CN114890679A - Tempered glass, phase-splitting glass, and preparation method and application thereof - Google Patents
Tempered glass, phase-splitting glass, and preparation method and application thereof Download PDFInfo
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- CN114890679A CN114890679A CN202210623192.6A CN202210623192A CN114890679A CN 114890679 A CN114890679 A CN 114890679A CN 202210623192 A CN202210623192 A CN 202210623192A CN 114890679 A CN114890679 A CN 114890679A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/04—Particles; Flakes
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- 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
Abstract
The invention relates to tempered glass, split-phase glass, and a preparation method and application thereof. The phase-separated glass comprises the following components in percentage by mole: SiO 2 2 60％～67％、Al 2 O 3 6％～16％、Li 2 O 5％～12％、Na 2 O5％～12％、K 2 O 0～2％、MgO 1％～3％、CaO 0～3％、ZrO 2 0.5％～3％、B 2 O 3 0-2% and 0-2% ZnO; li 2 O and Na 2 The mass ratio of O is (0.9-1.1): 1, and Li 2 O and Na 2 Sum of mass of O and Al 2 O 3 The mass ratio of (A) to (B) is 1.45-1.75. By reasonable proportioning of the components, the split-phase glass has better mechanical property and processing property, and the softening point of the split-phase glass is lower than that of microcrystalline glass, so that the split-phase glass is suitable for 3D hot bending.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to tempered glass, split-phase glass, and a preparation method and application thereof.
Background
As mobile electronic devices such as notebook computers, portable navigators, smart phones, etc. are being developed to be lighter and more powerful, higher demands are being made on the packaging or housing materials of the electronic devices, i.e., the packaging or housing materials are made to be lighter and thinner, and the packaging or housing materials are made to be harder and stronger. Currently, ion-exchange strengthened soda-aluminosilicate glasses are commonly used as encapsulation or housing materials.
Compared with common glass, the microcrystalline glass comprises a crystalline phase and a glass phase, and the crystalline phase provides better mechanical strength for the microcrystalline glass. Compared with the ion exchange reinforced sodium aluminosilicate glass, the ion exchange reinforced microcrystalline glass has more excellent comprehensive mechanical properties. However, the production process of the glass ceramics usually comprises two steps of nucleation and crystallization, and the production energy consumption and the production cost are high. And because the microcrystalline glass contains a large amount of crystals, the microcrystalline glass is extremely difficult to grind and polish in the deep processing process. In addition, ion exchange of the glass ceramics requires higher temperature and longer time due to the presence of a large amount of crystals. These greatly reduce the production and processing efficiency of the chemically strengthened glass ceramics.
Meanwhile, when the cover glass is subjected to 3D molding, the glass product needs to be heated and thermally bent by the graphite mold, but too high temperature may cause accelerated oxidation of the graphite mold, affect the service life thereof, and increase the production cost. Then, the softening temperature of the crystallized glass is generally greatly increased after the crystallization of the glass ceramics is finished, so that the glass ceramics is not suitable for hot bending 3D forming. The high-alumina glass is also a commonly used cover plate glass material in the market, the higher the alumina content is, the higher the strength of the glass is, however, the too high alumina content also greatly raises the softening point temperature of the glass, and the process performance of 3D forming of the glass is influenced.
Disclosure of Invention
Therefore, the split-phase glass which has better mechanical properties and lower softening point temperature and is easy to carry out 3D hot bending forming, and the preparation method and the application thereof are needed to be provided.
In addition, a strengthened glass prepared from the phase-separated glass is also provided.
In one aspect of the invention, a phase separation glass is provided, which comprises the following components in percentage by mole:
wherein, the Li 2 O and the Na 2 The molar ratio of O is (0.9-1.1): 1, and the Li 2 O and said Na 2 Sum of molar amount of O and the Al 2 O 3 The ratio of the molar amounts of (a) to (b) is 1.45 to 1.75.
In some of these embodiments, the phase-separated glass includes a glass matrix phase and a silicon-rich aluminum phase dispersed in the glass matrix; the silica-alumina rich phase is dispersed in the glass matrix phase in the form of spherical particles.
In some of these embodiments, the spherical particles have an average particle size of 100nm or less.
In some of these embodiments, the silica-alumina rich phase is present in the phase-separated glass in an amount of 10% to 90% by volume.
In some of these embodiments, the SiO 2 The mole percentage of the (B) is 62 to 66 percent; and/or the presence of a catalyst in the reaction mixture,
the Al is 2 O 3 The mole percentage of the component (A) is 10 to 14 percent; and/or the like, and/or,
the Li 2 The mol percentage of O is 7 to 12 percent; and/or the presence of a catalyst in the reaction mixture,
the Na is 2 The mol percentage of O is 7 to 12 percent.
In some embodiments, the average transmittance of the phase-separated glass in the spectral range of 360nm to 700nm is more than or equal to 88 percent; and/or the presence of a catalyst in the reaction mixture,
the softening point of the phase-separated glass is lower than 820 ℃; and/or the presence of a catalyst in the reaction mixture,
the Vickers hardness of the surface of the phase-separated glass is more than or equal to 650kgf/mm 2 。
In a second aspect, the invention also provides a preparation method of the phase separation glass, which comprises the following steps:
melting and molding the preparation raw materials to prepare precursor glass; the raw materials comprise the following components in percentage by mole: 60 to 67 percent of SiO 2 6 to 16 percent of Al 2 O 3 5 to 12 percent of Li 2 O, 5-12% of Na 2 O, 0 to 2% of K 2 O, 1 to 3 percent of MgO, 0 to 3 percent of CaO, and 0.5 to 3 percent of ZrO 2 0 to 2% of B 2 O 3 And 0-2% ZnO; the Li 2 O and the Na 2 The molar ratio of O is (0.9-1.1): 1, and the Li 2 O and said Na 2 Sum of molar amount of O and the Al 2 O 3 The ratio of the molar amount of (a) is 1.45-1.75;
and carrying out heat treatment on the precursor glass to prepare the phase-separated glass.
In some of these embodiments, the heat treating comprises:
cooling the precursor glass from the melting temperature to the annealing temperature at a rate of 0.5 ℃/min to 20 ℃/min; alternatively, the first and second electrodes may be,
holding the precursor glass at a temperature of 30 to 500 ℃ higher than the glass transition point; alternatively, the first and second electrodes may be,
annealing the precursor glass, then maintaining the temperature at a temperature of 30 to 500 ℃ higher than the glass transition point, and annealing again.
In a third aspect, the invention also provides application of the phase separation glass or the phase separation glass prepared by the phase separation glass preparation method in preparation of protective glass, photoelectric glass, fire-proof glass or architectural glass.
In a fourth aspect, the invention also provides a strengthened glass prepared from the phase-separated glass or the phase-separated glass prepared according to the phase-separated glass preparation method.
In a fifth aspect, the present invention also provides a method for preparing the above strengthened glass, comprising the following steps:
first strengthening treatment: subjecting the phase-separated glass to a first strengthening treatment in a first molten salt; the first molten salt comprises 50-60% of sodium nitrate and 40-50% of potassium nitrate by mass percent;
and (3) second strengthening treatment: subjecting the phase-separated glass subjected to the first strengthening treatment to a second strengthening treatment in a second molten salt; the second molten salt comprises 0-5% of sodium nitrate and 95-100% of potassium nitrate in percentage by mass.
The phase-separated glass comprises SiO with specific content proportion 2 、Al 2 O 3 、Li 2 O、Na 2 O、B 2 O 3 And ZnO. The split-phase glass has split phases, crystallization is replaced by the split phases, so that the split-phase glass has better mechanical properties, the crystallization is prevented from influencing the processing performance of the glass, and the formed split phases enable the softening point temperature of the split-phase glass to be obviously lower than that of microcrystalline glass, so that the split-phase glass is suitable for 3D hot bending forming.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the phase-separated glass obtained in example 1, under the heat treatment conditions: glass transition temperature (Tg) +30 ℃ for 2 h;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the phase-separated glass obtained in example 2, with the heat treatment conditions being: glass transition temperature (Tg) +30 ℃ for 2 h;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the phase-separated glass obtained in example 3, with the heat treatment conditions being: glass transition temperature (Tg) +30 ℃ for 2 h;
FIG. 4 is an X-ray diffraction pattern (XRD) of the phase-separated glass after the heat treatment phase separation in examples 1 to 3.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth 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 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 invention provides phase separation glass, which comprises the following components in percentage by mole:
wherein Li 2 O and Na 2 The molar ratio of O is (0.9-1.1): 1, and Li 2 O and Na 2 Sum of molar amount of O and Al 2 O 3 The ratio of the molar amounts of (a) to (b) is 1.45 to 1.75.
The phase-separated glass comprises SiO with specific content proportion 2 、Al 2 O 3 、Li 2 O、Na 2 O、B 2 O 3 And ZnO, and the phase separation glass contains phase separation. The differential thermal analysis (DSC) research shows that the phase-separated glass has no exothermic crystallization peak on the differential thermal curve, which indicates that the phase-separated glass is extremely difficult to crystallize. Phase separation is used for replacing crystallization, so that the phase separation glass has better mechanical property, the softening point of the phase separation glass is obviously lower than that of microcrystalline glass, and the phase separation glass is suitable for 3D hot bending forming.
SiO 2 Is an oxide that is involved in glass shaping, is a main glass-forming oxide for the base glass, and is useful for stabilizing the network structure of the glass. SiO when the precursor glass is heat-treated to be converted into a phase-separated glass 2 Should be high enough to control the size of the phase separated particles. However, high SiO 2 The melting temperature of the glass is undesirable. Thus, in embodiments of the invention, SiO is present in the phase separated glass 2 The mole percentage of (A) is 60-67%. Alternatively, SiO 2 Is 60%, 61%, 62%, 63%, 64%, 66% or 67%. Further, SiO 2 Mole ofThe percentage is 62 percent to 66 percent. Further, SiO 2 The mole percentage of (A) is 62.9% -65.4%.
Al 2 O 3 The network may also be stabilized and also provide improved mechanical properties and chemical durability. If Al is present 2 O 3 Too high content of (b) results in difficulty in growing the phase-separated particles. Al (Al) 2 O 3 Has higher melting temperature, can be used as a network intermediate and can regulate Al 2 O 3 The amount of (c) to control the viscosity. If Al is present 2 O 3 Too high, also generally increases the viscosity of the melt. Al in phase-separated glass 2 O 3 The Li-Na and Na-K ion exchange capacity can be enhanced. Therefore, in the embodiment of the present invention, Al 2 O 3 The mole percentage of (A) is 6-16%. Alternatively, Al 2 O 3 Is 6%, 8%, 10%, 12%, 14%, 15% or 16% by mole. Further, Al 2 O 3 The mole percentage of (A) is 7-14%. Further, Al 2 O 3 The mole percentage of (A) is 7-12% or 10-14%.
Na 2 O and K 2 O is an alkali metal oxide which mainly plays a role in breaking bonds in the glass structure, and aims to reduce the viscosity of the glass, reduce the crystallization tendency of the glass and increase the transparency and the gloss of the glass. Na (Na) 2 O is an exo-oxide of the borosilicate glass network and provides free oxygen to break Si-O bonds, thereby lowering the viscosity and melting temperature of the borosilicate glass. Na (Na) 2 Too high an amount of O increases the thermal expansion coefficient and decreases the chemical stability. Na (Na) 2 The content of O is too low, which is not favorable for melting and forming of glass. Thus, in the embodiments of the present invention, Na 2 The mol percentage of O is 5 to 12 percent. Alternatively, Na 2 The mole percentage of O is 5%, 6%, 7%, 8%, 9%, 10%, 11%, or 12%. Further, Na 2 The mol percentage of O is 7 to 12 percent.
K 2 O improves the melting behavior of the glass, with Li 2 O and Na 2 O can form mixed alkali effect to reduce the high temperature viscosity of the glass, but if K is used 2 If the content of O is too high, the glass network structure is deteriorated, the stability of the thermal properties is lowered, and the weather resistance is deteriorated. Thus, in an embodiment of the invention, K 2 The mol percentage of O is 0-2%. In some of these embodiments, K 2 The mole percentage of O is 0, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, or 2%. Further, K 2 The molar percentage of O is 0-1%.
Li 2 O is an alkali metal oxide commonly used for glass, but is different from Na 2 O and K 2 O due to Li + It is not inert gas type ion, has small radius, large field intensity and strong oxygen combining ability, and mainly plays a role in structure aggregation. Li 2 O substituted for the same amount of Na 2 O or K 2 O, it can improve the chemical stability and surface tension of glass, and increase the tendency of crystallization, and it has the functions of high-temp. fluxing and accelerating glass melting due to Li + The polarization characteristic of the resin can effectively reduce high-temperature viscosity at high temperature. In an embodiment of the present invention, Li 2 The mol percentage of O is 5 to 12 percent. In some of these embodiments, Li 2 The mole percentage of O is 5%, 6%, 7%, 8%, 9%, 10%, 11%, or 12%. Further, Li 2 The mol percentage of O is 5 to 12 percent.
MgO is a main component of the matrix phase in the split-phase glass, and in the present embodiment, the molar percentage of MgO is 1% to 3%. Alternatively, the molar percentage of MgO is 1%, 1.5%, 2%, 2.5%, or 3%. Furthermore, the molar percentage of MgO is 1% -2%.
CaO and ZnO are not essential components in the phase-separated glass, and their effects are similar to those of MgO. In an embodiment of the present invention, the molar percentage of CaO is 0 to 3%. Optionally, the molar percentage of CaO is 0, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, or 3%. In the embodiment of the invention, the molar percentage of ZnO is 0-2%. Alternatively, the molar percentage of ZnO is 0, 0.1%, 0.2%, 0.5%, 1%, 1.5%, or 2%.
ZrO 2 Can result in the production of phase-separated structuresAnd (4) generating. In the embodiment of the invention, ZrO 2 The mole percentage of (A) is 0.5% -3%. Alternatively, ZrO 2 Is 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, ZrO 2 The mole percentage of (A) is 1 to 2.5 percent or 1.5 to 2 percent.
In some of these embodiments, the phase-separated glass includes a glass matrix phase and a silicon-rich aluminum phase dispersed in the glass matrix phase; the silica-alumina rich phase is dispersed in the glass matrix phase in the form of spherical particles. In some of these embodiments, the silica-alumina rich phase is dispersed in the glass matrix phase in the form of individual spherical particles. In some of these embodiments, the spherical particles have a small number of linkages.
In some of these embodiments, the silicon-rich aluminum phase comprises SiO in addition to 2 And Al 2 O 3 Other oxides than oxygen.
In some of these embodiments, the silica-alumina rich phase has a viscosity greater than the viscosity of the matrix phase.
In some of these embodiments, the hardness of the silicon-aluminum rich phase is greater than the hardness of the matrix phase.
In some of these embodiments, the spherical particles have an average particle size of 100nm or less. Further, the average particle size of the spherical particles is not more than 80nm, not more than 60nm, not more than 40nm, not more than 20nm or not more than 10 nm.
In some of these embodiments, the silica-alumina rich phase of the phase-separated glass is present in an amount of 10% to 90% by volume. Optionally, the volume ratio of the silicon-rich aluminum phase is 10% -90%, 20% -90%, 30% -90%, 40% -90%, 50% -90%, 60% -90%, 70% -90% or 80% -90%.
In some of these embodiments, the average transmittance of the phase-separated glass in the spectral range of 360nm to 700nm is greater than or equal to 88%. In some embodiments, the split-phase glass article has an average transmittance of 90% or more, 91% or more, 92% or more, in the visible light spectral range of 390nm to 700nm for a thickness of 0.7 mm. In some of these embodiments, the split-phase glass article has an average transmittance of 85% or more, 88% or more, 91% or more, over the visible spectrum from 360nm to 450nm for a thickness of 0.7 mm.
In some of these embodiments, the haze is 0.4% or less, 0.3% or less, 0.2% or less, 0.1% or less for a 0.7mm thick phase separated glass article.
In some of these embodiments, the softening point of the phase separated glass is less than 820 ℃. Further, the softening point of the phase-separated glass is less than 800 ℃, 780 ℃ or 750 ℃. Because the softening point of the phase-separated glass is lower than 820 ℃, compared with microcrystalline glass, the phase-separated glass has lower softening point temperature, thereby being beneficial to 3D hot bending.
In some of these embodiments, the surface of the phase separated glass has a Vickers hardness of 650kgf/mm or more 2 。
Because the phase-separated glass does not contain a crystal phase, the phase-separated glass is easier to grind and polish compared with microcrystalline glass. Meanwhile, the split-phase glass of the invention also has higher fracture toughness and better mechanical property. In some of these examples, the fracture toughness of the phase separated glass is 0.6 MPa-m or more 1/2 . Furthermore, the fracture toughness of the split-phase glass is more than or equal to 0.75 MPa.m 1/2 、≥0.9MPa·m 1/2 Or more than or equal to 1.05 MPa.m 1/2 。
In some of these embodiments, the 3D hot bending temperature of the phase separated glass is 850 ℃ or less. Furthermore, the 3D hot bending temperature of the split-phase glass is less than or equal to 800 ℃, less than or equal to 750 ℃ or less than or equal to 700 ℃.
The invention also provides a preparation method of the phase separation glass, which comprises the following steps of S110 and S120.
Step S110: melting and molding the preparation raw materials to prepare precursor glass; the preparation method comprises the following steps of: 60 to 67 percent of SiO 2 6 to 16 percent of Al 2 O 3 5 to 12 percent of Li 2 O, 5-12% of Na 2 O, 0 to 2% of K 2 O, 1 to 3 percent of MgO, 0 to 3 percent of CaO, and 0.5 to 3 percent of ZrO 2 0 to 2% of B 2 O 3 And 0-2% ZnO; li 2 O and Na 2 The mass ratio of O is (0.9-1.1): 1, and Li 2 O and Na 2 Sum of mass of O and Al 2 O 3 The mass ratio of (A) to (B) is 1.45-1.75.
In some of these embodiments, the preparation feedstock further comprises a fining agent. In some of these embodiments, the fining agent is selected from at least one of tin oxide, cerium oxide, chloride, carbonate, nitrate, and sulfate.
In some of these embodiments, the temperature of the melt is 1500 ℃ to 1600 ℃.
In some embodiments, the molding may be selected from one of cast molding, float molding, calender molding, overflow molding, and draw-down molding.
Step S120: and carrying out heat treatment on the precursor glass to prepare the phase-separated glass.
In some of these embodiments, the heat treatment comprises at least one of (1) to (3):
(1) the precursor glass is cooled from the melting temperature to the annealing temperature at a rate of 0.5 ℃/min to 20 ℃/min.
(2) The precursor glass is heat-insulated at a temperature of 30 to 500 ℃ above the glass transition point.
(3) The precursor glass is annealed, then heat-preserved at a temperature of 30 to 500 ℃ above the glass transition point, and then annealed again.
In some embodiments, the heat treatment is carried out in the mode (2), and the heat preservation time is 1-8 h.
In some of these embodiments, the annealing temperature is 450 ℃ to 650 ℃.
The invention also provides application of the phase separation glass or the phase separation glass prepared by the phase separation glass preparation method in preparation of protective glass, photoelectric glass, fire-proof glass or architectural glass.
Another embodiment of the invention also provides a strengthened glass prepared from the phase-separated glass or the phase-separated glass prepared according to the phase-separated glass preparation method.
In some of these embodiments, the strengthened glass has an average surface compressive stress of 800MPa or greater. Further, the average surface compressive stress of the tempered glass is not less than 900MPa, not less than 1000MPa, or not less than 1100 MPa.
In some of these embodiments, the Depth (DOL) of the CS layer of the strengthened glass is greater than or equal to 80 μm. Further, the Depth (DOL) of the CS layer of the tempered glass is not less than 90 μm or not less than 100 μm.
Another embodiment of the present invention further provides a method for manufacturing the strengthened glass, including the following steps S210 and S220.
Step S210, a first reinforcement process: carrying out first strengthening treatment on the split-phase glass in first molten salt; the first molten salt comprises 50-60% of sodium nitrate and 40-50% of potassium nitrate by mass percent.
In some of these embodiments, the first molten salt comprises, in mass percent, 55% sodium nitrate and 45% potassium nitrate.
Step S220, second enhancement: carrying out second strengthening treatment on the split-phase glass subjected to the first strengthening treatment in second molten salt; the second molten salt comprises 0-5% of sodium nitrate and 95-100% of potassium nitrate in percentage by mass.
In some of these embodiments, the second molten salt comprises, in mass percent, 5% sodium nitrate and 95% potassium nitrate.
The following are specific examples.
Referring to tables 1 to 4, compositions of the phase-separated glasses of examples 1 to 24 and comparative examples 1 to 8, precursor glasses were prepared by melt-molding the compositions of the phase-separated glasses at 1500 to 1600 ℃. Then the precursor glass is kept for 1 to 8 hours at the temperature of 30 to 500 ℃ higher than the glass transition point (the specific heat treatment process is shown in the table 1 to the table 4) to prepare the phase separation glass.
Test part:
and (3) testing the phase separation condition and the crystallization condition:
the devitrification was judged from the results of the X-ray diffractometer (XRD, PANALYTICAL X' Pert Pro, the Netherlands) and the glass was considered to have no devitrification when the diffraction peak exhibited a typical vitreous phase steamed bread peak. The phase separation was measured using a scanning electron microscope (SEM, Hitachi S-4800; 10 kV). The samples were prepared using conventional preparation methods.
And (3) transmittance test: the transmittance in the range of 390nm to 700nm and the transmittance in the range of 360nm to 450nm are respectively measured by using an ultraviolet-visible spectrophotometer (UV-Vis-NIR spectrophotometer, Lambda 750S; Perkin Elmer). The sample was a polished glass plate with a thickness of 0.7 mm.
And (3) testing fracture toughness: two approaches may be used. And (3) indentation: the test was carried out using a fully automatic microhardness tester (Vickers hardness tester, Qness Q10A +) to measure the indentation diagonal length and the propagation crack length, respectively. The sample was a polished glass plate with a thickness of 0.7 mm. Single-side beam pre-cracking method: the test was carried out using an electronic universal materials tester (Instron 5967). The national standard (GB/T23806-.
Softening point test: the softening point is measured by using a thermal expansion instrument (NETZSCH DIL402SE), and the heating rate is 10 ℃/min, wherein the softening point refers to the expansion softening point.
The test data for examples 1-24 and comparative examples 1-8 are reported in tables 1-4.
TABLE 1 compositions and Properties of the phase-separated glasses of examples 1 to 8
The phase-separated glass of embodiments 1 to 8 comprises the following components in percentage by mole: SiO 2 2 62.9％～65.4％、Al 2 O 3 11.6％、Li 2 O 10％、Na 2 O 10％、MgO 1.5％、ZrO 2 0.5% -3% and B 2 O 3 0～2％；Li 2 O and Na 2 The mass ratio of O is 1: 1, and Li 2 O and Na 2 Sum of mass of O and Al 2 O 3 The ratio of the mass of (a) to (b) is 1.72. The split-phase glass of the examples 1 to 8 has no crystallization after being treated for 2 hours at the temperature of Tg + (30 to 500 ℃), the average transmittance between 360nm and 450nm is more than or equal to 75 percent, the average transmittance between 390nm and 700nm is more than or equal to 85 percent, and the fracture toughness is more than or equal to 0.65 MPa.m 1/2 (ii) a The softening point temperature is lower than 820 ℃,is suitable for 3D hot bending.
Referring to FIG. 1, which is an SEM image of the phase-separated glass obtained by treating example 1 at the glass transition point temperature (Tg) +30 ℃ for 2h, it can be seen that the glass of example 1 is weakly phase-separated and the Si-Al rich phase is dispersed in the matrix glass phase as spherical particles under the heat treatment conditions.
Referring to FIG. 2, which is an SEM image of the phase-separated glass of example 2 obtained by treatment at a glass transition point temperature (Tg) +30 ℃ for 2 hours, it can be seen that under the heat treatment conditions, the phase-separated glass particles of example 2 are more numerous than those of FIG. 1, and the Si-Al rich phase is dispersed in the matrix glass phase as spherical particles.
Referring to FIG. 3, which is an SEM picture of the phase-separated glass of example 3 obtained by treatment at a glass transition point temperature (Tg) +30 ℃ for 2h, it can be seen that the glass of example 3 is more strongly phase-separated under the heat treatment conditions, and a large amount of the Si-Al rich phase is dispersed in the matrix glass phase as spherical particles.
Referring to FIG. 4, which is an X-ray diffraction pattern of the phase-separated glass after heat treatment of examples 1 to 3, it can be seen that no crystal is precipitated in the phase-separated glass of examples 1 to 3 treated under the conditions shown in the figure.
TABLE 2 compositions and Properties of the phase-separated glasses of examples 9 to 16
The phase-separated glass of embodiments 9 to 16 comprises the following components in percentage by mole: SiO 2 2 61.4％～67％、Al 2 O 3 7％～11.6％、Li 2 O 6％～10％、Na 2 O 6％～10％、K 2 O 0～2％、MgO 1％～3％、CaO 0～3％、ZrO 2 2％、B 2 O 3 1% -2% and 0-2% of ZnO; li 2 O and Na 2 The mass ratio of O is 1: 1, and Li 2 O and Na 2 Sum of mass of O and Al 2 O 3 The mass ratio of (A) to (B) is 1.62-1.73. The split-phase glass of the embodiment 9 to 16 has no crystallization, the average transmittance between 360nm and 450nm is more than or equal to 78 percent, the average transmittance between 390nm and 700nm is more than or equal to 80 percent, and the fracture toughness is more than or equal to 0.64 MPa.m 1/2 (ii) a The softening point temperature is lower than 755 ℃, and the method is suitable for 3D hot bending.
TABLE 3 compositions and Properties of the phase-separated glasses of examples 17 to 24
The phase-separated glass of embodiments 17 to 24 comprises the following components in percentage by mole: SiO 2 2 60％～67％、Al 2 O 3 9％～14％、Li 2 O 7％～12％、Na 2 O 7％～12％、K 2 O 0～1％、MgO 1％～3％、CaO 0～2％、ZrO 2 1.5％、B 2 O 3 0.5% and 0-2% of ZnO; li 2 O and Na 2 The mass ratio of O is (0.9-1.1): 1, and Li 2 O and Na 2 Sum of mass of O and Al 2 O 3 The mass ratio of (A) to (B) is 1.45-1.73. The split-phase glass of the embodiment 17 to 24 has no crystallization after being processed for 4 hours at the Tg + (50 to 150 ℃), the average transmittance between 360nm and 450nm is more than or equal to 78 percent, the average transmittance between 390nm and 700nm is more than or equal to 83 percent, and the fracture toughness is more than or equal to 0.74 MPa.m 1/2 (ii) a The softening point temperature is lower than 758 ℃, and the method is suitable for 3D hot bending.
TABLE 4 compositions and Properties of the phase-separated glasses of comparative examples 1 to 8
Note: in Table 4, "- -" indicates that no relevant heat treatment was performed.
The glasses of comparative examples 1 to 8 adjusted the raw material composition of the glass, and the produced glasses crystallized or no phase separation occurred at all after heat treatment. The average transmittance of the devitrified glass is remarkably reduced. The fracture toughness of the glasses of comparative examples 1 to 8 is 0.66 to 0.75MPa m 1/2 (ii) a The softening point temperature is 712-860 ℃.
Referring to table 5, the compositions of the tempered glasses of examples 25 to 32 were prepared by melt-molding raw materials at 1500 to 1600 ℃. Then the precursor glass is kept at the temperature of 100 ℃ higher than the glass transition point for 5 hours to prepare the phase-separated glass. The phase-separated glass was treated according to the chemical strengthening process of table 5 to prepare strengthened glass. The DOL and the average surface Compressive Stress (CS) of the strengthened glass are obtained by testing a scattered photoelastic stress meter SLP-2000 or a surface stress meter FSM-6000. The test results are recorded in table 5.
TABLE 5 compositions and Properties of the strengthened glasses of examples 25-32
The tempered glasses of examples 25-32 were prepared by phase separation glass chemical tempering, the stress layer depth DOL of the tempered glass was 75-100 μm, and the average surface Compressive Stress (CS) was 950-1115 MPa.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (11)
1. The phase separation glass is characterized by comprising the following components in percentage by mole:
wherein, the Li 2 O and the Na 2 The molar ratio of O is (0.9-1.1): 1, and the Li 2 O and said Na 2 Sum of molar amount of O and the Al 2 O 3 The ratio of the molar amounts of (a) to (b) is 1.45 to 1.75.
2. The phase-separated glass according to claim 1, wherein the phase-separated glass comprises a glass matrix phase and a silicon-rich aluminum phase dispersed in the glass matrix phase; the silica-alumina rich phase is dispersed in the glass matrix phase in the form of spherical particles.
3. A phase-separated glass according to claim 2, wherein the spherical particles have an average particle size of 100nm or less.
4. The phase-separated glass according to claim 1, wherein the volume ratio of the silicon-aluminum-rich phase in the phase-separated glass is 10% to 90%.
5. A phase separated glass according to any of claims 1 to 4, wherein the SiO is 2 The mole percentage of the (B) is 62 to 66 percent; and/or the presence of a catalyst in the reaction mixture,
the Al is 2 O 3 The mole percentage of the component (A) is 10 to 14 percent; and/or the presence of a catalyst in the reaction mixture,
the Li 2 The mol percentage of O is 7 to 12 percent; and/or the presence of a catalyst in the reaction mixture,
the Na is 2 The mol percentage of O is 7 to 12 percent.
6. A phase-separated glass according to any one of claims 1 to 4, wherein the average transmittance of the phase-separated glass in the spectral range of 360nm to 700nm is greater than or equal to 88%; and/or the presence of a catalyst in the reaction mixture,
the softening point of the phase-separated glass is lower than 820 ℃; and/or the like, and/or,
the Vickers hardness of the surface of the phase-separated glass is more than or equal to 650kgf/mm 2 。
7. The preparation method of the phase separation glass is characterized by comprising the following steps:
melting and molding the preparation raw materials to prepare precursor glass; the raw materials comprise the following components in percentage by mole: 60 to 67 percent of SiO 2 6 to 16 percent of Al 2 O 3 5 to 12 percent of Li 2 O, 5-12% of Na 2 O, 0 to 2% of K 2 O, 1 to 3 percent of MgO, 0 to 3 percent of CaO, and 0.5 to 3 percent of ZrO 2 0 to 2% of B 2 O 3 And 0-2% ZnO; the Li 2 O and the Na 2 The molar ratio of O is (0.9-1.1): 1, and the Li 2 O and said Na 2 Sum of molar amount of O and the Al 2 O 3 The ratio of the molar amount of (a) is 1.45-1.75;
and carrying out heat treatment on the precursor glass to prepare the phase-separated glass.
8. The method for producing a phase-separated glass according to claim 7, wherein the heat treatment comprises:
cooling the precursor glass from the melting temperature to the annealing temperature at a rate of 0.5 ℃/min to 20 ℃/min; alternatively, the first and second electrodes may be,
holding the precursor glass at a temperature of 30 to 500 ℃ higher than the glass transition point; alternatively, the first and second electrodes may be,
annealing the precursor glass, then maintaining the temperature at a temperature of 30 to 500 ℃ higher than the glass transition point, and annealing again.
9. Use of the phase-separated glass according to any one of claims 1 to 6 or the phase-separated glass prepared by the phase-separated glass preparation method according to claim 7 or 8 in the preparation of protective glass, photovoltaic glass, fire-proof glass or architectural glass.
10. A tempered glass produced from the phase-separated glass according to any one of claims 1 to 6 or the phase-separated glass produced by the method according to claim 7 or 8.
11. The method for producing a strengthened glass according to claim 10, comprising the steps of:
first strengthening treatment: subjecting the phase-separated glass to a first strengthening treatment in a first molten salt; the first molten salt comprises 50-60% of sodium nitrate and 40-50% of potassium nitrate by mass percent;
and (3) second strengthening treatment: subjecting the phase-separated glass subjected to the first strengthening treatment to a second strengthening treatment in a second molten salt; the second molten salt comprises 0-5% of sodium nitrate and 95-100% of potassium nitrate in percentage by mass.
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