Disclosure of Invention
The invention mainly aims to provide aluminosilicate glass and a preparation method thereof, so as to improve the heat transfer efficiency of the aluminosilicate glass and solve the problem of difficulty in clarifying molten glass.
The technical scheme of the invention is as follows:
the invention provides an aluminosilicate glass, which takes oxides as a reference and comprises the following components in percentage by mass:
meanwhile, the aluminosilicate glass also comprises 150 ppm-550 ppm of Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 25 to 35 percent.
Preferably, the aluminosilicate glass comprises the following components in percentage by mass on the basis of oxides:
meanwhile, the aluminosilicate glass also comprises 150 ppm-550 ppm of Fe2O3And is Fe2O3At 150ppm to 300ppm, the mass of divalent iron ions and the mass of total iron ionsThe ratio Redox of (A) is 35-45%; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 25 to 35 percent.
Preferably, the aluminosilicate glass comprises the following components in percentage by mass on the basis of oxides:
meanwhile, the aluminosilicate glass also comprises 150 ppm-550 ppm of Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 25 to 35 percent.
Preferably, the aluminosilicate glass has a visible light transmission Tvis of 91.0% to 100% at an equivalent thickness of 1.1 mm.
Preferably, the aluminosilicate glass has a composition in which SiO is present2+A12O370 to 83 wt%.
More preferably, SiO is contained in the aluminosilicate glass2+A12O3Is 73-83 wt%.
Preferably, in the composition of the aluminosilicate glass, Li2O+Na2O+K2O is 8 to 25 wt%.
More preferably, in the aluminosilicate glass, Li is contained2O+Na2O+K2O is 10 to 20 wt%.
Preferably, the aluminosilicate glass comprises a glass plate, and the thickness of the glass plate is 0.1-1.5 mm.
The invention also provides a preparation method of the aluminosilicate glass, which comprises the following steps:
weighing 59-70 wt% of SiO by mass percent based on oxide213 to 23 wt% of Al2O35 to 15 wt% of Na2O, 1 to 7 wt% of K2O, 0 to 0.1 wt% CaO, 1 to 7 wt% MgO, 0.2 to 2 wt% ZrO20 to 4.5 wt% of B2O30 to 4 wt% of Li2O, 150ppm to 550ppm of Fe2O3Forming a batch;
mixing, melting, homogenizing, molding and annealing the weighed batch mixture in sequence to obtain aluminosilicate glass;
wherein, during the melting process, when Fe2O3When the mass is 150ppm to 300ppm, controlling the ratio Redox of the mass of the ferrous ions to the mass of all the ferric ions to be 35 to 45 percent; when Fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the ferrous ions to the mass of all the ferric ions is controlled to be 25 to 35 percent.
The aluminosilicate glass comprises 150 ppm-550 ppm Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the ferrous ions to the mass of all the ferrous ions is 25 to 35 percent, so that the heat transfer efficiency of the molten glass in the kiln can be improved while the good transmittance of the glass is ensured, and the clarification of the molten glass is simple.
Detailed Description
Hereinafter, embodiments of the present invention will be described in further detail.
Aluminum silicate glass
The aluminosilicate glass of the embodiment of the invention takes oxides as a reference, and comprises the following components in percentage by mass:
meanwhile, the aluminosilicate glass also comprises 150 ppm-550 ppm of Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 25 to 35 percent.
Preferably, the aluminosilicate glass comprises the following components in percentage by mass on the basis of oxides:
meanwhile, the aluminosilicate glass also comprises 150 ppm-550 ppm of Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 25 to 35 percent.
Further preferably, the aluminosilicate glass comprises the following components in percentage by mass on the basis of oxides:
meanwhile, the aluminosilicate glass also comprises 150 ppm-550 ppm of Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 25 to 35 percent.
The action of the individual components of the glass according to the invention is illustrated below:
SiO2is the main body of the network structure of the glass, and can improve the chemical stability, the thermal stability, the mechanical strength and the like of the glass. If the content is less than 59.0%, the glass is difficult to form and tends to crystallize, and the chemical resistance is lowered. But SiO2Is a substance which is difficult to melt and has a content of more than 70 percent.0%, the glass melting and fining temperatures will be higher and the viscosity will rise, making the glass difficult to homogenize and unsuitable for manufacturing by the float process. Thus, the SiO of the invention2The content range is required to be 59.0-70.0%.
Al2O3Can reduce the crystallization tendency of glass, improve the chemical stability, thermal stability, mechanical strength and hardness of glass, and is also an essential component for improving the elastic modulus of glass, but if Al is used2O3The viscosity of the glass increases excessively, and the glass is likely to be crystallized and difficult to be formed into a glass sheet by a float method, an overflow down-draw method, or the like. Al in aluminosilicate glasses3+Tend to form an alundum tetrahedral network (AlO)4]Which is greater than silicon oxygen tetrahedron [ SiO ]4]The network space is much larger, and the larger network space makes the ion exchange easier, so that the Al content in the glass is high2O3The content can promote ion exchange, and is beneficial to ion exchange at lower temperature and shorter time. Thus, on the one hand, Al2O3The content of more than 23.0 percent can increase the crystallization tendency and high-temperature viscosity of the glass, so that the glass is difficult to melt, and further, the softening point temperature of the glass is increased, and the hot working temperature of the glass is increased; on the other hand, Al2O3When the content is too small, the ion exchange performance of the glass cannot be sufficiently exhibited. Therefore, Al in the present invention2O3The content of (b) is in the range of 13 to 23%, preferably 13 to 18%, more preferably 13.5 to 17.5%.
If SiO2And A12O3Total content of SiO2+A12O3If the content exceeds 83%, the viscosity of the glass at high temperature increases, and the glass melting becomes difficult. Thus, the SiO of the invention2+A12O3The total content of (A) is at most 83%. If SiO2+A12O3Less than 70% in total, the shatter resistance of the glass is reduced. Thus, the SiO of the invention2+A12O3Is at least 73%.
Li2O is an ion-exchange component and can lower the high-temperature viscosity of the glass, improve the meltability of the glass,Formability. Li2O has the greatest effect on the increase in the compressive stress value of the glass among alkali metal oxides, but contains 5% or more of Na2In the glass of O, if Li2When the content of O is large, the compression stress value tends to be lowered. In addition, if Li2When the content of O is too large, the glass is easily devitrified, and the expansion coefficient becomes too high, resulting in a decrease in thermal shock resistance. Furthermore, Li2When the content of O is too large, the low-temperature viscosity of the glass is too low, which tends to cause stress relaxation, and conversely, the compressive stress value of the glass is lowered. Thus, Li in the present invention2The content of O is not essential, and the content range is 0 to 4%.
Na2O is a component for forming a surface compressive stress layer by ion exchange and for improving the melting property of glass, and Na is2O is also an essential component for improving glass devitrification. If Na2When the content of O is less than 5%, the glass has a low melting property, and it is difficult to form a desired surface compressive stress layer by ion exchange. In the present invention, Na2The content of O is at least 5%. If Na2When the content of O is too large, the thermal expansion coefficient of the glass becomes too high, the thermal shock resistance is lowered, the strain point is lowered, the glass is not resistant to chemical attack, and the weather resistance is also lowered. Thus Na2The content of O is at most 15%.
K2O is a component for improving glass meltability and for increasing an ion exchange rate in chemical strengthening to obtain a desired surface compressive stress and stress layer depth, and is also a component for improving resistance to devitrification. Note that, for example, K is added to glass2O, the lower limit of the amount is 1% or more, otherwise the effect of improving the ion exchange rate of the glass in chemical strengthening is not good. If K2When the content of O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance is lowered, and the strain point is lowered, so that it is preferably 7% or less. Thus, in the present invention, K2The content of O is 1-7%, preferably, K2The content of O is 1.5-7%.
Li2O+Na2O+K2O is an ion exchange component in the aluminosilicate glass, and also reduces the high-temperature viscosity of the glass and improves the melting of the glassSex and moldability components, Li2O+Na2O+K2When O is too much, the glass is easily devitrified. Further, the thermal expansion coefficient is excessively increased, the thermal shock resistance is lowered, and it is difficult to match the thermal expansion coefficient of the peripheral material. In addition, the strain point is lowered too much, and it is difficult to increase the compressive stress after chemical strengthening. On the other hand, Li2O+Na2O+K2When O is too small, the ion exchange performance and the glass meltability are deteriorated. Thus, Li2O+Na2O+K2The total amount of O is 8 to 25 wt%, preferably Li2O+Na2O+K2The total amount of O is 10-20 wt%.
CaO enables the formation of silicon-oxygen tetrahedrons [ SiO ]4]The formed network structure is loosened and broken to improve the melting property of the glass at a high temperature or to make the glass easy to be shaped, but the introduction of CaO seriously hinders the ion exchange property of the glass to affect the chemical strengthening property thereof, and thus it may be contained at most 0.1%, and is preferably not additionally introduced as an effective ingredient.
MgO is an external oxide of a glass network, and when the content of MgO is not more than 7.0%, the MgO is helpful for reducing the high-temperature viscosity of the glass to improve the meltability of the glass, improve the uniformity and increase the hydrolysis resistance. MgO stabilizes the glass, improves the durability of the glass, prevents the glass from crystallizing, and suppresses the movement of alkali metal ions in the glass, and similarly has a function of improving the elastic modulus of the glass. However, if the MgO content is too large, for example, > 7%, the density and thermal expansion coefficient of the glass become high and the glass tends to devitrify, so that the content is in the range of 1.0 to 7.0%, preferably 2.5 to 6.5%, most preferably 3.0 to 6.0%.
ZrO2The ion exchange performance of the aluminosilicate glass can be obviously improved, so that the surface compressive stress of the glass is increased, and the strain point of the glass can be improved. But if ZrO2If the content is too large, the density of the glass may become too high, and the devitrification resistance may be lowered. ZrO2May remain in the glass as crushed stones, reducing the shatter resistance of the glass. It is noted that, in order to improve the ion exchange property, ZrO2The content of (A) is at least 0.2% or more. Accordingly, the inventionZrO2The content is in the range of 0.2 to 2 wt%, preferably ZrO2The content is 0.5-1.5%.
B2O3Can reduce the high-temperature viscosity and density of the glass and improve the crystallization resistance of the glass. However, if B2O3Too high a content lowers the water resistance of the glass. In the melting, refining and shaping steps of the glass in the production of sheet glass, B2O3Are volatile and affect the homogeneity and flatness of the glass sheet. In addition, boron oxide in the glass forms dense boron-oxygen tetrahedra [ BO4]The network thereby restricts the migration of ions in the glass, thins the stress layer, and reduces the compressive stress value of the glass. Thus, B2O3Is 0 to 4.5%, preferably, does not contain B2O3。
The aluminosilicate glass of the invention Fe2O3The content is 150 ppm-550 ppm, and if the total content of iron oxide in the glass is less than 150ppm, the heat transfer efficiency of the glass liquid can be reduced, the heat-conducting property of the glass in the subsequent processing process is influenced, and the production cost is greatly increased. If the total iron oxide content is higher than 550ppm, the transmittance of the glass is affected, and the quality and the appearance of the glass when used as a glass cover plate are affected.
In addition, the total iron Fe in aluminosilicate glasses2O3Both FeO and Fe2O3In the form, bivalent iron has a strong absorption peak near the wavelength of 1000nm, trivalent iron has an absorption peak near the wavelength of 380nm, and the absorption coefficient of bivalent iron is generally more than 7 times of that of trivalent iron, so that bivalent iron of the glass is improved, and heat transfer and heating of the glass are facilitated. In addition, the invention also needs to utilize Fe2O3Decomposing at high temperature to release O2To eliminate bubbles in the glass (iron oxide pyrolysis reaction: Fe)2O3→FeO+O2↑)。
Therefore, in the present invention, when total iron (as Fe)2O3Expressed) is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45%; if Redox is lower than35 percent, the content of ferrous ions is too low to be beneficial to the heat conduction of the molten glass, if the content is higher than 45 percent, Fe2O3Relatively low content of decomposed O2The amount is small, and bubbles in the glass are difficult to eliminate; when total iron (as Fe)2O3Expressed in terms of Fe) is 300ppm to 550ppm, the ratio Redox of the mass of the divalent iron ion to the mass of the total iron ion is 25 to 35%, since the total iron (in terms of Fe)2O3Expressed) the content is relatively increased, Redox can be reduced to 25-35%.
The aluminosilicate glass comprises 150 ppm-550 ppm Fe2O3And is Fe2O3When the mass is 150ppm to 300ppm, the ratio Redox of the mass of the divalent iron ions to the mass of all the iron ions is 35 to 45 percent; fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the ferrous ions to the mass of all the ferrous ions is 25 to 35 percent, so that the heat transfer efficiency of the molten glass in the kiln can be improved while the good transmittance of the glass is ensured, and the clarification of the molten glass is simple.
As is well known to those skilled in the art, the manner of Redox value control may be: controlling the content of reducer (such as carbon powder and sulfide), the ratio of mirabilite to carbon powder, the atmosphere in the furnace, and the melting temperature.
The visible light transmittance Tvis of the aluminosilicate glass is 91.0-100%, preferably 91.0-95.0% under the equivalent thickness of 1.1 mm.
Second, glass plate
The glass sheet in the embodiment of the present invention is one of the aforementioned aluminosilicate glasses, and has the same composition as the aforementioned aluminosilicate glass, and is not described herein again.
Preferably, the thickness of the glass plate is 0.1-1.5 mm. If the thickness of the glass plate is less than 0.1mm, the brittleness of the glass is increased, and the object to be protected is not good; if the thickness is more than 1.5mm, light transmittance may be reduced, and when the glass plate is used as a protective member of a display device, a display effect may be reduced, and the thicker the glass, the greater the influence on the touch feeling of the touch screen.
Preparation method of aluminosilicate glass
The preparation method of the aluminosilicate glass comprises the following steps:
weighing 59-70 wt% of SiO by mass percent based on oxide213 to 23 wt% of Al2O35 to 15 wt% of Na2O, 1 to 7 wt% of K2O, 0 to 0.1 wt% CaO, 1 to 7 wt% MgO, 0.2 to 2 wt% ZrO20 to 4.5 wt% of B2O30 to 4 wt% of Li2O, 150ppm to 550ppm of Fe2O3Forming a batch;
and sequentially mixing, melting, homogenizing, molding and annealing the weighed batch mixture to obtain the aluminosilicate glass. The forming process may be a float process, an overflow process, a downdraw process, or the like.
Wherein, during the melting process, when Fe2O3When the mass is 150ppm to 300ppm, controlling the ratio Redox of the mass of the ferrous ions to the mass of all the ferric ions to be 35 to 45 percent; when Fe2O3When the concentration is 300ppm to 550ppm, the ratio Redox of the mass of the ferrous ions to the mass of all the ferric ions is controlled to be 25 to 35 percent.
As previously mentioned, the manner of Redox value control can be as follows: controlling the content of reducer (such as carbon powder and sulfide), the ratio of mirabilite to carbon powder, the atmosphere in the furnace, and the melting temperature.
The preparation method of the aluminosilicate glass of the invention is characterized in that in the melting process, Fe is used as Fe2O3When the mass is 150ppm to 300ppm, controlling the ratio Redox of the mass of the ferrous ions to the mass of all the ferric ions to be 35 to 45 percent; when Fe2O3When the concentration is 300-550 ppm, the ratio Redox of the mass of the ferrous ions to the mass of all the iron ions is controlled to be 25-35%, the ferrous ions are favorable for heat conduction, and Fe2O3The glass liquid clarifying device is beneficial to clarifying the glass liquid, so that the heat transfer efficiency of the glass liquid in the kiln can be improved while the good transmittance of the glass is ensured, and the clarifying of the glass liquid is simple.