High-strength explosion-proof glass material and production process thereof

Abstract

The application discloses a kind of high-strength explosion-proof glass materials and production process thereof, it is related to the field of special glass material, high-strength explosion-proof glass material includes toughness layer and the surface strengthening layer distributed in its both sides;Surface strengthening layer is formed by the glass ceramic component of glass powder and nucleating agent in situ crystallization reaction;Toughness layer is formed by the flexible hybrid polymer component of organic-inorganic hybrid precursor by condensation reaction;Wherein, continuous transition region is formed between flexible hybrid polymer component and surface glass ceramic component.The high-strength explosion-proof glass material provided by the application significantly improves the impact strength of the material through the combined structure of toughness layer and surface strengthening layer, and maintains the overall integrity when broken, avoiding the common interface delamination and fragment scattering problems in traditional laminated structure.

Description

Technical Field

[0001] This invention belongs to the field of special glass materials, specifically relating to a high-strength explosion-proof glass material and its production process. Background Technology

[0002] Existing explosion-proof glass materials mostly rely on physical or chemical tempering combined with organic interlayers or multi-layer composite structures to achieve impact resistance. However, physical tempering is prone to spontaneous breakage and stress spots, chemical tempering suffers from compressive stress relaxation over time, and organic interlayers are prone to aging and delamination failures under high temperature, ultraviolet radiation, or humid environments. In addition, traditional processes usually require high-temperature melting or high-pressure lamination, which has drawbacks such as high energy consumption, limited thickness, loss of light transmittance, and easy scattering of fragments after breakage, making it difficult to simultaneously meet the requirements of high impact resistance, maintaining overall integrity after explosion-proof breakage, and long-term environmental stability. Summary of the Invention

[0003] To solve the above-mentioned technical problems, the present invention provides a high-strength explosion-proof glass material and its manufacturing process, the specific technical solution of which is as follows: A high-strength explosion-proof glass material includes a toughness layer and a surface reinforcement layer distributed on both sides of the toughness layer; The surface strengthening layer is composed of a glass-ceramic component formed by in-situ crystallization reaction of glass micropowder and nucleating agent; The toughness layer is composed of a flexible hybrid polymer component formed by the condensation reaction of an organic-inorganic hybrid precursor; A continuous transition region is formed between the flexible hybrid polymer component and the surface glass-ceramic component.

[0004] Preferably, the material is made of the following components in parts by weight: 80-120 parts glass micropowder, 0.5-5 parts nucleating agent, 15-45 parts organic-inorganic hybrid precursor, 1-5 parts low-melting-point additive, and 0.5-3 parts multifunctional gradient stabilizer.

[0005] Preferably: The glass powder is a SiO2-Al2O3-B2O3 series glass powder with a particle size of 0.1~5μm; The organic-inorganic hybrid precursor is phenyl polysilsesquioxane; The low-melting-point additive is selected from at least one of bismuth-based glass powder, phosphate glass powder, and boron-zinc-based glass powder. The multifunctional gradient stabilizer is a surface-modified SiO2 aerogel microsphere.

[0006] Preferably, the nucleating agent is selected from any one of the following: BaO-La2O3 composite nucleating agent, wherein the mass ratio of BaO to La2O3 in the BaO-La2O3 composite nucleating agent is 1:(0.5~3); A core-shell type ceramic nano-anchoring agent, comprising a Ba-La composite core and a ZrO2 shell or TiO2 shell covering the composite core.

[0007] Preferably, the raw material components of the material further include 0.3 to 3.6 parts of a siloxane precursor containing dynamic functional groups, wherein the dynamic functional groups are urea groups and / or amide groups.

[0008] The present invention also provides a manufacturing process for a high-strength explosion-proof glass material as described in any one of the above claims, comprising the following steps: S1. Preparation of hybrid slurry: Organic-inorganic hybrid precursor, glass micro powder, nucleating agent, low melting agent and multifunctional gradient stabilizer are blended in proportion to prepare hybrid precursor slurry; S2. Molding process: The hybrid precursor slurry is prepared into a preform of a predetermined shape; S3. Gradient forming: The billet is placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field is applied to the upper and lower surfaces of the billet, while ultrasonic-assisted vibration is applied to form a component concentration gradient distribution. S4. Heat treatment: Under an inert atmosphere, the surface of the billet is rapidly radiated and heated until the surface temperature of the billet reaches 600~850℃, then held at that temperature for 20~40 seconds, and then cooled to room temperature.

[0009] Preferably: In step S3, the electric field-acoustic field coupling device includes an interdigitated electrode array disposed on the upper and lower surfaces of the blank; the interdigitated electrode array includes alternating positive and negative electrode strips, the width of the electrode strips is 0.5~2mm, and the spacing between adjacent electrode strips is 1~3mm; In step S3, the frequency range of the non-uniform alternating electric field is 10Hz~1MHz, the frequency of the ultrasonic-assisted vibration is 20kHz~100kHz, and the action time is 5~60 minutes. In step S4, the rapid radiative heating uses an infrared radiation heat source, and the cooling rate is 1~10℃ / min.

[0010] Preferably, the organic-inorganic hybrid precursor is phenyl polysilsesquioxane, which is added after pre-crosslinking treatment through the following steps: S01. Disperse phenyl polysilsesquioxane in anhydrous ethanol or isopropanol, stir until homogeneous, and prepare a solution with a concentration of 30~60wt%. SO2. Under nitrogen protection, add an acidic or basic catalyst, control the pH of the reaction system to 3.0~4.5 or 9.0~10.5, and stir the reaction at 80~120℃ for 2~6 hours. S03. After the reaction is complete, remove the solvent by vacuum distillation at 50~70℃ and -0.08~-0.1MPa until the product is viscous and transparent.

[0011] Preferably, the nucleating agent is a core-shell type ceramic nano-anchoring agent, which is prepared by the following steps: S001. Core liquid preparation: BaO and La2O3 mixed powder with a mass ratio of 1:(0.5~3) is used as the composite core, dispersed in anhydrous ethanol solvent at a mass fraction of 5%~15%, add dispersant and sonicate for 30~60 minutes to obtain core suspension; S002. Addition of shell precursor: Add a shell precursor solution to the core suspension, wherein the shell precursor is selected from at least one of zirconium oxychloride, titanium tetrachloride, n-butyl titanate, and zirconium isopropoxide; wherein the mass ratio of the shell precursor to the composite core is 1:(2~6). S003. Hydrolysis and coating: Maintain the system temperature at 40~65℃, slowly add 5%~10% ammonia solution to the system, adjust the pH value of the system to 8.5~10.5, and continue stirring the reaction for 3~6 hours; S004. Washing and calcining: After centrifugation and washing of the reaction product in step S003, and drying at 80~110℃, the product is calcined at a constant temperature of 550~750℃ for 2~4 hours at a heating rate of 2~5℃ / min to obtain the core-shell ceramic nano-anchoring agent.

[0012] Preferably, step S1 further includes the addition of a siloxane precursor containing dynamic functional groups, which is prepared by the following steps: S10. Disperse the aminosilane coupling agent and isocyanate monomer in an anhydrous solvent at a mass ratio of 1:(0.4~1.2), wherein the anhydrous solvent is selected from at least one of tetrahydrofuran, ethyl acetate, and dimethylformamide; and stir the reaction at 0~60°C for 2~6 hours under nitrogen protection. S20. The product obtained in step S10 is obtained by removing the solvent by vacuum distillation.

[0013] The high-strength explosion-proof glass material provided by this invention, through the combined structure of a toughening layer and a surface strengthening layer, allows impact energy to be effectively dispersed first in the rigid glass-ceramic component of the surface strengthening layer, then deflected through the organic-inorganic continuous transition region, and finally fully absorbed in the flexible hybrid polymer component of the toughening layer through a multi-level dissipation mechanism. This significantly improves the material's impact resistance and maintains its overall integrity upon breakage, avoiding the common problems of interface delamination and fragment scattering in traditional laminated structures. It provides a solution with both high strength and high safety for explosion-proof applications in construction, vehicles, and industry. Detailed Implementation

[0014] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below. The description in this part is only exemplary and explanatory, and should not be used to limit the scope of protection of the present invention in any way.

[0015] This embodiment provides a high-strength explosion-proof glass material, including a toughening layer and a surface strengthening layer distributed on both sides of the toughening layer.

[0016] The surface strengthening layer is composed of glass ceramic components formed by in-situ crystallization reaction of glass micropowder and nucleating agent.

[0017] The toughening layer is composed of a flexible hybrid polymer component formed by the condensation reaction of organic-inorganic hybrid precursors.

[0018] A continuous transition region is formed between the flexible hybrid polymer component and the surface glass-ceramic component.

[0019] Specifically, the surface strengthening layer is composed of a glass-ceramic component formed by in-situ crystallization of glass micropowder and nucleating agent. The physical meaning of this glass-ceramic component is that a rigid structure with a continuous glass phase and a dispersed nanoscale crystalline phase is formed in the material surface area through in-situ crystallization. This rigid structure can effectively disperse external impact loads and form a pre-compression stress gradient on the surface, thereby improving the material's ability to resist the initiation of initial cracks.

[0020] The toughening layer is composed of a flexible hybrid polymer component formed by the condensation reaction of an organic-inorganic hybrid precursor. The chemical nature of this flexible hybrid polymer component is an interpenetrating network structure formed by the interconnection of siloxane networks and organic side chains. When subjected to external forces, it can achieve multi-level energy dissipation through chain segment slip, viscoelastic hysteresis, and the breaking and reconstruction of reversible bonds.

[0021] A continuous transition region is formed between the flexible hybrid polymer component and the surface glass-ceramic component, realizing a continuous transition between the organic and inorganic phases, eliminating stress concentration at the macroscopic interface, and enabling the load to be smoothly transferred between the rigid and flexible phases.

[0022] The glass-ceramic component of the surface strengthening layer can be selected from combinations of glass micropowders and nucleating agents with different compositions, thereby controlling the degree of crystallization and the distribution of the rigid phase; the flexible hybrid polymer component of the toughening layer can be adjusted based on organic-inorganic hybrid precursors with different types of organic side chains and cross-linking densities of inorganic networks to meet different toughness requirements; the organic-inorganic continuous transition region can control its penetration depth and continuity through blending process conditions and heat treatment parameters.

[0023] The high-strength explosion-proof glass material provided in this embodiment utilizes a combination structure of a toughening layer and a surface strengthening layer. This structure allows impact energy to be effectively dispersed first in the rigid glass-ceramic component of the surface strengthening layer, then deflected through a continuous organic-inorganic transition region, and finally fully absorbed in the flexible hybrid polymer component of the toughening layer through a multi-stage dissipation mechanism. This significantly improves the material's impact resistance and maintains its overall integrity upon breakage, avoiding the common problems of interface delamination and fragment scattering in traditional laminated structures. It provides a solution with both high strength and high safety for explosion-proof applications in construction, vehicles, and industry.

[0024] Furthermore, the material is made of the following components in parts by weight: 80-120 parts glass micropowder, 0.5-5 parts nucleating agent, 15-45 parts organic-inorganic hybrid precursor, 1-5 parts low-melting-point additive, and 0.5-3 parts multifunctional gradient stabilizer.

[0025] Among them, glass micropowder and nucleating agent provide the main inorganic components for forming the glass-ceramic component of the surface strengthening layer, while organic-inorganic hybrid precursor provides the main source for forming the flexible hybrid polymer component of the toughening layer. Low-melting-point additives assist in regulating the fluidity and compatibility of the system during heat treatment, enabling the glass-ceramic component and the flexible hybrid polymer component to form a stable organic-inorganic continuous transition region in in-situ reaction. Multifunctional gradient stabilizer, as a rheology modifier, is used to stabilize the particle distribution state after electric field induction, preventing secondary sedimentation or diffusion of components after the electric field is removed and before thermal curing is completed. At the same time, its specific dielectric properties help enhance the system's response sensitivity to the electric field.

[0026] Furthermore: The glass micro powder is a SiO2-Al2O3-B2O3 series glass powder with a particle size of 0.1~5μm.

[0027] The organic-inorganic hybrid precursor is phenyl polysilsesquioxane.

[0028] The low-melting-point additive is selected from at least one of bismuth-based glass powder, phosphate glass powder, and boron-zinc-based glass powder; The multifunctional gradient stabilizer is a surface-modified SiO2 aerogel microsphere.

[0029] Among them, SiO2-Al2O3-B2O3-based glass powder, with its specific oxide composition and particle size of 0.1~5μm, serves as the main source of the glass phase during heat treatment, participating in the in-situ crystallization reaction together with the nucleating agent to form the glass-ceramic component of the surface-strengthening layer; phenyl polysilsesquioxane, as an organic-inorganic hybrid precursor, forms the flexible hybrid polymer component that constructs the toughening layer in the subsequent condensation reaction; bismuth-based glass powder, phosphate glass powder, or boron-zinc-based glass powder, as low-melting-point additives, reduce the viscosity of the system during heat treatment, promoting the flow and interpenetration of the glass phase and the hybrid polymer phase; and surface-modified SiO2 aerogel microspheres have a particle size of 50~200nm and a specific surface area ≥300m². 2 / g, with a surface modified by a phenylsilane coupling agent, has a dielectric constant that matches the organic precursor and has a significant difference, making it clearly stressed in a non-uniform electric field and able to accurately respond to changes in electric field parameters (frequency, amplitude).

[0030] Furthermore, the nucleating agent is selected from any of the following: BaO-La2O3 composite nucleating agent, wherein the mass ratio of BaO to La2O3 in the BaO-La2O3 composite nucleating agent is 1:(0.5~3).

[0031] Core-shell ceramic nano-anchoring agents include a Ba-La composite core and a ZrO2 shell or TiO2 shell covering the composite core.

[0032] Among them, the BaO-La2O3 composite nucleating agent or core-shell ceramic nano-anchoring agent regulates the precipitation and distribution of crystalline phases of glass-ceramic components in the surface strengthening layer by inducing in-situ crystallization reaction during heat treatment. The BaO-La2O3 composite system can reduce the crystallization activation energy and promote the uniform precipitation of nanoscale grains, while the core-shell ceramic nano-anchoring agent, through its special structure, exerts a pinning effect on grain growth during crystallization, thereby stabilizing the glass-ceramic interface and locking residual stress.

[0033] The Ba-La composite core of the core-shell ceramic nano-anchor provides nucleation active sites, while the ZrO2 shell or TiO2 shell provides structural stability and interfacial anchoring effect, enabling the crystallization reaction to proceed controllably in the surface strengthening layer.

[0034] Beneficially, the choice of nucleating agent enables the glass-ceramic component of the surface strengthening layer to achieve higher crystallinity, uniform nanocrystal distribution, and more stable residual compressive stress, thereby significantly improving the surface hardness, scratch resistance, and thermal shock resistance of the material. Under impact loads, the surface strengthening layer can more effectively disperse initial energy, reduce crack initiation, and transfer the remaining energy to the flexible hybrid polymer component for dissipation through the organic-inorganic continuous transition region with the toughening layer. Ultimately, this improves the overall explosion resistance and reliability of maintaining integrity after breakage, while also enhancing the environmental stability of the material during long-term service.

[0035] Furthermore, the raw material components of the material also include 0.3 to 3.6 parts of a siloxane precursor containing dynamic functional groups, wherein the dynamic functional groups are urea groups and / or amide groups.

[0036] The flexible polymer component, constructed by the synergistic development of siloxane precursors containing dynamic functional groups and organic-inorganic hybrid precursors, is essentially a dynamic network with adaptive damping properties. Urea and / or amide groups form numerous dynamic cross-points through intermolecular hydrogen bonds. When the material is subjected to impact energy, these dynamic cross-points, acting as sacrificial bonds, break preferentially over covalent bonds, converting mechanical energy into potential energy and thermal energy of molecular chain segments for dissipation. Simultaneously, due to the reversibility of the dynamic bonds, they can rearrange after unloading, maintaining the material's fatigue life under high-frequency variable loads. This molecular-level energy absorption mechanism, in conjunction with the pre-stressed layer of the surface reinforcement layer, constructs a dual explosion-proof system of "rigid dispersion-dynamic dissipation."

[0037] Advantageously, the introduction of siloxane precursors containing dynamic functional groups constructs an energy dissipation network based on dynamic reversible hydrogen bonds in the toughening layer. Under high-frequency impact or explosive loads, the dynamic sacrificial bonds (urea / amide hydrogen bonds) in this network absorb a large amount of impact kinetic energy through instantaneous dissociation, and uniformly distribute local stress throughout the entire organic-inorganic hybrid network, effectively suppressing the propagation of macroscopic cracks induced by stress waves. This dynamic response mechanism endows the material with excellent impact toughness and structural integrity, ensuring that the material does not undergo large-area pulverization and fragmentation under extreme loads.

[0038] This embodiment also provides a manufacturing process for the high-strength explosion-proof glass material as described in any of the above embodiments, comprising the following steps: S1. Preparation of hybrid slurry: Organic-inorganic hybrid precursor, glass micro powder, nucleating agent, low melting point aid and multifunctional gradient stabilizer are blended in proportion to prepare hybrid precursor slurry.

[0039] S2. Molding process: The hybrid precursor slurry is prepared into a preform of a preset shape.

[0040] S3. Gradient forming: The billet is placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field is applied to the upper and lower surfaces of the billet. At the same time, ultrasonic-assisted vibration is applied to form a gradient distribution of component concentration.

[0041] S4. Heat treatment: Under an inert atmosphere, the surface of the billet is rapidly radiated and heated until the surface temperature reaches 600~850℃, then held for 20~40 seconds, and then cooled to room temperature.

[0042] In step S1, an organic-inorganic hybrid precursor, glass micropowder, nucleating agent, low-melting-point additive, and multifunctional gradient stabilizer are blended in proportion to form a uniform hybrid precursor slurry, which provides a reaction precursor for subsequent in-situ reactions. In step S2, the slurry is shaped into a preform of a preset shape, giving the material a macroscopic geometric morphology. In step S3, the shaped preform is placed between parallel plate electrodes or needle-plate electrodes, and a high-frequency AC voltage is applied. A non-uniform AC electric field is applied in the thickness direction of the preform, and the glass micropowder and nucleating agent with high dielectric constant are induced to migrate directionally to the high field strength region (i.e., the upper and lower surfaces of the preform) by using the dielectric electrophoresis mechanism. This spontaneously constructs a component distribution with continuously changing concentration from the surface to the interior within the preform. At the same time, the introduction of ultrasonic-assisted vibration generates an acoustic cavitation effect, breaking the particle crowding state in the high solid content system and instantly reducing the apparent viscosity, so that the micron-sized glass micropowder can achieve local rearrangement and form a gradient under the drive of the electric field. This concentration gradient, induced by an electric field, ensures the spatial selectivity of the crystallization reaction during subsequent heat treatment, thus achieving a symmetrical gradient structure without a macroscopic interface. Specifically, the polarization direction of the particles can be controlled by adjusting the frequency (10Hz~1MHz), while the migration rate and the final enrichment thickness of the surface layer can be controlled by adjusting the voltage amplitude.

[0043] Step S3 pre-sets a composition gradient in the thickness direction. Step S4 uses infrared rapid radiation heating combined with the low thermal conductivity of surface-modified SiO2 aerogel microspheres. The aerogel microspheres construct a nanoscale thermal insulation barrier inside the material. Due to the surface effect of radiation heating and the time lag of heat conduction, while the surface strengthening layer reaches 600~850℃ to induce crystallization, the temperature of the central toughening layer can still be maintained at a lower temperature. This non-equilibrium temperature field ensures the structural integrity of phenyl polysilsesquioxane and dynamic functional groups, thereby preserving the flexibility of the material.

[0044] Furthermore: In step S3, the electric field-acoustic field coupling device includes an interdigitated electrode array disposed on the upper and lower surfaces of the blank; the interdigitated electrode array includes alternating positive and negative electrode strips, the width of the electrode strips is 0.5~2mm, and the spacing between adjacent electrode strips is 1~3mm.

[0045] In step S3, the frequency range of the non-uniform alternating electric field is 10Hz~1MHz, the frequency of the ultrasonic-assisted vibration is 20kHz~100kHz, and the action time is 5~60 minutes.

[0046] In step S4, rapid radiative heating uses an infrared radiation heat source, and the cooling rate is 1~10℃ / min.

[0047] Specifically, by utilizing the edge electric field effect generated by the interdigitated electrodes, a high field strength gradient is generated in the region near the surface of the billet, inducing high dielectric particles to migrate directionally to the surface; at the same time, since the field strength decays rapidly with increasing depth, the central region of the billet maintains a low field strength state, thereby achieving a symmetrical gradient distribution of component concentration.

[0048] Furthermore, the organic-inorganic hybrid precursor is phenyl polysilsesquioxane, which is added after pre-crosslinking treatment via the following steps: S01. Disperse phenyl polysilsesquioxane in anhydrous ethanol or isopropanol, stir until homogeneous, and prepare a solution with a concentration of 30~60wt%.

[0049] SO2. Under nitrogen protection, add an acidic or basic catalyst, control the pH of the reaction system to 3.0~4.5 or 9.0~10.5, and stir the reaction at 80~120℃ for 2~6 hours.

[0050] S03. After the reaction is complete, remove the solvent by vacuum distillation at 50~70℃ and -0.08~-0.1MPa until the product is viscous and transparent.

[0051] Specifically, during the construction of the surface strengthening layer, the phenyl polysilsesquioxane on the surface undergoes an in-situ transformation from an organic hybrid state to an amorphous Si-OC ceramic state. The removal of side chain groups occurs before the material is fully vitrified, achieved through controlled expulsion via the micron-level gaps in the porous precursor preform. This in-situ transformation forms a ceramic phase that covalently bonds with the SiO2 network resulting from the molten inorganic glass powder, thus constituting this "continuous transition region."

[0052] Furthermore, the nucleating agent is a core-shell type ceramic nano-anchoring agent, which is prepared through the following steps: S001. Core liquid preparation: BaO and La2O3 mixed powder with a mass ratio of 1:(0.5~3) is used as the composite core, dispersed in anhydrous ethanol solvent at a mass fraction of 5%~15%, add dispersant and sonicate for 30~60 minutes to obtain core suspension.

[0053] S002. Addition of shell precursor: Add a shell precursor solution to the core suspension. The shell precursor is selected from at least one of zirconium oxychloride, titanium tetrachloride, n-butyl titanate, and zirconium isopropoxide. The mass ratio of the shell precursor to the composite core is 1:(2~6).

[0054] S003. Hydrolysis and coating: Maintain the system temperature at 40~65℃, slowly add 5%~10% ammonia solution to the system, adjust the pH value of the system to 8.5~10.5, and continue stirring the reaction for 3~6 hours.

[0055] S004. Washing and calcining: After centrifugation and washing of the reaction product in step S003, and drying at 80~110℃, the product is calcined at a constant temperature of 550~750℃ for 2~4 hours at a heating rate of 2~5℃ / min to obtain the core-shell ceramic nano-anchoring agent.

[0056] Furthermore, step S1 also includes the addition of a siloxane precursor containing dynamic functional groups, which is prepared through the following steps: S10. Disperse the aminosilane coupling agent and isocyanate monomer in an anhydrous solvent at a mass ratio of 1:(0.4~1.2), wherein the anhydrous solvent is selected from at least one of tetrahydrofuran, ethyl acetate, and dimethylformamide; and stir the reaction at 0~60℃ for 2~6 hours under nitrogen protection.

[0057] S20. The product obtained in step S10 is obtained by removing the solvent by vacuum distillation.

[0058] The aminosilane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane (APTES) and γ-aminopropyltrimethoxysilane (APTMS); the isocyanate monomer is selected from at least one of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate (MDI).

[0059] Specific embodiments are provided below. These embodiments are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way.

[0060] In the following embodiments, by adjusting the frequency of the alternating electric field to match the relaxation frequency of the glass microparticles, the dielectric electrophoretic force can be maximized. For glass microparticles with a particle size of 1~3µm, a frequency of 50~200kHz can obtain the best migration efficiency.

[0061] Example 1

[0062] Weigh 300g of phenyl polysilsesquioxane and add 450g of anhydrous ethanol, stirring until a solution is prepared. Under nitrogen protection, adjust the pH to 3.5 with 0.1mol / L hydrochloric acid solution, and stir at 80-110℃ for 4 hours to perform pre-crosslinking. After the reaction is complete, remove the solvent by vacuum distillation at 55℃ and -0.09MPa until the product is viscous and transparent, obtaining the pre-crosslinked phenyl polysilsesquioxane precursor.

[0063] Weigh 1000g of SiO2-Al2O3-B2O3 glass micropowder (particle size 0.1~5μm), 20g of BaO-La2O3 composite nucleating agent (BaO to La2O3 mass ratio 1:1.5), 30g of low-melting flux (bismuth-based glass powder), and 15g of surface-modified SiO2 aerogel microspheres (particle size 50~150nm, phenylsilane modified). Add 280g of the pre-crosslinked phenyl polysilsesquioxane precursor mentioned above. Stir and mix in a high-speed disperser at room temperature for 2.5 hours to obtain a uniform hybrid precursor slurry (solid content about 78%).

[0064] The hybrid precursor slurry was poured into a 300mm×300mm polytetrafluoroethylene mold, cast, and naturally dried at room temperature for 12 hours before demolding to obtain a preform with a thickness of about 6mm.

[0065] The demolded blank was placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field with a frequency of 100 kHz and a peak-to-peak value of 2000 V was applied along the thickness direction of the blank. Simultaneously, ultrasonic-assisted vibration with a frequency of 40 kHz was applied for 20 minutes. The treated blank was then transferred to a rapid processing chamber equipped with an infrared radiation heat source, and the surface of the blank was rapidly radiated and heated under an inert atmosphere (N2) to a surface temperature of 750 °C, which was then held for 20 seconds. After removing the heat source, the blank was cooled to room temperature in a controlled manner at a rate of 5 °C / min, yielding a transparent glass material sample with a thickness of approximately 5 mm.

[0066] The prepared samples were placed in an environment of 23±2℃ and 50±5%RH for 24 hours before testing. Bending strength was measured using the three-point bending method according to GB / T658.1-2008, with a span of 200 mm and a loading rate of 0.5 mm / min. Impact energy absorption was measured using a drop hammer impact test with a 5 kg, 20 mm diameter hammer, gradually increasing the height from different heights until sample failure, and the absorbed energy was calculated. Fragmentation distance was measured using a simulated explosion shock wave test, with an explosion equivalent to 0.5 kg TNT, and the furthest fragment dispersion distance was recorded. Light transmittance was measured using the method of GB / T2680-2022, with wavelengths from 400 to 700 nm and the average value taken. Ultraviolet aging degradation was measured using the method of GB / T1865-2009, using a UVA-340 lamp, with 8 hours of UV exposure followed by 4 hours of condensation cycling, for a cumulative total of 1000 hours.

[0067] The test data is shown in Table 1 below: Table 1: Test Data Table for Example 1

[0068] The glass material prepared in Example 1 has high bending strength and impact energy absorption capacity, effectively controls the distance of fragment scattering, and maintains excellent light transmittance and weather resistance, fully verifying the technical effect of the technical solution.

[0069] Example 2 8g of BaO powder and 12g of La2O3 powder were weighed and dispersed in 450g of anhydrous ethanol. 1.5g of polyvinylpyrrolidone (PVPK30) was added as a dispersant, and the mixture was sonicated for 45 minutes to obtain a core suspension. 5g of zirconium oxychloride (ZrOCl2·8H2O) was added to the core suspension, and the system temperature was maintained at 55℃. An 8% ammonia solution was slowly added dropwise to adjust the pH to 9.5, and the reaction was continuously stirred for 4 hours. The reaction product was centrifuged, washed, and dried at 105℃. Then, it was calcined at 650℃ for 3 hours at a heating rate of 3℃ / min to obtain a core-shell ceramic nano-anchoring agent.

[0070] The preparation method of the pre-crosslinked phenyl polysilsesquioxane precursor is the same as in Example 1.

[0071] Weigh 1000g of SiO2-Al2O3-B2O3 glass micropowder (particle size 0.1~5μm), 20g of the core-shell ceramic nano-anchoring agent prepared above, 30g of low-melting-point additive (bismuth-based glass powder), and 15g of surface-modified SiO2 aerogel microspheres (particle size 50~150nm, modified with phenylsilane). Add 280g of the pre-crosslinked phenyl polysilsesquioxane precursor mentioned above, and follow the same stirring and blending process as in Example 1 to obtain a uniform hybrid precursor slurry.

[0072] The hybrid precursor slurry was poured into a 300mm×300mm polytetrafluoroethylene mold, cast, and naturally dried at room temperature for 12 hours before demolding to obtain a preform with a thickness of about 6mm.

[0073] The demolded blank was placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field with a frequency of 100 kHz and a peak-to-peak value of 2500 V was applied along the thickness direction of the blank; simultaneously, ultrasonic-assisted vibration with a frequency of 40 kHz was applied for 25 minutes. The treated blank was then transferred to a rapid processing chamber equipped with an infrared radiation heat source, and the surface of the blank was rapidly radiated and heated under an inert atmosphere (N2), causing the surface temperature of the blank to rise rapidly to 750 °C, and held at this temperature for 25 seconds. After the heat source was removed, the blank was cooled to room temperature in a controlled manner at a rate of 5 °C / min, yielding a transparent glass material sample with a thickness of approximately 5 mm.

[0074] The prepared samples were placed in an environment of 23±2℃ and 50±5%RH for 24 hours before testing. The testing methods for various mechanical and optical properties were the same as in Example 1. In addition, a thermal shock resistance test was added: the samples were kept at 800℃ for 30 minutes and then immediately immersed in 0℃ ice water, and the cycle was repeated until visible cracks appeared.

[0075] The test data is shown in Table 2 below: Table 2: Test Data Table for Example 2

[0076] Example 2 introduces a core-shell ceramic nano-anchor (ZrO2 shell). The material's flexural strength and impact energy absorption capacity are further improved, fragmentation distance is further reduced, and thermal shock resistance is significantly enhanced, while light transmittance and weather resistance remain excellent. This demonstrates that the synergistic effect of the core-shell ceramic nano-anchor and the gradient structure can further strengthen the performance of the surface reinforcement layer.

[0077] Example 3 15 g of γ-aminopropyltriethoxysilane (APTES) and 12 g of hexamethylene diisocyanate (HDI) were weighed and dispersed in 200 g of tetrahydrofuran. The mixture was stirred and reacted at room temperature (25 °C) for 4 hours under nitrogen protection. After the reaction was completed, the solvent was removed by vacuum distillation to obtain a siloxane precursor containing dynamic functional groups.

[0078] The preparation method of the pre-crosslinked phenyl polysilsesquioxane precursor is the same as in Example 1.

[0079] Weigh 1000g of SiO2-Al2O3-B2O3 glass micropowder (particle size 0.1~5μm), 20g of BaO-La2O3 composite nucleating agent (BaO:La2O3 mass ratio 1:1.5), 30g of low-melting flux (bismuth-based glass powder), and 15g of surface-modified SiO2 aerogel microspheres (particle size 50~150nm, modified with phenylsilane coupling agent). Add 280g of the pre-crosslinked phenyl polysilsesquioxane precursor and 25g of the siloxane precursor containing dynamic functional groups prepared above. The remaining stirring and blending process is the same as in Example 1 to obtain a uniform hybrid precursor slurry (solid content about 78%).

[0080] The casting, drying, and demolding steps are exactly the same as in Example 1, resulting in a blank with a thickness of approximately 6 mm.

[0081] The demolded blank was placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field with a frequency of 100 kHz and a peak-to-peak value of 2200 V was applied along the thickness direction of the blank; simultaneously, ultrasonic-assisted vibration with a frequency of 40 kHz was applied for 20 minutes. The blank was then transferred into a rapid processing chamber equipped with an infrared radiation heat source, and the surface of the blank was rapidly radiated and heated under an inert atmosphere (N2), causing the surface temperature of the blank to rise rapidly to 720 °C, and held at this temperature for 20 seconds. Subsequently, it was cooled to room temperature in a controlled manner at a rate of 5 °C / min, yielding a transparent glass material sample with a thickness of approximately 5 mm.

[0082] The testing methods for all mechanical and optical properties are the same as in Example 1. In addition, dynamic energy dissipation and interfacial bonding force tests are added; the dynamic loss factor test is performed using a dynamic mechanical analyzer (DMA) in single cantilever mode, with a test frequency of 1 Hz, an amplitude of 20 μm, and a test temperature of 25℃. The interfacial peel strength test (after impact) is conducted according to GB / T 2790 standard, first subjecting the sample to a 50 J drop hammer pre-impact, followed by a 180° peel test at a speed of 50 mm / min on a tensile testing machine.

[0083] The test data is shown in Table 3 below: Table 3: Test Data Table for Example 3

[0084] Example 3 introduces a siloxane precursor (urea / amide) containing dynamic functional groups. Results show that the material has a dynamic loss factor of 0.292; a peel strength of 16.5 N / mm demonstrates that the dynamic bonds effectively suppress stress concentration at the interface, ensuring the material maintains good structural continuity after impact. Simultaneously, it maintains good mechanical properties and weather resistance, significantly improving service reliability.

[0085] Example 4 The preparation method of the core-shell ceramic nano-anchor is the same as in Example 2, the preparation method of the siloxane precursor containing dynamic functional groups is the same as in Example 3, and the preparation method of the pre-crosslinked phenyl polysilsesquioxane precursor is the same as in Example 1.

[0086] Weigh 1000g of SiO2-Al2O3-B2O3 glass micropowder (particle size 0.1~5μm), 20g of the core-shell ceramic nano-anchoring agent prepared above, 30g of low-melting-point additive (bismuth-based glass powder), 20g of surface-modified SiO2 aerogel microspheres (particle size 50~150nm, modified with phenylsilane coupling agent), add 280g of the pre-crosslinked phenyl polysilsesquioxane precursor prepared above and 25g of the siloxane precursor containing dynamic functional groups prepared above, and stir and mix in a high-speed disperser at room temperature for 3 hours to obtain a uniform hybrid precursor slurry (solid content about 78%).

[0087] The casting, drying, and demolding steps are exactly the same as in Example 1, resulting in a blank with a thickness of approximately 6 mm.

[0088] The demolded blank was placed in an electric field-acoustic field coupling device. A non-uniform alternating electric field with a frequency of 100 kHz and a peak-to-peak value of 2800 V was applied along the thickness direction of the blank; simultaneously, ultrasonic-assisted vibration with a frequency of 40 kHz was applied for 30 minutes. The blank was then moved into a rapid processing chamber equipped with an infrared radiation heat source, and the surface of the blank was rapidly radiated and heated under an inert atmosphere (N2), causing the surface temperature of the blank to rise rapidly to 760 °C. This temperature was held for 30 seconds, and then the blank was cooled to room temperature in a controlled manner at a rate of 5 °C / min, resulting in a transparent glass material sample with a thickness of approximately 5 mm.

[0089] The prepared samples were placed in an environment of 23±2℃ and 50±5%RH for 24 hours before testing. The test items included bending strength, impact energy absorption, fragment scattering distance, light transmittance, UV aging decay (same as Example 1), thermal shock resistance (same as Example 2), dynamic loss factor test (same as Example 3), and interface peel strength test (same as Example 3).

[0090] The test data is shown in Table 4 below: Table 4: Test Data Table for Example 4

[0091] Example 4 simultaneously introduced a core-shell ceramic nano-anchor (ZrO2 shell) and a siloxane precursor containing dynamic functional groups. Results showed that the material exhibited excellent flexural strength, impact energy absorption, and interfacial peel strength. Analysis suggests that the core-shell anchor stabilized residual compressive stress in the surface reinforcement layer through an interfacial pinning effect, while the dynamic sacrificial bond network in the toughening layer absorbed residual impact kinetic energy through an efficient energy dissipation mechanism. The synergistic effect of these two components resulted in the material exhibiting extremely high integrity and excellent dynamic loss characteristics under simulated explosive impact.

[0092] Comparative Example 1 In this comparative example, the pretreatment of the organic-inorganic hybrid precursor, the preparation of the hybrid slurry, and the molding process are all the same as in Example 1.

[0093] After obtaining a blank with a thickness of about 6 mm, the blank is directly transferred into a rapid processing chamber. The surface of the blank is rapidly radiantly heated under an inert atmosphere to raise the surface temperature to 750°C, held for 20 seconds, and then cooled to room temperature in a controlled manner at a rate of 5°C / min to obtain a glass material sample with a thickness of about 5 mm.

[0094] The prepared samples were placed at 23±2℃ and 50±5%RH for 24 hours before testing. The test items and methods were the same as in Example 1.

[0095] The test data is shown in Table 5 below: Table 5: Test Data Table for Comparative Example 1

[0096] Comparative Example 1 used the same raw material components as Example 1, but without applying electric field-acoustic field coupling treatment; it only underwent treatment. The results showed that the bending strength and impact energy absorption were significantly lower than those of Example 1, the fragment scattering distance increased significantly, and the light transmittance and weather resistance also decreased significantly.

[0097] Comparative Example 2 A 6mm thick sodium-calcium-silicate glass plate was selected and first subjected to physical tempering treatment (heated to 650℃ and then rapidly cooled). Then, a 0.76mm thick polyvinyl butyral (PVB) film was sandwiched between the two tempered glass plates. The plate was then hot-pressed in an autoclave at 135℃ and 1.2MPa for 30 minutes to obtain a laminated explosion-proof glass sample (total thickness of about 7.5mm).

[0098] The prepared samples were placed in an environment of 23±2℃ and 50±5%RH for 24 hours before testing. The test items and methods (flexural strength, impact energy absorption, fragment scattering distance, light transmittance, and UV aging attenuation) were the same as in Example 1.

[0099] The test data is shown in Table 6 below: Table 6: Test Data Table for Comparative Example 2

[0100] Comparative Example 2 employed a traditional physical tempering combined with an organic sandwich composite process. Test results showed that its bending strength and impact energy absorption were significantly lower than those of Examples 1-4, and its fragment dispersion distance was much greater than that of the samples obtained in the examples. This fully demonstrates the substantial progress achieved by the embodiments in terms of high strength, explosion-proof integrity, weather resistance, and other dimensions.

[0101] Comparative Example 3 This comparative example used essentially the same raw material components as Example 4, specifically including: 1000g of SiO2-Al2O3-B2O3 glass micro powder (particle size 0.1~5μm), 20g of core-shell ceramic nano-anchoring agent, 30g of low-melting-point additive (bismuth-based glass powder), 280g of pre-crosslinked phenyl polysilsesquioxane precursor, and 25g of siloxane precursor containing dynamic functional groups.

[0102] The difference is that no multifunctional gradient stabilizer (surface-modified SiO2 aerogel microspheres) was added during the preparation of the hybrid slurry.

[0103] The remaining mixing, casting, drying and demolding steps are the same as in Example 4.

[0104] The obtained blank was placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field with a frequency of 100kHz and a peak-to-peak value of 2800V and ultrasonic-assisted vibration with a frequency of 40kHz were applied for 30 minutes. It was then moved into a rapid processing chamber for rapid radiant heating (process as in Example 4), and cooled to room temperature at a rate of 5℃ / min to obtain a glass material sample with a thickness of about 5mm.

[0105] The prepared samples were placed at 23±2℃ and 50±5%RH for 24 hours before testing. The test items and methods were the same as in Example 4. The test data are shown in Table 7 below: Table 7: Test Data Table for Comparative Example 3

[0106] Comparative Example 3 used essentially the same raw material components and pre-crosslinking treatment process as Example 4, and also employed the same molding and heat treatment processes. However, no multifunctional gradient stabilizer was added during the preparation of the hybrid slurry. The results showed that its dynamic loss factor and impact energy absorption were significantly lower than those of Example 4, and the interfacial peel strength after impact was extremely low, indicating obvious interfacial delamination failure.

[0107] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of the present invention. The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the technical scope disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be within the scope of protection of the present invention.

Claims

1. A high-strength explosion-proof glass material, characterized in that, It includes a toughening layer and surface reinforcement layers distributed on both sides of the toughening layer; The surface strengthening layer is composed of a glass-ceramic component formed by in-situ crystallization reaction of glass micro powder and nucleating agent; The toughness layer is composed of a flexible hybrid polymer component formed by the condensation reaction of an organic-inorganic hybrid precursor; A continuous transition region is formed between the flexible hybrid polymer component and the surface glass-ceramic component.

2. The high-strength explosion-proof glass material according to claim 1, characterized in that, The material is made of the following components in parts by weight: 80-120 parts glass micropowder, 0.5-5 parts nucleating agent, 15-45 parts organic-inorganic hybrid precursor, 1-5 parts low-melting-point additive, and 0.5-3 parts multifunctional gradient stabilizer.

3. The high-strength explosion-proof glass material according to claim 2, characterized in that: The glass powder is a SiO2-Al2O3-B2O3 series glass powder with a particle size of 0.1~5μm; The organic-inorganic hybrid precursor is phenyl polysilsesquioxane; The low-melting-point additive is selected from at least one of bismuth-based glass powder, phosphate glass powder, and boron-zinc-based glass powder. The multifunctional gradient stabilizer is a surface-modified SiO2 aerogel microsphere.

4. The high-strength explosion-proof glass material according to claim 2 or 3, characterized in that, The nucleating agent is selected from any one of the following: BaO-La2O3 composite nucleating agent, wherein the mass ratio of BaO to La2O3 in the BaO-La2O3 composite nucleating agent is 1:(0.5~3); A core-shell type ceramic nano-anchoring agent, comprising a Ba-La composite core and a ZrO2 shell or TiO2 shell covering the composite core.

5. The high-strength explosion-proof glass material according to claim 2 or 3, characterized in that, The raw material components of the material also include 0.3 to 3.6 parts of a siloxane precursor containing dynamic functional groups, wherein the dynamic functional groups are urea groups and / or amide groups.

6. A manufacturing process for the high-strength explosion-proof glass material as described in any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Preparation of hybrid slurry: Organic-inorganic hybrid precursor, glass micro powder, nucleating agent, low melting agent and multifunctional gradient stabilizer are blended in proportion to prepare hybrid precursor slurry; S2. Molding process: The hybrid precursor slurry is prepared into a preform of a predetermined shape; S3. Gradient forming: The billet is placed in an electric field-acoustic field coupling device, and a non-uniform alternating electric field is applied to the upper and lower surfaces of the billet, while ultrasonic-assisted vibration is applied to form a component concentration gradient distribution. S4. Heat treatment: Under an inert atmosphere, the surface of the billet is rapidly radiated and heated until the surface temperature of the billet reaches 600~850℃, then held at that temperature for 20~40 seconds, and then cooled to room temperature.

7. The production process according to claim 6, characterized in that: In step S3, the electric field-acoustic field coupling device includes an interdigitated electrode array disposed on the upper and lower surfaces of the blank; the interdigitated electrode array includes alternating positive and negative electrode strips, the width of the electrode strips is 0.5~2mm, and the spacing between adjacent electrode strips is 1~3mm; In step S3, the frequency range of the non-uniform alternating electric field is 10Hz~1MHz, the frequency of the ultrasonic-assisted vibration is 20kHz~100kHz, and the action time is 5~60 minutes. In step S4, the rapid radiative heating uses an infrared radiation heat source, and the cooling rate is 1~10℃ / min.

8. The production process according to claim 6, characterized in that, The organic-inorganic hybrid precursor is phenyl polysilsesquioxane, which is added after pre-crosslinking treatment through the following steps: S01. Disperse phenyl polysilsesquioxane in anhydrous ethanol or isopropanol, stir until homogeneous, and prepare a solution with a concentration of 30~60wt%. SO2. Under nitrogen protection, add an acidic or basic catalyst, control the pH of the reaction system to 3.0~4.5 or 9.0~10.5, and stir the reaction at 80~120℃ for 2~6 hours. S03. After the reaction is complete, remove the solvent by vacuum distillation at 50~70℃ and -0.08~-0.1MPa until the product is viscous and transparent.

9. The production process according to claim 6, characterized in that, The nucleating agent is a core-shell type ceramic nano-anchoring agent, which is prepared through the following steps: S001. Core liquid preparation: BaO and La2O3 mixed powder with a mass ratio of 1:(0.5~3) is used as the composite core, dispersed in anhydrous ethanol solvent at a mass fraction of 5%~15%, add dispersant and sonicate for 30~60 minutes to obtain core suspension; S002. Addition of shell precursor: Add a shell precursor solution to the core suspension, wherein the shell precursor is selected from at least one of zirconium oxychloride, titanium tetrachloride, n-butyl titanate, and zirconium isopropoxide; wherein the mass ratio of the shell precursor to the composite core is 1:(2~6). S003. Hydrolysis and coating: Maintain the system temperature at 40~65℃, slowly add 5%~10% ammonia solution to the system, adjust the pH value of the system to 8.5~10.5, and continue stirring the reaction for 3~6 hours; S004. Washing and calcining: After centrifugation and washing of the reaction product in step S003, and drying at 80~110℃, the product is calcined at a constant temperature of 550~750℃ for 2~4 hours at a heating rate of 2~5℃ / min to obtain the core-shell ceramic nano-anchoring agent.

10. The production process according to claim 6, characterized in that, Step S1 also includes the addition of a siloxane precursor containing dynamic functional groups, which is prepared through the following steps: S10. Disperse the aminosilane coupling agent and isocyanate monomer in an anhydrous solvent at a mass ratio of 1:(0.4~1.2), wherein the anhydrous solvent is selected from at least one of tetrahydrofuran, ethyl acetate, and dimethylformamide; and stir the reaction at 0~60°C for 2~6 hours under nitrogen protection. S20. The product obtained in step S10 is obtained by removing the solvent by vacuum distillation.

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