CN117510065A - Tempered borosilicate glass and preparation method and application thereof - Google Patents
Tempered borosilicate glass and preparation method and application thereof Download PDFInfo
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- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000005496 tempering Methods 0.000 claims abstract description 141
- 239000000126 substance Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 22
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000203 mixture Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000005341 toughened glass Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/04—Tempering or quenching glass products using gas
-
- 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
-
- 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
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- 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)
- Glass Compositions (AREA)
Abstract
The application relates to toughened borosilicate glass and a preparation method and application thereof. The preparation method comprises the following steps: performing physical tempering treatment on borosilicate glass with the thickness of 3-15 mm, and controlling the surface of the borosilicate glass to form a stress layer with the depth of more than or equal to 800 mu m, wherein the physical tempering treatment comprises a heating stage and a cooling tempering stage which are sequentially performed, the heating temperature of the heating stage is 700-780 ℃, and the wind pressure of the cooling tempering stage is 19000 Pa~23000 Pa; performing chemical tempering treatment on the borosilicate glass subjected to the physical tempering treatment to prepare tempered borosilicate glass; wherein, the borosilicate glass comprises the following components in percentage by mass: 50% -70% of SiO 2 5% -25% of Al 2 O 3 3% -13% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O、0MgO in an amount of 5%, caO in an amount of 9% to 20%, and Fe in an amount of 0.01% to 0.1% 2 O 3 。
Description
Technical Field
The application relates to the technical field of toughened glass, in particular to toughened borosilicate glass and a preparation method and application thereof.
Background
Borosilicate glass has lower expansion coefficient and higher light transmittance, so that the borosilicate glass can be widely applied to the fields of optical glass, precision instrument glass, lamp glass, daily glass and the like, but the strength of the borosilicate glass needs to be improved. The strength performance of borosilicate glass is improved by physical tempering or chemical tempering in the traditional technology, however, the tempered borosilicate glass prepared by the traditional tempering method still cannot meet the increasingly severe application requirements.
Therefore, how to prepare the toughened borosilicate glass with better strength performance becomes a technical problem to be solved urgently.
Disclosure of Invention
Based on the above, it is necessary to provide a tempered borosilicate glass, and a preparation method and application thereof, wherein the preparation method can obtain the tempered borosilicate glass with better strength performance.
In a first aspect of the present application, a method for preparing tempered borosilicate glass is provided, comprising the steps of:
performing physical tempering treatment on borosilicate glass with the thickness of 3-15 mm, and controlling the surface of the borosilicate glass to form a stress layer with the depth of more than or equal to 800 mu m, wherein the physical tempering treatment comprises a heating stage and a cooling tempering stage which are sequentially performed, the heating temperature of the heating stage is 700-780 ℃, and the wind pressure of the cooling tempering stage is 19000 Pa~23000 Pa;
performing chemical tempering treatment on the borosilicate glass subjected to the physical tempering treatment to prepare tempered borosilicate glass;
wherein, the borosilicate glass comprises the following components in percentage by mass: 50% -70% of SiO 2 5% -25% of Al 2 O 3 3% -13% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 0-5% MgO, 9-20% CaO and 0.01-0.1% Fe 2 O 3 。
According to the preparation method, the borosilicate glass is subjected to physical tempering treatment and chemical tempering treatment in sequence, so that a stress layer with larger depth and surface compressive stress can be formed, and the tempered borosilicate glass with better strength performance is obtained. Specifically, firstly, borosilicate glass with specific thickness and composition is subjected to physical tempering treatment by adopting specific heating temperature and air pressure, and in the process, all components in the glass are mutually matched in a synergistic way, so that a stress layer with the depth of more than or equal to 800 mu m is formed on the surface of the borosilicate glass, and a good foundation is provided for the subsequent chemical tempering treatment; and then carrying out chemical tempering treatment on the borosilicate glass subjected to the physical tempering treatment, so that the surface compressive stress of the stress layer can be improved. In addition, compared with borosilicate glass which is not subjected to physical tempering treatment, the surface stress layer formed after the physical tempering treatment has larger volume and looser structure, is favorable for ion exchange in the chemical tempering treatment process, can improve the effect of the chemical tempering treatment, and further improves the strength of the tempered borosilicate glass.
In some embodiments, the borosilicate glass comprises the following components in percentage by mass: 55% -65% of SiO 2 8% -14% of Al 2 O 3 5% -9% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 2% -4% MgO, 12% -18% CaO and 0.03% -0.08% Fe 2 O 3 。
In some of these embodiments, the wind pressure is 20000 Pa~22000 Pa.
In some embodiments, the heat preservation time of the heating stage is 290 s-600 s.
In some embodiments, the stress layer of the borosilicate glass after the physical tempering treatment is controlled to have a depth of 800-930 μm.
In some embodiments, the surface stress value of the borosilicate glass after the physical tempering treatment is controlled to be 100-200 MPa.
In some embodiments, the chemical tempering treatment satisfies at least one of the following (1) - (3):
(1) The chemically tempered salt comprises potassium nitrate;
(2) The temperature of the chemical tempering treatment is 390-450 ℃;
(3) The chemical tempering treatment time is 4-8 hours.
In a second aspect of the present application, there is provided a tempered borosilicate glass produced according to the production method of the first aspect.
In some embodiments, the tempered borosilicate glass satisfies at least one of the following (1) - (2):
(1) The surface stress value of the toughened borosilicate glass is 290-450 MPa;
(2) The depth of the surface stress layer of the toughened borosilicate glass is more than or equal to 800 mu m.
In a third aspect of the present application, there is provided the use of the toughened borosilicate glass of the second aspect in the manufacture of curtain wall glass, fire protection glass, heat resistant glassware, medicinal glass, automotive glass or display devices.
Detailed Description
In order to facilitate an understanding of the present application, a more complete description of the present application will follow. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the weight described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
In this application, reference is made to a value interval (i.e., a range of values), where a distribution of selectable values is considered continuous and includes two endpoints of the value interval and each value between the two endpoints unless otherwise indicated. Where multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges may be combined,
the toughened glass is glass which is subjected to toughening treatment and forms a stress layer on the surface of the glass. When the toughened glass is acted by external force, the stress layer can counteract the action of the external force, so that the bearing capacity of the glass is improved, and the mechanical strength, the thermal shock resistance and other performances of the glass are enhanced. At present, toughened glass has been applied to the fields of automobiles, buildings, aviation, electronics and the like. The tempering method of the glass comprises physical tempering and chemical tempering, wherein the physical tempering is to heat and quench the glass to ensure that the surface and the inside of the glass form volume difference, and then compressive stress and tensile stress are formed on the surface and the inside of the glass. Chemical tempering is to place glass in molten salt for ion exchange to change the composition of the glass surface layer and thus form a surface stress layer. However, it is difficult for the tempered glass obtained by conventional physical tempering and chemical tempering to satisfy increasingly severe application requirements. In addition, for borosilicate glass with a smaller thermal expansion coefficient, the traditional tempering method is difficult to effectively temper the borosilicate glass, so that tempered borosilicate glass with good strength performance is difficult to obtain. Based on the method, the brand new borosilicate glass tempering method is provided, and tempered borosilicate glass with good strength performance can be prepared.
An embodiment of the application provides a preparation method of tempered borosilicate glass, which comprises the following steps S12-S14.
And S12, performing physical tempering treatment on borosilicate glass with the thickness of 3-15 mm, controlling the surface of the borosilicate glass to form a stress layer with the depth of more than or equal to 800 mu m, wherein the physical tempering treatment comprises a heating stage and a cooling tempering stage which are sequentially performed, the heating temperature of the heating stage is 700-780 ℃, and the wind pressure of the cooling tempering stage is 19000 Pa~23000 Pa.
Wherein, the borosilicate glass comprises the following components in percentage by mass: 50% -70% of SiO 2 5% -25% of Al 2 O 3 3% -13% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 0-5% MgO, 9-20% CaO and 0.01-0.1% Fe 2 O 3 。
As can be appreciated, the physical tempering treatment is heating (corresponding to a heating stage) and quenching (corresponding to a cooling tempering stage) of the glass such that the glass is softened first, and upon quenching, the glass surface rapidly changes from a liquefied state to a solidified state. During quenching, the glass surface is broken by chemical bonds and then reconnected, and the glass has been transformed into a solidified state, and the volume of the glass after cooling is larger than the volume before heating. The inner part of the glass is cooled by the heat conduction of molecular movement with the outer layer glass, and the cooling speed of the glass is slower more inwards, so that the broken chemical bonds in the glass can be reconnected in the cooling process, and the volume of the cooled glass is basically the same as that before heating. Thus, the volume of the glass surface is greater than the volume of the interior, the glass surface generates compressive stress to the interior, and the interior generates tensile stress to the surface. In the embodiment, the tempering treatment is carried out by adopting the heating temperature of 700-780 ℃ and the wind pressure of 19000 Pa~23000 Pa, and the tempering treatment is adapted to the thickness of borosilicate glass, so that a stress layer with the depth of more than or equal to 800 mu m is formed on the surface of the borosilicate glass. In addition, the tempering effect of physical tempering treatment can be further improved by adjusting and controlling the composition of borosilicate glass.
The stress layer depth is the depth of the boundary between the compressive stress layer and the internal tensile stress layer of the glass surface, and is generally expressed by DOL.
Alternatively, the thickness of the borosilicate glass may be 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm 12 mm, 13 mm, 14 mm or 15 mm, and the thickness of the borosilicate glass may be other suitable selected within the range of 3 mm to 15 mm.
Alternatively, the heating temperature in the heating stage may be 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃ or 780 ℃, and the heating temperature may be selected from the range of 700 ℃ to 780 ℃ as appropriate.
Alternatively, the wind pressure may be 19000 Pa, 19500 Pa, 20000 Pa, 20500 Pa, 21000 Pa, 21500 Pa, 22000 Pa, 22500 Pa or 23000 Pa, and the wind pressure may be selected within the range of 19000 Pa~23000 Pa.
Optionally, siO is calculated according to the mass percentage of borosilicate glass 2 The mass percentage of the catalyst may be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70%, siO 2 The mass percentage of the (C) can be selected in a range of 50% -70% by mass.
Optionally, al is calculated according to the mass percentage of borosilicate glass 2 O 3 The mass percentage of the aluminum alloy can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, al 2 O 3 The mass percentage of the (C) can be selected in a range of 5% -25% by mass.
Optionally, B is calculated according to the mass percentage of borosilicate glass 2 O 3 Can be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12% or 13% by mass, B 2 O 3 The mass percentage of the (C) can be selected in a range of 3% -13% as well.
Optionally, na is calculated according to the mass percentage of borosilicate glass 2 O mass percentThe amount can be 1%, 2%, 3% or 4%, na 2 The mass percentage of O can be selected in the range of 1% -4% as well.
Optionally, K is calculated according to the mass percentage of borosilicate glass 2 The mass percentage of O can be 0, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09% or 0.1%, K 2 The mass percentage of O can be selected in the range of 0-0.1% as well.
Optionally, the mass percentage of MgO may be 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% according to the mass percentage of borosilicate glass, and the mass percentage of MgO may be selected within the range of 0 to 5%.
Optionally, the mass percentage of CaO may be 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% according to the mass percentage of borosilicate glass, and the mass percentage of CaO may be further selected within the range of 9% -20%.
Optionally, in terms of mass percent of borosilicate glass, fe 2 O 3 Can be 0.01%, 0.02%, 0.04%, 0.06%, 0.08% or 0.1% by mass of Fe 2 O 3 The mass percentage of the (C) can be selected in the range of 0.01% -0.1% as well.
In some of these embodiments, the borosilicate glass consists of, in mass percent: 50% -70% of SiO 2 5% -25% of Al 2 O 3 3% -13% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 0-5% MgO, 9-20% CaO and 0.01-0.1% Fe 2 O 3 。
In some of these embodiments, the borosilicate glass comprises the following components in mass percent: 55% -65% of SiO 2 8% -14% of Al 2 O 3 5% -9% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 2% -4% MgO, 12% -18% CaO and 0.03% -0.08% Fe 2 O 3 . When the borosilicate glass comprises the components in percentage by massThe effect of physical tempering treatment can be further improved, and the ion exchange in the subsequent chemical tempering treatment process is facilitated, so that the strength performance of the obtained tempered borosilicate glass is better.
In some of these embodiments, the cooled wind pressure of the physical tempering process is 20000 Pa~22000 Pa.
In some embodiments, the heat preservation time of the heating stage is 290 s-600 s.
In some embodiments, the stress layer depth of the borosilicate glass after the physical tempering treatment is controlled to be 800-930 μm. When the depth of the stress layer after the physical tempering treatment is controlled within the range, the strengthening effect can be further improved, and the ion exchange of the subsequent chemical tempering treatment is facilitated.
In some embodiments, the surface stress value of the borosilicate glass after the physical tempering treatment is controlled to be 100-200 MPa. When the surface stress value of the borosilicate glass after the physical tempering treatment is controlled within the range, the strengthening effect can be further improved, so that the strength performance and the mechanical property of the obtained tempered borosilicate glass are improved.
And S14, performing chemical tempering treatment on the borosilicate glass subjected to the physical tempering treatment to prepare tempered borosilicate glass.
As can be appreciated, chemical tempering is the dipping of glass into molten tempering salt, the ion exchange of glass with molten salt occurs, and some of the alkali ions on the glass surface diffuse into the molten salt, thereby forming vacancies that are occupied by alkali ions in the molten salt, such that the chemical composition of the glass surface layer changes, lowering the coefficient of thermal expansion of the glass surface, and forming a surface stress layer. In this embodiment, a stress layer with a larger depth is formed on the surface of borosilicate glass after physical tempering treatment, but the stress layer has a smaller surface stress value (CS) and a smaller resistance to external force, so that chemical tempering treatment is adopted to improve the surface stress value, and the prepared tempered borosilicate glass has higher mechanical strength. Compared with the glass which is not subjected to physical tempering treatment, the glass after physical tempering has relatively large surface volume and relatively loose structure, so that the mutual diffusion of alkali metal and molten salt in the glass is more facilitated, and a stress layer with high surface stress value and large depth is formed. In the traditional chemical tempering method, ion exchange can only be carried out to a position with a shallower surface of the glass, and the depth of the formed surface stress layer is mostly 10-200 mu m.
In some of these embodiments, the chemically tempered tempering salt comprises potassium nitrate.
In some embodiments, the chemical tempering treatment is performed at a temperature of 390 ℃ to 450 ℃. Alternatively, the temperature of the chemical tempering treatment may be 390 ℃, 395 ℃, 400 ℃, 405 ℃, 410 ℃, 415 ℃, 420 ℃, 425 ℃, 430 ℃, 435 ℃, 440 ℃, 445 ℃ or 450 ℃, and the temperature of the chemical tempering treatment may be other suitable choices in the range of 390 ℃ to 450 ℃.
In some embodiments, the chemical tempering treatment is performed for 4-8 hours. Optionally, the chemical tempering treatment time may be 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h or 8 h, and the chemical tempering treatment time may be selected from the range of 4 h to 8 h.
In a specific embodiment, the chemically tempered salt comprises potassium nitrate, the temperature of the chemical tempering treatment is 390-450 ℃, and the time of the chemical tempering treatment is 4-8 hours.
According to the preparation method, the borosilicate glass is subjected to physical tempering treatment and chemical tempering treatment in sequence, so that a stress layer with larger depth and surface compressive stress can be formed, and the tempered borosilicate glass with better strength performance is obtained. Specifically, firstly, borosilicate glass with specific thickness and composition is subjected to physical tempering treatment by adopting specific heating temperature and air pressure, and in the process, all components in the glass are mutually matched in a synergistic way, so that a stress layer with the depth of more than or equal to 800 mu m is formed on the surface of the borosilicate glass, and a good foundation is provided for the subsequent chemical tempering treatment; and then carrying out chemical tempering treatment on the borosilicate glass subjected to the physical tempering treatment, so that the surface compressive stress of the stress layer can be improved. In addition, compared with borosilicate glass which is not subjected to physical tempering treatment, the surface stress layer formed after the physical tempering treatment has larger volume and looser structure, is favorable for ion exchange in the chemical tempering treatment process, can improve the effect of the chemical tempering treatment, and further improves the strength of the tempered borosilicate glass.
The application also provides the toughened borosilicate glass prepared by the preparation method.
The toughened borosilicate glass has the advantages of higher strength, lower expansion coefficient, higher light transmittance, better chemical stability and high temperature resistance.
In some embodiments, the surface stress value of the tempered borosilicate glass is 290-450 MPa.
In some of these embodiments, the depth of the surface stress layer of the tempered borosilicate glass is greater than or equal to 800 μm.
In a specific embodiment, the surface stress value of the toughened borosilicate glass is 290-450 MPa, and the depth of the surface stress layer is more than or equal to 800 mu m.
In addition, the application also provides application of the toughened borosilicate glass in preparation of curtain wall glass, fireproof glass, heat-resistant glassware, medicinal glass, automobile glass or display devices.
Unless otherwise specified, the raw materials used in each of the following experiments are commercially available.
The performance test method is as follows:
test method of stress depth of layer (DOL): DOL of glass after physical tempering treatment by adopting surface stress instrument SLP-2000 1 DOL of glass subjected to chemical tempering treatment by adopting surface stress instrument FSM6000UV test 2 。
Test method of surface Compressive Stress (CS): CS of glass after physical tempering treatment by adopting surface stress instrument SLP-2000 1 CS of surface stress instrument FSM6000UV test glass after chemical tempering treatment 2 。
The following are specific examples.
Example 1
Dust impurities adhered to the surface of borosilicate glass having a composition shown in table 1 and a thickness of 15. 15 mm were washed and dried.
Physical temperingAnd (3) treatment: placing the dried borosilicate glass in a heating section of a tempering furnace, heating to 750 ℃, and keeping the temperature for 400 s; and then sending the heated glass into a cooling tempering section, and blowing the two sides of the glass by using high-pressure cold air to cool the glass to room temperature rapidly and uniformly, wherein the air pressure is 21000 and Pa, so that the borosilicate glass after the physical tempering treatment is obtained. The method in the specification is adopted to test the performance parameters of borosilicate glass after physical tempering treatment, and DOL is measured 1 802 μm, CS 1 Is 101 MPa.
Chemical tempering treatment: the borosilicate glass after the physical tempering treatment is placed in a potassium nitrate solution, and ion exchange is carried out at 420 ℃ for 5 h.
And cleaning the borosilicate glass subjected to chemical tempering treatment to obtain tempered borosilicate glass. The performance parameters of borosilicate glass after chemical tempering treatment are tested by adopting the method in the specification, and DOL is measured 2 At 7.4 μm, CS 2 Is 338 MPa.
Examples 2 to 10
The preparation methods of examples 2 to 10 are basically the same as those of example 1, except that: the composition and thickness of borosilicate glass are shown in Table 1.
Examples 11 to 16
The preparation methods of examples 11 to 16 are basically the same as that of example 9, except that: the physical tempering treatment conditions are specifically shown in table 1.
Examples 17 to 20
The preparation methods of examples 17 to 20 are basically the same as those of example 9, except that: the chemical tempering treatment conditions are specifically shown in table 1.
Comparative example 1
The preparation method of comparative example 1 was substantially the same as that of example 9, except that: only physical tempering treatment is carried out, and chemical tempering treatment is not carried out.
Comparative example 2
The preparation method of comparative example 2 was substantially the same as that of example 9, except that: only chemical tempering treatment is carried out, physical tempering treatment is not carried out, and the specific chemical tempering treatment steps are as follows: the dried borosilicate glass was placed in a potassium nitrate solution and ion exchanged at 390 ℃ for 5 h.
Comparative example 3
The preparation method of comparative example 3 was substantially the same as that of example 9, except that: the method comprises the following steps of performing physical tempering treatment, namely performing chemical tempering treatment firstly, and performing specific tempering treatment:
chemical tempering treatment: the dried borosilicate glass was placed in a potassium nitrate solution and ion-exchanged at 420 ℃ for 5 h.
Physical tempering treatment: placing the borosilicate glass subjected to chemical tempering treatment in a heating section of a tempering furnace, and heating to 750 ℃ for 400 s; and then the heated glass is sent to a cooling tempering section, and both sides of the glass are purged by high-pressure cold air, so that the glass is rapidly and uniformly cooled to room temperature, and the wind pressure is 21000 and Pa.
And cleaning the borosilicate glass subjected to the physical tempering treatment to obtain tempered borosilicate glass.
Comparative example 4
The preparation method of comparative example 4 was substantially the same as that of example 9, except that: the composition of borosilicate glass is shown in Table 1. Comparative example 4 during the preparation, the glass melt formed by softening the borosilicate glass during the physical tempering treatment was stuck to the rolls, resulting in a stoppage, and tempered borosilicate glass could not be obtained.
Comparative example 5
The preparation method of comparative example 5 was substantially the same as that of example 9, except that: the thickness of borosilicate glass is shown in Table 1. In the preparation process of comparative example 5, borosilicate glass was thin, light in weight, and relatively large in wind pressure, and borosilicate glass was blown away, and was not completely discharged, and tempered borosilicate glass was not obtained.
Comparative example 6
The preparation method of comparative example 6 was substantially the same as that of example 9, except that: the wind pressure of the physical tempering treatment is shown in table 1. In the preparation process of comparative example 6, borosilicate glass is not burned out due to low wind pressure, so that stress of the borosilicate glass is uneven, the glass is cracked when being discharged, and tempered borosilicate glass cannot be obtained.
Comparative example 7
The preparation method of comparative example 7 was substantially the same as that of example 9, except that: the heating temperature of the physical tempering treatment is specifically shown in table 1. In the preparation process of comparative example 7, the borosilicate glass was not burned out due to the low temperature, so that the stress of the borosilicate glass was not uniform, the glass was cracked when being discharged, and the tempered borosilicate glass could not be obtained.
Tables 1 to 4 show the compositions and thicknesses of borosilicate glasses of examples 1 to 20 and comparative examples 1 to 7, conditions of physical tempering treatment and chemical tempering treatment, and corresponding glass performance parameters after the physical tempering treatment and the chemical tempering treatment.
In tables 1 to 4, CS of the tempered borosilicate glass is CS 1 And CS (common services) 2 DOL is DOL 1 And DOL 2 Wherein the maximum value of (3) is obtained by performing chemical tempering treatment and then physical tempering treatment, and heating temperature is increased to near softening point of borosilicate glass during physical tempering process, so that stress relaxation and surface stress of glass are reduced, i.e. stress layer is destroyed after chemical tempering treatment, CS 2 Is difficult to maintain, so the CS of the tempered borosilicate glass of comparative example 3 is physically tempered CS 1 To be accurate.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from the test results in tables 1 to 4, the toughened borosilicate glass prepared in examples 1 to 20 has higher CS value and DOL value, which indicates that the strength performance is better. Whereas comparative example 1 was subjected to only physical tempering treatment, its CS value was low; comparative example 2 was subjected to only chemical tempering treatment, and had a low DOL value; comparative example 3 advanced chemical tempering treatment to form CS 2 The stress layer with higher value is destroyed in the subsequent physical tempering treatment process, and the CS value of the obtained tempered borosilicate glass is lower; the borosilicate glass composition of comparative example 4 did not meet the requirements of the present application, and the softening temperature thereof was low, and the glass melt formed by softening could adhere to the rolls of the tempering apparatus, resulting in shutdown; the borosilicate glass of comparative example 5 did not meet the requirements of the present application, and tapping could not be completed in the physical tempering treatment; the lower wind pressure of comparative example 6 and the lower heating temperature of comparative example 7 do not meet the requirements of the present application, and the resulting glass is cracked. In summary, tempered borosilicate glass with higher strength performance could not be obtained in comparative examples 1 to 7.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (10)
1. The preparation method of the toughened borosilicate glass is characterized by comprising the following steps of:
performing physical tempering treatment on borosilicate glass with the thickness of 3-15 mm, and controlling the surface of the borosilicate glass to form a stress layer with the depth of more than or equal to 800 mu m, wherein the physical tempering treatment comprises a heating stage and a cooling tempering stage which are sequentially performed, the heating temperature of the heating stage is 700-780 ℃, and the wind pressure of the cooling tempering stage is 19000 Pa~23000 Pa;
performing chemical tempering treatment on the borosilicate glass subjected to the physical tempering treatment to prepare tempered borosilicate glass;
wherein, the borosilicate glass comprises the following components in percentage by mass: 50% -70% of SiO 2 5% -25% of Al 2 O 3 3% -13% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 0-5% MgO, 9-20% CaO and 0.01-0.1% Fe 2 O 3 。
2. The method for preparing tempered borosilicate glass according to claim 1, wherein said borosilicate glass comprises the following components in percentage by mass: 55% -65% of SiO 2 8% -14% of Al 2 O 3 5% -9% of B 2 O 3 1% -4% of Na 2 O, 0-0.1% K 2 O, 2% -4% MgO, 12% -18% CaO and 0.03% -0.08% Fe 2 O 3 。
3. The method for producing a tempered borosilicate glass as claimed in claim 1, wherein said wind pressure is 20000 Pa~22000 Pa.
4. The method for preparing tempered borosilicate glass as claimed in claim 1, wherein the heat preservation time in the heating stage is 290 s-600 s.
5. The method for producing a tempered borosilicate glass as claimed in any one of claims 1 to 4, wherein the depth of the stress layer of the borosilicate glass after the physical tempering treatment is controlled to be 800 μm to 930 μm.
6. The method for producing a tempered borosilicate glass according to any one of claims 1 to 4, wherein the surface stress value of the borosilicate glass after the physical tempering treatment is controlled to be 100 MPa to 200 MPa.
7. The method for producing a tempered borosilicate glass as defined in any one of claims 1 to 4, wherein said chemical tempering treatment satisfies at least one of the following (1) to (3):
(1) The chemically tempered salt comprises potassium nitrate;
(2) The temperature of the chemical tempering treatment is 390-450 ℃;
(3) The chemical tempering treatment time is 4-8 hours.
8. Tempered borosilicate glass, characterized in that it is produced according to the production method of any one of claims 1 to 7.
9. The toughened borosilicate glass of claim 8, wherein said toughened borosilicate glass meets at least one of the following (1) - (2):
(1) The surface stress value of the toughened borosilicate glass is 290-450 MPa;
(2) The depth of the surface stress layer of the toughened borosilicate glass is more than or equal to 800 mu m.
10. Use of the tempered borosilicate glass of claim 8 or 9 for the preparation of curtain wall glass, fire glass, heat resistant glassware, medicinal glass, automotive glass or display devices.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200716499A (en) * | 2005-10-31 | 2007-05-01 | mao-sheng Wu | The manufacturing method of fire-proof glass |
| TW201204655A (en) * | 2010-06-30 | 2012-02-01 | Asahi Glass Co Ltd | Method for heightening strength of glass substrate for front plate of display device |
| CN104261675A (en) * | 2005-08-15 | 2015-01-07 | 安瀚视特股份有限公司 | Glass Composition And Process For Producing Glass Composition |
| JP2019001662A (en) * | 2015-11-10 | 2019-01-10 | Ａｇｃ株式会社 | Glass for wind cooling strengthening, and wind cooled strengthen glass |
| CN113480195A (en) * | 2021-06-29 | 2021-10-08 | 江苏铁锚玻璃股份有限公司 | Preparation method of antibacterial glass |
-
2023
- 2023-10-30 CN CN202311420401.8A patent/CN117510065A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261675A (en) * | 2005-08-15 | 2015-01-07 | 安瀚视特股份有限公司 | Glass Composition And Process For Producing Glass Composition |
| TW200716499A (en) * | 2005-10-31 | 2007-05-01 | mao-sheng Wu | The manufacturing method of fire-proof glass |
| TW201204655A (en) * | 2010-06-30 | 2012-02-01 | Asahi Glass Co Ltd | Method for heightening strength of glass substrate for front plate of display device |
| JP2019001662A (en) * | 2015-11-10 | 2019-01-10 | Ａｇｃ株式会社 | Glass for wind cooling strengthening, and wind cooled strengthen glass |
| CN113480195A (en) * | 2021-06-29 | 2021-10-08 | 江苏铁锚玻璃股份有限公司 | Preparation method of antibacterial glass |
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