CN112358198B - Composite reinforcing method for high-alkali aluminosilicate glass - Google Patents
Composite reinforcing method for high-alkali aluminosilicate glass Download PDFInfo
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- CN112358198B CN112358198B CN202011329467.2A CN202011329467A CN112358198B CN 112358198 B CN112358198 B CN 112358198B CN 202011329467 A CN202011329467 A CN 202011329467A CN 112358198 B CN112358198 B CN 112358198B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
- C03C21/003—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions under application of an electrical potential difference
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
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Abstract
The invention relates to the technical field of inorganic glass reinforcement, in particular to a composite reinforcement method of high-alkali aluminosilicate glass. The composite reinforcing method of the high-alkali aluminosilicate glass provided by the invention comprises the step of carrying out chemical reinforcement on the high-alkali aluminosilicate glass twice, and the step of thermal field-electric field composite treatment is also included between the two chemical reinforcement steps. The method is particularly suitable for reinforcing thin high-alkali aluminosilicate glass for transparent parts, and the prepared reinforced high-alkali aluminosilicate glass has higher surface compressive stress and deeper stress layer and lower internal tensile stress, so that the glass has excellent impact resistance, toughness and scratch resistance, and excellent overall mechanical properties, and the application range of the thin high-alkali aluminosilicate glass is greatly widened.
Description
Technical Field
The invention relates to the technical field of inorganic glass reinforcement, in particular to a composite reinforcement method of high-alkali aluminosilicate glass and reinforced high-alkali aluminosilicate glass prepared by the method.
Background
The high-alkali aluminosilicate glass is novel high-strength glass which has high aluminum and alkali contents and is suitable for chemical strengthening, and a plurality of enterprises realize mass production at present, so that the high-alkali aluminosilicate glass has better market prospect. The high-alkali aluminosilicate glass contains higher Al content 2 O 3 The high-alkali aluminosilicate glass is very easy to chemically reinforce, has excellent mechanical properties after being reinforced, is particularly remarkable in the aspects of hardness, toughness, scratch resistance and the like, has high transmittance in a visible light wave band, and is continuously widened in application field.
For some thin (the thickness is below 3.0 mm) high-alkali aluminosilicate glass and some curved surface high-alkali aluminosilicate glass products, physical toughening cannot be carried out, and only a chemical enhancement method can be adopted to improve the mechanical property. In some high-end glass product fields, the glass is required to have good toughness, scratch resistance and impact resistance, which provides a new challenge for a glass reinforcing method. It should be noted that the scratch resistance of the glass is closely related to the depth of the stress layer besides the surface compressive stress, and related tests show that the scratch resistance is more sensitive to the change of the depth of the stress layer. In particular, for thinner overbased aluminosilicate glasses, the surface compressive stress is too high and even if the stress layer is shallower, the toughness and impact resistance may be poor. At present, although the scratch resistance of glass can be obviously improved by one-step chemical reinforcement disclosed in the prior art, the central tensile stress of the glass is larger, and the higher central tensile stress can obviously reduce the impact resistance of the glass and weaken the mechanical property of the glass. This is even more evident on some special equipment transparencies: taking 1.8mm high alumina glass for a thin aircraft transparent part as an example, the central tensile stress of the glass is about 20-30 MPa after the glass is enhanced by a common one-step method or two-step method, and the glass is broken when being impacted at the height of about 5m by adopting 228g of steel balls. Therefore, a special reinforcing method is needed, which has better toughness and impact resistance and excellent scratch resistance while ensuring a deeper stress layer.
Disclosure of Invention
The invention aims to provide a composite reinforcing method of high-alkali aluminosilicate glass, and the invention also aims to provide the reinforced high-alkali aluminosilicate glass prepared by the method, and the glass can be applied to products with higher requirements on impact property and scratch resistance.
In order to achieve the purpose, the invention provides a three-stage composite enhancement method based on full research and massive practice on the influence factors of the composition structure and the mechanical property of the high-alkali aluminosilicate glass, which comprises two chemical enhancement steps and a thermal field-electric field composite treatment step between the two chemical enhancement steps. In the research and development process, the invention discovers that the traditional one-step or two-step chemical enhancement method is adopted to enhance the high-alkali aluminosilicate glass with the thickness less than or equal to 3mm (particularly the thickness of 1.5-3 mm), and the condition parameters of the enhancement reaction are difficult to optimize while ensuring higher toughness, scratch resistance and impact resistance. And the thermal field-electric field composite treatment is carried out between the chemical enhancement steps, and the composition of the two sections of chemically enhanced ion exchange mixed salts is correspondingly adjusted at the same time, so that the problems can be solved to a certain extent, the higher toughness, scratch resistance and impact resistance can be ensured simultaneously, and the overall mechanical property of the glass can be obviously improved.
Specifically, the invention provides the following technical scheme:
in a first aspect, the invention provides a composite reinforcement method of high-alkali aluminosilicate glass, which comprises the steps of carrying out two times of chemical reinforcement on the high-alkali aluminosilicate glass, and a step of thermal field-electric field composite treatment is also included between the two chemical reinforcement steps; wherein the first mixed exchange salt used for the first chemical enhancement comprises potassium nitrate with a molar ratio of more than or equal to 93 percent, sodium nitrate with a molar ratio of less than or equal to 6 percent and sodium hydroxide and potassium hydroxide with a molar ratio sum of 1 to 3 percent; the second mixed exchange salt used for the second chemical enhancement comprises 98 to 99.5 mole percent of potassium nitrate and 0.5 to 2 mole percent of cesium nitrate; the thermal field-electric field composite treatment is to place the glass subjected to the first chemical enhancement treatment in an electric field space and apply a temperature field to the glass simultaneously to carry out composite treatment. The invention discovers that the introduction of the thermal field-electric field composite treatment step is beneficial to the improvement of the mechanical property of the glass, but the better enhancement effect can be realized only by matching with the exchange salt with a specific composition used for twice chemical enhancement. Moreover, it is not guaranteed that the desired enhancement effect is achieved only by ensuring that the two chemically enhanced exchange salts differ. Through screening of ion exchange salts, the invention discovers that compared with other ion exchange salts (such as potassium carbonate, potassium sulfate, sodium carbonate, sodium sulfate and the like), the mixed salt containing potassium nitrate, sodium hydroxide and potassium hydroxide (which can be only composed of the salts) is used as the exchange salt in the first chemical enhancement, the sodium salt is removed in the second chemical enhancement, only potassium nitrate and cesium nitrate are used as the exchange salt, and the thermal field-electric field composite treatment step of combining the two chemical enhancement reactions between the two can simultaneously and remarkably improve the toughness, scratch resistance and impact resistance of the high-alkali aluminosilicate glass.
Specifically, in the first chemical strengthening, a first compressive stress layer is formed on the surface of the glass body, and the required surface compressive stress, stress layer depth and central tensile stress are obtained; the thermal field-electric field composite treatment step can accelerate the migration of potassium ions on the surface of the glass subjected to the first chemical enhancement treatment into the glass, increase the depth of a stress layer and reduce the surface compressive stress value of the glass; the glass treated by the thermal field-electric field composite treatment is subjected to ion exchange in a very short time in the second chemical enhancement, and cesium nitrate is used as a key exchange salt, so that a high compression stress layer can be obtained on the surface of the glass in the short-time exchange process, the central tensile stress in the high-alkali aluminosilicate glass is changed only in a small range, and the central tensile stress is not greater than the strength of the glass body.
Preferably, the first mixed exchange salt used for the first chemical enhancement comprises potassium nitrate in a molar ratio of 94% to 98%, sodium nitrate in a molar ratio of 1% to 5%, and sodium hydroxide and potassium hydroxide in a molar ratio that together add up to 1%.
In the first mixed exchange salt described above, the molar ratio of sodium hydroxide to potassium hydroxide is preferably (1 to 2): 1. more preferably 1. The invention finds that controlling the sodium hydroxide and the potassium hydroxide in the first mixed exchange salt in the above ratio can better ensure the improvement of the glass surface compressive stress and the stress layer depth.
In the second mixed exchange salt described above, the molar ratio of potassium nitrate to cesium nitrate is preferably (40 to 200): 1. the invention finds that controlling the potassium nitrate and cesium nitrate in the second mixed exchange salt in the above ratio range can ensure both higher surface compressive stress and smaller changes in the central tensile stress inside the high alkali aluminosilicate glass.
In order to obtain better overall mechanical property of the glass, preferably, the molar ratio of potassium ions to sodium ions in the first mixed exchange salt is (15-75): 1. more preferably, the molar ratio of potassium nitrate to potassium hydroxide is (180 to 200): 1, the molar ratio of sodium nitrate to sodium hydroxide is (2-10): 1.
in the thermal field-electric field composite treatment, the electric field is generated by two electrode plates with positive charges, and the voltage of the electrode plates is 12-72 v; preferably 12v to 48v.
In the thermal field-electric field composite treatment, the temperature of the temperature field is 360-400 ℃.
Preferably, the time of the thermal field-electric field composite treatment is 0.5 h-2 h.
In the above method, the reaction temperature of the first chemical enhancement and the second chemical enhancement is preferably 420 to 440 ℃.
And (3) rapidly cooling the sample after the thermal field-electric field composite treatment, wherein the cooling rate is 15-20 ℃/min. Preferably, the temperature is controlled to be reduced to room temperature within 30 minutes.
In the method, after the high-alkali aluminosilicate glass is subjected to the first chemical strengthening treatment, a first pressure stress layer is formed on the surface of the glass, and after the high-alkali aluminosilicate glass is subjected to heat treatment, the surface pressure stress is reduced, but the reduction amplitude of the surface pressure stress value needs to be controlled, and the reduction amplitude is too large to be beneficial to the improvement of the overall mechanical property of the glass. Preferably, the CS of the first compressive stress layer formed by the first chemical enhancement is more than or equal to 600Mpa, and the DOL is more than or equal to 40 μm.
The treatment time for the first chemical enhancement depends on the glass thickness. For example: the treatment time for the first chemical strengthening is preferably 3.5 to 4.5 hours at a glass thickness of 1.5 to 2 mm.
Preferably, the CS reduction amplitude of the first compressive stress layer after the thermal field-electric field composite treatment is less than or equal to 30%.
And after the second chemical strengthening treatment, a second pressure stress layer is further formed on the surface of the glass, wherein the second pressure stress layer is a high-pressure stress layer with a shallower surface. Preferably, DOL of the second pressure stress layer formed by the second chemical strengthening is less than or equal to 15 micrometers, CS is greater than or equal to 1000MPa, and the change delta CT of the central tensile stress in the high-alkali aluminosilicate glass before and after the second chemical strengthening is less than or equal to 2MPa.
In order to meet the requirement that the second pressure stress layer has the mechanical parameters, the reaction time of the second chemical enhancement is preferably controlled to be less than or equal to 0.25h.
The composite reinforcing method is very suitable for reinforcing thin high-alkali aluminosilicate glass, and can remarkably improve the overall mechanical property of the high-alkali aluminosilicate glass with the thickness less than or equal to 3mm compared with the conventional reinforcing method.
Preferably, the thickness of the high alkali aluminosilicate glass is 1.5 to 3mm.
The overbased aluminosilicate glasses of the present invention preferably have the following composition:
SiO 2 ：60-65wt％；
Al 2 O 3 ：12-24wt％；
Na 2 O：5-15wt％；
K 2 O：5-15wt％；
MgO：5-10wt％；
ZrO 2 ：1-5wt％。
wherein the total content of sodium oxide and potassium oxide is preferably 12 to 24wt%.
The high alkali aluminosilicate glass of the invention does not contain Li element.
As a preferable scheme of the invention, the composite reinforcing method of the high-alkali aluminosilicate glass comprises the following steps:
(1) First chemical enhancement: mixing potassium nitrate and sodium nitrate, then adding mixed salt of potassium hydroxide and sodium hydroxide, melting and clarifying to obtain molten mixed exchange salt, wherein in the mixed exchange salt, the molar ratio of potassium nitrate is 94-98%, the molar ratio of sodium nitrate is 1-5%, the sum of the molar ratios of potassium hydroxide and sodium hydroxide is 1%, and the molar ratio of sodium hydroxide to potassium hydroxide is (1-2): 1;
preheating a high-alkali aluminosilicate glass sample to 360-370 ℃, putting the high-alkali aluminosilicate glass sample into high-temperature mixed molten salt for ion exchange, controlling the exchange temperature to be 420-440 ℃, and determining the exchange time according to the thickness of the glass; after the exchange is finished, taking out a sample, cooling, cleaning and drying to obtain chemically-enhanced high-alkali aluminosilicate glass, and forming a first pressure stress layer on the surface of a high-alkali aluminosilicate glass body, wherein the CS is more than or equal to 600Mpa, the DOL is more than or equal to 40 mu m, and the CT is less than or equal to 20Mpa;
(2) Thermal field-electric field composite treatment: rapidly preheating the high-alkali aluminosilicate glass sample after the chemical reinforcement in the step (1) to 300 ℃, and then placing the high-alkali aluminosilicate glass sample in a constant temperature box with double electrode plates for thermal field-electric field composite treatment; the voltage of the positive plate is 12 v-48 v, the temperature of the temperature field is 360-400 ℃, the time of the thermal field-electric field composite treatment is controlled to be 0.5-2 h according to different use requirements, and the CS reduction amplitude of the first pressure stress layer after the thermal field-electric field composite treatment is less than or equal to 30%.
After the thermal field-electric field composite treatment is finished, rapidly cooling the sample, wherein the cooling rate is controlled to be 15-20 ℃/min, and the temperature is controlled to be reduced to the room temperature within 30 minutes; taking out the sample, measuring CS, DOL and CT values, and ensuring to obtain required corresponding data;
(3) And (3) second chemical enhancement: and (3) putting the high-alkali aluminosilicate glass sample obtained in the step (2) into molten potassium nitrate and cesium nitrate mixed exchange salt (98-99.5% of potassium nitrate and 0.5-2% of cesium nitrate) for chemical enhancement, and selectively controlling the ion exchange temperature and time according to the mechanical property requirement of the product: the ion exchange temperature range is 420-440 ℃, the exchange time is not more than 0.25h, a second pressure stress layer (the outermost laminated stress layer) is formed on the surface of the high-alkali aluminosilicate glass, the CS of the outermost laminated stress layer is not less than 1000MPa, the DOL of the outermost laminated stress layer is not more than 15 mu m, the CT of the outermost laminated stress layer is not more than 20MPa, and the CT change value of the interior of the glass treated by the step is not more than 2MPa.
The invention also provides a strengthened high-alkali aluminosilicate glass, which comprises a high-alkali aluminosilicate glass body, a first pressure stress layer covering the surface of the high-alkali aluminosilicate glass body and a second pressure stress layer covering the first pressure stress layer; the thickness of the high-alkali aluminosilicate glass body is 1.5-3 mm; the CS of the first pressure stress layer is more than or equal to 600Mpa, the DOL of the first pressure stress layer is more than or equal to 40 mu m, and the CT of the first pressure stress layer is less than or equal to 20Mpa; the DOL of the second pressure stress layer is less than or equal to 15 mu m, the CS is more than or equal to 1000Mpa, and the CT is less than or equal to 20Mpa.
The strengthened high-alkali aluminosilicate glass is prepared by the composite strengthening method.
Preferably, the above-described high alkali aluminosilicate glass body does not contain Li element and comprises the following components:
SiO 2 ：60-65wt％；
Al 2 O 3 ：12-24wt％；
Na 2 O：5-15wt％；
K 2 O：5-15wt％；
MgO：5-10wt％；
ZrO 2 ：1-5wt％；
wherein the total content of sodium oxide and potassium oxide is preferably 12 to 24wt%.
The invention further provides the application of the composite reinforcing method or the reinforced high-alkali aluminosilicate glass in the preparation of optical transparencies of special equipment.
The optical transparent part of the special equipment comprises but is not limited to an optical transparent part applied to aviation, aerospace and rail transit.
The invention has the beneficial effects that: the invention provides a composite reinforcing method of high-alkali aluminosilicate glass, which adopts a composite processing method combining chemical reinforcement of two-step ion exchange and thermal field-electric field composite processing, and is particularly suitable for reinforcing thin high-alkali aluminosilicate glass.
By using the method, the high-alkali aluminosilicate glass can have two surface compression stress layers, each compression stress layer has different CS and DOL values, and the outermost layer has the highest compression stress and a shallower compression stress layer, so that the high-alkali aluminosilicate glass has lower internal tensile stress while having deeper all compression stress layers.
The strengthened high-alkali aluminosilicate glass prepared by the method has higher surface compressive stress, deeper stress layer and lower internal tensile stress, so that the glass has excellent mechanical properties, especially impact resistance, toughness and scratch resistance, and the application range of the thin high-alkali aluminosilicate glass is greatly widened. Experiments prove that by adopting the composite reinforcing method, the central tensile stress of the thin high-alkali aluminosilicate glass can be reduced to be within 20MPa, the falling ball impact resistance height of the glass reaches about 6m, the falling ball impact resistance height is improved by 20 percent, and the impact resistance is greatly enhanced.
The composite reinforcing method of the high-alkali aluminosilicate glass has the advantages of simple steps and strong operability, and is suitable for industrial batch production.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The samples of the overbased aluminosilicate glass used in the following examples and comparative examples were sheet glass frits having a glass composition of: siO 2 2 ：62wt％，Al 2 O 3 ：14.7wt％，Na 2 O：9.3wt％，K 2 O：5.8wt％，MgO：5.7wt％，ZrO 2 :1.7wt%, 1.8mm thick, machined with a CNC machine and edge polished with a high mesh abrasive wheel, sample size 300mm 1.8mm.
Example 1
The embodiment provides a composite reinforcing method of high-alkali aluminosilicate glass, which comprises the following steps:
(1) First chemical enhancement: preparing 50kg of molten salt by using 96% of potassium nitrate, 3% of sodium nitrate, 0.5% of potassium hydroxide and 0.5% of sodium hydroxide according to the molar ratio, putting the molten salt into a salt tank, and then melting and clarifying the molten salt in a muffle furnace for 24 hours to obtain mixed exchange molten salt;
placing a high-alkali aluminosilicate glass sample on a tool rack, preheating for 15min in a high-temperature furnace at the preheating temperature of 380 ℃, then immersing the high-alkali aluminosilicate glass sample into molten mixed molten salt, carrying out high-temperature molten salt ion exchange, setting the exchange time to be 4h, setting the exchange temperature to be 420 ℃, taking the tool rack out of the molten salt after the exchange is finished, reducing the temperature to normal temperature at the cooling rate of 15 ℃/min, cleaning the glass sample by deionized water, wiping the glass sample clean to obtain chemically-enhanced high-alkali aluminosilicate glass, testing CS, DOL and CT by FSM-6000LE, and testing the CS value, the DOL value and the CT value to be 710MPa, the DOL value to be 42 mu m and the CT value to be 16MPa after the test.
(2) Thermal field-electric field composite treatment: preheating a glass sample subjected to first chemical strengthening treatment to 300 ℃ within 10min, placing the glass sample into heat treatment equipment, simultaneously placing an electrode plate with the size not smaller than that of the glass on each side of the glass, enabling the two electrode plates to be positively charged, setting the voltage to be 36v, setting the temperature of the heat treatment equipment to be 380 ℃, carrying out constant temperature treatment for 1h, taking out the glass sample, reducing the temperature to the normal temperature at a cooling rate of 15 ℃/min, and testing the CS value to be 610MPa, the DOL to be 51 mu m and the CT to be 16.1MPa.
(3) And (3) second chemical enhancement: 50kg of mixed molten salt is prepared according to the molar ratio of 99.5% potassium nitrate and 0.5% cesium nitrate, the mixed molten salt is placed into a muffle furnace for melting and clarification for 24h, then a glass sample after heat treatment is preheated and placed into the mixed molten salt for chemical enhancement treatment, the exchange temperature is 430 ℃, the exchange time is 15min, and an SLP-2000 full-automatic surface stress instrument is adopted to test CS, DOL and CT data on the surface of the glass sample, wherein the CS is 1020MPa, the DOL is 59 mu m, the thickness of the outermost high stress layer is 10 mu m, and the CT is 16.5MPa.
Example 2
The embodiment provides a composite reinforcing method of high-alkali aluminosilicate glass, which comprises the following steps:
(1) First chemical enhancement: preparing 50kg of molten salt according to the molar ratio of 97% potassium nitrate, 2% sodium nitrate, 0.5% potassium hydroxide and 0.5% sodium hydroxide, putting the molten salt into a salt tank, and then melting and clarifying the molten salt in a muffle furnace for 24 hours to obtain mixed exchange molten salt;
placing a high-alkali aluminosilicate glass sample on a tool rack, preheating for 15min in a high-temperature furnace at the preheating temperature of 380 ℃, then immersing the high-alkali aluminosilicate glass sample into molten mixed molten salt, carrying out high-temperature molten salt ion exchange, setting the exchange time to be 4h, setting the exchange temperature to be 420 ℃, taking the tool rack out of the molten salt after the exchange is finished, reducing the temperature to normal temperature at the cooling rate of 15 ℃/min, cleaning the glass sample by deionized water, wiping the glass sample clean to obtain chemically enhanced high-alkali aluminosilicate glass, testing CS, DOL and CT by FSM-6000LE, and testing the CS value, the DOL value and the CT value to be 760MPa, 42 mu m and 16.6MPa after the test.
(2) Thermal field-electric field composite treatment: preheating a glass sample subjected to first chemical enhancement treatment to 300 ℃ within 10min, placing the glass sample into heat treatment equipment, simultaneously placing an electrode plate with the size not smaller than that of the glass on each side of the glass, enabling the two electrode plates to be positively charged, setting the voltage to be 36v, setting the temperature of the heat treatment equipment to be 370 ℃, carrying out constant temperature treatment for 2h, taking out the glass sample, reducing the temperature to the normal temperature at a cooling rate of 15 ℃/min, and testing the CS value to be 700MPa, the DOL to be 48 mu m and the CT to be 16.3MPa.
(3) And (3) second chemical enhancement: preparing 50kg of mixed molten salt according to molar ratio of 99% potassium nitrate and 1% cesium nitrate, putting the mixed molten salt into a muffle furnace for melting and clarifying for 24h, then preheating a glass sample after heat treatment, putting the glass sample into the mixed molten salt for chemical enhancement treatment, carrying out exchange at the temperature of 430 ℃ for 15min, and testing CS, DOL and CT data on the surface of the glass sample by adopting an SLP-2000 full-automatic surface stress meter, wherein the CS is 1010MPa, the DOL is 66 mu m, the thickness of the outermost high-stress layer is 11 mu m, and the CT is 17.1MPa.
Example 3
The embodiment provides a composite reinforcing method of high-alkali aluminosilicate glass, which comprises the following steps:
(1) First chemical treatment: preparing 50kg of molten salt according to the molar ratio of 98% potassium nitrate, 1% sodium nitrate, 0.5% potassium hydroxide and 0.5% sodium hydroxide, putting the molten salt into a salt tank, and then melting and clarifying the molten salt in a muffle furnace for 24 hours to obtain mixed exchange molten salt;
placing a high-alkali aluminosilicate glass sample on a tool frame, preheating for 15min in a high-temperature furnace at the preheating temperature of 380 ℃, then immersing the high-alkali aluminosilicate glass sample into molten mixed molten salt, carrying out high-temperature molten salt ion exchange, setting the exchange time to be 4h, setting the exchange temperature to be 420 ℃, taking the tool frame out of the molten salt after the exchange is finished, reducing the temperature to the normal temperature at the cooling rate of 15 ℃/min, cleaning the glass sample by deionized water, wiping the glass sample clean to obtain chemically-enhanced high-alkali aluminosilicate glass, testing CS, DOL and CT by FSM-6000LE, and testing the CS value, the DOL value and the CT value after the test to be 800MPa, the DOL value to be 42 mu m and the CT value to be 16.9MPa.
(2) Thermal field-electric field composite treatment: preheating a glass sample subjected to first chemical enhancement treatment to 300 ℃ within 10min, placing the glass sample into heat treatment equipment, simultaneously placing electrode plates with the size not smaller than that of the glass on two sides of the glass respectively, enabling the two electrode plates to be positively charged, setting the voltage to be 36v, setting the temperature of the heat treatment equipment to be 390 ℃, carrying out constant temperature treatment for 1.5h, taking out the glass sample, reducing the temperature to the normal temperature at the rate of 15 ℃/min, and testing the CS value to be 700MPa, the DOL to be 52 mu m and the CT to be 16.1MPa.
(3) And (3) second chemical enhancement: preparing 50kg of mixed molten salt according to the mol ratio of 99% potassium nitrate and 1% cesium nitrate, putting the mixed molten salt into a muffle furnace for melting and clarifying for 24h, then preheating a glass sample subjected to heat treatment, putting the glass sample into the mixed molten salt for chemical enhancement treatment, carrying out exchange at the temperature of 430 ℃ for 15min, and testing CS, DOL and CT data on the surface of the glass sample by adopting an SLP-2000 full-automatic surface stress meter, wherein the CS is 1020MPa, the DOL is 61 mu m, the thickness of the outermost high-stress layer is 10 mu m, and the CT is 17.2MPa.
Example 4
The embodiment provides a composite reinforcing method of high-alkali aluminosilicate glass, which comprises the following steps:
(1) First chemical treatment: preparing 50kg of molten salt according to the molar ratio of 94% potassium nitrate, 5% sodium nitrate, 0.5% potassium hydroxide and 0.5% sodium hydroxide, placing the molten salt into a salt tank, melting in a muffle furnace, and clarifying for 24 hours to obtain mixed exchange molten salt;
placing a high-alkali aluminosilicate glass sample on a tool rack, preheating for 15min in a high-temperature furnace at the preheating temperature of 380 ℃, then immersing the high-alkali aluminosilicate glass sample into molten mixed molten salt, carrying out high-temperature molten salt ion exchange, setting the exchange time to be 4h, setting the exchange temperature to be 420 ℃, taking the tool rack out of the molten salt after the exchange is finished, reducing the temperature to normal temperature at the cooling rate of 15 ℃/min, cleaning the glass sample by deionized water, wiping the glass sample clean to obtain chemically enhanced high-alkali aluminosilicate glass, testing CS, DOL and CT by FSM-6000LE, and testing the CS value, the DOL value and the CT value to be 630MPa, and the CT value to be 15.7MPa after the test.
(2) Thermal field-electric field composite treatment: preheating a glass sample subjected to first chemical enhancement treatment to 300 ℃ within 10min, placing the glass sample into heat treatment equipment, simultaneously placing electrode plates with the size not smaller than that of the glass on two sides of the glass respectively, enabling the two electrode plates to be positively charged, setting the voltage to be 48v, setting the temperature of the heat treatment equipment to be 370 ℃, carrying out constant temperature treatment for 1h, taking out the glass sample, reducing the temperature to the normal temperature at a cooling rate of 15 ℃/min, and testing the CS value to be 580MPa, the DOL to be 47 mu m and the CT to be 15.5MPa.
(3) And (3) second chemical enhancement: 50kg of mixed molten salt is prepared by 98.5 percent of potassium nitrate and 1.5 percent of cesium nitrate according to the molar ratio, the mixed molten salt is placed into a muffle furnace for melting and clarification for 24h, then a glass sample after heat treatment is preheated and placed into the mixed molten salt for chemical enhancement treatment, the exchange temperature is 430 ℃, and the exchange time is 15min. The SLP-2000 full-automatic surface stress meter is adopted to test CS, DOL and CT data of the surface of the glass sample, wherein the CS is 1060MPa, the DOL is 61 mu m, the thickness of the outermost high-stress layer is 11 mu m, and the CT is 16.5MPa.
Example 5
The embodiment provides a composite reinforcing method of high-alkali aluminosilicate glass, which comprises the following steps:
(1) First chemical treatment: preparing 50kg of molten salt according to the molar ratio of 0.5% of each of 98% potassium nitrate, 1% sodium nitrate, sodium hydroxide and potassium hydroxide, placing the molten salt into a salt tank, melting the molten salt in a muffle furnace, and clarifying the molten salt for 24 hours to obtain mixed exchange molten salt;
placing a high-alkali aluminosilicate glass sample on a tool rack, preheating the high-alkali aluminosilicate glass sample in a high-temperature furnace for 15min at the preheating temperature of 380 ℃, then immersing the high-alkali aluminosilicate glass sample into molten mixed molten salt, carrying out high-temperature molten salt ion exchange, setting the exchange time to be 4h, setting the exchange temperature to be 420 ℃, taking the tool rack out of the molten salt after the exchange is finished, cooling to the normal temperature at the cooling rate of 15 ℃/min, cleaning the glass sample by deionized water, wiping the glass sample to obtain chemically-enhanced high-alkali aluminosilicate glass, testing CS, DOL and CT by FSM-6000LE, and testing the CS value to be 810MPa, the DOL value to be 42 mu m and the CT value to be 17MPa after the test.
(2) Thermal field-electric field composite treatment: preheating a glass sample subjected to first chemical enhancement treatment to 300 ℃ within 10min, placing the glass sample into heat treatment equipment, simultaneously placing electrode plates with the size not smaller than that of the glass on two sides of the glass respectively, enabling the two electrode plates to be positively charged, setting the voltage to be 48v, setting the temperature of the heat treatment equipment to be 390 ℃, carrying out constant temperature treatment for 0.5h, taking out the glass sample, reducing the temperature to the normal temperature at a cooling rate of 15 ℃/min, and testing the CS value to be 770MPa, the DOL to be 48 mu m and the CT to be 16.7MPa.
(3) And (3) second chemical treatment: preparing 50kg of mixed molten salt according to the molar ratio of 98% potassium nitrate and 2% cesium nitrate, putting the mixed molten salt into a muffle furnace for melting and clarifying for 24h, then preheating a glass sample subjected to heat treatment, putting the glass sample into the mixed molten salt for chemical enhancement treatment, carrying out exchange at the temperature of 420 ℃ for 15min, and testing CS, DOL and CT data on the surface of the glass sample by adopting an SLP-2000 full-automatic surface stress meter, wherein the CS is 1080MPa, the DOL is 60 mu m, the thickness of the outermost high-stress layer is 14 mu m, and the CT is 18.2MPa.
Comparative example
The comparative example provides a composite reinforcement method for high alkali aluminosilicate glass, comprising the steps of:
(1) 50kg of molten salt is prepared by 100 percent potassium nitrate, and the molten salt is placed in a salt tank, melted and clarified in a high-temperature furnace for 24 hours;
(2) Clamping a high-alkali aluminosilicate glass sample by using a clamp, preheating the high-alkali aluminosilicate glass sample in a high-temperature furnace for 15min, then immersing the high-alkali aluminosilicate glass sample into a molten salt bath for high-temperature ion exchange, setting the exchange time to be 6h, setting the exchange temperature to be 420 ℃, taking the clamp out of the molten salt after the exchange is finished, cooling the clamp to the normal temperature, cleaning the glass sample by using deionized water, and wiping the glass sample clean to obtain the chemically-enhanced high-alkali aluminosilicate glass.
The chemically strengthened glass samples of the comparative examples were tested to have a CS of 925MPa, a DOL of 51 μm and a CT of 23MPa.
The results of measuring various performance parameters of the high alkali aluminosilicate glasses obtained in examples 1 to 5 and comparative example are shown in Table 1.
TABLE 1 Property parameters of the high alkali aluminosilicate glasses prepared in examples 1-5 and comparative examples
The samples of the high alkali aluminosilicate glass obtained by the reinforcing method of examples 1 to 5 and comparative example were subjected to a falling ball impact test using 227g steel ball and a hardness test using HX-1000TM/LCD type microhardness tester with a test force of 0.981N (100 gf) and a loading time of 10s in accordance with GB/T5137-2002. Specific results are shown in Table 2.
TABLE 2 falling ball impact and hardness test results
The results show that after the high-alkali aluminosilicate glass is subjected to composite reinforcement treatment, the composite reinforcement method of the embodiments 1-5 can effectively reduce the internal tensile stress of the glass on the premise of the same stress layer depth, greatly improve the falling ball impact resistance, and improve the lifting amplitude by about 25%; meanwhile, the hardness of the glass is obviously improved, and the scratch resistance is further improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (6)
1. The composite reinforcing method of the high-alkali aluminosilicate glass is characterized by comprising the steps of carrying out chemical reinforcement on the high-alkali aluminosilicate glass twice, and a thermal field-electric field composite treatment step is also included between the two chemical reinforcement steps;
wherein the first mixed exchange salt used in the first chemical enhancement treatment is potassium nitrate with a molar ratio of more than or equal to 93 percent, sodium nitrate with a molar ratio of less than or equal to 6 percent, and sodium hydroxide and potassium hydroxide with a molar ratio sum of 1 to 3 percent;
in the first mixed exchange salt, the molar ratio of sodium hydroxide to potassium hydroxide is (1 to 2): 1, the molar ratio of potassium ions to sodium ions is (15 to 75): 1, the molar ratio of potassium nitrate to potassium hydroxide is (180 to 200): 1, the molar ratio of sodium nitrate to sodium hydroxide is (2 to 10): 1;
the second mixed exchange salt used in the second chemical enhancement treatment comprises 98-99.5 mol% of potassium nitrate and 0.5-2 mol% of cesium nitrate;
in the second mixed exchange salt, the molar ratio of potassium nitrate to cesium nitrate is (40-200): 1;
the reaction temperature of the first chemical enhancement and the second chemical enhancement is 420-440 ℃;
the reaction time of the second chemical enhancement is less than or equal to 0.25h;
the thermal field-electric field composite treatment is to place the glass subjected to the first chemical enhancement treatment in an electric field space and apply a temperature field to carry out composite treatment;
the electric field is generated by two electrode plates with positive charges, and the voltage of the electrode plates is 12v to 72v;
the temperature of the temperature field is 360-400 ℃;
the time of the thermal field-electric field composite treatment is 0.5h to 2h;
the components of the high-alkali aluminosilicate glass do not contain Li element.
2. The composite reinforcing method as claimed in claim 1, wherein the voltage of the electrode plate is 12v to 48v.
3. The composite reinforcement method according to claim 1, wherein the DOL of the second compressive stress layer formed by the second chemical reinforcement is not more than 15 μm, the CS is not less than 1000MPa, and the change of central tensile stress Δ CT inside the overbased aluminosilicate glass before and after the second chemical reinforcement is not more than 2MPa;
the CS of the first pressure stress layer formed by the first chemical enhancement is more than or equal to 600Mpa, and the DOL of the first pressure stress layer is more than or equal to 40 mu m; the CS reduction amplitude of the first pressure stress layer after the thermal field-electric field composite treatment is less than or equal to 30 percent.
4. The composite reinforcement method according to any one of claims 1 to 3, wherein the thickness of the alkali aluminosilicate glass is 1.5 to 3mm.
5. The strengthened high-alkali aluminosilicate glass is characterized by comprising a high-alkali aluminosilicate glass body, a first pressure stress layer covering the surface of the high-alkali aluminosilicate glass body and a second pressure stress layer covering the first pressure stress layer;
the thickness of the high-alkali aluminosilicate glass body is 1.5 to 3mm; the CS of the first pressure stress layer is more than or equal to 600Mpa, the DOL of the first pressure stress layer is more than or equal to 40 mu m, and the CT of the first pressure stress layer is less than or equal to 20Mpa; the DOL of the second pressure stress layer is less than or equal to 15 mu m, the CS is more than or equal to 1000Mpa, and the CT is less than or equal to 20Mpa;
the strengthened high alkali aluminosilicate glass is prepared by the composite strengthening method of any one of claims 1 to 4.
6. Use of the strengthened overbased aluminosilicate glass of claim 5 in the preparation of an optically transparent part for specialty equipment.
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