1-7, wherein, The dispersant causes amorphous silica agglomerates to adhere to the first surface of the glass product.

14. The coated glass article as claimed in claim 1, wherein, The release agent is a dried release layer, and the coated glass article includes a haze range of 0% to 50%.

15. A stack of glass articles, the stack comprising: A first glass article, comprising a first surface and a second surface opposite to the first surface; A second glass article disposed above a first surface of a first glass article, the second glass article comprising a first surface and a second surface opposite to the first surface; as well as A release layer disposed between the first surface of the first glass article and the second surface of the second glass article. The release layer can be any of the following: It adheres directly to the first surface of the first glass article and is in direct contact with the second surface of the second glass article, but does not adhere to the second surface of the second glass article; or It adheres directly to the second surface of the second glass product and is in direct contact with the first surface of the first glass product, but does not adhere to the first surface of the first glass product. The release layer is formed by a release agent comprising an aqueous dispersion containing amorphous silica agglomerates and a dispersant, the release agent having a pH range of 9.5 to 11, and the dispersant comprising a hydroxide.

16. The glass article stack as described in claim 15, wherein, The release layer contains silicon dioxide.

17. The glass article stack as described in claim 15, wherein, The release layer contains amorphous silica agglomerate particles.

18. The glass article stack as claimed in claim 17, wherein, Silica agglomerates include average agglomerate particle sizes ranging from 100 nanometers to 20 micrometers.

19. The stack of glass articles as claimed in any one of claims 15-18, wherein, The release layer has a thickness ranging from 1 micrometer to 5 micrometers.

20. The stack of glass articles as claimed in any one of claims 15-18, wherein, The release layer comprises an average dry cover of 0.5 gsm to 1.5 gsm.

21. The stack of glass articles as claimed in any one of claims 15-18, wherein, The release layer has a thickness uniformity of + / -0.5 gsm.

22. A method for ceramicizing multiple glass articles, the method comprising: A release agent is coated on a first surface of a first glass article, the release agent comprising an aqueous dispersion containing amorphous silica agglomerate particles and a dispersant; This allows the mold release agent on the first surface of the first glass article to dry; The second glass article is placed in direct contact with the dry release agent to form a glass stack including the first glass article, the second glass article and the dry release agent; as well as Expose the glass stacks to a ceramicizing cycle sufficient to ceramicize the first and second glass articles into glass-ceramic articles. The release agent comprises an aqueous dispersion containing amorphous silica agglomerates and a dispersant, the release agent having a pH range of 9.5 to 11, and the dispersant comprising a hydroxide.

23. The method of claim 22, wherein, Applying a release agent to a first surface of a first glass article includes a coating process in which the release agent is not applied to a second surface of the first glass article opposite to the first surface.

24. The method of claim 22, wherein, The release agent contains: 0.25% to 1% by weight of dispersant, and 10% to 30% by weight of amorphous silica agglomerates.

25. The method according to any one of claims 22-24, wherein, The dried release layer is directly adhered to the first surface of the first glass article, and wherein the dried release layer is in direct contact with the second surface of the second glass article but is not adhered to the second surface of the second glass article.

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