CN113480167A - Composite glass clarifying agent, boroaluminosilicate glass and preparation method and application thereof - Google Patents
Composite glass clarifying agent, boroaluminosilicate glass and preparation method and application thereof Download PDFInfo
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- CN113480167A CN113480167A CN202110768797.XA CN202110768797A CN113480167A CN 113480167 A CN113480167 A CN 113480167A CN 202110768797 A CN202110768797 A CN 202110768797A CN 113480167 A CN113480167 A CN 113480167A
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- 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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Abstract
The invention relates to a composite glass clarifying agent, boroaluminosilicate glass, and a preparation method and application thereof. The composite glass clarifying agent comprises the following components in parts by weight: NaCl 5-20 weight portions and CeO22 to 7 parts by weight, and KNO31-3 parts; and CeO2The mass content of the composite glass clarifying agent is 13-41%. The composite glass clarifying agent can ensure that the molten glass can continuously discharge bubbles with different sizes at different temperature sections, thereby obtaining glass with less bubbles, high transmittance and good mechanical property. And the composite glass clarifying agent does not contain sulfur and fluorine, does not release toxic and harmful gases, and does not cause environmental pollution, reduce the service life of the kiln and other negative effects.
Description
Technical Field
The invention relates to the technical field of glass, and particularly relates to a composite glass clarifying agent, boroaluminosilicate glass, and a preparation method and application thereof.
Background
The glass cover plate is widely applied to a front cover and a rear cover of a display device such as a smart phone, a folding mobile phone and a tablet computer to protect a precise display liquid crystal panel and resist external impact force to a certain extent. Along with terminal equipment such as smart mobile phones and tablet computers, becoming lighter and thinner and multifunctional integration, the requirement of the market for the mechanical property of cover glass is also improved. Therefore, chemically strengthened glass is used as the cover glass for the cover glass.
Generally, the strengthening effect of the glass is achieved by ion exchange, namely: the glass sheet is immersed in a molten salt containing sodium ions and/or potassium ions at a temperature of 370 ℃ to 480 ℃ to exchange lithium ions and sodium ions on the surface of the glass with sodium ions and potassium ions in the molten salt, thereby forming a compressive stress layer on the surface of the glass. If a certain amount of bubbles are present in the glass melt itself, it is easy to cause breakage of the glass sheet during the strengthening treatment and to greatly reduce the mechanical properties of the glass sheet, and thus it is difficult to use it as a protective glass cover plate. Also, high-alumina cover glass used as a display panel, such as boroaluminosilicate glass, has a high viscosity and is difficult to remove bubbles, as compared to ordinary soda-lime glass. In addition, bubbles in the glass adversely affect the color tone, transmittance, and refractive index of the glass, and reduce the display effect of the display panel.
Disclosure of Invention
Accordingly, there is a need for a boroaluminosilicate glass with less bubbles, higher transmittance and good mechanical properties, and a preparation method and applications thereof.
In addition, a composite glass fining agent is also provided.
The invention provides a composite glass clarifying agent, which comprises the following components in parts by weight:
5-20 parts of NaCl;
CeO22-7 parts; and
KNO31-3 parts;
the CeO2The mass content of the composite glass clarifying agent is 13-41%.
In some embodiments, the NaCl accounts for 5-12 parts by weight, and the CeO accounts for2Is 3 to 7 parts by mass, and the KNO3Is 1 to 2.5 parts by mass, and the CeO2The mass content of the composite glass clarifying agent is 16-35%.
In some embodiments, the NaCl accounts for 5-10 parts by weight, and the CeO accounts for23.5 to 6.5 parts by mass, and the KNO3Is 1 to 2 parts by mass, and the CeO2The mass content of the composite glass clarifying agent is 18-28%.
On the other hand, the invention also provides boroaluminosilicate glass, and the preparation raw materials of the boroaluminosilicate glass comprise a glass main material and the composite glass clarifying agent;
in the preparation raw materials, the mass content of the composite glass clarifying agent is 0.9-2.7%.
In some embodiments, the boroaluminosilicate glass comprises, by mass percent:
in some of these embodiments, the SiO2Quality of (1)The weight percentage content is 55.8% -59.8%, and the Al is2O3The mass percentage content of the P is 21.5-25.5 percent, and the P is2O5The mass percentage content of (A) is 1.2-3.2%, and the Li2The mass percentage content of O is 3.2-5.1%, and the Na is2The mass percentage of O is 3.5-5.5%, and the K is20.7-1% of O, 2-2.5% of MgO and ZrO2The mass percentage content of the components is 0.23-1.7%.
In some of these embodiments, the boroaluminosilicate glass has a Vickers hardness of 588MPa to 630MPa and a Young's modulus of 75.4GPa to 80.7 GPa; the linear expansion coefficient of the boron-aluminum silicate glass at the temperature of between 50 and 350 ℃ is 48.3 multiplied by 10-7/℃～77.7×10-7/℃。
In another aspect of the present invention, a method for preparing the above-mentioned boroaluminosilicate glass is also provided, which comprises the following steps:
mixing the above prepared raw materials, and performing melting treatment to obtain molten glass; and
and forming the molten glass, and then carrying out annealing treatment.
In another aspect of the invention, a strengthened glass is provided, which is prepared by chemically strengthening the boron aluminosilicate glass through ion exchange.
In another aspect of the invention, an electronic product is also provided, and the cover plate of the protective glass adopts the strengthened glass.
The composite glass clarifying agent consists of NaCl and CeO2And KNO3The components of the NaCl and the CeO2And KNO3The mass ratio of (5-20): (2-7): (1 to 3) and CeO2The mass content of the composite glass clarifying agent is 13-41%. The composite glass clarifying agent can enable glass liquid to continuously discharge bubbles with different sizes at different temperature sections, thereby obtaining glass with less bubbles, higher transmittance and good mechanical property. The composite glass clarifying agent does not contain sulfur and fluorine, does not release toxic and harmful gases, does not cause environmental pollution, reduces the service life of the kiln and the likeNegative effects.
Drawings
Fig. 1 is a flow chart of a method of making a boroaluminosilicate glass in accordance with an embodiment of the present invention.
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 a composite glass clarifying agent, which comprises the following components in parts by weight:
5-20 parts of NaCl;
CeO22-7 parts; and
KNO31-3 parts;
CeO2the mass content of the composite glass clarifying agent is 13-41%.
NaCl (sodium chloride) performs a clarifying function when the glass composition is dissolved. Above 1500 ℃, on the one hand the sodium chloride reacts with the moisture in the batch or kiln, i.e.: 2NaCl + H2O→Na2O +2HCl, producing hydrogen chloride vapor; on the other hand, NaCl is easy to volatilize at high temperature, and about half of NaCl is steam to escape; these promote the escape of bubbles in the molten glass. However, vapors of NaCl may deposit to clog the flue, and thus in some embodiments, the glass composition has a NaCl content of 0.5% to 2% by mass.
CeO2(cerium oxide) is a fining agent in the glass melting process, and the cerium oxide can generate decomposition reaction at the temperature of about 1400 ℃ to release oxygen, namely: CeO (CeO)2→Ce2O3+O2The separated oxygen can permeate into bubbles in the molten glass through diffusion to enlarge the bubbles, so that the bubbles in the molten glass are promoted to escape. Meanwhile, oxygen decomposed and separated from cerium oxide can be used for dissolving Fe with strong coloring capacity in glass2+Oxidation to Fe with weak coloring power3+Thereby making the glass nearly colorless and increasing the transmittance.
KNO3(potassium nitrate) undergoes a gradual decomposition reaction when heated above 400 ℃, releasing nitrogen and oxygen, namely: KNO3→K2O+N2+O2The gas enters into the bubbles of the molten glass and the bubbles are discharged to the outside of the molten glass as the volume of the bubbles increases.
The composite glass clarifying agent consists of NaCl and CeO2And KNO3Component composition of NaCl, CeO2And KNO3The mass ratio of (5-20): (2-7): (1 to 3) and CeO2The mass content of the composite glass clarifying agent is 13-41%. Through reasonable proportioning, the following beneficial effects can be produced: (1) the composite glass clarifying agent can enable glass liquid to continuously discharge bubbles with different sizes at different temperature sections, thereby obtaining glass with less bubbles, higher transmittance and good mechanical property. (2) The clarification effect of the three agents is synergistically promoted to be far higher than that of any one clarifier used alone. And because the composite glass clarifying agent does not contain sulfur and fluorine, the negative effects of environmental pollution, reduction of the service life of the kiln and the like are avoided. (3) CeO (CeO)2And KNO3It also has decolorizing effect, and oxygen generated by pyrolysis can be used for coloring Fe in glass2+Oxidation to Fe with weak coloring power3+Thereby making the glass nearly colorless and increasing the transmittance.
In some embodiments, the mass fraction of NaCl is 5-12 parts, and the CeO2Is 3 to 7 parts by mass, and the KNO3Is 1 to 2.5 parts by mass, and the CeO2In the composite glassThe mass content of the clarifying agent is 16-35%.
In some embodiments, the mass fraction of NaCl is 5-10 parts, and the CeO23.5 to 6.5 parts by mass, and the KNO3Is 1 to 2 parts by mass, and the CeO2The mass content of the composite glass clarifying agent is 18-28%.
The invention also provides boroaluminosilicate glass, and the preparation raw materials comprise a glass main material and the composite glass clarifying agent;
in the preparation of raw materials, the mass content of the composite glass clarifying agent is 0.9-2.7%.
The boron-aluminum silicate glass comprises NaCl and CeO with specific contents2And KNO3As the composite glass clarifying agent, bubbles with different sizes can be continuously discharged at different temperature sections, so that glass with fewer bubbles and good mechanical property is obtained, and the light transmittance is good.
In some embodiments, the glass main material of the boroaluminosilicate glass comprises, by mass:
in some embodiments, the boroaluminosilicate glass comprises, in mass percent:
SiO2(silica) is an important glass-forming oxide and is an essential component for forming a glass skeleton. If SiO2When the mass content of (b) is less than 54%, the mechanical properties of the glass are poor and the weatherability is poor; if the melting point exceeds 62%, the melting point is too high, which is disadvantageous in producing a glass having excellent mechanical properties without bubbles. In the present embodiment, SiO2The content of (b) is 54-62% by mass, preferably 56-61% by mass.
Al2O3(alumina) is a component for improving weather resistance, and can reduce the crystallization tendency of glass, and improve the chemical stability, thermal stability, mechanical strength and hardness of glass, in aluminosilicate glass, Al2O3Can participate in the network to play the role of a network generation body. Due to [ AlO ]4]The tetrahedral space being greater than [ SiO ]4]Tetrahedral space, so that the increased alumina content is beneficial for ion exchange. If Al is present2O3If the content of (b) is too high, the meltability is remarkably deteriorated. In the present embodiment, Al2O3The content of (b) is 21.5-27 wt%, preferably 22-26 wt%.
B2O3(boron oxide) ability to lower the liquidus temperature and expansion coefficient of the glass, while increasing the strain point and chemical stability of the glass. In this embodiment, B2O3The mass percentage of (B) is 2-6.1%, preferably 2.8-5.2%.
P2O5(phosphorus pentoxide) capable of reducing the viscosity of the glass, wherein B2O3Help P to2O5With [ BPO ]4]The form of the unit is fixed in the glass structure, thereby improving the fracture toughness of the glass. On the other hand, in view of cost, the phosphorus-containing raw material is expensive, the high-phosphorus glass is likely to undergo phase separation, and the production difficulty is large, so that P in the present embodiment2O5The mass percentage of (B) is 1.2-4.5%, preferably 1.8-3.5%.
Na2O (sodium oxide) is a necessary component to significantly lower the melting temperature of aluminosilicate glass. Na (Na)2When the content of O is too low, the glass has poor melting property, and Na2If the content of O is too high, the glass will have poor weather resistance. In this embodiment, Na2The mass percentage of O is 3.5-7.5%, preferably 4-6.5%. Li2O (lithium oxide) and K2O (potassium oxide) is reacted with Na2O a component of similar nature, K2O can significantly lower the melting temperature of the glass, but the addition amount is not so large, and in the present embodiment, K is added2The mass percentage of O is0.5 to 1.8 percent, preferably 0.8 to 1.5 percent. Li2Li of O+The ionic radius is small, and the glass is also a substance for ion exchange in the glass phase besides the effect of reducing the melting temperature of the glass, and the mechanical property of the glass can be improved by ion exchange with alkali metal ions outside the glass phase. In the present embodiment, Li2The mass percentage of O is 3 to 6.5 percent, and the preferable mass percentage is 3.5 to 5.5 percent.
MgO (magnesium oxide) can reduce the high-temperature viscosity of the glass at high temperature, improve the uniformity, increase the hydrolyzability, promote the melting and clarification of the glass, improve the Young modulus and the chemical resistance of the glass and reduce the density of the glass. MgO also stabilizes the glass, improves the durability of the glass, prevents the glass from crystallizing, improves the elastic modulus of the glass, and suppresses the occurrence of cracks. However, if the MgO content is too high, the glass may be easily devitrified, and if the MgO content is too low, the viscosity of the glass melt increases and the meltability decreases. Therefore, in the present embodiment, the MgO content is 2% to 5% by mass, preferably 2.5% to 4.5%.
ZrO2(zirconia) is a component that increases the compressive stress on the glass surface, increases the hardness of the glass, and improves the weatherability and stability of the glass, but excess ZrO2The possibility of cracking of the glass self-indentation increases. In the present embodiment, ZrO2The mass percentage content is 0.2-1.7%, preferably 0.4-1.2%.
The boroaluminosilicate glass has lower melting temperature and density, and has higher Young modulus and Vickers hardness to enhance the mechanical property of the glass. The boron aluminosilicate glass has high melting viscosity, and the composite glass clarifying agent can efficiently promote clarification of the glass during melting, so that the glass with bright color and less bubbles is obtained. The boron-aluminum silicate glass has good mechanical property and optical property, and is particularly suitable for preparing a protective glass cover plate.
In some of these embodiments, the boroaluminosilicate glass is SiO255.8 to 59.8 percent of Al2O3The mass percentage content of (A) is 21.5-25%.5％，P2O5The mass percentage of the Li is 1.2-3.2 percent2The mass percentage of O is 3.2-5.1 percent, and Na2The mass percentage of O is 3.5-5.5 percent, and K20.7 to 1 percent of O, 2 to 2.5 percent of MgO and ZrO2The mass percentage content of the components is 0.23-1.7%.
In some of these embodiments, the boroaluminosilicate glass has a Vickers hardness of 588MPa to 630MPa and a Young's modulus of 75.4GPa to 80.7 GPa; the linear expansion coefficient of the boron-aluminum silicate glass in the range of 50-350 ℃ is 48.3 multiplied by 10-7/℃～77.7×10-7/℃。
The boron aluminosilicate glass has high Vickers hardness and Young modulus, and is high in scratch resistance and falling resistance; and the linear expansion coefficient is low, the thermal shrinkage of the glass sheet is reduced after the glass sheet is subjected to post-processing tapping treatment and high-temperature treatment, the glass sheet is favorably and accurately attached to a display device, and the bad phenomenon of dislocation of tapping positions cannot occur.
In some embodiments, the boroaluminosilicate glass comprises, in mass percent: 0.2 to 0.7 percent of CeO2. Because cerium oxide is not easy to volatilize, CeO of composite glass clarifying agent is also contained in boron-aluminum silicate glass2. NaCl and KNO in the composite glass clarifier3There is only a small amount of residue in the boroaluminosilicate glass.
Referring to fig. 1, another embodiment of the present invention further provides a method for preparing the boroaluminosilicate glass, including the following steps S1-S2.
Step S1: mixing the preparation raw materials, and performing melting treatment to obtain glass liquid.
Specifically, the temperature of the melting treatment is 1600-1640 ℃, and the time of the melting treatment is 4-8 hours.
Step S2: and forming the molten glass, and then carrying out annealing treatment.
In some of these embodiments, the molding is by casting.
In some of these embodiments, the temperature of the annealing process is 620 ℃ to 670 ℃. Specifically, the time of the annealing treatment is 1 to 3 hours.
The preparation method of the boron-aluminum silicate glass is simple to operate and easy for industrial production. Because the raw materials comprise the composite glass clarifying agent, the glass liquid is obtained by clarifying treatment in the melting process. The composite glass clarifying agent used in the preparation method of the boroaluminosilicate glass does not contain sulfate, fluorine-containing compounds and the like, does not release toxic and harmful gases, is not easy to corrode a kiln, and can improve the service life of the kiln. The boroaluminosilicate glass prepared by the method has fewer bubbles, has the characteristics of lower melting temperature, high strain point, higher Young modulus and Vickers hardness, light weight and environmental protection, and has excellent properties.
The invention also provides a strengthened glass, which is obtained by immersing the boroaluminosilicate glass in the alkali metal molten salt with the temperature of 370-480 ℃ for ion exchange.
The strengthened glass can further obtain glass with better mechanical property through strengthening treatment.
The invention also provides an electronic product, and the cover plate of the protective glass adopts the strengthened glass.
The electronic products include, but are not limited to, smart phones and folding phones. Tablet personal computers and displays.
The following are examples of the following (the following examples, unless otherwise specified, contain no other components not specifically indicated except for unavoidable impurities):
example 1 to example 7:
the boroaluminosilicate glasses of examples 1-7 were prepared as follows:
(1) weighing raw materials and a glass clarifying agent according to the mass percentage of each component of the boroaluminosilicate glass in the table 1, and mechanically mixing the prepared raw materials for 1 hour.
(2) The mechanically mixed preparation raw materials are poured into a platinum-rhodium crucible, and the crucible is subjected to heat preservation for 8 hours at the melting temperature of 1620 ℃ in the table 1 so as to be melted and clarified, and then the molten glass is obtained.
(3) Pouring the glass liquid into a stainless steel mold for molding, then carrying out heat preservation annealing at 620 ℃ for 2 hours, and then cooling to room temperature along with the furnace to obtain the boron-aluminum silicate glass.
Example 8 to example 14:
the boroaluminosilicate glasses of examples 8-14 were prepared as follows:
(1) weighing raw materials and a glass clarifying agent according to the mass percentage of each component of the boroaluminosilicate glass in the table 2, and mechanically mixing the prepared raw materials for 1 hour.
(2) The mechanically mixed preparation raw materials are poured into a platinum-rhodium crucible, and are subjected to melting and clarification treatment by keeping the temperature for 4 hours at the melting temperature of 1640 ℃ in the table 2, so as to obtain glass liquid.
(3) Pouring the glass liquid into a stainless steel mold for molding, then carrying out heat preservation annealing at 660 ℃ for 3 hours, and then cooling to room temperature along with the furnace to obtain the boron-aluminum silicate glass.
Comparative examples 1 to 4:
the boroaluminosilicate glasses of comparative examples 1-4 were prepared as follows:
(1) weighing raw materials and a glass clarifying agent according to the mass percentage of each component of the boroaluminosilicate glass in the table 3, and mechanically mixing the prepared raw materials for 1 hour.
(2) The mechanically mixed preparation raw materials are poured into a platinum-rhodium crucible, and the crucible is subjected to heat preservation for 8 hours at the melting temperature of 1620 ℃ in the table 2 so as to be melted and clarified, and then the molten glass is obtained.
(3) Pouring the glass liquid into a stainless steel mold for molding, then carrying out heat preservation annealing at 620 ℃ for 2 hours, and then cooling to room temperature along with the furnace to obtain the boron-aluminum silicate glass.
And (3) testing:
the boroaluminosilicate glasses of examples 1 to 14 and comparative examples 1 to 4 were cut with a wire cutting machine into sliced glass samples having a thickness of 0.3mm, and then the slices were ground and polished for finish machining, and finally the physical and chemical properties of the sliced glass samples of the boroaluminosilicate glasses of examples 1 to 14 and the boroaluminosilicate glasses of comparative examples 1 to 4 were tested.
(1) The glass density was determined by reference to Archimedes' method.
(2) Young's modulus was measured by a flexural resonance method.
(3) The expansion coefficient (50-350 ℃) and the softening point are measured by a German DIL-402PC horizontal dilatometer, and the heating rate is 5 ℃/min.
(4) Vickers hardness is measured using a Vickers hardness tester, in accordance with the standard ASTM E-384.
(5) The melting temperature is determined by measuring the viscosity with a high temperature viscometer and then calculating by the Vogel-Fulcher-Tamann formula.
(6) The light transmittance, color L, a and b value are tested by an ultraviolet-visible spectrophotometer;
(7) bubble quantity measuring method: the glass sheet obtained by the invention is irradiated by a halogen lamp, the size is determined by a scale ruler, the quantity of bubbles is counted, the quantity of bubbles with the bubble diameter larger than 0.1mm in each kilogram of glass can be quickly and accurately calculated, and the quantity of bubbles with the bubble diameter smaller than 0.1mm, which is more than 0.05mm, is counted by a German Leica polarization microscope.
The density, Young's modulus, expansion coefficient, Vickers hardness, softening point, transmittance, Lab value and number of bubbles of the sliced glass samples obtained from the boroaluminosilicate glasses of examples 1 to 7 are shown in Table 1, the density, Young's modulus, expansion coefficient, Vickers hardness, softening point, transmittance, Lab value and number of bubbles of the sliced glass samples obtained from the boroaluminosilicate glasses of examples 8 to 14 are shown in Table 2, and the density, Young's modulus, expansion coefficient, Vickers hardness, softening point, transmittance, Lab value and number of bubbles of the sliced glass samples of the boroaluminosilicate glasses of comparative examples 1 to 4 are shown in Table 3.
TABLE 1
Note: each chemical formula in the table represents the mass content of the raw materials in the preparation; NaCl + KNO3+CeO2Representing the mass content of the composite glass clarifying agent in the preparation raw materials; CeO (CeO)2/(CeO2+NaCl+KNO3) Representing CeO in the composite glass refining agent2Mass content of (a).
TABLE 2
Note: each chemical formula in the table represents the mass content of the raw materials in the preparation; NaCl + KNO3+CeO2Representing the mass content of the composite glass clarifying agent in the preparation raw materials; CeO (CeO)2/(CeO2+NaCl+KNO3) Representing CeO in the composite glass refining agent2Mass content of (a).
TABLE 3
Note: each chemical formula in the table represents the mass content of the raw materials in the preparation; NaCl + KNO3+CeO2Representing the mass content of the composite glass clarifying agent in the preparation raw materials; CeO (CeO)2/(CeO2+NaCl+KNO3) Representing CeO in the composite glass refining agent2Mass content of (a).
As can be seen from tables 1 and 2, the boroaluminosilicate glasses of examples 1 to 14 had densities of 2.358g/cm3～2.456g/cm3The coefficient of linear expansion (50 ℃ C. -350 ℃ C.) is 48.3X 10-7/℃～77.7×10-7V deg.C, Young's modulus 75.4-80.7 GPa, Vickers hardness 588 MPa-630 MPa, and melting temperature T2The temperature is 1600-1640 ℃, bubbles with the diameter of more than 0.1mm in the glass are 0, and the number of bubbles with the diameter of more than 0.05mm and less than 0.1mm in the glass is 0-6 bubbles/kg, so that the clean bubble-free glass can be obtained. Meanwhile, the light transmittance of the glass is more than 92%, and the glass has transparent luster, so that the use requirement of the protective glass is met. The embodiments 1-14 also have higher Young modulus and Vickers hardness, are beneficial to post-processing and long-distance transportation of glass, and can meet the use requirements of the cover plate glass on falling resistance and scratch resistance. Specifically, compare traditional cover plate glass, the linear expansion coefficient of boron aluminosilicate glass of embodiment 1 ~ 14 is lower, is favorable to carrying out accurate aftertreatment to the glass piece. The boroaluminosilicate glasses of examples 1 to 14 had glass transition points of 594 ℃ to 649 ℃, softening points of 706 ℃ to 762 ℃, higher glass transition points and softening points, wider heat-treatable temperature ranges, and no defects such as deformation and warpage.
As can be seen from tables 1 to 3, compared with examples 5, 12 and 14, the boroaluminosilicate glasses of comparative examples 1 to 4 have a certain number of bubbles with diameters larger than 0.1mm, and the number of bubbles with diameters larger than 0.05mm and smaller than 0.1mm is larger, which affects the quality of the glass, and further brings defects to the glass and reduces the yield. Meanwhile, the boroaluminosilicate glasses of comparative examples 1-4 have transmittances lower than 92%, and do not meet the use requirements of protective glass.
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 (10)
1. The composite glass clarifying agent is characterized by comprising the following components in parts by mass:
5-20 parts of NaCl;
CeO22-7 parts; and
KNO31-3 parts;
the CeO2The mass content of the composite glass clarifying agent is 13-41%.
2. The composite glass refining agent according to claim 1, wherein the NaCl is present in an amount of 5 to 12 parts by mass, and the CeO is present in an amount of 5 to 12 parts by mass2Is 3 to 7 parts by mass, and the KNO3Is 1 to 2.5 parts by mass, and the CeO2The mass content of the composite glass clarifying agent is 16-35%.
3. The composite glass refining agent according to claim 1, wherein the NaCl is 5 to 10 parts by mass and the CeO is23.5 to 6.5 parts by mass, and the KNO3Is 1 to 2 parts by mass, and the CeO2The mass content of the composite glass clarifying agent is 18-28%.
4. A boroaluminosilicate glass, characterized in that, the preparation raw materials comprise a glass main material and a composite glass clarifier as any one of claims 1 to 3;
in the preparation raw materials, the mass content of the composite glass clarifying agent is 0.9-2.7%.
5. The boroaluminosilicate glass according to claim 4, wherein the boroaluminosilicate glass comprises the following components in percentage by mass:
6. the boroaluminosilicate glass of claim 5, wherein the SiO is2The mass percentage content of the Al is 55.8-59.8 percent, and the Al is2O3The mass percentage content of the P is 21.5-25.5 percent, and the P is2O5The mass percentage content of (A) is 1.2-3.2%, and the Li2The mass percentage content of O is 3.2-5.1%, and the Na is2The mass percentage of O is 3.5-5.5%, and the K is20.7-1% of O, 2-2.5% of MgO and ZrO2The mass percentage content of the components is 0.23-1.7%.
7. A boroaluminosilicate glass according to claim 5 or 6, wherein the boroaluminosilicate glass has a Vickers hardness of 588MPa to 630MPa, a Young's modulus of 75.4GPa to 80.7 GPa; the linear expansion coefficient of the boron-aluminum silicate glass at the temperature of between 50 and 350 ℃ is 48.3 multiplied by 10-7/℃～77.7×10-7/℃。
8. A method for preparing boroaluminosilicate glass is characterized by comprising the following steps:
mixing the raw materials for preparing boroaluminosilicate glass according to any one of claims 4 to 7, and carrying out melting treatment to obtain molten glass; and
and forming the molten glass, and then carrying out annealing treatment.
9. A strengthened glass, which is obtained by chemically strengthening the boroaluminosilicate glass according to any one of claims 4 to 7 by ion exchange.
10. An electronic product comprising a glass cover plate, wherein the glass cover plate is the strengthened glass of claim 9.
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