High-strength glass bottle and preparation method thereof

Abstract

The invention belongs to the technical field of glass products and manufacturing, and particularly relates to a high-strength glass bottle and a preparation method thereof.The preparation method comprises the following steps that 1, a glass bottle base body is annealed for 1-2 h at the temperature of 550-650 DEG C; (2) immersing the annealed glass bottle substrate into the silane modified nano silicon dioxide sol for 10-30 minutes; (3) heating the infiltrated glass bottle matrix in sections, and preserving heat for 3-5 hours; (4) gradient cooling is carried out, and the cooling process is as follows: in the first stage, cooling is carried out to 500 DEG C at the speed of 100-120 DEG C / h; and in the second stage, cooling to 300 DEG C at 50-60 DEG C / h, and then slowly cooling to room temperature at a constant speed to prepare the high-strength glass bottle. According to the scheme, the silane modified nano silicon dioxide sol is added, the process is improved, the surface stress distribution state of the glass bottle is optimized, and the mechanical strength of the glass bottle is high.

Description

Technical Field

[0001] This invention belongs to the field of glass products and manufacturing technology, specifically a high-strength glass bottle and its preparation method. Background Technology

[0002] With the widespread application of glass products in industrial and daily life sectors, high-strength glass bottles have become a key area of ​​research and development due to their excellent mechanical properties and durability. However, existing high-strength glass bottles and their preparation methods still have certain shortcomings in terms of improving glass strength, enhancing impact resistance, and optimizing production processes, which limits their further promotion in high-end applications.

[0003] CN108689612B discloses a fire-resistant glass and its preparation method. By using a fire-retardant liquid to induce a displacement reaction on the glass surface, combined with a tempering process, the high-temperature resistance, fire resistance, and impact resistance of the glass are significantly improved. However, this technical solution mainly focuses on improving fire resistance; its preparation process has a limited effect on enhancing the overall strength of the glass, especially in addressing the brittleness problem under complex stress environments. Furthermore, the preparation and application processes of the fire-retardant liquid are relatively complex, potentially increasing production costs, and its adaptability for large-scale industrial production needs further improvement.

[0004] The aforementioned problems indicate that existing high-strength glass and its preparation methods still have room for improvement in terms of enhancing the overall mechanical strength of the glass, optimizing its impact resistance, and simplifying the production process. Therefore, this invention provides a high-strength glass bottle and its preparation method, aiming to significantly improve the strength and impact resistance of the glass bottle by optimizing the material formulation and process flow, while simultaneously reducing production costs and meeting the demand for high-performance glass bottles in high-end applications. Summary of the Invention

[0005] To address the shortcomings in mechanical strength of existing high-strength glass bottles, this invention provides a high-strength glass bottle and its preparation method. By adding silane-modified nano-silica sol and synergistically improving the process, the surface stress distribution of the glass bottle is optimized. The silane-modified nano-silica sol formulation is simple, easy to mass-produce industrially, and has mature production support, meeting the demand for high-performance glass bottles in high-end applications.

[0006] A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the glass bottle substrate at 550-650℃ for 1-2 hours to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-sized silica particles with a particle size of 20-50 nm and a mass fraction of 5-15 wt%; γ-aminopropyltriethoxysilane (KH540) was added at an amount of 1-3 wt% of the total mass of the silane-modified nano-silica sol. Boric acid, added at a rate of 0.5-2 wt% of the total mass of the silane-modified nano-silica sol; Fluoride salts, added at a rate of 0.1-1 wt% of the total mass of the silane-modified nano-silica sol; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, heat to 600℃ at a rate of 100-200℃ / h; Step (3-2): Nitrogen gas mixed with 5-10% by volume of ammonia is heated to 620-750℃ at a rate of 20-50℃ / h. Keep warm for 3-5 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100-120℃ / h; In the second stage, the temperature is cooled to 300℃ at a rate of 50-60℃ / h, and then slowly and uniformly cooled to room temperature to obtain a high-strength glass bottle.

[0007] Preferably, the preparation of the silane-modified nano-silica sol in step (2) includes the following operations: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane (KH540) was added. The mixture was ball-milled for 30-60 minutes at pH 4-6. Boric acid and fluoride salts were then added and stirred until homogeneous.

[0008] Preferably, the glass bottle substrate is a sodium-based glass bottle substrate, and the composition of the silane-modified nano-silica sol is as follows: Nano-silica particles: particle size 20-50nm, mass fraction 5-10wt%; γ-aminopropyltriethoxysilane (KH540): mass fraction 1-2 wt%; Boric acid: mass fraction 0.5-1 wt%; The fluoride salt is magnesium fluoride, with a mass fraction of 0.1-0.5 wt%.

[0009] Preferably, the glass bottle substrate is a high borosilicate glass substrate, and the composition of the silane-modified nano-silica sol is as follows: Nano-silica particles: particle size 20-50nm, mass fraction 10-15wt%; γ-aminopropyltriethoxysilane (KH540): 2-3 wt% by mass; Boric acid: mass fraction 0.5-1.5 wt%; The fluoride salt is aluminum fluoride with a mass fraction of 0.1-0.5 wt%.

[0010] Preferably, the glass bottle substrate is a sodium-based glass bottle substrate. Step (3): The impregnated glass bottle is heated in sections. Step (3-1): Under nitrogen atmosphere, heat to 600℃ at a rate of 100-200℃ / h; Step (3-2): Nitrogen gas mixed with 5-10% ammonia by volume is heated to 620-640℃ at a rate of 20-30℃ / h.

[0011] Preferably, the glass bottle substrate is a high borosilicate glass bottle substrate. Step (3): The impregnated glass bottle substrate is heated in sections. Step (3-1): Under nitrogen atmosphere, heat up to 600℃ at a rate of 100-200℃ / h; Step (3-2): Nitrogen gas mixed with 5-10% ammonia by volume is heated to 700-750℃ at a rate of 30-50℃ / h.

[0012] Preferably, in step (2), the immersion time of the glass bottle substrate is 10-30 minutes and the lifting speed is 2-5 mm / s.

[0013] The present invention also discloses the application of the above-mentioned high-strength glass bottle, which is suitable for high-end packaging fields, such as packaging containers for cosmetics, pharmaceuticals and food.

[0014] The method for preparing the high-strength glass bottle provided by this invention includes the following technical steps: First, a glass bottle substrate is provided, and a stress-relief annealing treatment is performed on the glass bottle substrate. The glass bottle substrate is preferably soda-lime glass or borosilicate glass, with a bottle wall thickness set within the range of 1.5-10.0 mm. The purpose of performing the stress-relief annealing treatment is to completely eliminate the internal residual stress generated by uneven thermal shrinkage during the molding and cooling process of the glass bottle, ensuring that the substrate is in a homogeneous and isotropic initial state, providing an ideal, stress-free base for the uniform growth and firm adhesion of the subsequent surface chemical modification layer. The specific process parameters for this annealing treatment are as follows: the glass bottle substrate is placed in a programmable control annealing furnace and heated to the annealing temperature point at a preset heating rate, which is precisely controlled within the range of 550-650°C. Within this temperature range, the compositional activity of the glass substrate is enhanced, sufficient to relax the internal atomic network, thereby releasing macroscopic stress. Subsequently, a isothermal holding treatment is performed at this annealing temperature point, with the isothermal time set to 1-2 hours, to ensure that the stress is fully and completely eliminated. After annealing, cooling is carried out at a controlled, slow rate to avoid introducing new thermal stress during the cooling process.

[0015] Second, a silane-modified nano-silica sol specifically for surface functionalization is prepared, and the glass bottle substrate after the stress-relief annealing treatment is immersed in the sol. The core objective of this step is to uniformly deposit a precursor film containing all the chemical elements required for subsequent high-temperature reactions on the inner and outer surfaces of the glass bottle substrate through an dip-coating method. The silane-modified nano-silica sol comprises, by mass percentage: a nano-silica particle dispersion phase with a nano-silica mass fraction of 5-15%; a silane modifier accounting for 1-3% of the total mass of the silane-modified nano-silica sol; a boron source compound accounting for 0.5-2% of the total mass of the silane-modified nano-silica sol; and a fluoride salt accounting for 0.1-1% of the total mass of the silane-modified nano-silica sol.

[0016] In a preferred embodiment of the present invention, the average particle size of the nano-silica particles is controlled between 20-50 nm. This particle size range is chosen because, on the one hand, the silica particles have extremely high specific surface area and surface energy, exhibiting excellent sintering and chemical reactivity in subsequent high-temperature reactions; on the other hand, particles of this size can form a stable and uniform colloidal dispersion in the sol system, and form a dense and smooth precursor coating after dip-coating. The silane modifier is specifically γ-aminopropyltriethoxysilane. In the structure of this molecule, the triethoxy group at one end can hydrolyze in an aqueous environment to generate active silanol groups. These silanol groups can undergo condensation reactions with the hydroxyl groups on the surface of the nano-silica particles, or chemically bond with the silanol groups on the surface of the glass substrate, thereby firmly anchoring the modifier molecule to the silica particles and the glass substrate surface. The amino group at the other end serves as an auxiliary nitrogen source for the subsequent high-temperature nitriding reaction and can effectively improve the wettability and adhesion between the precursor film and the glass substrate. The boron source compound is specifically boric acid, which decomposes during subsequent high-temperature processing and serves as a source of boron, participating in the formation of the borosilicate network and boron nitride structure. The fluoride salt is specifically aluminum fluoride or magnesium fluoride, selected based on the glass substrate material. At high temperatures, it acts as a catalyst and flux, effectively lowering the melting point of the reaction system, disrupting the silicon-oxygen network on the glass substrate surface, and promoting the diffusion and penetration of elements such as boron and nitrogen. The fluoride salt also acts as a mineralizing agent, reducing the reaction activation energy.

[0017] Furthermore, the preparation process of the silane-modified nano-silica sol includes the following precisely controlled steps: First, a specific amount of nano-silica particles are added to accurately measured deionized water, and ball milling is performed for 30-60 minutes until a uniform, non-agglomerated nano-silica aqueous dispersion is formed. Subsequently, the pH of the dispersion is adjusted to a weakly acidic range of 4-6. Under these pH conditions, a measured amount of γ-aminopropyltriethoxysilane is added. The weakly acidic environment effectively catalyzes the hydrolysis reaction of silane while inhibiting its self-condensation rate, promoting preferential grafting with the hydroxyl groups on the surface of the nano-silica particles. This hydrolysis and condensation reaction is carried out under ball milling conditions for 30-60 minutes to ensure sufficient and uniform chemical modification of the silane molecules on the surface of the nano-silica particles. After silane modification is completed, measured amounts of boric acid and fluoride powder are sequentially added to the sol.

[0018] The annealed glass bottle substrate is completely immersed in the prepared sol for 10-30 minutes to ensure full contact and wetting between the sol and the substrate surface. Then, the glass bottle substrate is vertically lifted from the sol at a constant lifting speed of 2-5 mm / s. This lifting speed is precisely selected to utilize the balance between liquid viscosity and surface tension to form a uniform, drip-free wet film on the substrate surface.

[0019] Third, the glass bottle substrate with the precursor wet film adhering to its surface is placed in a high-temperature reactor with precise atmosphere and temperature program control functions to perform a multi-stage, atmosphere-controlled high-temperature thermochemical reaction treatment. This step is the core of the method of this invention, and its purpose is to cause a series of complex solid-phase and gas-solid-phase chemical reactions between the components in the precursor film and the surface layer of the glass substrate. The specific process parameters of this thermochemical reaction treatment are as follows: First, high-purity nitrogen is introduced into the furnace as a protective atmosphere, and the heating program is initiated. The heating process is divided into two stages: In the first stage, the furnace temperature is raised from room temperature to 600℃ at a heating rate of 100-200℃ / h. In this stage, the moisture and organic solvents in the precursor film are evaporated, γ-aminopropyltriethoxysilane decomposes, its organic segments are removed by pyrolysis, and simultaneously, the silanol groups further condense with the hydroxyl groups of the matrix and silica particles to form a preliminary Si-O-Si framework.

[0020] Secondly, when the furnace temperature reaches 600℃, ammonia gas is introduced into the furnace to form a nitrogen-ammonia mixed reaction atmosphere with the existing nitrogen gas at a volume concentration ratio of 5-10%. At this time, the second heating stage is initiated, raising the furnace temperature from 600℃ to the final reaction temperature at a slower rate. The final reaction temperature is set according to the softening temperature of the glass substrate. The reason for introducing ammonia gas only above 600℃ is that ammonia gas can only partially decompose into highly reactive nitrogen and hydrogen free radicals above this temperature. These reactive nitrogen species then undergo a displacement reaction with the silicon-oxygen network and boron-oxygen network of the precursor layer and the surface of the glass substrate, i.e., a nitriding reaction. The slower heating rate provides sufficient time for these diffusion and reaction processes, ensuring the uniformity and depth of the nitriding reaction.

[0021] Next, once the furnace temperature reaches the preset reaction temperature, it enters a constant-temperature holding stage. Throughout this stage, a nitrogen-ammonia mixed atmosphere is continuously introduced, and the holding time is set to 3-5 hours. Although this temperature is insufficient to fully activate all the ammonia, under the conditions of ammonia volume content and holding, the nitriding reaction, boronizing reaction, and fluorine catalysis / curing reaction can proceed sufficiently. Specifically, the main chemical transformations include: the Si-O-Si bonds in the glass matrix and nano-silica particles partially break under high temperature and the catalytic action of fluoride ions, reacting with active nitrogen species to form Si-N bonds with higher chemical bond energy and a more stable structure, forming silicon oxynitride or silicon nitride structural units. Simultaneously, boron oxide produced by the decomposition of boric acid reacts with the silicon-oxygen network to form a borosilicate structure, and reacts with active nitrogen species to form extremely strong BN bonds, forming boron nitride-like structural units. Ultimately, a three-dimensional covalent network structure is formed on the surface and subsurface of the glass bottle substrate, which is composed of various chemical bonds such as Si-O-Si, Si-OB, Si-N, BN, and Si-OB, and is seamlessly connected to the glass substrate through chemical bonds.

[0022] Fourth, after completing the above-mentioned high-temperature insulation reaction, a precisely controlled gradient cooling procedure is performed on the glass bottle. The purpose of this step is to avoid harmful thermal mismatch stress between the reinforcing layer and the substrate due to excessively rapid cooling rate. At the same time, by controlling the cooling rate in different temperature zones, a beneficial, small residual compressive stress is introduced on the outermost surface of the reinforcing layer, further enhancing its resistance to mechanical damage.

[0023] The gradient cooling process comprises three stages: The first cooling stage involves cooling the glass bottle from the reaction temperature to 500°C at a rate of 100-120°C / h. This is near the upper boundary of the stress relaxation zone in the glass; the faster cooling rate aims to freeze the dense network structure formed at high temperatures. The second cooling stage involves cooling the glass bottle from 500°C to 300°C at an extremely slow rate of 50°C / h. This is the glass transition zone; the slow cooling allows the stress generated between the reinforcing layer and the glass matrix due to the slight difference in their coefficients of thermal expansion to be fully and uniformly released and redistributed, preventing the formation of microcracks. Finally, the glass is slowly and uniformly cooled to room temperature to obtain a high-strength glass bottle, avoiding the introduction of harmful stress.

[0024] This solution also proposes a method for preparing the aforementioned high-strength glass bottle.

[0025] Compared with the prior art, the present invention has the following advantages: 1. The high-strength glass bottle of the present invention optimizes the surface stress distribution of the glass bottle by introducing a complex collaborative network structure and adding silane-modified nano-silica sol. The silane-modified nano-silica sol formulation is simple, easy to mass-produce industrially, and has mature production support, meeting the needs of high-end application fields for high-performance glass bottles.

[0026] 2. Based on the material characteristics of the glass bottle substrate, this invention adaptively adjusts the composition of the modified nano-silica sol and correspondingly adjusts the heat treatment process, resulting in better product adaptability. Detailed Implementation

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0029] Example 2 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 600℃ for 1.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 25nm; mass fraction of nano silica 6wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.2 wt%; Boric acid: 0.6 wt% (mass fraction); Magnesium fluoride: 0.2 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 40 min at pH 4.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 15 minutes, and the lifting speed was 4 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 180℃ / h; Step (3-2): Nitrogen gas mixed with 6% ammonia gas is heated to 650℃ at a rate of 30℃ / h. Keep warm for 3.5 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 110℃ / h; The second stage involves cooling to 300℃ at a rate of 50℃ / h. The third stage involves cooling the glass to room temperature at 150℃ / h to produce a high-strength glass bottle.

[0030] Example 3 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 580℃ for 1.5h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 30nm; mass fraction of nano-silica 7wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.5 wt% Boric acid: 0.7 wt% (mass fraction); Magnesium fluoride: 0.3 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 45 min at pH 5.0. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 20 minutes, and the lifting speed was 3 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 150℃ / h; Step (3-2): Nitrogen gas mixed with 5% ammonia gas is heated to 640℃ at a rate of 25℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0031] Example 4 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 640℃ for 1.2h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 40nm; mass fraction of nano-silica 9wt% γ-Aminopropyltriethoxysilane KH540: 2.0 wt% (mass fraction); Boric acid: 0.9 wt% (mass fraction); Magnesium fluoride: 0.5 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 35 min at pH 6.0. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The glass bottle substrate was immersed for 30 minutes, and the lifting speed was 2 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 120℃ / h; Step (3-2): Nitrogen gas mixed with 5% ammonia gas is heated to 650℃ at a rate of 20℃ / h. Insulate for 5.0 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0032] Example 5 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 650℃ for 1.8h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 45nm; mass fraction of nano-silica 10wt% γ-Aminopropyltriethoxysilane KH540: mass fraction 1.0 wt% Boric acid: 1.0 wt% (mass fraction); Magnesium fluoride: 0.1 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 60 min at pH 4.0. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate is 10 minutes, and the lifting speed is 5 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 100℃ / h; Step (3-2): Nitrogen gas mixed with 9% ammonia gas is heated to 620℃ at a rate of 20℃ / h. Insulate for 3.0 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0033] Example 6 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the high borosilicate glass bottle substrate at 580℃ for 1.5h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 35nm; mass fraction of nano-silica 12wt%; γ-aminopropyltriethoxysilane KH540: mass fraction 2.5 wt%; Boric acid: 1.0 wt% (mass fraction); Aluminum fluoride: 0.3 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 45 min at pH 5.0. Then boric acid and aluminum fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 20 minutes, and the lifting speed was 3 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 150℃ / h; Step (3-2): Nitrogen gas mixed with 6% ammonia gas is heated to 700℃ at a rate of 30℃ / h. Insulate for 4.0 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0034] Example 7 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the high borosilicate glass bottle substrate at 620℃ for 1.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 45nm; mass fraction of nano-silica 14wt%; γ-aminopropyltriethoxysilane KH540: mass fraction 2.8 wt% Boric acid: 1.3 wt% (mass fraction); Aluminum fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 4.5. Then boric acid and aluminum fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 180℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 730℃ at a rate of 40℃ / h. Insulate for 3.0 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0035] Example 8 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the high borosilicate glass bottle substrate at 650℃ for 1.8h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 25nm; mass fraction of nano-silica 15wt% γ-Aminopropyltriethoxysilane KH540: 2.0 wt% (mass fraction); Boric acid: 0.5 wt% (mass fraction); Aluminum fluoride: 0.1 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 30 min at pH 5.5. Then boric acid and aluminum fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate is 10 minutes, and the lifting speed is 2 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 10% ammonia gas is heated to 750℃ at a rate of 50℃ / h. Insulate for 5.0 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0036] Comparative Example 1 A high-strength glass bottle is prepared by the following steps: Step (1): Immerse the glass bottle substrate in silane-modified nano-silica sol, which also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (2): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (3): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0037] Comparative Example 2 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 500℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0038] Comparative Example 3 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Heat the glass bottle base in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Step (3): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0039] Comparative Example 4 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5, and then magnesium fluoride was added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0040] Comparative Example 5 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5, and then boric acid was added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0041] Comparative Example 6 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water and ball-milled for 50 minutes at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0042] Comparative Example 7 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 35nm; mass fraction of nano-silica 12wt%; γ-aminopropyltriethoxysilane KH540: mass fraction 2.5 wt%; Boric acid: 1.2 wt% (mass fraction); Magnesium fluoride: 0.6 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0043] Comparative Example 8 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Under nitrogen atmosphere, the temperature is increased to 640℃ at a rate of 20℃ / h; Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0044] Comparative Example 9 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 6 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0045] Comparative Example 10 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 800℃ at a rate of 90℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0046] Comparative Example 11 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (4): Cool directly to room temperature at a cooling rate of 50℃ / h to obtain a high-strength glass bottle.

[0047] Comparative Example 12 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 5 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 4 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0048] Comparative Example 13 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the sodium-based glass bottle substrate at 620℃ for 2.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano silica particles: particle size 35nm; mass fraction of nano silica 8wt% γ-aminopropyltriethoxysilane KH540: mass fraction 1.8 wt% Boric acid: 0.8 wt% (mass fraction); Magnesium fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 5.5. Then boric acid and magnesium fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4.5 mm / s; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Keep warm for 2 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0049] Comparative Example 14 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the high borosilicate glass bottle substrate at 620℃ for 1.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 45nm; mass fraction of nano-silica 10wt% γ-Aminopropyltriethoxysilane KH540: 2.0 wt% (mass fraction); Boric acid: 0.5 wt% (mass fraction); Aluminum fluoride: 0.1 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 4.5. Then boric acid and aluminum fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 180℃ / h; Step (3-2): Nitrogen gas mixed with 4% ammonia gas is heated to 730℃ at a rate of 40℃ / h; Insulate for 1.0 hour; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0050] Comparative Example 15 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the high borosilicate glass bottle substrate at 620℃ for 1.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 45nm; mass fraction of nano-silica 14wt%; γ-aminopropyltriethoxysilane KH540: mass fraction 2.8 wt% Boric acid: 1.3 wt% (mass fraction); Aluminum fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 4.5. Then boric acid and aluminum fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 200℃ / h; Step (3-2): Nitrogen gas mixed with 8% ammonia gas is heated to 640℃ at a rate of 20℃ / h. Insulate for 1.0 hour; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0051] Comparative Example 16 A high-strength glass bottle is prepared by the following steps: Step (1): Anneal the high borosilicate glass bottle substrate at 620℃ for 1.0h to eliminate residual stress; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano-silica sol. The modified nano-silica sol also contains the following components: Nano-silica particles: particle size 45nm; mass fraction of nano-silica 14wt%; γ-aminopropyltriethoxysilane KH540: mass fraction 2.8 wt% Boric acid: 1.3 wt% (mass fraction); Aluminum fluoride: 0.4 wt% by mass; The preparation of silane-modified nano-silica sol includes the following steps: Nano-silica particles were mixed with deionized water, and γ-aminopropyltriethoxysilane KH540 was added. The mixture was ball-milled for 50 min at pH 4.5. Then boric acid and aluminum fluoride were added and stirred until homogeneous. The immersion time for the glass bottle substrate was 25 minutes, and the lifting speed was 4 mm / s. Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, the temperature is increased to 600℃ at a rate of 180℃ / h; Step (3-2): Under nitrogen atmosphere, the temperature is increased to 730℃ at a rate of 40℃ / h; Insulate for 1.0 hour; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100℃ / h; In the second stage, the glass was cooled to 300°C at a rate of 50°C / h, and then slowly cooled to room temperature at a rate of 1°C / min to obtain a high-strength glass bottle.

[0052] The substrate composition of the glass bottles used in the above embodiments and comparative examples is shown in Table 1.

[0053] Table 1. Substrate composition (wt%) of the glass bottles used in the examples and comparative examples.

[0054] Performance testing: The Vickers hardness of the outer surfaces of samples S1 and D1 was tested using a DUH-211S type ultra-micro dynamic hardness tester manufactured by Shimadzu Corporation of Japan (load 10mN, hold pressure 15s). The fracture toughness was tested using the single-sided pre-cracked beam method (SEPB) and an MTS Insight 10 universal testing machine. The surface residual stress was measured using an FSM-6000LE surface stress meter manufactured by Orihara Manufacturing Co., Ltd. of Japan. The thickness of the reinforcement layer in sample S1 was measured using an IMS 7f secondary ion mass spectrometer (SIMS) manufactured by Cameca GmbH, Germany.

[0055] The test results are shown in Table 2.

[0056] Table 2. Performance test results of glass bottles prepared in the examples and comparative examples. (In the table, negative values ​​of surface residual stress represent tensile stress.)

[0057] This invention achieves the fabrication of high-strength glass bottles through molecular-level design: First, a silane-coupled nano-silica network is constructed on the surface of a glass substrate, where the amino and ethoxy groups of γ-aminopropyltriethoxysilane provide nitridation reaction sites and interfacial anchoring effects, respectively. After annealing to eliminate internal stress, segmented heat treatment triggers multi-stage reactions—the precursor undergoes dehydration condensation at 600℃ to form a continuous framework, and active nitrogen atoms generated by the decomposition of ammonia above 600℃ permeate into the interior of the glass network, replacing silicon-oxygen bonds under the catalysis of fluoride ions to generate high-strength Si-N covalent bonds. Simultaneously, boric acid decomposition products react with nitrogen to form a boron nitride-like BN network. Finally, a gradient cooling process rapidly freezes the surface layer to form a dense Si-OBN composite structure, while the core slowly cools to release thermal stress, forming a uniform compressive stress field on the surface. This design enables the glass bottle surface to form a chemically bonded ceramic reinforcement layer, whose high bond energy network resists plastic deformation, while the compressive stress induced by the gradient thermal expansion coefficient difference inhibits crack initiation, achieving a synergistic improvement in strength and toughness while maintaining lightweight design.

[0058] The comparative performance degradation stems from the instability of the reinforcing layer structure due to the absence of key components or processes: In the soda-lime glass system, the lack of annealing treatment causes the residual stress in the matrix to superimpose with the shrinkage stress of the reinforcing layer, leading to interfacial microcracks; the absence of boric acid prevents the construction of the boron-nitrogen network, relying solely on silicon-oxygen bonds for reinforcement; the lack of fluorine salt catalysis results in insufficient cleavage of the silicon-oxygen network, hindering nitrogen atom diffusion; the absence of ammonia completely disables the nitriding reaction, preventing the formation of high-strength Si-N bonds; excessively fast pulling speed leads to uneven coating thickness, creating stress-weak areas; and overheating causes glass softening and deformation, disrupting network continuity. In the high borosilicate glass bottle matrix system, insufficient temperature prevents the boron-oxygen three-membered ring from opening and participating in the reaction, insufficient heat preservation results in a low BN bond formation rate, and insufficient ammonia concentration limits the nitriding depth. The common defect is that process deviations disrupt the stoichiometry of the Si-OBN quaternary network or interrupt the formation of the gradient stress field, resulting in structural discontinuities, weakened interfacial bonding, or harmful tensile stress concentrations in the reinforcing layer, ultimately manifesting as a systematic decrease in hardness and toughness.

Claims

1. A method for preparing a high-strength glass bottle, characterized in that, Includes the following steps: Step (1): Anneal the glass bottle substrate at 550-650℃ for 1-2 hours; Step (2): Immerse the annealed glass bottle substrate in silane-modified nano silica sol for 10-30 minutes; Step (3): Heat the impregnated glass bottle substrate in sections: Step (3-1): Under nitrogen atmosphere, heat to 600℃ at a rate of 100-200℃ / h; Step (3-2): Nitrogen gas mixed with 5-10% by volume of ammonia is heated to 620-750℃ at a rate of 20-50℃ / h. Keep warm for 3-5 hours; Step (4): Perform gradient cooling. The cooling process is as follows: The first stage involves cooling to 500℃ at a rate of 100-120℃ / h; The second stage involves cooling the glass to 300℃ at a rate of 50-60℃ / h, followed by slow and uniform cooling to room temperature to produce a high-strength glass bottle. The silane-modified nano-silica sol contains 5-15 wt% nano-silica and also includes the following components: γ-aminopropyltriethoxysilane, added at an amount of 1-3 wt% of the total mass of the silane-modified nano-silica sol; Boric acid, added at a rate of 0.5-2 wt% of the total mass of the silane-modified nano-silica sol; Fluoride salts are added at a rate of 0.1-1 wt% of the total mass of the silane-modified nano-silica sol.

2. The method for preparing a high-strength glass bottle as described in claim 1, characterized in that, The preparation of the silane-modified nano-silica sol in step (2) includes the following processes: According to the formula, mix nano-silica particles with deionized water, add γ-aminopropyltriethoxysilane, ball mill for 30-60 minutes under pH 4-6 conditions, then add boric acid and fluoride and stir evenly.

3. The method for preparing a high-strength glass bottle as described in claim 1, characterized in that, The glass bottle substrate is a sodium-based glass substrate or a borosilicate glass substrate.

4. The method for preparing a high-strength glass bottle as described in claim 3, characterized in that, The glass bottle substrate is a sodium-based glass substrate, and the composition of the silane-modified nano-silica sol is as follows: Nano-silica particles: particle size 20-50nm, mass fraction 5-10wt%; γ-aminopropyltriethoxysilane (KH540): mass fraction 1-2 wt%; Boric acid: mass fraction 0.5-1 wt%; The fluoride salt is magnesium fluoride, with a mass fraction of 0.1-0.5 wt%.

5. The method for preparing a high-strength glass bottle as described in claim 3, characterized in that, The glass bottle substrate is a high borosilicate glass substrate, and the composition of the silane-modified nano-silica sol is as follows: Nano-silica particles: particle size 20-50nm, mass fraction 10-15wt%; γ-aminopropyltriethoxysilane: mass fraction 2-3 wt%; Boric acid: mass fraction 0.5-1.5 wt%; The fluoride salt is aluminum fluoride with a mass fraction of 0.1-0.5 wt%.

6. The method for preparing a high-strength glass bottle as described in claim 3, characterized in that, The glass bottle substrate is a sodium-based glass substrate. Step (3): Heat the impregnated glass bottle in sections: Step (3-1): Under nitrogen atmosphere, heat to 600℃ at a rate of 100-200℃ / h; Step (3-2): Nitrogen gas mixed with 5-10% ammonia by volume is heated to 620-640℃ at a rate of 20-30℃ / h.

7. The method for preparing a high-strength glass bottle as described in claim 3, characterized in that, The glass bottle substrate is a high borosilicate glass substrate. Step (3): The impregnated glass bottle substrate is heated in sections: Step (3-1): Under nitrogen atmosphere, heat up to 600℃ at a rate of 100-200℃ / h; Step (3-2): Nitrogen gas mixed with 5-10% ammonia by volume is heated to 700-750℃ at a rate of 30-50℃ / h.

8. The method for preparing a high-strength glass bottle as described in claim 1, characterized in that, The lifting speed of the glass bottle substrate after impregnation in step (2) is 2-5 mm / s.

9. The method for preparing a high-strength glass bottle as described in claim 1, characterized in that, In step (4), the cooling rate for slowly and uniformly cooling to room temperature is 1℃ / min.

10. A high-strength glass bottle, prepared by the method for preparing a high-strength glass bottle according to any one of claims 1-9.

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