CN113603344B - Pretreatment method before glass strengthening treatment and glass strengthening treatment method comprising same - Google Patents
Pretreatment method before glass strengthening treatment and glass strengthening treatment method comprising same Download PDFInfo
- Publication number
- CN113603344B CN113603344B CN202111097535.1A CN202111097535A CN113603344B CN 113603344 B CN113603344 B CN 113603344B CN 202111097535 A CN202111097535 A CN 202111097535A CN 113603344 B CN113603344 B CN 113603344B
- Authority
- CN
- China
- Prior art keywords
- glass
- water
- molten salt
- temperature
- strengthening treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
-
- 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
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention provides a pretreatment method before glass strengthening treatment and a glass strengthening treatment method comprising the same, and relates to the technical field of glass strengthening. The pretreatment method before glass strengthening treatment comprises the steps of firstly providing glass to be treated, and then sequentially preheating and rinsing the glass to obtain pretreated glass; the rinsing furnace water for rinsing is potassium-sodium mixed salt furnace water, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%. The pretreatment method utilizes the high-temperature and strong oxidation characteristics of potassium-sodium mixed salt furnace water to perform cleaning oxidation on surface dirt of a product before strengthening, residual molten salt on the surface of the product before strengthening is deposited on the surface after rinsing, and the surface cleanliness of glass before entering the furnace is ensured. Therefore, the pretreatment method before the glass strengthening treatment of the invention overcomes the defects of watermark, poor concave-convex property and the like after the glass is strengthened for one time on the premise of not influencing the better comprehensive effect of the product with the DOL value and the CS value.
Description
Technical Field
The invention relates to the technical field of glass strengthening treatment, in particular to a pretreatment method before glass strengthening treatment and a glass strengthening treatment method comprising the same.
Background
The chemically strengthened glass product is widely applied to the electronic fields of mobile phones, watches, computers, touch panels and the like due to the characteristics of good light transmission, excellent touch and hand feeling and the like. As the requirements for bending resistance and hardness of strengthened glass are continuously increased, the strengthening process of glass is also gradually complicated. At present, the glass processing industry generally needs a strengthened glass product with a high DOL (Depth Of layer) value and a high CS (Compressive Stress) value, and the strengthened glass product generally cannot simultaneously meet the two values by one-time strengthening, so that the requirement Of a user on the product performance cannot be met. In order to further improve the DOL value and the CS value of the tempered glass and improve the bending resistance and scratch resistance of the tempered glass, the glass is generally treated by adopting a twice-tempering process, so that the service life of a product is further prolonged.
Specifically, the conventional glass processing techniques in the art generally include two strengthening processes, including: primary preheating → primary ion exchange → cooling → washing with water for multiple times in a trough → secondary preheating → secondary ion exchange → air cooling. Wherein, high DOL value of the glass is obtained by one-time ion exchange; the high CS value of the glass is improved by secondary ion exchange, and the ion exchange is generally carried out at low temperature and in short time. However, the pretreatment of the product before strengthening is simple by the processing method, and only one-time product preheating is adopted, so that the yield of the strengthened product obtained in the traditional technology is only 60-80%, and the reject ratio of watermarks and concave-convex defects is as high as 20-40%. The water stain or the stubborn dirt (such as silica gel oil) residue of the product before strengthening can cause the defects of watermark generation or concave-convex badness (local ion exchange can be caused due to the stubborn dirt) and the like of the glass product after one-time ion exchange, the yield of the glass product is seriously influenced, and the enterprise loss is caused.
Therefore, it is necessary and urgent to develop a new pretreatment process before glass strengthening and a new glass strengthening method to overcome the defects of watermark, concave-convex defect and the like after the glass is strengthened for one time, so that the glass product has better bending resistance and scratch resistance and can effectively improve the appearance quality of the product.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a pretreatment method before glass strengthening treatment, which overcomes the defects of watermarks, poor concave-convex property and the like after the glass is strengthened for one time on the premise of not influencing the comprehensive effect of better DOL value and CS value of a product, so that the glass product has better bending resistance and scratch resistance and the appearance quality of the product is effectively improved.
A second object of the present invention is to provide a glass strengthening treatment method including the above pretreatment method before glass strengthening treatment.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a pretreatment method before glass strengthening treatment, which comprises the following steps: providing glass to be treated, and then sequentially preheating and rinsing the glass to obtain pretreated glass;
the rinsing furnace water for rinsing is potassium-sodium mixed salt furnace water, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%.
Further, the preheating temperature is 280-380 ℃, and the time is 60-90 min.
Furthermore, the temperature of rinsing furnace water in the rinsing process is 370-400 ℃, and the rinsing time is 0.5-5 min.
Further, the pretreatment comprises the following steps:
(a) primary preheating: preheating glass to be processed at 280-380 ℃ for 60-90 min;
(b) and rinsing: rinsing the glass preheated in the step (a) for 0.5-5 min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 370-400 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%;
the invention provides a glass strengthening treatment method, which comprises the pretreatment method before the glass strengthening treatment.
Further, the glass strengthening treatment method comprises the following steps:
the glass to be treated is pretreated by adopting the pretreatment method before glass strengthening treatment, and then primary ion exchange, water soaking, secondary preheating, secondary ion exchange and air cooling are sequentially carried out on the glass, so that the strengthened glass is obtained.
Further, the temperature of the primary ion exchange is 380-450 ℃, and the time is 1.5-4 h;
preferably, the molten salt used in the primary ion exchange is a first mixed molten salt, the first mixed molten salt is a mixed molten salt of sodium nitrate and potassium nitrate, and the content of sodium nitrate in the mixed molten salt is 35-75 wt%.
Further, the temperature of the secondary ion exchange is 380-450 ℃, and the time is 5-45 min;
preferably, the molten salt used in the secondary ion exchange is a second mixed molten salt, the second mixed molten salt is a mixed molten salt of sodium nitrate and potassium nitrate, and the content of sodium nitrate in the mixed molten salt is 0.1-10 wt%.
Further, the soaking water is multi-groove soaking water, and preferably 5-groove soaking water;
preferably, the step of soaking the water in the 5-groove comprises the following steps: soaking the glass in water from the first tank to the fifth tank in sequence, wherein:
the first tank is soaked in pure water at the temperature of 60-70 ℃ for bubbling for 15-18 min;
the second tank is soaked in water containing 1% citric acid at 20-25 ℃ for 10-12 min;
soaking in a third tank by bubbling in pure water at 40-50 ℃ for 15-18 min;
soaking in a fourth tank by bubbling in pure water at the temperature of 60-70 ℃ for 15-18 min;
and the fifth tank is soaked in pure water at the temperature of 20-25 ℃ for circulating overflow for 15-18 min.
Further, the glass strengthening treatment method comprises the following steps:
(a) primary preheating: preheating glass to be processed at 280-380 ℃ for 60-90 min;
(b) and rinsing: rinsing the glass preheated in the step (a) for 0.5-5 min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 370-400 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%;
(c) and primary ion exchange: performing ion exchange on the rinsed glass in the first mixed molten salt at the temperature of 380-450 ℃ for 1.5-4 h;
the first mixed molten salt is mixed molten salt of sodium nitrate and potassium nitrate, and the content of the sodium nitrate in the mixed molten salt is 35-75 wt%;
(d) and soaking in multiple grooves: soaking the glass subjected to the primary ion exchange treatment in the step (c) in water in a first tank to a fifth tank in sequence, wherein:
the first tank is soaked in pure water at the temperature of 60-70 ℃ for bubbling for 15-18 min;
the second tank is soaked in water containing 1% citric acid at 20-25 ℃ for 10-12 min;
soaking in a third tank by bubbling in pure water at 40-50 ℃ for 15-18 min;
soaking in a fourth tank by bubbling in pure water at the temperature of 60-70 ℃ for 15-18 min;
soaking in a fifth tank, namely circulating overflow in pure water at the temperature of 20-25 ℃ for 15-18 min;
(e) and secondary preheating: preheating the glass soaked in the multi-groove water in the step (d) for 60-90 minutes at 280-380 ℃;
(f) and secondary ion exchange: performing ion exchange on the glass preheated for the second time in the step (e) in a second mixed molten salt at the temperature of 380-450 ℃ for 5-45 min;
the second mixed molten salt is a molten salt composed of sodium nitrate and potassium nitrate, wherein the content of the sodium nitrate is 0.1-10 wt%;
(g) and air cooling: and (f) taking out the glass subjected to the secondary ion exchange in the step (f), and air-cooling to obtain the strengthened glass.
Compared with the prior art, the invention has the beneficial effects that:
the pretreatment method before glass strengthening treatment provided by the invention comprises the following steps of firstly providing glass to be treated, and then sequentially preheating and rinsing the glass to obtain pretreated glass; the rinsing furnace water for rinsing is potassium-sodium mixed salt furnace water, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%. The method for rinsing the glass by using the potassium-sodium mixed salt furnace water before the glass is subjected to strengthening treatment fills the technical blank that no further pretreatment is performed on the product before strengthening in the prior art after primary preheating, the surface smudge of the product before strengthening is cleaned and oxidized by using the high-temperature and strong oxidation characteristics of the potassium-sodium mixed salt furnace water, and the residual molten salt on the surface of the product before strengthening is deposited on the surface after rinsing, so that the surface cleanliness of the glass before entering the furnace is ensured. Meanwhile, the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%, so that the concentration of rinsing furnace water is approximately the same as that of molten salt for subsequent treatment, and the stress of a product cannot be influenced in the later strengthening process. Therefore, the pretreatment method before glass strengthening treatment of the invention overcomes the defects of watermark, poor concave-convex property and the like after the glass is strengthened for one time on the premise of not influencing the comprehensive effect of better DOL value and CS value of the product, so that the glass product has better bending resistance and scratch resistance and simultaneously effectively improves the appearance quality of the product.
The glass strengthening treatment method provided by the invention comprises the pretreatment method before the glass strengthening treatment. The glass strengthening treatment method overcomes the defects of watermarks, poor concave-convex property and the like after the glass is strengthened for one time on the premise of not influencing the comprehensive effect of better DOL value and CS value of the product, so that the glass product has better bending resistance and scratch resistance and the appearance quality of the product is effectively improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to an aspect of the present invention, a pretreatment method before glass strengthening treatment, the pretreatment method comprising: providing glass to be treated, and then sequentially preheating and rinsing the glass to obtain pretreated glass;
the rinsing furnace water for rinsing is potassium-sodium mixed salt furnace water, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%.
The pretreatment method before glass strengthening treatment provided by the invention comprises the following steps of firstly providing glass to be treated, and then sequentially preheating and rinsing the glass to obtain pretreated glass; the rinsing furnace water for rinsing is potassium-sodium mixed salt furnace water, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%. The method for rinsing the glass by using the potassium-sodium mixed salt furnace water before the glass is subjected to strengthening treatment fills the technical blank that no further pretreatment is performed on the product before strengthening in the prior art after primary preheating, the surface smudge of the product before strengthening is cleaned and oxidized by using the high-temperature and strong oxidation characteristics of the potassium-sodium mixed salt furnace water, and the residual molten salt on the surface of the product before strengthening is deposited on the surface after rinsing, so that the surface cleanliness of the glass before entering the furnace is ensured. Meanwhile, the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%, so that the concentration of rinsing furnace water is approximately the same as that of molten salt for subsequent treatment, and the stress of a product cannot be influenced in the later strengthening process. Therefore, the pretreatment method before glass strengthening treatment of the invention overcomes the defects of watermark, poor concave-convex property and the like after the glass is strengthened for one time on the premise of not influencing the comprehensive effect of better DOL value and CS value of the product, so that the glass product has better bending resistance and scratch resistance and simultaneously effectively improves the appearance quality of the product.
In a preferred embodiment of the present invention, the preheating temperature is 280-380 ℃ and the preheating time is 60-90 min.
In a preferred embodiment of the invention, the temperature of the rinsing furnace water in the rinsing process is 370-400 ℃, and the rinsing time is 0.5-5 min.
In a preferred embodiment, the rinsing process utilizes the strong oxidation property of the potassium-sodium mixed salt furnace water under high temperature conditions, so that the dirt on the surface of the glass product before strengthening can be effectively cleaned and oxidized.
In a preferred embodiment of the present invention, the pretreatment comprises the steps of:
(a) primary preheating: preheating glass to be processed at 280-380 ℃ for 60-90 min;
(b) and rinsing: rinsing the glass preheated in the step (a) for 0.5-5 min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 370-400 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%;
in a preferred embodiment, the pretreated glass utilizes the high-temperature and strong oxidation characteristics of the potassium-sodium mixed salt furnace water to perform 'cleaning oxidation' on the surface dirt of the product before strengthening, and simultaneously, residual molten salt on the surface of the product before strengthening after rinsing is deposited on the surface, so that the surface cleanliness of the glass before entering the furnace is ensured.
According to one aspect of the present invention, a glass strengthening treatment method includes the above pretreatment method before glass strengthening treatment.
The glass strengthening treatment method provided by the invention comprises the pretreatment method before the glass strengthening treatment. The glass strengthening treatment method overcomes the defects of watermarks, poor concave-convex property and the like after the glass is strengthened for one time on the premise of not influencing the comprehensive effect of better DOL value and CS value of the product, so that the glass product has better bending resistance and scratch resistance and the appearance quality of the product is effectively improved.
In a preferred embodiment of the present invention, the glass strengthening treatment method includes the steps of:
the glass to be treated is pretreated by adopting the pretreatment method before glass strengthening treatment, and then primary ion exchange, water soaking, secondary preheating, secondary ion exchange and air cooling are sequentially carried out on the glass, so that the strengthened glass is obtained.
In a preferred embodiment of the invention, the temperature of the primary ion exchange is 380-450 ℃ and the time is 1.5-4 h;
in the above preferred embodiment, the molten salt used in the primary ion exchange is a first mixed molten salt, the first mixed molten salt is a mixed molten salt of sodium nitrate and potassium nitrate, and the content of sodium nitrate in the mixed molten salt is 35 to 75 wt%.
As a preferable embodiment, the content of sodium nitrate in the first mixed molten salt used in the primary ion exchange is 35-75 wt%, so that the concentration of the potassium-sodium mixed molten salt used in rinsing is not obviously changed, and the stress in the product strengthening process is not influenced.
In a preferred embodiment of the invention, the temperature of the primary ion exchange is 380-450 ℃ and the time is 5-45 min;
in the above preferred embodiment, the molten salt used in the secondary ion exchange is a second mixed molten salt, the second mixed molten salt is a mixed molten salt of sodium nitrate and potassium nitrate, and the content of sodium nitrate in the mixed molten salt is 0.1 to 10 wt%.
In a preferred embodiment of the invention, the soaking water is multi-groove soaking water, preferably 5-groove soaking water;
in the above preferred embodiment, the step of soaking in water in 5 tanks includes: soaking the glass in water in the first to fifth grooves in sequence, wherein:
the first tank is soaked in pure water at the temperature of 60-70 ℃ for bubbling for 15-18 min;
the second tank is soaked in water containing 1% citric acid at 20-25 ℃ for 10-12 min;
soaking in a third tank by bubbling in pure water at 40-50 ℃ for 15-18 min;
soaking in a fourth tank by bubbling in pure water at the temperature of 60-70 ℃ for 15-18 min;
and the fifth tank is soaked in pure water at the temperature of 20-25 ℃ for circulating overflow for 15-18 min.
As a preferred embodiment, the water-soaking step of the present application has the following technical advantages: 1. a bubbling mode is added, so that the water flow in the soaking tank is kept to be surged up and down to form moving water instead of static water, and the cleaning effect is improved; 2. 1 percent of citric acid is added, so that some intractable stains which are not dissolved in water on the surface of the glass are dissolved in acid water by chemical reaction; 3. meanwhile, the potassium nitrate on the surface of the glass and the dirt dissolved in water can be fully dissolved in the water by soaking water in the first to fifth grooves for a longer time, so that the dirt brought in by the potassium nitrate and the dirt dissolved in the water is reduced; 4. the overflow circulating water aims to keep the water quality in the water soaking tank clean, so that the carried dirt flows out along with the water, and new clean pure water is supplemented, thus the impurities dissolved in the water soaking tank cannot be saturated.
In a preferred embodiment of the present invention, the glass strengthening treatment method includes the steps of:
(a) primary preheating: preheating glass to be processed at 280-380 ℃ for 60-90 min;
it should be noted that, in mass production, the glass enters the furnace water rinsing step after the primary preheating step is completed, and when the preheating temperature is too low, the glass surface is cracked or cracked after the furnace water rinsing is completed, and even the product is stacked in a scattered manner. When the primary preheating temperature is too high, the strengthening frame and the glass have local reaction, and adverse results are generated. If the preheating time is too short, the related adverse phenomenon occurs when the preheating temperature is too low.
(b) And rinsing: rinsing the glass preheated in the step (a) for 0.5-5 min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 370-400 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%;
the furnace water rinsing step is performed in an intensified furnace (rinsing furnace) molten salt, and requires the use of a molten salt of a mixture of potassium nitrate and sodium nitrate (for example, 99.9% technical-grade potassium nitrate and 99.9% technical-grade sodium nitrate), a rinsing temperature: 370-400 ℃, preferably 380 ℃, rinsing time: 0.5-5 minutes, preferably 1-3 minutes, and controlling the content of sodium nitrate in the mixed molten salt to be 38-50 wt%.
In the present invention, if the temperature of the mixed molten salt in the furnace water rinsing is higher than 400 ℃, for example, 410 ℃, a certain amount of ion exchange will be continued in the "furnace water rinsing" step, which will affect the effect of the primary ion exchange in step (3). If the temperature of the molten salt for the fast rinsing is lower than 370 ℃, for example 360 ℃, the molten salt will crystallize due to the inevitable natural cooling of the glass transferred from step (1), which obviously affects the cleaning effect of the rinsing.
Similarly, the time of the furnace water rinsing in the present invention is important, and if the rinsing time is too short, the residual dirt on the glass surface cannot be cleaned by "oxidation cleaning". If the rinsing time is too long, the effect of one-time ion exchange will be affected, and the quality of the glass product will be further affected.
(c) And primary ion exchange: performing ion exchange on the rinsed glass in the first mixed molten salt at the temperature of 380-450 ℃ for 1.5-4 h;
the first mixed molten salt is mixed molten salt of sodium nitrate and potassium nitrate, and the content of the sodium nitrate in the mixed molten salt is 35-75 wt%;
the primary ion exchange is performed at 380-450 ℃, sodium nitrate accounts for 35-75 wt% of the mixed molten salt, preferably 35-50 wt% of the mixed molten salt, the exchange time is 1.5-4 hours, and the required stress layer can be obtained through a lower temperature and a longer time or a higher temperature and a shorter time in the primary ion exchange step. After the molten salt with the mass ratio is used for primary ion exchange, the stress value of the obtained glass is 450-640 MPa, and the stress layer is 120-140 um; if the surface stress value exceeds 640MPa or the stress layer exceeds 140um, the internal stress CT is increased, so that the glass self-explosion rate exceeds 0.1 percent; if the surface stress value is lower than 450MPa or the stress layer is lower than 120um, the bending strength of the glass workpiece is not obviously improved.
(d) And soaking in multiple grooves: soaking the glass subjected to the primary ion exchange treatment in the step (c) in water in a first tank to a fifth tank in sequence, wherein:
the first tank is soaked in pure water at the temperature of 60-70 ℃ for bubbling for 15-18 min;
the second tank is soaked in water containing 1% citric acid at 20-25 ℃ for 10-12 min;
soaking in a third tank by bubbling in pure water at 40-50 ℃ for 15-18 min;
soaking in a fourth tank by bubbling in pure water at the temperature of 60-70 ℃ for 15-18 min;
soaking in a fifth tank, namely circulating overflow in pure water at the temperature of 20-25 ℃ for 15-18 min;
it should be noted that, this application multislot bubble water is 5 full-automatic bubble water in groove: first tank/65 ± 5 ℃/15 min/bubbling/tap water → second tank/normal temperature water/1% citric acid/10 min/pure water → third tank/45 ± 5 ℃/15 min/bubbling/pure water → fourth tank/65 ± 5 ℃/15 min/bubbling/pure water → fifth tank/normal temperature water/15 min/circulating water/pure water; if the water soaking time is less than 10 min/groove or no bubbling or overflowing can cause the cleanliness of the glass surface not to reach the standard, and dirt enters secondary ion exchange furnace water along with a workpiece, thereby influencing the bad defects of rack marks, water mark marks, concave-convex marks and the like of products.
(e) And secondary preheating: preheating the glass soaked in the multi-groove water in the step (d) for 60-90 minutes at 280-380 ℃;
the temperature of the secondary preheating is set to be 280-380 ℃, the time is 60-90 minutes, and air is heated. The same preheating step and the "secondary preheating" step in the conventional technology are different in magnitude, and the time control of the secondary preheating needs to be paid attention to. If the secondary preheating temperature is lower than 280 ℃, the temperature of the molten salt is reduced by more than 8 ℃ due to the secondary ion exchange, so that the temperature of the molten salt is lower than the set temperature after the secondary ion exchange step is finished, and the parameter requirement of the secondary ion exchange cannot be met. If the secondary preheating temperature is higher than 380 ℃, the glass begins to have secondary ion migration in the secondary preheating step, thus influencing the parameter requirement of secondary ion exchange. If the secondary preheating time is too short, the temperature of the workpiece is also reduced after entering the secondary ion exchange step, and if the secondary preheating time is too long, the glass starts to have secondary ion migration in the secondary preheating step, so that the parameters of the secondary ion exchange are also influenced.
(f) And secondary ion exchange: performing ion exchange on the glass preheated for the second time in the step (e) in a second mixed molten salt at the temperature of 380-450 ℃ for 5-45 min;
the second mixed molten salt is a molten salt composed of sodium nitrate and potassium nitrate, wherein the content of the sodium nitrate is 0.1-10 wt%;
the secondary ion exchange is performed at 380-450 ℃ in molten salt consisting of sodium nitrate and potassium nitrate, wherein the content of sodium nitrate is 0.1-10 wt%, and the ion exchange time is 5-45 minutes, preferably 28-35 minutes. This step is largely the same as the "secondary ion exchange" step in the prior art. When NaNO is in secondary molten salt 3 When the content is too low, the DOL value is reduced by 10um after the secondary ion exchange step is finished, and NaNO in the secondary molten salt 3 Too low content can also cause too high CS value to cause larger central stress of the glass workpiece, thereby increasing the self-explosion risk of the glass workpiece; when NaNO is in secondary molten salt 3 When the content is too high, the CS value is less than 720MPa after the secondary ion exchange step is finished, and the strength of the glass workpiece in a four-point bending test is poor due to too low CS value.
(g) And air cooling: and (f) taking out the glass subjected to the secondary ion exchange in the step (f), and air-cooling to obtain the strengthened glass.
The time for entering the air cooling step after the secondary ion exchange step is finished is less than or equal to 1 minute, and the air cooling time of the air cooling step is 0-10 minutes. If the product is moved to an air cooling area within 1 minute, the CS value fluctuates within +/-10 MPa, and the DOL value fluctuates within +/-0.3 um; if the glass is moved to an air cooling area within 1-3 minutes, the fused salt on the surface of the product continuously undergoes ion exchange, the surface stress of the glass product is reduced rapidly, stress tests show that the CS value of the product in the same furnace of secondary ion exchange is up to 890MPa at most, the minimum is only 800MPa, the DOL value is up to 8.4um at most, the minimum is 9.1um, and the stability of the CS value and the DOL value is poor.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
A glass strengthening treatment method, comprising the steps of:
(a) primary preheating: preheating glass to be processed for 80min at 350 ℃;
(b) and rinsing: rinsing the glass preheated in the step (a) for 3min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 395 ℃, the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 50wt%, and the content of potassium nitrate is 50 wt%;
(c) and primary ion exchange: carrying out ion exchange on the rinsed glass in first mixed molten salt at the temperature of 420 ℃ for 2.5 h;
the first mixed molten salt is mixed molten salt of sodium nitrate and potassium nitrate, and the content of the sodium nitrate in the mixed molten salt is 50 wt%;
(d) and soaking water in multiple grooves: soaking the glass subjected to the primary ion exchange treatment in the step (c) in water in a first tank to a fifth tank in sequence, wherein:
the first tank is soaked by bubbling in pure water at 65 ℃ for 16 min;
the second tank is soaked in water containing 1% citric acid at 22 deg.C for 11 min;
soaking in a third tank by bubbling in pure water at 45 deg.C for 16 min;
soaking in a fourth tank by bubbling in pure water at 65 deg.C for 16 min;
soaking in a fifth tank, namely circulating overflow in pure water at 22 ℃ for 16 min;
(e) and secondary preheating: preheating the glass soaked in the water in the multiple grooves in the step (d) for 80 minutes at 320 ℃;
(f) and secondary ion exchange: carrying out ion exchange on the glass preheated for the second time in the step (e) in a second mixed molten salt at the temperature of 420 ℃ for 30 min;
the second mixed molten salt is a molten salt consisting of sodium nitrate and potassium nitrate, wherein the content of the sodium nitrate is 1 wt%;
(g) and air cooling: and (f) taking out the glass subjected to the secondary ion exchange in the step (f), and air-cooling to obtain the strengthened glass.
Example 2
A glass strengthening treatment method, comprising the steps of:
(a) the same as in example 1;
(b) and rinsing: rinsing the glass preheated in the step (a) for 3min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 380 ℃, the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38 wt%, and the content of potassium nitrate is 62 wt%;
(c) examples (a) and (g) are the same as example 1.
Example 3
A glass strengthening treatment method, comprising the steps of:
(a) the same as in example 1;
(b) and rinsing: rinsing the glass preheated in the step (a) for 5min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 400 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 50 wt%;
(c) examples (a) and (g) are the same as example 1.
Example 4
A glass strengthening treatment method, comprising the steps of:
(a) the same as in example 1;
(b) and rinsing: rinsing the glass preheated in the step (a) for 10min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 420 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 50 wt%;
(c) examples (a) and (g) are the same as example 1.
Comparative example 1
A glass strengthening treatment method as in example 1 except that step (b) is not included, and the glass to be processed after the primary preheating in step (a) is directly subjected to the primary ion exchange in step (c).
Comparative example 2
A glass strengthening treatment method similar to example 1 except that the rinsing furnace water used in step (b) was furnace water containing 1 wt% of sodium nitrate.
Comparative example 3
A glass strengthening treatment method similar to example 1 except that the rinsing furnace water used in step (b) was a furnace water containing 20 wt% of sodium nitrate.
Comparative example 4
A glass strengthening treatment method similar to example 1 except that the rinsing furnace water used in step (b) was a furnace water containing 80 wt% of sodium nitrate.
Experimental example 1
Taking industrial general tempered glass as an example, a furnace water rapid rinsing pretreatment processing method is added to a product before tempering, and after all the steps of the tempering process are completed, the stress and reliability test results of the product prepared in example 1 are compared with those of the prior art (comparative example 1), and the results show no influence, and are specifically shown in the following table 1:
table 1:
note: DOL: depth of surface stress layer; DOC: ion exchange stress layer total depth; CS: surface compressive stress; CSK: corner compressive stress; CT: a central tensile stress; and the stress values are averages.
Note: the above reliability test values are all average values.
The results of "watermarks, concave-convex defect rates, and product yields" of the glasses treated by the glass strengthening treatment methods of examples 1 to 4 and comparative examples 1 to 4 of the present application were measured as shown in the following table:
in conclusion, the glass products obtained by the glass strengthening treatment method in the embodiments 1 to 4 of the application have a yield of more than 85%, and have extremely low watermark and concave-convex defective rates; the technical proposal that the step of pretreatment rinsing is not included in the comparative example 1, and the ion exchange is directly carried out, has the defect rate of watermarks and concave-convex parts as high as 13.21 percent, and has the yield of only 78.12 percent; meanwhile, the comparative examples 2 to 4 are embodiments in which the content of sodium nitrate in the potassium-sodium mixed salt furnace water used in the step (b) is not within the scope of claim 1 of the present application, and the "watermark and concave-convex defect rate" is as high as 3.56 to 6.25%, and the technical effect is also poor. It is fully demonstrated that in embodiments 1 to 4 of the present application, by using the high temperature and strong oxidation characteristics of potassium-sodium mixed salt furnace water with a sodium nitrate content of 38 to 50wt%, surface contamination of a product before strengthening is "cleaned and oxidized", residual molten salt on the surface of the product before strengthening after rinsing is deposited on the surface, so that the surface cleanliness of glass before entering the furnace is ensured, and further, on the premise that the product has a better comprehensive effect of a DOL value and a CS value, the defects of watermarks, unevenness and the like after one-time strengthening of the glass are effectively overcome.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. A pretreatment method before glass strengthening treatment, which is characterized by comprising the following steps: providing glass to be treated, and then sequentially preheating and rinsing the glass to obtain pretreated glass;
the rinsing furnace water for rinsing is potassium-sodium mixed salt furnace water, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%;
the temperature of rinsing furnace water in the rinsing process is 370-400 ℃, and the rinsing time is 0.5-5 min.
2. The pretreatment method before glass strengthening treatment according to claim 1, wherein the preheating temperature is 280 to 380 ℃ and the time is 60 to 90 min.
3. A glass strengthening treatment method comprising the pretreatment method before glass strengthening treatment according to claim 1 or 2.
4. The glass strengthening treatment method according to claim 3, comprising the steps of:
the glass to be treated is pretreated by the pretreatment method before glass strengthening treatment, which is defined in claim 1 or 2, and then the glass is subjected to primary ion exchange, water soaking, secondary preheating, secondary ion exchange and air cooling in sequence to obtain the strengthened glass.
5. The glass strengthening treatment method according to claim 4, wherein the temperature of the primary ion exchange is 420 to 450 ℃ and the time is 1.5 to 4 hours.
6. The glass strengthening treatment method according to claim 5, wherein the molten salt used in the primary ion exchange is a first mixed molten salt, the first mixed molten salt is a mixed molten salt of sodium nitrate and potassium nitrate, and the content of sodium nitrate in the mixed molten salt is 35 to 75 wt%.
7. The glass strengthening treatment method according to claim 4, wherein the temperature of the secondary ion exchange is 420 to 450 ℃ and the time is 5 to 45 min.
8. The glass strengthening treatment method according to claim 7, wherein the molten salt used in the secondary ion exchange is a second mixed molten salt, the second mixed molten salt is a mixed molten salt of sodium nitrate and potassium nitrate, and the content of sodium nitrate in the mixed molten salt is 0.1 to 10 wt%.
9. The glass strengthening treatment method according to claim 4, wherein the bubble water is multi-channel bubble water.
10. The glass strengthening treatment method according to claim 4, wherein the bubble water is 5-tank bubble water;
the step of soaking water in the 5 grooves comprises the following steps: soaking the glass in water in the first to fifth grooves in sequence, wherein:
the first tank is soaked in pure water at the temperature of 60-70 ℃ for bubbling for 15-18 min;
the second tank is soaked in water containing 1% citric acid at 20-25 ℃ for 10-12 min;
the third tank is soaked in pure water at the temperature of 40-50 ℃ for bubbling for 15-18 min;
soaking in a fourth tank by bubbling in pure water at the temperature of 60-70 ℃ for 15-18 min;
and the fifth tank is soaked in pure water at the temperature of 20-25 ℃ for circulating overflow for 15-18 min.
11. The glass strengthening treatment method according to claim 3, comprising the steps of:
(a) primary preheating: preheating glass to be processed for 60-90 min at the temperature of 280-380 ℃;
(b) and rinsing: rinsing the glass preheated in the step (a) for 0.5-5 min by using potassium-sodium mixed salt furnace water;
the temperature of the potassium-sodium mixed salt furnace water is 370-400 ℃, and the content of sodium nitrate in the potassium-sodium mixed salt furnace water is 38-50 wt%;
(c) and primary ion exchange: performing ion exchange on the rinsed glass in the first mixed molten salt at the temperature of 380-450 ℃ for 1.5-4 h;
the first mixed molten salt is mixed molten salt of sodium nitrate and potassium nitrate, and the content of the sodium nitrate in the mixed molten salt is 35-75 wt%;
(d) and soaking water in multiple grooves: soaking the glass subjected to the primary ion exchange treatment in the step (c) in water in a first tank to a fifth tank in sequence, wherein:
the first tank is soaked in pure water at the temperature of 60-70 ℃ for bubbling for 15-18 min;
the second tank is soaked in water containing 1% citric acid at 20-25 ℃ for 10-12 min;
soaking in a third tank by bubbling in pure water at 40-50 ℃ for 15-18 min;
soaking in a fourth tank for bubbling in pure water at the temperature of 60-70 ℃ for 15-18 min;
soaking in a fifth tank, namely circulating overflow in pure water at the temperature of 20-25 ℃ for 15-18 min;
(e) and secondary preheating: preheating the glass soaked in the multi-groove water in the step (d) for 60-90 minutes at 280-380 ℃;
(f) and secondary ion exchange: performing ion exchange on the glass preheated for the second time in the step (e) in a second mixed molten salt at the temperature of 380-450 ℃ for 5-45 min;
the second mixed molten salt is a molten salt composed of sodium nitrate and potassium nitrate, wherein the content of the sodium nitrate is 0.1-10 wt%;
(g) and air cooling: and (f) taking out the glass subjected to the secondary ion exchange in the step (f), and air-cooling to obtain the strengthened glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111097535.1A CN113603344B (en) | 2021-09-18 | 2021-09-18 | Pretreatment method before glass strengthening treatment and glass strengthening treatment method comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111097535.1A CN113603344B (en) | 2021-09-18 | 2021-09-18 | Pretreatment method before glass strengthening treatment and glass strengthening treatment method comprising same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113603344A CN113603344A (en) | 2021-11-05 |
| CN113603344B true CN113603344B (en) | 2022-09-16 |
Family
ID=78310612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111097535.1A Active CN113603344B (en) | 2021-09-18 | 2021-09-18 | Pretreatment method before glass strengthening treatment and glass strengthening treatment method comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113603344B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292034B (en) * | 2021-12-23 | 2023-12-12 | 四川虹科创新科技有限公司 | Chemical strengthening method for anti-falling lithium aluminum silicon glass |
| CN114477792A (en) * | 2022-02-25 | 2022-05-13 | Oppo广东移动通信有限公司 | Method for strengthening microcrystalline glass, cover plate, and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4846868A (en) * | 1986-09-05 | 1989-07-11 | Central Glass Company, Limited | Chemically strengthened glass article and method of producing same |
| JP2002220260A (en) * | 2001-01-22 | 2002-08-09 | Matsushita Electric Ind Co Ltd | Glass substrate and method of manufacturing it, and recording medium and method of manufacturing the same |
| WO2014057861A1 (en) * | 2012-10-11 | 2014-04-17 | セントラル硝子株式会社 | Method for cleaning glass substrate |
| CN106348621A (en) * | 2015-07-17 | 2017-01-25 | 蓝思科技股份有限公司 | Toughening method for toughened glass |
| CN108069624A (en) * | 2016-11-11 | 2018-05-25 | 蓝思科技股份有限公司 | A kind of reinforcing process method of glass |
-
2021
- 2021-09-18 CN CN202111097535.1A patent/CN113603344B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4846868A (en) * | 1986-09-05 | 1989-07-11 | Central Glass Company, Limited | Chemically strengthened glass article and method of producing same |
| JP2002220260A (en) * | 2001-01-22 | 2002-08-09 | Matsushita Electric Ind Co Ltd | Glass substrate and method of manufacturing it, and recording medium and method of manufacturing the same |
| WO2014057861A1 (en) * | 2012-10-11 | 2014-04-17 | セントラル硝子株式会社 | Method for cleaning glass substrate |
| CN106348621A (en) * | 2015-07-17 | 2017-01-25 | 蓝思科技股份有限公司 | Toughening method for toughened glass |
| CN108069624A (en) * | 2016-11-11 | 2018-05-25 | 蓝思科技股份有限公司 | A kind of reinforcing process method of glass |
Non-Patent Citations (1)
| Title |
|---|
| 再制造清洗熔盐配方改进及去除作用研究;张保财等;《高校化学工程学报》;20200815(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113603344A (en) | 2021-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113603344B (en) | Pretreatment method before glass strengthening treatment and glass strengthening treatment method comprising same | |
| CN108069624B (en) | Glass strengthening processing method | |
| US4671814A (en) | Method of strengthening glass article formed of float glass by ion exchange | |
| US10065885B2 (en) | Glass sheet for pigment printing, pigment-printed glass sheet, production method therefor, and image display device | |
| CN111348841A (en) | Chemical strengthening method for improving falling resistance and surface hardness of glass | |
| JP2006501123A (en) | Method for producing float glass with reduced defect density | |
| CN110885997A (en) | Manufacturing method of cold-rolled electroplated tin steel plate | |
| CN111875264B (en) | Cover plate glass strengthening process | |
| CN113816618A (en) | Chemical strengthening method for glass and glass prepared by chemical strengthening method | |
| CN106348621A (en) | Toughening method for toughened glass | |
| CN110981220A (en) | Chemical toughening method for glass | |
| CN100588634C (en) | Compositions for reinforcing glass and its reinforcing method | |
| CN112209625A (en) | AG glass polishing solution and preparation method thereof | |
| KR101239473B1 (en) | pickling agent and pickling process of stainless steel | |
| KR101073186B1 (en) | Method for pickling low chrome ferritic stainless steel | |
| CN108623140A (en) | A kind of fused salt and its steel process for ultra-thin soda-lime glass chemical tempering | |
| KR20120038079A (en) | Manufacturing method for tempered glass and tempered glass thereof | |
| CN110952120A (en) | Aluminum alloy nickel plating pretreatment method | |
| KR101073279B1 (en) | Method for pickling molybdenum added ferritic stainless steel | |
| CN114230196B (en) | Reinforced glass with scratch resistance and preparation method thereof | |
| CN110102537B (en) | Method for cleaning high-abrasion low-chemical-stability optical glass | |
| JP2587258B2 (en) | Method for producing reflow tin or tin alloy plated material using copper or copper alloy as base material | |
| CN108950296A (en) | A kind of preparation method of ultra-white float glass tin liquor additive | |
| CN114873927B (en) | UTG chemical strengthening process | |
| KR101073262B1 (en) | Method for pickling niobium added ferritic stainless steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |