A method for preparing high-transparency impact-resistant glass based on a rapid annealing technique

Abstract

The application relates to the field of glass manufacturing, and discloses a high-transmittance impact-resistant glass preparation method based on a rapid annealing technology, S1, specific glass raw materials are selected, primary glass products are prepared after high-temperature melting, clarification and homogenization; S2, initial rapid cooling is applied to the primary products, and the primary products are rapidly cooled to a preset annealing temperature; S3, in the interval from the upper limit of annealing to the strain point, the products are subjected to time-space conditioning, electromagnetic excitation and acoustic auxiliary relaxation are applied thereto, and precise programmed cooling is combined; S4, the products subjected to the cooperative annealing are subjected to final rapid cooling to room temperature, and the high-transmittance impact-resistant glass is obtained. The application adopts specific glass components, and combines the innovative electromagnetic and acoustic time-space conditioning multi-physical field cooperative rapid annealing technology, so that the comprehensive performance of the glass is efficiently improved, the annealing period is greatly shortened, the energy consumption is reduced, and uniform ultra-low residual stress is realized.

Description

Technical Field

[0001] This invention relates to the field of glass manufacturing technology, and in particular to a method for preparing high-transparency and impact-resistant glass based on rapid annealing technology. Background Technology

[0002] As a fundamental and widely used material, glass inevitably experiences internal stress due to temperature differences during its molding and cooling process. If these stresses are not properly managed, they will significantly reduce the mechanical strength of the glass, making it prone to breakage during use and potentially adversely affecting its optical uniformity and stability. Therefore, annealing, a crucial step in glass manufacturing, aims to eliminate or reduce these harmful permanent internal stresses to the greatest extent possible through specific heat treatment processes, optimizing the glass's microstructure and thus endowing glass products with superior mechanical properties, thermal stability, and optical quality to meet increasingly stringent application requirements.

[0003] Currently, the common practice for glass annealing is based on the traditional heat-driven principle. This method typically involves heating the glass to its upper limit of annealing temperature (generally slightly above the glass's strain point) and holding it at that temperature for a period of time to allow the glass network structure to relax, thereby releasing internal stress. Subsequently, through a carefully controlled, usually very slow, cooling process, the glass smoothly passes through the strain point and glass transition temperature range, eventually cooling to room temperature. In some cases, to improve the annealing effect or adapt to specific glass types, strategies such as segmented cooling or adjusting the holding time are also employed.

[0004] While existing technologies can eliminate internal stress in glass to some extent through prolonged heat treatment, several shortcomings remain. Traditional annealing processes often suffer from extremely long processing cycles, directly leading to low production efficiency and high energy consumption per unit product, making it difficult to meet the demands of modern industrial production for high efficiency and low cost. Furthermore, relying solely on thermal energy for stress relaxation is insufficient to completely eliminate internal stress under rapid cooling conditions. For specialty glasses requiring high impact resistance and high optical transmittance, traditional methods have limited ability to precisely control stress distribution uniformity and achieve extremely low residual stress levels in a short time, often failing to completely avoid potential impacts on optical uniformity while improving mechanical properties. Simultaneously, traditional processes promote the relaxation of the glass's internal structure relatively slowly, failing to fully utilize the material's inherent response to other physical stimuli (such as electromagnetic or acoustic fields) to accelerate this process, thus limiting further improvements in annealing efficiency and final product performance. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing high-transparency 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 internal stress and obtaining excellent comprehensive performance in glass annealing technology in a short time.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing high-transparency and impact-resistant glass based on rapid annealing technology, comprising the following steps:

[0007] S1. Select glass raw materials, melt, clarify and homogenize the glass raw materials in a high-temperature melting furnace to prepare glass melt, and then make the glass melt into primary glass products;

[0008] S2. The obtained primary glass product is subjected to an initial rapid cooling treatment to reduce its temperature from the high temperature state after molding to the preset annealing temperature.

[0009] S3. Perform time-controlled multi-physics field synergistic annealing on the primary glass product after the initial rapid cooling treatment. This process involves applying electromagnetic excitation and acoustic-assisted relaxation in synergistically while cooling the primary glass product from the upper limit of the annealing temperature to a preset strain point temperature range, combined with programmed cooling.

[0010] S4. The primary glass product that has undergone the time-controlled multi-physics field synergistic annealing process is subjected to a final rapid cooling treatment to room temperature to obtain high-transparency and impact-resistant glass.

[0011] In summary, the present invention has at least one of the following beneficial technical effects:

[0012] 1. This invention, by employing a specific glass raw material composition ratio and combining it with an innovative time-controlled multi-physics field synergistic rapid annealing technology, can significantly improve the overall performance of the final glass products, particularly their impact resistance and optical transmittance. This performance improvement stems from the superior response characteristics of specific components to multi-physics fields (such as electromagnetic excitation and acoustic assistance), allowing for more effective optimization of the glass's microstructure and more thorough elimination of internal stress during rapid annealing, thereby achieving an ideal combination of high light transmittance and high impact resistance.

[0013] 2. The overall rapid annealing process proposed in this invention significantly shortens the total heat treatment time of glass by introducing innovative steps such as initial rapid cooling, core multi-physics field-assisted precision annealing, and final rapid cooling. Compared with the traditional lengthy annealing process, this invention can significantly improve production efficiency and reduce energy consumption per unit product, thereby bringing considerable economic benefits. This is due to the high integration and optimization of the entire heat treatment process, as well as the significantly accelerated stress relaxation rate under the assistance of physical fields.

[0014] 3. The core step of this invention, the "time-controlled multi-physics field synergistic annealing treatment," particularly its dynamic control strategy based on real-time glass state feedback, enables more precise control over the internal stress distribution of the glass, resulting in glass products with extremely low and highly uniform residual stress. This intelligent annealing process ensures thorough and uniform stress relaxation, avoiding the problems of uneven stress or incomplete stress elimination that may occur in traditional processes, thereby improving the stability and reliability of the product. This represents a significant improvement over traditional fixed-procedure annealing.

[0015] 4. This invention, through the innovative synergistic application of multi-physics fields (electromagnetic excitation and acoustic assistance) in the key stages of glass annealing, can more effectively promote viscoelastic flow and structural relaxation within the glass, thereby achieving or even surpassing the stress relief levels achievable only through traditional long-term annealing in a shorter time. This synergistic mechanism enables the effective viscosity of the glass to be efficiently reduced even under rapid cooling conditions, accelerating the stress relaxation characteristic time and ultimately endowing the glass products with excellent mechanical properties and internal quality. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the method flow of the present invention. Detailed Implementation

[0017] The following is in conjunction with the appendix Figure 1 The present invention will be further described in detail below.

[0018] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0019] This invention provides a method for preparing high-transparency and impact-resistant glass based on rapid annealing technology. It uses specific glass components and combines innovative electromagnetic and acoustic time-controlled multi-physics field synergistic rapid annealing technology to efficiently improve the overall performance of the glass, significantly shorten the annealing cycle, reduce energy consumption, and achieve uniform ultra-low residual stress.

[0020] like Figure 1 As shown, the method for preparing high-transparency and impact-resistant glass based on rapid annealing technology may include the following steps:

[0021] The core objective of S1 is to prepare a high-quality glass melt with uniform chemical composition, consistent physical properties, and minimal defects, and to preliminarily shape it into primary glass products required for subsequent processing. This step specifically includes the following key steps:

[0022] First, the glass raw materials are precisely selected and formulated. By weight, the main glass raw materials include:

[0023] As the main component of the glass network forging, 60-75 parts of silicon dioxide are selected. Silicon dioxide is the basis for forming the glass framework, and its content directly affects the structural stability and basic physicochemical properties of the glass, such as hardness, chemical stability, and coefficient of thermal expansion.

[0024] Alkali metal oxides are introduced as network modifiers to adjust the melting characteristics, forming properties, and certain physicochemical properties of the final product of glass. The alkali metal oxides are selected from at least one of sodium oxide and potassium oxide. If sodium oxide is used, its dosage is 8-16 parts; if potassium oxide is used, its dosage is 0-8 parts. Regardless of whether one or both are chosen, the total dosage of alkali metal oxides is controlled within the range of 10-20 parts. The introduction of alkali metal oxides can effectively reduce the melting temperature and viscosity of glass, which is beneficial to the melting process, and also affects the refractive index and density of the glass.

[0025] Meanwhile, to further optimize the glass's properties, particularly its mechanical properties and chemical stability, alkaline earth metal oxides were introduced as network modifiers. These alkaline earth metal oxides were selected from at least one of calcium oxide and magnesium oxide. If calcium oxide was used, its dosage was 5-15 parts; if magnesium oxide was used, its dosage was 1-8 parts. Similarly, regardless of whether one or two combinations were chosen, the total dosage of alkaline earth metal oxides was controlled within the range of 5-18 parts. Alkaline earth metal oxides can improve the glass's hardness, hydrolysis resistance, and structural stability at high temperatures to a certain extent.

[0026] Furthermore, to further enhance the overall performance of the glass, such as increasing its mechanical strength, improving its chemical durability, or adjusting its optical properties, 0.5-5 parts of alumina and / or 0.1-3 parts of zirconium oxide can be selectively added. Alumina, as an intermediate oxide, can enhance the bonding strength of the glass network and improve its hardness and chemical stability; the addition of zirconium oxide can significantly improve the flexural strength and fracture toughness of the glass.

[0027] In practice, the raw materials selected are preferably of high purity, such as analytical grade or industrial high-purity chemical reagents, to reduce the impact of harmful impurities on glass quality. For example, silica can be derived from high-purity quartz sand, and other metal oxides can be derived from their corresponding high-purity compounds such as carbonates, nitrates, or oxides. All raw materials should preferably be thoroughly dried before use to remove adsorbed moisture and prevent the introduction of unnecessary bubbles or interference with the chemical reaction process during high-temperature melting.

[0028] After the glass raw materials are proportioned and prepared, the high-temperature melting stage begins. This stage is the core process of transforming solid powdered raw materials into a homogeneous liquid glass melt, specifically including three sub-steps: melting, clarification, and homogenization. The thoroughly mixed glass batch (mechanical mixing, such as using a V-type mixer or ball mill, to ensure uniform distribution of components at the microscale) is placed in a suitable high-temperature furnace. In the melting sub-step, to effectively remove bubbles from the glass melt and improve the transparency of the final glass, a suitable amount of clarifying agent is usually added to the batch, typically 0.05-1.0 parts by weight. The type of clarifying agent can be selected based on the glass composition and melting process. Examples include sulfates (such as sodium sulfate), halides, or oxides with variable valence elements (such as antimony trioxide, cerium dioxide, etc.). At high temperatures, these agents promote the coalescence, rising, and escape of small bubbles by decomposing to generate gas, changing the surface tension of the melt, or undergoing redox reactions. Subsequently, the crucible containing the batch material and clarifying agent (preferably made of a high-temperature resistant material that does not contaminate the molten glass, such as a platinum crucible or a high-silica crucible) is heated in a high-temperature melting furnace. The heating process can be programmed, raising the temperature at a certain rate (e.g., preferably 5-10°C / min to avoid damage to the crucible or material splashing due to excessively rapid heating) to a preset melting temperature, which is set in the range of 1450°C-1600°C. After reaching the melting temperature, it is held at that temperature for 4-8 hours. Under such high temperatures and sufficiently long holding times, the components in the glass batch undergo complex physicochemical reactions, gradually transforming into a viscous liquid state, thus forming the initial glass melt. This process aims to ensure that all raw material particles are completely melted and initially mixed.

[0029] The next step is a clarification process. The purpose of clarification is to further eliminate residual microbubbles in the glass melt, which are among the main defects affecting the optical quality of the glass. Clarification is typically carried out at the aforementioned melting temperature (1450℃-1600℃) for 2-4 hours. During this stage, the clarifying agent plays a crucial role in promoting bubble elimination. To enhance the clarification effect, in some cases, gentle mechanical stirring or control of the melting atmosphere may be used.

[0030] Following the clarification process, a homogenization sub-step is performed. The purpose of homogenization is to eliminate any potential chemical inhomogeneities (such as streaks or inclusions) and temperature inhomogeneities within the glass melt, thereby obtaining a glass melt with highly consistent physicochemical properties. This is crucial for subsequent forming and the final properties of the glass. Homogenization is typically carried out slightly below the main melting temperature; specifically, the temperature of the glass melt is adjusted and maintained within the range of 1400℃-1500℃ for 2-4 hours. During homogenization, extending the holding time or employing specific stirring methods (e.g., using a platinum stirrer at low speed) can promote mass migration and energy transfer within the melt, thus achieving a highly homogeneous state.

[0031] The final step in step S1 is to form the prepared glass melt into primary glass products. This process involves giving the molten glass a specific shape and size to facilitate subsequent rapid annealing. Molding (pouring the glass melt into a preheated mold and pressing it into shape) or casting (pouring the glass melt onto a flat plate and allowing it to flow and level naturally) can be used. For industrial production, continuous or semi-continuous forming processes such as float glass, calendering, and blowing can be considered.

[0032] In this embodiment, step S2, which involves initial rapid cooling of the primary glass product obtained in step S1, aims to quickly and controllably cool the primary glass product, which has just been removed from the high-temperature forming state, to a preset temperature range suitable for subsequent precision annealing, i.e., near the upper limit of the annealing temperature. This step is a crucial transitional link between high-temperature forming and precision annealing, and is of great significance for ensuring the performance of the final glass product.

[0033] Specifically, after step S1, the resulting primary glass product is still at a relatively high temperature, typically much higher than the annealing temperature range where its structure begins to solidify and stress relaxation can be effectively achieved. Directly cooling this high-temperature product slowly or subjecting it to a complex time-controlled annealing process could not only lead to a lengthy processing cycle but also potentially cause undesirable structural changes such as devitrification due to prolonged exposure to unsuitable temperature ranges, or generate uncontrollable initial thermal stress. Therefore, the "initial rapid cooling treatment" employed in step S2 is particularly necessary.

[0034] The "initial rapid cooling process" aims to quickly reduce the overall temperature of the primary glass product from its post-forming high temperature at a relatively fast cooling rate. "Rapid" here refers to the extremely slow cooling rate compared to traditional annealing processes; the goal is to efficiently bring the glass product to the starting temperature point for subsequent precision annealing. Despite the rapid cooling, this process still needs to be controlled to avoid generating instantaneous thermal stress within the glass due to excessive temperature gradients, which could lead to cracking or damage. Preferably, the average cooling rate at this stage can be adjusted according to the thickness, geometry, and thermophysical properties of the glass product; for example, an average cooling rate of tens to two hundred degrees Celsius per minute can be used.

[0035] There are various ways to achieve initial rapid cooling. For example, hot primary glass products can be placed in an environment with forced convection cooling, and rapid cooling can be achieved by controlling the flow rate and temperature of the cooling medium (such as air). Another preferred method is to quickly move the primary glass products into a holding furnace or cooling chamber preheated to near or slightly above the upper limit of the annealing temperature, and use the temperature difference between the products and the environment for controlled rapid cooling.

[0036] The endpoint 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°C to 600°C. This temperature range, for the typical silicate-based high-transparency and impact-resistant glass involved in this invention, is generally above its glass transition temperature. In this temperature range, the internal structural units of the glass still possess a certain degree of mobility, sufficient for effective stress relaxation during subsequent annealing, but the viscosity of the glass is high enough to essentially maintain its post-forming shape. Cooling the primary glass product to near this upper limit of the annealing temperature ensures that subsequent steps can begin in an ideal and well-defined initial thermal state, which is crucial for achieving precise and efficient stress relief and structural optimization. The term "near" means that in actual operation, a small, acceptable fluctuation range is allowed around the target temperature.

[0037] In this embodiment, step S3, which involves applying a crucial time-controlled multi-physics field synergistic annealing treatment to the primary glass product after the initial rapid cooling process in step S2, is the core technical step in obtaining high-transparency and impact-resistant glass. The essence of this process lies in the innovative synergistic application of electromagnetic excitation and acoustic-assisted relaxation physical fields during the precise cooling of the primary glass product from the upper limit of the annealing temperature (preferably 500℃-600℃) to a preset strain point temperature range (preferably corresponding to 450℃-550℃). This is combined with a precise programmed cooling strategy to achieve deep stress elimination and microstructure optimization.

[0038] Specifically, when the primary glass product undergoes initial rapid cooling in step S2 and its overall temperature reaches near the upper limit of the annealing temperature, the synergistic annealing process in step S3 is initiated. This temperature range (from the upper limit of annealing 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 migration capability.

[0039] In time-controlled multiphysics synergistic annealing, the synergistic application of electromagnetic excitation plays a crucial role. Its purpose is not macroscopic heating of the glass, but rather to achieve subresonant interactions between electromagnetic fields with specific ionic groups, dipoles, or interfaces within the glass, thereby effectively perturbing or suppressing the formation and development of stress concentration regions at the microscopic level. This may also lower the energy barrier for structural unit migration, promoting rapid stress release in localized areas. Specifically, applying electromagnetic excitation involves applying radio frequency or microwave fields in the frequency range of 1MHz-10GHz to the primary glass product. This frequency range is chosen to ensure that electromagnetic energy can effectively couple with the dielectric response mechanism within the glass material.

[0040] Preferably, the electromagnetic excitation is applied via pulse modulation. Pulse modulation, for example, setting the pulse width to 1 microsecond to 100 milliseconds and the duty cycle to 10% to 80%, allows for the instantaneous application of high-energy perturbations to excite microstructural relaxation, while simultaneously providing the system with sufficient response and energy dissipation time during the pulse intervals, avoiding unnecessary overall temperature rise. Of course, continuous wave application can also be used under specific conditions.

[0041] To ensure that the electromagnetic excitation primarily functions as a microscopic disturbance rather than a macroscopic heating effect, the average input power density of the electromagnetic excitation is preferably controlled within the range of 0.01-1 W / cm². 3 The temperature rise rate of the glass caused directly by electromagnetic excitation is kept at a low level, or monitored to ensure that it is controlled within an extremely low range of 1-5℃ / min.

[0042] Its local unit volume absorbed power density P abs (r,t) can be characterized by the following formula:

[0043] P abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 ;

[0044] Among them, P abs (r,t) represents the power density absorbed per unit volume of the glass at position r and time t; f e ∈ 0 is the frequency of the electromagnetic field; ∈ 0 is the vacuum permittivity; ∈ ″ (fe T(r,t)) represents the glass at frequency f e The dielectric loss factor at temperature T(r,t); |E(r,t)| 2 Let r be the amplitude of the electromagnetic field strength at position r and time t. By adjusting these parameters, spatiotemporal selective control of energy input into the glass can be achieved.

[0045] Meanwhile, the coordinated application of acoustic-assisted relaxation is another key physical field technique in step S3. Its core function is to utilize high-frequency mechanical vibration energy to promote viscoelastic flow within the glass at both macroscopic and mesoscopic scales, accelerate the stress relaxation process, and help achieve a uniform distribution of residual stress throughout the entire volume of the glass product.

[0046] Applying acoustic-assisted relaxation specifically involves 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 within the glass material and produce significant mechanical effects.

[0047] The optimal sound intensity of ultrasound is controlled between 1-50 W / cm. 2 Within a certain range, appropriate sound intensity can provide enough energy to overcome the potential barrier for 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.

[0048] Stress relaxation characteristic time τ relax Its relationship with materials and sound fields can be conceptually characterized by the following formula: τ relax =η(T,W a ) / G;

[0049] Where, τ relax The characteristic time of stress relaxation; η(T,W) a ) represents the effective viscosity of the glass, which is related to temperature T and sound field energy density W. a The function is given by ; G is the shear modulus of the glass. This formula aims to illustrate that the input of acoustic energy helps to accelerate the relaxation process.

[0050] The aforementioned electromagnetic excitation and acoustic-assisted relaxation 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 non-linear cooling curve. Specifically, during the critical stress relaxation stage from the upper limit of the annealing temperature to the strain point temperature range, the cooling rate is strictly controlled at a low level of 0.2-2℃ / min. This slow and precise cooling rate provides the necessary time window for sufficient adjustment of the glass's internal structure and effective stress release, avoiding the reintroduction or "freezing" of new stress due to excessively rapid cooling.

[0051] Furthermore, the core of step S3 lies in the implementation of time-controlled cooling. The parameters of electromagnetic excitation (such as frequency, power, pulse parameters, field distribution, etc.), the parameters of acoustic-assisted relaxation (such as frequency, sound intensity, action time, spatial distribution, etc.), and the programmed cooling rate are not fixed, but are dynamically adjusted according to the real-time state of the primary glass product during the annealing process.

[0052] This time-temperature control specifically includes: based on the real-time temperature distribution of the primary glass product during the annealing process (e.g., monitored by means of infrared thermal imagers) and / or the internal stress development state (e.g., preliminarily assessed by online polarizers or predicted based on models), a preferred feedback or feedforward control system is used to dynamically and collaboratively adjust the applied parameters of the aforementioned physical fields and the cooling curves.

[0053] For example, when the temperature is high and the viscosity is low in the early stage of annealing, a physical field with a certain combination of parameters 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 obtained throughout the entire annealing range.

[0054] Furthermore, the temporal coordination between electromagnetic excitation and acoustic-assisted relaxation is also adjustable. It can be performed synchronously, partially overlapped, or sequentially according to specific needs, in order to achieve optimal coupling of different physical field effects.

[0055] In this embodiment, step S4, which is to perform a final rapid cooling treatment to room temperature on the primary glass product that has undergone the air-conditioning multi-physics field synergistic annealing treatment in step S3, is the final step in the entire preparation process. Its core objective is to safely and efficiently cool the glass product, which has undergone precise stress control and structural optimization, from the lower limit temperature of the annealing region (i.e., the strain point temperature range) to the ambient temperature, while maintaining the low stress state and excellent microstructure obtained in step S3 to the maximum extent, so as to finally obtain the expected high-transparency and impact-resistant glass.

[0056] Specifically, after completing the time-controlled multiphysics synergistic annealing treatment in step S3, the permanent stress inside the primary glass product has been significantly eliminated or reduced to an extremely low level, and its microstructure tends to be uniform and stable. At this point, the glass product is typically near its strain point temperature, which is a critical state. Below this temperature, the glass behaves more like an elastic solid, the migration ability of its internal structural units decreases significantly, and once new permanent stress is formed, it is difficult to eliminate through its own relaxation. Therefore, the subsequent cooling process starting from this temperature point is crucial for maintaining the excellent properties already obtained.

[0057] The "final rapid cooling" strategy employed in step S4 is "rapid" in contrast to the programmed slow cooling in step S3, which occurs within the range from the upper limit of the annealing temperature to the strain point temperature. After the critical stress relaxation phase has been completed, continuing with an excessively slow cooling rate is unnecessary and may even prolong the production cycle. More importantly, in the temperature range below the strain point, improper cooling, such as significant and prolonged temperature gradients between different parts of the glass product, can reintroduce non-negligible temporary thermal stresses due to asynchronous shrinkage, and in some cases, even transform into new permanent residual stresses, although their magnitude is usually much smaller than the original stresses without annealing. Therefore, a controlled rapid cooling method is employed to allow the glass product as a whole to pass through this temperature range dominated by elastic behavior as quickly and relatively uniformly as possible, thereby reducing the chance and magnitude of new stress generation.

[0058] 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 can be used, such as using a filtered, temperature-controlled flow of air or inert gas to purge the glass surface. The flow rate, temperature, and purging method of the cooling medium can be optimized to ensure that the surface and interior temperatures of the glass product decrease as synchronously as possible, avoiding excessively large instantaneous temperature gradients.

[0059] The final step of the entire rapid cooling process is to reduce the temperature of the glass product to "room temperature." Room temperature usually refers to the ambient operating temperature, such as 20°C-25°C.

[0060] Example 1:

[0061] Step S1: Selection of glass raw materials, melt preparation and primary glass product forming:

[0062] The glass raw materials selected include, by weight, the following components:

[0063] Silicon dioxide: 67.5 parts; Sodium oxide: 10 parts; Potassium oxide: 5 parts (total 15 parts); Calcium oxide: 7 parts; Magnesium oxide: 4.5 parts (total 11.5 parts); Aluminum oxide: 2.75 parts; Oxide: 1.55 parts; Clarifying agent (mixture of antimony trioxide and sodium nitrate): 0.525 parts

[0064] The thoroughly mixed glass raw materials are placed in a platinum crucible and then fed into a high-temperature melting furnace.

[0065] Melting process: The temperature is increased to 1525°C at a rate of about 8°C / min and held at this melting temperature for 6 hours to form a glass melt.

[0066] Clarification treatment: Continue to hold at 1525℃ for 3 hours to fully eliminate air bubbles in the glass melt.

[0067] Homogenization treatment: The temperature of the glass melt is then adjusted to 1450℃ and held at this temperature for 3 hours. At the same time, low-speed platinum stirring can be used to ensure a high degree of uniformity in the chemical composition and temperature of the glass melt.

[0068] After homogenization, the resulting uniform glass melt is molded into primary glass products of predetermined size and shape, such as glass plates with a thickness of 5 mm.

[0069] Step S2, Initial rapid cooling process:

[0070] The hot primary glass product obtained in step S1 is rapidly cooled from the forming temperature (e.g., about 1000°C). This process involves moving the product into a cooling device preheated to near the upper limit of the annealing temperature, and using controlled forced air convection to reduce its temperature to around 550°C at an average rate of about 100°C / minute, which is the preset upper limit of the annealing temperature in this embodiment.

[0071] Step S3, Time-controlled multi-physics field synergistic annealing:

[0072] For primary glass products that have undergone initial rapid cooling, a multi-physics field synergistic annealing process is performed from 550°C (the upper limit of the annealing temperature) to a preset strain point temperature of 500°C.

[0073] Electromagnetic excitation application: During this cooling process, a pulse-modulated microwave field is applied to the primary glass product.

[0074] Frequency: 2.45GHz.

[0075] Application method: pulse modulation, pulse width set to 50 milliseconds, duty cycle of 45%.

[0076] Power control: Average input power density is controlled at approximately 0.5 W / cm². 3 By precisely controlling the electromagnetic field strength distribution E(r,t) and considering the glass's real-time temperature T(r,t) and frequency f... e The dielectric loss factor ∈ ″ (f e ,T(r,t)), according to formula P abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 ;

[0077] Among them, P abs (r,t) represents the power density absorbed per unit volume of the glass at position r and time t; f e∈ 0 is the frequency of the electromagnetic field; ∈ 0 is the vacuum permittivity; ∈ ″ (f e T(r,t)) represents the glass at frequency f e The dielectric loss factor at temperature T(r,t); |E(r,t)| 2 The amplitude of the electromagnetic field strength at position r and time t is used to regulate the local power density absorbed per unit volume, aiming at microscopic perturbation rather than significant macroscopic heating.

[0078] Acoustic-assisted relaxation application: Applying ultrasound simultaneously or in a specific sequence.

[0079] Frequency: 1MHz.

[0080] Sound intensity control: The sound intensity of the ultrasound is controlled at approximately 25.5 W / cm². 2 This acoustic energy input is designed to reduce the effective viscosity η(T,W) of the glass. a This accelerates stress relaxation and shortens the stress relaxation characteristic time τ. relax =η(T,W a ) / G; where τ relax The characteristic time of stress relaxation; η(T,W) a ) represents the effective viscosity of the glass, which is related to temperature T and sound field energy density W. a The function is ; G is the shear modulus of the glass.

[0081] Programmed cooling: Using a multi-step or smooth nonlinear cooling curve, the average cooling rate is strictly controlled at 1.1℃ / minute during the critical stress relaxation stage of cooling from 550℃ to 500℃.

[0082] Time-based control: Throughout the S3 process, real-time state parameters of the primary glass product are acquired through an online monitoring system (e.g., an infrared thermal imager to monitor temperature distribution and a polarizing stress meter to preliminarily assess stress state). Based on these parameters, the pulse parameters and power of the electromagnetic excitation, the acoustic intensity and timing of the acoustic-assisted relaxation, and the specific rate curve of the programmed cooling are dynamically adjusted through feedback or feedforward control logic. The application of electromagnetic excitation and acoustic-assisted relaxation can be performed synchronously, partially overlapping, or sequentially, depending on the optimization scheme.

[0083] Step S4, Final rapid cooling process:

[0084] Once the temperature of the primary glass product reaches 500°C (near the strain point temperature), the air-conditioning-controlled multi-physics synergistic annealing process is stopped, and a final rapid cooling process is immediately initiated. Forced air convection is used to cool it to room temperature (e.g., 25°C) at an average rate of approximately 30°C / minute, resulting in high-transparency, impact-resistant glass.

[0085] Optional follow-up steps: If necessary, the resulting high-transparency and impact-resistant glass can be post-treated, for example, by chemical etching with a 3 vol% hydrofluoric acid solution for 2.5 minutes, to further improve surface quality or specific properties.

[0086] Example 2:

[0087] This embodiment provides a method for preparing high-transparency 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 claims:

[0088] Step S1: Selection of glass raw materials, melt preparation and primary glass product forming

[0089] The glass raw materials selected include, by weight, the following components:

[0090] Silicon dioxide: 60 parts; Sodium oxide: 8 parts; Potassium oxide: 2 parts (total amount of alkali metal oxides is 10 parts); Calcium oxide: 5 parts; Magnesium oxide: 1 part (total amount of alkaline earth metal oxides is 6 parts); Aluminum oxide: 0.5 parts; Zirconia: 0.1 parts; Clarifying agent (mixture of antimony trioxide and sodium nitrate): 0.05 parts.

[0091] After the above raw materials are mixed evenly, they are placed in a corundum crucible and sent into a high-temperature melting furnace.

[0092] Melting treatment: Heat to 1450℃ and hold for 4 hours. Clarification treatment: Continue to hold at 1450℃ for 2 hours.

[0093] Homogenization treatment: Adjust the temperature to 1400℃ and keep it warm for 2 hours.

[0094] Subsequently, the molten glass is cast into primary glass products, such as thin sheets of a specific shape.

[0095] Step S2, Initial rapid cooling process:

[0096] The primary glass product is rapidly cooled from its post-forming high temperature 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, for example, at 80°C / minute.

[0097] Step S3, Time-controlled multi-physics field synergistic annealing:

[0098] For primary glass products, a multi-physics field synergistic annealing process is performed from 500℃ to a preset strain point temperature of 450℃ using air conditioning.

[0099] Electromagnetic excitation applied:

[0100] Frequency: 1MHz (RF range) selected.

[0101] Application method: pulse modulation, pulse width of 1 microsecond, duty cycle of 10%.

[0102] Power control: Average input power density is controlled at 0.01W / cm². 3 Its energy absorption also follows the P-law. abs (r,t)=2·π·f e ·∈0·∈″(f e ,T(r,t))·|E(r,t)| 2 The principle of;

[0103] Acoustic-assisted relaxation application:

[0104] Frequency: 20kHz.

[0105] Sound intensity control: The sound intensity is controlled at 1 W / cm. 2 The aim is to influence the effective viscosity η(T,W) through acoustic energy input. a and stress relaxation characteristic time τ relax .

[0106] Programmed cooling: During the critical stage of cooling from 500°C to 450°C, the average cooling rate is controlled at 0.2°C / minute.

[0107] Real-time cooling mechanism: Also based on real-time monitoring of the glass condition (temperature, stress indicators), the electromagnetic field, acoustic field parameters, and cooling rate are dynamically fine-tuned by the control system to ensure effective stress relaxation even under low parameter input conditions. Electromagnetic and acoustic excitation can be achieved, for example, by applying alternating pulses.

[0108] Step S4, Final rapid cooling process:

[0109] When the temperature of a glass product reaches 450°C, it is cooled to room temperature by means of natural convection in clean air (for thin and small products) or gentle forced air cooling to obtain high-transparency and impact-resistant glass.

[0110] Optional follow-up steps: The glass product can be flame polished or chemically etched with a 1 vol% hydrofluoric acid solution for 30 seconds.

[0111] Example 3:

[0112] This embodiment provides a method for preparing high-transparency and impact-resistant glass based on rapid annealing technology. The specific steps and parameters are as follows, focusing on the application of the upper limit of the claims:

[0113] Step S1: Selection of glass raw materials, melt preparation and primary glass product forming

[0114] The glass raw materials selected include, by weight, the following components:

[0115] Silicon dioxide: 75 parts; Sodium oxide: 16 parts; Potassium oxide: 4 parts (total alkali metal oxides: 20 parts); Calcium oxide: 15 parts; Magnesium oxide: 3 parts (total alkaline earth metal oxides: 18 parts); Aluminum oxide: 5 parts; Zirconia: 3 parts; Clarifying agent (e.g., a mixture of antimony trioxide and sodium nitrate) 1.0 part.

[0116] After the above raw materials are thoroughly mixed, they are placed in a high-purity quartz ceramic crucible and sent into a high-temperature melting furnace.

[0117] Melting treatment: Heat to 1600℃ and hold for 8 hours.

[0118] Clarification treatment: Continue to keep warm at 1600℃ for 4 hours.

[0119] Homogenization: Adjust the temperature to 1500℃ and keep it warm for 4 hours. This can be combined with efficient stirring.

[0120] Subsequently, the glass melt is formed into continuous primary glass strips or sheets by drawing or rolling.

[0121] Step S2, Initial rapid cooling process:

[0122] The primary glass product undergoes efficient initial rapid cooling from its post-forming high temperature state, reducing its temperature to 600°C, which serves as the upper limit of the preset annealing temperature for subsequent annealing. This process can employ a strong air quenching initial stage, with an average cooling rate reaching, for example, 150°C / minute or higher.

[0123] Step S3, Time-controlled multi-physics field synergistic annealing:

[0124] For primary glass products, a multi-physics field synergistic annealing process is performed from 600℃ to a preset strain point temperature of 550℃ using air conditioning.

[0125] Electromagnetic excitation applied:

[0126] Frequency: 10GHz (microwave high frequency band) is selected.

[0127] Application method: pulse modulation, pulse width of 100 milliseconds, duty cycle of 80%.

[0128] Power control: Instead of directly controlling the average input power density, the rate of glass temperature rise caused directly by electromagnetic excitation is controlled at 5°C / min by controlling the electromagnetic field parameters. The energy absorption mechanism still follows P abs (r,t) related formulas.

[0129] Acoustic-assisted relaxation application:

[0130] Frequency: 2MHz.

[0131] Sound intensity control: The sound intensity is controlled at 50W / cm². 2 A strong acoustic energy input promotes efficient stress relaxation.

[0132] Programmed cooling: During the critical stage of cooling from 600°C to 550°C, the average cooling rate is controlled at 2°C / minute.

[0133] Time-temperature control: Based on precise online sensing data of the internal temperature field and stress distribution of glass products (especially those that are large or have complex shapes), advanced control algorithms dynamically optimize the electromagnetic field distribution (e.g., using phased array antennas or multimode cavities), the focusing and scanning modes of the acoustic transducer array, and the spatiotemporal gradient of the cooling program to adapt to the requirements of rapid response and uniform processing under high parameter inputs. Electromagnetic and acoustic excitations can be applied in an efficient synchronous superposition manner.

[0134] Step S4, Final rapid cooling process:

[0135] When the temperature of the glass product reaches 550℃, a multi-stage controllable rate forced air cooling system is used to quickly and evenly cool it to room temperature, resulting in high-transparency and impact-resistant glass.

[0136] Optional follow-up steps: The glass product may be subjected to surface ion exchange enhancement treatment or chemical etching treatment with a 5 vol% hydrofluoric acid solution for 5 minutes to obtain specific surface properties.

[0137] Comparative Example 1: Compared with Example 1, the difference lies in the composition of the glass raw material: it does not contain alumina and zirconium oxide, and the amount of silicon dioxide is adjusted to 72.05 parts. The remaining steps and parameters are the same as in Example 1.

[0138] 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 in Example 1.

[0139] Comparative Example 3: Compared with Example 1, the difference lies in the composition of the glass raw materials in step S1: the amount of alumina 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 in Example 1.

[0140] Comparative Example 4: Compared with Example 1, the difference is that in step S3, no electromagnetic excitation or acoustic-assisted relaxation is 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.

[0141] Comparative Example 5: Compared with Example 1, the difference lies 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 ms, duty cycle 45%, average input power density 0.5 W / cm²) are different. 3 ), parameters of acoustic-assisted relaxation (frequency 1MHz, sound intensity 25.5W / cm²) 2 The programmed cooling rate (average 1.1°C / minute from 550°C to 500°C) is a fixed preset value and is not dynamically adjusted based on the real-time temperature distribution and / or internal stress development of the primary glass product during annealing. That is, the "time-based cooling" step is omitted. All other steps and parameters are the same as in Example 1.

[0142] Comparative Example 6: Compared with Example 1, the difference lies in step S3 (time-controlled multi-physics field synergistic annealing): In this step, only electromagnetic excitation is applied, and acoustic-assisted relaxation is not applied. The remaining steps and parameters are the same as in Example 1.

[0143] Comparative Example 7: Compared with Example 1, the difference lies in step S3 (time-controlled multi-physics synergistic annealing): in this step, only acoustic-assisted relaxation is applied, and electromagnetic excitation is not applied. The remaining steps and parameters are the same as in Example 1.

[0144] Comparative Example 8: Compared with Example 1, the difference is that step S2 (initial rapid cooling treatment) is omitted. That is, after the primary glass article is formed in step S1, it is directly and slowly cooled (e.g., at a rate of 10°C / min) to the upper limit of the annealing temperature of 550°C, and then steps S3 and S4 are performed exactly the same as in Example 1. The remaining steps and parameters are the same as in Example 1.

[0145] Comparative Example 9: The difference from Example 1 lies in step S4 (final rapid cooling treatment): In this step, instead of rapid cooling, the primary glass product is cooled from 500°C (near the strain point temperature) to room temperature at a very slow rate (e.g., 0.3°C / min, referring to the slow cooling section of a conventional annealing process). All other steps and parameters are the same as in Example 1.

[0146] Comparative Example 10: The difference from Example 1 is the rate of programmed cooling in step S3: a faster cooling rate, such as 5°C / minute, is used during the critical stress relaxation stage of cooling from 550°C to 500°C. All other steps and parameters are the same as in Example 1.

[0147] Test Example 1:

[0148] Experimental sample:

[0149] The following four groups of glass samples were selected for this experiment and prepared according to the aforementioned method: Sample 1 of Example; Sample 1 of Comparative Example; Sample 2 of Comparative Example; Sample 3 of Comparative Example; Each group of samples was prepared with specimens of the same size and surface treatment (e.g., 100mm x 100mm x 5mm cut and polished plates).

[0150] Experimental steps:

[0151] Impact resistance test (falling ball impact test):

[0152] Instrument Preparation: Prepare a falling ball impact testing machine equipped with a standard weight steel ball (e.g., 227 g or 500 g, depending on the expected strength of the sample). Ensure the testing machine platform is level and the support clamps are secure.

[0153] Sample placement: Place the sample to be tested horizontally on the sample support platform of the testing machine, ensuring that the placement position and support conditions are consistent each time, and select the impact point at the center of the sample.

[0154] Impact Test: Release a steel ball from a low initial height and allow it to fall freely and impact the center of the specimen. If the specimen does not break, gradually increase the drop height of the steel ball in fixed increments (e.g., 5 cm or 10 cm) and repeat the impact test. Record the drop height of the steel ball that causes the specimen to first crack or completely break; this height is the critical impact height of the specimen.

[0155] Data Recording and Processing: Repeat step c above for all specimens in each sample group, recording the critical impact height for each specimen. Calculate the average critical impact height for each sample group and record the raw data points.

[0156] Optical transmittance test:

[0157] Instrument preparation: Prepare the UV-Vis-NIR spectrophotometer. Perform instrument warm-up and baseline calibration.

[0158] Sample preparation: Select samples with clean surfaces and no obvious scratches.

[0159] Transmittance Measurement: Place the sample vertically into the sample chamber of the spectrophotometer, ensuring the light beam passes perpendicularly through the sample. Scan the transmittance of the sample within the visible light wavelength range (e.g., 400 nm to 700 nm). Record the average transmittance over the entire scan range, or the transmittance at a specific wavelength of interest (e.g., 550 nm).

[0160] Data recording and processing: Measure the average transmittance of visible light for multiple samples in each group of samples or different locations of the same sample.

[0161] Residual stress level assessment (polarizing stress meter method):

[0162] Instrument preparation: Prepare a transmission polarizing stress meter and adjust the light source and polarizer (usually in orthogonal polarization state).

[0163] Sample observation: Place the sample to be tested on the stage of the polarizer, between the polarizer and the analyzer. Observe the interference fringes, colors, densities, and distribution patterns (photoelastic fringes) formed by the polarized light passing through the sample.

[0164] Data recording and processing: The stress fringes of each group of samples were recorded qualitatively, and the maximum optical path difference measured at key observation points was also recorded. The experimental results are shown in Table 1.

[0165] Table 1: Data on the Influence of Glass Composition on Sample Properties under Rapid Annealing Process

[0166]

[0167]

[0168] From Table 1, we can obtain:

[0169] The sample of Example 1, with its carefully formulated glass raw material composition, exhibits a high critical height for impact resistance, excellent average transmittance of visible light, and a very low level of residual stress, manifested as uniform and sparse stress fringes and a low optical path difference value.

[0170] In contrast, Comparative Example 1, lacking two important network-reinforcing and stabilizing components—alumina and zirconium oxide—did not show a significant decrease in visible light transmittance, but its critical impact resistance height was significantly lower than that of Example 1, and its residual stress level (judged by optical path difference and qualitative description) was higher. This reveals the positive role of alumina 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 Example 1 under the same rapid annealing conditions. Furthermore, the content of the main oxides in Comparative Example 2 was below the suitable range, resulting in significantly inferior performance indicators compared to Example 1, manifested as the lowest impact strength, lower transmittance, and high and unevenly distributed residual stress.

[0171] The sample in Comparative Example 3 showed that when the content of certain added components (alumina and zirconium oxide) exceeded a certain upper limit, it could also adversely affect the final performance; its impact resistance and residual stress control were not as good as those in Example 1. This further confirms that the precise control of glass composition selection is one of the key factors in achieving the expected high performance. The data from Test Example 1 show that simply adding or increasing a certain component does not improve performance; rather, a precise balance between the components and a comprehensive formulation highly compatible with the subsequent rapid annealing process are required.

[0172] Test Example 2:

[0173] Experimental Samples: The following five groups of glass samples, prepared according to the aforementioned method, were selected for this experiment:

[0174] Example 1; Comparative Examples 4, 5, 6, and 7. Each group of samples was prepared with specimens of the same size and surface treatment (e.g., 100mm x 100mm x 5mm cut and polished plates).

[0175] Experimental steps:

[0176] Impact resistance test: Same as in test example 1.

[0177] Data recording and processing: Repeat the above steps for all samples in each group of samples;

[0178] Record the critical impact height for each specimen. Calculate the average critical impact height for each group of specimens and record the original data points.

[0179] The optical transmittance test is the same as in Test Example 1.

[0180] Data recording and processing: Measure the average transmittance of visible light for multiple samples in each group of samples or different locations of the same sample.

[0181] Residual stress level assessment: Same as in Test Example 1.

[0182] Qualitative description and semi-quantitative evaluation: Similar to Test Example 1, a qualitative description of the stress fringes was recorded, and the optical path difference (OPD) was measured at key observation points.

[0183] Data recording and processing: The stress fringes of each group of samples were recorded qualitatively, and the maximum optical path difference measured at key observation points was also recorded. The experimental results are shown in Table 2.

[0184] Table 2: Comparative test data on the impact of step S3 treatment on the properties of glass samples

[0185]

[0186]

[0187]

[0188] From Table 2, we can obtain:

[0189] Example 1, after undergoing a complete S3 process including electromagnetic excitation, acoustic-assisted relaxation, time-controlled air conditioning and precise programmed cooling, exhibits excellent shock resistance (highest average shock resistance critical height), extremely low internal residual stress (minimum optical path difference and almost invisible stress fringes) and excellent optical transmittance.

[0190] Although its optical transmittance was acceptable, its impact resistance decreased sharply, and its internal residual stress level was extremely high, manifested as dense and brightly colored stress fringes and significant optical path difference values. This intuitively reflects that, without the assistance of an external physical field, programmed cooling alone is insufficient to fully eliminate the permanent stress inside the glass within a rapidly annealed framework. Further observation of the results of Comparative Examples 6 and 7, which were achieved by applying only electromagnetic excitation or only acoustic-assisted relaxation (both combined with timed air conditioning and programmed cooling) in step S3, showed that while the performance of these two groups of samples was superior to that of Comparative Example 4, demonstrating the positive effect of a single physical field on stress release, their impact resistance and residual stress control levels failed to reach the level of Example 1.

[0191] Although Comparative Example 5 also applied electromagnetic excitation and acoustic-assisted relaxation, along with the same programmed cooling, its physical field parameters were fixed and not dynamically adjusted based on the real-time state of the glass. The results showed that its impact resistance and residual stress control were inferior to Example 1, although superior to Comparative Example 4. This indicates that even with the introduction of multiphysics, the annealing effect is still limited without intelligent time-space control.

[0192] Test Example 3:

[0193] Experimental Samples: The following four groups of glass samples, prepared according to the aforementioned method, were used in this experiment:

[0194] Samples of Example 1, Comparative Example 8, Comparative Example 9, and Comparative Example 10 were prepared. Each group of samples had specimens with the same size and surface treatment (e.g., a 100mm x 100mm x 5mm cut and polished plate).

[0195] Experimental procedure: Impact resistance test, the procedure is the same as that in test example 1.

[0196] Data recording and processing: Repeat the above steps for all samples in each group of samples;

[0197] Record the critical impact height for each specimen. Calculate the average critical impact height for each group of specimens and record the original data points.

[0198] Optical transmittance test: The procedure is the same as in Test Example 1.

[0199] Data recording and processing: Measure the average transmittance of visible light for multiple samples in each group of samples or different locations of the same sample.

[0200] Residual stress level assessment: The procedure is the same as in Test Example 1.

[0201] Sample observation: The procedure is the same as in test example 1.

[0202] Qualitative description and semi-quantitative evaluation: The procedure is the same as 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.

[0203] Data recording and processing: The stress fringes of each group of samples were recorded qualitatively, and the maximum optical path difference measured at key observation points was also recorded. The experimental results are shown in Table 3.

[0204] Table 3: Comparative test data on the effects of each heat treatment stage in the overall rapid annealing process on the properties of glass samples

[0205]

[0206]

[0207] From Table 3, we can obtain:

[0208] The sample in Example 1 underwent a complete and optimized process, including initial rapid cooling in step S2, a specific programmed cooling rate in the core annealing stage in step S3, and final rapid cooling in step S4. It exhibited the highest critical impact resistance height, excellent average visible light transmittance, and the lowest and most uniformly distributed internal residual stress. This demonstrates that the entire heat treatment process designed in this invention works synergistically to maximize the advantages of each stage. In particular, the initial rapid cooling in step S2 establishes a uniform and favorable thermal starting point for the subsequent precision annealing in step S3, avoiding potential problems caused by prolonged exposure of the glass to high temperatures and improving process integration efficiency. The subsequent final rapid cooling in step S4 effectively "freezes" the low-stress state achieved in step S3 and maintains it to room temperature, preventing the introduction of new stress due to inappropriate thermal gradients during subsequent cooling.

[0209] The results of Comparative Example 8 show that when the primary glass product is cooled to the initial 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 in Example 1, a very slow final cooling rate is used in step S4, and its impact resistance and residual stress control are also significantly inferior to those of Example 1.

[0210] Finally, the results of Comparative Example 10 fully emphasize the importance of precise control of the programmed cooling rate in the core annealing stage of step S3. In this comparative example, although electromagnetic excitation and acoustic-assisted relaxation were also applied in step S3, the cooling rate in the critical stress relaxation stage was set too fast, resulting in a significant decrease in its shock resistance and a significant increase in the level of internal residual stress, which was far worse than in Example 1.

[0211] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing high-transparency and impact-resistant glass based on rapid annealing technology, characterized in that, Includes the following steps: S1. Select glass raw materials, melt, clarify and homogenize the glass raw materials in a high-temperature melting furnace to prepare glass melt, and then make the glass melt into primary glass products. S2. The obtained primary glass product is subjected to an initial rapid cooling treatment to reduce its temperature from the high temperature state after molding to the preset annealing temperature. S3. Perform time-controlled multi-physics field synergistic annealing on the primary glass product after the initial rapid cooling treatment. This process involves applying electromagnetic excitation and acoustic-assisted relaxation in synergistically while cooling the primary glass product from the upper limit of the annealing temperature to a preset strain point temperature range, combined with programmed cooling. S4. The primary glass product that has undergone the time-controlled multi-physical field synergistic annealing process is subjected to a final rapid cooling treatment to room temperature to obtain high-transparency and impact-resistant glass. The glass raw material comprises the following components in parts by weight: Silica: 60-75 parts; It is selected from at least one of sodium oxide: 8-16 parts and potassium oxide: 0-8 parts, and the total amount is 10-20 parts; It is selected from at least one of calcium oxide: 5-15 parts and magnesium oxide: 1-8 parts, and the total amount is 5-18 parts; Add 0.5-5 parts of alumina and / or 0.1-3 parts of zirconium oxide; In the time-controlled multiphysics synergistic annealing process, the step of applying electromagnetic excitation includes: A radio frequency field or microwave field with a frequency in the range of 1MHz to 10GHz is applied to the primary glass article; The electromagnetic excitation is applied via pulse modulation, 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 within 0.01-1 W / cm². 3 Or the rate of temperature rise caused by electromagnetic excitation is controlled at 1-5℃ / minute; Among them, the local unit volume absorbed power density Characterized by the following formula: ； in, For the glass in position and time Power density absorbed per unit volume; The frequency of the electromagnetic field; It is the vacuum permittivity; For glass at frequency and temperature Dielectric loss factor below; The amplitude of the electromagnetic field strength at position and time ; In the time-controlled multi-physics field synergistic annealing process, the application of acoustic-assisted relaxation specifically includes: Ultrasonic waves with a frequency in the range of 20 kHz to 2 MHz are applied to the primary glass product, and the sound intensity is controlled between 1-50 W / cm. 2 Within the range; Among them, stress relaxation characteristic time Characterized by the following formula: ； in, The characteristic time of stress relaxation; The effective viscosity of glass is determined by temperature. Sound field energy density The function; This is the shear modulus of the glass.

2. The method for preparing high-transparency 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 material in a high-temperature furnace include: Add 0.05-1.0 parts by weight of clarifying agent and melt at a melting temperature of 1450-1600℃ for 4-8 hours to form a glass melt; Clarification is carried out by holding the temperature at this melting temperature for 2-4 hours, followed by homogenization by holding the temperature at 1400-1500℃ for 2-4 hours.

3. The method for preparing high-transparency and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that, The preset annealing temperature is 500-600℃.

4. The method for preparing high-transparency and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that, In the time-controlled multi-physics field synergistic annealing process, the preset strain point temperature range corresponds to a temperature of 450-550℃.

5. The method for preparing high-transparency and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that, In the time-limited multi-physics collaborative annealing process, the time-limited mechanism includes: Based on the real-time temperature distribution and / or internal stress development state of the primary glass product during the annealing process, the parameters of the electromagnetic excitation, the parameters of the acoustic-assisted relaxation, and the rate of the programmed cooling are dynamically adjusted through a feedback or feedforward control system. The electromagnetic excitation and the acoustic-assisted relaxation are applied synchronously in time, or partially overlap in time, or are performed sequentially in time.

6. The method for preparing high-transparency 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 non-linear cooling curve, and in the critical 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℃ / min.

7. The method for preparing high-transparency and impact-resistant glass based on rapid annealing technology according to claim 1, characterized in that, The method further includes a surface post-treatment of the obtained high-transparency and impact-resistant glass after the final rapid cooling process. The surface post-treatment includes chemical etching of the high-transparency and impact-resistant glass using a 1-5 vol% hydrofluoric acid solution for a processing time of 30 seconds to 5 minutes.

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