Preparation method of high-transmittance impact-resistant glass based on rapid annealing technology

Abstract

The invention relates to the field of glass manufacturing, and discloses a high-transmittance impact-resistant glass preparation method based on a rapid annealing technology, which comprises the following steps: S1, selecting a specific glass raw material, and carrying out high-temperature melting, clarification and homogenization to prepare a primary glass product; s2, initial rapid cooling is conducted on the primary product, and the primary product is rapidly cooled to the preset annealing temperature; s3, in an interval from an annealing upper limit to a strain point, performing space-time modulation on the product, cooperatively applying electromagnetic excitation and acoustically assisted relaxation, and cooling in combination with precision programming; and S4, finally and quickly cooling the product subjected to synergistic annealing to room temperature to obtain the high-transmittance impact-resistant glass. Specific glass components are adopted, and an innovative electromagnetic and acoustic space-time modulation multi-physical field collaborative rapid annealing technology is combined, so that the comprehensive performance of the glass is efficiently improved, the annealing period is greatly shortened, the energy consumption is reduced, and uniform ultralow residual stress is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of glass manufacturing, in particular to a method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology. Background Art

[0002] As a fundamental and widely used material, glass inevitably generates internal stresses during the molding and cooling process due to internal and external temperature differences. If these stresses are not properly addressed, they will significantly reduce the mechanical strength of the glass, making it susceptible to breakage during use and potentially adversely affecting its optical uniformity and stability. Annealing, therefore, is a key step in glass manufacturing. Its purpose is to eliminate or minimize these harmful internal permanent stresses through a specific heat treatment regime, optimizing the glass's microstructure and ultimately imparting superior mechanical properties, thermal stability, and optical quality to glass products to meet increasingly demanding application requirements.

[0003] Currently, the common practice of glass annealing is based on the traditional thermal energy-driven principle. This method usually involves heating the glass product to its upper annealing temperature limit (generally slightly above the strain point of the glass) and maintaining it at this temperature for a period of time to relax the glass network structure and release internal stress. Subsequently, through a carefully controlled, usually very slow cooling process, the glass smoothly passes through the strain point and glass transition temperature region, and finally cools to room temperature. In some cases, in order to improve the annealing effect or adapt to specific glass types, staged cooling or adjustment of the holding time strategy will also be adopted.

[0004] Although the existing technology can eliminate the internal stress of glass to a certain extent through long-term heat treatment, there are still some shortcomings: the traditional annealing process often faces the problem of extremely long processing cycle, which directly leads to low production efficiency and high energy consumption per unit product, and it is difficult to adapt to the requirements of modern industrial production for high efficiency and low cost. In addition, it is difficult to completely eliminate internal stress under conditions of rapid cooling by relying solely on thermal energy for stress relaxation. Moreover, for special glass that pursues comprehensive high-performance indicators such as high impact strength and high optical transmittance, traditional methods have limited ability to finely control the uniformity of stress distribution and achieve extremely low residual stress levels in a short period of time. It is often difficult to completely avoid the potential impact on optical uniformity while improving mechanical properties. At the same time, the traditional process promotes the relaxation of the internal structure of glass relatively slowly, and fails to fully utilize the response characteristics of the material itself to other physical stimuli (such as electromagnetic fields or sound fields) to accelerate this process, which limits the further improvement of annealing efficiency and final product performance. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology, which solves the problems of long processing cycle, high energy consumption and difficulty in efficiently eliminating the internal stress of the glass and obtaining excellent comprehensive performance in a short time in the existing glass annealing technology.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology, comprising the following steps: S1. Selecting glass raw materials, melting, clarifying, and homogenizing the glass raw materials in a high-temperature melting furnace to prepare a glass melt, and then manufacturing the glass melt into a primary glass product; S2. performing an initial rapid cooling treatment on the obtained primary glass product to reduce its temperature from a high temperature state after forming to a preset annealing temperature; S3. performing a spatiotemporal multi-physics coordinated annealing treatment on the primary glass product that has undergone the initial rapid cooling treatment, wherein the treatment process comprises synergistically applying electromagnetic excitation and acoustically assisted relaxation in combination with programmed cooling while cooling the primary glass product from the upper annealing temperature limit to a preset strain point temperature range; S4. Performing a final rapid cooling treatment on the primary glass product that has undergone the spatiotemporal modulation multi-physical field coordinated annealing treatment to room temperature, thereby obtaining a high-transmittance and impact-resistant glass.

[0007] In summary, the present invention includes at least one of the following beneficial technical effects: 1. This invention utilizes a specific glass raw material composition ratio, combined with an innovative spatiotemporal modulation multi-physics field coordinated rapid annealing technology, to significantly enhance the overall performance of the final glass product, particularly its impact strength and optical transmittance. This performance improvement stems from the superior response characteristics of these specific components to multi-physics fields (such as electromagnetic excitation and acoustic assistance). This allows for more effective microstructural optimization and more complete elimination of internal stresses during the rapid annealing process, resulting in an ideal combination of high light transmittance and high impact resistance.

[0008] 2. The integrated rapid annealing process proposed in this invention significantly shortens the total glass heat treatment time by incorporating innovative steps such as initial rapid cooling, core multi-physics field-assisted precision annealing, and final rapid cooling. Compared to traditional, lengthy annealing processes, this invention significantly improves production efficiency and reduces energy consumption per unit product, resulting in substantial economic benefits. This is due to the highly integrated and optimized heat treatment process and the significantly accelerated stress relaxation rate assisted by the physical field.

[0009] 3. The core "temporal and spatial modulation of multi-physics field collaborative annealing" step of this invention, particularly its dynamic control strategy based on real-time glass state feedback, enables more precise control of the internal stress distribution of the glass, resulting in glass products with extremely low and highly uniform residual stress distribution. This intelligent annealing process ensures thorough and uniform stress relaxation, avoiding the uneven or incomplete stress relaxation that can occur in traditional processes, thereby improving product stability and reliability. This is a significant improvement over traditional fixed-program annealing.

[0010] 4. This invention utilizes a multi-physics field (electromagnetic excitation and acoustic assistance) in a critical stage of glass annealing to more effectively promote viscoelastic flow and structural relaxation within the glass, thereby achieving, or even exceeding, stress relief levels achieved through traditional, long annealing processes in a shorter time. This synergistic mechanism effectively reduces the effective viscosity of the glass, accelerating the characteristic stress relaxation time, even under rapid cooling conditions, ultimately imparting superior mechanical properties and internal quality to the glass products. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 Schematic diagram of the method of the present invention. DETAILED DESCRIPTION

[0012] The following is combined with Figure 1 , the present invention is described in further detail.

[0013] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0014] The present invention provides a method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology. It adopts specific glass components and combines innovative electromagnetic and acoustic spatiotemporal modulation multi-physical field collaborative rapid annealing technology to efficiently improve the comprehensive performance of the glass, significantly shorten the annealing cycle, reduce energy consumption and achieve uniform ultra-low residual stress.

[0015] like Figure 1 As shown, the method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology may include the following steps: The core purpose of S1 is to produce high-quality glass melt with uniform chemical composition, uniform physical properties and minimal defects, and to initially shape it into primary glass products required for subsequent processing. This step specifically includes the following key steps: First, the glass raw materials are accurately selected and prepared. In terms of weight, the glass raw materials mainly include: As the main component of the glass network former, 60-75 parts of silicon dioxide are selected. Silicon dioxide is the basis of the glass skeleton, and its content directly affects the structural stability and basic physical and chemical properties of the glass, such as hardness, chemical stability and thermal expansion coefficient.

[0016] To adjust the melting characteristics, forming properties, and certain physical and chemical properties of the final product, alkali metal oxides are introduced as network modifiers. The alkali metal oxide is selected from at least one of sodium oxide and potassium oxide. If sodium oxide is used, the dosage is 8-16 parts; if potassium oxide is used, the dosage is 0-8 parts. Regardless of whether one or a combination of two is selected, the total dosage of the alkali metal oxide is controlled within the range of 10-20 parts. The introduction of alkali metal oxides can effectively lower the melting temperature and viscosity of the glass, facilitate the melting process, and affect the refractive index, density, and other aspects of the glass.

[0017] To further optimize the glass's performance, particularly its mechanical properties and chemical stability, alkaline earth metal oxides are introduced as network modifiers. The alkaline earth metal oxide is selected from at least one of calcium oxide and magnesium oxide. If calcium oxide is used, its dosage is 5-15 parts; if magnesium oxide is used, its dosage is 1-8 parts. Similarly, whether one or a combination of the two is selected, the total dosage of the alkaline earth metal oxide is controlled within the range of 5-18 parts. Alkaline earth metal oxides can, to a certain extent, improve the glass's hardness, hydrolysis resistance, and structural stability at high temperatures.

[0018] In addition, to further enhance the overall performance of glass, such as increasing its mechanical strength, improving its chemical durability, or adjusting its optical properties, 0.5-5 parts of aluminum oxide and / or 0.1-3 parts of zirconium oxide can be optionally added. As an intermediate oxide, aluminum oxide can strengthen the connectivity of the glass network, increasing the hardness and chemical stability of the glass; while the addition of zirconium oxide can significantly improve the flexural strength and fracture toughness of the glass.

[0019] In practice, the various raw materials selected are preferably of high purity, such as analytically pure or industrially pure chemical reagents, to minimize the impact of harmful impurities on glass quality. For example, silicon dioxide can be derived from high-purity quartz sand, while other metal oxides can be derived from high-purity compounds such as their corresponding carbonates, nitrates, or oxides. All raw materials are preferably thoroughly dried before use to remove adsorbed moisture, thereby preventing the introduction of unnecessary bubbles during the high-temperature melting process or the impact on the progress of chemical reactions.

[0020] After completing the proportioning and preparation of the glass raw materials, the high-temperature melting stage is entered. This stage is the core process of converting the solid powdered raw materials into a uniform liquid glass melt, which specifically includes three sub-steps: melting, clarifying, and homogenizing. The above-mentioned glass batch materials that have been fully mixed (mechanical mixing can be performed using a V-type mixer or a ball mill to ensure the uniform distribution of each component on a microscopic scale) are placed in a suitable high-temperature melting furnace. In the melting sub-step, in order to effectively remove bubbles in the glass melt and improve the transparency of the final glass, an appropriate amount of clarifier is usually added to the batch materials, and its amount is 0.05-1.0 parts by weight. The type of clarifier can be selected according to the composition and melting process of the glass. For example, it can be sulfates (such as sodium sulfate), halides, or oxides with variable valence elements (such as antimony trioxide, cerium dioxide, etc.), which promote the merging, floating, and escape of small bubbles by decomposing and generating gas, changing the surface tension of the melt, or undergoing redox reactions at high temperatures. Subsequently, the crucible containing the batch material and the clarifier (preferably made of a material that is resistant to high temperatures and does not pollute the glass liquid, such as a platinum crucible or a high-silica crucible) is heated in a high-temperature melting furnace. The heating process can be program-controlled and raised to a preset melting temperature at a certain rate (for example, preferably 5-10°C / minute to avoid damage to the crucible or splashing of materials due to excessive heating). The melting temperature is set in the range of 1450°C-1600°C. After reaching the melting temperature, it is kept warm for 4-8 hours. Under such a high temperature and a sufficiently long holding time, the components in the glass batch undergo complex physical and chemical reactions and gradually turn into a viscous liquid, forming an initial glass melt. This process is designed to ensure that all raw material particles are completely melted and preliminarily mixed.

[0021] The fining step then follows. The purpose of this fining step is to further eliminate tiny bubbles remaining in the glass melt, which are a major defect affecting the optical quality of the glass. This fining step is typically performed at the aforementioned melting temperature (i.e., 1450°C-1600°C) for 2-4 hours. During this stage, the fining agent fully exerts its effect, promoting the elimination of bubbles. To enhance the fining effect, slight mechanical stirring or controlled melting atmosphere may be used in some cases.

[0022] After the clarification treatment, the homogenization sub-step is carried out. The purpose of homogenization is to eliminate the chemical composition unevenness (such as streaks, stones) and temperature unevenness that may exist in the glass melt, so as to obtain a glass melt with highly consistent physical and chemical properties, which is crucial for subsequent molding and the final performance of the glass. The homogenization treatment is usually carried out under conditions slightly lower than the main melting temperature. Specifically, the temperature of the glass melt is adjusted and maintained in the range of 1400℃-1500℃ for 2-4 hours. During the homogenization process, the material migration and energy transfer inside the melt can be promoted by extending the holding time or adopting a specific stirring method (for example, using a platinum stirrer to stir at a low speed), so as to achieve a highly homogenized state.

[0023] The final step in step S1 is to form the prepared molten glass into a primary glass product. This process imparts a specific shape and size to the liquid molten glass to facilitate subsequent rapid annealing. Compression molding (pour the molten glass into a preheated mold and press-form) or casting (pour the molten glass onto a flat plate and allow it to naturally level out) can be used. For industrial production, continuous or semi-continuous molding processes such as float, calendaring, and blowing can be considered.

[0024] In this embodiment, step S2 involves performing an initial rapid cooling process on the primary glass product obtained in step S1. Its core purpose is to rapidly and controllably cool the primary glass product, fresh from the high-temperature forming state, to a predetermined temperature range suitable for subsequent precision annealing, i.e., near the upper annealing temperature limit. This step is a critical transition link between high-temperature forming and precision annealing, and is crucial for ensuring the performance of the final glass product.

[0025] Specifically, after step S1, the resulting primary glass product is still at a relatively high temperature, typically well above the annealing temperature range where its structure begins to solidify and stress relaxation can occur. Directly cooling this high-temperature product slowly or directly subjecting it to a complex time-space controlled annealing process can not only result in lengthy processing cycles, but can also lead to undesirable structural changes such as devitrification or the generation of difficult-to-control initial thermal stresses due to prolonged exposure to unsuitable temperature ranges. Therefore, the "initial rapid cooling treatment" employed in step S2 is particularly necessary.

[0026] The "initial rapid cooling treatment" is intended to rapidly reduce the overall temperature of the primary glass product from its high temperature state after forming at a relatively fast cooling rate. The "rapid" here is relative to the extremely slow cooling rate in traditional annealing processes. Its purpose is to efficiently bring the glass product to the starting temperature point of subsequent precision annealing. Although it is a rapid cooling process, this process still needs to be controlled to avoid the generation of transient thermal stresses sufficient to cause cracking or damage inside the glass due to excessive temperature gradients. Preferably, the average cooling rate at this stage can be adjusted according to the thickness, geometry and thermophysical properties of the glass product itself. For example, an average cooling rate of several tens to one or two hundred degrees Celsius per minute can be adopted.

[0027] There are various ways to achieve rapid initial cooling. For example, the high-temperature primary glass product can be placed in a forced convection cooling environment, where the flow rate and temperature of the cooling medium (e.g., air) can be controlled to achieve rapid cooling. Another preferred method is to quickly move the primary glass product into a holding furnace or cooling chamber preheated to a temperature close to or slightly above the upper annealing temperature limit, and then utilize the temperature difference between the product and the surrounding environment to achieve controlled rapid cooling.

[0028] The end point of this step is to reduce the temperature of the primary glass product to "near the preset upper limit of the annealing temperature". The preset upper limit of the annealing temperature is set in the range of 500℃-600℃. For the typical silicate-based high-transmittance and impact-resistant glass involved in the present invention, this temperature range is usually above its glass transition temperature. In this temperature region, the structural units inside the glass still have a certain degree of mobility, which is sufficient to effectively relax stress during the subsequent annealing process, but the viscosity of the glass is high enough to basically maintain its shape after forming. Cooling the primary glass product to near this upper limit of the annealing temperature ensures that the subsequent steps can be started in an ideal and clear initial thermal state, which is crucial for achieving precise and efficient stress relief and structural optimization. The so-called "near" means that in actual operation, a small and acceptable fluctuation range is allowed above and below the target temperature.

[0029] In this embodiment, step S3, which involves subjecting the primary glass product, which has undergone the initial rapid cooling treatment in step S2, to a critical spatiotemporal multi-physics field synergistic annealing process, is the core technical step in achieving high-transmittance and impact-resistant glass. The essence of this process lies in the innovative and coordinated application of electromagnetic excitation and acoustically assisted relaxation during the precise cooling of the primary glass product from the upper annealing temperature (preferably 500°C-600°C) to a predetermined strain point temperature range (preferably 450°C-550°C). This is combined with a sophisticated programmed cooling strategy to achieve deep stress relief and microstructural optimization.

[0030] Specifically, when the primary glass product reaches near the upper annealing temperature limit after the initial rapid cooling in step S2, the coordinated annealing process in step S3 is initiated. This temperature range (from the upper annealing temperature limit to the strain point) is the most active and critical stage for stress relaxation within the glass. The glass is still in a viscoelastic state, and its atoms or structural units have a certain degree of mobility.

[0031] In the spatiotemporal modulation of multi-physics field collaborative annealing treatment, the coordinated application of electromagnetic excitation plays an important role. Its purpose is not to heat the glass macroscopically, but to achieve sub-resonant interaction between the electromagnetic field of specific parameters and the microscopic structural units such as specific ionic groups, dipoles or interfaces inside the glass, thereby effectively disturbing or inhibiting the formation and development of stress concentration areas at the microscopic level, and possibly reducing the energy barrier for the migration of structural units, and promoting the rapid release of stress in local areas. The application of electromagnetic excitation specifically includes: applying a radio frequency field or microwave field with a frequency in the range of 1MHz-10GHz to the primary glass product. This frequency range is selected to ensure that the electromagnetic energy can effectively couple with the dielectric response mechanism inside the glass material.

[0032] Preferably, the electromagnetic excitation is applied using pulse modulation. Pulse modulation, for example, with a pulse width of 1 microsecond to 100 milliseconds and a duty cycle of 10% to 80%, allows for instantaneous application of high-energy perturbations to stimulate microstructural relaxation, while simultaneously allowing the system ample time to respond and dissipate energy during the interpulse intervals, thus avoiding unnecessary overall temperature rise. Of course, continuous wave application can also be employed under specific conditions.

[0033] In order to ensure that the electromagnetic excitation mainly plays a role of microscopic perturbation rather than macroscopic heating, the average input power density of the electromagnetic excitation is preferably controlled at 0.01-1 W / cm 3 The lower level, or through monitoring, ensure that the glass temperature rise rate caused directly by electromagnetic excitation is controlled within an extremely low range of 1-5℃ / minute.

[0034] Its local unit volume absorbed power density P abs (r,t) can be represented by the following formula: P abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 ; Among them, P abs (r, t) is the power density per unit volume absorbed by the glass at position r and time t; f e is the electromagnetic field frequency; ∈0 is the vacuum dielectric constant; ∈ ″ (f e,T(r,t)) is the glass at frequency f e and dielectric loss factor at temperature T(r,t); |E(r,t)| 2 is the electromagnetic field intensity at position r and time t. By regulating these parameters, the spatiotemporal selective control of energy input inside the glass can be achieved.

[0035] Acoustic-assisted relaxation is another key physical field method in step S3. Its core function is to use high-frequency mechanical vibration energy to promote viscoelastic flow within the glass at both macroscopic and mesoscopic scales, accelerate stress relaxation, and help achieve a uniform distribution of residual stress throughout the entire volume of the glass product.

[0036] Applying acoustic assisted relaxation specifically includes applying ultrasonic waves with a frequency range of 20 kHz to 2 MHz to the primary glass product. Sound waves in this frequency range can effectively propagate in the glass material and produce significant mechanical effects.

[0037] The ultrasonic sound intensity is preferably controlled at 1-50W / cm 2 The appropriate sound intensity can provide enough energy to overcome the potential barrier of structural unit migration, but not enough to cause macroscopic damage to the material. The introduction of sound waves can effectively reduce the effective viscosity of glass, thereby shortening its stress relaxation characteristic time.

[0038] Stress relaxation characteristic time τ relax Its relationship with materials and sound fields can be conceptually represented by the following formula: relax =η(T,W a ) / G; Among them, τ relax is the stress relaxation characteristic time; η(T,W a ) is the effective viscosity of the glass, which is the temperature T and the sound field energy density W a G is the shear modulus of glass. This formula is intended to illustrate that the input of acoustic energy helps accelerate the relaxation process.

[0039] The electromagnetic excitation and acoustically assisted relaxation described above are not applied in isolation, but are closely integrated with a carefully designed programmed cooling strategy. Programmed cooling preferably employs a multi-step cooling curve or a nonlinear cooling curve. In particular, during the critical stress relaxation phase, from the upper annealing temperature to the strain point, the cooling rate is strictly controlled to a low level of 0.2-2°C / minute. This slow and precise cooling rate provides the necessary time window for the glass's internal structure to fully adjust and effectively release stresses, avoiding the reintroduction or "freezing" of new stresses due to excessively rapid cooling.

[0040] The core of step S3 is the realization of spatiotemporal modulation. The parameters of electromagnetic excitation (such as frequency, power, pulse parameters, and field distribution), acoustically assisted relaxation (such as frequency, sound intensity, duration, and spatial distribution), and programmed cooling rate are not fixed but are dynamically adjusted based on the real-time state of the primary glass product during the annealing process.

[0041] This spatiotemporal modulation specifically includes dynamically and collaboratively adjusting the applied parameters of the aforementioned physical fields and the cooling curve based on the real-time temperature distribution of the primary glass product during the annealing process (e.g., monitored by infrared thermal imaging cameras and / or the internal stress development state (e.g., preliminary evaluation by an online polarization stress meter or model-based prediction) through a preferred feedback or feedforward control system.

[0042] For example, at the beginning of annealing, when the temperature is high and the viscosity is low, a physical field with a certain parameter combination can be used to promote rapid relaxation; as the temperature decreases and the viscosity increases, the parameters of the physical field and the cooling rate are adjusted accordingly to adapt to the changes in the glass response characteristics, ensuring that the best stress relief and structural homogenization effects can be achieved throughout the annealing range.

[0043] In addition, the temporal synergistic relationship between electromagnetic excitation and acoustic-assisted relaxation is also adjustable. They can be performed synchronously, partially overlapped, or successively in time according to specific needs to achieve optimal coupling of different physical field effects.

[0044] In this embodiment, step S4, i.e., the final rapid cooling treatment to room temperature of the primary glass product that has undergone the spatiotemporal modulation multi-physical field coordinated annealing treatment in step S3, is the final step of the entire preparation process. Its core goal is to safely and efficiently cool the glass product that has undergone precise stress control and structural optimization from the lower limit temperature of the annealing zone (i.e., the strain point temperature range) to ambient temperature, while maximally maintaining the low stress state and excellent microstructure obtained in step S3, thereby ultimately obtaining the desired high-transmittance and impact-resistant glass.

[0045] Specifically, after completing the spatiotemporal multi-physics field synergistic annealing treatment in step S3, the permanent stresses within the primary glass product have been significantly eliminated or reduced to extremely low levels, and its microstructure has become uniform and stable. At this point, the glass product is typically near its strain point temperature, a critical state. Below this temperature, the glass behaves more like an elastic solid, the mobility of internal structural units is significantly reduced, and once formed, new permanent stresses are difficult to eliminate through self-relaxation. Therefore, the subsequent cooling process from this temperature point is crucial to maintaining the excellent properties achieved.

[0046] The "final rapid cooling treatment" strategy adopted in this step S4 is "rapid" in comparison with the programmed slow cooling in the temperature range from the upper limit of the annealing temperature to the strain point in step S3. After completing the critical stress relaxation stage, it is no longer necessary to continue to use an excessively slow cooling rate, which may even extend the production cycle. More importantly, in the temperature range below the strain point, if the cooling is improper, for example, there is a significant temperature gradient between the various parts of the glass product and it lasts for a long time, it may reintroduce non-negligible temporary thermal stresses due to asynchronous shrinkage, and even in some cases transform into new permanent residual stresses, although the magnitude is usually much smaller than the original stress without annealing. Therefore, a controlled rapid cooling method is adopted to allow the entire glass product to pass through this temperature range dominated by elastic behavior as quickly and relatively uniformly as possible to reduce the chance and magnitude of new stress generation.

[0047] The method for achieving the final rapid cooling process can be selected based on the size, shape, thickness, and production efficiency requirements of the glass product. Preferably, forced convection cooling is employed, for example, by sweeping a stream of filtered, temperature-controlled air or inert gas across the glass surface. The flow rate, temperature, and sweeping pattern of the cooling medium can be optimized to ensure that the surface and interior temperatures of the glass product drop as synchronously as possible, avoiding excessive transient temperature gradients.

[0048] The end point of the entire final rapid cooling process is to reduce the temperature of the glass product to "room temperature". Room temperature generally refers to the ambient working temperature, such as 20°C-25°C.

[0049] Example 1: Step S1: Selection of glass raw materials, melt preparation and primary glass product forming: Glass raw materials are selected, and the components thereof include, by weight: Silicon dioxide: 67.5 parts; Sodium oxide: 10 parts; Potassium oxide: 5 parts (total amount is 15 parts); Calcium oxide: 7 parts; Magnesium oxide: 4.5 parts (total amount is 11.5 parts); Aluminum oxide: 2.75 parts; Oxide: 1.55 parts; Clarifier (a mixture of antimony trioxide and sodium nitrate): 0.525 parts The above-mentioned fully mixed glass raw materials are placed in a platinum crucible and sent into a high-temperature melting furnace.

[0050] Melting treatment: heating to 1525°C at a rate of about 8°C / min and maintaining at the melting temperature for 6 hours to form a glass melt.

[0051] Clarification treatment: Continue to keep the temperature at 1525℃ for 3 hours to fully eliminate bubbles in the glass melt.

[0052] Homogenization treatment: The glass melt temperature is then adjusted to 1450°C and kept at this temperature for 3 hours. It can also be supplemented with low-speed platinum stirring to ensure high uniformity of the chemical composition and temperature of the glass melt.

[0053] After homogenization, the uniform glass melt is molded into a primary glass product of a predetermined size and shape, such as a glass plate with a thickness of 5 mm.

[0054] Step S2: Initial rapid cooling process: The hot primary glass product obtained in step S1 is rapidly cooled from the forming temperature (e.g., approximately 1000° C.) to an initial rapid cooling process. This process involves moving the product into a cooling device preheated to a temperature close to the upper limit of the annealing temperature. The product is then cooled by controlled forced air convection at an average rate of approximately 100° C. / minute to approximately 550° C., which is the predetermined upper limit of the annealing temperature in this embodiment.

[0055] Step S3: Spatiotemporal modulation of multi-physics field collaborative annealing process: For the primary glass products that have undergone initial rapid cooling treatment, a spatiotemporal multi-physics field coordinated annealing treatment is performed starting from 550°C (the upper limit of annealing temperature) to the preset strain point temperature of 500°C.

[0056] Electromagnetic excitation application: During this cooling process, a pulsed microwave field is applied to the primary glass product.

[0057] Frequency: 2.45GHz is selected.

[0058] Application mode: pulse modulation, pulse width is set to 50 milliseconds, duty cycle is 45%.

[0059] Power control: The average input power density is controlled at about 0.5W / cm 3 By precisely controlling the electromagnetic field intensity distribution E(r,t) and considering the glass in real-time temperature T(r,t) and frequency f e The dielectric loss factor ∈ ″ (f e ,T(r,t)), according to the formula P abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 ; Among them, P abs (r, t) is the power density per unit volume absorbed by the glass at position r and time t; f e is the electromagnetic field frequency; ∈0 is the vacuum dielectric constant; ∈ ″ (f e ,T(r,t)) is the glass at frequency fe and dielectric loss factor at temperature T(r,t); |E(r,t)| 2 The electromagnetic field intensity amplitude at position r and time t is used to regulate the local unit volume absorption power density, aiming at microscopic perturbations rather than significant macroscopic heating.

[0060] Acoustically assisted relaxation application: Ultrasound waves are applied simultaneously or in a specific sequence.

[0061] Frequency: 1MHz is selected.

[0062] Sound intensity control: The sound intensity of the ultrasound is controlled at about 25.5W / cm 2 This acoustic energy input is intended to reduce the effective viscosity η(T,W a ), thereby accelerating stress relaxation and shortening the stress relaxation characteristic time τ relax =η(T,W a ) / G; where τ relax is the stress relaxation characteristic time; η(T,W a ) is the effective viscosity of the glass, which is the temperature T and the sound field energy density W a function; G is the shear modulus of glass.

[0063] Programmed cooling: Using a multi-step or smooth nonlinear cooling curve, during the critical stress relaxation stage from 550°C to 500°C, the average cooling rate is strictly controlled at 1.1°C / minute.

[0064] Spatiotemporal Modulation: Throughout the S3 process, online monitoring systems (e.g., infrared thermal imaging for temperature distribution and polarimetric stress meters for preliminary stress assessment) capture real-time state parameters of the primary glass product. Based on these parameters, feedback or feedforward control logic dynamically adjusts the pulse parameters and power of the electromagnetic excitation, the intensity and timing of the acoustically assisted relaxation, and the specific rate curve of the programmed cooling. The timing of electromagnetic excitation and acoustically assisted relaxation can be synchronized, partially overlapped, or sequentially applied, depending on the optimization strategy.

[0065] Step S4: Final rapid cooling process: When the temperature of the primary glass product reaches 500°C (near the strain point), the time-space controlled multi-physics coordinated annealing process is terminated, and the final rapid cooling process begins immediately. Forced air convection is used to cool the product to room temperature (e.g., 25°C) at an average rate of approximately 30°C / minute, resulting in a highly transparent and impact-resistant glass.

[0066] Optional subsequent steps: As needed, the obtained high-transmittance and impact-resistant glass can be subjected to surface post-treatment, such as chemical etching with a 3 vol% hydrofluoric acid solution for 2.5 minutes, to further improve surface quality or specific properties.

[0067] Example 2: This embodiment provides a method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology. The specific steps and parameters are as follows, focusing on the application of the lower limit of the claim range: Step S1: Selection of glass raw materials, melt preparation and primary glass product forming Glass raw materials are selected, and the components thereof include, by weight: Silicon dioxide: 60 parts; sodium oxide: 8 parts; potassium oxide: 2 parts (the total amount of alkali metal oxides is 10 parts); calcium oxide: 5 parts; magnesium oxide: 1 part (the total amount of alkaline earth metal oxides is 6 parts); aluminum oxide: 0.5 parts; zirconium oxide: 0.1 parts; clarifier (a mixture of antimony trioxide and sodium nitrate): 0.05 parts.

[0068] After the above raw materials are mixed evenly, they are placed in a corundum crucible and sent into a high-temperature melting furnace.

[0069] Melting treatment: Heat to 1450℃ and keep at this temperature for 4 hours. Clarifying treatment: Keep at 1450℃ for 2 hours.

[0070] Homogenization treatment: adjust the temperature to 1400℃ and keep it warm for 2 hours.

[0071] Subsequently, the glass melt is cast into primary glass products, such as thin sheets of a specific shape.

[0072] Step S2: Initial rapid cooling process: The primary glass product is rapidly cooled from its high temperature state after forming to 500° C., which serves as the upper limit of the preset annealing temperature for subsequent annealing. The average cooling rate of this process can be controlled at, for example, 80° C. / minute.

[0073] Step S3: Spatiotemporal modulation of multi-physics field collaborative annealing process: For primary glass products, a spatiotemporal multi-physics field coordinated annealing treatment is carried out starting from 500°C and moving towards the preset strain point temperature of 450°C.

[0074] Electromagnetic excitation application: Frequency: Select 1MHz (RF range).

[0075] Application mode: pulse modulation, pulse width is 1 microsecond, duty cycle is 10%.

[0076] Power control: The average input power density is controlled at 0.01W / cm3 Its energy absorption also follows P abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 ; principle.

[0077] Acoustically assisted relaxation is applied: Frequency: 20kHz is selected.

[0078] Sound intensity control: Sound intensity is controlled at 1W / cm 2 The purpose is to influence the effective viscosity η(T,W) by acoustic energy input. a ) and stress relaxation characteristic time τ relax .

[0079] Programmed cooling: During the critical stage of cooling from 500°C to 450°C, the average cooling rate is controlled at 0.2°C / min.

[0080] Spatiotemporal modulation: Also based on real-time monitoring of the glass state (temperature, stress signatures), the control system dynamically fine-tunes electromagnetic and acoustic field parameters and the cooling rate to ensure effective stress relaxation even under low parameter input conditions. Electromagnetic and acoustic excitation can be applied, for example, using alternating pulses.

[0081] Step S4: Final rapid cooling process: When the temperature of the glass product reaches 450° C., it is cooled to room temperature by natural convection (for thin and small products) or gentle forced air cooling in clean air to obtain high-transmittance and impact-resistant glass.

[0082] Optional subsequent steps: The glass product may be subjected to a surface flame polishing treatment, or a chemical etching treatment using a 1 vol% hydrofluoric acid solution for 30 seconds.

[0083] Example 3: This embodiment provides a method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology. The specific steps and parameters are as follows, focusing on the upper limit of the scope of the claims: Step S1: Selection of glass raw materials, melt preparation and primary glass product forming Glass raw materials are selected, and the components thereof include, by weight: Silicon dioxide: 75 parts; sodium oxide: 16 parts; potassium oxide: 4 parts (the total amount of alkali metal oxides is 20 parts); calcium oxide: 15 parts; magnesium oxide: 3 parts (the total amount of alkaline earth metal oxides is 18 parts); aluminum oxide: 5 parts; zirconium oxide: 3 parts; clarifier (for example, a composite clarifier such as a mixture of antimony trioxide and sodium nitrate): 1.0 part.

[0084] After the above raw materials are fully mixed, they are placed in a high-purity quartz ceramic crucible and sent into a high-temperature melting furnace.

[0085] Melting treatment: heat to 1600℃ and keep warm for 8 hours.

[0086] Clarification treatment: Continue to keep the temperature at 1600℃ for 4 hours.

[0087] Homogenization treatment: adjust the temperature to 1500℃ and keep it warm for 4 hours, which can be combined with efficient stirring.

[0088] Subsequently, the glass melt is formed into a continuous primary glass ribbon or plate by drawing or rolling.

[0089] Step S2: Initial rapid cooling process: The primary glass product is efficiently and rapidly cooled from its high temperature state after forming to 600°C, which serves as the upper limit of the subsequent annealing temperature. This process can use a strong air quenching initial stage, with an average cooling rate of, for example, over 150°C / minute.

[0090] Step S3: Spatiotemporal modulation of multi-physics field collaborative annealing process: For primary glass products, a spatiotemporal multi-physics field coordinated annealing treatment is carried out starting from 600°C and moving towards the preset strain point temperature of 550°C.

[0091] Electromagnetic excitation application: Frequency: 10GHz (microwave high frequency band) is selected.

[0092] Application mode: pulse modulation, pulse width is 100 milliseconds, duty cycle is 80%.

[0093] Power control: Instead of directly controlling the average input power density, the electromagnetic field parameters are controlled so that the glass temperature rise rate caused by electromagnetic excitation is controlled within 5°C / minute. The energy absorption mechanism still follows P abs (r,t) related formula.

[0094] Acoustically assisted relaxation is applied: Frequency: 2MHz is selected.

[0095] Sound intensity control: Sound intensity is controlled at 50W / cm 2 . Promote efficient stress relaxation with strong acoustic energy input.

[0096] Programmed cooling: During the critical stage of cooling from 600°C to 550°C, the average cooling rate is controlled at 2°C / min.

[0097] Spatiotemporal modulation: Based on precise online sensor data of the internal temperature field and stress distribution of glass products (especially those with large sizes or complex shapes), advanced control algorithms dynamically optimize the electromagnetic field distribution (such as using phased array antennas or multi-mode cavities), the focusing and scanning patterns of the acoustic transducer array, and the spatiotemporal gradient of the cooling program to meet the requirements of rapid response and uniform processing under high parameter input. Electromagnetic and acoustic excitation can be applied in an efficient and simultaneous superposition manner.

[0098] Step S4: Final rapid cooling process: When the temperature of the glass product reaches 550°C, a multi-stage controlled-rate forced air cooling system is used to quickly and evenly cool it to room temperature to obtain highly transparent and impact-resistant glass.

[0099] Optional subsequent steps: The glass article may be subjected to surface ion exchange enhancement treatment, or chemical etching treatment using a 5 vol% hydrofluoric acid solution for 5 minutes to obtain specific surface properties.

[0100] Comparative Example 1: Compared with Example 1, the difference lies in the composition of the glass raw materials: no aluminum oxide and zirconium oxide are contained, the amount of silicon dioxide is adjusted to 72.05 parts, and the remaining steps and parameters are the same as those in Example 1.

[0101] Comparative Example 2: Compared with Example 1, the difference lies in the composition of the glass raw materials: the amount of silicon dioxide is 55 parts, the amount of sodium oxide is 6 parts, and the amount of potassium oxide is 7 parts. The remaining steps and parameters are the same as those in Example 1.

[0102] Comparative Example 3: Compared with Example 1, the difference lies in the composition of the glass raw materials in step S1: the amount of aluminum oxide is increased to 8 parts, the amount of zirconium oxide is increased to 5 parts, and the remaining steps and parameters are the same as those in Example 1.

[0103] Comparative Example 4: Compared to Example 1, the difference is that in step S3, no electromagnetic excitation and acoustic-assisted relaxation are applied. Only programmed cooling is performed, that is, the primary glass product is cooled from 550°C to 500°C at an average cooling rate of 1.1°C / min. The remaining steps and parameters are the same as in Example 1.

[0104] Comparative Example 5: Compared with Example 1, the difference is that in step S3, although electromagnetic excitation and acoustic assisted relaxation are applied, and programmed cooling is performed, the parameters of the electromagnetic excitation (frequency 2.45 GHz, pulse width 50 milliseconds, duty cycle 45%, average input power density 0.5 W / cm 3 ), acoustically assisted relaxation parameters (frequency 1 MHz, sound intensity 25.5 W / cm 2) and the programmed cooling rate (an average of 1.1°C / minute from 550°C to 500°C) are both fixed preset values ​​and are not dynamically adjusted based on the real-time temperature distribution and / or internal stress development of the primary glass product during annealing. In other words, the "spatiotemporal modulation" step is omitted. The remaining steps and parameters are the same as in Example 1.

[0105] Comparative Example 6: Compared with Example 1, the difference lies in step S3 (spatiotemporal modulation of multi-physical field collaborative annealing treatment): in this step, only electromagnetic excitation is applied, and acoustic-assisted relaxation is not applied. The remaining steps and parameters are the same as those in Example 1.

[0106] Comparative Example 7: Compared with Example 1, the difference lies in step S3 (spatiotemporal modulation of multi-physical field collaborative annealing treatment): in this step, only acoustic-assisted relaxation is applied, and no electromagnetic excitation is applied. The remaining steps and parameters are the same as those in Example 1.

[0107] Comparative Example 8: Compared to Example 1, step S2 (initial rapid cooling) was omitted. Specifically, after the primary glass product was formed in step S1, it was directly slowly cooled (e.g., at a rate of 10°C / minute) to the upper annealing temperature of 550°C. Then, steps S3 and S4 were performed, identical to those in Example 1. The remaining steps and parameters were the same as in Example 1.

[0108] Comparative Example 9: Compared to Example 1, the difference lies in step S4 (final rapid cooling): in this step, rapid cooling is not performed. Instead, the primary glass product is cooled from 500°C (near the strain point) to room temperature at a very slow rate (e.g., 0.3°C / minute, referring to the slow cooling stage of a conventional annealing process). All other steps and parameters are the same as in Example 1.

[0109] Comparative Example 10: Compared with Example 1, the difference lies in the rate of programmed cooling in step S3: in the critical stress relaxation stage of cooling from 550°C to 500°C, a faster cooling rate, for example 5°C / min, is adopted, and all other steps and parameters are the same as in Example 1.

[0110] Test Example 1: Experimental samples: This experiment selected the following four groups of glass samples prepared according to the above method: Example 1 sample; Comparative Example 1 sample; Comparative Example 2 sample; Comparative Example 3 sample; each group of samples prepared with specimens having the same size and surface treatment status (for example, 100mmx100mmx5mm cut and polished plates).

[0111] Experimental steps: Impact resistance test (drop ball impact test): Equipment preparation: Prepare a drop ball impact tester equipped with a standard weight steel ball (for example, 227 grams or 500 grams, depending on the expected strength of the sample). Ensure that the testing machine platform is level and the supporting fixture is stable.

[0112] Sample placement: Place the sample to be tested horizontally on the sample support table of the testing machine, ensuring that the placement position and support conditions are consistent each time, and the impact point is selected at the center of the sample.

[0113] Impact test: Release a steel ball from a low initial height, allowing it to freely fall and impact the center of the specimen. If the specimen does not crack, gradually increase the drop height of the steel ball by fixed increments (for example, 5 cm or 10 cm) and repeat the impact. Record the drop height that causes the specimen to first crack or completely break; this height is the critical impact resistance height of the specimen.

[0114] Data Recording and Processing: Repeat step c above for all specimens in each sample group, recording the critical impact height of each specimen. Calculate the average critical impact height of each sample group and record the original data points.

[0115] Optical transmittance test: Instrument Preparation: Prepare the UV-Vis-NIR spectrophotometer. Perform instrument warm-up and baseline calibration.

[0116] Sample preparation: Select a sample with a clean surface and no obvious scratches.

[0117] Transmittance measurement: Place the sample vertically in the spectrophotometer's sample chamber, ensuring the light beam passes perpendicularly through the sample. Scan the sample's transmittance over the visible light wavelength range (e.g., 400nm to 700nm). Record the average transmittance over the entire scan range or the transmittance at a specific wavelength of interest (e.g., 550nm).

[0118] Data recording and processing: Measure multiple samples in each group of samples or different positions of the same sample, and record their average visible light transmittance.

[0119] Residual stress level assessment (polarized stress meter method): Instrument preparation: Prepare a transmission polarization stress meter and adjust the light source and polarizer (usually in orthogonal polarization state).

[0120] Sample Observation: Place the sample to be tested on the stage of the polarization stress meter, between the polarizer and analyzer. Observe the interference fringes, color, density, and distribution (photoelastic fringes) formed by the polarized light passing through the sample.

[0121] Data recording and processing: The qualitative description of the stress fringes of each group of samples was recorded, and the maximum optical path difference value measured at the key observation points was recorded. The experimental results are shown in Table 1.

[0122] Table 1: Data on the influence of glass composition on sample properties under rapid annealing process From Table 1, we can get: The sample of Example 1, due to its carefully formulated glass raw material composition, exhibits a high critical impact height, excellent average visible light transmittance, and a very low residual stress level, which is manifested as uniform and sparse stress fringes and a low optical path difference value.

[0123] In contrast, due to the lack of aluminum oxide and zirconium oxide, two important network strengthening and stabilizing components, in Comparative Example 1, although its visible light transmittance did not drop significantly, its critical impact resistance height was significantly lower than that of Example 1, and the residual stress level (judged by optical path difference and qualitative description) increased. This reveals the positive role of aluminum oxide and zirconium oxide in improving the mechanical properties of the glass matrix and assisting in the uniform release of stress; their absence makes it difficult for the glass to achieve a low stress state and high impact resistance comparable to that of Example 1 under the same rapid annealing conditions. Furthermore, the content of the main oxides in Comparative Example 2 is lower than the appropriate range, resulting in its various performance indicators being significantly inferior to those of Example 1, manifested as the lowest impact strength, lower transmittance, and high and unevenly distributed residual stress.

[0124] The sample from Comparative Example 3 demonstrates that even when the content of specific added components (alumina and zirconia) exceeds a certain upper limit, it can adversely affect the final performance, with both impact resistance and residual stress control inferior to those of Example 1. This further confirms that the precise control of glass component selection in the present invention is a key factor in achieving the expected high performance. Comprehensive data from Test Example 1 demonstrates that simply adding or increasing a component is not enough to improve performance; rather, a comprehensive formulation with a precise balance between components and a high degree of compatibility with the subsequent specific rapid annealing process is required.

[0125] Test Example 2: Experimental samples: This experiment uses the following five groups of glass samples prepared according to the above method: Example 1, Comparative Example 4, Comparative Example 5, Comparative Example 6, Comparative Example 7. For each group of samples, specimens having the same size and surface treatment state (eg, cut and polished plates of 100 mm x 100 mm x 5 mm) were prepared.

[0126] Experimental steps: Impact resistance test: same as in Test Example 1.

[0127] Data recording and processing: Repeat the above steps for all samples in each sample group; Record the critical impact height of each specimen. Calculate the average critical impact height of each group of samples and record the original data points.

[0128] The optical transmittance test is the same as that of Test Example 1.

[0129] Data recording and processing: Measure multiple samples in each group of samples or different positions of the same sample, and record their average visible light transmittance.

[0130] Residual stress level assessment: Same as Test Case 1.

[0131] Qualitative description and semi-quantitative evaluation: Same as Test Example 1, record the qualitative description of stress fringes and measure the optical path difference (OPD) at key observation points.

[0132] Data recording and processing: The qualitative description of the stress fringes of each group of samples was recorded, and the maximum optical path difference value measured at the key observation points was recorded. The experimental results are shown in Table 2.

[0133] Table 2: Comparative test data of the effects of step S3 treatment on glass sample performance From Table 2, we can get: Example 1, which has undergone a complete S3 treatment including electromagnetic excitation, acoustically assisted relaxation, spatiotemporal modulation, and precision programmed cooling, exhibits excellent impact resistance (the highest average critical impact height), extremely low internal residual stress (the optical path difference is the smallest and the stress fringes are almost invisible), and excellent optical transmittance.

[0134] Although its optical transmittance is acceptable, its impact resistance drops sharply and the internal residual stress level is extremely high, which is manifested as dense and colorful stress stripes and significant optical path difference values. This intuitively reflects that without the assistance of an external physical field, it is difficult to fully eliminate the permanent stress inside the glass within the framework of rapid annealing by relying solely on programmed cooling. Further observing the results of Comparative Examples 6 and 7, they respectively applied only electromagnetic excitation or only acoustic-assisted relaxation in the S3 step (both in conjunction with spatiotemporal modulation and programmed cooling). Although the performance of these two groups of samples is better than that of Comparative Example 4, showing the positive effect of a single physical field on stress release, their impact resistance and residual stress control level failed to reach the level of Example 1.

[0135] Although the sample in Comparative Example 5 also applied electromagnetic excitation and acoustically assisted relaxation, along with the same programmed cooling, its physical field parameters were fixed, without dynamic adjustment based on the real-time state of the glass. The results showed that its impact resistance and residual stress control were inferior to those of Example 1, although superior to those of Comparative Example 4. This demonstrates that even with the introduction of multiple physical fields, the lack of intelligent spatiotemporal modulation can still limit annealing effectiveness.

[0136] Test Example 3: Experimental samples: This experiment uses the following four groups of glass samples prepared according to the above method: For the samples of Example 1, Comparative Example 8, Comparative Example 9, and Comparative Example 10, each group of samples had specimens with the same size and surface treatment state (for example, a cut and polished plate of 100 mm x 100 mm x 5 mm).

[0137] Experimental steps: Impact resistance test, the steps are the same as those in Test Example 1.

[0138] Data recording and processing: Repeat the above steps for all samples in each sample group; Record the critical impact height of each specimen. Calculate the average critical impact height of each group of samples and record the original data points.

[0139] Optical transmittance test: The steps are the same as those in Test Example 1.

[0140] Data recording and processing: Measure multiple samples in each group of samples or different positions of the same sample, and record their average visible light transmittance.

[0141] Residual stress level assessment: Same steps as Test Case 1.

[0142] Sample observation: The steps are the same as those in Test Example 1.

[0143] Qualitative description and semi-quantitative evaluation: The steps are the same as those in Test Example 1. The qualitative description of the stress fringes is recorded and the optical path difference (OPD) is measured at key observation points.

[0144] Data recording and processing: The qualitative description of the stress fringes of each group of samples was recorded, and the maximum optical path difference value measured at the key observation points was recorded. The experimental results are shown in Table 3.

[0145] Table 3: Comparative test data of the effects of various heat treatment stages on glass sample properties in the overall rapid annealing process From Table 3 we can get: The sample of Example 1 completely executed all the optimized processes including the initial rapid cooling of step S2, the specific programmed cooling rate of the core annealing stage of step S3, and the final rapid cooling of step S4. It showed the highest critical height of impact resistance, excellent average transmittance of visible light, and the lowest and most evenly distributed internal residual stress. This shows that the full-process heat treatment scheme designed by the present invention can work synergistically to maximize the advantages of each stage. In particular, the initial rapid cooling of step S2 lays a uniform and favorable thermal state starting point for the subsequent S3 precision annealing, avoids potential problems that may be caused by the glass staying in the high temperature section for too long, and improves the process connection efficiency. The subsequent final rapid cooling of step S4 effectively "freezes" the low stress state achieved in the S3 stage and maintains it to room temperature, preventing the introduction of new stresses due to improper thermal gradients during the subsequent cooling process.

[0146] The results of Comparative Example 8 show that when the primary glass product is cooled to the starting annealing temperature in step S3 by direct slow cooling, the impact resistance and residual stress control of the final product are inferior to those of Example 1. Similarly, in Comparative Example 9, although the S3 treatment is the same as that in Example 1, a very slow final cooling rate is used in step S4, and the impact resistance and residual stress control effects are also significantly inferior to those of Example 1.

[0147] Finally, the results of Comparative Example 10 highlight the importance of precise control of the programmed cooling rate during the core annealing phase, step S3. Although electromagnetic excitation and acoustically assisted relaxation were also applied in step S3, the cooling rate during the critical stress relaxation phase was set too fast, resulting in a significant decrease in impact resistance and a significant increase in internal residual stress levels, far inferior to those in Example 1.

[0148] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology, characterized in that: The following steps are involved: S1. Selecting glass raw materials, melting, clarifying, and homogenizing the glass raw materials in a high-temperature melting furnace to prepare a glass melt, and then manufacturing the glass melt into a primary glass product; S2. performing an initial rapid cooling treatment on the obtained primary glass product to reduce its temperature from a high temperature state after forming to a preset annealing temperature; S3. performing a spatiotemporal multi-physics coordinated annealing treatment on the primary glass product that has undergone the initial rapid cooling treatment, wherein the treatment process comprises synergistically applying electromagnetic excitation and acoustically assisted relaxation in combination with programmed cooling while cooling the primary glass product from the upper annealing temperature limit to a preset strain point temperature range; S4. Performing a final rapid cooling treatment on the primary glass product that has undergone the spatiotemporal modulation multi-physical field coordinated annealing treatment to room temperature, thereby obtaining a high-transmittance and impact-resistant glass.

2. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: The glass raw material includes the following components in parts by weight: Silicon dioxide: 60-75 parts; At least one selected from sodium oxide: 8-16 parts and potassium oxide: 0-8 parts, and the total amount is 10-20 parts; At least one selected from calcium oxide: 5-15 parts and magnesium oxide: 1-8 parts, and the total amount is 5-18 parts; 0.5-5 parts of aluminum oxide and / or 0.1-3 parts of zirconium oxide are added.

3. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: The steps of melting, clarifying and homogenizing the glass raw materials in a high-temperature melting furnace include: Adding 0.05-1.0 parts by weight of a clarifier, and melting at a melting temperature of 1450-1600° C. for 4-8 hours to form a glass melt; The smelting temperature is maintained for 2-4 hours for clarification, and then the smelting temperature is maintained for 2-4 hours for homogenization.

4. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: The preset upper limit of the annealing temperature is 500-600°C.

5. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: In the spatiotemporal modulation multi-physical field coordinated annealing treatment step, the preset strain point temperature range corresponds to a temperature of 450-550°C.

6. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: In the spatiotemporal modulation multi-physics field collaborative annealing process, the step of applying electromagnetic excitation includes: Applying a radio frequency field or a microwave field with a frequency in the range of 1 MHz to 10 GHz to the primary glass product; applying the electromagnetic excitation in a pulse modulation manner, with a pulse width of 1 microsecond to 100 milliseconds and a duty cycle of 10% to 80%; The average input power density of the electromagnetic excitation is controlled at 0.01-1 W / cm 3 , or the temperature rise rate caused by electromagnetic excitation is controlled at 1-5℃ / min; Among them, the local unit volume absorbed power density P abs (r,t) can be represented by the following formula: P abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 ; Among them, P abs (r, t) is the power density per unit volume absorbed by the glass at position r and time t; f e is the electromagnetic field frequency;∈0 is the vacuum dielectric constant;∈″(f e ,T(r,t)) is the glass at frequency f e and dielectric loss factor at temperature T(r,t); |E(r,t)| 2 is the electromagnetic field strength amplitude at position r and time t.

7. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: In the spatiotemporal modulation multi-physics field collaborative annealing process, applying acoustically assisted relaxation specifically includes: Apply ultrasonic waves with a frequency of 20kHz to 2MHz to the primary glass product, and control the sound intensity to be 1-50W / cm 2 within the scope; Among them, the stress relaxation characteristic time τ relax It can be represented by the following formula: t relax =η(T,W a ) / G; Among them, τ relax is the stress relaxation characteristic time; η(T,W a ) is the effective viscosity of the glass, which is the temperature T and the sound field energy density W a function; G is the shear modulus of glass.

8. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: In the spatiotemporal modulation multi-physics field collaborative annealing process, the spatiotemporal modulation includes: Dynamically adjusting the parameters of the electromagnetic excitation, the parameters of the acoustically assisted relaxation, and the rate of the programmed cooling through a feedback or feedforward control system according to the real-time temperature distribution and / or internal stress development state of the primary glass product during the annealing process; The electromagnetic excitation and the acoustic-assisted relaxation are performed synchronously in time, partially overlapped in time, or successively in time.

9. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: The programmed cooling adopts a multi-step cooling curve or a nonlinear cooling curve, and in the key stage of cooling from the upper limit of the annealing temperature to the strain point temperature range, the cooling rate is controlled at 0.2-2°C / min.

10. The method for preparing high-transmittance and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that: The method further comprises performing surface post-treatment on the obtained high-transmittance and impact-resistant glass after the final rapid cooling treatment, wherein the surface post-treatment comprises chemically etching the high-transmittance and impact-resistant glass, using an etchant of 1-5 vol% hydrofluoric acid solution for a treatment time of 30 seconds to 5 minutes.

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