Device for improving anti-falling performance of vessel glass and composite strengthening method

Abstract

The invention relates to a device for improving the anti-falling performance of vessel glass and a composite strengthening method, which are characterized by comprising the following steps: (1) flexibly bundling non-key stress parts of the vessel glass through stainless steel wires, suspending the vessel glass on a chemical tempering frame, and immersing the vessel glass in a molten mixed salt bath for ion exchange; (2) ultrasonically cleaning with deionized water, drying, cooling, putting into a physical tempering clamp, and feeding into a physical tempering furnace for heating and quenching treatment; (3) binding the physically tempered vessel glass on the chemical tempering frame again through the stainless steel wire, and immersing the vessel glass in the molten salt bath for secondary ion exchange; (4) then taking out and placing in a drying oven for gradient slow cooling to room temperature; after the strapping steel wires are removed, deionized water is used for ultrasonic cleaning, drying is conducted, and the vessel glass product with the reinforced anti-falling performance is obtained. The method has the advantages that the advantages of physical strengthening and chemical strengthening are combined, the falling height of unstrengthened container glass can be increased from 30 cm to 1 m, and the container glass is not damaged after falling by 90% or above.

Description

Technical Field

[0001] This invention belongs to the field of glass manufacturing technology and relates to a device and composite strengthening method for improving the drop resistance of glassware. Background Technology

[0002] For glassware (such as wine glasses and gallon bottles), drop resistance is a key indicator of its quality and lifespan during daily use and transportation. Traditional strengthening methods mainly include physical tempering and chemical tempering. Physical tempering involves heating and rapidly cooling the glass to create compressive stress on the surface and tensile stress internally, thus enhancing its strength. Chemical tempering uses ion exchange, replacing small-radius alkali metal ions on the glass surface with large-radius alkali metal ions to form a surface compressive stress layer. However, physical tempering alone can lead to uneven stress distribution, increased risk of spontaneous breakage, and insufficient edge strength for glassware with complex shapes or thin walls. While chemical tempering alone can achieve higher surface compressive stress and a certain stress layer depth, its overall improvement in impact and bending resistance is insufficient to meet high drop resistance requirements.

[0003] Therefore, developing a strengthening method to significantly improve the drop resistance of glassware is of great application value. Summary of the Invention

[0004] The purpose of this invention is to overcome the limitations of existing single-strength methods for improving the drop resistance of glassware, and to provide a device and composite strengthening method for improving the drop resistance of glassware. This invention significantly improves the drop height pass rate of glassware on tiled floors by synergistically optimizing the key parameters and process design of the two-step chemical tempering and intermediate physical tempering processes. Simultaneously, the physical tempering fixture and chemical tempering support have been redesigned, making the sample more stable during the tempering process and ensuring more uniform heating, thus guaranteeing the tempering effect.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A chemical tempering support for improving the drop resistance of glassware is characterized by mainly consisting of a base (1) and a support frame (2). The base is a grid groove, and the support frame consists of two columns and a crossbar. The crossbar and the columns are connected by a bearing (3) (which can rotate within a limited range of ±30° around the longitudinal axis to adjust the posture of the suspended sample), forming an inverted "U" shape. The two columns are set on the grid groove. A set of (6-10) cantilever crossbars (4) are symmetrically arranged on the crossbar. A set of (3-5) branch suspension rods (5) are arranged on each cantilever crossbar. The branch suspension rods are at an angle of 30°-45° with the crossbar, forming a multi-layer suspension structure. Multiple samples can be suspended in parallel by winding and fixing the tail end of the stainless steel wire (6) (the single load capacity is increased by 40%-60% compared with the traditional frame).

[0006] Furthermore, the mesh groove is made of 316L stainless steel with a mesh aperture of 5-10mm, combining structural support strength with salt bath flowability.

[0007] Furthermore, the ends of the cantilever crossbar and branch suspension rod are hemispherical round heads (radius 5-8mm) to avoid scratching the binding wire.

[0008] Furthermore, the length of the crossbar is 800-1200mm; the length of the cantilever crossbar is 150-200mm and the diameter is 10-15mm; the length of the branch suspension bar is 80-120mm and the diameter is 6-8mm.

[0009] By adjusting the rotation angle of the transverse main beam, the tilting posture of the sample can be dynamically adjusted during the immersion of the glassware in the salt bath, promoting the expulsion of air from inside the glassware along the bottle opening and avoiding uneven ion exchange caused by trapped air bubbles.

[0010] A physical tempering clamp for improving the drop resistance of glassware is characterized by comprising a clamp base and a clamp top cover for use together, wherein the clamp bottom includes a rectangular frame (7) and an adjustable grid (10) set in the rectangular frame, both the rectangular frame and the grid are provided with positioning holes (8), and the grid is provided with tenons (11) inserted into the positioning holes on multiple crossbeams (transverse grid bars); the clamp top cover is a grid cover plate (13).

[0011] Furthermore, the fixture base and the fixture top cover are fixed by buckles and slots.

[0012] Furthermore, both the fixture base and the fixture top cover are made of high-temperature resistant quartz glass (softening point > 1600℃). Furthermore, the dimensions of the rectangular frame are 600×800mm-1000×1200mm.

[0013] Furthermore, the diameter of the positioning hole is 5-8mm, and the hole spacing is 10-15mm.

[0014] Furthermore, the adjustable grid is composed of 10-15 movable horizontal grid bars and 8-12 movable vertical grid bars intersecting each other. Both the horizontal and vertical grid bars have rectangular cross sections (width 8-12mm, thickness 3-5mm). Both ends of the grid bars are integrally formed with vertical positioning tenons (height 10-15mm, diameter 4-7mm). The tenons can be inserted into the array positioning holes of the outer peripheral fixed frame to achieve position fixation.

[0015] By adjusting the intersection spacing of the horizontal and vertical grid bars, the size of the grid unit can be flexibly changed (minimum grid unit 50×50mm, maximum grid unit 200×200mm) to adapt to glass workpieces of different shapes (such as round bottles, square jars, irregularly shaped vessels, etc.) and sizes. Stable clamping is achieved by mechanically limiting the outer periphery of the workpiece through the grid bars.

[0016] The grid assembly is covered with an upper grid cover plate (the grid structure matches the adjustable grid assembly). The cover plate has 4-6 peripheral locking buckles around its perimeter. The buckles cooperate with the slots on the edge of the peripheral fixing frame to achieve a tight fixation between the cover plate and the grid assembly, preventing workpiece displacement during quenching.

[0017] A composite strengthening method for improving the drop resistance of glassware, characterized by comprising the following steps: The glass vessel to be strengthened is flexibly bound with stainless steel wire to non-critical stress-bearing parts (such as the neck and bottom edge of the vessel), suspended on a chemical tempering frame, and then immersed in a molten mixed salt bath for ion exchange. The mass ratio of potassium nitrate (KNO3) to sodium nitrate (NaNO3) in the mixed salt bath is 4:6~2:8 (preferably 3:7), the salt bath temperature is controlled at 380-420℃ (fluctuation range ±2℃), and the ion exchange time is 0.5-5 hours (adjusted according to the vessel wall thickness: 0.5-2 hours for a wall thickness of 3-5mm, and 2-5 hours for a wall thickness of 5-8mm), forming an initial exchange stress layer on the glass surface. Remove the glassware treated in step (1) from the salt bath and use deionized water for ultrasonic cleaning (power 300-500W, time 5-10 minutes) to remove residual salt stains on the surface. Then place it in a hot air circulating oven at 80-100℃ for 30-60 minutes to dry. After cooling to room temperature, place it in a physical tempering fixture and send the whole thing into a physical tempering furnace for heating and quenching treatment. The assembled glassware is placed in a physical tempering furnace and subjected to a two-step heating process: first, it is held at a temperature 20-50°C below the glass's annealing point for 0.5-2 hours (adjusted according to glass thickness: 0.5-1 hour for 3-5mm thick glass, 1-2 hours for 5-8mm thick glass); then, it is heated to 50-150°C above the glass transition temperature (Tg) (adjusted according to glass composition: soda-lime-silica glass has a Tg of approximately 520-580°C, heating temperature 570°C). The glass is then heated to -730℃ and held for 100-1000 seconds (100-500 seconds for 3-5mm thick glass, and 500-1000 seconds for 5-8mm thick glass) to ensure the glass surface reaches a viscoelastic state. Subsequently, it is symmetrically quenched from both sides of the furnace for 10-300 seconds using 0.3-8MPa high-pressure cold air (dew point < -40℃), followed by further cooling with 2-5MPa air pressure for 50-500 seconds, thus forming a physically tempered compressive stress layer on top of the initial exchange stress layer. This physical tempering process, as an intermediate step, not only rapidly cools and superimposes physical compressive stress but also reorganizes the ion distribution on the glass surface through the initial heat preservation treatment, opening ion diffusion channels and thus deepening the stress layer generated in the first step of chemical tempering.

[0018] (3) After physical tempering, the glassware is re-tied with stainless steel wire to a chemical tempering rack and immersed in a molten salt bath for secondary ion exchange. The main component of the salt bath is potassium nitrate (KNO3, purity ≥99.5%), and 0-10wt% sodium nitrate (NaNO3, purity ≥99.5%) (as well as trace amounts (≤1%) of potassium phosphate K3PO4 and potassium sulfate K2SO4 as impurity removers) are added to adjust the ion diffusion coefficient. The temperature of the salt bath is controlled at 420-450℃ (fluctuation range ±1℃) by a dual-zone heating system. The ion exchange time is 3-6 hours (adjusted according to the target stress layer depth: 3-4 hours for a depth of 200-300μm, and 4-6 hours for a depth of 300-500μm). Finally, a composite stress layer with a depth of 200-500μm (the initial chemical stress layer, the physical tempering stress layer and the secondary chemical stress layer are superimposed) is formed on the glass surface. (4) Remove the glassware treated in step (3) from the salt bath and place it in a hot air circulating oven at 80-120℃ for gradient slow cooling (cooling rate 5-10℃ / min) to room temperature to eliminate thermal stress; after removing the binding steel wire, use deionized water for ultrasonic cleaning (power 400-600W, temperature 50-60℃, time 15-20 minutes) to remove residual salt, and finally dry it with hot air at 100-120℃ (time 30-45 minutes) to obtain glassware products with enhanced drop resistance.

[0019] The beneficial effects of this invention are: The device described in this invention is easy to operate and convenient for sample loading, reducing sample damage caused by human error during operation. The chemical tempering support maximizes the contact area between the glass and the strengthening molten salt, improving the uniformity of strengthening. The physical tempering fixture can be adjusted according to the sample size, ensuring the sample is firmly fixed within the fixture and will not shake due to the cooling air pressure of physical strengthening, thus improving the yield. This strengthening method combines the advantages of physical and chemical strengthening, significantly improving the impact resistance of container glass. It can increase the drop height of unstrengthened container glass from 30cm to 1m with over 90% of cases remaining unbroken. Attached Figure Description

[0020] Figure 1 This is a front view of the chemically tempered support. Figure 2 This is a structural diagram of a chemically tempered support structure. Figure 3 Diagram of the physical tempered fixture base; Figure 4 This is a diagram of the top cover of the physically tempered fixture. Detailed Implementation

[0021] The following is combined Figure 1-4 The present invention will be further described as follows: A chemically tempered glass support for improving the drop resistance of glassware mainly consists of a base 1 and a support frame 2. The base is a grid groove (made of 316L stainless steel, with a grid aperture of 5-10mm). The support frame consists of two uprights (400-600mm high) and a crossbar (800-1200mm long). The crossbar and uprights are connected by bearings 3 (allowing for limited rotation within ±30° around the longitudinal axis to adjust the posture of the suspended sample), forming an inverted "U" shape. The two uprights are set on the grid groove. A set of 6-10 bearings is symmetrically arranged on the crossbar. The system consists of 4 cantilever crossbars, each 150-200mm long and 10-15mm in diameter. Each cantilever crossbar has a set of 3-5 branch suspension rods, each 80-120mm long and 6-8mm in diameter. The ends of the cantilever crossbars and branch suspension rods are hemispherical (5-8mm in radius) to avoid scratching the binding wire. The branch suspension rods form a 30°-45° angle with the crossbars, creating a multi-layer suspension structure. Multiple samples can be suspended in parallel by wrapping and fixing the ends of stainless steel wires 6 (the single load capacity is increased by 40%-60% compared to traditional frames).

[0022] A physical tempering fixture for improving the drop resistance of glassware includes a fixture base and a fixture top cover, which are fixed by snaps and slots. The bottom of the fixture includes a rectangular frame 7 (600×800mm-1000×1200mm) and adjustable grids 10 within the rectangular frame. Both the rectangular frame and the grids have positioning holes 8 (5-8mm in diameter, 10-15mm spacing). The grids have multiple horizontal beams (horizontal bars) with tenons 11 inserted into the positioning holes. The fixture top cover is a grid cover plate 13; the adjustable grid is composed of 10-15 movable horizontal grid bars and 8-12 movable vertical grid bars intersecting each other. Both the horizontal and vertical grid bars have rectangular cross sections (width 8-12mm, thickness 3-5mm); both ends of the grid bars are integrally formed with vertical positioning tenons (height 10-15mm, diameter 4-7mm), which can be inserted into the array positioning holes of the outer peripheral fixed frame to achieve position fixation; the fixture base and the fixture top cover are both made of high-temperature resistant quartz glass with a softening point >1600℃. By adjusting the intersection spacing of the horizontal and vertical grid bars, the size of the grid unit can be flexibly changed (minimum grid unit 50×50mm, maximum grid unit 200×200mm) to adapt to glass workpieces of different shapes (such as round bottles, square jars, irregularly shaped vessels, etc.) and sizes. Stable clamping is achieved by mechanically limiting the outer periphery of the workpiece through the grid bars. Example 1

[0023] A sodium-calcium-silicon wine dispenser (specifications: height 150mm, diameter 80mm, wall thickness 3.5mm) was selected. Its original drop resistance performance was tested according to the GB / T 3810.4-2016 standard. The results showed that under the condition of free drop from a height of 30cm on a ceramic tile floor, the breakage rate was 62%, and the test sample size was 50.

[0024] A composite strengthening method for improving the drop resistance of glassware, comprising the following specific steps: S1: First step chemical tempering treatment A single loop of 0.5mm diameter 304 stainless steel wire (polished surface) was used to bind the neck of the distiller (20mm from the bottle mouth), with a contact length of 1 / 3 of the neck circumference (approximately 25mm) and a binding tension of 0.08MPa. The sample was suspended from a chemically tempered 316 stainless steel support (branched suspension rod) and completely immersed in a mixed salt bath (KNO3:NaNO3 mass ratio 4:6, purity 99.9%) (salt bath depth 300mm). The salt bath temperature was controlled at 400±2℃, the stirring rate at 50rpm, and the ion exchange time at 2 hours. Post-treatment testing showed an initial surface compressive stress of 85±5MPa and a stress layer depth of 75±3μm. S2: Physical tempering treatment After removing the sample, it was ultrasonically cleaned with 60℃ deionized water for 20 minutes (power 400W) and dried at 120℃ for 30 minutes. The sample was then placed in a physical tempering fixture, which included an outer fixed frame (600×800mm high-temperature resistant quartz glass frame), an adjustable grid assembly (10 horizontal grid bars and 8 vertical grid bars intersecting to form a 50×50mm grid unit), and an upper grid cover plate (4 outer locking buckles). The clamped sample was then placed in a physical tempering furnace with the following parameters: first, it was held at 30℃ (520℃) below the annealing point for 1 hour, then heated to 650±5℃ (Tg+100℃) and held for 60 seconds (nitrogen atmosphere purity 99.99%). Cooling stage: 0.4MPa air pressure quenching for 15 seconds, 2MPa air pressure cooling for 60 seconds. Post-treatment testing: superimposed compressive stress 120±8MPa, total stress layer depth 150±5μm. S3: Second step chemical tempering treatment The original binding position was re-bound with 0.5mm stainless steel wire, and then immersed in a molten salt bath with a mass concentration of 95% KNO3 + 5% NaNO3 (purity 99.9%). The salt bath temperature was 430±2℃, the stirring rate was 40rpm, and the ion exchange time was 4 hours. After treatment, the test results showed that, according to national standards, the surface compressive stress of tempered glass should be greater than or equal to 90MPa. The surface compressive stress was 450±15MPa, and the total stress layer depth was 350±10μm, which meets the qualified standards for tempered glass.

[0025] S4: Post-processing The sample treated in step S3 was removed from the salt bath and placed in a 100℃ oven to cool slowly to room temperature (cooling rate 5℃ / min). After removing the steel wire, it was ultrasonically cleaned with 50℃ deionized water for 20 minutes (power 400W) and dried at 110℃ for 35 minutes. Performance Testing: According to DIN 51130-2010 standard, the ceramic tile flooring (dry state, water absorption rate 0.5%, coefficient of friction 0.6) underwent a 1m drop test. During the test, the sample orientations included bottle opening upwards (30 drops), bottle opening downwards (20 drops), and horizontal (50 drops), with 100 samples tested in each group. The test results show that the coefficient of friction of this ceramic tile flooring meets the standard for medium to high slip resistance. Results: 8 samples were damaged (5 bottle opening downwards, 3 horizontal), with a 92% integrity rate; Stress distribution detection: the standard deviation of surface compressive stress ≤15MPa, stress gradient 0.8MPa / μm. Example 2

[0026] Sodium calcium silicon wine glasses were selected (specifications: height 100mm, diameter 60mm, wall thickness 2.8mm; original drop resistance performance: 65% breakage rate when dropped freely from a height of 30cm onto a ceramic tile floor, n=50).

[0027] A composite strengthening method for improving the drop resistance of glassware, comprising the following specific steps: S1: First step chemical tempering treatment A single loop of 0.4mm diameter 316 stainless steel wire (polished surface) was used to bind the neck of the wine glass (15mm from the rim), with a contact length of 1 / 4 of the neck circumference (approximately 18mm) and a binding tension of 0.06MPa. The sample was suspended from a chemically tempered 316 stainless steel support (branched suspension rod) and completely immersed in a mixed salt bath (KNO3:NaNO3 mass ratio 3:7, purity 99.9%) (salt bath depth 250mm); the salt bath temperature was controlled at 410±2℃, the stirring rate at 45rpm, and the ion exchange time at 2.5 hours; post-treatment testing showed an initial surface compressive stress of 75±4MPa and a stress layer depth of 65±3μm. S2: Physical tempering treatment After removing the sample, ultrasonically clean it with 55℃ deionized water for 15 minutes (power 400W) and dry it at 110℃ for 25 minutes. The sample was placed in a physical tempering fixture, which included an outer fixed frame (800×1000mm high-temperature resistant quartz glass frame), an adjustable grid assembly (12 horizontal grid bars and 10 vertical grid bars intersecting to form an 80×80mm grid unit), and an upper grid cover plate (6 outer locking buckles). The clamped sample was then placed in a physical tempering furnace with the following parameters: first, it was held at 40℃ (510℃) below the annealing point for 0.8 hours, then heated to 680±5℃ (Tg+110℃) and held for 45 seconds (nitrogen atmosphere purity 99.99%). Cooling stage: 0.5MPa air pressure quenching for 20 seconds, 2.5MPa air pressure cooling for 80 seconds. Post-treatment testing: superimposed compressive stress 110±7MPa, total stress layer depth 130±6μm. S3: Second step chemical tempering treatment The original binding position was re-bound with 0.4mm stainless steel wire, and then immersed in a molten salt bath with a mass concentration of 92% KNO3 + 8% NaNO3 (purity 99.9%). The salt bath temperature was 440±2℃, the stirring rate was 35rpm, and the ion exchange time was 5 hours. After treatment, the total surface compressive stress was 420±12MPa, and the total stress layer depth was 320±8μm. S4: Post-processing The sample treated in step S3 was removed from the salt bath and placed in a 110℃ oven to cool slowly to room temperature (cooling rate 4℃ / min). After removing the steel wire, it was ultrasonically cleaned with 45℃ deionized water for 20 minutes (power 350W) and dried at 75℃ for 1.5 hours.

[0028] Performance Testing: A 1m drop test was conducted on ceramic tile flooring (dry state, water absorption rate 0.4%, coefficient of friction 0.55). Sample orientations included cup-up (40 drops), cup-down (20 drops), and horizontal (40 drops), with 100 samples tested per group. Results: 11 samples were damaged (7 cup-down, 4 horizontal), resulting in an integrity rate of 89%. Stress distribution analysis: Surface compressive stress 420±12MPa, stress layer depth 320±8μm. Standard deviation of surface compressive stress ≤18MPa, stress gradient 0.7MPa / μm. Example 3

[0029] Sodium-calcium-silicon gallon bottles were selected (specifications: height 300mm, diameter 150mm, wall thickness 5.0mm; original drop resistance performance: 58% breakage rate when dropped freely from a height of 30cm onto a ceramic tile floor, n=50).

[0030] A composite strengthening method for improving the drop resistance of glassware, comprising the following specific steps: S1: First step chemical tempering treatment A double-loop binding was applied to the neck of the gallon bottle (30 mm from the mouth) using 0.6 mm diameter 304 stainless steel wire (polished surface), with a contact length of 1 / 3 of the neck circumference (approximately 40 mm) and a binding tension of 0.10 MPa. The sample was suspended from a chemically tempered 316 stainless steel support (branched suspension rod) and completely immersed in a mixed salt bath (KNO3:NaNO3 mass ratio 2:8, purity 99.9%) (salt bath depth 400 mm). The salt bath temperature was controlled at 390±2℃, the stirring rate at 55 rpm, and the ion exchange time at 3 hours. Post-treatment testing showed an initial surface compressive stress of 90±6 MPa, indicating the formation of an initial exchange stress layer. S2: Physical tempering treatment After removing the sample, it was ultrasonically cleaned with 60℃ deionized water for 20 minutes (power 400W) and dried at 120℃ for 30 minutes. The sample was then placed in a physical tempering fixture, which included an outer fixed frame (1000×1200mm high-temperature resistant quartz glass frame), an adjustable grid assembly (15 horizontal grid bars and 12 vertical grid bars intersecting to form a 100×100mm grid unit), and an upper grid cover plate (6 outer locking buckles). Physical tempering furnace parameters: first, it was held at 30℃ (520℃) below the annealing point for 1 hour, then heated to 700±5℃ (Tg+120℃) and held for 150 seconds (nitrogen atmosphere purity 99.99%); cooling stage: quenching with 5MPa air pressure for 200 seconds, and cooling with 3MPa air pressure for 300 seconds. Post-treatment testing: superimposed compressive stress 130±8MPa, and the total stress layer depth was further increased. This physical tempering process is located between two chemical tempering steps. It not only superimposes physical tempering compressive stress on the initial chemical tempering stress layer, but also serves as a heat treatment process to reorganize the ion distribution on the glass surface and open ion diffusion channels, thereby deepening the stress layer generated in the first step of chemical tempering.

[0031] S3: Second step chemical tempering treatment The original binding position was re-bound with 0.6mm stainless steel wire, and then immersed in a molten salt bath with a mass concentration of 98% KNO3 + 2% NaNO3 (purity 99.9%). The salt bath temperature was 425±2℃, the stirring rate was 50rpm, and the ion exchange time was 5.5 hours. After treatment, the total surface compressive stress was 480±15MPa, and the total stress layer depth was 380±10μm. S4: Post-processing The sample treated in step S3 was removed from the salt bath and placed in a 120℃ oven to cool slowly to room temperature (cooling rate 6℃ / min). After removing the steel wire, it was ultrasonically cleaned with 60℃ deionized water for 20 minutes (power 500W) and dried at 120℃ for 40 minutes.

[0032] Performance testing: A 1m drop test was conducted on ceramic tile flooring (dry state, water absorption rate 0.6%, coefficient of friction 0.65). Sample orientations included bottle opening upwards (25 drops), bottle opening downwards (15 drops), and horizontal (60 drops), with 100 samples tested per group. Results: 13 samples were damaged (9 horizontally damaged, 4 bottle opening downwards damaged), resulting in an integrity rate of 87%. Stress distribution testing: Surface compressive stress standard deviation ≤20MPa, stress gradient 0.9MPa / μm. Example 4

[0033] The water cup is made of high borosilicate glass (specifications: height 120mm, diameter 70mm, wall thickness 3.0mm). Under normal use conditions, it has good drop resistance. Even if dropped freely from a height of 30cm on a tile floor, the breakage rate is only 48% (n=50).

[0034] A composite strengthening method for improving the drop resistance of glassware, comprising the following specific steps: S1: First step chemical tempering treatment A single loop of 0.45mm diameter 316 stainless steel wire (polished surface) was used to bind the neck of the water cup (25mm from the rim), with a contact length of 1 / 3 of the neck circumference (approximately 22mm) and a binding tension of 0.07MPa. The sample was suspended from a chemically tempered 316 stainless steel support (branched suspension rod) and completely immersed in a 3.5:6.5 (KNO3:NaNO3, purity 99.9%) mixed salt bath (salt bath depth 300mm); the salt bath temperature was controlled at 405±2℃, the stirring rate at 48rpm, and the ion exchange time at 2 hours; post-treatment testing showed an initial surface compressive stress of 80±5MPa, indicating the formation of an initial exchange stress layer; S2: Physical tempering treatment After removing the sample, it was ultrasonically cleaned with 58℃ deionized water for 18 minutes (power 450W) and dried at 115℃ for 30 minutes. The sample was then placed in a physical tempering fixture, which included an outer fixed frame (800×1000mm high-temperature resistant quartz glass frame), an adjustable grid assembly (12 horizontal grid bars and 10 vertical grid bars intersecting to form a 60×60mm grid unit), and an upper grid cover plate (4 outer locking buckles). The clamped sample was then placed in a physical tempering furnace with the following parameters: first, it was held at 25℃ (530℃) below the annealing point for 0.8 hours, then heated to 670±5℃ (Tg+90℃) and held for 200 seconds (nitrogen atmosphere purity 99.99%). Cooling stage: quenching with 4MPa air pressure for 150 seconds, followed by cooling with 2.5MPa air pressure for 200 seconds. Post-treatment testing showed a superimposed compressive stress of 115±7MPa, with a further increase in the total stress layer depth. This physical tempering process is located between two chemical tempering steps. It not only superimposes physical tempering compressive stress on the initial chemical tempering stress layer, but also serves as a heat treatment process to reorganize the ion distribution on the glass surface and open ion diffusion channels, thereby deepening the stress layer generated in the first step of chemical tempering.

[0035] S3: Second-step chemical enhancement treatment The original binding position was re-bound using 0.45mm stainless steel wire. The sample was then immersed in a molten salt bath with a mass concentration of 94% KNO3 + 6% NaNO3 (purity 99.9%) at a temperature of 435±2℃, a stirring rate of 42rpm, and an ion exchange time of 4.5 hours. Post-treatment testing showed that the total surface compressive stress was 460±14MPa and the total stress layer depth was 360±9μm.

[0036] S4: Post-processing The sample treated in step S3 was removed from the salt bath and placed in a 105℃ oven to cool slowly to room temperature (cooling rate 5.5℃ / min). After removing the steel wire, it was ultrasonically cleaned with 52℃ deionized water for 20 minutes (power 400W) and dried at 110℃ for 35 minutes.

[0037] Performance testing: A 1m drop test was conducted on the ceramic tile floor (dry state, water absorption rate 0.45%, coefficient of friction 0.58). Sample orientations included cup-up (35 drops), cup-down (25 drops), and horizontal (40 drops), with 100 samples tested per group. Results: 7 samples were damaged (4 horizontally damaged, 3 cup-down damaged), resulting in a 93% integrity rate. Stress distribution testing: Surface compressive stress standard deviation ≤16MPa, stress gradient 0.75MPa / μm. Example 5

[0038] Sodium-calcium-silicon infusion bottles were selected (specifications: height 220mm, diameter 90mm, wall thickness 4.0mm, original drop resistance performance: 55% breakage rate when dropped freely from a height of 30cm on a ceramic tile floor, n=50).

[0039] A composite strengthening method for improving the drop resistance of glassware, comprising the following specific steps: S1: First step chemical tempering treatment A double-loop binding was applied to the neck of the infusion bottle (25 mm from the bottle opening) using 0.5 mm diameter 316 stainless steel wire (polished surface), with a contact length of 1 / 3 (approximately 30 mm) of the neck circumference and a binding tension of 0.09 MPa. The sample was suspended in a chemical tempering frame and completely immersed in a 3:7 (KNO3:NaNO3) mixed salt bath. The salt bath temperature was controlled at 400 ± 2℃, the stirring rate at 50 rpm, and the ion exchange time at 2.5 hours.

[0040] S2: Physical tempering treatment After removing the sample, it was ultrasonically cleaned with 57℃ deionized water for 16 minutes (500W power) and dried at 118℃ for 22 minutes. The sample was placed in a physical tempering fixture, which included an outer fixed frame (900×1100mm high-temperature resistant quartz glass frame), an adjustable grid assembly (14 horizontal grid bars and 11 vertical grid bars intersecting to form a 90×90mm grid unit), and an upper grid cover plate (5 outer locking buckles). The clamped sample was placed in a physical tempering furnace with the following parameters: first, it was held at 40℃ (510℃) below the annealing point for 1.2 hours, then heated to 660±5℃ (Tg+80℃) and held for 300 seconds (nitrogen atmosphere purity 99.99%). Cooling stage: quenching with 3MPa air pressure for 250 seconds, and cooling with 4MPa air pressure for 400 seconds. Post-treatment test: superimposed compressive stress 105±6MPa, and the total stress layer depth was further increased. This physical tempering process is located between two chemical tempering steps. It not only superimposes physical tempering compressive stress on the initial chemical tempering stress layer, but also serves as a heat treatment process to reorganize the ion distribution on the glass surface and open ion diffusion channels, thereby deepening the stress layer generated in the first step of chemical tempering.

[0041] S3: Second step chemical tempering treatment The original binding points were re-bound using 0.55mm stainless steel wire. The sample was then immersed in a molten salt bath containing 96% KNO3 + 4% NaNO3 (99.9% purity) at a temperature of 445±2℃, a stirring rate of 38 rpm, and an ion exchange time of 3.5 hours. Post-treatment testing showed a total surface compressive stress of 430±13MPa and a total stress layer depth of 330±8μm.

[0042] S4: Post-processing The sample treated in step S3 was removed from the salt bath and placed in a 95℃ oven to cool slowly to room temperature (cooling rate 4.5℃ / min). After removing the steel wire, it was ultrasonically cleaned with 48℃ deionized water for 20 minutes (power 500W) and dried at 115℃ for 35 minutes.

[0043] Performance Testing: The ceramic tile flooring (dry state, water absorption rate 0.55%, coefficient of friction 0.62) underwent a 1-meter drop test to evaluate its durability and safety. During the test, the sample orientation included bottle opening upwards (30 drops), bottle opening downwards (25 drops), and horizontal (45 drops). 100 samples were used in each test group to ensure the reliability of the results. Results: 10 samples were damaged (6 bottle opening downwards, 4 horizontally), resulting in a 90% intact rate. Stress distribution detection: the standard deviation of surface compressive stress was ≤17 MPa, and the stress gradient was 0.85 MPa / μm. Comparative Example 1

[0044] A sodium-calcium-silicon dispensing device (specifications: height 150mm, diameter 80mm, wall thickness 3.5mm, initial breakage rate 62%, n=50) identical to that used in Example 1 was selected. The processing steps are as follows: S1: First step chemical tempering treatment: Same as step S1 in Example 1, but using a chemical tempering bracket; S2: Physical tempering treatment: The physical tempering fixture (outer peripheral fixed frame + adjustable grid assembly) in the patent was not used; instead, a traditional fixing frame (without grid adjustment function) was used. The parameters of the physical tempering furnace were the same as in Example 1, but the sample shook during the cooling stage due to unstable fixing, resulting in severely uneven stress distribution. Test results: The superimposed compressive stress was only 80±10MPa (33% lower than Example 1), and the total stress layer depth was 120±6μm (20% lower).

[0045] Performance Testing: A 1m drop test on the ceramic tile floor resulted in 65 broken samples (65% breakage rate, a 27% decrease compared to the 92% intact rate in Example 1). Analysis showed that traditional clamps cannot accommodate complex shapes, and cooling air pressure caused sample displacement, significantly increasing the risk of breakage in stress concentration areas. Conclusion: The lack of stable fixation and grid adjustment functions in the patented physical tempering clamps led to disordered stress distribution and a substantial increase in the breakage rate.

[0046] Comparative Example 2

[0047] Select the same sodium-calcium-silicon wine glass as in Example 2 (specifications: height 100mm, diameter 60mm, wall thickness 2.8mm, initial breakage rate 65%, n=50). The processing steps are as follows: S1: First step chemical tempering treatment: Instead of using the patented chemical tempering support (inverted "U" shaped multi-layer suspension structure), an ordinary suspension support (without rotation adjustment function) was used, the sample tilt posture could not be adjusted, and air bubbles were trapped in the salt bath; Test results: The initial compressive stress on the surface was only 50±5MPa (33% lower than in Example 2), and the stress layer depth was 50±3μm (23% lower).

[0048] S2: Physical tempering treatment: Same as step S2 in Example 2; S3: Second step chemical tempering treatment: still using ordinary suspension racks, which exacerbates uneven ion exchange.

[0049] Performance Testing: A 1m drop test on the ceramic tile floor resulted in 45 broken samples (55% intact rate, a 36% decrease compared to 91% in Example 2). Stress distribution analysis showed a surface compressive stress standard deviation of ≥35MPa (far exceeding ≤18MPa in Example 2), with a stress difference of 40MPa between the bottle bottom and the cup rim, causing the weakest areas to break first during the drop. Conclusion: The lack of dynamic posture adjustment and multi-layer suspension structure in the patented chemical tempering frame hinders ion exchange and drastically deteriorates the uniformity of tempering.

[0050] Comparative Example 3

[0051] A sodium-calcium-silica gallon bottle (specifications: height 300mm, diameter 150mm, wall thickness 5.0mm, initial breakage rate 58%, n=50) identical to that used in Example 3 was selected. The processing steps are as follows: Alternative treatment: Only a single chemical tempering process is used (without intermediate physical tempering steps), specifically: two chemical tempering treatments are performed using a patented chemical tempering bracket (steps S1+S3), omitting the physical tempering step S2; Test results: Total surface compressive stress 300±15MPa (37% lower than 480MPa in Example 3), stress layer depth 200±10μm (47% lower).

[0052] Performance Testing: A 1m drop test on the ceramic tile floor resulted in 75 broken samples (only 25% intact, a 62% decrease compared to 87% in Example 3). Analysis indicates that the lack of a physically tempered, superimposed compressive stress layer and ion channel reconstruction leads to insufficient stress layer depth and significantly weakened impact resistance. Conclusion: Without the patented physicochemical synergistic strengthening method, the stress layer is shallow and lacks a composite reinforcement effect, resulting in drop performance far inferior to the example.

[0053] This invention, through the synergistic strengthening of two-step chemical tempering and intermediate physical tempering, increases the integrity rate of glassware dropped from a height of 1m on a ceramic tile floor to 87%-93%, an improvement of at least 93% compared to traditional single-strength methods (integrity rate ≤45%). Surface compressive stress reaches 420-480MPa, and stress layer depth is 200-500μm, an improvement of 29%-49% compared to comparative examples. The intermediate physical tempering process, through the construction of a microcrack network and the opening of ion channels, improves the efficiency of the second-step chemical tempering by 40%-60%, solving the technical problems of uneven stress distribution and insufficient edge and corner strength when strengthening glassware with complex shapes.

Claims

1. A chemically tempered glass support for improving the drop resistance of glassware, characterized in that... It mainly consists of a base and a support frame. The base is a grid groove, and the support frame consists of two columns and a crossbar. The crossbar and the columns are connected by bearings to form an inverted "U" shape. The two columns are set on the grid groove. A set of cantilever crossbars are symmetrically arranged on the crossbar. Each cantilever crossbar is equipped with a set of branch suspension rods. The branch suspension rods are at an angle of 30°-45° with the crossbar, forming a multi-layer suspension structure. Multiple samples can be suspended in parallel by wrapping and fixing them with the tail end of stainless steel wire.

2. The chemically tempered glass support for improving the drop resistance of glassware according to claim 1, characterized in that: The mesh groove is made of 316L stainless steel with a mesh aperture of 5-10mm.

3. The chemical tempering support for improving the drop resistance of glassware according to claim 1, characterized in that: The ends of the cantilever crossbar and branch suspension rod are hemispherical rounded to avoid scratching the binding wire.

4. A chemically tempered glass support for improving the drop resistance of glassware according to any one of claims 1-3, characterized in that: The length of the crossbar is 800-1200mm; the length of the cantilever crossbar is 150-200mm and the diameter is 10-15mm; the length of the branch suspension bar is 80-120mm and the diameter is 6-8mm.

5. A physical tempering clamp for improving the drop resistance of glassware, characterized in that... It includes a clamp base and a clamp top cover for use together. The clamp base includes a rectangular frame and an adjustable grid set in the rectangular frame. Both the rectangular frame and the grid are provided with positioning holes. The grid is provided with tenons that insert into the positioning holes on multiple crossbeams. The clamp top cover is a grid cover plate.

6. The chemical tempering support for improving the drop resistance of glassware according to claim 5, characterized in that: The clamp base and clamp top cover are fixed by buckles and slots.

7. The chemical tempering support for improving the drop resistance of glassware according to claim 5, characterized in that: Both the fixture base and the fixture top cover are made of high-temperature resistant quartz glass with a softening point >1600℃.

8. The chemical tempering support for improving the drop resistance of glassware according to claim 5, characterized in that: The diameter of the positioning hole is 5-8mm, and the hole spacing is 10-15mm.

9. A chemically tempered glass support for improving the drop resistance of glassware according to any one of claims 5-8, characterized in that: The adjustable grid is composed of 10-15 movable horizontal grid bars and 8-12 movable vertical grid bars intersecting each other. Both the horizontal and vertical grid bars have rectangular cross sections. Both ends of the grid bars are integrally formed with vertical positioning tenons, which can be inserted into the array positioning holes of the outer peripheral fixed frame to achieve position fixation.

10. A composite strengthening method for improving the drop resistance of glassware, employing the apparatus described in claim 1 or 5, characterized in that... Includes the following steps: (1) The glassware to be strengthened is flexibly bound with stainless steel wire to non-critical stress parts and suspended on a chemical tempering frame. Then, the whole glassware is immersed in a molten mixed salt bath for ion exchange. The mass ratio of potassium nitrate to sodium nitrate in the mixed salt bath is 4:6 to 2:

8. The temperature of the salt bath is controlled at 380-420℃ and the ion exchange time is 0.5-5 hours to form an initial exchange stress layer on the glass surface. The glassware treated in step (1) is taken out of the salt bath, ultrasonically cleaned with deionized water to remove residual salt stains on the surface, then dried in a hot air circulating oven, cooled to room temperature and placed in a physical tempering fixture, and then sent into a physical tempering furnace for heating and quenching treatment. (2) Place the assembled glassware in a physical tempering furnace and perform a two-step heating process: first, keep it at a temperature 20-50°C below the glass annealing point for 0.5-2 hours, then heat it to 50-150°C above the glass transition temperature and keep it at that temperature for 100-1000 seconds, depending on the glass thickness, to ensure that the glass surface reaches a viscoelastic state; then use 0.3-8MPa high-pressure cold air to quench it symmetrically from the top and bottom sides of the furnace for 10-300 seconds, and then use 2-5MPa air pressure to continue cooling for 50-500 seconds, so that a physical tempering compressive stress layer is formed on the basis of the initial exchange stress layer; (3) After physical tempering, the glassware is re-tied with stainless steel wire to a chemical tempering frame and immersed in a molten salt bath for secondary ion exchange. The main component of the salt bath is potassium nitrate, and 0-10wt% of potassium phosphate (K3PO4) and potassium sulfate (K2SO4) are added as impurity removers to adjust the ion diffusion coefficient. The temperature of the salt bath is controlled at 420-450℃ by a dual-zone heating system, and the ion exchange time is 3-6 hours. Finally, a composite stress layer with a depth of 200-500μm is formed on the glass surface. (4) Take the glassware treated in step (3) out of the salt bath and place it in a hot air circulating oven at 80-120℃ for gradual cooling to room temperature to eliminate thermal stress; after removing the binding steel wire, use deionized water for ultrasonic cleaning to remove residual salt, and finally dry it with hot air at 100-120℃ to obtain glassware products with enhanced drop resistance.

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