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CN111116057A - Chemical strengthening additive and method for chemical strengthening using the same - Google Patents

Chemical strengthening additive and method for chemical strengthening using the same Download PDF

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Publication number
CN111116057A
CN111116057A CN201911406264.6A CN201911406264A CN111116057A CN 111116057 A CN111116057 A CN 111116057A CN 201911406264 A CN201911406264 A CN 201911406264A CN 111116057 A CN111116057 A CN 111116057A
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ion exchange
metal
additive
metal ion
chemical strengthening
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何俊
沈健
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Henan Yuzhan Precision Technology Co Ltd
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Henan Yuzhan Precision Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment 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
    • C03C21/002Treatment 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The invention provides a chemical strengthening additive, which is used for being added into an ion exchange tank of a base material, wherein the base material generates free first metal ions in the metal ion exchange process, the chemical strengthening additive comprises a main agent and an additive, the main agent is a basic metal compound containing at least one second metal, and the additive is an acidic compound; the main agent is used for carrying out metal ion exchange with the first metal ions and generating precipitable precipitates, and the additive is used for adjusting the pH value of the ion exchange tank. The invention also provides a method, which comprises the following steps: providing one or more substrates; immersing the base material in a metal ion exchange tank; chemical strengthening additives are added to the metal ion exchange cell to produce precipitable precipitates. The method provided by the invention adds a chemical strengthening additive into the metal ion exchange pool to combine with the free first metal ions to generate precipitable precipitate; and the pH value of the ion exchange tank can be adjusted in the metal ion exchange process.

Description

Chemical strengthening additive and method for chemical strengthening using the same
Technical Field
The invention relates to the field of glass, in particular to a chemical strengthening additive and a chemical strengthening method using the chemical strengthening additive.
Background
At present, the display panel of electronic products is mostly strengthened by chemical strengthening. The chemical strengthening method is to chemically change the surface composition of the glass and increase the surface lamination stress so as to increase the mechanical strength and thermal stability of the glass. The method is characterized in that the surface composition of the glass is changed according to the mechanism of ion diffusion, namely the glass is immersed into high-temperature molten salt under a certain temperature condition, and alkali metal ions in the glass and alkali metal ions in the molten salt are mutually exchanged due to diffusion, so that the surface of the glass generates compressive stress, and the strength of the glass is improved.
When the glass is subjected to strengthening treatment, lithium ions in the glass can diffuse into the high-temperature molten salt until the lithium ion content in the high-temperature molten salt is saturated. At the moment, a proper amount of sodium phosphate needs to be added into the high-temperature molten salt, and phosphate radicals decomposed in the high-temperature molten salt by the sodium phosphate are combined with lithium ions to generate precipitates so as to reduce the content of the lithium ions in the high-temperature molten salt and enable the glass to be continuously subjected to strengthening treatment. However, sodium phosphate is an alkaline metal compound, and as the addition amount of the sodium phosphate increases, the PH of the high-temperature molten salt increases continuously (the alkalinity increases), and when the PH increases to a certain PH, the sodium phosphate may corrode glass to a certain extent, thereby affecting the strength of the glass.
Disclosure of Invention
In view of the above, it is necessary to provide a chemical strengthening additive and a method for chemical strengthening using the chemical strengthening additive to solve the above problems.
The invention provides a chemical strengthening additive, which is used for being added into an ion exchange pool of a base material, wherein the base material generates free first metal ions in the process of metal ion exchange, the chemical strengthening additive comprises a main agent and an additive, the main agent is a basic metal compound containing at least one second metal, and the additive is an acidic compound; the main agent is used for carrying out metal ion exchange with first metal ions and generating precipitable precipitates, and the additive is used for adjusting the pH value of the ion exchange tank.
Further, the first metal ion is lithium, and the second metal is at least one of sodium and potassium.
Further, the main agent is at least one of a phosphoric acid metal compound, a carbonic acid metal compound, a sulfuric acid metal compound, or a metal fluoride.
Further, the main agent is at least one of sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium fluoride and potassium fluoride.
Further, the additive is at least one of silicic acid and alumina.
The invention also provides a method for carrying out chemical strengthening by using the chemical strengthening additive, which comprises the following steps:
providing one or more substrates;
immersing a substrate in a metal ion exchange cell to free first metal ions in the substrate;
adding a chemical enhancing additive to the metal ion exchange cell to produce a precipitable precipitate.
Further, the metal ion exchange pool comprises potassium nitrate and sodium nitrate, and the volume percentage ratio of the potassium nitrate to the sodium nitrate is (8-9): (1-2).
Further, when the concentration of the first metal ions reaches a preset threshold value, the base material is taken out and a chemical strengthening additive is added.
Further, the precipitate is filtered from the metal ion exchange cell using a filtration device.
Further, the chemical strengthening additive is stored in the filtering device, and the precipitate can be collected in the filtering device.
The chemical toughening additive provided by the invention can perform metal ion exchange with the first metal ions, generate precipitable precipitate and adjust the pH value of the metal ion exchange tank. The chemical strengthening method provided by the invention comprises the steps of immersing a base material in a metal ion exchange tank to enable first metal ions in the base material to be free; adding a chemical strengthening additive into the metal ion exchange tank to combine with the free first metal ions to generate precipitable precipitates; and the pH value of the metal ion exchange tank can be adjusted in the metal ion exchange process, so that certain corrosion of the glass caused by overhigh alkalinity of the metal ion exchange tank is avoided.
Drawings
FIG. 1 is a flow chart of a method of chemical strengthening using a chemical strengthening additive according to one embodiment of the present invention.
Figure 2 is an assembly view of the reinforcing apparatus, basket and filter device of one embodiment of the present invention.
Fig. 3 is a top view of the filter device of fig. 2.
Description of the main elements
Reinforcement device 100
Furnace body 10
Furnace cover 20
Filter apparatus 200
Filter screen 210
First filter 211
Second filter 212
Third filter 213
Lock catch 220
Hanging basket 300
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. When an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention provides a chemical strengthening additive in a preferred embodiment for addition to an ion exchange cell of a substrate that generates free first metal ions during a metal ion exchange process.
In this example, the substrate is a glass substrate made of lithium aluminosilicate. It is understood that in other embodiments, glass substrates of other materials including lithium may be used.
Specifically, the first metal ions in this embodiment are lithium ions.
In this embodiment, the metal ion exchange tank includes potassium nitrate and sodium nitrate. Wherein the sum of the volume percentages of the potassium nitrate and the sodium nitrate is 100 percent. The volume percentage ratio of potassium nitrate to sodium nitrate is (8-9): (1-2). For example, the percentage of potassium nitrate is 87% and the percentage of sodium nitrate is 13%.
It will be appreciated that in other embodiments, the metal ion exchange cell may consist of sodium nitrate alone.
It will be appreciated that in other embodiments, the metal ion exchange cell may also consist of potassium nitrate alone.
It will be appreciated that in other embodiments, the metal ion exchange cells comprise potassium nitrate, sodium nitrate and lithium nitrate, wherein the sum of the percentages of potassium nitrate, sodium nitrate and lithium nitrate is 100%. The percentage ratio of potassium nitrate, sodium nitrate and lithium nitrate is (80-90): (10-20): (1.5-2.5). For example, the percentage of potassium nitrate is 86%, the percentage of sodium nitrate is 12%, and the percentage of lithium nitrate is 2%.
In this embodiment, the glass substrate can precipitate free lithium ions at a preset rate in a molten salt consisting of potassium nitrate, sodium nitrate, and lithium nitrate; when free lithium ions do not exist in the molten salt initially, namely the molten salt does not contain lithium nitrate, the lithium ions can be separated out from the substrate at a higher speed under the larger content difference because the difference between the lithium ion content in the molten salt and the lithium ion content in the substrate is larger, and at the moment, the lithium ions in the surface layer and the middle layer of the substrate can be separated out into the metal ion exchange pool; after ion exchange, because part of sodium ions or potassium ions can reach the surface layer of the base material firstly, other subsequent sodium ions or potassium ions cannot reach the middle layer of the base material, so that only lithium ions are separated out from the middle layer of the base material without exchange of the sodium ions or the potassium ions, and the strength of the middle layer of the base material after ion exchange is influenced; after a certain amount of lithium nitrate is added into the molten salt, the lithium ions in the molten salt can slow down the precipitation rate of the lithium ions in the base material, only the lithium ions on the surface layer of the base material are precipitated into the metal ion exchange tank and subjected to ion exchange, and the base material with high overall strength can be obtained after the ion exchange.
Specifically, the chemical strengthening additive comprises a main agent and an additive.
The main agent is a basic metal compound containing at least one second metal, and is used for carrying out metal ion exchange with the first metal ions and generating precipitable precipitates.
Wherein the second metal is at least one of sodium and potassium.
The main agent is at least one of phosphoric acid metal compound, carbonic acid metal compound, sulfuric acid metal compound or metal fluoride.
Specifically, the main agent is at least one of sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium fluoride and potassium fluoride.
Specifically, when the metal ion exchange cell consists of sodium nitrate alone, the second metal is sodium. In this case, the main agent may be only sodium phosphate, or sodium phosphate and sodium nitrate. But is not limited thereto.
When the metal ion exchange cell consists only of potassium nitrate, the second metal is potassium. In this case, the main agent may be only sodium phosphate, or potassium phosphate and potassium nitrate. But is not limited thereto.
When the metal ion exchange cell is comprised of sodium nitrate and potassium nitrate, the second metal is sodium and potassium. In this case, the main agent can be sodium phosphate or potassium nitrate; or potassium phosphate, sodium nitrate; or sodium phosphate, potassium nitrate, sodium nitrate, or potassium phosphate, potassium nitrate, sodium nitrate. But is not limited thereto.
Specifically, the metal ion exchange cell in this example is composed of sodium nitrate and potassium nitrate. The main agent is preferably sodium phosphate, sodium nitrate and potassium nitrate.
The additive is an acidic compound and is used for adjusting the pH value of the metal ion exchange tank.
Specifically, the additive is at least one of silicic acid and alumina.
Wherein the alumina can adjust the pH value of the molten salt.
The silicic acid can adsorb impurity ions (such as calcium ions) in molten nitrate, and can adjust the pH value of the molten salt.
In particular, the additives in this embodiment are silicic acid and alumina.
Specifically, the chemical strengthening additive in the embodiment comprises, by weight, 6 parts to 14 parts of sodium phosphate, 4.5 parts to 11 parts of sodium nitrate, 6 parts to 15 parts of potassium nitrate, 0.08 part to 0.2 part of silicic acid and 0.05 part to 0.12 part of aluminum oxide.
Referring to fig. 1, the present invention also provides a method for chemical strengthening using the chemical strengthening additive. The method mainly comprises the following steps:
s101: one or more substrates are provided.
Specifically, the substrate is a glass substrate made of lithium aluminosilicate.
S102: the substrate is immersed in a metal ion exchange cell to free the first metal ions in the substrate.
Specifically, molten salt is added to the strengthening apparatus to form a metal ion exchange cell. As shown in fig. 2, the strengthening apparatus 100 includes a furnace body 10, a furnace cover 20, and a heating member (not shown). The furnace body 10 is used for placing nitrate. The heating member is provided in the furnace body 10 and serves to heat the nitrate to a molten state.
The metal ion exchange pool is composed of potassium nitrate and sodium nitrate. Wherein the percentage of potassium nitrate is 87 percent, and the percentage of sodium nitrate is 13 percent.
When the nitrate in the metal ion exchange tank is heated to a molten state, the base material is immersed in the metal ion exchange tank, so that lithium ions in the base material and sodium ions or potassium ions in the metal ion exchange tank are subjected to ion exchange.
S103: chemical strengthening additives are added to the metal ion exchange cell to produce precipitable precipitates.
Specifically, the chemical strengthening additive comprises a main agent and an additive.
The main agent is a basic metal compound containing at least one second metal, and is used for carrying out metal ion exchange with the first metal ions and generating precipitable precipitates.
Wherein the second metal is at least one of sodium and potassium.
The main agent is at least one of phosphoric acid metal compound, carbonic acid metal compound, sulfuric acid metal compound or metal fluoride.
Specifically, the main agent is at least one of sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium fluoride and potassium fluoride.
Specifically, when the metal ion exchange cell consists of sodium nitrate alone, the second metal is sodium. In this case, the main agent may be only sodium phosphate, or sodium phosphate and sodium nitrate. But is not limited thereto.
When the metal ion exchange cell consists only of potassium nitrate, the second metal is potassium. In this case, the main agent may be only sodium phosphate, or potassium phosphate and potassium nitrate. But is not limited thereto.
When the metal ion exchange cell is comprised of sodium nitrate and potassium nitrate, the second metal is sodium and potassium. In this case, the main agent can be sodium phosphate or potassium nitrate; or potassium phosphate, sodium nitrate; or sodium phosphate, potassium nitrate, sodium nitrate, or potassium phosphate, potassium nitrate, sodium nitrate. But is not limited thereto.
Specifically, the ion exchange cell in this example is composed of sodium nitrate and potassium nitrate. The main agent is preferably sodium phosphate, sodium nitrate and potassium nitrate.
The additive is an acidic compound and is used for adjusting the pH value of the ion exchange tank.
Specifically, the additive is at least one of silicic acid and alumina.
Wherein the alumina can adjust the pH value of the molten salt.
The silicic acid can adsorb impurity ions (such as calcium ions) in molten nitrate, and can adjust the pH value of the molten salt.
In particular, the additives in this embodiment are silicic acid and alumina.
Specifically, the chemical strengthening additive in the embodiment comprises, by weight, 6 parts to 14 parts of sodium phosphate, 4.5 parts to 11 parts of sodium nitrate, 6 parts to 15 parts of potassium nitrate, 0.08 part to 0.2 part of silicic acid and 0.05 part to 0.12 part of aluminum oxide.
In the method, the glass substrate is provided with an ion exchange stress layer, and lithium ions in the ion exchange stress layer can be dissociated into the furnace body 10 and perform ion exchange with potassium ions and sodium ions in the furnace body 10, so that the surface of the glass substrate generates compressive stress, and the strength of the glass substrate is improved.
When the concentration of the first metal ions reaches a predetermined threshold value, that is, according to actual production, for example, when the content of lithium ions in the nitrate in a molten state reaches 500mg/L, the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the furnace body 10, that is, the lithium ions are saturated.
And if the metal ion exchange is just finished when the chemical strengthening additive is added, taking out the base material, and combining phosphate radical and disodium phosphate in the main agent with free lithium ions to generate lithium phosphate precipitate and disodium phosphate precipitate. In addition, sodium nitrate and potassium nitrate in the main agent can supplement potassium ions and sodium ions consumed in the original metal ion exchange tank, so that the normal operation of ion exchange is ensured. Then, the other substrate is immersed in an ion exchange tank for chemical strengthening.
If the metal ion exchange is not finished when the chemical strengthening additive is added, the base material is not taken out, so that phosphate radical and disodium phosphate in the main agent are combined with free lithium ions to generate lithium phosphate precipitate and disodium phosphate lithium precipitate.
In addition, sodium nitrate and potassium nitrate in the main agent can supplement potassium ions and sodium ions consumed in the original metal ion exchange tank, so that the normal operation of ion exchange is ensured. And taking out the base material after the ion exchange is finished.
The additive is an acidic compound and is used for adjusting the pH value of the metal ion exchange tank. In particular, the additives in the present process are silicic acid and alumina.
Wherein, adding the main agent into the metal ion exchange tank, so that in the process of exchanging metal ions, phosphate ions in the metal ion exchange tank can be hydrolyzed, so that the content of hydroxide in the metal ion exchange tank can be increased, and when the content of hydroxide in the metal ion exchange tank reaches a certain value, the hydroxide in the metal ion exchange tank can corrode and destroy the surface layer of the substrate. The method also adds an additive consisting of silicic acid and aluminum oxide, and the silicic acid and the aluminum oxide can be combined by hydroxyl in the metal ion exchange tank, so that the content of the hydroxyl in the metal ion exchange tank is reduced, the surface layer of the base material can be effectively prevented from being corroded, and the surface stress of the strengthened base material is enhanced to a certain extent.
In at least one embodiment, the phosphate and disodium phosphate in the host can be combined with free lithium ions to form lithium phosphate precipitate using a filtration device and the disodium lithium phosphate precipitate can be filtered from the metal ion exchange cell.
In this embodiment, when the chemical strengthening additive is added to the metal ion exchange tank and no more precipitate is generated in the metal ion exchange tank, the precipitate can be filtered out from the metal ion exchange tank by the filtering device.
It is understood that the chemical strengthening additive may also be stored in the filter unit, and the phosphate radical and disodium phosphate in the main agent are combined with free lithium ion to produce lithium phosphate precipitate and the lithium disodium phosphate precipitate may be collected directly in the filter unit.
Specifically, please refer to fig. 2 and fig. 3 together. The filtering apparatus 200 includes a plurality of screens 210, and the screens 210 are used for depositing one of lithium phosphate, lithium carbonate, lithium sulfate and lithium fluoride.
The filter 210 includes a first filter 211, a second filter 212, and a third filter 213, the second filter 212 is disposed between the first filter 211 and the third filter 213, and the first filter 211 is disposed at an inner side of the second filter 212. Specifically, the first filter screen is a 50-mesh filter screen, the second filter screen is a 100-mesh filter screen, and the third filter screen is a 200-mesh filter screen. A plurality of filtering nets are used to prevent the precipitation from entering the furnace body 10 from the filtering apparatus 200 and depositing on the bottom of the furnace body 10.
In this embodiment, the screen 210 is made of high temperature resistant SUS316 stainless steel.
In this embodiment, the filtering apparatus 200 further includes two latches 220, and the two latches 220 are disposed on the top of the filter screen 210 and located on two opposite sides of the filter screen 210, and are used for clamping the filtering apparatus 200 in the furnace body 10 of the strengthening device 100.
In this embodiment, before the filtering device 200 is placed in the furnace body 10, the filtering device 200 is placed in a basket 300 (as shown in fig. 2), and then the basket 300 and the filtering device 200 are placed in the furnace body 10 together.
The temperature of the nitrate in the molten state is 400-550 ℃, and the reaction time is 2-4 h. Chemical reactions occur during ion exchange: PO (PO)4 -3+3Li+→Li3PO4(ii) a That is, the chemical-enhancing additive ionizes phosphate ions in molten nitrate, which react with lithium ions within the enhancing apparatus 100 to form lithium phosphate precipitates.
After the ion exchange is completed, the filter device 200 and the basket 300 are taken out of the reinforcing apparatus 100. Because the precipitates generated by the reaction are all deposited in the filtering device 200, the precipitates are not deposited at the bottom of the furnace body 10 while lithium ions are removed and molten nitrate is purified on line, the effective loading quantity of glass substrates is increased, no impurity ions are introduced and no waste gas is generated, and the cost is economic. In addition, the purification frequency of the nitrate in the molten state is not limited, and the defects that the uniformity of a thermal field is poor and the purification frequency is limited due to the fact that the nitrate is deposited at the bottom of the furnace body 10 in the prior art are overcome.
The technical solution of the present invention is further illustrated by the following examples.
The chemical strengthening additive comprises, by weight, 6-14 parts of sodium phosphate, 4.5-11 parts of sodium nitrate, 6-15 parts of potassium nitrate, 0.08-0.2 part of silicic acid and 0.05-0.12 part of aluminum oxide.
Wherein the chemical strengthening additive comprises, by mass (g), 6g to 14g of sodium phosphate, 4.5g to 11g of sodium nitrate, 6g to 15g of potassium nitrate, 0.08g to 0.2g of silicic acid and 0.05g to 0.12g of aluminum oxide.
Example 1
Adding 87 percent of potassium nitrate and 13 percent of sodium nitrate into a furnace body 10 to form a metal ion exchange pool, and heating the potassium nitrate and the sodium nitrate to 475 ℃ to be molten; then the surface area was 1m2The glass substrate made of the lithium aluminosilicate material is put into a metal ion exchange pool; adding chemical strengthening additives into the metal ion exchange tank after 1 hour, wherein the chemical strengthening additives comprise 6g of sodium phosphate, 4.5g of sodium nitrate, 6g of potassium nitrate, 0.08g of silicic acid and 0.05g of aluminum oxide; after 1 hour, the glass substrate was removed and tested for surface stress.
When the glass substrate is placed in the metal ion exchange tank for 1 hour, lithium ions in the molten salt are saturated, and the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the metal ion exchange tank. Further, the surface area was 1m2Approximately 1 glass substrate.
Example 2
Adding 87 percent nitric acid into the furnace body 10Potassium and 13 percent sodium nitrate form a metal ion exchange pool, and potassium nitrate and sodium nitrate are heated to 475 ℃ and are molten; then the surface area was 1m2The glass substrate made of the lithium aluminosilicate material is put into a metal ion exchange pool; adding chemical strengthening additives into the metal ion exchange tank after 1 hour, wherein the chemical strengthening additives comprise 10g of sodium phosphate, 7.75g of sodium nitrate, 10.5g of potassium nitrate, 0.14g of silicic acid and 0.085g of aluminum oxide; after 1 hour, the glass substrate was removed and tested for surface stress.
When the glass substrate is placed in the metal ion exchange tank for 1 hour, lithium ions in the molten salt are saturated, and the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the metal ion exchange tank. Further, the surface area was 1m2Approximately 1 glass substrate.
Example 3
Adding 87 percent of potassium nitrate and 13 percent of sodium nitrate into a furnace body 10 to form a metal ion exchange pool, and heating the potassium nitrate and the sodium nitrate to 475 ℃ to be molten; then the surface area was 1m2The glass substrate made of the lithium aluminosilicate material is put into a metal ion exchange pool; adding chemical strengthening additives into the metal ion exchange tank after 1 hour, wherein the chemical strengthening additives comprise 14g of sodium phosphate, 11g of sodium nitrate, 15g of potassium nitrate, 0.2g of silicic acid and 0.12g of alumina; after 1 hour, the glass substrate was removed and tested for surface stress.
When the glass substrate is placed in the metal ion exchange tank for 1 hour, lithium ions in the molten salt are saturated, and the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the metal ion exchange tank. Further, the surface area was 1m2Approximately 1 glass substrate.
Example 4
Adding 87 percent of potassium nitrate and 13 percent of sodium nitrate into the furnace body 10 to form a metal ion exchange pool, and heating the potassium nitrate and the sodium nitrate to 475 percentMelting the mixture at a temperature of DEG C; then the surface area was 1m2The glass substrate made of the lithium aluminosilicate material is put into a metal ion exchange pool; after 1 hour, placing a chemical strengthening additive in the filtering device, placing the filtering device in a metal ion exchange tank, and taking out the filtering device after 30 minutes, wherein the chemical strengthening additive comprises 10g of sodium phosphate, 7.75g of sodium nitrate, 10.5g of potassium nitrate, 0.14g of silicic acid and 0.085g of alumina; the glass substrate was removed 30 minutes after the filter was removed and tested for surface stress.
When the glass substrate is placed in the metal ion exchange tank for 1 hour, lithium ions in the molten salt are saturated, and the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the metal ion exchange tank. Further, the surface area was 1m2Approximately 1 glass substrate.
Comparative example 1
Adding 87 percent of potassium nitrate and 13 percent of sodium nitrate into a furnace body 10 to form a metal ion exchange pool, and heating the potassium nitrate and the sodium nitrate to 475 ℃ to be molten; then the surface area was 1m2The glass substrate made of the lithium aluminosilicate material is put into a metal ion exchange pool; adding a chemical strengthening additive into the metal ion exchange tank after 1 hour, wherein the chemical strengthening additive comprises 10g of sodium phosphate; after 1 hour, the glass substrate was removed and tested for surface stress.
When the glass substrate is placed in the metal ion exchange tank for 1 hour, lithium ions in the molten salt are saturated, and the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the metal ion exchange tank. Further, the surface area was 1m2Approximately 1 glass substrate.
Comparative example 2
Adding 87 percent of potassium nitrate and 13 percent of sodium nitrate into a furnace body 10 to form a metal ion exchange pool, and heating the potassium nitrate and the sodium nitrate to 475 ℃ to be molten; then the surface area was 1m2Lithium (ii) ofPutting the aluminosilicate glass substrate into a metal ion exchange tank; adding chemical strengthening additives into the metal ion exchange tank after 1 hour, wherein the chemical strengthening additives comprise 10g of sodium phosphate, 7.75g of sodium nitrate and 10.5g of potassium nitrate; after 1 hour, the glass substrate was removed and tested for surface stress.
When the glass substrate is placed in the metal ion exchange tank for 1 hour, lithium ions in the molten salt are saturated, and the lithium ions in the glass substrate ion exchange stress layer cannot be ion-exchanged with potassium ions and sodium ions in the metal ion exchange tank. Further, the surface area was 1m2Approximately 1 glass substrate.
Please refer to the table one below, which is the surface stress value of the strengthened glass substrate of examples 1 to 4 after the stress test.
Figure BDA0002348721290000141
From the above table one can derive: the strengthened glass substrate obtained in example 1 had a surface stress average of 560 MPa; the surface stress average of the strengthened glass substrate obtained in example 2 was 626 MPa; the surface stress of the strengthened glass substrate obtained in example 3 was 581MPa on average. And the maximum and minimum values of the surface stress of the strengthened glass substrate obtained in example 2 were both greater than the maximum and minimum values of the surface stress of the strengthened glass substrates obtained in examples 1 and 3. Therefore, the embodiment 2 is the most preferable embodiment.
Next, from example 2 and example 4, it is possible to obtain: the surface stress average of the strengthened glass substrate obtained in example 4 was 635MPa, which was greater than the surface stress average of the strengthened glass substrate obtained in example 2, and the surface stress maximum and minimum values of the strengthened glass substrate obtained in example 4 were each greater than the surface stress maximum and minimum values of the strengthened glass substrate obtained in example 2.
The difference between example 2 and example 4 is that in example 4, a filter for removing the precipitate is added. In example 2, after the chemical strengthening additive is added to the metal ion exchange tank, phosphate radicals and disodium phosphate radicals in the chemical strengthening additive are combined with lithium ions in the metal ion exchange tank to generate lithium phosphate precipitates and disodium phosphate lithium precipitates, and the lithium phosphate precipitates and the disodium phosphate lithium precipitates are deposited at the bottom of the ion exchange tank, so that the uniformity of a thermal field of molten salt in the ion exchange tank is poor, the corresponding ion exchange speed is reduced, the ion exchange amount is reduced, and the surface stress of the strengthened glass substrate is affected. In example 4, the lithium phosphate precipitate and the disodium lithium phosphate precipitate can be removed in the metal ion exchange process by a filter device, the uniformity of the thermal field of the molten salt in the ion exchange tank is not affected, the corresponding ion exchange speed is not reduced, and the ion exchange amount is not reduced, so that the surface stress of the strengthened glass substrate is higher than that of the strengthened glass substrate in example 2.
Please refer to the following second table, which is the surface stress values of the strengthened glass substrates in example 2, comparative example 1 and comparative example 2 after the stress test.
Figure BDA0002348721290000151
From the above table two, we can obtain: the average surface stress values of the strengthened glass substrates obtained in example 2 and comparative example 2 were both greater than the average surface stress value of the strengthened glass substrate obtained in comparative example 1. And the maximum and minimum values of the surface stress of the strengthened glass substrates obtained in example 2 and comparative example 2 were both greater than the maximum and minimum values of the surface stress of the strengthened glass substrate obtained in comparative example 1.
Wherein the chemical-strengthening additive in example 2 and comparative example 2 has more components of sodium nitrate and potassium nitrate than the chemical-strengthening additive in comparative example 1. After the chemical strengthening additive is added into the metal ion exchange tank, the sodium nitrate and the potassium nitrate in the example 2 and the comparative example 2 can supplement sodium ions and lithium ions consumed in the original metal ion exchange tank, so that the normal operation of metal ion exchange is ensured; while the chemical additive in comparative example 1 only includes sodium phosphate, after the sodium ions and potassium ions in the ion exchange tank are completely consumed, the metal ion exchange process is finished, that is, part of lithium ions in the surface layer of the glass substrate can not be subjected to ion exchange, so that the surface stress value of the finally obtained strengthened glass substrate is small.
From the above table two, it can also be derived: the average value of the surface stress of the strengthened glass substrate obtained in example 2 is greater than the average value of the surface stress of the strengthened glass substrate obtained in comparative example 2, and the maximum value and the minimum value of the surface stress of the strengthened glass substrate obtained in example 2 are both greater than the maximum value and the minimum value of the surface stress of the strengthened glass substrate obtained in comparative example 2.
Wherein, the chemical strengthening additive in the embodiment 2 has more silicic acid and alumina than the chemical strengthening additive in the comparison 2, and after the chemical strengthening additive is added into the metal ion exchange tank, the alumina can adjust the pH value of the metal ion exchange tank; the silicic acid can adsorb impurity ions (such as calcium ions) in the metal ion exchange pool, and can adjust the pH value of the molten salt. The method can effectively prevent the metal ion exchange pool from reacting with silicate in the glass substrate due to overhigh alkalinity, thereby reducing the surface stress of the glass substrate.
The chemical strengthening additive provided by the invention can perform metal ion exchange with the first metal ions, generate precipitable precipitates and adjust the pH value of the metal ion exchange tank. The chemical strengthening method provided by the invention comprises the steps of immersing a base material in a metal ion exchange tank to enable first metal ions in the base material to be free; adding a chemical strengthening additive into the metal ion exchange tank to combine with the free first metal ions to generate precipitable precipitates; and the pH value of the ion exchange tank can be adjusted in the metal ion exchange process, so that certain erosion of the glass caused by overhigh alkalinity of the metal ion exchange tank is avoided.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned. Furthermore, it is obvious that the word "comprising" does not exclude other elements or steps, and the singular does not exclude the plural.
Finally, it should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A chemical strengthening additive is used for being added into a metal ion exchange pool of a substrate, the substrate generates free first metal ions in the metal ion exchange process, the chemical strengthening additive comprises a main agent and an additive, the main agent is a basic metal compound containing at least one second metal, and the additive is an acidic compound; the main agent is used for carrying out metal ion exchange with first metal ions and generating precipitable precipitates, and the additive is used for adjusting the pH value of the ion exchange tank.
2. The chemical strengthening additive of claim 1, wherein the first metal ion is lithium and the second metal is at least one of sodium and potassium.
3. The chemical strengthening additive of claim 1, wherein the primary agent is at least one of a metal phosphate compound, a metal carbonate compound, a metal sulfate compound, or a metal fluoride.
4. The chemical strengthening additive of claim 3, wherein the primary agent is at least one of sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium fluoride, and potassium fluoride.
5. The chemical strengthening additive of claim 3, wherein the additive is at least one of silicic acid or aluminum oxide.
6. A method of chemical strengthening using a chemical strengthening additive of any of claims 1-5, comprising the steps of:
providing one or more substrates;
immersing a substrate in a metal ion exchange cell to free first metal ions in the substrate;
adding a chemical enhancing additive to the metal ion exchange cell to produce a precipitable precipitate.
7. The method of claim 6, wherein the metal ion exchange cell comprises potassium nitrate and sodium nitrate, and the ratio of the volume percentages of the potassium nitrate and the sodium nitrate is (8-9): (1-2).
8. The method of claim 6, wherein the substrate is removed and a chemical strengthening additive is added when the first metal ion concentration reaches a predetermined threshold.
9. The method of claim 6, wherein the precipitate is filtered from the metal ion exchange cell using a filtration device.
10. The method of claim 9, wherein the chemical enhancing additive is stored in the filter device and the precipitate is collected in the filter device.
CN201911406264.6A 2019-12-31 2019-12-31 Chemical strengthening additive and method for chemical strengthening using the same Pending CN111116057A (en)

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