Glass ceramic, preparation method thereof and wearable equipment

Abstract

The embodiment of the invention provides microcrystalline glass, the composition of the microcrystalline glass is Re2O3-TiO2-HfO2-A l2O3-X2O5, Re is at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium, and X is at least one of vanadium, niobium and tantalum. According to the glass ceramic, a plurality of different oxides are adopted, and the optical properties, structural characteristics and the like of the glass ceramic are adjusted by reasonably adjusting the ratio of each compound, so that the glass ceramic has the optical properties of high refractive index, high light transmittance and the like, and the average transmittance of visible light with the wavelength range of 400-800nm of the glass ceramic reaches 80-96%; and the refractive index of the microcrystalline glass is 1.8-2.0, so that the microcrystalline glass meets the use requirements of wearable equipment. The embodiment of the invention further provides a preparation method of the microcrystalline glass and wearable equipment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lighting display, in particular to a microcrystalline glass, a preparation method thereof and a wearable device. BACKGROUND

[0002] Augmented Reality (AR) and Mixed Reality (MR) display glasses and other wearable devices can superimpose virtual visual information on a real scene. The wide range of application scenarios and immersive experience have attracted widespread attention.

[0003] In the prior art, a virtual image is projected onto a light-transmitting glass by a wearable device. A user can obtain a real scene and virtual visual information through the light-transmitting glass, thereby realizing the effect of virtual visual superposition. However, the volume of the light-transmitting glass is limited due to the comfort of wearing, and a glass with high refractive index and high light transmittance is needed to solve the problem of how a small-volume light-transmitting glass can have brighter images and capture a larger image area. SUMMARY

[0004] Embodiments of the present application provide a microcrystalline glass, a preparation method thereof and a wearable device to at least partially improve the above technical problems.

[0005] In a first aspect, the embodiments of the present application provide a microcrystalline glass, and the composition of the microcrystalline glass comprises:

[0006] Re2O3-TiO2-HfO2-Al2O3-X2O5

[0007] wherein Re is at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium, and X is at least one of vanadium, niobium and tantalum.

[0008] In an embodiment, in the microcrystalline glass, the molar content of Re2O3 is 10mol%-37mol%, the molar content of TiO2 is 16mol%-36mol%, the molar content of HfO2 is 2mol%-20mol%, the molar content of Al2O3 is 20mol%-50mol%, and the molar content of X2O5 is 10mol%-20mol%.

[0009] In an embodiment, the microcrystalline glass further comprises an additive with a molar content of 1mol%-5mol%, and the additive is selected from at least one of silicon dioxide, calcium oxide, zinc oxide, germanium oxide, barium oxide, lead oxide and zirconium oxide.

[0010] In one embodiment, the microcrystalline glass has a refractive index in the range of 1.8-2.0, measured at wavelengths of 400 nm-800 nm.

[0011] In one embodiment, the microcrystalline glass has an average transmittance of 80%-96%, which is measured at wavelengths of 400nm-800nm.

[0012] In one embodiment, the Young's modulus of the glass-ceramic is 100 GPa-200 GPa.

[0013] In one embodiment, the fracture toughness of the glass-ceramic is 1.20 MPa·m. 1 / 2 -2.5MPa·m 1 / 2 .

[0014] In one embodiment, the hardness of the microcrystalline glass is 8 GPa-20 GPa.

[0015] Secondly, embodiments of this application provide a wearable device including the microcrystalline glass described in the first aspect.

[0016] Thirdly, embodiments of this application provide a method for preparing microcrystalline glass, comprising:

[0017] Re2O3, TiO2, HfO2, Al2O3, and X2O5 are mixed to form a powder, a solvent is added to form a slurry, the slurry is heated to form a glass precursor, the glass precursor is processed to form a sheet, and the sheet is heat-treated to produce microcrystalline glass.

[0018] Wherein, Re is at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium, and X is at least one of vanadium, niobium, and tantalum.

[0019] The microcrystalline glass and wearable device provided in this application embodiment use a variety of different oxides. By reasonably adjusting the ratio of each compound, the optical properties and structural characteristics of the microcrystalline glass are adjusted so that the microcrystalline glass has optical properties such as high refractive index and high light transmittance. This makes the average transmittance of visible light in the wavelength range of 400nm-800nm ​​reach 80%-96%, and the refractive index of the microcrystalline glass is 1.8-2.0, which meets the usage requirements of wearable devices.

[0020] The method for preparing glass-ceramics provided in this application involves heat-treating a glass precursor to obtain glass-ceramics. The heat treatment process strengthens and toughens the glass-ceramics, improving their Young's modulus and fracture toughness. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0022] Figure 1 This is a schematic diagram of the structure of a wearable device according to an embodiment of this application;

[0023] Figure 2 This is a schematic diagram of the structure of another wearable device proposed in an embodiment of this application;

[0024] Figure 3 This is a schematic diagram of the structure of another wearable device proposed in the embodiments of this application;

[0025] Figure 4 This is a flowchart illustrating a method for preparing microcrystalline glass according to an embodiment of this application.

[0026] Reference numerals: Wearable device 1, microcrystalline glass 10, coupling element 11, coupling element 12, light source device 20, body 30, spatial light modulator 40. Detailed Implementation

[0027] To enable those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present application without inventive effort are within the scope of protection of the present application.

[0028] In this application, unless otherwise expressly specified or limited, the terms "installation," "connection," "fixation," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components; they can refer to mere surface contact; or they can refer to surface contact connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0029] Furthermore, the terms "first," "second," etc., are used only for distinguishing descriptions and should not be construed as referring to specific or particular structures. The terms "some embodiments," "other embodiments," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this application, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. Furthermore, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this application, as well as the features of different embodiments or examples.

[0030] This application provides a wearable device 1, please refer to... Figure 1 Wearable device 1 may have one or more speakers and an integrated display. Alternatively, wearable device 1 may be configured to receive an external display (e.g., a smartphone). Wearable device 1 may incorporate one or more imaging sensors for capturing images or video of the physical environment and / or one or more microphones for capturing audio of the physical environment. Wearable device 1 may have a transparent, semi-transparent, or opaque display. The transparent or semi-transparent display may have a medium through which light representing the image is directed to the human eye. The medium may be an optical waveguide, a holographic medium, an optical combiner, an optical reflector, or any combination thereof. Projection-based systems may employ retinal projection technology, which projects graphic images onto the human retina. Projection systems may also be configured to project virtual objects onto the physical environment, such as as holograms or on physical surfaces. Wearable device 1 may employ augmented reality, mixed reality, and extended-range (XR) technologies to provide users with a more realistic experience and strong sensory stimulation, or to facilitate users in various aspects such as smart manufacturing, education and training, and process design.

[0031] Please continue reading. Figure 1 as well as Figure 2The wearable device 1 may include a microcrystalline glass 10, a light source device 20, and a body 30. The microcrystalline glass 10 and the light source device 20 are disposed within the body 30. The microcrystalline glass 10 can serve as a display medium for the wearable device 1, and the light beam from the light source device 20 can be displayed in the microcrystalline glass 10. In one embodiment, the light source device 20 emits a light beam, and the microcrystalline glass 10 is disposed in the optical path of the emitted light beam. Further, the microcrystalline glass 10 may include an insertion region and an exit region. The insertion region is correspondingly provided with an insertion element 11, and the exit region is correspondingly provided with an exit element 12. The light beam can enter the microcrystalline glass 10 from the insertion element 11, and the emitted light beam can undergo total internal reflection within the microcrystalline glass 10, reducing light beam loss. The light beam exits from the exit element 12 of the microcrystalline glass 10 so that the light beam can be acquired by the user. The exit region may be a region of the microcrystalline glass 10 corresponding to the user's naked eye, and thus the exit element 12 may also be corresponding to the user's naked eye. At the same time, the microcrystalline glass 10 has high light transmittance, such as Figure 2 As shown by the dotted line, beams of light from the external environment can be simultaneously captured by the user through the microcrystalline glass 10, achieving the effect of overlaying virtual content with real-world scene content.

[0032] In some embodiments of this application, please refer to Figure 3 The wearable device 1 may further include a spatial light modulator 40, which is disposed between the microcrystalline glass 10 and the light source device 20. The spatial light modulator 40 modulates the emitted light beam from the light source device 20 to form image light. The image light is emitted into the microcrystalline glass 10. The image light can undergo total internal reflection within the microcrystalline glass 10, and is emitted when it reaches a predetermined position on the microcrystalline glass 10, making it accessible to the user.

[0033] In another embodiment, a reflective device is provided between the light source device 20 and the spatial light modulator 40, or between the spatial light modulator 40 and the microcrystalline glass 10. This reflective device can deflect the light beam's path, reducing the distance between the light source device 20 and the microcrystalline glass 10, thus altering the fixed propagation path of the light beam to better suit the small size of the wearable device 1 or situations where the light path is limited, and preventing the size of the wearable device 1 along the beam emission direction from being too large. This structure increases the portability of the wearable device 1, enabling it to be applied in various scenarios.

[0034] Understandably, the microcrystalline glass 10 can also be applied to optical equipment, medical equipment, building materials, etc. Specifically, the microcrystalline glass 10 can be applied to projectors, optical microscopes, curtain wall materials, etc., but this embodiment does not impose any limitations.

[0035] However, traditional oxide glasses always use network forgings such as SiO2, B2O3, and P2O5 as the matrix. Although these network forgings have extremely strong glass-forming capabilities, Si... 4+ B 3+ P 5+ The small radius, high valence, and susceptibility to polarization by an applied electric field of cations greatly limit the improvement of optical properties such as refractive index in glass composition. Therefore, the inventors of this application propose the following technical solution to address these problems.

[0036] In some embodiments of this application, the composition of the microcrystalline glass 10 can be Re2O3-TiO2-HfO2-Al2O3-X2O5, where Re in Re2O3 can be at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc). In other embodiments of this application, Re2O3 can be selected from at least one of La2O3, Ce2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Y2O3, and Sc2O3. For example, the composition of the glass-ceramic 10 can be a mixture of La2O3, Ce2O3, TiO2, HfO2, Al2O3, and X2O5. La2O3 can help improve the optical properties, thermal stability, and physical and mechanical properties of the glass-ceramic 10. Furthermore, La2O3 can influence the crystallization process of the glass-ceramic 10, promoting crystal formation and growth, thereby optimizing the microstructure of the glass-ceramic 10. Ce2O3 can act as a nucleating agent, promoting crystal formation and growth in the glass-ceramic 10, and can also improve the optical properties of the glass-ceramic 10. Besides La2O3 and Ce2O3, other types of components also have the effect of regulating the structure and optical properties of the glass-ceramic 10, which are not enumerated in this application.

[0037] Titanium oxide (TiO2) can significantly affect the viscosity of glass-ceramic 10. For example, as the temperature increases, the viscosity-reducing effect of TiO2 on glass-ceramic 10 tends to strengthen, which helps to accelerate the melting process of glass-ceramic 10. TiO2 has certain melting-promoting and fusibility properties.

[0038] Hafnium oxide (HfO2) can be added to the glass-ceramic 10 along with other components. HfO2 can affect the performance of the glass-ceramic 10, such as its refractive index and thermal stability.

[0039] Alumina (Al2O3) can make the internal structure of the glass-ceramic 10 more compact. Specifically, adding Al2O3 to the glass-ceramic 10 helps reduce the tendency to crystallize and suppress phase separation, thereby improving the chemical stability, thermal stability, and mechanical strength of the glass-ceramic 10.

[0040] In X₂O₅, X can be at least one of vanadium (V), niobium (Nb), and tantalum (Ta), and X₂O₅ can be at least one of V₂O₅, Nb₂O₅, and Ta₂O₅. V₂O₅ can improve the internal structure of the glass-ceramic 10, thereby increasing its bending strength and Rockwell hardness. Nb₂O₅ has a high refractive index, and adjusting its content can change the refractive index of the glass-ceramic 10. Ta₂O₅ contributes to the stable formation of the glass-ceramic 10. The composition and specific content of X₂O₅ can be selected and designed according to implementation requirements, and the embodiments of this application are not limited thereto.

[0041] Understandably, the components and specific proportions of the microcrystalline glass 10 can be selected and designed according to specific implementation requirements and parameters, and this implementation does not impose any restrictions.

[0042] In the embodiments of the glass-ceramic 10 described herein, the constituent components (e.g., TiO2, Al2O3, etc.) are expressed as a molar percentage (mol%) based on oxides, unless otherwise stated. The sum of the molar percentages of the constituent components of the glass-ceramic 10 is 100 mol%. In some embodiments of this application, the molar content of Re2O3 in the glass-ceramic 10 is 10 mol%-37 mol%. In one embodiment of this application, the molar content of Re2O3 is 10 mol%, 15%, 20%, 25%, 30%, 35%, and 37 mol. Various constituent components of Re2O3 have different characteristics; taking La2O3 as an example, this will be described. If the molar content of La2O3 is too high, the thermal stability and chemical stability of the glass-ceramic 10 may decrease. If the molar content of La2O3 is too low, the number of crystals in the glass-ceramic 10 may decrease or become unevenly distributed, thereby affecting its overall performance. With an appropriate molar content of La2O3, the refractive index of glass-ceramic 10 will also increase, and its dispersion performance will be optimized. In addition, Re2O3 can also improve the thermal stability of glass-ceramic 10 to a certain extent, helping it to maintain stable performance at high temperatures.

[0043] The molar content of TiO2 is 16 mol%-36 mol%. In one embodiment of this application, the molar content of TiO2 is 16 mol%, 20%, 25%, 30%, 35%, and 36 mol%. When the molar content of TiO2 is too high, the melting behavior and viscosity of the glass-ceramic 10 change, and its molding and processing may become more difficult. When the molar content of TiO2 is too low, the optical properties of the glass-ceramic 10 decrease, such as reduced light transmittance and color changes. Furthermore, the number of crystals in the glass-ceramic 10 also decreases or becomes unevenly distributed. An appropriate molar content of TiO2 can increase the light transmittance of the glass-ceramic 10 and improve its UV resistance, resulting in better durability for outdoor applications. In addition, the addition of TiO2 can also improve the mechanical strength of the glass-ceramic 10, enhancing its impact and abrasion resistance.

[0044] The molar content of HfO2 is 2 mol%-20 mol%. In one embodiment of this application, the molar content of HfO2 is 2 mol%, 5%, 8%, 12%, 15%, 18%, and 20%. When the molar content of HfO2 is too high, the physical properties of the glass-ceramic 10 decrease, its melting behavior and viscosity change, and its processing difficulty increases. When the molar content of HfO2 is too low, the structure of the glass-ceramic 10 may become unstable, and its overall performance weakens. An appropriate molar mass percentage of HfO2 can significantly improve the refractive index and dispersion properties of the glass-ceramic 10, giving it higher application value in the optical field. Simultaneously, HfO2 can also enhance the chemical stability of the glass-ceramic 10 and improve its resistance to acid and alkali corrosion.

[0045] The molar content of Al2O3 is 20 mol%-50 mol%. In one embodiment of this application, the molar content of Al2O3 is 20%, 25%, 30%, 35%, 40 mol%, 45 mol%, and 50 mol%. When the molar content of Al2O3 is too high, the viscosity of the glass-ceramic 10 will increase significantly, and the excessively high viscosity will make the processing of the glass-ceramic 10 difficult. Furthermore, an excessively high alumina content may lead to excessive inhibition of the crystallization process of the glass-ceramic 10, affecting the formation and distribution of crystals in the glass-ceramic 10. When the molar content of Al2O3 is too low, the chemical stability and mechanical properties of the glass-ceramic 10 decrease, making it prone to breakage or deformation. An appropriate molar mass percentage of Al2O3 allows the glass-ceramic 10 to maintain high light transmittance while possessing better thermal and chemical stability.

[0046] The molar content of X2O5 is 10 mol%-20 mol%. In one embodiment of this application, the molar content of X2O5 is 10%, 12%, 14%, 16%, 18%, and 20%. Different components of X2O5 have different characteristics; taking V2O5 as an example, this will be discussed further. If the molar content of V2O5 is too high, the light transmittance and refractive index of the glass-ceramic 10 may decrease. If the molar content of V2O5 is too low, the color of the glass-ceramic 10 will not be vivid enough, and its structural properties such as hardness and wear resistance will decrease. An appropriate molar content of V2O5 can further optimize the optical properties, thermal stability, and mechanical properties of the glass-ceramic 10.

[0047] In another embodiment of this application, Re2O3 and X2O5 may also include other components. Appropriate amounts of other components can improve the structural and optical properties of the glass-ceramic 10, but their content being too high or too low may affect the structural, optical, and production efficiency of the glass-ceramic 10. This application does not enumerate all such components.

[0048] Understandably, in the glass-ceramic 10, the molar content of Re2O3 can be 0.5-3.7 times the molar content of X2O5. However, the specific compositions of Re2O3 and X2O5 can be adjusted according to the implementation requirements of the glass-ceramic 10. When different compositions of Re2O3 and X2O5 are used, their specific ratio will also be appropriately adjusted to enable the glass-ceramic 10 to have better structural and optical properties. For example, when La2O3 is chosen as Re2O3 and V2O5 is chosen as X2O5, the molar ratio between Re2O3 and X2O5 can be 1:2. Or, when Ce2O3 is chosen as Re2O3 and Nb2O5 is chosen as X2O5, the molar ratio between Re2O3 and X2O5 can be 3:1.

[0049] In some embodiments of this application, in order to further optimize the performance of the glass-ceramic 10, the glass-ceramic 10 also includes additives. The addition of additives can further regulate the crystal structure of the glass-ceramic 10 and improve its optical performance, thermal stability and mechanical properties.

[0050] More specifically, the additives can be selected from at least one of silicon dioxide, calcium oxide, zinc oxide, germanium oxide, barium oxide, lead oxide, and zirconium oxide. Silicon dioxide can combine with other oxides to form a stable network structure of the glass-ceramic 10, improving its hardness and wear resistance. Calcium oxide can improve the chemical stability and corrosion resistance of the glass-ceramic 10, while also adjusting its refractive index and coefficient of thermal expansion. Appropriate amounts of calcium oxide help improve the processing performance and impact resistance of the glass-ceramic 10. Zinc oxide lowers the sintering temperature of the glass-ceramic 10, promoting its formation. Zinc oxide can also improve the transparency and gloss of the glass-ceramic 10, enhancing its aesthetics. Furthermore, it increases the hardness and wear resistance of the glass-ceramic 10, extending its service life. Germanium oxide can increase the refractive index of the glass-ceramic 10, expanding its application range. Simultaneously, germanium oxide can improve the thermal and chemical stability of the glass-ceramic 10. Barium oxide can be used to adjust the refractive index and density of the glass-ceramic 10, helping to optimize its optical properties. Lead oxide can significantly lower the melting temperature of the glass-ceramic 10, promote its formation, and simultaneously increase its density and refractive index, thus improving its optical properties. Zirconia, with its high hardness, high melting point, and high chemical stability, can significantly improve the hardness and wear resistance of the glass-ceramic 10, and enhance its thermal shock resistance. Furthermore, zirconium oxide can also improve the optical properties of the glass-ceramic 10, increasing its transparency and gloss.

[0051] Understandably, suitable additives can improve the production efficiency and optical properties of the glass-ceramic 10, and promote the formation of the glass-ceramic 10. The specific composition and ratio of the additives can be selected and designed according to the main components of the glass-ceramic 10 and the process steps, and this embodiment does not impose any limitations.

[0052] In some embodiments of this application, the molar content of the additive in the glass-ceramic 10 can be 1 mol% to 5 mol%. For example, the molar content of the additive in the glass-ceramic 10 can be 1 mol%, 2 mol%, 3 mol%, 4 mol%, or 5 mol%. In the glass-ceramic 10, an additive with too low a molar content will have a weakened promoting effect on the preparation of the glass-ceramic 10, while an additive with too low a molar content will affect the optical and structural properties of the glass-ceramic 10 after molding. An appropriate amount of additive can improve optical properties and promote the formation of the glass-ceramic 10. This additive content configuration can avoid the effects of too little or too much additive molar content on the optical and sintering properties of the glass-ceramic 10.

[0053] In one or more embodiments, the glass-ceramic 10 has a refractive index of 1.8-2.0. In some cases, the refractive index of the glass-ceramic 10 may be about 1.80, 1.85, 1.90, 1.95, or 2.0. In a specific embodiment, the refractive index is measured at wavelengths between 400 nm and 800 nm. When measured at wavelengths between 400 nm and 800 nm, the refractive index of the same glass-ceramic 10 may fluctuate depending on the measurement wavelength.

[0054] In one or more embodiments, the glass-ceramic 10 exhibits high transmittance when measured relative to a thickness of 1 micrometer, 2 micrometer, or 3 micrometers. For example, the glass-ceramic 10 exhibits an average transmittance of 80%-96% in the optical wavelength region ranging from about 400 nm to about 800 nm (“optical wavelength region”). In one or more embodiments, the glass-ceramic 10 exhibits an average transmittance of about 80% or higher, about 82% or higher, about 84% or higher, about 86% or higher, about 88% or higher, about 90% or higher, about 92% or higher, about 94% or higher, about 95% or higher, or about 96% or higher throughout the optical wavelength region, and this is measured relative to a thickness of 1 micrometer. As used herein, the term “transmittance” is defined as the percentage of incident light power that passes through a material (e.g., the glass-ceramic 10, the article, the substrate, or a portion thereof) within a given wavelength range.

[0055] In one or more embodiments, the glass-ceramic 10 may have an elastic modulus (or Young's modulus) in the range of 100 GPa to 200 GPa. In some cases, the elastic modulus of the glass-ceramic 10 may be 100 GPa, 120 GPa, 150 GPa, 180 GPa, 200 GPa, and all ranges in between.

[0056] In one or more embodiments, the fracture toughness of the microcrystalline glass 10 is 1.20 MPa·m. 1 / 2 -2.5MPa·m 1 / 2 In some cases, the fracture toughness of the microcrystalline glass 10 can reach 1.20 MPa·m. 1 / 2 1.40 MPa·m 1 / 2 1.60 MPa·m 1 / 2 1.80 MPa·m 1 / 2 20MPa·m 1 / 2 22MPa·m 1 / 2 25MPa·m 1 / 2 .

[0057] The hardness of the glass-ceramic 10 (and articles comprising the glass-ceramic 10) can be described, and the hardness is determined by a Brinell indenter hardness test. In one or more embodiments, the hardness of the glass-ceramic 10 is 8 GPa-20 GPa, and in some cases, the hardness of the glass-ceramic 10 is 8 GPa, 10 GPa, 12 GPa, 14 GPa, 16 GPa, 18 GPa, or 20 GPa. This intrinsic maximum hardness is determined by a Brinell indenter hardness test along an indentation depth of about 100 nm or more on the main surface of a material with a thickness of 400 nm, 500 nm, 1 μm, or 2 μm. The intrinsic maximum hardness means the hardness of the material itself, regardless of any substrate or surface below on which the material may be disposed.

[0058] Understandably, the specific components of the additives can be adjusted according to the specific process design of the microcrystalline glass 10, and the specific content of the corresponding components can also be adjusted appropriately so that the microcrystalline glass 10 can be better fused.

[0059] The aforementioned microcrystalline glass 10 can be prepared according to the following method, please refer to [reference needed]. Figure 4 The preparation method in this embodiment may include:

[0060] Step S210: Mix Re2O3, TiO2, HfO2, Al2O3, and X2O5 to form powder, and add solvent to form slurry.

[0061] Regarding the selection and proportioning of Re2O3 and X2O5, Re2O3 can be selected from at least one of La2O3, Ce2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, Y2O3, and Sc2O3. X2O5 can be selected from at least one of V2O5, Nb2O5, and Ta2O5. When Re2O3 and / or X2O5 have two or more different components, the proportioning can be determined based on the specific characteristics and properties of each component.

[0062] The system provides Re2O3, TiO2, HfO2, Al2O3, and X2O5, with the molar proportions of each component determined according to the specific general formula for microcrystalline glass. Re2O3, TiO2, HfO2, Al2O3, and X2O5 are mixed to form a powder. After uniform mixing, a solvent is added, and the mixture is ground and blended to form a slurry. The mass ratio of powder to solvent is 0.8-1.8. The solvent can be an ethanol solution, such as anhydrous ethanol, where anhydrous ethanol concentration is 99% or higher. A suitable mass ratio of powder ensures the slurry's viscosity, facilitating subsequent processes. Furthermore, this powder mass ratio setting avoids particle agglomeration and uneven mixing due to excessive powder mass ratio, while also preventing excessively fluid slurry due to insufficient powder mass ratio, which would negatively impact subsequent operational efficiency.

[0063] Step S220: Heat the slurry to form a glass precursor.

[0064] The slurry is heated, and during this process, the solvent or other volatile substances in the slurry gradually evaporate, causing the slurry to become increasingly viscous. The slurry then begins a melting reaction, forming a more compact and ordered structure in its molten state. After cooling and solidification, a glass precursor is formed. This glass precursor provides the necessary material basis and conditions for the nucleation and crystallization processes of glass-ceramics. By optimizing the precursor preparation process, uniform mixing and melting of raw materials can be achieved, reducing the generation of impurities and bubbles, improving the purity and uniformity of glass-ceramics, and reducing the manufacturing cost of glass-ceramics. It should be noted that in some embodiments of this application, the chemical components in the molten slurry do not undergo chemical reactions, but rather physical reactions, and the proportion of the chemically reacting components to the total mass of the powder does not exceed 2%.

[0065] In some embodiments of this application, heating the slurry to form a glass precursor can be performed as follows: granulating the slurry to form granulated powder, and then heating and melting the granulated powder to form the glass precursor. More specifically, the slurry can be granulated using a spray drying method to form granulated powder. Spray drying can rapidly evaporate volatile substances in the slurry and simultaneously complete the granulation process to form granulated powder. The granulated powder can be fed into a powder feeder for heating; for example, the granulated powder can be fed into an oxyacetylene flame, where the temperature can reach 3000℃-3500℃. At least a portion of the granulated powder melts upon heating, and the molten granulated powder can form a more compact and ordered structure. The molten granulated powder is then sprayed into a cooling medium, where it rapidly cools to form the glass precursor. The cooling medium can be water or the like.

[0066] In some embodiments of this application, the particle size of the glass precursor can be 10 μm-100 μm. A glass precursor of suitable size can melt rapidly, which is beneficial for improving melting efficiency. Furthermore, suitable particle size parameters help reduce the generation of bubbles during the melting process of the glass precursor, thereby improving the transparency of the glass-ceramic.

[0067] In some embodiments of this application, heating the slurry to form a glass precursor can also be performed as follows: after drying the slurry, it is pressed to form a blank, and the blank is suspended and heated at 2700℃-2900℃ for 10s-60s to form a glass precursor. More specifically, the uniformly mixed slurry is placed in a forced-air drying oven until the volatile substances in the slurry are completely evaporated to form a mixed powder. The dried mixed powder is pressed into blocks of suitable size under a predetermined pressure, which can be 20MPa-70MPa. The shape of the blocks can be cylindrical, cubic, etc. The blocks can be crushed to form small-sized samples, the size of which matches the nozzle size of the pneumatic suspension-laser heating system. The pneumatic suspension-laser heating system is a system that can drive the sample to a suspended state using a carrier gas and heat the sample using a laser. More specifically, the pneumatic suspension-laser heating system uses high-purity oxygen or the like as a carrier gas, and the sample tends to be stably suspended by adjusting the flow rate of the carrier gas. The laser is turned on, emitting laser light. The laser's emission direction is calibrated to the sample, allowing for continuous laser irradiation. The pneumatic levitation-laser heating system allows adjustment of the laser power to ensure the sample is heated to 2700℃-2900℃, with a selectable temperature of 2800℃. Under continuous laser irradiation for 10-60 seconds, the sample completely melts. The laser is then turned off, and the sample cools and solidifies, yielding a spherical, transparent glass precursor.

[0068] Step S230: Process the glass precursor to form a sheet, and heat-treat the sheet to produce microcrystalline glass.

[0069] The sheet is heated to 500℃-1000℃ and held at that temperature for 0.5h-10h, then polished to form microcrystalline glass. Specifically, the glass precursor is cut and polished into a sheet, which can be circular in shape. The sheet is then placed in air for heat treatment, during which crystal nuclei form within the sheet. These nuclei can further grow to form microcrystalline glass with properties such as high refractive index. The heat treatment temperature can be 500℃-1000℃; in some embodiments of this application, the heat treatment temperature is 600℃-800℃, and the holding time is 0.5h-10h; in other embodiments, the holding time is 2h-6h. The microcrystalline glass can also undergo double-sided polishing to improve its surface flatness, ensuring its light transmittance and image quality.

[0070] The solution of this application will be described in more detail below with reference to specific embodiments.

[0071] Example 1

[0072] This embodiment provides a microcrystalline glass, wherein Re2O3 is selected from Gd2O3 and Y2O3, and X2O5 is selected from Nd2O5.

[0073] The aforementioned glass-ceramic is prepared in the following manner:

[0074] Gd₂O₃, Y₂O₃, TiO₂, HfO₂, Al₂O₃, and Nd₂O₅ were mixed in a molar ratio of 10:27:20:10:20:10 to form a powder. Silica (SiO₂) and calcium oxide (CaO₂) were selected as additives, with Gd₂O₃, SiO₂, and CaO₂ mixed in a molar ratio of 10:2:1. The sum of the molar percentages of the components of the microcrystalline glass was 100 mol%. The mixed additives were then added to the powder.

[0075] After Gd2O3, Y2O3, TiO2, HfO2, Al2O3, Nd2O5, SiO2, and CaO2 are mixed evenly, anhydrous ethanol with a mass ratio of 0.8 to the powder is added to the powder, and the powder is mixed with anhydrous ethanol to form a slurry through grinding.

[0076] The slurry is granulated using a spray drying method to form granulated powder. The granulated powder is fed into an oxyacetylene flame for heating via a powder feeder. At least a portion of the granulated powder melts upon heating. The molten granulated powder is then sprayed and quenched in water, and the molten granulated powder is rapidly cooled to form a glass precursor.

[0077] The glass precursor is cut and polished into sheets, which are then heat-treated at 600℃ for 0.5 hours to obtain microcrystalline glass.

[0078] Testing revealed that the microcrystalline glass obtained in this embodiment has a refractive index of 1.9, a Young's modulus as high as 180 GPa, and a hardness as high as 13.3 GPa. The average transmittance of the microcrystalline glass in the visible light range of 400 nm to 800 nm reaches 82%. The materials and preparation method selected in this embodiment can effectively improve impact resistance and abrasion resistance. Under irradiation with visible light in the wavelength range of 400 nm to 800 nm, the average transmittance of the microcrystalline glass reaches 82%, and the microcrystalline glass also possesses characteristics such as high refractive index.

[0079] Example 2

[0080] This embodiment provides a microcrystalline glass, wherein Re2O3 is selected from Y2O3 and Lu2O3, and X2O5 is selected from Nd2O5.

[0081] The aforementioned glass-ceramic is prepared in the following manner:

[0082] Y₂O₃, LuO₂, TiO₂, HfO₂, Al₂O₃, and Nd₂O₅ were mixed in a molar ratio of 5:1:4:2:5:2 to form a powder. Silica (SiO₂) and zirconium oxide (ZrO₂) were selected as additives, and Y₂O₃, SiO₂, and ZrO₂ were mixed in a molar ratio of 25:3:2. The sum of the molar percentages of the components of the microcrystalline glass was 100 mol%. The mixed additives were then added to the powder.

[0083] After Y2O3, LuO2, TiO2, HfO2, Al2O3, Nd2O5, SiO2, and ZrO2 are mixed evenly, anhydrous ethanol with a mass ratio of 1.0 to ethanol is added to the powder and then mixed by grinding to form a slurry.

[0084] The slurry is granulated using a spray drying method to form granulated powder. The granulated powder is fed into an oxyacetylene flame for heating via a powder feeder. At least a portion of the granulated powder melts upon heating. The molten granulated powder is then sprayed and quenched in water, and the molten granulated powder is rapidly cooled to form a glass precursor.

[0085] The glass precursor is cut and polished into sheets, which are then heat-treated at 650°C for 5 hours to obtain microcrystalline glass.

[0086] Testing revealed that the microcrystalline glass obtained in this embodiment has a refractive index of 2.0, a Young's modulus as high as 182 GPa, and a hardness as high as 12.5 GPa. The average transmittance of the microcrystalline glass in the visible light range of 400 nm to 800 nm reaches 82%. The materials and preparation method selected in this embodiment can effectively improve impact resistance and abrasion resistance. Under irradiation with visible light in the wavelength range of 400 nm to 800 nm, the average transmittance of the microcrystalline glass reaches 82%, and the microcrystalline glass also possesses characteristics such as high refractive index.

[0087] Example 3

[0088] This embodiment provides a microcrystalline glass, where Re2O3 is Y2O3 and X2O5 is Ta2O5.

[0089] The aforementioned glass-ceramic is prepared in the following manner:

[0090] Y₂O₃, TiO₂, HfO₂, Al₂O₃, and Ta₂O₅ were mixed in a molar ratio of 5:4:2:6:2 to form a powder. Silica (SiO₂) and calcium oxide (CaO₂) were selected as additives, and Y₂O₃, SiO₂, and CaO₂ were mixed in a molar ratio of 25:3:2. The sum of the molar percentages of the components of the microcrystalline glass was 100 mol%. The mixed additives were then added to the powder.

[0091] After Y2O3, TiO2, HfO2, Al2O3, Ta2O5, SiO2, and CaO2 are mixed evenly, anhydrous ethanol with a mass ratio of 1.2 of powder to ethanol is added to the powder, and the powder is mixed with anhydrous ethanol to form a slurry through grinding.

[0092] The slurry is granulated using a spray drying method to form granulated powder. The granulated powder is fed into an oxyacetylene flame for heating via a powder feeder. At least a portion of the granulated powder melts upon heating. The molten granulated powder is then sprayed and quenched in water, and the molten granulated powder is rapidly cooled to form a glass precursor.

[0093] The glass precursor is cut and polished into sheets, which are then heat-treated at 600℃ for 10 hours to obtain microcrystalline glass.

[0094] Testing revealed that the microcrystalline glass obtained in this embodiment has a refractive index of 1.9, a Young's modulus as high as 185 GPa, and a hardness as high as 13.5 GPa. The average transmittance of the microcrystalline glass in the visible light range of 400 nm to 800 nm reaches 85%. The materials and preparation method selected in this embodiment can effectively improve impact resistance and abrasion resistance. Under irradiation with visible light in the wavelength range of 400 nm to 800 nm, the average transmittance of the microcrystalline glass reaches 85%, and the microcrystalline glass also possesses characteristics such as high refractive index.

[0095] Example 4

[0096] This embodiment provides a microcrystalline glass, where Re2O3 is Y2O3 and X2O5 is Nd2O5.

[0097] The aforementioned glass-ceramic is prepared in the following manner:

[0098] Y₂O₃, TiO₂, HfO₂, Al₂O₃, and Nd₂O₅ were mixed in a molar ratio of 5:4:2:6:2 to form a powder. Silicon dioxide (SiO₂) and calcium oxide (GeO₂) were selected as additives, and Y₂O₃, SiO₂, and GeO₂ were mixed in a molar ratio of 25:3:2. The sum of the molar percentages of the components of the microcrystalline glass was 100 mol%. The mixed additives were then added to the powder.

[0099] After Y2O3, TiO2, HfO2, Al2O3, Nd2O5, SiO2, and GeO2 are mixed evenly, anhydrous ethanol with a mass ratio of 1.4 to the powder is added into the powder, and the powder is mixed with anhydrous ethanol to form a slurry through grinding.

[0100] The slurry is granulated using a spray drying method to form granulated powder. The granulated powder is fed into an oxyacetylene flame for heating via a powder feeder. At least a portion of the granulated powder melts upon heating. The molten granulated powder is then sprayed and quenched in water, and the molten granulated powder is rapidly cooled to form a glass precursor.

[0101] The glass precursor is cut and polished into sheets, which are then heat-treated at 600℃ for 10 hours to obtain microcrystalline glass.

[0102] Testing revealed that the microcrystalline glass obtained in this embodiment has a refractive index of 2.0, a Young's modulus as high as 175 GPa, and a hardness as high as 13 GPa. The average transmittance of the microcrystalline glass in the visible light range of 400 nm to 800 nm reaches 88%. The materials and preparation method selected in this embodiment can effectively improve impact resistance and abrasion resistance. Under irradiation with visible light in the wavelength range of 400 nm to 800 nm, the average transmittance of the microcrystalline glass reaches 88%, and the microcrystalline glass also possesses characteristics such as high refractive index.

[0103] The microcrystalline glass and wearable device provided in this application embodiment use a variety of different oxides. By reasonably adjusting the ratio of each compound, the optical properties and structural characteristics of the microcrystalline glass are adjusted so that the microcrystalline glass has optical properties such as high refractive index and high light transmittance. This makes the average transmittance of visible light in the wavelength range of 400nm-800nm ​​reach 80%-96%, and the refractive index of the microcrystalline glass is 1.8-2.0, which meets the usage requirements of wearable devices.

[0104] The method for preparing glass-ceramics provided in this application involves heat-treating a glass precursor to obtain glass-ceramics. The heat treatment process strengthens and toughens the glass-ceramics, improving their Young's modulus and fracture toughness.

[0105] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application.

Claims

1. A microcrystalline glass, characterized in that, The composition of the microcrystalline glass is as follows: Re2O3-TiO2-HfO2-Al2O3-X2O5 Wherein, Re is at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium, and X is at least one of vanadium, niobium, and tantalum.

2. The microcrystalline glass according to claim 1, characterized in that, In the microcrystalline glass, the molar content of Re2O3 is 10 mol%-37 mol%, the molar content of TiO2 is 16 mol%-36 mol%, the molar content of HfO2 is 2 mol%-20 mol%, the molar content of Al2O3 is 20 mol%-50 mol%, and the molar content of X2O5 is 10 mol%-20 mol%.

3. The microcrystalline glass according to claim 1, characterized in that, The microcrystalline glass further includes an additive with a molar content of 1 mol% to 5 mol%, wherein the additive is selected from at least one of silicon dioxide, calcium oxide, zinc oxide, germanium oxide, barium oxide, lead oxide, and zirconium oxide.

4. The microcrystalline glass according to any one of claims 1-3, characterized in that, The microcrystalline glass has a refractive index in the range of 1.8-2.0, which is measured at wavelengths of 400nm-800nm.

5. The microcrystalline glass according to any one of claims 1-3, characterized in that, The microcrystalline glass has an average transmittance of 80%-96%, which is measured at wavelengths of 400nm-800nm.

6. The microcrystalline glass according to any one of claims 1-3, characterized in that, The Young's modulus of the microcrystalline glass is 100 GPa-200 GPa.

7. The microcrystalline glass according to any one of claims 1-3, characterized in that, The fracture toughness of the microcrystalline glass is 1.20 MPa·m. 1 / 2 -2.5MPa·m 1 / 2 .

8. The microcrystalline glass according to any one of claims 1-3, characterized in that, The hardness of the microcrystalline glass is 8 GPa-20 GPa.

9. A wearable device, characterized in that, include: The microcrystalline glass as described in any one of claims 1-8.

10. A method for preparing microcrystalline glass, characterized in that, include: Re2O3, TiO2, HfO2, Al2O3, and X2O5 are mixed to form a powder, a solvent is added to form a slurry, the slurry is heated to form a glass precursor, the glass precursor is processed to form a sheet, and the sheet is heat-treated to produce microcrystalline glass. Wherein, Re is at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium, and X is at least one of vanadium, niobium, and tantalum.

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