Boron aluminum silicate glass, preparation method thereof, glass product and electronic device

Abstract

The invention relates to the technical field of glass, in particular to boroaluminosilicate glass, a preparation method thereof, a glass product and an electronic device. The boron aluminum silicate glass provided by the invention is prepared from the following chemical components in percentage by mass: 55 percent to 65 percent of SiO2, 5 percent to 10 percent of B2O3, 0.1 percent to 0.9 percent of P2O5, 11 percent to 18 percent of Al2O3, 1 percent to 4 percent of Na2O, 5 percent to 9 percent of MgO, 8 percent to 15 percent of CaO, 0.01 percent to 1.1 percent of La2O3 and 0.005 percent to 0.05 percent of Co2O3. According to the boroaluminosilicate glass provided by the invention, the content of SiO2 and Al2O3 is reduced by finely adjusting the proportion of each oxide composition, so that the melting temperature of the boroaluminosilicate glass is reduced, and the boroaluminosilicate glass provided by the invention has relatively low thermal expansion coefficient and excellent dielectric property.

Description

Technical Field

[0001] The present application relates to the field of glass technology, and in particular to a boroaluminosilicate glass and a preparation method thereof, a glass product, and an electronic device. Background Art

[0002] The fifth generation (5G) and sixth generation (6G) mobile communication systems require high-speed data transmission, low latency, and multi-connection facilities. To achieve high data transmission rates at high frequencies, the use of high frequencies will generate dielectric losses as reverse losses increase. This requires the dielectric glass used as the substrate of communication devices to have lower dielectric constants and dielectric losses in high-frequency bands to meet the requirements. At the same time, the substrate of communication devices also needs to have a low thermal expansion coefficient to meet stability.

[0003] As a common low-dielectric glass, boroaluminosilicate glass has excellent chemical stability and mechanical strength, but its SiO2 and Al2O3 contents are relatively high, resulting in high melting temperatures and poor high-temperature fluidity. In addition, the dielectric constant of boroaluminosilicate glass is generally greater than 5.0, which cannot meet the requirements for glass substrates in 5G mobile communication systems or even 6G mobile communication systems. Summary of the invention

[0004] Based on this, the present application provides a boroaluminosilicate glass and a preparation method thereof, a glass product, and an electronic device. The boroaluminosilicate glass provided by the present application reduces the content of SiO2 and Al2O3 by finely adjusting the ratio between the oxide components, thereby reducing its melting temperature, and the boroaluminosilicate glass provided by the present application has both a low thermal expansion coefficient and excellent dielectric properties.

[0005] In a first aspect of the present application, a boroaluminosilicate glass is provided. The chemical components of the boroaluminosilicate glass include, in mass percentage, 55% to 65% SiO2, 5% to 10% B2O3, 0.1% to 0.9% P2O5, 11% to 18% Al2O3, 1% to 4% Na2O, 5% to 9% MgO, 8% to 15% CaO, 0.01% to 1.1% La2O3, and 0.005% to 0.05% Co2O3.

[0006] In one embodiment, the chemical composition of the boroaluminosilicate glass includes, by mass percentage, 55% to 63% SiO2, 6.5% to 8.5% B2O3, 0.3% to 0.65% P2O5, 12% to 16% Al2O3, 1.5% to 3.5% Na2O, 6% to 8% MgO, 9% to 13% CaO, 0.01% to 0.6% La2O3, and 0.005% to 0.03% Co2O3.

[0007] In one embodiment, the value of (La2O3+Co2O3) / (SiO2+B2O3+P2O5) is 0.0003~0.062 in mass percentage.

[0008] In one embodiment, the sum of the mass percentages of La2O3 and Co2O3 is 0.02% to 0.62% by mass.

[0009] In one embodiment, the boroaluminosilicate glass further comprises the following components, measured by mass percentage: 0.1% to 0.5% of a clarifier;

[0010] Optionally, the clarifier comprises NaCl.

[0011] In one embodiment, the boroaluminosilicate glass has one or more of the following characteristics:

[0012] (1) The dielectric constant of the boroaluminosilicate glass is ≤5.3;

[0013] (2) The dielectric loss of the boroaluminosilicate glass is ≤4.1×10 -3 ;

[0014] (3) The thermal expansion coefficient of the boron aluminosilicate glass in the range of 30°C to 350°C is ≤70×10 -7 ℃ -1 .

[0015] In a second aspect of the present application, a method for preparing boroaluminosilicate glass is provided, comprising the following steps:

[0016] Providing raw materials according to the components of the boroaluminosilicate glass described in any embodiment of the first aspect of the present application, melting the raw materials to prepare a molten liquid;

[0017] The molten liquid is subjected to a molding process to prepare a prefabricated glass;

[0018] The prefabricated glass is annealed to prepare the boroaluminosilicate glass.

[0019] In one embodiment, the preparation method has one or more of the following characteristics:

[0020] (1) The process parameters of the melting treatment include: a melting temperature of 1500°C to 1600°C;

[0021] (2) The process parameters of the annealing treatment include: the annealing temperature is 560°C~620°C.

[0022] The third aspect of the present application provides a glass product obtained by processing the boroaluminosilicate glass as described in any embodiment of the first aspect of the present application.

[0023] In a fourth aspect of the present application, an electronic device is provided, comprising the boroaluminosilicate glass described in any one of the embodiments of the first aspect of the present application or the glass product described in the third aspect of the present application.

[0024] The boroaluminosilicate glass provided in the present application has at least the following beneficial effects:

[0025] The present application regulates the types and mass percentages of glass components, and the components cooperate and work synergistically with each other, which can effectively reduce the content of SiO2 and Al2O3, thereby lowering the melting temperature and ensuring its excellent processability.

[0026] Furthermore, the present application finely adjusts the ratio between each oxide composition so that the various chemical components in the boroaluminosilicate glass cooperate with each other to improve the stability of the frame structure in the glass structure. This stable structure can effectively resist the interference of electric field changes, thereby exhibiting good dielectric properties. At the same time, when the temperature changes, the above-mentioned stable glass structure can also suppress excessive thermal motion of atoms or ions, so that the volume of the glass will not expand significantly due to temperature increase, thereby reducing the thermal expansion coefficient. Therefore, the boroaluminosilicate glass provided by the present application has excellent processability, excellent dielectric properties and a low thermal expansion coefficient. DETAILED DESCRIPTION

[0027] In order to facilitate understanding of the present application, the present application will be described more comprehensively below. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0029] the term

[0030] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0031] Herein, "preferred", "better", "more preferred", and "suitable" are only used to describe implementation methods or examples with better effects, and it should be understood that they do not constitute a limitation on the scope of protection of this application. If multiple "preferred" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "preferred" item is independent.

[0032] In the present application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present application.

[0033] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions of the listed features.

[0034] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for broadly including quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0035] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0036] As the transmission frequency continues to increase, the performance requirements for communication transmission devices are becoming increasingly stringent. At present, communication transmission devices generally use glass as the substrate, which requires the glass substrate to have excellent dielectric properties. Under the action of high-frequency electromagnetic wave fields, low dielectric constant means reduced propagation delay, while low dielectric loss means reduced propagation loss. Therefore, glass needs to have a lower dielectric constant and dielectric loss.

[0037] In addition, due to the energy loss during signal transmission and the heating of electronic components themselves, communication transmission devices will generate heat during operation. Therefore, this requires the glass substrate to have a low thermal expansion coefficient to keep the internal structure of the communication transmission device relatively stable, thereby maintaining the stability of signal transmission.

[0038] At present, the glass used as the base material of communication transmission devices mainly includes the following types: (1) E glass; in terms of mass percentage, the chemical composition of E glass mainly includes: 55% SiO2, 13% Al2O3, 3.5% Na2O, 4% MgO, 19% CaO and 5.5% B2O3. However, the dielectric constant of E glass at 1MHz is 6.1, and the dielectric loss is 38×10 -4 , which can no longer meet the requirements of high-frequency microwave communications. (2) Quartz glass; in terms of mass percentage, the chemical composition of quartz glass mainly includes: 100% SiO2. The dielectric constant of quartz glass at 1MHz is 3.7, and the dielectric loss is 2×10 -4 , which has excellent chemical stability, mechanical properties and low thermal expansion coefficient, but it is difficult to melt, the melting temperature is too high (>1800℃), the melting time is long, and the melting equipment requirements are high. (3) Borosilicate glass. In terms of mass percentage, the chemical components of this glass mainly include: 60%~80% SiO2, 7%~22% B2O3, and 0~13% Al2O3. Among them, the embodiment composition of 75% SiO2, 22% B2O3 and 3% Al2O3 has the lowest dielectric constant and dielectric loss. Its dielectric constant in the 1MHZ frequency band is 3.82 and the dielectric loss is 4.5×10 -4 , but the SiO2 content of this embodiment is relatively high, and its melting temperature is high, making it difficult to prepare. (4) Boroaluminosilicate glass. In terms of mass percentage, the chemical composition of this glass mainly includes: 48%~57% SiO2, 15%~26% B2O3, 12~18% Al2O3, 0.25%~7% CaO, 0~8% P2O5, 0~5% MgO, and 0~6% TiO2. Its dielectric constant in the 1MHZ frequency band is 4.22~4.56, and its dielectric loss is 18~25×10 -4 However, too much B2O3 is added, resulting in poor uniformity of the low dielectric constant glass fiber component, which affects other properties such as heat resistance.

[0039] The present application aims to solve the following problems existing in glass substrates of traditional communication transmission devices: first, the problem of excessive dielectric constant and dielectric loss in high frequency bands; second, the temperature at which the thermal expansion coefficient of the glass substrate is relatively large; and third, the problem of high melting temperature and inconvenient processing.

[0040] Based on this, in the first aspect of the present application, a boroaluminosilicate glass is provided. The chemical components of the boroaluminosilicate glass include, in mass percentage: 55%~65% SiO2, 5%~10% B2O3, 0.1%~0.9% P2O5, 11%~18% Al2O3, 1%~4% Na2O, 5%~9% MgO, 8%~15% CaO, 0.01%~1.1% La2O3, and 0.005%~0.05% Co2O3.

[0041] The present application regulates the types and mass percentages of the glass components, and the various components cooperate and synergize with each other, which can effectively reduce the content of SiO2 and Al2O3, thereby reducing its melting temperature and ensuring its excellent processability. Furthermore, the present application finely adjusts the ratio between the oxide compositions so that the various chemical components in the boroaluminosilicate glass cooperate with each other to improve the stability of the frame structure in the glass structure. This stable structure can effectively resist the interference of electric field changes, thereby showing good dielectric properties. At the same time, when the temperature changes, the above-mentioned stable glass structure can also suppress the excessive thermal motion of atoms or ions, so that the volume of the glass will not expand significantly due to the increase in temperature, so as to reduce the thermal expansion coefficient. Therefore, the boroaluminosilicate glass provided by the present application has excellent processability, excellent dielectric properties and a low thermal expansion coefficient.

[0042] Specifically, SiO2 constitutes the main body of the glass network, and its stable silicon-oxygen tetrahedral structure helps to reduce the thermal expansion coefficient and provide good dielectric insulation performance; B2O3 and P2O5 can synergistically change and optimize the network structure of the glass, and the formation of the glass structure is conducive to reducing the thermal expansion coefficient and has a positive effect on the dielectric properties. Al2O3 plays a role in strengthening the network structure in the glass, improves the chemical stability of the glass, and helps to reduce the thermal expansion coefficient. By accurately regulating the aforementioned chemical components, the content of alkali metal oxides such as Na2O in the present application is reduced, thereby reducing the adverse effects of alkali metal ion migration on dielectric properties. Further, the addition of La2O3 and Co2O3 can further modify the microstructure of the glass, so that the network structure of the glass can effectively reduce the degree of deformation of the electron cloud under the action of the external electric field under the action of the electric field. Therefore, the chemical components at a specific mass percentage cooperate with each other, so that the boron aluminosilicate glass exhibits excellent dielectric properties and a lower thermal expansion coefficient.

[0043] It is understandable that in the present application, the mass percentage of SiO2 can be selected from any value between 55% and 65%. For example, the mass percentage of SiO2 includes but is not limited to 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64% or 65%, or a range consisting of any two of the above point values ​​as endpoint values.

[0044] SiO2 is the main component of boroaluminosilicate glass. In the glass structure, silicon atoms (Si) and oxygen atoms (O) exist in the form of silicon-oxygen tetrahedrons (SiO4). The silicon-oxygen tetrahedrons are interconnected by oxygen atoms sharing vertices to form a three-dimensional network structure, which provides basic mechanical strength and stability for the glass. This application limits the mass percentage of SiO2 to 55% to 65%. At this time, the silicon-oxygen tetrahedrons formed can effectively limit the movement of ions inside the glass to avoid the dielectric loss caused by the migration of ions under the action of the electric field to generate the conduction current. In addition, the silicon-oxygen bond has a high bond energy, and the polarization degree of the chemical bond is relatively low under the action of the electric field, which can effectively avoid the dielectric loss caused by the polarization of the dielectric. Therefore, this application limits the mass percentage of SiO2 to 55% to 65%, which can effectively avoid the problems of low silicon-oxygen tetrahedron content and incomplete glass network caused by low SiO2 content, and can effectively inhibit the migration and polarization of ions and avoid the increase of dielectric loss. At the same time, this mass percentage can also avoid the problem of significantly increased difficulty in melting and forming the glass caused by excessively high SiO2 content.

[0045] It is understandable that in the present application, the weight fraction of B2O3 can be selected from any value between 5% and 10%. For example, the weight fraction of B2O3 includes but is not limited to 5%, 5.3%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.8%, 7%, 7.3%, 7.5%, 7.8%, 8%, 8.3%, 8.5%, 8.8%, 9%, 9.2%, 9.5%, 9.8% or 10%, or any two of the above points as the range of endpoint values.

[0046] B2O3 plays a structural modification role in boroaluminosilicate glass. Boron atoms (B) can enter the glass network structure, and they usually exist in the form of triangles (BO3); this triangular structure can be interwoven with silicon-oxygen tetrahedrons to fill the gaps in the network and further optimize the network structure of the glass. This tight structure can effectively limit the movement of ions inside the glass, thereby reducing the dielectric loss caused by ion migration. The present application limits the weight fraction of B2O3 to 5%~10%, which can effectively avoid the shortcomings caused by too high or too low B2O3 content. Specifically, if the weight fraction of B2O3 is too high, the network structure of the glass will be excessively changed, and the structure of the glass may become too loose. This is mainly because if there are too many triangular structures of B2O3, the tight network structure originally based on silicon-oxygen tetrahedrons will be destroyed, thereby increasing the thermal expansion coefficient of the glass, which is not conducive to its use in application scenarios such as communication transmission devices with high requirements for temperature stability. If the weight fraction of B2O3 is too low, it cannot optimize the network structure based on silicon-oxygen tetrahedron, and thus the limiting effect on ion migration is insufficient, resulting in increased dielectric loss and failure to meet the requirements of communication transmission devices for low dielectric loss.

[0047] It can be understood that in the present application, the mass percentage of P2O5 can be selected from any value between 0.1% and 0.9%. For example, the mass percentage of P2O5 includes but is not limited to 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85% or 0.9%, or any two of the above points as the range of endpoint values.

[0048] P2O5 plays a variety of important roles in boroaluminosilicate glass. From the perspective of glass structure, P2O5 can enter the glass network structure. Phosphorus atoms (P) usually exist in the form of phosphorus oxygen tetrahedrons (PO4), which can interact with silicon oxygen tetrahedrons (SiO4) and boron oxygen triangles (BO3) to make the glass network structure more complex and stable; at the same time, it can fill some gaps in the network to further enhance the overall structural strength of the glass. In addition, an appropriate amount of P2O5 can also improve the melting performance, so that the glass raw materials can be better melted and mixed evenly. When the P2O5 content is too high, too much phosphorus oxygen tetrahedron will destroy the network structure of the glass, resulting in an increase in the thermal expansion coefficient of the glass and a reduction in the thermal stability of the glass. If the P2O5 content is too low, its strengthening effect on the glass network structure will be very limited, and the dielectric constant and dielectric loss of the glass will increase significantly.

[0049] It is understandable that in the present application, the mass percentage of Al2O3 can be selected from any value between 11% and 18%. For example, the mass percentage of Al2O3 includes but is not limited to 11%, 11.3%, 11.4%, 11.42%, 11.44%, 11.45%, 11.5%, 11.8%, 12%, 12.3%, 12.5%, 12.7%, 13%, 13.3%, 13.5%, 13.8%, 14%, 14.3%, 14.5%, 14.8%, 15%, 15.3%, 15.5%, 15.8%, 16%, 16.3%, 16.5%, 16.8%, 17%, 17.3%, 17.5% or 18%, or any two of the above points are used as endpoint values.

[0050] In the glass structure, Al2O3 can enter the glass network structure, and aluminum atoms (Al) can exist in the form of aluminum oxide tetrahedrons (AlO4), which are interconnected with silicon oxide tetrahedrons (SiO4), playing a role in strengthening the network structure, making the structure of the glass more compact and stable, thereby helping to reduce the thermal expansion coefficient of the glass, making the volume change of the glass smaller when the temperature changes, and having better thermal stability. In terms of dielectric properties, Al2O3 can not only strengthen the network structure of the glass, but its aluminum oxide tetrahedron structure can also limit the migration of ions, thereby reducing the dielectric loss caused by ion migration. When the Al2O3 content is low, the aluminum oxide tetrahedron network structure formed is insufficient, the glass strength will be reduced, and it will also cause the glass to separate into silicon-rich and boron-rich phases.

[0051] It is understandable that in the present application, the mass percentage of Na2O can be selected from any value between 1% and 4%. For example, the mass percentage of Na2O includes but is not limited to 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.8% or 4%, or any two of the above points as the range of endpoint values.

[0052] Na2O plays a major role in melting and modifying boroaluminosilicate glass. In the glass preparation process, Na2O can lower the melting temperature of glass, making it easier for glass raw materials to melt and mix evenly at a lower temperature, which helps to reduce energy consumption in the production process. In terms of glass structure modification, the sodium ions (Na + ) can enter the glass network structure and play a role in breaking the network. It will break some silicon-oxygen bonds (Si-O) and change the network structure of the glass, thereby adjusting the physical properties of the glass to a certain extent, such as reducing the viscosity of the glass and making the glass have better fluidity during the molding process.

[0053] It can be understood that the mass percentage of MgO can be selected from any value between 5% and 9%. For example, the mass percentage of MgO is 5%, 5.5%, 5.7%, 6%, 6.2%, 6.3%, 6.5%, 6.6%, 6.8%, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8% or 9%, or in the range consisting of any two of the above-mentioned points as endpoint values.

[0054] As a network external oxide, MgO has many important characteristics and functions. It can effectively reduce the melting point of glass and reduce the viscosity of glass under high temperature environment. At the same time, MgO can also strengthen the stability of the glass network space and reduce the thermal expansion coefficient of glass within a certain range. However, if its content is too high, it will cause the glass network to break, which will lead to the deterioration of the dielectric properties of the glass.

[0055] It is understandable that the mass percentage of CaO can be selected from any value between 8% and 15%. For example, the mass percentage of CaO includes but is not limited to 8%, 8.5%, 8.8%, 8.9%, 9%, 9.3%, 9.4%, 9.5%, 9.8%, 10%, 10.2%, 10.5%, 10.8%, 11%, 11.2%, 11.5%, 11.8%, 12%, 12.2%, 12.5%, 12.8%, 13%, 13.2%, 13.5%, 13.8%, 14%, 14.2%, 14.5%, 14.8% or 15%, or any two of the above points are used as endpoints.

[0056] The calcium ions in CaO can act as network exosome ions and enter the gaps in the glass network structure. It can balance the charge and fill the vacancies, making the glass structure more stable. However, excessive CaO content will cause the glass network to break, affecting its weather resistance and deteriorating dielectric properties.

[0057] It is understandable that the mass percentage of La2O3 can be selected from any value between 0.01% and 1.1%. For example, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.17%, 0.19%, 0.2%, 0.22%, 0.25%, 0.28%, 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48%, 0.5%, 0.52%, 0.53%, 0.55%, 0.58%, 0.6%, 0.62%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%, 1.03%, 1.05%, 1.08% or 1.1%, or any two of the above points as the range of endpoints.

[0058] La in La2O3 3+ Ions with large radius and high charge number will produce strong ion polarization under the action of electric field. This polarization will deform the surrounding electron cloud, thereby reducing the propagation and effect of the electric field in the glass, resulting in a decrease in the dielectric constant.

[0059] It can be understood that the mass percentage of Co2O3 can be selected from 0.005%, 0.008%, 0.01%, 0.012%, 0.015%, 0.018%, 0.02%, 0.023%, 0.025%, 0.028%, 0.03%, 0.033%, 0.035%, 0.038%, 0.04%, 0.043%, 0.045%, 0.048% or 0.05%, or within the range consisting of any two of the above point values ​​as endpoint values.

[0060] The cobalt ions in Co2O3 can enter the glass network structure and play a certain role in modification. Although its content is very small, it can affect the local structure of the glass network and improve the stability of the glass to a certain extent. At the same time, an appropriate amount of Co2O3 will also participate in the regulation of the electromagnetic properties of the glass to synergistically reduce the dielectric loss of the glass.

[0061] The present application has found that the content of chemical components in boroaluminosilicate glass has a great influence on its dielectric properties and thermal expansion coefficient. Because the content of various chemical components in the glass is different, the number and migration characteristics of mobile ions will be different. When ions are easy to migrate under the action of an electric field, this will increase the dielectric loss. At the same time, the polarizable components in the glass components are also different, which leads to different dielectric losses.

[0062] Furthermore, the chemical composition of the boroaluminosilicate glass includes, by mass percentage, 55% to 63% SiO2, 6.5% to 8.5% B2O3, 0.3% to 0.65% P2O5, 12% to 16% Al2O3, 1.5% to 3.5% Na2O, 6% to 8% MgO, 9% to 13% CaO, 0.01% to 0.6% La2O3, and 0.005% to 0.03% Co2O3.

[0063] The present application finds that when the chemical components of boroaluminosilicate glass are selected from the above-mentioned mass percentages, the synergistic effect between the components is better, and glass with lower dielectric loss, lower dielectric constant and lower thermal expansion coefficient can be obtained, which can be effectively applied to the fifth generation wireless communication technology.

[0064] In one example, in terms of mass percentage, the value of (La2O3+Co2O3) / (SiO2+B2O3+P2O5) is 0.0003-0.062. For example, the value of (La2O3+Co2O3) / (SiO2+B2O3+P2O5) includes, but is not limited to, 0.0003, 0.0004, 0.0005, 0.0008, 0.001, 0.002, 0.003, 0.004, 0.0042, 0.0045, 0.0048, 0.005, 0.051, 0.052, 0.0053, 0.0054, 0.0055, 0.0058, 0.006, 0.0061 or 0.0062, or a range formed by any two of the above point values ​​as endpoint values.

[0065] In one of the examples, the sum of the mass percentages of La2O3 and Co2O3 is 0.02% to 0.62% by mass.

[0066] The combined effect of La2O3 and Co2O3 helps the glass resist the erosion of chemicals, prolongs the service life of the glass, and can also maintain a good balance in dielectric properties to a certain extent. For example, the sum of the mass percentages of La2O3 and Co2O3 includes, but is not limited to, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.28%, 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48%, 0.5%, 0.52%, 0.55%, 0.58%, 0.59%, 0.6%, 0.61% or 0.62%, or any two of the above points as endpoint values.

[0067] In one example, the boroaluminosilicate glass further includes the following components by mass percentage: 0.1% to 0.5% of a clarifier.

[0068] Clarifiers can remove bubbles in the glass melt, reduce defects in the glass, and make the structure of the glass more uniform and dense.

[0069] Optionally, the clarifier comprises NaCl.

[0070] In one example, the dielectric constant of the boroaluminosilicate glass is ≤5.3. Furthermore, the dielectric constant of the boroaluminosilicate glass is 4.2-5.3. For example, the dielectric constant of the boroaluminosilicate glass includes but is not limited to 4.2, 4.25, 4.3, 4.35, 4.4, 4.45, 4.5, 4.55, 4.6, 4.65, 4.7, 4.75, 4.8, 4.85, 4.9, 4.95, 5, 5.05, 5.1, 5.15, 5.2, 5.25 or 5.3, or any two of the above points are used as endpoint values. It can be understood that the dielectric constants mentioned in this application are measured under 1MHz conditions.

[0071] The boroaluminosilicate glass of the present application has a low dielectric constant, which can effectively increase the signal transmission speed and reduce the transmission delay of high-frequency signals.

[0072] In one example, the dielectric loss of the boroaluminosilicate glass is ≤4.1×10 -3 Low dielectric loss means that during signal transmission, the glass can greatly reduce the dissipation of electromagnetic energy, which is extremely critical for 5G high-frequency signal transmission. It can be understood that the dielectric loss mentioned in this application is measured under 1MHz conditions.

[0073] Furthermore, the dielectric loss of the boroaluminosilicate glass is (3.3-4.1)×10 -3 For example, the dielectric loss of boroaluminosilicate glass includes, but is not limited to, 3.3×10 -3 , 3.4×10 -3 , 3.5×10 -3 , 3.6×10 -3 , 3.7×10 -3 , 3.8×10 -3 , 3.9×10 -3 , 4×10 -3 or 4.1×10 -3 , or within the range formed by any two of the above point values ​​as endpoint values.

[0074] In one example, the thermal expansion coefficient of the boroaluminosilicate glass in the range of 30°C to 350°C is ≤70×10 -7 ℃ -1 .

[0075] Furthermore, the thermal expansion coefficient of the boron aluminosilicate glass in the range of 30°C to 350°C is (58-70)×10 -7 ℃ -1 For example, the thermal expansion coefficient of the borosilicate glass in the range of 30°C to 350°C includes but is not limited to 58×10 -7 ℃-1 59×10 -7 ℃ -1 , 60×10 -7 ℃ -1 ,61×10 -7 ℃ -1 , 62×10 -7 ℃ -1 , 63×10 -7 ℃ -1 , 64×10 -7 ℃ -1 , 65×10 -7 ℃ -1 , 66×10 -7 ℃ -1 , 67×10 -7 ℃ -1 , 68×10 -7 ℃ -1 ,69×10 -7 ℃ -1 or 70×10 -7 ℃ -1 , or within the range formed by any two of the above point values ​​as endpoint values.

[0076] In a second aspect of the present application, a method for preparing boroaluminosilicate glass is provided, comprising the following steps:

[0077] Providing raw materials according to the components of the boroaluminosilicate glass described in any example of the first aspect of the present application, melting the raw materials to prepare a molten liquid;

[0078] The molten liquid is subjected to a molding process to prepare a prefabricated glass;

[0079] The prefabricated glass is annealed to prepare the boroaluminosilicate glass.

[0080] In one example, the process parameters of the melting process include: a melting temperature of 1500° C. to 1600° C. For example, the melting temperature includes 1500° C., 1530° C., 1550° C., 1560° C., 1580° C. or 1600° C., or a range consisting of any two of the above point values ​​as endpoint values.

[0081] Furthermore, the melting time is 4 hours to 8 hours. For example, the melting time includes but is not limited to 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, or a range formed by any two of the above points as endpoint values.

[0082] The present invention can effectively reduce the content of silicon dioxide based on the precise control of the chemical components of each oxide, thereby reducing its melting temperature, which is lower than 1650°C of the traditional technology.

[0083] In one example, the process parameters of the annealing treatment include: an annealing temperature of 560° C. to 620° C. For example, the annealing temperature includes but is not limited to 560° C., 570° C., 580° C., 590° C., 600° C., 610° C. or 620° C., or a range formed by any two of the above point values ​​as endpoint values.

[0084] The third aspect of the present application provides a glass product obtained by processing the boroaluminosilicate glass as described in any example of the first aspect of the present application.

[0085] In a fourth aspect of the present application, an electronic device is provided, comprising the boroaluminosilicate glass described in any example of the first aspect of the present application or the glass product described in the third aspect of the present application.

[0086] In order to make it easier to understand and implement the present invention, the following more specific and detailed embodiments and comparative examples which are easier to implement are provided as references.

[0087] Unless otherwise specified, the raw materials used in the following tests can be purchased from the market. The performance test methods are as follows:

[0088] Test method:

[0089] Thermal properties: The glass samples were subjected to high temperature viscosity test using the high temperature viscometer of ORTON, USA, to obtain the temperature-viscosity curve data, and the viscosity-temperature fitting curve within the glass float forming temperature range was obtained to determine the glass melting temperature T m (10 2.0 dPa.s). The thermal expansion performance test was carried out according to GB / T16920-2015, using the PC402L horizontal expansion instrument from NETZSCH of Germany to obtain the thermal expansion coefficient CTE (50-300°C) and transition temperature Tg.

[0090] Dielectric properties: Referring to the test method in ASTM-D150-18, the glass to be tested was processed into a rectangular sheet sample of 10.16 mm × 22.86 mm × 1 mm. The dielectric constant and dielectric loss of the glass sample at a frequency of 10 GHz were measured using a PNA-N5234A vector network analyzer and a waveguide method.

[0091] The chemical components of the boroaluminosilicate glass in the examples and comparative examples of the present application are shown in Tables 1 to 3. The preparation method of the boroaluminosilicate glass in the examples and comparative examples includes the following steps:

[0092] Provide raw materials according to the components of boroaluminosilicate glass, stir and mix the raw materials thoroughly; place the mixed materials in a crucible for melting treatment at 1500°C to 1600°C, and the melting and clarification time is 4 to 8 hours; prepare a molten liquid. Cast the molten liquid into a mold to prepare a prefabricated glass. Place the prefabricated glass in an annealing furnace for annealing at a temperature of 560 to 620°C to obtain boroaluminosilicate glass.

[0093] Table 1 Glass composition and properties of Examples 1 to 7

[0094]

[0095] Table 2 Glass properties and performance of Examples 8 to 16

[0096]

[0097] Table 3 Glass properties and performance of Comparative Examples 1 to 5

[0098]

[0099] There is no P2O5, Co2O3, or La2O3 in Comparative Example 1. The dielectric constant of the boroaluminosilicate glass in Comparative Example 1 is 6.8 at 1MHZ, which cannot meet the requirements of high-frequency microwave communication. In Comparative Example 2, Na2O is too high, which causes the glass to become devitrified and has poor uniformity, affecting the performance of the product. In Comparative Example 3, Na2O is too high, the thermal expansion coefficient is too high, and the dielectric constant and dielectric loss are too high, which cannot meet the requirements of high-frequency microwave communication. In Comparative Example 4, La2O3 is too high, the glass becomes devitrified, has poor uniformity, and the high content of high-field-strength ions will increase the melting temperature, increase the difficulty of production, and is not easy to prepare. In Comparative Example 5, Co2O3 is too high, the glass is darker in color, and the color is dark blue, which does not meet the requirements for preparing a transparent substrate.

[0100] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0101] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A boroaluminosilicate glass, characterized in that: The chemical composition of the boroaluminosilicate glass includes, in percentage by mass, 55% to 65% SiO2, 5% to 10% B2O3, 0.1% to 0.9% P2O5, 11% to 18% Al2O3, 1% to 4% Na2O, 5% to 9% MgO, 8% to 15% CaO, 0.01% to 1.1% La2O3, and 0.005% to 0.05% Co2O3.

2. The boroaluminosilicate glass according to claim 1, characterized in that: The chemical components of the boroaluminosilicate glass include, in percentage by mass, 55% to 63% SiO2, 6.5% to 8.5% B2O3, 0.3% to 0.65% P2O5, 12% to 16% Al2O3, 1.5% to 3.5% Na2O, 6% to 8% MgO, 9% to 13% CaO, 0.01% to 0.6% La2O3, and 0.005% to 0.03% Co2O3.

3. The boroaluminosilicate glass according to claim 1 or 2, characterized in that: In terms of mass percentage, the value of (La2O3+Co2O3) / (SiO2+B2O3+P2O5) is 0.0003~0.

062.

4. The boroaluminosilicate glass according to claim 1 or 2, characterized in that: In terms of mass percentage, the sum of the mass percentages of La2O3 and Co2O3 is 0.02%~0.62%.

5. The boroaluminosilicate glass according to claim 1 or 2, characterized in that: The boron aluminosilicate glass further comprises the following components by mass percentage: 0.1% to 0.5% of a clarifier; Optionally, the clarifier comprises NaCl.

6. The boroaluminosilicate glass according to claim 1 or 2, characterized in that: The boroaluminosilicate glass has one or more of the following characteristics: (1) The dielectric constant of the boroaluminosilicate glass is ≤5.3; (2) The dielectric loss of the boroaluminosilicate glass is ≤4.1×10 -3 ; (3) The thermal expansion coefficient of the boron aluminosilicate glass in the range of 30°C to 350°C is ≤70×10 -7 ℃ -1 .

7. A method for preparing boroaluminosilicate glass, characterized in that: The following steps are involved: Providing raw materials according to the components of the boroaluminosilicate glass according to any one of claims 1 to 6, melting the raw materials to prepare a molten liquid; The molten liquid is subjected to a molding process to prepare a prefabricated glass; The prefabricated glass is annealed to prepare the boroaluminosilicate glass.

8. The method for preparing boroaluminosilicate glass according to claim 7, characterized in that: The preparation method has one or more of the following characteristics: (1) The process parameters of the melting treatment include: a melting temperature of 1500°C to 1600°C; (2) The process parameters of the annealing treatment include: the annealing temperature is 560°C~620°C.

9. A glass product, characterized in that: Obtained by processing the boroaluminosilicate glass according to any one of claims 1 to 6.

10. An electronic device, characterized in that: The boroaluminosilicate glass comprising any one of claims 1 to 6 or the glass product comprising claim 9.

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