Color photosensitive glass-ceramics, and preparation method and application thereof

Abstract

The application belongs to the technical field of photosensitive glass, and discloses a kind of color photosensitive glass-ceramics and its preparation method and application, wherein the preparation method of the color photosensitive glass-ceramics includes mixing SiO2, Al2O3, B2O3, Li2O, Na2O, MgO, ZnO, ZrO2, CeO2, Ag2O, Sb2O3, F ‑ , Cl ‑ , Br ‑ , clarifying agent, to obtain a mixture, sequentially melting, clarifying and forming the mixture to obtain a formed glass, and heat treating the formed glass to obtain the color photosensitive glass-ceramics; the application adopts a decoupling doping strategy of "photosensitizer-coloring agent-crystal nucleus agent" through component gradient design and multi-stage heat treatment system innovation, realizes color development, crystallization and transparency under different heat treatment systems, and can prepare color photosensitive glass-ceramics with color development function and photosensitive crystallization characteristics.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photosensitive glass, in particular to a color photosensitive glass-ceramics and a preparation method and application thereof. BACKGROUND

[0002] Photosensitive glass is a functional material that can respond to external light stimuli and change its structure and phase under certain light conditions. It was first discovered by S. Donald Stookey in 1937. The principle is to introduce photosensitive chemicals into the glass body, expose it to short-wave radiation (such as ultraviolet light), reduce noble metal ions (such as silver, gold, and copper ions) into atoms, and then heat them to form larger particles, resulting in visible colored images in the exposed area of the glass.

[0003] With the development of electronic products and other fields, the functional requirements of glass materials are increasing. For example, smart watches need to monitor vital signs and require glass to be partially transparent and able to block light. Photosensitive glass can achieve this function through mask exposure and has wide application prospects in photolithography masks, optical diffraction gratings, and microfluidic chips. Therefore, it has received increasing attention and related research and technology have been continuously developed.

[0004] However, there is a key and difficult problem in the application and development of traditional photosensitive glass, which is the inability to balance coloration function and photosensitive crystallization characteristics. From the perspective of coloration function, to meet the diverse display needs, the glass needs to have rich and stable color performance to accurately present various images and information. However, when traditional material formulations and processes achieve good coloration, they often interfere with the photosensitive crystallization process. In terms of photosensitive crystallization characteristics, photosensitive crystallization is a key to endowing glass with special properties such as high hardness and high refractive index. However, pursuing efficient photosensitive crystallization can easily destroy the coloration structure inside the glass, leading to color distortion, fading, or poor color uniformity.

[0005] Therefore, there is an urgent need for a photosensitive glass that can solve the above technical problems. SUMMARY

[0006] The present application aims to provide a color photosensitive glass-ceramics and a preparation method and application thereof to overcome the problems in the prior art. The present application adopts a "photosensitizer-coloring agent-crystal nucleus agent" decoupling doping strategy through component gradient design and multi-stage heat treatment system innovation to realize coloration, crystallization, and transparency under different heat treatment systems, enabling the preparation of color photosensitive glass-ceramics with coloration function and photosensitive crystallization characteristics.

[0007] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0008] In a first aspect, the present invention provides a colored photosensitive microcrystalline glass, which is prepared from raw materials comprising the following components in molar percentage:

[0009] 67%≤SiO2≤71%, 2%≤Al2O3≤6%, 0%≤B2O3≤1%, 0%≤Li2O≤3%, 11.5%≤Na2O≤17%, 0%≤MgO≤4%, 0%≤ZnO≤3%, 0%≤ZrO2≤4%, 0.01%≤CeO2≤0.05%, 0.02%≤Ag2O≤0.1%, 0.03%≤Sb2O3≤0.15%, 5%≤F - ≤9%, 0%≤Cl - ≤1.2%, 0%≤Br - ≤1.2%, 0%≤clarifying agent≤0.05%;

[0010] F - / (Cl - + Br - The ratio of F to F is 5~10.97. - / Na + The ratio is 0.37~0.64, of which Na + It comes from Na2O, 1%≤MgO+ZnO+ZrO2≤5.5%, the ratio of (Li2O+Na2O) / Al2O3 is 2.5~7.25, the ratio of (Ag2O+CeO2) / Sb2O3 is 0.5~1.17, and Ag2O / CeO2>1;

[0011] Furthermore, the colored photosensitive microcrystalline glass contains 13% ≤ Li₂O + Na₂O ≤ 17.1%;

[0012] Furthermore, the clarifying agent includes at least one of SnO and NaCl;

[0013] Furthermore, the thickness of the colored photosensitive microcrystalline glass is 0.2~20 mm.

[0014] Secondly, the present invention provides a method for preparing colored photosensitive microcrystalline glass, comprising the following steps:

[0015] Step 1: Weigh the raw materials according to the composition and molar percentage of the colored photosensitive microcrystalline glass, and mix the raw materials to obtain a mixture;

[0016] Step two: The mixture is melted, clarified, and shaped sequentially to obtain shaped glass;

[0017] Step 3: Heat treat the formed glass to obtain colored photosensitive microcrystalline glass;

[0018] Furthermore, the melting temperature is 1500~1650 °C;

[0019] Further, the heat treatment comprises: sequentially performing heat preservation and gradient cooling on the shaped glass, wherein the gradient cooling comprises first stage cooling and second stage cooling;

[0020] Further, the heat preservation temperature is 400-800 ℃, and the heat preservation time is 120-240 min;

[0021] The first stage cooling comprises: starting from the heat preservation temperature, cooling to 100-200 ℃ below the heat preservation temperature, and the first stage cooling rate is 0.1-1 ℃ / min;

[0022] The second stage cooling comprises: starting from the temperature at which the first stage cooling ends, cooling to 200-375 ℃ below the heat preservation temperature, and the second stage cooling rate is 0.5-1 ℃ / min;

[0023] Further, the gradient cooling further comprises third stage cooling;

[0024] The third stage cooling comprises: starting from the temperature at which the second stage cooling ends, cooling to room temperature, and the third stage cooling rate is 1-2 ℃ / min.

[0025] In a third aspect, the present application provides an application of the color photosensitive glass ceramic on electronic glass, display screen, camera and back cover.

[0026] The above technical solution has the following advantages or beneficial effects:

[0027] In a first aspect, the present application provides a color photosensitive glass ceramic, by precisely controlling the mole percentage of each raw material, the comprehensive performance of the color photosensitive glass ceramic is improved, and the color photosensitive glass ceramic performs well in hardness, refractive index and the like, specifically including: first, F - , Cl - , Br - and ZrO2 are used as crystal nucleus agents, by limiting F - / (Cl - + Br - ) and F - / Na +crystals such as NaF, can synergistically regulate the phase separation and crystallization behavior of color photosensitive glass-ceramics; Ag2O and CeO2 as photosensitizers, by limiting the ranges of (Ag2O+CeO2) / Sb2O3 and Ag2O / CeO2, significantly enhance the ultraviolet photosensitivity, enabling photosensitive exposure and realizing selective color microcrystallization, breaking through the bottleneck of traditional photosensitive glass that is difficult to simultaneously consider coloration function and photosensitive microcrystallization characteristics, and opening up a new path for the development of glass materials; Sb2O3 as a colorant, with the photosensitizer satisfying the ratio of (Ag2O+CeO2) / Sb2O3 of 0.5-1.12, can interact with silver particles during heat treatment to produce bright colors; secondly, by using the mixed alkali effect of Li2O+Na2O and controlling the range of (Li2O+Na2O) / Al2O3, the grain size can be refined, and the color photosensitive glass-ceramics after crystallization still maintain high transparency and mechanical strength; by controlling 1%≤MgO+ZnO+ZrO2≤5.5%, the chemical stability and thermal shock resistance of the color photosensitive glass-ceramics can be enhanced.

[0028] Further, by accurately controlling the total mole percentage of Li2O and Na2O to be 14%-17% and forming a synergy with the Al2O3 content, the network structure of the color photosensitive glass-ceramics is effectively optimized, which not only ensures good melting performance and photosensitivity of the glass, but also provides a suitable driving force for subsequent heat treatment and crystallization.

[0029] Further, the selected fining agent has high efficiency in removing bubbles and functional compatibility, can quickly remove gas impurities in low-temperature melting, significantly reduces glass defects, and at the same time avoids pre-reaction or redox with photosensitive components (Ag + / Ce 3+ ) to protect the photosensitive center activity, providing a high-uniform and defect-free glass matrix foundation for subsequent ultraviolet exposure and crystallization.

[0030] Further, by limiting the glass thickness to 0.2-20 mm, it can not only ensure the effective penetration of ultraviolet light to induce the uniform generation of color centers inside, but also make the heat conduction uniform and controllable during heat treatment, thereby realizing overall consistent crystallization and avoiding problems such as uneven coloration, cracking or deformation caused by excessive thickness or thinness, ensuring product yield and performance; at the same time, it can also flexibly meet the needs of different scenarios, providing better material options for related industries.

[0031] In a second aspect, the present application provides a preparation method of a color photosensitive glass-ceramics. Firstly, the method of the present application uses a decoupling doping strategy of "photosensitizer-coloring agent-crystal nucleus agent", so that the color photosensitive glass-ceramics can realize the switching of coloration, crystallization and transparent state at the same time under the heat treatment system. The prepared color photosensitive glass-ceramics not only has rich color performance, but also can form a microcrystalline structure, and also maintains good transparency, greatly improves the comprehensive performance of the glass, and breaks through the limitation of single function of traditional glass-ceramics. Secondly, by carefully designing and adjusting the ratio of each oxide, the color photosensitive glass-ceramics of the present application has diversified color presentation ability. Under different heat treatment process conditions, the color photosensitive glass-ceramics can obtain rich and varied colors and apparent effects. In addition, precise control of heat treatment can not only obtain color photosensitive glass-ceramics, but also obtain transparent photosensitive glass-ceramics. The flexibility of heat treatment significantly improves the quality of the product, which can meet the use requirements in different scenes and broaden the application range of the product.

[0032] Further, the melting temperature is accurately controlled at 1500-1650 ℃, which can ensure sufficient reaction and homogenization of raw materials, and at the same time avoid excessive loss of volatile components such as fluorine and chlorine caused by high temperature, so as to accurately maintain the ratio of F - / (Cl - + Br - ), so as to ensure the phase separation behavior and photosensitive activity of the color photosensitive glass-ceramics, and lay a uniform component foundation for subsequent crystallization and coloration.

[0033] Further, by stage gradient cooling heat treatment, first, the pre-phase separation area is promoted to precipitate nanocrystal nucleus, and then the crystal growth rate is accurately controlled, so as to realize high crystallization while ensuring that the crystal size is much smaller than the visible light wavelength, effectively avoiding light scattering, and finally making the color photosensitive glass-ceramics still maintain excellent light transmittance and uniform color after coloration.

[0034] Further, by accurately controlling the holding temperature and time, and combining two-stage gradient cooling, the uniform formation and controllable growth of nanocrystal nucleus in the color photosensitive glass-ceramics are realized, which ensures that the crystal size is small and uniformly distributed, and finally makes the color photosensitive glass-ceramics maintain high transparency and color consistency while efficiently crystallizing and coloring.

[0035] Further, by introducing a third stage gradient cooling process (1-2 ℃ / min slow cooling to room temperature), the risk of internal stress accumulation and explosion caused by excessive temperature difference between the inside and outside of the glass product is effectively avoided. The above fine temperature control process promotes the stable formation of the microstructure, significantly improves the mechanical strength, optical uniformity and color stability of the color photosensitive glass-ceramics, and ensures the synchronous optimization of product yield and performance.

[0036] In a third aspect, the application provides an application of the color photosensitive glass ceramic in electronic glass, display screen, camera, back cover, etc. The color photosensitive glass ceramic prepared by the application has color display and photosensitive crystallization characteristics, can present rich colors, improve visual experience, and the crystalline structure enhances hardness and wear resistance. In the application of display screen, the color photosensitive glass ceramic prepared by the application can effectively resist scratching and collision, and does not affect the display effect of the screen. In the application of camera, the color photosensitive glass ceramic prepared by the application has high transparency, can ensure clear imaging, has good physical properties, and is used for preventing damage. In the application of back cover, the color photosensitive glass ceramic prepared by the application has colorful appearance, can add aesthetic degree, the crystallization characteristics improve impact resistance and corrosion resistance, can prolong the service life of electronic products, and enhance the market competitiveness of products. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 A flowchart of a preparation method of the color photosensitive glass ceramic. DETAILED DESCRIPTION

[0038] In the following, only certain exemplary embodiments are simply described. As those skilled in the art can recognize, the described embodiments can be modified in various different ways without departing from the spirit or scope of the application. Therefore, the drawings and the description are considered to be exemplary in nature rather than limiting.

[0039] In addition, the terms "first", "second" are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first", "second" can explicitly or implicitly include one or more of the features. In the description of the application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0040] The technical solutions in the embodiments of the application will be described clearly and completely in the drawings of the embodiments of the application. Obviously, the described embodiments are only some of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0041] The target glass is mainly prepared by casting method in the application. The main purpose of the method is to facilitate experimental research, but the preparation method of the color photosensitive glass ceramic can also be any one of the conventional glass preparation processes such as overflow down-drawing method, float method, and calendering method. The embodiments provided by the application are only examples, and are not limited to this method.

[0042] The color photosensitive glass-ceramics obtained by the present application is prepared from the following raw materials in terms of mole percentage:

[0043] 67%≤SiO2≤71%, 2%≤Al2O3≤6%, 0%≤B2O3≤1%, 0%≤Li2O≤3%, 11.5%≤Na2O≤17%, 0%≤MgO≤4%, 0%≤ZnO≤3%, 0%≤ZrO2≤4%, 0.01%≤CeO2≤0.05%, 0.02%≤Ag2O≤0.1%, 0.03%≤Sb2O3≤0.15%, 5%≤F - ≤9%, 0%≤Cl - ≤1.2%, 0%≤Br - ≤1.2%, 0%≤clarifier≤0.05%;

[0044] F - / (Cl - +Br - ) is 5~10.97, F - / Na + is 0.37~0.64, wherein, Na + is from Na2O, 1%≤MgO+ZnO+ZrO2≤5.5%, (Li2O+Na2O) / Al2O3 is 2.5~7.25, (Ag2O+CeO2) / Sb2O3 is 0.5~1.17, Ag2O / CeO2>1;

[0045] Preferably, 13%≤Li2O+Na2O≤17.1%; the thickness of the color photosensitive glass-ceramics is 0.2~20 mm;

[0046] Specifically, SiO2 is an important glass forming oxide, the main framework of the glass-ceramics, which forms irregular glass network skeleton in the form of silicon oxygen tetrahedron [SiO4]; the amount introduced in the present application is 67%≤SiO2≤71%, and in the more preferred embodiment, 68.04%≤SiO2≤70%; maintaining the amount of SiO2 introduced greater than 67% is conducive to forming a relatively dense glass network skeleton and improving the intrinsic strength of the glass, but the content should not be too high, as too high SiO2 content will increase the viscosity of the glass, increase the clarification temperature, and make the melting difficult, which will increase the risk and cost of production;

[0047] Specifically, Al2O3 belongs to intermediate oxide, when the free oxygen content in the glass is sufficient, the alumina connects the network with [AlO4] form to form a continuous network framework with [SiO4]; when the free oxygen is insufficient, an octahedron is formed, which is in the form of network outer body in the hole of silicon oxygen structure, which can effectively avoid the situation that the transmittance of the transparent part of the colored photosensitive glass-ceramics and the corresponding product decreases after mask exposure and heat treatment; the introduction amount in the application is 2%≤Al2O3≤6%, preferably 3%≤Al2O3≤5%, in the application, Al is all in the form of [AlO4] to form a network framework with [SiO4], thereby improving the mechanical strength of the glass;

[0048] Specifically, B2O3 belongs to network forming oxide, which can form a network alone; in the silicate glass system, B 3 + [BO4] form to take free oxygen and participate in network to improve the low temperature viscosity of the glass and prevent glass crystallization; when the content of B2O3 is higher than 15%, the overall viscosity of the system can be reduced; when the content of B2O3 is lower than 15%, the low temperature viscosity can be increased and the high temperature viscosity can be reduced; the introduction amount in the application is 0%≤B2O3≤1%, preferably 0%<B2O3≤0.5%;

[0049] Specifically, Na2O acts as a network outer body oxide in the network system, has a good network breaking effect, and therefore can significantly reduce the viscosity, and in the system, is an important crystal component element and a monovalent modified ion; the introduction amount in the application is 11.5%≤Na2O≤17%, more preferably 14%≤Na2O≤16%; when the content of Na2O is higher than 17%, the chemical stability of the glass is reduced, and when the content is lower, the glass melting and crystal formation are not conducive;

[0050] Specifically, Li2O is an important component of forming a two-strong glass, and can reduce the viscosity of the glass, wherein the two-strong glass refers to a glass type which is surface strengthened through ion exchange process and has high impact strength, in addition, Li + is an important component element of binary ion exchange, so that there is a compressive stress on the surface of the glass to improve the strength, but the content of Li2O should not be too high, and when it is higher than 7%, Li + has a large ion field strength, obvious aggregation effect and easy crystallization, so that the stability of the glass is poor, the introduction content in the application is 0%≤Li2O≤3%, preferably 0%<Li2O≤1%;

[0051] Specifically, MgO exists in two coordination modes of four or six in silicate glass, but most of them are in octahedron, which belongs to network outer body oxide; only when the content of alkali metal oxide is too high and Al2O3 is not present, Mg2+ Only possible in tetrahedron; MgO can reduce the melting temperature of glass, so that the glass melts faster and easier, at the same time, MgO can form a uniform network structure, enhance the strength and stability of the glass, so that it is not easy to soften deformation under high temperature conditions, but too high MgO content will also increase the surface tension of the glass; the introduction amount in the application is 0%≤MgO≤4%, preferably 2%≤MgO≤4%;

[0052] Specifically, ZnO can increase the alkali resistance of glass, and ZnO is a wide band gap semiconductor (band gap about 3.37eV), which can effectively absorb ultraviolet light, and can significantly enhance the photosensitivity and imaging quality of the system by widening the light absorption range, improving the electron transfer efficiency and providing nucleation sites; the introduction amount in the application is 0%≤ZnO≤3%, more preferably 2%≤ZnO≤3%;

[0053] Specifically, ZrO2 can improve the crystallization performance of glass, refine the grain size, reduce the crystallization shrinkage of the substrate glass, further stabilize the glass structure, and inhibit unintended crystallization, but when the content of ZrO2 is higher than 5%, it may cause uncontrollable devitrification of the glass during melting and casting, therefore, the introduction amount in the application is 0%≤ZrO2≤4%, more preferably 2%≤ZrO2≤4%;

[0054] Specifically, CeO2 is the core photosensitizer, Ce 3+ Under ultraviolet light, Ag + Provides electrons to promote the aggregation of Ag atoms to form colloids, at the same time, Ce 3+ The light color can assist in adjusting the color saturation, but not as the main coloring source; however, when the content of CeO2 is lower than 0.01%, it cannot provide enough electrons, resulting in too low crystal content, therefore, the introduction amount in the application is 0.01%≤CeO2≤0.05%, more preferably 0.02%≤CeO2≤0.03%;

[0055] Specifically, Ag2O has two important roles in the application: first, Ag + Can be deposited as colloidal silver particles during heat treatment, and due to the different diameters of colloidal particles, selective absorption can occur to make the glass show different colors, or form a precipitate with halides in the system on the fluoride cubic surface, and then form isotropic silver, and then the selective light absorption of silver makes the glass show different colors, it should be noted that the annealing and heat treatment coloring process in the system may be a mixture of the above two mechanisms; second, as the crystal nucleus agent of the transparent precursor photosensitive glass-ceramics and photosensitive glass-ceramic product of the application; therefore, the preferred introduction amount in the application is 0.02%≤Ag2O≤0.1%;

[0056] Specifically, Sb2O3 is a reducing agent, which can keep the balance of Ce 3+ and Ce 4+ in the glass, and the amount of Sb2O3 introduced in the application is 0.03%≤Sb2O3≤0.15%, preferably 0.03%≤Sb2O3≤0.1%;

[0057] Specifically, F - is a crystal component element in the system, and has two important roles in the application: one is that F is precipitated as opal NaF crystal during heat treatment and color development, and serves as a carrier for colloidal silver particles to display special patterns; the other is that F is induced by Ag + colloidal particles to form cubic NaF crystals; the amount of F introduced in the application is 5%≤F - ≤9%, preferably 6%≤F - ≤7.5%;

[0058] Specifically, Cl - and Br - are phase equilibrium elements in the system, which are used to assist in inducing selective absorption of silver to make the glass show different colors, and the preferred amount of Br introduced in the application is 0%≤Br - ≤1.2% and 0%≤Cl - ≤1.2%;

[0059] Specifically, the fining agent can include at least one of SnO and NaCl, or other clarifying oxides. Due to the diversity of elements and the complexity of the chemical environment, SnO is mainly used as the fining agent in the application, and the content is limited to 0%≤fining agent≤0.05%.

[0060] Example 1:

[0061] Referring to Figure 1 , the application provides a preparation method of colored photosensitive microcrystalline glass, including the following steps:

[0062] Step one, mixing 68.92% SiO2, 4% Al2O3, 0% B2O3, 1.5% Li2O, 14.5% Na2O, 0% MgO, 0% ZnO, 3% ZrO2, 0.03% CeO2, 0.05% Ag2O, 0.13% Sb2O3, 7.03% F - , 0% Cl - , 0.82% Br - , 0.02% SnO in mole percentage to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 8.57, and F - / Na+ a ratio of (Li2O+Na2O) / Al2O3 is 4, Li2O+Na2O is 16, a ratio of (Ag2O+CeO2) / Sb2O3 is 0.62, a ratio of Ag2O / CeO2 is 1.67;

[0063] Step two, put the mixture into a platinum crucible, put the platinum crucible with the mixture into a high-temperature lifting furnace, melt at 1550 ℃ for 8 h to obtain a melted mixture, then sequentially clarify the melted mixture to obtain a clarified mixture, and then cast the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0064] Step three, heat treat the shaped glass, the heat treatment including: heat treating the shaped glass at 500 ℃ for 240 min, then cooling from 500 ℃ to 400 ℃ at a rate of 0.1 ℃ / min, and then cooling from 400 ℃ to room temperature (25 ℃) at a rate of 0.5 ℃ / min to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process, and shows a wine red and opal spectrum superimposed color;

[0065] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0066] Example 2:

[0067] Different from example 1, in step three, the formed glass is heat treated, the heat treatment comprises: after the formed glass is kept at 800 ℃ for 210 min, the temperature is decreased from 800 ℃ to 700 ℃ at a rate of 0.1 ℃ / min, then the temperature is decreased from 700 ℃ to 500 ℃ at a rate of 0.5 ℃ / min, and then the temperature is decreased from 500 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the temperature decreasing stage is continuous, so that the annealing and the heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and shows devitrification.

[0068] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2-20 mm.

[0069] Example 3:

[0070] Different from example 1, in step three, the formed glass is heat treated, the heat treatment comprises: after the formed glass is kept at 450 ℃ for 150 min, the temperature is decreased from 450 ℃ to 350 ℃ at a rate of 0.5 ℃ / min, and then the temperature is decreased from 350 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the temperature decreasing stage is continuous, so that the annealing and the heat treatment of the glass are simultaneously performed, and the thickness of the obtained colored photosensitive glass-ceramics is 0.7 mm, and the colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and shows transparency.

[0071] Example 4:

[0072] Different from example 1, in step three, the formed glass is heat treated, the heat treatment comprises: after the formed glass is kept at 500 ℃ for 240 min, the formed glass is cooled from 500 ℃ to 400 ℃ at a rate of 0.1 ℃ / min, and then the formed glass is cooled from 400 ℃ to room temperature (25 ℃) at a rate of 0.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the annealing and the heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process, and the colored photosensitive glass-ceramics displays a light spectrum superimposed color of light yellow and opal;

[0073] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2 mm to 20 mm.

[0074] Example 5:

[0075] Different from example 1, in step three, the formed glass is heat treated, the heat treatment comprises: after the formed glass is kept at 500 ℃ for 180 min, the formed glass is cooled from 500 ℃ to 400 ℃ at a rate of 0.2 ℃ / min, and then the formed glass is cooled from 400 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the annealing and the heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process, and the colored photosensitive glass-ceramics displays a light spectrum superimposed color of light yellow and opal;

[0076] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0077] Example 6:

[0078] Different from Example 1, in step three, the formed glass is subjected to heat treatment, which comprises: after holding the formed glass at 600 ℃ for 180 min, cooling the formed glass from 600 ℃ to 400 ℃ at a rate of 0.5 ℃ / min, then cooling the formed glass from 400 ℃ to 200 ℃ at a rate of 1 ℃ / min, and finally cooling the formed glass from 200 ℃ to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process and display a dark brown color.

[0079] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0080] Example 7:

[0081] Different from the embodiment 1, in the step three, the heat treatment of the shaped glass comprises: after the shaped glass is kept at 650 ℃ for 240 min, the shaped glass is cooled from 650 ℃ to 500 ℃ at a rate of 0.2 ℃ / min, then the shaped glass is cooled from 500 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and then the shaped glass is cooled from 300 ℃ to room temperature (25 ℃) at a rate of 1.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuously carried out, so that the annealing and the heat treatment of the glass are synchronously carried out, and the obtained colored photosensitive glass-ceramics can realize the coloring under the controllable heat treatment process, and the colored photosensitive glass-ceramics is displayed as yellow-brown;

[0082] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2-20 mm.

[0083] As can be seen from the embodiments 1-7, by adjusting the proportion of each oxide, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, that is, the colored photosensitive glass-ceramics, and by controlling the heat treatment process, the transparent photosensitive glass-ceramics can also be obtained.

[0084] Embodiment 8:

[0085] Referring to Figure 1 The application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0086] In step one, 70.92% of SiO2, 3% of Al2O3, 0% of B2O3, 0.8% of Li2O, 13.2% of Na2O, 4% of MgO, 1.5% of ZnO, 0% of ZrO2, 0.02% of CeO2, 0.05% of Ag2O, 0.08% of Sb2O3, 5.8% of F - , 0.6% of Cl - , 0% of Br -, 0.03% SnO are mixed to obtain a mixture, wherein, the ratio of F - / (Cl - + Br - ) is 9.67, the ratio of F - / Na + is 0.44, MgO + ZnO + ZrO2 is 5%, the ratio of (Li2O + Na2O) / Al2O3 is 4.67, Li2O + Na2O is 14, the ratio of (Ag2O + CeO2) / Sb2O3 is 0.88, and the ratio of Ag2O / CeO2 is 2.5;

[0087] Step two, the mixture is placed in a platinum crucible, the platinum crucible with the mixture is placed in a high temperature lifting furnace, and the mixture is melted at 1550 ℃ for 8 h to obtain a melted mixture. The melted mixture is sequentially clarified to obtain a clarified mixture, and the clarified mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0088] Step three, the shaped glass is heat treated, and the heat treatment includes: the shaped glass is heat treated at 800 ℃ for 210 min, then cooled from 800 ℃ to 700 ℃ at a rate of 0.1 ℃ / min, then cooled from 700 ℃ to 500 ℃ at a rate of 0.5 ℃ / min, and then cooled from 500 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the glass annealing and heat treatment are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process and display as devitrification.

[0089] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value between 0.2 mm and 20 mm.

[0090] Example 9:

[0091] Different from example 8, in step three, the formed glass is heat treated, the heat treatment comprises: after the formed glass is kept at 800 ℃ for 180 min, the formed glass is cooled from 800 ℃ to 600 ℃ at a rate of 0.2 ℃ / min, then the formed glass is cooled from 600 ℃ to 400 ℃ at a rate of 0.5 ℃ / min, and then the formed glass is cooled from 400 ℃ to room temperature (25 ℃) at a rate of 1.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuous, so that the annealing and the heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process, and shows devitrification.

[0092] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2 mm to 20 mm.

[0093] Example 10:

[0094] Different from example 8, in step three, the formed glass is heat treated, the heat treatment comprises: after the formed glass is kept at 800 ℃ for 210 min, the formed glass is cooled from 800 ℃ to 700 ℃ at a rate of 0.1 ℃ / min, then the formed glass is cooled from 700 ℃ to 500 ℃ at a rate of 0.5 ℃ / min, and then the formed glass is cooled from 500 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuous, so that the annealing and the heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process, and shows devitrification.

[0095] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0096] Example 11:

[0097] Different from example 8, in step three, the formed glass is subjected to heat treatment, the heat treatment comprising: after the formed glass is kept at 400 DEG C for 120 min, the formed glass is cooled from 400 DEG C to 300 DEG C at a rate of 0.5 DEG C / min, and then cooled from 300 DEG C to room temperature (25 DEG C) at a rate of 1 DEG C / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuously performed, so that the glass annealing and the heat treatment are synchronously performed, the thickness of the obtained colored photosensitive glass-ceramics is 0.7 mm, the coloring under the controllable heat treatment process can be realized, and the colored photosensitive glass-ceramics is transparent.

[0098] As can be seen from examples 8-11, by adjusting the proportion of each oxide, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, i.e., the colored photosensitive glass-ceramics, and by controlling the heat treatment process, the transparent photosensitive glass-ceramics can also be obtained.

[0099] Example 12:

[0100] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0101] Step one, in terms of mole percentage, 69.5% SiO2, 5.2% Al2O3, 1% B2O3, 1.5% Li2O, 11.5% Na2O, 1.5% MgO, 0% ZnO, 4% ZrO2, 0.01% CeO2, 0.02% Ag2O, 0.06% Sb2O3, 5% F - , 0.35% Cl - , 0.36% Br -, 0% SnO are mixed to obtain a mixture, wherein F - / (Cl - + Br - ) is 7.04, F - / Na + is 0.4, MgO + ZnO + ZrO2 is 5.5%, (Li2O + Na2O) / Al2O3 is 2.5, Li2O + Na2O is 13, (Ag2O + CeO2) / Sb2O3 is 0.5, and Ag2O / CeO2 is 2.

[0102] Step two, the mixture is placed in a platinum crucible, the platinum crucible with the mixture is placed in a high temperature lifting furnace, and the mixture is melted at 1550 ℃ for 8 h to obtain a melted mixture. The melted mixture is sequentially clarified to obtain a clarified mixture, and the clarified mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0103] Step three, the shaped glass is heat treated, and the heat treatment includes: the shaped glass is heat treated at 800 ℃ for 180 min, then cooled from 800 ℃ to 600 ℃ at a rate of 0.2 ℃ / min, then cooled from 600 ℃ to 400 ℃ at a rate of 0.5 ℃ / min, and then cooled from 400 ℃ to room temperature (25 ℃) at a rate of 1.5 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the glass annealing and heat treatment are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process and show devitrification.

[0104] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0105] Example 13:

[0106] Different from the embodiment 12, in step three, the heat treatment of the shaped glass comprises: after the shaped glass is kept at 400 ℃ for 120 min, the shaped glass is cooled from 400 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and then the shaped glass is cooled from 300 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuously performed, so that the annealing and the heat treatment of the glass are synchronously performed, the colored photosensitive glass-ceramics obtained has a thickness of 0.7 mm, and can realize the coloring under the controllable heat treatment process and display the transparency.

[0107] It can be seen from the embodiments 12-13 that, by adjusting the proportions of the oxides, the photosensitive glass-ceramics obtained can realize different colors and appearances under different heat treatment processes, that is, the colored photosensitive glass-ceramics, and by controlling the heat treatment process, the transparent photosensitive glass-ceramics can also be obtained.

[0108] Embodiment 14:

[0109] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0110] Step one, 67.4% SiO2, 4.5% Al2O3, 0.3% B2O3, 1.1% Li2O, 16% Na2O, 0% MgO, 1.5% ZnO, 0.5% ZrO2, 0.05% CeO2, 0.09% Ag2O, 0.14% Sb2O3, 7.68% F - , 0.34% Cl - , 0.36% Br - , 0.04% SnO are mixed in a molar percentage to obtain a mixture, wherein the ratio of F - / (Cl - + Br - ) is 10.97, the ratio of F - / Na + is 0.48, MgO+ZnO+ZrO2 is 2%, the ratio of (Li2O+Na2O) / Al2O3 is 3.8, Li2O+Na2O is 17.1, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 1.8;

[0111] Step two, the mixture is put into a platinum crucible, the platinum crucible with the mixture is placed in a high-temperature lifting furnace, and the mixture is melted at 1500 ℃ for 8 h to obtain a melted mixture, the melted mixture is sequentially subjected to clarification to obtain a clarified mixture, and the clarified mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0112] Step three, heat treating the shaped glass, the heat treatment comprising: after the shaped glass is kept at 700 ℃ for 240 min, cooling from 700 ℃ to 500 ℃ at a rate of 0.1 ℃ / min, then cooling from 500 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and cooling from 300 ℃ to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so as to realize the synchronization of glass annealing and heat treatment, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and shows opalescent;

[0113] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2-20 mm.

[0114] Example 15:

[0115] Different from example 14, step three, heat treating the shaped glass, the heat treatment comprising: after the shaped glass is kept at 500 ℃ for 240 min, cooling from 500 ℃ to 400 ℃ at a rate of 0.1 ℃ / min, then cooling from 400 ℃ to room temperature (25 ℃) at a rate of 0.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so as to realize the synchronization of glass annealing and heat treatment, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and shows wine red and opal spectrum superimposed color;

[0116] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0117] Example 16:

[0118] Different from example 14, in step three, the formed glass is heat treated, the heat treatment comprising: after the formed glass is kept at 400℃ for 120 min, the formed glass is cooled from 400℃ to 300℃ at a rate of 0.5℃ / min, and then cooled from 300℃ to room temperature (25℃) at a rate of 1℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the thickness of the obtained colored photosensitive glass-ceramics is 0.7 mm, which can realize the coloring under the controllable heat treatment process and show transparency.

[0119] As can be seen from examples 14-16, by adjusting the ratio of each oxide, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, i.e., colored photosensitive glass-ceramics, and by controlling the heat treatment process, transparent photosensitive glass-ceramics can also be obtained.

[0120] Example 17:

[0121] Referring to Figure 1 , the present application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0122] Step one, in terms of mole percentage, 70.5% SiO2, 3% Al2O3, 0.5% B2O3, 0.2% Li2O, 13% Na2O, 2.5% MgO, 1.5% ZnO, 1% ZrO2, 0.03% CeO2, 0.06% Ag2O, 0.13% Sb2O3, 6.76% F - , 0.8% Cl - , 0% Br -, 0.02% NaCl are mixed to obtain a mixture, wherein the ratio of F - / (Cl - + Br - ) is 8.45, the ratio of F - / Na + is 0.52, wherein Na + is from Na2O, MgO + ZnO + ZrO2 is 5%, the ratio of (Li2O + Na2O) / Al2O3 is 4.4, Li2O + Na2O is 13.2, the ratio of (Ag2O + CeO2) / Sb2O3 is 0.69, and the ratio of Ag2O / CeO2 is 2;

[0123] Step two, the mixture is placed in a platinum crucible, the platinum crucible with the mixture is placed in a high temperature lifting furnace, and the mixture is melted at 1600 ℃ for 8 h to obtain a melted mixture. The melted mixture is sequentially clarified to obtain a clarified mixture. The clarified mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0124] Step three, the shaped glass is heat treated, and the heat treatment includes: the shaped glass is heat treated at 600 ℃ for 180 min, then cooled from 600 ℃ to 400 ℃ at a rate of 0.5 ℃ / min, then cooled from 400 ℃ to 200 ℃ at a rate of 1 ℃ / min, and then cooled from 200 ℃ to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the glass annealing and heat treatment are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process and display a dark brown color.

[0125] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0126] Example 18:

[0127] Referring to Figure 1 The present application provides a preparation method of color photosensitive glass-ceramics, comprising the following steps:

[0128] Step one, mixing 69.8% SiO2, 5% Al2O3, 0.1% B2O3, 1% Li2O, 14% Na2O, 1.5% MgO, 0.5% ZnO, 2% ZrO2, 0.04% CeO2, 0.07% Ag2O, 0.13% Sb2O3, 5.32% F - , 0.37% Cl - , 0.16% Br - , 0.01% SnO in mole percentage, to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 10.04, the ratio of F - / Na + is 0.38, MgO+ZnO+ZrO2 is 4%, the ratio of (Li2O+Na2O) / Al2O3 is 3, Li2O+Na2O is 15, the ratio of (Ag2O+CeO2) / Sb2O3 is 0.85, and the ratio of Ag2O / CeO2 is 1.75;

[0129] Step two, placing the mixture into a platinum crucible, and placing the platinum crucible with the mixture into a high-temperature lifting furnace, melting the mixture at 1550 ℃ for 8 h to obtain a melted mixture, and sequentially clarifying the melted mixture to obtain a clarified mixture, and pouring the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0130] Step three, heat treating the shaped glass, the heat treatment comprising: heat treating the shaped glass at 450 ℃ for 150 min, then cooling from 450 ℃ to 350 ℃ at a rate of 0.5 ℃ / min, and then cooling from 350 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain the color photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the color photosensitive glass-ceramics obtained has a thickness of 0.7 mm and can realize coloring under controllable heat treatment process and display transparency.

[0131] Example 19:

[0132] Referring to Figure 1 The present application provides a preparation method of color photosensitive glass-ceramics, comprising the following steps:

[0133] Step one, in terms of mole percentage, 69.25% SiO2, 4.2% Al2O3, 0.8% B2O3, 0.5% Li2O, 16.15% Na2O, 0.5% MgO, 1% ZnO, 0.5% ZrO2, 0.02% CeO2, 0.03% Ag2O, 0.05% Sb2O3, 6% F - , 0.5% Cl - , 0.5% Br - , 0% SnO are mixed to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 6, the ratio of F - / Na + is 0.37, MgO+ZnO+ZrO2 is 2%, the ratio of (Li2O+Na2O) / Al2O3 is 3.96, Li2O+Na2O is 16.65, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 1.5;

[0134] Step two, the mixture is placed in a platinum crucible, the platinum crucible with the mixture is placed in a high-temperature lifting furnace, and the mixture is melted at 1550 ℃ for 8 h to obtain a melted mixture. The melted mixture is sequentially refined to obtain a refined mixture. The refined mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0135] Step three, the shaped glass is heat treated, and the heat treatment includes: the shaped glass is heat treated at 400 ℃ for 120 min, then cooled from 400 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and then cooled from 300 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min. A colored photosensitive glass-ceramic is obtained, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed. The colored photosensitive glass-ceramic obtained has a thickness of 0.7 mm and can realize coloring under controllable heat treatment process and display transparency.

[0136] Example 20:

[0137] Different from the embodiment 19, in step three, the heat treatment of the shaped glass comprises: after the shaped glass is kept at 500 ℃ for 240 min, the shaped glass is cooled from 500 ℃ to 400 ℃ at a rate of 0.1 ℃ / min, and then the shaped glass is cooled from 400 ℃ to room temperature (25 ℃) at a rate of 0.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuously performed, so that the annealing and the heat treatment of the glass are synchronously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process, and the colored photosensitive glass-ceramics displays a light spectrum superimposed color of light yellow and opal;

[0138] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2 mm to 20 mm.

[0139] As can be seen from the embodiments 19-20, by adjusting the proportions of the oxides, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, that is, the colored photosensitive glass-ceramics, and by controlling the heat treatment process, the transparent photosensitive glass-ceramics can also be obtained.

[0140] Embodiment 21:

[0141] Referring to Figure 1 The application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0142] Step one, 70.6% SiO2, 2% Al2O3, 0.2% B2O3, 2% Li2O, 12.5% Na2O, 1.4% MgO, 0.5% ZnO, 2% ZrO2, 0.01% CeO2, 0.02% Ag2O, 0.03% Sb2O3, 7.5% F - , 0.75% Cl - , 0.44% Br - , 0.05% SnO are mixed in a molar percentage to obtain a mixture, wherein F- / (Cl - + Br - ) is 6.3, F - / Na + is 0.6, MgO + ZnO + ZrO2 is 3.9%, (Li2O + Na2O) / Al2O3 is 7.25, Li2O + Na2O is 14.5, (Ag2O + CeO2) / Sb2O3 is 1, Ag2O / CeO2 is 2;

[0143] Step two, put the mixture into a platinum crucible, put the platinum crucible containing the mixture into a high-temperature lifting furnace, melt at 1550 ℃ for 8 h, obtain the melted mixture, and then sequentially clarify the melted mixture to obtain a clarified mixture, and then cast the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0144] Step three, heat treat the shaped glass, the heat treatment including: heat treating the shaped glass at 500 ℃ for 240 min, then cooling from 500 ℃ to 400 ℃ at a rate of 0.1 ℃ / min, and then cooling from 400 ℃ to room temperature (25 ℃) at a rate of 0.5 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process, and shows a light yellow and opal spectrum superimposed color;

[0145] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0146] Example 22:

[0147] Different from the embodiment 21, in step three, the heat treatment of the shaped glass comprises: after the shaped glass is kept at 600 ℃ for 180 min, the shaped glass is cooled from 600 ℃ to 400 ℃ at a rate of 0.5 ℃ / min, then the shaped glass is cooled from 400 ℃ to 200 ℃ at a rate of 1 ℃ / min, and then the shaped glass is cooled from 200 ℃ to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuously performed, so that the annealing and the heat treatment of the glass are synchronously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process, and the colored photosensitive glass-ceramics is displayed as dark brown;

[0148] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2-20 mm.

[0149] As can be seen from the embodiments 21-22, by adjusting the proportion of each oxide, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, that is, the colored photosensitive glass-ceramics.

[0150] Embodiment 23:

[0151] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0152] Step one, 67.06% SiO2, 6% Al2O3, 0% B2O3, 3% Li2O, 12% Na2O, 2% MgO, 1% ZnO, 1.5% ZrO2, 0.04% CeO2, 0.08% Ag2O, 0.12% Sb2O3, 6% F - , 1.2% Cl - , 0% Br - , 0% SnO are mixed to obtain a mixture, wherein F - / (Cl- + Br - a ratio of 5, F - / Na + a ratio of 0.5, MgO+ZnO+ZrO2 is 4.5%, a ratio of (Li2O+Na2O) / Al2O3 is 2.5, Li2O+Na2O is 15, a ratio of (Ag2O+CeO2) / Sb2O3 is 1, a ratio of Ag2O / CeO2 is 2;

[0153] Step two, put the mixture into a platinum crucible, put the platinum crucible containing the mixture into a high temperature lifting furnace, melt at 1550 ℃ for 8 h, get the melted mixture, and then sequentially clarify the melted mixture to get the clarified mixture, and then cast the clarified mixture into a preheated stainless steel mold to get the shaped glass;

[0154] Step three, heat treat the shaped glass, the heat treatment includes: heat the shaped glass at 450 ℃ for 240 min, then start cooling from 450 ℃ to 350 ℃ at a rate of 0.1 ℃ / min, and then start cooling from 350 ℃ to room temperature (25 ℃) at a rate of 0.5 ℃ / min, to get the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so as to realize the synchronization of glass annealing and heat treatment, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process and show devitrification;

[0155] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0156] Example 24:

[0157] Different from the embodiment 23, in step three, the heat treatment of the shaped glass comprises: after the shaped glass is kept at 800 ℃ for 180 min, the shaped glass is cooled from 800 ℃ to 600 ℃ at a rate of 0.2 ℃ / min, then the shaped glass is cooled from 600 ℃ to 400 ℃ at a rate of 0.5 ℃ / min, and then the shaped glass is cooled from 400 ℃ to room temperature (25 ℃) at a rate of 1.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuously performed, so that the annealing and the heat treatment of the glass are synchronously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under a controllable heat treatment process and show devitrification.

[0158] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2-20 mm.

[0159] As can be seen from the embodiments 23-24, by adjusting the proportions of the oxides, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, i.e., the colored photosensitive glass-ceramics.

[0160] Embodiment 25:

[0161] Referring to Figure 1 The present application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0162] In step one, 67.07% SiO2, 3.2% Al2O3, 0.4% B2O3, 0% Li2O, 16.1% Na2O, 0.8% MgO, 1.2% ZnO, 0.8% ZrO2, 0.05% CeO2, 0.1% Ag2O, 0.15% Sb2O3, 9% F - , 0.1% Cl - , 1% Br - , 0.03% SnO are mixed in a molar percentage to obtain a mixture, wherein F- / (Cl - + Br - ) is 8.18, F - / Na + is 0.56, MgO+ZnO+ZrO2 is 2.8%, (Li2O+Na2O) / Al2O3 is 5.03, Li2O+Na2O is 16.1, (Ag2O+CeO2) / Sb2O3 is 1, Ag2O / CeO2 is 2;

[0163] Step two, put the mixture into a platinum crucible, put the platinum crucible containing the mixture into a high temperature lifting furnace, melt at 1550 ℃ for 8 h, get the melted mixture, then sequentially clarify the melted mixture, get the clarified mixture, and then cast the clarified mixture into a preheated stainless steel mold, get the shaped glass;

[0164] Step three, heat treat the shaped glass, the heat treatment includes: heat the shaped glass at 500 ℃ for 180 min, then start cooling from 500 ℃ to 400 ℃ at a rate of 0.2 ℃ / min, and then start cooling from 400 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, get the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so as to realize the synchronization of glass annealing and heat treatment, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and show yellow-brown color;

[0165] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0166] Example 26:

[0167] Different from example 25, in step three, the formed glass is heat treated, the heat treatment includes: after the formed glass is kept at 700 ℃ for 240 min, the formed glass is cooled from 700 ℃ to 500 ℃ at a rate of 0.1 ℃ / min, then the formed glass is cooled from 500 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and then the formed glass is cooled from 300 ℃ to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and the colored photosensitive glass-ceramics is opaque;

[0168] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value in the range of 0.2-20 mm.

[0169] As can be seen from examples 25-26, by adjusting the ratio of each oxide, the obtained photosensitive glass-ceramics can obtain different colors and appearances under different heat treatment processes, that is, the colored photosensitive glass-ceramics.

[0170] The components of examples 1-26 of the present application are shown in Table 1:

[0171] Table 1 Components of examples 1-26

[0172]

[0173] Example 27:

[0174] Referring to Figure 1 The present application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0175] Step one, in terms of mole percentage, 68.45% SiO2, 4.8% Al2O3, 0.5% B2O3, 1.2% Li2O, 14.8% Na2O, 0.9% MgO, 0% ZnO, 0.9% ZrO2, 0.03% CeO2, 0.04% Ag2O, 0.07% Sb2O3, 7.4% F - , 0.63% Cl - , 0.27% Br - , 0.01% SnO are mixed to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 8.22, the ratio of F - / Na + is 0.5, MgO+ZnO+ZrO2 is 1.8%, the ratio of (Li2O+Na2O) / Al2O3 is 3.33, Li2O+Na2O is 16, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 1.33;

[0176] Step two, the mixture is placed in a platinum crucible, the platinum crucible with the mixture is placed in a high-temperature lifting furnace, and the mixture is melted at 1550 ℃ for 8 h to obtain a melted mixture. The melted mixture is sequentially refined to obtain a refined mixture. The refined mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0177] Step three, the shaped glass is heat treated, and the heat treatment includes: the shaped glass is kept at 800 ℃ for 210 min, then cooled from 800 ℃ to 700 ℃ at a rate of 0.1 ℃ / min, then cooled from 700 ℃ to 500 ℃ at a rate of 0.5 ℃ / min, and then cooled from 500 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process and shows devitrification.

[0178] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0179] Example 28:

[0180] Referring to Figure 1 , the present application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0181] Step one, mixing 69.8% SiO2, 5.2% Al2O3, 0.9% B2O3, 0.8% Li2O, 13.5% Na2O, 0.8% MgO, 0.1% ZnO, 1% ZrO2, 0.02% CeO2, 0.05% Ag2O, 0.06% Sb2O3, 6.75% F - , 0.5% Cl - , 0.5% Br - , 0.02% SnO in mole percentage to obtain a mixture, wherein the ratio of F - / (Cl - + Br - ) is 6.75, the ratio of F - / Na + is 0.5, MgO+ZnO+ZrO2 is 1.9%, the ratio of (Li2O+Na2O) / Al2O3 is 2.75, Li2O+Na2O is 14.3, the ratio of (Ag2O+CeO2) / Sb2O3 is 1.17, and the ratio of Ag2O / CeO2 is 2.5;

[0182] Step two, placing the mixture into a platinum crucible, and placing the platinum crucible containing the mixture into a high-temperature lifting furnace to melt at 1550 ℃ for 8 h to obtain a molten mixture, and sequentially clarifying the molten mixture to obtain a clarified mixture, and casting the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0183] Step three, heat treating the shaped glass, the heat treatment comprising: keeping the shaped glass at 400 DEG C for 120 min, then cooling from 400 DEG C to 300 DEG C at a rate of 0.5 DEG C / min, and then cooling from 300 DEG C to room temperature (25 DEG C) at a rate of 1 DEG C / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the glass annealing and heat treatment are simultaneously performed, and the colored photosensitive glass-ceramics obtained has a thickness of 0.7 mm and can realize coloring under controllable heat treatment process and show transparency.

[0184] Example 29:

[0185] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0186] Step one, mixing 70.22% SiO2, 3.8% Al2O3, 0% B2O3, 1.5% Li2O, 14.2% Na2O, 2.5% MgO, 0.5% ZnO, 0.5% ZrO2, 0.01% CeO2, 0.03% Ag2O, 0.04% Sb2O3, 6.1% F - , 0.6% Cl - , 0% Br - , 0% SnO in mole percentage to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 10.17, the ratio of F - / Na + is 0.43, MgO+ZnO+ZrO2 is 3.5%, the ratio of (Li2O+Na2O) / Al2O3 is 4.13, Li2O+Na2O is 15.7, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 3;

[0187] Step two, placing the mixture into a platinum-gold crucible, and placing the platinum-gold crucible containing the mixture into a high-temperature lifting furnace, melting the mixture at 1550 DEG C for 8 h to obtain a molten mixture, then sequentially clarifying the molten mixture to obtain a clarified mixture, and pouring the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0188] Step three, heat treating the shaped glass, the heat treatment comprising: keeping the shaped glass at 650 ℃ for 240 min, then cooling from 650 ℃ to 500 ℃ at a rate of 0.2 ℃ / min, then cooling from 500 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and then cooling from 300 ℃ to room temperature (25 ℃) at a rate of 1.5 ℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stages are continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treatment process, and shows yellow-brown color;

[0189] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0190] Example 30:

[0191] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0192] Step one, mixing 67% SiO2, 5.5% Al2O3, 0.5% B2O3, 0% Li2O, 15% Na2O, 1% MgO, 2% ZnO, 1% ZrO2, 0.04% CeO2, 0.06% Ag2O, 0.1% Sb2O3, 7.1% F - , 0.65% Cl - , 0% Br - , 0.05% SnO in terms of mole percentage, to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 10.92, and the ratio of F - / Na +the ratio of (Li2O+Na2O) / Al2O3 is 2.73, Li2O+Na2O is 15, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 1.5;

[0193] Step two, put the mixture into a platinum crucible, put the platinum crucible containing the mixture into a high-temperature lifting furnace, melt at 1550 ℃ for 8 h, obtain the melted mixture, and then sequentially clarify the melted mixture to obtain a clarified mixture, and then cast the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0194] Step three, heat treat the shaped glass, the heat treatment including: heat treating the shaped glass at 700 ℃ for 240 min, then cooling from 700 ℃ to 500 ℃ at a rate of 0.1 ℃ / min, then cooling from 500 ℃ to 300 ℃ at a rate of 0.5 ℃ / min, and then cooling from 300 ℃ to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stages are continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process and show devitrification;

[0195] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0196] Example 31:

[0197] Referring to Figure 1 The present application provides a preparation method of a colored photosensitive glass-ceramic, comprising the following steps:

[0198] Step 1: Using molar percentages, combine 70% SiO2, 4% Al2O3, 0% B2O3, 0.5% Li2O, 16% Na2O, 0% MgO, 1% ZnO, 0% ZrO2, 0.05% CeO2, 0.1% Ag2O, 0.15% Sb2O3, and 7.45% F. - 0.7% Cl - 0% Br - 0.05% SnO was mixed to obtain a mixture, wherein F - / (Cl - +Br - The ratio of F to F is 10.64. - / Na + The ratio of MgO to ZnO to ZrO2 is 0.47, the ratio of (Li2O to Na2O) to Al2O3 is 4.13, the ratio of Li2O to Na2O is 16.5, the ratio of (Ag2O to CeO2) to Sb2O3 is 1, and the ratio of Ag2O to CeO2 is 2.

[0199] Step 2: Place the mixture into a platinum crucible, place the platinum crucible containing the mixture into a high-temperature lifting furnace, and melt it at 1550 ℃ for 8 h to obtain the molten mixture. Clarify the molten mixture sequentially to obtain the clarified mixture. Cast the clarified mixture into a preheated stainless steel mold to obtain the shaped glass.

[0200] Step 3: Heat treatment of the formed glass. The heat treatment includes: holding the formed glass at 600 ℃ for 180 min, then cooling it down to 400 ℃ at a rate of 1 ℃ / min, then cooling it down to 200 ℃ at a rate of 1 ℃ / min, and then cooling it down to room temperature (25 ℃) at a rate of 2 ℃ / min, to obtain colored photosensitive microcrystalline glass. The cooling stage is carried out continuously, so as to realize the simultaneous annealing and heat treatment of the glass. The resulting colored photosensitive microcrystalline glass can achieve coloring under controllable heat treatment process and is displayed as brown.

[0201] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0202] Example 32:

[0203] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0204] Step one, mixing 68.04% SiO2, 4.6% Al2O3, 0.7% B2O3, 1.8% Li2O, 13.2% Na2O, 2% MgO, 1% ZnO, 1% ZrO2, 0.03% CeO2, 0.05% Ag2O, 0.08% Sb2O3, 6.6% F - , 0.2% Cl - , 0.68% Br - , 0.02% SnO in mole percentage to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 7.5, the ratio of F - / Na + is 0.5, MgO+ZnO+ZrO2 is 4%, the ratio of (Li2O+Na2O) / Al2O3 is 3.26, Li2O+Na2O is 15, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 1.67;

[0205] Step two, placing the mixture into a platinum crucible, and placing the platinum crucible containing the mixture into a high-temperature lifting furnace to melt at 1550 ℃ for 8 h to obtain a molten mixture, and sequentially clarifying the molten mixture to obtain a clarified mixture, and pouring the clarified mixture into a preheated stainless steel mold to obtain a shaped glass.

[0206] Step three, heat treating the shaped glass, the heat treatment comprising: keeping the shaped glass at 450 DEG C for 150 min, then cooling from 450 DEG C to 350 DEG C at a rate of 0.5 DEG C / min, and then cooling from 350 DEG C to room temperature (25 DEG C) at a rate of 1 DEG C / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the glass annealing and heat treatment are simultaneously performed, and the colored photosensitive glass-ceramics obtained has a thickness of 0.7 mm and can realize coloring under controllable heat treatment process and show transparency.

[0207] Example 33:

[0208] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0209] Step one, mixing 69.35% SiO2, 3.2% Al2O3, 0.3% B2O3, 0.7% Li2O, 15.5% Na2O, 1.2% MgO, 1.8% ZnO, 0.8% ZrO2, 0.02% CeO2, 0.04% Ag2O, 0.06% Sb2O3, 6.2% F - , 0.71% Cl - , 0.11% Br - , 0.01% SnO in mole percentage to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 7.56, the ratio of F - / Na + is 0.4, MgO+ZnO+ZrO2 is 3.8%, the ratio of (Li2O+Na2O) / Al2O3 is 5.06, Li2O+Na2O is 16.2, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 2;

[0210] Step two, placing the mixture into a platinum crucible, and placing the platinum crucible with the mixture into a high-temperature lifting furnace to melt the mixture at 1550 DEG C for 8 h to obtain a molten mixture, then sequentially clarifying the molten mixture to obtain a clarified mixture, and then casting the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0211] Step three, heat treating the shaped glass, the heat treatment comprising: keeping the shaped glass at 400 DEG C for 120 min, then cooling from 400 DEG C to 300 DEG C at a rate of 0.5 DEG C / min, and then cooling from 300 DEG C to room temperature (25 DEG C) at a rate of 1 DEG C / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so that the annealing and heat treatment of the glass are simultaneously performed, and the colored photosensitive glass-ceramics obtained has a thickness of 0.7 mm and can realize coloring under controllable heat treatment process and show transparency.

[0212] Example 34:

[0213] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0214] Step one, mixing 71% SiO2, 2.6% Al2O3, 0.2% B2O3, 0% Li2O, 17% Na2O, 0.4% MgO, 0.4% ZnO, 0.4% ZrO2, 0.01% CeO2, 0.02% Ag2O, 0.03% Sb2O3, 6.72% F - , 0% Cl - , 1.2% Br - , 0.02% SnO in mole percentage to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 5.6, the ratio of F - / Na + is 0.4, MgO+ZnO+ZrO2 is 1.2%, the ratio of (Li2O+Na2O) / Al2O3 is 6.54, Li2O+Na2O is 17, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 2;

[0215] Step two, placing the mixture into a platinum-gold crucible, and placing the platinum-gold crucible containing the mixture into a high-temperature lifting furnace, melting the mixture at 1650 DEG C for 8 h to obtain a molten mixture, then sequentially clarifying the molten mixture to obtain a clarified mixture, and pouring the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0216] Step three, heat treating the shaped glass, the heat treating comprising: keeping the shaped glass at 500℃ for 120min, then cooling from 500℃ to 300℃ at a rate of 0.5℃ / min, and then cooling from 300℃ to room temperature (25℃) at a rate of 1℃ / min, to obtain the colored photosensitive glass-ceramics, wherein the cooling stage is continuous, so as to realize the synchronization of glass annealing and heat treating, and the obtained colored photosensitive glass-ceramics can realize coloring under controllable heat treating process, and shows yellow-brown color;

[0217] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0218] Example 35:

[0219] Referring to Figure 1 , the application provides a preparation method of colored photosensitive glass-ceramics, comprising the following steps:

[0220] Step one, mixing 67.2% SiO2, 5.9% Al2O3, 1% B2O3, 3% Li2O, 12% Na2O, 3% MgO, 0.5% ZnO, 0.5% ZrO2, 0.05% CeO2, 0.08% Ag2O, 0.12% Sb2O3, 6% F - , 0.05% Cl - , 0.55% Br - , 0.05% SnO in mole percentage, to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 10, and the ratio of F - / Na +the ratio of (Li2O+Na2O) / Al2O3 is 2.54, Li2O+Na2O is 15, the ratio of (Ag2O+CeO2) / Sb2O3 is 1.08, the ratio of Ag2O / CeO2 is 1.6;

[0221] Step two, put the mixture into a platinum crucible, put the platinum crucible containing the mixture into a high-temperature lifting furnace, melt at 1550 ℃ for 8 h, obtain the melted mixture, and then sequentially clarify the melted mixture to obtain a clarified mixture, and then cast the clarified mixture into a preheated stainless steel mold to obtain a shaped glass;

[0222] Step three, heat-treat the shaped glass, which includes: heat-treating the shaped glass at 450 ℃ for 240 min, then cooling from 450 ℃ to 350 ℃ at a rate of 0.1 ℃ / min, and then cooling from 350 ℃ to room temperature (25 ℃) at a rate of 1 ℃ / min, to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuous, so that the annealing and heat-treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat-treatment process and show devitrification;

[0223] Preferably, the thickness of the obtained colored photosensitive glass-ceramic can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0224] Example 36:

[0225] Referring to ​ The present application provides a preparation method of a colored photosensitive glass-ceramic, which comprises the following steps:

[0226] Step one, in terms of mole percentage, 67% SiO2, 4.5% Al2O3, 0.4% B2O3, 1% Li2O, 13.24% Na2O, 0.5% MgO, 3% ZnO, 0% ZrO2, 0.03% CeO2, 0.06% Ag2O, 0.09% Sb2O3, 9% F - , 0.58% Cl - , 0.58% Br - , 0.02% SnO are mixed to obtain a mixture, wherein the ratio of F - / (Cl - +Br - ) is 7.76, the ratio of F - / Na + is 0.64, MgO+ZnO+ZrO2 is 3.5%, the ratio of (Li2O+Na2O) / Al2O3 is 3.16, Li2O+Na2O is 14.24, the ratio of (Ag2O+CeO2) / Sb2O3 is 1, and the ratio of Ag2O / CeO2 is 2;

[0227] Step two, the mixture is placed in a platinum crucible, the platinum crucible with the mixture is placed in a high-temperature lifting furnace, and the mixture is melted at 1550 ℃ for 8 h to obtain a melted mixture, the melted mixture is sequentially subjected to refining to obtain a refined mixture, and the refined mixture is cast in a preheated stainless steel mold to obtain a shaped glass.

[0228] Step three, the shaped glass is subjected to heat treatment, and the heat treatment comprises: after the shaped glass is kept at 500 ℃ for 180 min, the shaped glass is cooled at a rate of 0.2 ℃ / min from 500 ℃ to 400 ℃, and then cooled at a rate of 1 ℃ / min from 400 ℃ to room temperature (25 ℃) to obtain a colored photosensitive glass-ceramic, wherein the cooling stage is continuously performed, so that the annealing and heat treatment of the glass are simultaneously performed, and the obtained colored photosensitive glass-ceramic can realize coloring under controllable heat treatment process and displays brownish color.

[0229] Preferably, the thickness of the obtained colored photosensitive glass-ceramics can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm, 19 mm, 19.5 mm, 20 mm, or any value within the range of 0.2-20 mm.

[0230] The components of Examples 27-36 of the present application are shown in Table 2.

[0231] Table 2: Component table of Examples 27-36

[0232]

[0233] In summary, the colored photosensitive glass-ceramics provided in the present application can ensure that the prepared glass has different appearances under different heat treatment processes, such as wine red and opal superimposed color, dark brown, yellowish brown, transparent, devitrification, and the like.

[0234] The transparent photosensitive glass-ceramics obtained in Examples 3, 11, 13, 16, 18, 19, 28, 32, and 33 were size-adjusted to obtain photosensitive glass-ceramic bricks with appropriate sizes, which were precisely cut, ground, and polished by a wire cutting machine, a CNC (Computer Numerical Control) precision carving machine, and a flat grinding and polishing machine to obtain samples with a size of 145.98 x 67.78 x 0.7 mm. The transparent photosensitive glass-ceramics were then masked, exposed to light, and heat-treated, and the light excitation conditions were as follows: the wavelength of the ultraviolet light source was 320 nm, the intensity of the ultraviolet light source was 7.02 mW / cm 2 , and the light exposure time was 15 min. After the transparent photosensitive glass-ceramics were excited by light, they were subjected to secondary heat treatment at a temperature of 400 ℃ for 45 min at a heating rate of 5 ℃ / min, and then cooled down with the furnace. The transmittance was then tested, and the results are shown in Table 3.

[0235] Table 3: Transmittance test results

[0236]

[0237] In the table, T 透明 represents the visible light transmittance in the transparent state; T 透明 550 nm% represents the visible light transmittance at a wavelength of 550 nm in the transparent state; T 掩膜 represents the visible light transmittance after the mask; T 掩膜 550 nm% represents the visible light transmittance at a wavelength of 550 nm after the mask;

[0238] In T 透明 550 nm%, examples 3, 11, 13, 16, 18, 19, 28, 32 and 33 are close to the transmittance level of ordinary glass (usually > 90%) when untreated, suitable for high light transmittance applications; in T 掩膜 550 nm%, the light transmittance of examples 3, 11, 13, 16, 18, 19, 28, 32 and 33 is significantly reduced (0.8%~2.8%), with a large decrease (about 88%~90% in general), indicating that the precise control of light transmittance is successfully achieved through the ultraviolet mask exposure and heat treatment (400 ℃ / 45 min) process, realizing the reversible or irreversible change from high light transmittance to almost no light transmittance, which has wide application potential in electronic glass, display screen, camera, back cover.

[0239] It is worth noting that the transparent photosensitive microcrystalline glass mask exposure and heat treatment process provided by the present application is only to illustrate that the transparent photosensitive microcrystalline glass has photosensitive properties, and is not the best exposure and heat treatment process of the transparent photosensitive microcrystalline glass. Any modification, equivalent replacement, improvement, etc. made within the basis and principles of the present application shall be included within the protection scope of the present application.

[0240] The basic principles and main features of the present application are shown and described above, and the advantages of the present application are shown and described above. It is obvious for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be realized in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be regarded as exemplary and non-limiting in any respect, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application. Any reference signs in the claims should not be regarded as limiting the claims involved.

[0241] Furthermore, it should be understood that although the specification is described in terms of embodiments, each of which contains only one independent technical solution, the specification is described in this way only for the sake of clarity, and the skilled person should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that the skilled person can understand. The above is only to illustrate the technical idea of the present application, and cannot limit the protection scope of the present application. Any modification made on the basis of the technical solutions according to the technical idea of the present application falls within the protection scope of the claims of the present application.

Claims

1. A colored photosensitive microcrystalline glass, characterized in that, Prepared from raw materials containing the following components, in molar percentage: 67%≤SiO2≤71%, 2%≤Al2O3≤6%, 0%≤B2O3≤1%, 0%≤Li2O≤3%, 11.5%≤Na2O≤17%, 0%≤MgO≤4%, 0%≤ZnO≤3%, 0%≤ZrO2≤4%, 0.01%≤CeO2≤0.05%, 0.02%≤Ag2O≤0.1%, 0.03%≤Sb2O3≤0.15%, 5%≤F - ≤9%, 0%≤Cl - ≤1.2%, 0%≤Br - ≤1.2%, 0%≤clarifying agent≤0.05%; F - / (Cl - +Br - The ratio of F to F is 5~10.

97. - / Na + The ratio is 0.37~0.64, 1%≤MgO+ZnO+ZrO2≤5.5%, (Li2O+Na2O) / Al2O3 ratio is 2.5~7.25, (Ag2O+CeO2) / Sb2O3 ratio is 0.5~1.17, and Ag2O / CeO2>1.

2. The colored photosensitive microcrystalline glass according to claim 1, characterized in that, In molar percentage terms, the colored photosensitive microcrystalline glass contains 13% ≤ Li₂O + Na₂O ≤ 17.1%.

3. The colored photosensitive microcrystalline glass according to claim 1, characterized in that, The clarifying agent includes at least one of SnO and NaCl.

4. A colored photosensitive microcrystalline glass according to claim 1, characterized in that, The thickness of the colored photosensitive microcrystalline glass is 0.2~20 mm.

5. A method for preparing a colored photosensitive microcrystalline glass, characterized in that, Based on the colored photosensitive microcrystalline glass according to any one of claims 1-4, the process includes the following steps: Weigh the raw materials according to the composition and molar percentage of the colored photosensitive microcrystalline glass, mix the raw materials to obtain a mixture; The mixture is melted, clarified, and shaped sequentially to obtain shaped glass; The molded glass is heat-treated to obtain colored photosensitive microcrystalline glass.

6. A method for preparing a colored photosensitive microcrystalline glass according to claim 5, characterized in that, The melting temperature is 1500~1650 ℃.

7. The method for preparing a colored photosensitive microcrystalline glass according to claim 5, characterized in that, The heat treatment includes: sequentially heat preservation and gradient cooling of the formed glass, wherein the gradient cooling includes a first stage of cooling and a second stage of cooling.

8. A method for preparing a colored photosensitive microcrystalline glass according to claim 7, characterized in that, The heat preservation temperature is 400~800 ℃, and the heat preservation time is 120~240 min; The first stage of cooling includes: starting from the insulation temperature, cooling down to 100~200 ℃ below the insulation temperature, and the cooling rate of the first stage is 0.1~1 ℃ / min; The second stage of cooling includes: starting from the temperature at the end of the first stage of cooling, cooling down to 200~375 ℃ below the holding temperature, with a cooling rate of 0.5~1 ℃ / min.

9. The method for preparing a colored photosensitive microcrystalline glass according to claim 8, characterized in that, The gradient cooling also includes a third stage of cooling; The third stage of cooling includes: starting from the temperature at the end of the second stage of cooling, cooling down to room temperature, with a cooling rate of 1~2 ℃ / min.

10. An application of the colored photosensitive microcrystalline glass according to any one of claims 1-4 in electronic glass, display screen, camera, and back cover.

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