3D crystallized glass, its manufacturing method, and its use

Abstract

The present invention provides a 3D crystallized glass, which is characterized in that the crystallization degree of the 3D crystallized glass is 14-100wt%, the average grain size of the crystal of the 3D crystallized glass is 10-100nm, and the thickness of the 3D crystallized glass is 0.02-5mm. The manufacturing method of the 3D crystallized glass of the present invention has a low processing difficulty, low processing cost, and the time of 3D hot bending crystallization is much shorter than the time of normal crystallization, saving time and energy in heat treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of glass manufacturing, and more particularly to 3D crystallized glass and its manufacturing method and use.

Background Art

[0002] Crystallized glass, which is a new generation of high-strength glass, has higher performance than conventional lithium aluminosilicate glass. Since a large amount of nanoscale crystals exist inside the crystallized glass, it has a more stable structure, and through chemical strengthening, a cover plate product with higher strength can be obtained.

[0003] The equipment and raw materials required in the 3D hot bending process of the cover plate of a mobile phone include a 3D hot bending machine, a 3D hot bending mold (generally a graphite mold), a glass material, etc. The processing process of 3D hot bending glass for a mobile phone cover plate is generally carried out by the following steps. First, it is formed into a glass plate by methods such as the float method, calendering, overflow, etc., and further steps of cutting and thinning are carried out, and then processes such as CNC processing, grinding, 3D hot bending, 3D grinding, chemical strengthening, etc. are carried out. 3D hot bending is carried out by a hot bending machine, and the hot bending machine includes a preheating station, a forming station and a cooling station. The preheating station includes a preheating mold and a glass sheet, and its role is to promote the uniformization of the temperature inside and outside the glass. The cooling station rapidly cools the mold with cooling water to gradually lower the temperature of the glass from the forming temperature to the demolding temperature. The 3D hot bending mold is a graphite mold, which is divided into upper and lower parts. After putting the glass sheet into the mold, the entire 3D hot bending process flow is carried out in the preheating station, the forming station and the cooling station. In order to ensure the production efficiency of the 3D hot bending process, there are requirements for the length of time at each station. When actually working, the processed and washed glass sheet is put into the 3D mold, the mold is put into the 3D hot bending machine, and 3D hot bending is carried out according to a preset process.

[0004] The principle used in the 3D hot bending process is as follows: After heating glass or glass ceramic near its softening point, its shape can be changed by the action of an external force. After the shape is changed, rapid cooling maintains the shape obtained by hot pressing. The preheating step in the 3D hot bending process flow prevents the glass from being heated to a high temperature during molding and bursting. Since the molding temperature is above the softening point, the glass softens rapidly, and at the same time, the glass sheet is bent by applying pressure to the top and bottom surfaces of the mold with a pressing rod. The pressure is maintained before cooling to preserve the shape of the glass sheet, and then the mold is rapidly cooled with cooling water. In addition, the entire 3D hot bending process is protected with nitrogen to avoid oxidation of the mold.

[0005] After shaping, cutting, and thinning the glass plate, defects such as cracks on the edges are reduced using CNC, and the top and bottom surfaces of the glass plate are ground to achieve a polished effect. Performing 3D hot bending on the glass plate after CNC and grinding can reduce the rate of glass plate breakage during the hot bending process. [Overview of the project] [Problems that the invention aims to solve]

[0006] Conventional 3D hot-bent crystallized glass is formed by hot-bending fully crystallized glass. The processing flow involves forming the glass sheet, nucleating and crystallizing the glass sheet, thinning the crystallized glass sheet, cutting the crystallized glass sheet, CNC machining, and grinding. After it is fully crystallized, processes such as 3D hot bending, 3D grinding, and chemical strengthening are performed. Conventional fully crystallized glass has higher mechanical strength and hardness, but the yield of machining before hot bending is low, resulting in high manufacturing costs.

[0007] Since the softening and molding temperature of conventional fully crystallized glass is generally above 700°C, the molding temperature for 3D hot bending must exceed 700°C. In the hot bending process, when fully crystallized glass is heated, its original crystalline phase type, crystal size, refractive index, Lab (chromaticity) value, haze, and transmittance change significantly. When used in the display field, the chromaticity and transmittance of crystallized glass directly affect the display effects such as resolution, color gamut, and saturation of the display. When used in camera objective lenses, the refractive index, haze, and transmittance of crystallized glass, especially in the ultraviolet and near-ultraviolet regions, greatly affect the optical system of photography and image capture. Furthermore, low transmittance in the ultraviolet and near-ultraviolet regions directly affects the quality of image formation.

[0008] Furthermore, conventional 3D hot bending of fully crystallized glass is solely for the purpose of hot bending, which can lead to repeated crystallization and waste of energy and time. Therefore, conventional 3D hot bending of fully crystallized glass is technically very difficult, and it is difficult to achieve the yield required for industrial manufacturing by processing it into a 3D shape using 3D hot bending.

[0009] However, when 3D hot bending is performed on nucleated glass rather than fully crystallized glass, the volume contraction caused by the growth of crystals at the interface between the crystal nuclei and the glass is very apparent in the early stages of crystallization during hot bending. The higher the ratio of growing crystals, the greater the change in the volume of the product, making it very difficult to control the size. Therefore, nucleated glass undergoes a large volume change during the hot bending crystallization process, affecting the accuracy of the size of the 3D hot-bent crystallized glass after molding.

[0010] In response to this, the present invention has found that when 3D hot bending is performed on partially crystallized glass, the glass deforms during hot bending and is simultaneously heated, causing it to crystallize further to reach the desired degree of crystallinity. This reduces the crystallization process during 3D hot bending, resulting in higher precision in the size of the 3D crystallized glass after hot bending.

[0011] Furthermore, in conventional techniques, the hot pressing time during hot bending is controlled to be short because if the hot pressing time is long, mold marks appear on the surface of the crystallized glass product, degrading the surface quality and affecting the yield rate. The method of the present invention performs 3D hot bending using a partially crystallized glass material. Partially crystallized glass material has a high initial degree of crystallinity, making it less likely for mold marks to appear. In addition, because the initial degree of crystallinity of the partially crystallized glass material is high, the amount of size deformation per unit time during the hot pressing process is small, allowing for longer hot pressing times, enabling more precise control of the deformation amount after 3D bending, resulting in less variation in the tolerance of the contour and greater size stability. [Means for solving the problem]

[0012] The present invention aims to provide 3D crystallized glass in order to solve the aforementioned technical problems, characterized in that the degree of crystallinity of the 3D crystallized glass is 14 to 100 wt%, and the average grain size of the crystals of the 3D crystallized glass is 10 to 100 nm.

[0013] Preferably, the degree of crystallinity of the 3D crystallized glass is 14-30 wt%, or 50-100 wt%, or 31-49 wt%, Alternatively, the average grain size of the crystals in the 3D crystallized glass is 15-30 nm. Alternatively, the thickness of the 3D crystallized glass is 0.02 to 5 mm, preferably 0.35 to 1.2 mm.

[0014] Preferably, the average transmittance of light with a wavelength of 380 to 780 nm to the 3D crystallized glass is 88 to 93%, preferably 90 to 91.5%. Alternatively, the average transmittance of light with a wavelength of 360-400 nm to the 3D crystallized glass is 65-91.5%, preferably 79-91%, and more preferably 85-91%.

[0015] Preferably, when the thickness of the 3D crystallized glass is 0.7 mm, the absolute value of the b value (yellow-blue value) is 0.1 to 3.5, preferably 0.3 to 1.5. Alternatively, the haze of the 3D crystallized glass is 0.07 to 1.0%, preferably 0.07 to 0.5%.

[0016] Preferably, the crystalline phase of the 3D crystallized glass is one or more of the following: lithium silicate, lithium disilicate, β-quartz, β-quartz solid solution, feldspar, β-sea pyroxene, β-sea pyroxene solid solution, nepheline, cordierite, mullite, apatite, zirconia, zinc spinel, magnesia-alumina-spinel, and rutile.

[0017] Preferably, the 3D crystallized glass contains oxides in the following proportions, calculated in mol%, Composition mol%: SiO255~74%, Al2O33 ~19%, B2O 30-4%, MgO 0-6%, Na2O 0-3%, Li2O 6-25%, K2O 0-1%, CaO 0-2%, ZnO 0-5%, Rare earth oxides 0-3% Here, the rare earth oxides are La2O3, Eu2O3, and Pr6O 11 One or more are selected from Nd2O3, Er2O3, and Dy2O3.

[0018] Preferably, the 3D crystallized glass has a total content of SiO2 and Al2O3 greater than 60%, preferably 68-80%, when calculated in mol%. Alternatively, the Na2O + Li2O content, when calculated in mol%, is 7-30%, preferably 10-26%.

[0019] Preferably, the 3D crystallized glass contains a nucleating agent, and calculated as an oxide, fluoride, or simple substance, the nucleating agent contains one or more of P2O5, TiO2, ZrO2, Cr2O3, CaF2, LiF, NaF, KF, Y2O3, Au, Ag, and Cu, and preferably one or more of P2O5, TiO2, and ZrO2.

[0020] Preferably, the 3D crystallized glass contains a fining agent, and the fining agent contains one or more of NaCl, Na2SO4, SnO2, As2O3, Sb2O3, NaNO3, KNO3, CeO2, and (NH4)2SO4, and preferably one or more of NaCl, SnO2, NaNO3, and CeO2.

[0021] Preferably, the crystallized glass material of the 3D crystallized glass is a glass sheet having crystals with an average particle size of 5 to 50 nm after nucleation and crystallization treatment.

[0022] Preferably, the crystallized glass material of the 3D crystallized glass is a glass sheet having a crystallinity of 5 to 90 wt% after nucleation and crystallization treatment.

[0023] Preferably, the 3D crystallized glass has a drop height greater than 1.5 m after chemical strengthening, and preferably, the Vickers hardness under a load of 300 gf for 10 seconds is greater than 650 kgf / mm2 greater.

[0024] The present invention also provides a method for manufacturing the 3D crystallized glass, and the manufacturing method includes the following steps. Step 1: Mix the raw materials for manufacturing the 3D crystallized glass, melt them, then cool them, and perform annealing treatment to obtain a glass substrate. Step 2: Perform nucleation treatment on the glass substrate obtained in Step 1, and cutting may be performed before and after the nucleation treatment as necessary. Step 3: Perform crystallization treatment on the glass substrate after nucleation in Step 2. Step 4: The glass substrate after crystallization treatment is cut as needed to obtain crystallized glass material. Step 5: After performing a 3D hot bending treatment on the crystallized glass material, a 3D crystallized glass sample is obtained. Step 5 involves a 3D hot bending process accompanied by a crystallization process.

[0025] Preferably, the method may further include the step of performing a chemical strengthening treatment on a 3D crystallized glass sample to obtain a finished 3D crystallized glass product.

[0026] Preferably, in step 1, the melting temperature is 1350 to 1700°C, preferably 1400 to 1650°C, and more preferably, it is cooled to 500 to 1000°C after melting.

[0027] Preferably, in step 1, the melting time is 1 to 5 hours; preferably, in step 3, a crystallization treatment is performed after holding the temperature at 500 to 900°C for 5 to 300 minutes; and more preferably, in step 3, one or more treatments from edge trimming, CNC machine machining, rough polishing and / or grinding are performed to obtain a crystallized glass material.

[0028] Preferably, the amount of nucleating agent added in step 1 is 1 to 9 mol% of the total amount of nucleating agent and crystallized glass oxide, and more preferably the amount of nucleating agent is 2 to 5 mol%.

[0029] Preferably, the amount of clarifying agent added in step 1 is 0 to 4 wt%, preferably 0.1 to 2 wt%, of the total mass of the nucleating agent and crystallized glass oxide.

[0030] Preferably, in step 2, the temperature of the nucleation treatment is 450 to 800°C and the duration of the nucleation treatment is 30 to 360 minutes, more preferably, the temperature of the nucleation treatment is 520 to 570°C and the duration of the nucleation treatment is 120 to 300 minutes.

[0031] Preferably, in step 3, the crystallization treatment temperature is 550 to 900°C, and the crystallization treatment time is 5 to 300 minutes. Preferably, the crystallization treatment temperature is 600-850°C, and the crystallization treatment time is 10-240 minutes. More preferably, the crystallization treatment temperature is 600 to 750°C, and the crystallization treatment time is 10 to 150 minutes.

[0032] Preferably, the hot bending process in step 5 includes a preheating station, a hot pressing station, and a cooling station.

[0033] Preferably, the preheating stations number 1 to 30, preferably 2 to 4; the hot press stations number 1 to 30, preferably 1 to 3; and the cooling stations number 1 to 30, preferably 2 to 4.

[0034] Preferably, the temperature of the preheating station is 300 to 850°C, the temperature of the hot press station is 600 to 920°C, the pressure is 0 to 6 MPa, and the temperature of the cooling station is 200 to 650°C.

[0035] Preferably, the operating time of the preheating station is 20 to 800 seconds, the operating time of the hot press station is 20 to 800 seconds, and the operating time of the cooling station is 20 to 800 seconds. Preferably, the operating time of the preheating station is 60 to 600 seconds, the operating time of the hot press station is 60 to 480 seconds, and the operating time of the cooling station is 60 to 600 seconds.

[0036] The present invention also provides 3D crystallized glass produced by the above manufacturing method.

[0037] Preferably, the 3D crystallized glass is characterized by being transparent or opaque, and preferably, having a curved or flat surface.

[0038] The present invention also provides the use of the 3D crystallized glass in mobile phone displays, tablet computer displays, portable game consoles, electronic terminals, portable digital devices, center console displays, electronic whiteboard glass, smart home touchscreens, vehicle windshields, aircraft windshields, or aircraft windshields. [Effects of the Invention]

[0039] The beneficial effects of this invention are as follows: 1. This invention involves 3D hot bending of partially crystallized glass. As the glass deforms during hot bending, it is heated and continues to crystallize to reach the desired degree of crystallinity. This reduces the crystallization process during 3D hot bending, resulting in higher precision in the size of the 3D crystallized glass after hot bending. The method for manufacturing 3D crystallized glass according to this invention is easy to process, inexpensive, time-saving, and energy-saving in heat treatment. Performing 3D hot bending on partially crystallized glass avoids the problem of repeated crystallization that occurs when conventional 3D hot bending of highly crystallized or completely crystallized glass.

[0040] 2. In the manufacturing process of 3D crystallized glass, planar polishing and grinding are performed before 3D hot bending as needed. The speed of planar polishing and grinding of 3D crystallized glass is related to its hardness; the higher the hardness, the more difficult and time-consuming the planar polishing and grinding becomes. This invention performs planar polishing and grinding on partially crystallized glass, which has a lower hardness than fully crystallized glass, thus reducing the difficulty of planar polishing and grinding the glass sheet and decreasing the required time.

[0041] 3. The 3D crystallized glass of the present invention has improved optical performance. Conventional fully crystallized glass generally has a softening and molding temperature of 700°C or higher. Therefore, in hot bending processes higher than 700°C, crystals continue to grow within the crystallized glass, and crystallization occurs again from the remaining glass mass, resulting in excessive crystallization and a significant decrease in the optical performance of the crystallized glass after hot bending. The optical performance of the 3D crystallized glass described in the present invention is such that the average transmittance of light with wavelengths of 380 to 780 nm is 88 to 93%, the average transmittance of light with wavelengths of 360 to 400 nm is 65 to 91.5%, and the absolute value of the b value (yellow-blue value) when the thickness of the 3D crystallized glass is 0.7 mm is 0.1 to 3.5.

[0042] 4. The accuracy of size control for the 3D crystallized glass of the present invention has been improved. 3D hot bending is performed on partially crystallized glass, and the glass is heated and continues to crystallize to reach the desired degree of crystallinity. In this process, the glass crystallizes and deforms simultaneously with the hot bending. However, this deformation is reduced because it decreases the crystallization process during 3D hot bending, which helps in controlling the accuracy of size of the 3D crystallized glass after hot bending.

[0043] 5. The yield rate of the 3D crystallized glass of the present invention has been improved. When nucleated glass or glass with a low initial degree of crystallinity is used as the material for 3D hot bending, the material needs to crystallize in large quantities within the short time of hot bending. However, different batches of material are affected by many changing factors in the 3D hot bending process, resulting in poor stability of crystal size, crystal type, and crystallinity between batches. When 3D hot bending is performed on partially crystallized glass, its degree of crystallinity is relatively high, the amount of crystal growth in the hot bending process is small, and the influence of changing factors is reduced. Therefore, it is easier to control the stability of 3D crystallized glass from different batches and improve the yield rate. [Brief explanation of the drawing]

[0044] [Figure 1]Figure 1 shows the XRD pattern of the glass block obtained in Example 25 after annealing in Step 2 but before nucleation. [Figure 2] Figure 2 shows the XRD pattern of the partially crystallized glass material obtained in step 4 in Example 25. [Figure 3] Figure 3 shows the XRD pattern of the partially crystallized glass material obtained in step 4 in Example 26. [Figure 4] Figure 4 shows the XRD pattern of the partially crystallized glass material obtained in step 4 of Example 30. [Modes for carrying out the invention]

[0045] The present invention provides 3D crystallized glass, characterized in that the degree of crystallinity of the 3D crystallized glass is 14 to 100 wt%, and the average grain size of the crystals of the 3D crystallized glass is 10 to 100 nm.

[0046] Preferably, the degree of crystallinity of the 3D crystallized glass is 14-30 wt%, or 50-100 wt%, or 31-49 wt%, or 10-20 wt%, 21-30 wt%, 31-40 wt%, 41-50 wt%, 51-60 wt%, 61-70 wt%, 71-80 wt%, 81-90 wt%, or 91-100 wt%.

[0047] Alternatively, the average grain size of the crystals in the 3D crystallized glass is 15-30 nm. Alternatively, the thickness of the 3D crystallized glass is 0.02 to 5 mm, preferably 0.35 to 1.2 mm.

[0048] Preferably, the average transmittance of light with a wavelength of 380 to 780 nm to the 3D crystallized glass is 88 to 93%, preferably 90 to 91.5%. Alternatively, the average transmittance of light with a wavelength of 360-400 nm to the 3D crystallized glass is 65-91.5%, preferably 79-91%, and more preferably 85-91%.

[0049] Preferably, when the thickness of the 3D crystallized glass is 0.7 mm, the absolute value of the b value (yellow-blue value) is 0.1 to 3.5, preferably 0.3 to 1.5. Alternatively, the haze of the 3D crystallized glass is 0.07 to 1.0%, preferably 0.07 to 0.5%.

[0050] Preferably, the crystalline phase of the 3D crystallized glass is one or more of the following: lithium silicate, lithium disilicate, β-quartz, β-quartz solid solution, feldspar, β-sea pyroxene, β-sea pyroxene solid solution, nepheline, cordierite, mullite, apatite, zirconia, zinc spinel, magnesia-alumina-spinel, and rutile.

[0051] Preferably, the 3D crystallized glass contains oxides in the following proportions, calculated in mol%, Composition mol%: SiO255~74%, Al2O33~19%, B2O30~4%, MgO 0~6%, Na2O 0~3%, Li2O 6~25%, K2O 0~1%, CaO 0~2%, ZnO 0~5%, rare earth oxides 0~3% Here, the rare earth oxides are La2O3, Eu2O3, and Pr6O 11 One or more are selected from Nd2O3, Er2O3, and Dy2O3.

[0052] Preferably, the 3D crystallized glass has a total content of SiO2 and Al2O3 greater than 60%, preferably 68-80%, when calculated in mol%. Alternatively, the Na2O + Li2O content, when calculated in mol%, is 7-30%, preferably 10-26%.

[0053] Preferably, the 3D crystallized glass contains a nucleating agent, and when calculated as an oxide, fluoride, or element, the nucleating agent contains one or more of P2O5, TiO2, ZrO2, Cr2O3, CaF2, LiF, NaF, KF, Y2O3, Au, Ag, and Cu, preferably one or more of P2O5, TiO2, and ZrO2.

[0054] Preferably, the 3D crystallized glass contains a clarifying agent, the clarifying agent containing one or more of NaCl, Na2SO4, SnO2, As2O3, Sb2O3, NaNO3, KNO3, CeO2, and (NH4)2SO4, and preferably one or more of NaCl, SnO2, NaNO3, and CeO2.

[0055] Preferably, the crystallized glass material of the 3D crystallized glass is a glass sheet having crystals with an average particle size of 5 to 50 nm after undergoing nucleation and crystallization treatment.

[0056] Preferably, the crystallized glass material of the 3D crystallized glass is a glass sheet having a crystallinity of 5 to 90 wt% after nucleation and crystallization treatment, and preferably the crystallinity is 5 to 10 wt%, 11 to 15 wt%, 16 to 20 wt%, 21 to 25 wt%, 26 to 30 wt%, 31 to 35 wt%, 36 to 40 wt%, or 41 to 45 wt%. These are t%, 46-50 wt%, 51-55 wt%, 56-60 wt%, 61-65 wt%, 66-70 wt%, 71-75 wt%, 76-80 wt%, 81-85 wt%, 86-90 wt%, 91-95 wt%, 96-100 wt%, 15-29 wt%, 30-75 wt%, 76-90 wt%, and / or 30-55 wt%.

[0057] Preferably, the 3D crystallized glass has a drop height greater than 1.5m after chemical strengthening, preferably 300 gf The Vickers hardness under a 10-second load of force is 650. kgf / mm2 Larger.

[0058] When the thickness of the 3D crystallized glass is 0.65 mm, after chemical strengthening, the total drop height when the glass falls onto a marble-based base plate under a load of 160 g is greater than 1.5 m, preferably 300 m. gf The Vickers hardness under a 10-second load of force is 650. kgf / mm2 Larger.

[0059] The present invention also provides a method for manufacturing the 3D crystallized glass, the manufacturing method comprising the following steps. Step 1: The raw materials for manufacturing 3D crystallized glass are mixed, melted, cooled, and then subjected to an annealing process to obtain a glass substrate. Step 2: The glass substrate obtained in Step 1 is subjected to a nucleation treatment, and cutting may be performed before and after the nucleation treatment as needed. Step 3: Crystallization treatment is performed on the glass substrate after nucleation in Step 2. Step 4: The glass substrate after crystallization treatment is cut as needed to obtain crystallized glass material. Step 5: After performing a 3D hot bending treatment on the crystallized glass material, a 3D crystallized glass sample is obtained. Step 5 involves a 3D hot bending process accompanied by a crystallization process.

[0060] In steps 4 and 5, the crystallized glass material may be a partially crystallized glass material.

[0061] Preferably, the method may further include the step of performing a chemical strengthening treatment on a 3D crystallized glass sample to obtain a finished 3D crystallized glass product.

[0062] Preferably, in step 1, the melting temperature is 1350 to 1700°C, preferably 1400 to 1650°C, and more preferably, it is cooled to 500 to 1000°C after melting.

[0063] Preferably, in step 1, the melting time is 1 to 5 hours; preferably, in step 3, a crystallization treatment is performed after holding the temperature at 500 to 900°C for 5 to 300 minutes; and more preferably, in step 3, one or more treatments from edge trimming, CNC machine machining, rough polishing and / or grinding are performed to obtain a crystallized glass material.

[0064] Preferably, the amount of nucleating agent added in step 1 is 1 to 9 mol% of the total amount of nucleating agent and crystallized glass oxide, and more preferably the amount of nucleating agent is 2 to 5 mol%.

[0065] Preferably, the amount of clarifying agent added in step 1 is 0 to 4 wt%, preferably 0.1 to 2 wt%, of the total mass of the nucleating agent and crystallized glass oxide.

[0066] Preferably, in step 2, the temperature of the nucleation treatment is 450 to 800°C and the duration of the nucleation treatment is 30 to 360 minutes, more preferably, the temperature of the nucleation treatment is 520 to 570°C and the duration of the nucleation treatment is 120 to 300 minutes.

[0067] Preferably, in step 3, the crystallization treatment temperature is 550 to 900°C, and the crystallization treatment time is 5 to 300 minutes. Preferably, the crystallization treatment temperature is 600-850°C, and the crystallization treatment time is 10-240 minutes. More preferably, the crystallization treatment temperature is 600 to 750°C, and the crystallization treatment time is 10 to 150 minutes.

[0068] Preferably, the hot bending process in step 5 includes a preheating station, a hot pressing station, and a cooling station.

[0069] Preferably, the preheating stations number 1 to 30, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, preferably 2 to 4, and the hot press stations number 1 to 30, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 The number of units is 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30, preferably 1 to 3 units. The cooling station comprises 1 to 30 units, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30, preferably 2 to 4 units.

[0070] Preferably, the temperature of the preheating station is 300 to 850°C, the temperature of the hot press station is 600 to 920°C, the pressure is 0 to 6 MPa, and the temperature of the cooling station is 200 to 650°C.

[0071] Preferably, the operating time of the preheating station is 20 to 800 seconds, the operating time of the hot press station is 20 to 800 seconds, and the operating time of the cooling station is 20 to 800 seconds. Preferably, the operating time of the preheating station is 60 to 600 seconds, the operating time of the hot press station is 60 to 480 seconds, and the operating time of the cooling station is 60 to 600 seconds.

[0072] The present invention also provides 3D crystallized glass produced by the above manufacturing method.

[0073] Preferably, the 3D crystallized glass is characterized by being transparent or opaque, and preferably, having a curved or flat surface.

[0074] The present invention also provides the use of the 3D crystallized glass in mobile phone displays, tablet computer displays, portable game consoles, electronic terminals, portable digital devices, center console displays, electronic whiteboard glass, smart home touchscreens, vehicle windshields, aircraft windshields, or aircraft windshields.

[0075] Explanation of terms: 3D crystallized glass: Both the top and bottom surfaces are made of non-planar crystallized glass. 2D crystallized glass: Both the top and bottom surfaces are flat crystallized glass. 2.5D crystallized glass: Crystallized glass in which one surface is flat and the other surface is non-flat. Crystallinity: Crystallized glass contains both a crystalline phase and a glassy phase, and the percentage of the mass of the crystalline phase relative to the total mass of the crystallized glass is the degree of crystallinity. Transmittance: This is the ratio of the irradiation energy projected and transmitted to an object to the total irradiation energy projected to the object as the incident light beam moves from the incident surface of the irradiated surface or medium to another surface and then leaves the object. Average transmittance: This value is obtained by measuring the transmittance at each wavelength at 10 nm intervals within a predetermined wavelength range, and then dividing the sum of the transmittances measured at each wavelength by the number of transmittances measured at each wavelength. For example, the method for calculating the average transmittance for wavelengths 360 to 400 nm is as follows: Measure the transmittance at wavelengths 360 nm, 370 nm, 380 nm, 390 nm, and 400 nm. The number of transmittances measured between 360 and 400 nm is 5. Divide the sum of these transmittances by 5 to obtain the average transmittance for wavelengths 360 to 400 nm. Nucleation: This is the process of growing crystal nuclei of approximately 5 nm in nucleating material within glass through heat treatment. Crystallization: The process of growing specific crystals on a crystal nucleus through heat treatment of glass. Average crystal grain size: This is the average value of the crystal grain length in the crystallized glass observed at a magnification of 100,000 to 1,000,000 times. It is measured by observation using a transmission electron microscope (model: ThermoFisher Scientific (formerly FEI) Talos F200S). During measurement, a magnified photograph is taken of the crystal grains in a specific area, and within the area of ​​the magnified photograph, there are a limited number of crystal grains. Based on the scale, the size of the limited crystal grains is noted, and the average is calculated. In the embodiment of the present invention, the magnification during measurement is 500,000 times.

[0076] b value: Represents the yellow-blue value of the material. In this invention, the b value is the b value of transmitted light. A positive b value indicates that the material is closer to blue, and it is measured using a chromatograph (model CM-3600A).

[0077] Haze: The percentage of the total transmitted light intensity where the transmitted light is outside a 2.5° angle from the incident light. Measured using a chromatograph (model CM-3600A).

[0078] When the thickness of the 3D crystallized glass is 0.65 mm, the optical performance is such that the absolute value of the b-value with a D65 light source is 0.1 to 3.5, preferably 0.3 to 1.5, and the transmittance of light at a wavelength of 360 nm is greater than or equal to 80%, preferably greater than or equal to 85%.

[0079] Nucleating agents include, but are not limited to, P2O5, TiO2, ZrO2, Cr2O3, CaF2, LiF, NaF, KF, Y2O3, Au, Ag, Cu, etc.

[0080] When partially crystallized glass is crystallized by hot bending, the crystallization rate can be controlled, which is useful for growing crystals with a particle size of 100 nm or less. By controlling the process, it is possible to ensure that the average particle size of the precipitated crystals is 10 to 100 nm, thereby improving the optical performance of 3D crystallized glass.

[0081] In some specific embodiments, a 3D hot bending process for partially crystallized crystallized glass is performed simultaneously with crystallization and 3D hot bending, and the hot bending time is generally within 30 minutes. Some embodiments demonstrate that partially crystallized crystallized glass, after 10-20 minutes of 3D hot bending using a suitable process, reaches a crystallinity of 80 wt% or more, and its optical performance meets the requirements.

[0082] The crystalline phase of the aforementioned 3D crystallized glass includes lithium silicate, lithium disilicate, β-quartz, β-quartz solid solution, feldspar, β-sea pyroxene, β-sea pyroxene solid solution, nepheline, cordierite, mullite, apatite, zirconia, zinc spinel, magnesia-alumina-spinel, rutile, and the like.

[0083] To further understand the present invention, the contents of the present invention will be explained below using examples.

[0084] The following describes the manufacturers of the raw materials and equipment used in this embodiment, as well as the equipment and analytical methods used for product analysis. Unless otherwise specified, all of the chemical substances are chemically pure, ordinary reagents.

[0085] The information regarding the raw materials used in the examples and comparative examples is shown in Table 1 below. [Table 1] JPEG0007869225000002.jpg228170

[0086] (Examples) The hot bending process of the embodiment is described in Table 2. For example, when process number 1, the hot bending process includes four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 430°C, the temperature of the second preheating station was 500°C, the temperature of the third preheating station was 600°C, and the temperature of the fourth preheating station was 680°C. The temperature of the first hot pressing station was 800°C, with an upper pressure of 0.4 MPa and a lower pressure of 0.4 MPa. The temperature of the second hot pressing station was 810°C, with an upper pressure of 0.4 MPa and a lower pressure of 0.4 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0.4 MPa and a lower pressure of 0.4 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each of the preheating stations, hot pressing stations, and cooling stations was the same, 20 seconds.

[0087] For example, the hot bending process numbered 12 was as follows: The hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 430°C, the second preheating station was 500°C, the third preheating station was 700°C, and the fourth preheating station was 850°C. The temperature of the first hot pressing station was 780°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the second hot pressing station was 760°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each of the preheating, hot pressing, and cooling stations was the same, 90 seconds. This is an example. [Table 2] JPEG0007869225000004.jpg220170JPEG0007869225000005.jpg224170JPEG0007869225000006.jpg228170JPEG0007869225000007.jpg136170

[0088] Example 1: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 62.00%, Al2O3 17.00%, MgO 2.50%, Na2O 2.50%, Li2O 10.00%, B2O 32.00%, rare earth oxide La2O 30.8%, nucleating agent (containing 2.00% P2O5 and 1.20% ZrO2), and clarifying agent NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and production materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1650°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved holding it at 620°C for 5 hours, then lowering the temperature to 30°C at a rate of 1°C / min), and finally transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 760°C, and the nucleation treatment time was 120 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 790°C for a duration of 10 minutes to obtain a partially crystallized glass block. Step 4: After partially crystallizing the glass block, the edges were trimmed using a polishing and grinding machine, then cut into sheets using a multi-wire cutting machine. These sheets were then processed using a CNC machine tool to obtain glass sheets with a length, width, and thickness of 158 × 75 × 0.65 mm. Subsequently, rough polishing and grinding treatments were performed using a surface polishing machine and a grinding machine, respectively, to obtain partially crystallized glass material. When measured, the degree of crystallinity was found to be 10 wt%.

[0089] Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 430°C, the second preheating station was 500°C, the third preheating station was 600°C, and the fourth preheating station was 680°C. The temperature of the first hot pressing station was 800°C, with an upper pressure of 0.4 MPa and a lower pressure of 0.4 MPa. The temperature of the second hot pressing station was 810°C, with an upper pressure of 0.4 MPa and a lower pressure of 0.4 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0.4 MPa and a lower pressure of 0.4 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each of the preheating stations, hot pressing stations, and cooling stations was the same, 20 seconds. Specifically, 3D crystallized glass sample 1 was obtained using the hot bending process shown as item 1 in Table 2.

[0090] When the 3D crystallized glass sample 1 was detected using a linear diffraction apparatus, with the voltage set to 40mV, current to 30mA, test range to 10-50°, scanning speed to 1° / min, and step width to 0.02° / step, the X-ray diffraction data was analyzed after detection. The crystallinity of the 3D crystallized glass sample 1 was 15wt%, the precipitated crystalline phase was β-lithia pyroxene, and the average crystal grain size was 37nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 1 was 2.30, the transmittance of light at a wavelength of 360nm was 76.30%, the average transmittance of light at wavelengths of 380-780nm was 88.20%, the average transmittance of light at wavelengths of 360-400nm was 80.10%, and the haze was 0.40%.

[0091] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment. The glass was immersed in a molten 100 wt% NaNO3 solution at a temperature of 430°C for 8 hours to obtain the final 3D crystallized glass product 1.

[0092] Example 2: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 64.00%, Al2O3 17.00%, Na2O 2.50%, Li2O 12.5%, B2O3 2.00%, nucleating agents (0.80% P2O5, 1.20% ZrO2), and a clarifying agent NaCl accounting for 0.8 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1650°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Steps 2 and 3 were the same as in Example 1. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 13 wt%. Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 2 was obtained using the hot bending process numbered 1 in Table 2 (you may also refer to Example 1).

[0093] Detection was performed on the 3D crystallized glass sample 2 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 2 after hot bending was 24 wt%, the precipitated crystalline phase was β-lithia pyroxene, and the average grain size of the crystals was 27 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 2 was 3.10, the transmittance of light at a wavelength of 360 nm was 76.00%, the average transmittance of light at wavelengths of 380-780 nm was 88.00%, the average transmittance of light at wavelengths of 360-400 nm was 78.00%, and the haze was 0.43%.

[0094] Step 6: Chemical strengthening treatment was performed on the 3D crystallized glass obtained in Step 5 after hot bending, using the same treatment conditions as in Example 1, and finally, 3D crystallized glass finished product 2 was obtained.

[0095] Example 3: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 63.64%, Al2O3 16.03%, Li2O 16.03%, B2O3 2.00%, nucleating agents (0.80% P2O5, 1.50% ZrO2), and a clarifying agent NaCl accounting for 0.8 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 610°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 705°C, and the nucleation treatment time was 120 minutes. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 775°C for a duration of 10 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 9 wt%.

[0096] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 3 was obtained using the hot bending process numbered 1 in Table 2 (see Example 1).

[0097] The 3D crystallized glass sample 3 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 3 after hot bending was 18 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 24 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 3 was 1.21, the transmittance of light at a wavelength of 360 nm was 83.71%, the average transmittance of light at wavelengths of 380-780 nm was 90.22%, the average transmittance of light at wavelengths of 360-400 nm was 84.56%, and the haze was 0.16%.

[0098] Example 4: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.63%, Al2O3 15.13%, MgO 4.76%, Na2O 1.55%, Li2O 8.65%, rare earth oxide La2O3 0.81%, nucleating agents (0.67% P2O5, 1.30% ZrO2, 0.50% Y2O3), and NaCl, which accounted for 0.8 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 610°C for 5 hours and then lowering it to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 720°C, and the nucleation treatment time was 120 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 780°C for a duration of 10 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 11 wt%.

[0099] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 4 was obtained using the hot bending process numbered 1 in Table 2 (you may also refer to Example 1).

[0100] The 3D crystallized glass sample 4 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 4 after hot bending was 23 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 27 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 4 was 1.48, the transmittance of light at a wavelength of 360 nm was 80.06%, the average transmittance of light at wavelengths of 380-780 nm was 89.5%, the average transmittance of light at wavelengths of 360-400 nm was 83.50%, and the haze was 0.25%.

[0101] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment. The glass was immersed in a molten 100 wt% NaNO3 solution at a temperature of 450°C for 7 hours to obtain the final 3D crystallized glass product 4.

[0102] Example 5: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.96%, Al2O3 14.20%, MgO 4.79%, Na2O 0.56%, Li2O 9.70%, rare earth oxide Er2O3 0.81%, nucleating agents (1.68% P2O5, 1.30% ZrO2), and clarifying agents including NaCl and 0.4 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1713.6 g). After thorough mixing, the mixture was melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for 5 hours. The melted mixture was then injected into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Steps 2 and 3 were the same as in Example 4. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 16 wt%.

[0103] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 5 was obtained using the hot bending process shown in Table 2, number 1 (see Example 1).

[0104] The 3D crystallized glass sample 5 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 5 after hot bending was 33 wt%, the precipitated crystalline phases were β-quartz solid solution and β-lithia pyroxene, and the average crystal grain size was 22 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 5 was 3.24, the transmittance of light at a wavelength of 360 nm was 72.00%, the average transmittance of light at wavelengths of 380 to 780 nm was 88.90%, the average transmittance of light at wavelengths of 360 to 400 nm was 78.60%, and the haze was 0.54%.

[0105] Example 6: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.95%, Al2O3 14.20%, MgO 2.29%, Na2O 1.56%, ZnO 1.00%, Li2O 9.70%, rare earth oxide La2O3 0.81%, nucleating agents (1.68% P2O5, 1.31% ZrO2, 0.5% Y2O3), and a clarifying agent NaCl accounting for 0.8 wt% of the total mass of the nucleating agents and production materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 4. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 765°C for a duration of 20 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 12 wt%.

[0106] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 6 was obtained using the hot bending process numbered 1 in Table 2 (you may also refer to Example 1).

[0107] The 3D crystallized glass sample 6 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 6 after hot bending was 23 wt%, the precipitated crystalline phases were β-quartz solid solution and β-lithia pyroxene, and the average crystal grain size was 30 nm. When the light source was limited to D65, the absolute value of the b-value was 3.4, the transmittance of light at a wavelength of 360 nm was 66.30%, the average transmittance of light at wavelengths of 380 to 780 nm was 88.30%, the average transmittance of light at wavelengths of 360 to 400 nm was 76.20%, and the haze was 0.96%.

[0108] Example 7: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.42%, Al2O3 14.09%, MgO 4.75%, Na2O 1.55%, Li2O 9.62%, nucleating agents (0.67% P2O5, 1.3% ZrO2, 1.6% TiO2), and NaCl, which accounted for 0.8 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 4. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 750°C for 20 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 17 wt%.

[0109] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 7 was obtained using the hot bending process shown in Table 2, number 1 (see Example 1).

[0110] The 3D crystallized glass sample 7 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 7 after hot bending was 34 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 24 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 7 was 1.20, the transmittance of light at a wavelength of 360 nm was 83.10%, the average transmittance of light at wavelengths of 380-780 nm was 90.28%, the average transmittance of light at wavelengths of 360-400 nm was 84.62%, and the haze was 0.15%.

[0111] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment. The glass was immersed in a molten 100 wt% NaNO3 solution at a temperature of 430°C for 9 hours to obtain the final 3D crystallized glass product 7.

[0112] Example 8: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.95%, Al2O3 13.20%, CaO 1.0%, MgO 3.79%, Na2O 1.56%, Li2O 9.70%, nucleating agents (1.68% P2O5, 1.51% ZrO2, 0.61% TiO2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 570°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 715°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 820°C for a duration of 10 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 28 wt%.

[0113] Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 480°C, the second preheating station was 635°C, the third preheating station was 685°C, and the fourth preheating station was 715°C. The temperature of the first hot pressing station was 745°C, with an upper pressure of 0.3 MPa and a lower pressure of 0.6 MPa. The temperature of the second hot pressing station was 760°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each of the preheating stations, hot pressing stations, and cooling stations was the same, 80 seconds. Specifically, 3D crystallized glass sample 8 was obtained using the hot bending process numbered 8 in Table 2.

[0114] The 3D crystallized glass sample 8 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 8 after hot bending was 45 wt%, the precipitated crystalline phases were β-quartz solid solution and β-lithia pyroxene, and the average crystal grain size was 37 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 8 was 2.90, the transmittance of light at a wavelength of 360 nm was 76.11%, the average transmittance of light at wavelengths of 380-780 nm was 88.10%, the average transmittance of light at wavelengths of 360-400 nm was 78.80%, and the haze was 0.63%.

[0115] Example 9: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.96%, Al2O3 13.20%, MgO 5.79%, Na2O 1.26%, Li2O 8.00%, B2O3 1.00%, rare earth oxide Er2O3 0.9%, nucleating agents (1.68% P2O5, 1.21% ZrO2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and production materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Steps 2 and 3 were the same as in Example 8. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 19 wt%.

[0116] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 9 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0117] The 3D crystallized glass sample 9 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 9 after hot bending was 32 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 24 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 9 was 1.30, the transmittance of light at a wavelength of 360 nm was 82.10%, the average transmittance of light at wavelengths of 380-780 nm was 89.40%, the average transmittance of light at wavelengths of 360-400 nm was 85.20%, and the haze was 0.21%.

[0118] Example 10: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 71.65%, Al2O3 13.20%, MgO 2.79%, Na2O 0.56%, Li2O 8.00%, rare earth oxide Er2O3 0.61%, nucleating agents (1.68% P2O5, 1.51% ZrO2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 8. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 800°C for a duration of 10 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 20 wt%.

[0119] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 10 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0120] The 3D crystallized glass sample 10 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 10 after hot bending was 37 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 27 nm. When the light source was limited to D65, the absolute value of the b-value was 1.60, the transmittance of light at a wavelength of 360 nm was 81.13%, the average transmittance of light at wavelengths of 380 to 780 nm was 89.60%, the average transmittance of light at wavelengths of 360 to 400 nm was 82.80%, and the haze was 0.19%.

[0121] Example 11: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 70.65%, Al2O3 13.20%, MgO 2.79%, Na2O 1.56%, Li2O 8.00%, rare earth oxide La2O 30.61%, nucleating agents (1.68% P2O5, 1.51% ZrO2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Steps 2 and 3 were the same as in Example 10. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 21 wt%.

[0122] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 11 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0123] The 3D crystallized glass sample 11 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 11 after hot bending was 41 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 22 nm. When the light source was limited to D65, the absolute value of the b-value was 1.10, the transmittance of light at a wavelength of 360 nm was 82.40%, the average transmittance of light at wavelengths of 380 to 780 nm was 90.60%, the average transmittance of light at wavelengths of 360 to 400 nm was 85.30%, and the haze was 0.13%.

[0124] Example 12: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 70.65%, Al2O3 12.92%, MgO 2.42%, ZnO 0.80%, Na2O 1.05%, Li2O 8.25%, rare earth oxide La2O3 1.22%, nucleating agents (1.37% P2O5, 1.32% Y2O3), and clarifying agents including NaNO3 (0.3 wt% of the total mass of the nucleating agents and raw materials) and As2O3 (0.4 wt%), with a total weight of 1711.9 g). After thorough mixing, the mixture was melt-molded in a high-temperature elevator furnace at a temperature of 1630°C for 5 hours. The melt-molding process was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 570°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 700°C, and the duration of the nucleation treatment was 200 minutes. Step 3 was the same as in Example 5. Step 4: The processes of edge trimming, cutting into sheet form, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 25 wt%.

[0125] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 12 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0126] The 3D crystallized glass sample 12 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 12 after hot bending was 43 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 24 nm. When the light source was limited to D65, the absolute value of the b-value was 1.15, the transmittance of light at a wavelength of 360 nm was 83.68%, the average transmittance of light at wavelengths of 380 to 780 nm was 90.56%, the average transmittance of light at wavelengths of 360 to 400 nm was 86.30%, and the haze was 0.17%.

[0127] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment. The chemical strengthening conditions were the same as in Example 7, and finally, a finished 3D crystallized glass product 12 was obtained.

[0128] Example 13: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 71.15%, Al2O3 12.70%, MgO 2.79%, Na2O 0.56%, Li2O 8.00%, B2O3 1.00%, rare earth oxide Nd2O3 0.61%, nucleating agents (1.68% P2O5, 1.51% CaF2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and production materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 570°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 710°C, and the nucleation treatment time was 200 minutes. Step 3 was the same as in Example 10. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 18 wt%.

[0129] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 13 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0130] The 3D crystallized glass sample 13 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 13 after hot bending was 34 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 35 nm. When the light source was limited to D65, the absolute value of the b-value was 1.75, the transmittance of light at a wavelength of 360 nm was 81.03%, the average transmittance of light at wavelengths of 380 to 780 nm was 89.00%, the average transmittance of light at wavelengths of 360 to 400 nm was 82.30%, and the haze was 0.23%.

[0131] Example 14: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 68.00%, Al2O3 12.00%, MgO 3.5%, Na2O 0.50%, Li2O 10.00%, B2O3 3.00%, nucleating agents (2.00% P2O5, 1.00% Y2O3), and clarifying agents including NaCl, 0.2 wt% of the total mass of the nucleating agents and raw materials, 0.2 wt% SnO2, and 0.2 wt% CeO2, with a total weight of 1711.9 g). After thorough mixing, the mixture was melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for 5 hours. The melted mixture was then injected into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 13. Step 3 was the same as in Example 1. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 35 wt%.

[0132] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 14 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0133] The 3D crystallized glass sample 14 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 14 after hot bending was 62 wt%, the precipitated crystalline phase was β-quartz solid solution + feldspar, and the average crystal grain size was 27 nm. When the light source was limited to D65, the absolute value of the b-value was 1.11, the transmittance of light at a wavelength of 360 nm was 84.20%, the average transmittance of light at wavelengths of 380 to 780 nm was 90.90%, the average transmittance of light at wavelengths of 360 to 400 nm was 85.80%, and the haze was 0.22%.

[0134] Example 15: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.95%, Al2O3 11.20%, CaO 1.20%, MgO 4.59%, Na2O 1.26%, Li2O 9.00%, B2O 32.00%, rare earth oxide Nd2O 30.61%, nucleating agents (1.68% P2O5, 1.51% ZrO2), and a clarifying agent NaCl accounting for 0.6 wt% of the total mass of the nucleating agents and production materials, with a total weight of 1710.2 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 550°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 690°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 750°C for 30 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 32 wt%.

[0135] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 15 was obtained using the hot bending process numbered 8 in Table 2 (see Example 8).

[0136] The 3D crystallized glass sample 15 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 15 after hot bending was 53 wt%, the precipitated crystalline phase was β-quartz solid solution + feldspar, and the average crystal grain size was 24 nm. When the light source was limited to D65, the absolute value of the b-value was 0.70, the transmittance of light at a wavelength of 360 nm was 85.22%, the average transmittance of light at wavelengths of 380 to 780 nm was 91.20%, the average transmittance of light at wavelengths of 360 to 400 nm was 87.50%, and the haze was 0.16%.

[0137] Example 16: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 65.10%, Al2O 38.51%, Na2O 1.00%, Li2O 20.83%, B2O 31.52%, nucleating agents (0.82% P2O5, 1.72% ZrO2, 0.5% NaF), and as clarifying agents, NaNO3 and As2O3, accounting for 0.3 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1710.2 g). After thorough mixing, the mixture was melt-formed in a high-temperature elevator furnace at a temperature of 1620°C for a melting time of 5 hours. The mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 550°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 670°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 710°C for a duration of 100 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 40 wt%.

[0138] Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the one specified as number 6 in Table 2, and the hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 450°C, the second preheating station was 600°C, the third preheating station was 650°C, and the fourth preheating station was 710°C. The temperature of the first hot pressing station was 730°C, with an upper pressure of 0.3 MPa and a lower pressure of 0.3 MPa. The temperature of the second hot pressing station was 740°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each of the preheating stations, hot pressing stations, and cooling stations was the same, 60 seconds. A 3D crystallized glass sample 16 was obtained.

[0139] The 3D crystallized glass sample 16 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 16 after hot bending was 60 wt%, the precipitated crystalline phase was β-quartz solid solution + feldspar, and the average crystal grain size was 21 nm. When the light source was limited to D65, the absolute value of the b-value was 0.62, the transmittance of light at a wavelength of 360 nm was 86.02%, the average transmittance of light at wavelengths of 380-780 nm was 91.10%, the average transmittance of light at wavelengths of 360-400 nm was 88.10%, and the haze was 0.17%.

[0140] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment. The glass was immersed in a molten 100 wt% NaNO3 solution at a temperature of 430°C for 11 hours to obtain the final 3D crystallized glass product 16.

[0141] Example 17: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 68.00%, Al2O 35.50%, CaO 0.50%, Na2O 1.00%, Li2O 21.00%, B2O 31.50%, nucleating agents (0.80% P2O5, 1.70% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 500°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 570°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 640°C for a duration of 100 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 78 wt%.

[0142] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 17 was obtained using the hot bending process numbered 6 in Table 2 (see Example 16).

[0143] The 3D crystallized glass sample 17 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 17 after hot bending was 91 wt%, the precipitated crystalline phase was β-quartz solid solution + feldspar, and the average crystal grain size was 21 nm. When the light source was limited to D65, the absolute value of the b-value was 1.0, the transmittance of light at a wavelength of 360 nm was 84.32%, the average transmittance of light at wavelengths of 380 to 780 nm was 90.80%, the average transmittance of light at wavelengths of 360 to 400 nm was 86.40%, and the haze was 0.16%.

[0144] Example 18: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 69.14%, Al2O 35.21%, Na2O 0.46%, Li2O 21.13%, B2O 31.52%, nucleating agents (0.82% P2O5, 1.72% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1550°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 490°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 530°C, and the duration of the nucleation treatment was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 640°C for a duration of 120 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 72 wt%.

[0145] Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the one numbered 13 in Table 2, and the hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 450°C, the second preheating station was 600°C, the third preheating station was 650°C, and the fourth preheating station was 710°C. The temperature of the first hot pressing station was 720°C, with an upper pressure of 0.3 MPa and a lower pressure of 0.3 MPa. The temperature of the second hot pressing station was 720°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each of the preheating stations, hot pressing stations, and cooling stations was the same, 90 seconds. A 3D crystallized glass sample 18 was obtained.

[0146] The 3D crystallized glass sample 18 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 18 after hot bending was 92 wt%, the precipitated crystalline phase was lithium disilicate + feldspar, and the average crystal grain size was 18 nm. When the light source was limited to D65, the absolute value of the b-value was 0.43, the transmittance of light at a wavelength of 360 nm was 87.17%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.10%, the average transmittance of light at wavelengths of 360 to 400 nm was 90.30%, and the haze was 0.11%.

[0147] Example 19: Method for manufacturing 3D crystallized glass Steps 1 and 2 were exactly the same as in Example 18. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 630°C for a duration of 120 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 60 wt%. Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 19 was obtained using the hot bending process numbered 13 in Table 2 (see Example 18).

[0148] Detection was performed on the 3D crystallized glass sample 19 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 19 after hot bending was 86 wt%, the precipitated crystalline phase was lithium disilicate + feldspar, and the average crystal grain size was 19 nm. When the light source was limited to D65, the absolute value of the b-value was 0.44, the transmittance of light at a wavelength of 360 nm was 87.31%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.30%, the average transmittance of light at wavelengths of 360 to 400 nm was 89.50%, and the haze was 0.11%.

[0149] Example 20: Method for manufacturing 3D crystallized glass Steps 1 and 2 were exactly the same as in Example 18. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 625°C for a duration of 120 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 51 wt%. Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 20 was obtained using the hot bending process numbered 13 in Table 2 (see Example 18).

[0150] The 3D crystallized glass sample 20 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 20 after hot bending was 73 wt%, the precipitated crystalline phase was lithium disilicate + feldspar, and the average crystal grain size was 23 nm. When the light source was limited to D65, the absolute value of the b-value was 0.58, the transmittance of light at a wavelength of 360 nm was 86.20%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.10%, the average transmittance of light at wavelengths of 360 to 400 nm was 87.80%, and the haze was 0.10%.

[0151] Example 21: Method for manufacturing 3D crystallized glass Steps 1 and 2 were exactly the same as in Example 18. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 620°C for a duration of 120 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 30 wt%. Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 21 was obtained using the hot bending process numbered 13 in Table 2 (see Example 18).

[0152] The 3D crystallized glass sample 21 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 21 after hot bending was 65 wt%, the precipitated crystalline phase was lithium disilicate + feldspar, and the average crystal grain size was 25 nm. When the light source was limited to D65, the absolute value of the b-value was 0.62, the transmittance of light at a wavelength of 360 nm was 85.14%, the average transmittance of light at wavelengths of 380-780 nm was 91.60%, the average transmittance of light at wavelengths of 360-400 nm was 88.10%, and the haze was 0.15%.

[0153] Example 22: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 69.5%, Al2O 35.3%, Na2O 1.60%, Li2O 20.5%, B2O 30.55%, nucleating agents (0.8% P2O5, 1.75% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1550°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 480°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 560°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 630°C for a duration of 100 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheet form, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured afterward to be 39 wt%.

[0154] Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the hot bending process number 15 in Table 2, and the hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 450°C, the temperature of the second preheating station was 600°C, the temperature of the third preheating station was 650°C, and the temperature of the fourth preheating station was 740°C. The temperature of the first hot pressing station was 770°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the second hot pressing station was 760°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each station—the preheating station, the hot press station, and the cooling station—was the same, 90 seconds. A 3D crystallized glass sample 22 was obtained.

[0155] The 3D crystallized glass sample 22 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 22 after hot bending was 85 wt%, the precipitated crystalline phase was feldspar + lithium disilicate, and the average crystal grain size was 19 nm. When the light source was limited to D65, the absolute value of the b-value was 0.42, the transmittance of light at a wavelength of 360 nm was 88.23%, the average transmittance of light at wavelengths of 380-780 nm was 92.10%, the average transmittance of light at wavelengths of 360-400 nm was 89.30%, and the haze was 0.15%.

[0156] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment. The glass was immersed in a molten 100 wt% NaNO3 solution at a temperature of 450°C for 9 hours to obtain the final 3D crystallized glass product 22.

[0157] Example 23: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 71.80%, Al2O 34.80%, MgO 1.40%, Na2O 1.00%, Li2O 18.80%, ZnO 0.3%, nucleating agents (0.8% P2O5, 1.1% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1550°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 480°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 545°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 610°C for a duration of 200 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 45 wt%.

[0158] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 23 was obtained using the hot bending process numbered 15 in Table 2 (see Example 22). The 3D crystallized glass sample 23 was subjected to detection using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 23 after hot bending was 92 wt%, the precipitated crystalline phase was feldspar + lithium disilicate, and the average crystal grain size was 20 nm. When the light source was limited to D65, the absolute value of the b-value was 0.61, the transmittance of light at a wavelength of 360 nm was 85.82%, the average transmittance of light at wavelengths of 380 to 780 nm was 91.50%, the average transmittance of light at wavelengths of 360 to 400 nm was 88.00%, and the haze was 0.15%.

[0159] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment, with the same treatment conditions as in Example 22, and finally a finished 3D crystallized glass product 23 was obtained.

[0160] Example 24: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 69.50%, Al2O 34.25%, Na2O 1.60%, Li2O 20.5%, B2O 31.60%, nucleating agents (0.8% P2O5, 1.75% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and production materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1550°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 480°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 538°C, and the nucleation treatment time was 200 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 620°C for a duration of 100 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 43 wt%.

[0161] Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the hot bending process number 14 in Table 2, and the hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 450°C, the temperature of the second preheating station was 600°C, the temperature of the third preheating station was 650°C, and the temperature of the fourth preheating station was 720°C. The temperature of the first hot pressing station was 750°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the second hot pressing station was 760°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each station—the preheating station, the hot press station, and the cooling station—was the same, 90 seconds. A 3D crystallized glass sample 24 was obtained.

[0162] beforeDetection was performed on the 3D crystallized glass sample 24 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 24 after hot bending was 82 wt%, the precipitated crystalline phase was feldspar + lithium disilicate, and the average crystal grain size was 22 nm. When the light source was limited to D65, the absolute value of the b-value was 0.43, the transmittance of light at a wavelength of 360 nm was 88.17%, the average transmittance of light at wavelengths of 380-780 nm was 92.60%, the average transmittance of light at wavelengths of 360-400 nm was 89.60%, and the haze was 0.11%.

[0163] Step 6: The 3D crystallized glass obtained in Step 5 after hot bending was subjected to chemical strengthening treatment, with the same treatment conditions as in Example 22, and finally a finished 3D crystallized glass product 24 was obtained.

[0164] Example 25: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 68.76%, Al2O 34.13%, MgO 0.98%, ZnO 0.98%, Na2O 0.45%, Li2O 20.71%, B2O 31.49%, nucleating agents (0.81% P2O5, 1.69% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1550°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 480°C for 5 hours and then lowering it to 30°C at a rate of 1°C / min). An XRD test was then performed on the resulting annealed glass block, and Figure 1 was obtained, confirming that it was in a glassy state. The block was then transferred to a precision annealing furnace for nucleation treatment, with a nucleation treatment temperature of 540°C and a duration of 200 minutes. Step 3 was the same as in Example 24. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 47 wt%. An XRD test was performed on the obtained partially crystallized glass material, and Figure 2 was obtained, showing that it was in a partially crystallized state.

[0165] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 25 was obtained using the hot bending process numbered 14 in Table 2 (see Example 24).

[0166] Detection was performed on the 3D crystallized glass sample 25 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 25 after hot bending was 87 wt%, the precipitated crystalline phase was lithium disilicate + feldspar + β-quartz solid solution, and the average crystal grain size was 18 nm. When the light source was limited to D65, the absolute value of the b-value was 0.39, the transmittance of light at a wavelength of 360 nm was 88.80%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.70%, the average transmittance of light at wavelengths of 360 to 400 nm was 89.80%, and the haze was 0.09%.

[0167] Step 6 : step 5The 3D crystallized glass obtained after hot bending was subjected to chemical strengthening treatment, and the glass was immersed in a molten 100 wt% NaNO3 solution at a temperature of 450°C for 10 hours to finally obtain the finished 3D crystallized glass product 25.

[0168] Example 26: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 68.73%, Al2O 34.13%, MgO 0.98%, ZnO 1.68%, Na2O 0.45%, Li2O 20.01%, B2O 31.49%, nucleating agents (0.81% P2O5, 1.72% ZrO2), and a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1550°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 25. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 615°C for a duration of 120 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 55 wt%. An XRD test was performed on the obtained partially crystallized glass material, and Figure 3 was obtained, showing that it was in a partially crystallized state.

[0169] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 26 was obtained using the hot bending process numbered 15 in Table 2 (see Example 22).

[0170] The 3D crystallized glass sample 26 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 26 after hot bending was 91 wt%, the precipitated crystalline phase was feldspar, and the average crystal grain size was 23 nm. When the light source was limited to D65, the absolute value of the b-value was 0.42, the transmittance of light at a wavelength of 360 nm was 88.13%, the average transmittance of light at wavelengths of 380-780 nm was 92.80%, the average transmittance of light at wavelengths of 360-400 nm was 89.90%, and the haze was 0.11%.

[0171] Example 27: Method for manufacturing 3D crystallized glass Step 1: This step is the same as in Example 18, except that the melt molding temperature is different. In this example, the melt molding temperature was 1610°C. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 460°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 480°C, and the duration of the nucleation treatment was 360 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 550°C for a duration of 300 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheet form, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 6 wt%.

[0172] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 27 was obtained using the hot bending process shown in Table 2, number 1 (the same as in Example 1).

[0173] Detection was performed on the 3D crystallized glass sample 27 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the crystallinity of the 3D crystallized glass sample 27 was 14 wt%, the precipitated crystalline phase was lithium silicate, and the average crystal grain size was 10 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 27 was 0.15, the transmittance of light at a wavelength of 360 nm was 90.60%, the average transmittance of light at wavelengths of 380 to 780 nm was 93.00%, the average transmittance of light at wavelengths of 360 to 400 nm was 91.40%, and the haze was 0.07%.

[0174] Example 28: Method for manufacturing 3D crystallized glass Step 1 was the same as in Example 27. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 460°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 500°C, and the duration of the nucleation treatment was 300 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 570°C for a duration of 280 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheet form, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 8 wt%.

[0175] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 28 was obtained using the hot bending process numbered 1 in Table 2.

[0176] The 3D crystallized glass sample 28 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the crystallinity of the 3D crystallized glass sample 28 was 16 wt%, the precipitated crystalline phase was lithium silicate, and the average crystal grain size was 15 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 28 was 0.25, the transmittance of light at a wavelength of 360 nm was 90.10%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.80%, the average transmittance of light at wavelengths of 360 to 400 nm was 91.20%, and the haze was 0.09%.

[0177] Example 29: Method for manufacturing 3D crystallized glass Step 1 was the same as in Example 27. Step 2 was the same as in Example 28. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 560°C for a duration of 240 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 9 wt%.

[0178] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 28 was obtained using the hot bending process numbered 1 in Table 2.

[0179] The 3D crystallized glass sample 29 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the crystallinity of the 3D crystallized glass sample 29 was 17 wt%, the precipitated crystalline phase was lithium silicate, and the average crystal grain size was 13 nm. When the light source was limited to D65, the absolute value of the b-value of the 3D crystallized glass sample 29 was 0.23, the transmittance of light at a wavelength of 360 nm was 90.50%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.70%, the average transmittance of light at wavelengths of 360 to 400 nm was 91.50%, and the haze was 0.08%.

[0180] Example 30: Method for manufacturing 3D crystallized glass Step 1 was the same as in Example 17. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 500°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 600°C, and the nucleation treatment time was 80 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 610°C for a duration of 180 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 37 wt%.

[0181] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 30 was obtained using the hot bending process number 3 in Table 2. An XRD test was performed on the obtained partially crystallized glass material, and Figure 4 was obtained, showing that it was in a partially crystallized state.

[0182] Detection was performed on the 3D crystallized glass sample 30 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 30 after hot bending was 75 wt%, the precipitated crystalline phase was a feldspar + β-quartz solid solution, and the average crystal grain size was 18 nm. When the light source was limited to D65, the absolute value of the b-value was 0.35, the transmittance of light at a wavelength of 360 nm was 88.20%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.60%, the average transmittance of light at wavelengths of 360 to 400 nm was 90.00%, and the haze was 0.11%.

[0183] Example 31: Method for manufacturing 3D crystallized glass Step 1 was the same as in Example 2. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 600°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 800°C, and the nucleation treatment time was 30 minutes. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 870°C for a duration of 15 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 88 wt%.

[0184] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 31 was obtained using the hot bending process numbered 4 in Table 2.

[0185] The 3D crystallized glass sample 31 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 31 after hot bending was 99 wt%, the precipitated crystalline phase was β-lithia pyroxene, and the average grain size of the crystals was 48 nm. When the light source was limited to D65, the absolute value of the b-value was 2.60, the transmittance of light at a wavelength of 360 nm was 74.10%, the average transmittance of light at wavelengths of 380 to 780 nm was 89.30%, the average transmittance of light at wavelengths of 360 to 400 nm was 80.50%, and the haze was 0.78%.

[0186] Example 32: Method for manufacturing 3D crystallized glass Step 1 was the same as in Example 2. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 600°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 780°C, and the nucleation treatment time was 60 minutes. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 900°C for a duration of 5 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 58 wt%.

[0187] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 32 was obtained using the hot bending process numbered 7 in Table 2.

[0188] The 3D crystallized glass sample 32 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 32 after hot bending was 98 wt%, the precipitated crystalline phase was β-lithia pyroxene, and the average grain size of the crystals was 81 nm. When the light source was limited to D65, the absolute value of the b-value was 2.80, the transmittance of light at a wavelength of 360 nm was 62.00%, the average transmittance of light at wavelengths of 380 to 780 nm was 88.60%, the average transmittance of light at wavelengths of 360 to 400 nm was 65.80%, and the haze was 0.72%.

[0189] Example 33: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 67.45%, Al2O3 14.20%, CaO 0.50%, MgO 1.79%, Na2O 1.56%, Li2O 9.70%, nucleating agents (2.18% P2O5, 0.81% TiO2, 1.31% ZrO2, 0.5% Y2O3), and a clarifying agent NaCl accounting for 0.8 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1713.5 g). After thorough mixing, the mixture was melted and molded in a high-temperature elevator furnace at a temperature of 1650°C for a melting time of 5 hours. The mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involves maintaining the temperature at 500°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 650°C, and the duration of the nucleation treatment was 160 minutes. Step 3: After nucleation, the glass block was further subjected to crystallization treatment in a precision annealing furnace at a temperature of 820°C for a duration of 30 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 90 wt%.

[0190] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 33 was obtained using the hot bending process numbered 6 in Table 2.

[0191] The 3D crystallized glass sample 33 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 33 after hot bending was 100 wt%, the precipitated crystalline phase was β-lithia pyroxene, and the average grain size of the crystals was 98 nm. When the light source was limited to D65, the absolute value of the b-value was 3.8, the transmittance of light at a wavelength of 360 nm was 63.10%, the average transmittance of light at wavelengths of 380 to 780 nm was 88.20%, the average transmittance of light at wavelengths of 360 to 400 nm was 65.40%, and the haze was 0.98%.

[0192] Example 34: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 66.65%, Al2O3 10.87%, MgO 2.44%, ZnO 2.82%, Na2O 0.21%, K2O 0.21%, Li2O 9.88%, B2O3 0.94%, nucleating agents (1.85% P2O5, 2.00% ZrO2, 2.13% CaF2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1640°C for a melting time of 4 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining a temperature of 500°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 620°C, and the duration of the nucleation treatment was 240 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 650°C for 40 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 68 wt%.

[0193] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 34 was obtained using the hot bending process numbered 7 in Table 2.

[0194] The 3D crystallized glass sample 34 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 34 after hot bending was 79 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 65 nm. When the light source was limited to D65, the absolute value of the b-value was 0.76, the transmittance of light at a wavelength of 360 nm was 84.22%, the average transmittance of light at wavelengths of 380 to 780 nm was 91.00%, the average transmittance of light at wavelengths of 360 to 400 nm was 87.50%, and the haze was 0.16%.

[0195] Example 35: Method for manufacturing 3D crystallized glass Step 1: Prepare and weigh the raw materials for glass production (calculated in mole percentages, the components were SiO2 64.55%, Al2O3 10.45%, MgO 2.37%, ZnO 2.73%, Na2O 0.21%, K2O 0.20%, Li2O 9.58%, B2O3 0.91%, nucleating agents (1.94% P2O5, 2.91% TiO2, 2.02% ZrO2, 2.13% CaF2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and raw materials; the total weight of the raw materials was 1711.9 g), and after thorough mixing, melt molding was carried out in a high-temperature elevator furnace at a melt molding temperature of 1640°C for a melting time of 4 hours, according to ASTM standards. A glass block was obtained by injecting SA213 / TP310S austenitic chromium-nickel stainless steel into a mold. Steps 2 and 3 were the same as in Example 35. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 82 wt%.

[0196] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 35 was obtained using the hot bending process numbered 6 in Table 2.

[0197] The 3D crystallized glass sample 35 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 35 after hot bending was 86 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 42 nm. When the light source was limited to D65, the absolute value of the b-value was 0.68, the transmittance of light at a wavelength of 360 nm was 85.42%, the average transmittance of light at wavelengths of 380-780 nm was 91.10%, the average transmittance of light at wavelengths of 360-400 nm was 87.20%, and the haze was 0.19%.

[0198] Example 36: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 70.13%, Al2O3 11.50%, MgO 2.57%, ZnO 2.97%, Na2O 0.22%, K2O 0.22%, Li2O 10.40%, B2O3 0.99%, nucleating agents (0.84% ​​P2O5, 0.16% CaF2), and a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1711.9 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1640°C for a melting time of 3 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Steps 2 and 3 were the same as in Example 34. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 63 wt%.

[0199] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 36 was obtained using the hot bending process numbered 5 in Table 2.

[0200] The 3D crystallized glass sample 36 was subjected to detection using a linear diffraction apparatus, with the same apparatus settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 36 after hot bending was 70 wt%, the precipitated crystalline phase was a β-quartz solid solution, and the average crystal grain size was 37 nm. When the light source was limited to D65, the absolute value of the b-value was 0.53, the transmittance of light at a wavelength of 360 nm was 86.00%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.20%, the average transmittance of light at wavelengths of 360 to 400 nm was 88.60%, and the haze was 0.10%.

[0201] Example 37: Method for manufacturing 3D crystallized glass Step 1: This step was the same as in Example 17, with the only differences being the temperature and melting time of the melting process. In this example, the melting process temperature was 1650°C and the melting time was 2 hours. Step 2: After cooling the glass block obtained in Step 1 to 800°C, it was transferred to an annealing furnace for annealing (the annealing process involved maintaining the temperature at 500°C for 5 hours and then lowering the temperature to 30°C at a rate of 1°C / min), and then transferred to a precision annealing furnace for nucleation treatment. The temperature for nucleation treatment was 600°C, and the nucleation treatment time was 80 minutes. Step 3: After nucleation, the glass block was further crystallized in a precision annealing furnace at a temperature of 600°C for a duration of 240 minutes to obtain a partially crystallized glass block. Step 4: The processes of edge trimming, cutting into sheets, rough polishing, and grinding were the same as in Example 1, and the degree of crystallinity was measured to be 75 wt%.

[0202] Step 5: A 3D hot bending treatment was performed on the partially crystallized glass material, and a 3D crystallized glass sample 37 was obtained using the hot bending process numbered 6 in Table 2.

[0203] Detection was performed on the 3D crystallized glass sample 37 using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 37 after hot bending was 88 wt%, the precipitated crystalline phase was a feldspar + β-quartz solid solution, and the average crystal grain size was 57 nm. When the light source was limited to D65, the absolute value of the b-value was 0.38, the transmittance of light at a wavelength of 360 nm was 88.40%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.80%, the average transmittance of light at wavelengths of 360 to 400 nm was 90.10%, and the haze was 0.12%.

[0204] Example 38: Method for manufacturing 3D crystallized glass Steps 1, 2, 3, and 4 were the same as in Example 22. Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the hot bending process number 20 in Table 2, and the hot bending process included three preheating stations, four hot pressing stations, and two cooling stations. The temperature of the first preheating station was 450°C, the temperature of the second preheating station was 600°C, and the temperature of the third preheating station was 650°C. The temperature of the first hot pressing station was 760°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the second hot pressing station was 750°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the third hot pressing station was 720°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the fourth hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each station—the preheating station, the hot press station, and the cooling station—was the same, 140 seconds, and a 3D crystallized glass sample 22F was obtained.

[0205] Detection was performed on the 3D crystallized glass sample 22F using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 22F after hot bending was 84 wt%, the precipitated crystalline phase was feldspar + lithium disilicate, and the average crystal grain size was 18 nm. When the light source was limited to D65, the absolute value of the b-value was 0.43, the transmittance of light at a wavelength of 360 nm was 88.15%, the average transmittance of light at wavelengths of 380 to 780 nm was 92.77%, the average transmittance of light at wavelengths of 360 to 400 nm was 89.45%, and the haze was 0.11%.

[0206] Example 39: Method for manufacturing 3D crystallized glass Steps 1, 2, 3, and 4 were the same as in Example 22. Step 5: Perform 3D hot bending on the partially crystallized glass material, and the hot bending process is shown. 2 Using the hot bending process number 21, the hot bending process included five preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 430°C, the temperature of the second preheating station was 500°C, the temperature of the third preheating station was 600°C, the temperature of the fourth preheating station was 680°C, and the temperature of the fifth preheating station was 720°C. The temperature of the first hot pressing station was 745°C, with an upper pressure of 0.5 MPa and a lower pressure of 0.5 MPa. The temperature of the second hot pressing station was 760°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each station—the preheating station, the hot press station, and the cooling station—was the same, 140 seconds, and a 22G 3D crystallized glass sample was obtained.

[0207] Detection was performed on the 3D crystallized glass sample 22G using a linear diffraction apparatus with the same settings as in Example 1. After detection, the X-ray diffraction data was analyzed and found that the degree of crystallinity of the 3D crystallized glass sample 22G after hot bending was 90 wt%, the precipitated crystalline phase was feldspar + lithium disilicate, and the average crystal grain size was 22 nm. When the light source was limited to D65, the absolute value of the b-value was 0.55, the transmittance of light at a wavelength of 360 nm was 86.12%, the average transmittance of light at wavelengths of 380-780 nm was 92.40%, the average transmittance of light at wavelengths of 360-400 nm was 88.40%, and the haze was 0.10%.

[0208] (Comparative example) Comparative Example 1: Method for manufacturing 3D crystallized glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 62.40%, Al2O3 13.24%, MgO 4.46%, Na2O 1.46%, Li2O 9.04%, nucleating agent (a total of 9.40% nucleating agent consisting of 0.94% P2O5, 6.58% ZrO2, and 1.88% TiO2), and NaCl, which accounted for 0.8 wt% of the total mass of the nucleating agent and raw materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 4, and it was found that crystals had already precipitated from the nucleated glass material, resulting in a ceramicized state that was not suitable for the subsequent hot bending process.

[0209] Comparative Example 2: Method for Manufacturing 3D Crystallized Glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 60.70%, Al2O3 12.87%, MgO 4.34%, Na2O 1.42%, Li2O 8.79%, nucleating agent (a total of 11.88% nucleating agent consisting of 0.91% P2O5, 9.14% ZrO2, and 1.83% TiO2), and NaCl, which accounted for 0.8 wt% of the total mass of the nucleating agent and raw materials, with a total weight of 1713.6 g), thoroughly mixed, and then melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The resulting mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: During the cooling process of the glass block obtained in Step 1 to 800°C, crystals precipitate from the center, creating a stress difference inside the glass block. This causes the glass block to burst, making machining impossible.

[0210] Comparative Example 3: Method for Manufacturing 3D Crystallized Glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 67.45%, Al2O3 14.20%, CaO 0.50%, MgO 1.79%, Na2O 1.56%, Li2O 9.70%, nucleating agents (2.18% P2O5, 1.31% ZrO2, 0.81% TiO2, 0.5% Y2O3), and a clarifying agent NaCl accounting for 0.8 wt% of the total mass of the nucleating agents and raw materials, with a total weight of 1708.5 g). After thorough mixing, the mixture was melt-formed in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours, and the resulting mixture was poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2 was the same as in Example 4. Step 3: After nucleation, the glass block is further crystallized in a precision annealing furnace at a temperature of 930°C for 30 minutes. After crystallization, the glass block undergoes uncontrollable crystallization due to the excessively high crystallization temperature, creating a stress difference inside the glass block, causing it to rupture and making machining impossible.

[0211] Comparative Example 4: Method for Manufacturing 3D Crystallized Glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 70.33%, Al2O3 14.82%, Na2O 1.63%, Li2O 10.11%, MgO 1.34%, ZnO 1.04%, nucleating agents (0.52% P2O5, 0.21% ZrO2), and clarifying agents NaCl and SnO2, each accounting for 0.4 wt% and 0.4 wt% of the total mass of the nucleating agents and raw materials, respectively; the total weight of the raw materials was 1708.5 g). After thorough mixing, the mixture was melted and molded in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The mixture was then poured into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Steps 2 and 3 were the same as those in Example 33. When an XRD test was performed on the glass block after the nucleation treatment, it was found that no crystal nuclei appeared because there was too little nucleating agent. Uncontrolled crystallization occurred during the crystallization treatment, resulting in a stress difference inside the glass, which caused the hot-bent glass to fracture.

[0212] Comparative Example 5: Method for Manufacturing 3D Crystallized Glass Step 1: The raw materials for glass production were prepared and weighed (calculated in mole percentages, the components were SiO2 70.45%, Al2O3 13.16%, MgO 2.78%, Na2O 0.56%, Li2O 7.98%, B2O3 1.00%, nucleating agents (1.67% P2O5, 1.30% ZrO2, 0.60% TiO2, 0.5% Y2O3), and clarifying agents NaCl and CeO2, accounting for 0.4 wt% and 0.3 wt% of the total mass of the nucleating agents and production materials, respectively; the total weight of the raw materials was 1711.9 g). After thorough mixing, the mixture was melt-formed in a high-temperature elevator furnace at a temperature of 1630°C for a melting time of 5 hours. The mixture was then injected into a mold made of ASTM SA213 / TP310S austenitic chromium-nickel stainless steel to obtain a glass block. Step 2: After cooling the glass block obtained in Step 1 to 900°C, it was transferred to a precision annealing furnace for nucleation treatment. The nucleation treatment temperature was 850°C and the treatment time was 120 minutes. After nucleation treatment, the glass block underwent uncontrollable crystallization due to the excessively high nucleation temperature, resulting in stress differences within the glass block. This caused the glass block to rupture, making further processing and manufacturing impossible.

[0213] Comparative Example 6: Method for Manufacturing 3D Crystallized Glass Steps 1, 2, 3, and 4 were the same as in Example 22. Step 5: Perform 3D hot bending treatment on the partially crystallized glass material. The hot bending process uses the hot bending process numbered 16 in Table 2. The hot bending treatment includes 4 preheating stations, 3 hot press stations, and 2 cooling stations. The temperature of the first preheating station is 480 °C, the temperature of the second preheating station is 600 °C, the temperature of the third preheating station is 650 °C, and the temperature of the fourth preheating station was 720 °C. The temperature of the first hot press station is 940 °C, the upper pressure is 0.1 MPa, the lower pressure is 0.1 MPa, the temperature of the second hot press station is 920 °C, the upper pressure is 0.1 MPa, the lower pressure is 0.1 MPa, the temperature of the third hot press station is 600 °C, the upper pressure is 0 MPa, and the lower pressure was 0 MPa. The temperature of the first cooling station is 450 °C, and the temperature of the second cooling station was 300 °C. The operating time of each station of the preheating station, hot press station, and cooling station is the same, which was 90 seconds. 3D crystallized glass sample 22B was obtained.

[0214] Detect the 3D crystallized glass sample 22B, use a line diffractometer, and the condition settings of the device are the same as in Example 1. After detection and analysis of the X-ray diffraction data, the crystallinity of the 3D crystallized glass sample 22B after hot bending is 100 wt%, the precipitated crystal phase is β-spodumene + lithium disilicate, and the average particle size of the crystals was 111 nm. When measured, when the light source is limited to D65, the absolute value of the b value is 7.45, the transmittance of light with a wavelength of 360 nm is 64.10%, the average transmittance of light with wavelengths of 380 - 780 nm is 86.50%, the average transmittance of light with wavelengths of 360 - 400 nm is 69.20%, and the haze is 0.99%. Because the temperature of the hot press is too high, the finally obtained crystallized glass has a very large average particle size of the crystals, the b value increases, the light transmittance decreases, and when the b value is too high, the crystallized glass is closer to blue, which affects image formation.

[0215] Comparative Example 7: Manufacturing method of 3D crystallized glass Steps 1, Step 2, Step 3, and Step 4 were the same as in Example 22. Step 5: Perform a 3D hot bending process on the partially crystallized glass material. The hot bending process utilized the hot bending process numbered 17 in Table 2. The hot bending process included four preheating stations, three hot press stations, and two cooling stations. The temperature of the first preheating station was 450°C, the temperature of the second preheating station was 600°C, the temperature of the third preheating station was 650°C, and the temperature of the fourth preheating station was 720°C. The temperature of the first hot press station was 930°C, the upper pressure was 0.1 MPa, the lower pressure was 0.1 MPa, the temperature of the second hot press station was 920°C, the upper pressure was 0.1 MPa, the lower pressure was 0.1 MPa, the temperature of the third hot press station was 600°C, the upper pressure was 0 MPa, and the lower pressure was 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time of each station of the preheating station, hot press station, and cooling station was the same, which was 90 seconds. 3D crystallized glass sample 22C was obtained.

[0216] Detect the 3D crystallized glass sample 22C using an X-ray diffractometer. The instrument settings were the same as in Example 1. After detection and analysis of the X-ray diffraction data, the crystallinity of the 3D crystallized glass sample 22C after hot bending was 100 wt%, the precipitated crystal phase was β-spodumene + lithium disilicate, and the average crystal grain size was 124 nm. When measured, when the light source was limited to D65, the absolute value of the b value was 7.86, the transmittance of light with a wavelength of 360 nm was 62.40%, the average transmittance of light with wavelengths of 380 - 780 nm was 87.30%, the average transmittance of light with wavelengths of 360 - 400 nm was 68.20%, and the haze was 1.10%. Because the temperature of the hot press was too high, the finally obtained crystallized glass had a very large average crystal grain size, the b value increased, the light transmittance decreased, and when the b value was too high, the crystallized glass was closer to blue, which affected image formation.

[0217] Comparative Example 8: Method for Manufacturing 3D Crystallized Glass Steps 1, 2, 3, and 4 were the same as in Example 22. Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the hot bending process number 18 in Table 2, and the hot bending process included four preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 450°C, the temperature of the second preheating station was 500°C, the temperature of the third preheating station was 650°C, and the temperature of the fourth preheating station was 650°C. The temperature of the first hot pressing station was 580°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the second hot pressing station was 600°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the third hot pressing station was 600°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each station—the preheating station, the hot press station, and the cooling station—was the same, 90 seconds. A 3D crystallized glass sample 22D was obtained. Due to the hot press temperature being too low, the 3D crystallized glass sample 22D could not be formed into the desired shape by hot bending.

[0218] Comparative Example 9: Method for Manufacturing 3D Crystallized Glass Steps 1, 2, 3, and 4 were the same as in Example 22. Step 5: A 3D hot bending process was performed on the partially crystallized glass material. The hot bending process used was the hot bending process number 19 in Table 2, and the hot bending process included three preheating stations, three hot pressing stations, and two cooling stations. The temperature of the first preheating station was 500°C, the temperature of the second preheating station was 550°C, and the temperature of the third preheating station was 600°C. The temperature of the first hot pressing station was 600°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the second hot pressing station was 580°C, with an upper pressure of 0.1 MPa and a lower pressure of 0.1 MPa. The temperature of the third hot pressing station was 550°C, with an upper pressure of 0 MPa and a lower pressure of 0 MPa. The temperature of the first cooling station was 450°C, and the temperature of the second cooling station was 300°C. The operating time for each station—the preheating station, the hot press station, and the cooling station—was the same, 90 seconds, and a 3D crystallized glass sample 22E was obtained. Due to the hot press temperature being too low, the 3D crystallized glass sample 22E could not be shaped into the desired form by hot bending.

[0219] (Example of use) Mechanical parameters were measured for the 3D crystallized glass obtained after chemical strengthening in Examples 1, 2, 4, 7, 12, 16, 22, 23, 24, and 25, with a test glass thickness of 0.65. mm The test results are shown in Table 3.

[0220] The test was conducted using an SLP-2000 stress meter, with the photoelastic modulus set to 25.5 and the refractive index to 1.54. It was a standard test, and the test results included surface compressive stress, depth of compressive stress, and mean tensile stress. The linear density of the tensile stress was a calculated value, obtained by dividing the sum of tensile stresses measured with the SLP-2000 stress meter by the thickness of the glass.

[0221] Surface compressive stress (MPa): After chemical strengthening of glass, alkali metal ions with small radii on the surface are replaced by alkali metal ions with larger radii. The concentration effect of these larger alkali metal ions creates compressive stress on the glass surface, which is called surface compressive stress. Depth of compressive stress (μm): This is the distance from the surface of the chemically strengthened glass to the point where the compressive stress is zero. Average tensile stress CT-AV (MPa): This is the ratio of the sum of tensile stresses measured with the SLP-2000 stress meter to the thickness of the tensile stress region. The linear density of tensile stress is obtained by testing with a CT-LD:SLP-2000 stress meter, and is the ratio of the integral of the tensile stress in the thickness cross-section of chemically strengthened glass to the thickness of the glass. Total drop test: A method for testing the strength of tempered glass, in which a tempered glass sheet is attached to an electronic device sample such as a mobile phone, and dropped from a height, and the height at which the glass shatters is recorded. This height can reflect the strength of the glass, and this test method is called a total drop test. In the present invention, the test method involves placing a 180g mobile phone on a tempered glass sheet and dropping it onto 120-mesh sandpaper, with the sandpaper in close contact with a marble base plate. Vickers hardness (Hv) (300) gf (Hold at this pressure for 10 seconds): Using a diamond cone indenter with a face angle of 136°, 300 gf The test sample is pressed into the surface with a load, held for 10 seconds, then the load is removed. The length d of the diagonal of the indentation is measured to calculate the surface area of ​​the indentation, and finally the average pressure across the surface area of ​​the indentation is determined. This is the Vickers hardness value of the glass, denoted by the symbol HV. [Table 3] JPEG0007869225000009.jpg170153

[0222] As can be seen from the table above, the surface compressive stress of the chemically strengthened 3D crystallized glass products in the examples was 108-514 MPa, the depth of the compressive stress was 109-121 μm, the average tensile stress CT-AV was 42-93 MPa, the linear density of the tensile stress CT-LD was 30145-43157, the height of the overall drop test was 1.51-1.82 m, and the Vickers hardness of the chemically strengthened 3D crystallized glass products was (300) gf The voltage (held for 10 seconds under this pressure) was 712-741 Hv.

[0223] The foregoing describes merely preferred embodiments of the present invention and does not constitute any formal limitation on the invention. Any amendments, equivalent substitutions, or improvements made to the spirit and scope of the invention shall be included within the scope of the claims of the present invention.

[0224] (Note) (Note 1) The degree of crystallinity is 14-100 wt%, and the average grain size of the crystals is 10-100 nm. A 3D crystallized glass characterized by the following features.

[0225] (Note 2) The degree of crystallinity of the 3D crystallized glass is 14-30 wt%, or the degree of crystallinity of the 3D crystallized glass is 50-100 wt%, or the degree of crystallinity of the 3D crystallized glass is 31-49 wt%, Alternatively, the average grain size of the crystals in the 3D crystallized glass is 15-30 nm. Alternatively, the thickness of the 3D crystallized glass is 0.02 to 5 mm, preferably 0.35 to 1.2 mm. 3D crystallized glass as described in Appendix 1.

[0226] (Note 3) The average transmittance of light with wavelengths of 380 to 780 nm to the 3D crystallized glass is 88 to 93%, preferably 90 to 91.5%. Alternatively, the average transmittance of light with a wavelength of 360 to 400 nm to the 3D crystallized glass is 65 to 91.5%, preferably 79 to 91%, more preferably 85 to 91%. The 3D crystallized glass according to Appendage 1 or 2.

[0227] (Appendage 4) When the thickness of the 3D crystallized glass is 0.7 mm, the absolute value of the b value (yellow-blue value) is 0.1 to 3.5, preferably 0.3 to 1.5. Alternatively, the haze of the 3D crystallized glass is 0.07 to 1.0%, preferably 0.07 to 0.5%. The 3D crystallized glass according to any one of Appendages 1 to 3.

[0228] (Appendage 5) The crystal phase of the 3D crystallized glass is one or more of lithium silicate, lithium disilicate, β-quartz, β-quartz solid solution, leaf feldspar, β-lithium pyroxene, β-lithium pyroxene solid solution, nepheline, cordierite, mullite, apatite, zirconia, zinc spinel, magnesia-alumina spinel, and rutile. The 3D crystallized glass according to any one of Appendages 1 to 4.

[0229] (Appendage 6) The 3D crystallized glass contains oxides in the following ratios, calculated in mol%. Composition mol%: SiO2 55 to 74%, Al2O3 3 to 19%, B2O3 0 to 4%, MgO 0 to 6%, Na2O 0 to 3%, Li2O 6 to 25%, K2O 0 to 1%, CaO 0 to 2%, ZnO 0 to 5%, Rare earth oxide 0 to 3% Here, the rare earth oxide is one or more selected from La2O3, Eu2O3, Pr6O 11 , Nd2O3, Er2O3, and Dy2O3. 3D crystallized glass as described in any one of the appendices 1 to 5.

[0230] (Note 7) The aforementioned 3D crystallized glass has a total content of SiO2 and Al2O3 that is greater than 60%, preferably 68-80%, when calculated in mol%. Alternatively, the Na2O + Li2O content, when calculated in mol%, is 7-30%, preferably 10-26%. 3D crystallized glass as described in Appendix 6.

[0231] (Note 8) The 3D crystallized glass contains a nucleating agent, and when calculated as an oxide, fluoride, or element, the nucleating agent contains one or more of the following: P2O5, TiO2, ZrO2, Cr2O3, CaF2, LiF, NaF, KF, Y2O3, Au, Ag, and Cu, preferably one or more of the following: P2O5, TiO2, and ZrO2. 3D crystallized glass as described in any one of the appendices 1 to 7.

[0232] (Note 9) The 3D crystallized glass contains a clarifying agent, which contains one or more of the following: NaCl, Na2SO4, SnO2, As2O3, Sb2O3, NaNO3, KNO3, CeO2, and (NH4)2SO4, preferably one or more of the following: 3D crystallized glass as described in any one of the appendices 1 to 8.

[0233] (Note 10) The crystallized glass material of the aforementioned 3D crystallized glass is a glass material having crystals with an average particle size of 5 to 50 nm after undergoing nucleation and crystallization treatment. 3D crystallized glass as described in any one of the appendices 1 to 9.

[0234] (Note 11) The crystallized glass material of the aforementioned 3D crystallized glass is a glass material having a degree of crystallinity of 5 to 90 wt% after undergoing nucleation and crystallization treatment. 3D crystallized glass as described in any one of the appendices 1 to 9.

[0235] (Note 12) The aforementioned 3D crystallized glass has a drop height greater than 1.5m after chemical strengthening, preferably 300 gf The Vickers hardness under a 10-second load of force is greater than 650. 3D crystallized glass as described in any one of the appendices 1 to 11.

[0236] (Note 13) Step 1 involves mixing the raw materials for manufacturing 3D crystallized glass, melting them, cooling them, and performing an annealing process to obtain a glass substrate. Step 2 involves performing a nucleation treatment on the glass substrate obtained in Step 1, and cutting may be performed before and after the nucleation treatment as needed. Step 3 involves performing a crystallization treatment on the glass substrate after nucleation in step 2, Step 4 involves cutting the glass substrate after crystallization treatment as needed to obtain a crystallized glass material, The process includes step 5, which involves performing a 3D hot bending treatment on a crystallized glass material to obtain a 3D crystallized glass sample, Step 5 involves a 3D hot bending process, followed by a crystallization process. A method for manufacturing 3D crystallized glass as described in any one of the appendices 1 to 12.

[0237] (Note 14) In step 1, the melting temperature is 1350 to 1700°C, preferably 1400 to 1650°C, more preferably cooled to 500 to 1000°C after melting, and more preferably the method further includes a step of performing a chemical strengthening treatment on the 3D crystallized glass sample to obtain a finished 3D crystallized glass product. The method described in Appendix 13.

[0238] (Note 15) In step 1, the melting time is 1 to 5 hours, preferably in step 3, the crystallization treatment is performed after holding the temperature at 500 to 900°C for 5 to 300 minutes, and more preferably in step 3, one or more treatments from edge trimming, CNC machine machining, rough polishing and / or grinding are performed to obtain a crystallized glass material. The method described in Appendix 13 or 14.

[0239] (Note 16) The amount of nucleating agent added in step 1 is 1 to 9 mol% of the total amount of nucleating agent and crystallized glass oxide, and more preferably the amount of nucleating agent is 2 to 5 mol%. The method described in any one of the appendices 13 to 15.

[0240] (Note 17) The amount of clarifying agent added in step 1 is 0 to 4 wt%, preferably 0.1 to 2 wt%, of the total mass of the nucleating agent and crystallized glass oxide. The method described in any one of the appendices 13 to 16.

[0241] (Note 18) The method according to any one of the appendices 13 to 17, wherein in step 2, the temperature of the nucleation treatment is 450 to 800°C, the duration of the nucleation treatment is 30 to 360 minutes, and more preferably, the temperature of the nucleation treatment is 520 to 570°C, and the duration of the nucleation treatment is 120 to 300 minutes.

[0242] (Note 19) In step 3, the crystallization treatment temperature is 550-900°C, and the crystallization treatment time is 5-300 minutes. Preferably, the crystallization treatment temperature is 600-850°C, and the crystallization treatment time is 10-240 minutes. More preferably, the crystallization treatment temperature is 600 to 750°C, and the crystallization treatment time is 10 to 150 minutes. The method described in any one of the appendices 13 to 18.

[0243] (Note 20) In step 5, the hot bending process includes a preheating station, a hot pressing station, and a cooling station. The method described in any one of the appendices 13 to 19.

[0244] (Note 21) The preheating stations number 1 to 30, preferably 2 to 4; the hot press stations number 1 to 30, preferably 1 to 3; and the cooling stations number 1 to 30, preferably 2 to 4. The method described in Appendix 20.

[0245] (Note 22) The temperature of the preheating station is 300-850°C, the temperature of the hot press station is 600-920°C, the pressure is 0-6 MPa, and the temperature of the cooling station is 200-650°C. The method described in Appendix 20 or 21.

[0246] (Note 23) The operating time of the preheating station is 20 to 800 seconds, the operating time of the hot press station is 20 to 800 seconds, and the operating time of the cooling station is 20 to 800 seconds. Preferably, the operating time of the preheating station is 60 to 600 seconds, the operating time of the hot press station is 60 to 480 seconds, and the operating time of the cooling station is 60 to 600 seconds. The method described in any one of the appendices 20 to 22.

[0247] (Note 24) 3D crystallized glass manufactured by the manufacturing method described in any one of the appendices 13 to 23.

[0248] (Note 25) The 3D crystallized glass is transparent or opaque, and preferably, the 3D crystallized glass is curved or flat. 3D crystallized glass as described in Appendix 24.

[0249] (Note 26) In mobile phone displays, tablet computer displays, portable game consoles, electronic terminals, portable digital devices, center console displays, electronic whiteboard glass, smart home touchscreens, vehicle windshields, aircraft windshields, or aircraft windshields, Use of 3D crystallized glass as described in any one of the appendices 1 to 12 or 3D crystallized glass as described in appendice 24 or 25.

Claims

1. The 3D crystallized glass has a crystallinity of 75 wt% to 100 wt% and an average crystal grain size of 10 to 57 nm. The aforementioned 3D crystallized glass contains oxides in the following proportions, calculated in mol%, Composition mol%: SiO 2 65.1% to 74%, Al 2 O 3 3% to 8.51%, B 2 O 3 0% to 4%, MgO 0% to 1.4%, Na 2 O 0% to 3%, Li 2 O 18.8% to 25%, K 2 O 0% to 1%, CaO 0% to 2%, ZnO 0% to 5%, Rare earth oxides 0% to 3% The 3D crystallized glass contains a nucleating agent, and the amount of the nucleating agent is 1 to 9 mol% of the total amount of the nucleating agent and the glass ceramic oxide. The 3D crystallized glass has an average transmittance of 88-93% at light wavelengths of 380-780 nm. The absolute value of the b-value of the aforementioned 3D crystallized glass is 0.1 to 1.

00. A 3D crystallized glass characterized by the following features.

2. The average grain size of the crystals in the 3D crystallized glass is 15 to 30 nm, Alternatively, the thickness of the 3D crystallized glass is 0.02 to 5 mm. The 3D crystallized glass according to claim 1.

3. The average transmittance of light with a wavelength of 380 to 780 nm to the 3D crystallized glass is 90 to 93%. Alternatively, the average transmittance of light with a wavelength of 360 to 400 nm to the 3D crystallized glass is 65 to 91.5%. The 3D crystallized glass according to claim 1.

4. Having an average transmittance of 90 to 91.5% at a wavelength of light of 380 to 780 nm, or having an average transmittance of 79 to 91% at a wavelength of light of 360 to 400 nm. The 3D crystallized glass according to claim 1.

5. The 3D crystallized glass, when calculated in mol%, Composition mol%: SiO₂ 68%–71.8%, and / or Al₂O₃ 3% to 5.5%, and / or Li₂O 20.01% to 25%, and / or B2O3 0% to 1.6%, and / or MgO 0% to 0.98%, and / or ZnO 0% to 1.68%, and / or The amount of the nucleating agent is 2 to 5 mol% of the total amount of the nucleating agent and the glass ceramic oxide. The 3D crystallized glass according to claim 1.

6. When the thickness of the 3D crystallized glass is 0.7 mm, the absolute value of the b value (yellow-blue value) is 0.1 to 0.

62. Alternatively, the haze of the 3D crystallized glass is 0.07 to 1.0%. The 3D crystallized glass according to claim 1.

7. The crystalline phase of the aforementioned 3D crystallized glass is one or more of the following: lithium silicate, lithium disilicate, β-quartz, β-quartz solid solution, feldspar, β-sea pyroxene, β-sea pyroxene solid solution, nepheline, cordierite, mullite, apatite, zirconia, zinc spinel, magnesia-alumina spinel, and rutile. The 3D crystallized glass according to claim 1.

8. The rare earth oxide is La ２ O ３ , Eu ２ O ３ , Pr ６ O １１ , Nd ２ O ３ , Er ２ O ３ and Dy ２ O ３ selected from one or more of The 3D crystallized glass according to claim 1.

9. The aforementioned 3D crystallized glass, when calculated in mol%, is SiO ２ and Al ２ O ３ The total content is 72.86-80%, Or, Na ２ O and Li ２ The total oxygen content, when calculated in mol%, is 19.8-30%. The 3D crystallized glass according to claim 1.

10. The 3D crystallized glass has a total content of SiO₂ and Al₂O₃ of 72.86 to 74.8% when calculated in mol%, Alternatively, the total content of Na₂O and Li₂O, when calculated in mol%, is 20.46-26%. The 3D crystallized glass according to claim 1.

11. The nucleating agent is P ２ O ５ , TiO ２ , ZrO ２ , Cr ２ O ３ CaF ２ , LiF, NaF, KF, Y ２ O ３ , containing one or more of Au, Ag, and Cu, and / or, the 3D crystallized glass contains a clarifying agent, the clarifying agent containing one or more of the following: NaCl, Na₂SO₄, SnO₂, As₂O₃, Sb₂O₃, NaNO₃, KNO₃, CeO₂, and (NH₄)₂SO₄. The 3D crystallized glass according to claim 1.

12. The 3D crystallized glass, when calculated in mol%, Composition mol%: SiO₂ 68%–69.5%, and / or Al₂O₃ 3% to 5.3%, and / or Li₂O 20.5% to 25%, and / or B2O3 0% to 1.5%, and / or ZnO 0% to 0.98%, That is, The 3D crystallized glass according to claim 1.

13. The aforementioned 3D crystallized glass, after chemical strengthening, can withstand a drop height greater than 1.5m. The 3D crystallized glass according to claim 1.

14. The Vickers hardness under a 10-second load of 300 gf is greater than 650 kgf / mm². The 3D crystallized glass according to claim 1.

15. Step 1 involves mixing the raw materials for manufacturing 3D crystallized glass, melting them, cooling them, and performing an annealing process to obtain a glass substrate. Step 2 involves performing a nucleation treatment on the glass substrate obtained in Step 1, and cutting may be performed before and after the nucleation treatment as needed. Step 3 involves performing a crystallization treatment on the glass substrate after nucleation in step 2, Step 4 involves cutting the glass substrate after crystallization treatment as needed to obtain a crystallized glass material, The process includes step 5, which involves performing a 3D hot bending treatment on a crystallized glass material to obtain a 3D crystallized glass sample, In step 5, the 3D hot bending process is accompanied by a crystallization process. Crystallized glass material is a glass material that undergoes nucleation and crystallization treatment, resulting in a crystallinity of 37 wt% to 90 wt%. Step 5, the hot bending process, includes a preheating station, a hot pressing station, and a cooling station. The number of preheating stations is 1 to 30, the number of hot press stations is 1 to 30, and the number of cooling stations is 1 to 30. The temperature of the preheating station is 300 to 850°C, the temperature of the hot press station is 600 to 920°C, the pressure is 0 to 6 MPa, and the temperature of the cooling station is 200 to 650°C. A method for producing 3D crystallized glass according to any one of claims 1 to 14.

16. In step 1, the melting temperature is 1350 to 1700°C and / or the melting time is 1 to 5 hours. A method for producing 3D crystallized glass according to claim 15.

17. The step in step 1 includes the step of performing a chemical strengthening treatment on a 3D crystallized glass sample to obtain a finished 3D crystallized glass product, A method for producing 3D crystallized glass according to claim 15.

18. In step 3, crystallization is performed after maintaining the temperature at 500 to 900°C for 5 to 300 minutes. and / or, in step 3, further comprising one or more selected from the group consisting of trimming, CNC machining, rough grinding and / or polishing, to obtain a crystallized glass raw material. A method for producing 3D crystallized glass according to claim 15.

19. The raw material for manufacturing the 3D crystallized glass has crystals with an average particle size of 5 to 50 nm after being subjected to nucleation and crystallization, and / or the raw material for manufacturing the 3D crystallized glass has a degree of crystallinity of 40 wt% to 90 wt% after being subjected to nucleation and crystallization. A method for producing 3D crystallized glass according to claim 15.

20. The amount of nucleating agent added in step 1 is 2 to 5 mol% of the total amount of nucleating agent and crystallized glass oxide. and / or the amount of clarifying agent added in step 1 is 0 to 4 wt% of the total mass of the nucleating agent and crystallized glass oxide. A method for producing 3D crystallized glass according to claim 15.

21. In step 2, the nucleation treatment temperature is 450 to 800°C, and the nucleation treatment time is 30 to 360 minutes. and / or in step 3, the crystallization temperature is 550 to 900°C and the crystallization time is 5 to 300 minutes. A method for producing 3D crystallized glass according to claim 15.

22. The raw material for manufacturing the 3D crystallized glass has a degree of crystallinity of 75 wt% to 90 wt% after nucleation and crystallization. A method for producing 3D crystallized glass according to claim 15.

23. The 3D crystallized glass is characterized by being transparent or opaque, and / or having a curved surface. The 3D crystallized glass according to any one of claims 1 to 14.

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