CN116023024A - High-alumina silicate glass and preparation method and application thereof - Google Patents
High-alumina silicate glass and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides high-alumina silicate glass, and a preparation method and application thereof. The high aluminosilicate glass comprises: 55mol% to 72mol% of SiO 2 8mol% to 25mol% of Al 2 O 3 0.1mol% to 10mol% of B 2 O 3 3 to 15mol% of Na 2 O,3mol% to 15mol% of Li 2 O,0mol% to 5mol% of K 2 O, mgO+CaO+SrO+BaO in an amount of 0-15 mol%, znO in an amount of 0-5mol%, and P in an amount of 0.01-5 mol% 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the mole percentage of each component is substituted into a formula to calculate and obtain a dielectric factor Y= (SiO) 2 +B 2 O 3 )/(Na 2 O+Li 2 O+K 2 O+P 2 O 5 ) X (MgO+ZnO) and satisfies 0.5.ltoreq.Y.ltoreq.5.5. The high-alumina silicate glass provided by the invention has the advantages of low dielectric constant and low dielectric loss, can reduce the loss of 5G high-frequency signals, has excellent mechanical property after strengthening, can well protect 5G communication equipment, and has the advantages of low liquidus temperature and high matching degree with a production process. Therefore, the aluminosilicate reinforced glass prepared by the invention can be used as the protective glass of various intelligent mobile equipment and other fields of chemically reinforced glass materials requiring excellent mechanical properties.
Description
Technical Field
The invention belongs to the field of glass products, and particularly relates to high-alumina silicate glass, and a preparation method and application thereof.
Background
With the rapid development of 5G communication technology, information transmission is moving toward higher speed and higher frequency. Smart phones, smart wearable devices and tablet computers are moving towards thinner and higher functional trends while bringing convenience to life of people. Under such a trend, a higher requirement is put on cover plate protection glass of the intelligent device. In the field of display screen protective glass, high-alumina silicate electronic glass subjected to chemical strengthening is generally adopted, and the glass subjected to chemical strengthening treatment has excellent anti-drop and scratch resistance; meanwhile, a protective glass for a high-frequency wireless communication device is required to have a low dielectric constant and dielectric loss to increase a signal transmission speed, reduce loss of a signal, and prevent distortion of a communication signal. Therefore, high aluminosilicate glass having a low dielectric constant and dielectric loss is a preferred cover plate protection material in the 5G communications era.
High aluminosilicate glasses typically contain a certain amount of Li 2 O、Na 2 O, but will cause the glass to exhibit a high dielectric constant and loss. Commonly used lowering of glass dielectric constantThe number and dielectric loss are achieved by introducing ZrO 2 By reacting it with SiO 2 Reaction to produce ZrSi with low dielectric constant x O y But ZrO 2 The melting of the glass can become difficult and the devitrification tendency of the glass can be exacerbated. That is, the existing cover glass is difficult to simultaneously satisfy the characteristics of good mechanical properties, small dielectric constant, low dielectric loss and high matching degree of the production process, and cannot satisfy the high requirements of the 5G communication equipment protection glass.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides high aluminosilicate glass. The glass has low dielectric constant and low dielectric loss, can reduce the loss of 5G high-frequency signals, has excellent mechanical property after strengthening, can well protect 5G communication equipment, and has the advantages of low liquidus temperature and high matching degree with a production process. The specific contents are as follows:
in a first aspect, the present invention provides a high aluminosilicate glass comprising, in mole percent: 55mol% to 72mol% of SiO 2 8mol% to 25mol% of Al 2 O 3 0.1mol% to 10mol% of B 2 O 3 3 to 15mol% of Na 2 O,3mol% to 15mol% of Li 2 O,0mol% to 5mol% of K 2 O, mgO+CaO+SrO+BaO in an amount of 0-15 mol%, znO in an amount of 0-5mol%, and P in an amount of 0.01-5 mol% 2 O 5 ；
Wherein, the mole percentage of each component is substituted into a formula to calculate and obtain a dielectric factor Y= (SiO) 2 +B 2 O 3 )/(Na 2 O+Li 2 O+K 2 O+P 2 O 5 ) X (MgO+ZnO) and satisfies 0.5.ltoreq.Y.ltoreq.5.5.
In some embodiments, the molar percentages of the components are calculated by substituting the molar percentages into the formula to yield the production factor x= (Na) 2 O+Li 2 O+K 2 O)×P 2 O 5 /(SiO 2 +Al 2 O 3 ) And X is more than or equal to 0.1 and less than or equal to 0.6.
In some embodiments, the mole percentages of the components are calculated by substituting the formula to give 1.ltoreq.Li 2 O+Na 2 O+K 2 O)/Na 2 O≤3，20≤(SiO 2 +Al 2 O 3 )/P 2 O 5 ≤160。
In some embodiments, the strengthening parameter Z of the high aluminosilicate glass ranges from 1.5 to 8.2 in mole percent;
Z＝(Al 2 O 3 +B 2 O 3 +P 2 O 5 )/(RO+ZnO)/Na 2 o, where ro=
MgO+CaO+SrO+BaO。
In some embodiments, the high aluminosilicate glass further comprises a fining agent; the content of clarifying agent is not more than 1mol% in terms of mole percent.
In some embodiments, the fining agent is at least one of a sulfate, nitrate, halide, tin oxide, and stannous oxide.
In some embodiments, the lithium aluminosilicate glass has a dielectric loss of 4.3X10 at 3GHz at room temperature -3 ～7.2×10 -3 The dielectric constant is 4.85-6.38.
In some embodiments, the glass surface after strengthening has a compressive stress of 850MPa or more and a Vickers hardness of 620kgf/mm or more 2 . For example, the surface compressive stress may be 850MPa, 995MPa, 1022MPa, 1032MPa, 1056MPa, 1078MPa, 1101MPa, and the Vickers hardness may be 620kgf/mm 2 、634kgf/mm 2 、659kgf/mm 2 、668kgf/mm 2 、672kgf/mm 2 。
In a second aspect, the present invention provides a method of preparing the high aluminosilicate glass of the first aspect, the method comprising:
fully stirring and mixing the raw materials according to the formula proportion to obtain a batch mixture;
melting the batch mixture at a high temperature;
casting the melted mixture into a mould, and annealing to obtain a glass raw sheet;
carrying out mechanical processing treatment on the glass raw sheet to obtain a glass product;
and carrying out chemical strengthening treatment on the glass product.
In a third aspect, the present invention provides the use of a high aluminosilicate glass as described in the first aspect above. Specifically, the application is: the high aluminosilicate glass is applied to cover glass of electronic products.
The invention provides high-alumina silicate glass, and a preparation method and application thereof. The high aluminosilicate glass comprises: 55mol% to 72mol% of SiO 2 8mol% to 25mol% of Al 2 O 3 0.1mol% to 10mol% of B 2 O 3 3 to 15mol% of Na 2 O,3mol% to 15mol% of Li 2 O,0mol% to 5mol% of K 2 O, mgO+CaO+SrO+BaO in an amount of 0-15 mol%, znO in an amount of 0-5mol%, and P in an amount of 0.01-5 mol% 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the mole percentage of each component is substituted into a formula to calculate and obtain a dielectric factor Y= (SiO) 2 +B 2 O 3 )/(Na 2 O+Li 2 O+K 2 O+P 2 O 5 ) X (MgO+ZnO) and satisfies 0.5.ltoreq.Y.ltoreq.5.5. The high-alumina silicate glass provided by the invention has the advantages of low dielectric constant and low dielectric loss, can reduce the loss of 5G high-frequency signals, has excellent mechanical property after strengthening, can well protect 5G communication equipment, and has the advantages of low liquidus temperature and high matching degree with a production process. Therefore, the aluminosilicate reinforced glass prepared by the invention can be used as the protective glass of various intelligent mobile equipment and other fields of chemically reinforced glass materials requiring excellent mechanical properties.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof. The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The embodiment of the invention provides high aluminosilicate glass with low dielectric constant and low dielectric loss. The specific contents are as follows:
in a first aspect, embodiments of the present invention provide a high aluminosilicate glass comprising, in mole percent: 55mol% to 72mol% of SiO 2 8mol% to 25mol% of Al 2 O 3 0.1mol% to 10mol% of B 2 O 3 3 to 15mol% of Na 2 O,3mol% to 15mol% of Li 2 O,0mol% to 5mol% of K 2 O, mgO+CaO+SrO+BaO in an amount of 0-15 mol%, znO in an amount of 0-5mol%, and P in an amount of 0.01-5 mol% 2 O 5 ；
Wherein, the mole percentage of each component is substituted into a formula to calculate and obtain a dielectric factor Y= (SiO) 2 +B 2 O 3 )/(Na 2 O+Li 2 O+K 2 O+P 2 O 5 ) X (MgO+ZnO) and satisfies 0.5.ltoreq.Y.ltoreq.5.5.
In the embodiment, the proportion of each oxide is limited to improve the dielectric property of the high-alumina silicate glass, and the cooperation of the components ensures that the high-alumina silicate glass has lower dielectric constant and dielectric loss on the premise of having excellent mechanical property. In particular, the preferred range of the dielectric factor Y is 4.8.gtoreq.Y.gtoreq.0.7.
In this embodiment, siO 2 As a component necessary for constituting the network structure, the addition thereof can improve the heat resistance and chemical durability of the glass, so that the glass can obtain higher strain point and strength, while too little SiO 2 The main network structure of the glass is deteriorated, the dielectric constant of the glass is increased, the mechanical property and the heat resistance are deteriorated, and excessive SiO is produced 2 The melting temperature is increased, the brittleness is increased, and the production process is excessively high, and meanwhile, the ion exchange is not beneficial to the chemical strengthening, and the efficiency of the chemical strengthening is affected. Therefore, in order to further improve the comprehensive properties of the glass produced, it is preferable that 55mol% or less of SiO in terms of mole percent 2 Less than or equal to 72mol percent. Further preferably, in molesThe mol percent is 57mol percent or less than or equal to SiO 2 ≤68mol％。
In this embodiment, al 2 O 3 The glass has the advantages that the glass has high rigidity, the brittleness of the glass is increased, the glass has short material property, the forming becomes difficult, and meanwhile, the glass is easy to devitrify, the high-temperature surface tension and the high-temperature viscosity are overlarge, so that the difficulty of the glass production process is increased. Al (Al) 2 O 3 The volume of the aluminum oxide tetrahedron formed in the glass is larger than that of the silicon oxide tetrahedron in the glass, and the volume of the glass is expanded, so that the density of the glass is reduced, a strengthening channel is provided for the glass in the ion strengthening process, the ion strengthening is promoted, but the dielectric constant of the glass is increased. When the content is too small, the space between glass networks becomes small, which is unfavorable for ion exchange and reduces the efficiency of chemical strengthening. Taken together, al, calculated as oxide, based on the molar mass of the composition 2 O 3 The content of (2) is in the range of 8mol% to 25 mol%. Further preferably, 10.5mol% or less of Al in terms of mole percent 2 O 3 ≤19.5mol％。
In this embodiment, B 2 O 3 As the formed oxide of the glass, the glass can be independently formed, the addition of the oxide can enhance the chemical stability and mechanical property of the glass, reduce the thermal expansion coefficient of the glass, reduce the dielectric constant of the glass, and accelerate the ion exchange process, B 2 O 3 Is also a good fluxing agent, can greatly reduce the glass melting temperature, and is beneficial to the vitrification process. But B is 2 O 3 When the content is too high, abnormal phenomena can occur, so that the heat resistance and the ion exchange capacity of the glass are obviously reduced. Comprehensively considering, based on the molar mass of the composition, B, calculated as oxide 2 O 3 The content of (C) is in the range of 0.1mol% to 10 mol%. Further preferably, 0.5mol% or less of B in terms of mole mass percent 2 O 3 ≤5.7mol％。
The implementation isIn the example, P 2 O 5 It is made of [ PO 4 ]The tetrahedrons are connected with each other to form a network, so that the glass network structure is in a loose state, and the network gaps become larger, thereby being beneficial to Na in the glass + K in ions and fused salts + Ion interdiffusion and ion strengthening play a role in promoting the glass strengthening process and play an important role in obtaining a higher compressive stress layer, but the dielectric constant of the glass is increased. Therefore, it is preferable that the content of the catalyst is 0.01mol% in terms of mole mass percent<P 2 O 5 Less than or equal to 5mol percent. Further preferably, 0.15mol% or less of P in terms of mole mass percent 2 O 5 ≤3.2mol％。
In this embodiment, li 2 O belongs to one of essential components of the base glass and belongs to an external network component, so that the viscosity of the glass can be obviously reduced, the melting difficulty of the glass is reduced, and meanwhile, the O is taken as the main component of ion exchange and is proper in Li 2 O can obviously improve the mechanical strength and the surface hardness of the glass and improve the ion exchange rate. During the strengthening process, naNO in molten salt is used for strengthening 3 Na of (a) + And the depth of the compressive stress layer of the glass is increased by ion exchange, so that the shock resistance of the glass is improved. Na (Na) 2 O is used as an external oxide of a glass network, and can provide free oxygen to break a silicon oxygen bond so as to reduce the viscosity and melting temperature of the glass, and excessive Na 2 O reduces the chemical stability and heat resistance of the glass. Na (Na) + As a component of ion exchange with K in molten salts + Chemical exchange is carried out to form a compressive stress layer on the surface of the glass, so that the surface compressive stress of the glass is increased, and more Na is added 2 O is not beneficial to the chemical exchange of the glass and affects the strength of the glass after strengthening. K (K) 2 O and Na 2 O has similar function in the glass structure and proper amount of K 2 O will be combined with Na 2 O generates mixed alkali effect, so that the glass performance is improved. Too much K 2 O may deteriorate the chemical resistance of the glass. Therefore, in order to further improve the comprehensive properties of the resultant glass, 3mol% or less of Na in terms of molar mass percent 2 O≤15mol％、3mol％≤Li 2 O≤15mol％、0mol％≤K 2 O is less than or equal to 5mol percent. Further preferably, in molesThe mass percentage of Na is more than or equal to 4mol percent 2 O≤13.2mol％、4mol％≤Li 2 O≤13.2mol％、0.01mol％≤K 2 O≤3mol％。
In this embodiment, mgO and CaO belong to network external oxides, and MgO has the characteristics of improving glass thermal stability and reducing brittleness, and helps to reduce glass melting point and high-temperature viscosity, and excessive content of MgO and CaO increases density, increases occurrence rate of cracks, devitrification and phase separation, and hinders ion exchange. CaO can relax and break the network structure of the glass and has fluxing effect to a certain extent, but too high content can deteriorate the chemical stability of the glass and seriously hinder ion exchange. MgO, caO, srO, baO are all alkaline earth oxides, and their addition is effective in reducing the high temperature viscosity of the glass to improve the meltability and formability of the glass and to increase the strain point of the glass. Therefore, in order to further improve the comprehensive properties of the obtained glass, it is preferable to contain MgO+CaO+SrO+BaO in an amount of 0mol% to 15mol%, and it is more preferable that MgO+CaO+SrO+BaO is 0.01mol% or less and 7.2mol% or less, in terms of mole percent. Still more preferably, 0.01mol% or less MgO or less than 5mol%,0mol% or less CaO or less than 3mol%,0mol% or less SrO or less 3mol%,0mol% or less BaO or less 3mol%.
In this example, znO has 18 outer-layer electronic structures, zn relative to alkaline earth metals 2+ Ions are more easily polarized, the viscosity of the glass (such as more than 1400 ℃) can be reduced at high temperature, the viscosity of the glass containing ZnO is smaller, the movement speed of atoms is higher, crystal nuclei are not easy to form, and therefore the crystallization upper limit temperature of the glass is reduced. In addition, zn 2+ And Mg (magnesium) 2+ The charge numbers are the same, the ionic radii are close, and when the charge numbers and the ionic radii are used together, the similar mixed alkaline earth effect can be generated, and the optimal toughness, chemical resistance and dielectric property can be generated. However, when the ZnO content is too high, the damage and depolymerization of the glass network structure by ZnO are increased, which is unfavorable for reducing the dielectric constant and dielectric loss of the glass. In combination, the ZnO content is 0 to 5mol% in terms of mole percent, and more preferably 0.01mol% or less and 3mol% or less in terms of mole percent.
The glass product prepared by the process provided by the invention has the advantages of low dielectric constant and low dielectric loss, can reduce the loss of 5G high-frequency signals, has excellent mechanical property after strengthening, can well protect 5G communication equipment, and has the advantages of low liquidus temperature and high matching degree with the production process. Therefore, the aluminosilicate reinforced glass prepared by the invention can be used as the protective glass of various intelligent mobile equipment and other fields of chemically reinforced glass materials requiring excellent mechanical properties.
In some embodiments, the molar percentages of the components are calculated by substituting the molar percentages into the formula to yield the production factor x= (Na) 2 O+Li 2 O+K 2 O)×P 2 O 5 /(SiO 2 +Al 2 O 3 ) And X is more than or equal to 0.1 and less than or equal to 0.6.
In specific implementation, the preferred range of the production factors is 0.55-0.15. In the embodiment, the production factor is set to be 0.55-0.15, so that the finally obtained glass has lower liquidus temperature and devitrification risk and can be highly matched with the existing production process.
In some embodiments, the mole percentages of the components are calculated by substituting the formula to give 1.ltoreq.Li 2 O+Na 2 O+K 2 O)/Na 2 O is less than or equal to 3 so as to improve the strengthening performance of the sample; by making the content of SiO 20 +. 2 +Al 2 O 3 )/P 2 O 5 Less than or equal to 160 percent, and can reduce the melting and forming difficulty of glass.
In the concrete implementation, the preferred value range is as follows in terms of mole mass percent: 1.3 is less than or equal to (Li) 2 O+Na 2 O+K 2 O)/Na 2 O≤2.8，30≤(SiO 2 +Al 2 O 3 )/P 2 O 5 ≤130。
In some embodiments, the strengthening parameter Z of the high aluminosilicate glass ranges from 1.5 to 8.2 in mole percent;
Z＝(Al 2 O 3 +B 2 O 3 +P 2 O 5 )/(RO+ZnO)/Na 2 o, where ro=
MgO+CaO+SrO+BaO. In this embodiment, the setting of the calculation formula of Z can improve the strengthening performance of the glass product, so that the CS30 and CS50 of the glass product are further improved, thereby achieving better impact resistance.
In particular, the preferred range of the strengthening parameter Z of the high aluminosilicate glass is 1.8 to 7.8 in terms of mole percent.
In some embodiments, the high aluminosilicate glass further comprises a fining agent; the content of clarifying agent is not more than 1mol% in terms of mole percent.
In some embodiments, the fining agent is at least one of a sulfate, nitrate, halide, tin oxide, and stannous oxide.
In this embodiment, the composition may further contain a fining agent, which is preferably at least one of sulfate, nitrate, halide, tin oxide, and stannous oxide, as a fining agent for glass melting, according to the glass manufacturing process; the content of the clarifying agent is not more than 1mol%, preferably 0.05 to 0.8mol%, based on the mol of each component. The specific selection of the clarifying agent is not particularly limited, and various kinds of agents commonly used in the art may be used, for example, sulfate may be sodium sulfate, nitrate may be sodium nitrate and/or potassium nitrate, chloride may be sodium chloride and/or strontium chloride, and fluoride may be calcium fluoride.
In some embodiments, the lithium aluminosilicate glass has a dielectric loss of 4.3X10 at 3GHz at room temperature -3 ～7.2×10 -3 The dielectric constant is 4.85-6.38.
In some embodiments, the glass surface after strengthening has a compressive stress of 850MPa or more and a Vickers hardness of 620kgf/mm or more 2 . For example, the surface compressive stress may be 850MPa, 995MPa, 1022MPa, 1032MPa, 1056MPa, 1078MPa, 1101MPa, and the Vickers hardness may be 620kgf/mm 2 、634kgf/mm 2 、659kgf/mm 2 、668kgf/mm 2 、672kgf/mm 2 。
In a second aspect, the present invention provides a method of making the high aluminosilicate glass of the first aspect described above. The method comprises the following steps:
fully stirring and mixing the raw materials according to the formula proportion to obtain a batch mixture;
melting the batch mixture at a high temperature;
casting the melted mixture into a mould, and annealing to obtain a glass raw sheet;
carrying out mechanical processing treatment on the glass raw sheet to obtain a glass product;
and (3) carrying out chemical strengthening treatment on the glass product.
In the embodiment, the melting system treatment temperature is 1500-1650 ℃ and the time is 4-8h. The specific melting temperature and melting time can be determined by those skilled in the art according to the actual situation, and are well known to those skilled in the art and will not be described here again.
In this example, the annealing temperature is 550-650 ℃ and the time is 1-3 hours. The specific annealing temperature and annealing time can be determined by those skilled in the art according to the actual situation, and are well known to those skilled in the art, and will not be described herein.
In this example, the machining treatment is not particularly limited, and various machining methods commonly known in the art may be used, and for example, cutting, grinding, polishing, and the like may be performed on the product obtained by the annealing treatment.
In this embodiment, the chemical strengthening treatment includes one chemical strengthening treatment and/or a plurality of chemical strengthening treatments. The chemical strengthening is realized by ion exchange on the surface of the glass plate, the chemical strengthening liquid is sodium nitrate, potassium nitrate and/or mixed melt of the sodium nitrate and the potassium nitrate, the ion exchange temperature is 390-450 ℃, the specific strengthening temperature and molten salt proportion can be determined by a person skilled in the art according to actual conditions, and the specific strengthening temperature and molten salt proportion are well known to the person skilled in the art and are not repeated herein.
At room temperature, the dielectric constant of 3GHz is 4.85-6.38, and the dielectric loss is 4.3X10 -3 ～7.2×10 -3 After strengthening, the glass surface has a compressive stress of 850MPa or more and a depth of 30 μm from the glass surfaceThe compressive stress (CS_30) is 160MPa or more, the compressive stress (CS_50) at a depth of 50 μm from the surface of the glass is 110MPa or more, the center tensile stress CT is 100MPa or less, and the four-point bending strength is 650MPa or more.
The high aluminosilicate glass provided by the embodiment of the invention has the dielectric constant of 4.85-6.38, the dielectric loss of 4.3 multiplied by 10, with the frequency of 3GHz at room temperature by reasonably adjusting the composition and the proportion of the components -3 ～7.2×10 -3 Young's modulus of 74Gpa or more and Vickers hardness of 550kgf/mm or more before strengthening 2 . After being treated by a proper strengthening system, the Vickers hardness is more than or equal to 620kgf/mm 2 The four-point bending strength is over 650MPa, the drop height of the 180-mesh sand paper is over 160cm, the compressive stress (CS_30) at the depth of 30 mu m from the surface of the glass is over 160MPa, the compressive stress (CS_50) at the depth of 50 mu m from the surface of the glass is over 110MPa, and the central tensile stress is less than or equal to 100MPa. The high-alumina silicate glass prepared by the invention has low dielectric constant and low dielectric loss, can reduce the loss of 5G high-frequency signals, has excellent mechanical property after strengthening, can well protect 5G communication equipment, and has the advantages of low liquidus temperature and high matching degree with a production process.
In a third aspect, the present invention provides the use of a high aluminosilicate glass as described in the first aspect above. Specifically, the application is: the high aluminosilicate glass is applied to cover glass of electronic products.
The aluminosilicate reinforced glass provided by the embodiment of the invention can be used as the protective glass of various intelligent mobile equipment and other fields of chemically reinforced glass materials requiring excellent mechanical properties.
In order to make the technical concept of the present invention more clearly understood by those skilled in the art, the present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples only. Meanwhile, in the following examples, each material used was commercially available as not specifically described, and the method used was a conventional method in the art as not specifically described. The specific contents are as follows:
in the following examples and comparative examples, glass density in g/cm was measured with reference to ASTM C-693 3 。
The coefficient of thermal expansion of glass at 50-350℃was measured with a horizontal dilatometer in units of 10 with reference to ASTM E-228 -7 /℃。
Young's modulus of glass in GPa was measured by reference to ASTM C-623 using a materials mechanics tester.
After the glass was sliced, ground and polished with reference to the test method in ASTM-D150, the dielectric constant and dielectric loss thereof were measured using a dielectric constant tester.
The Vickers hardness of glass was measured in kgf/mm using a Vickers hardness tester with reference to ASTM E-384 2 。
4PB was measured using a universal tester with reference to ASTM E-1820.
Glass strain points were measured in degrees celsius using an annealing point strain point tester with reference to ASTM C-336.
The glass height Wen Nianwen curve is determined with reference to ASTM C-965 using a rotary high temperature viscometer, wherein 40000P corresponds to a molding temperature T4 in degrees Celsius.
The glass liquidus temperature TL was measured in degrees Celsius using a step furnace method with reference to ASTM C-829.
The glass surface compressive stress (in MPa) was measured using an FSM-6000LE surface stress meter.
The ion exchange depth (in μm) and the central tensile stress (in MPa) of Na+ of the glass were measured using an SLP-2000 scattered light stress meter, the compressive stress (in MPa) at a depth of 30 μm from the surface of the glass, and the compressive stress (in MPa) at a depth of 50 μm from the surface of the glass.
Examples 1-36 and comparative examples 1-6 were operated as follows to produce the corresponding finished glass products.
The components were weighed according to the amounts shown in tables 1 to 7, mixed well, and the mixture was poured into a platinum crucible, then heated in a 1700 ℃ resistance furnace for 5 hours, and stirred using a platinum rod to discharge bubbles. Pouring the melted glass liquid into a stainless steel cast iron grinding tool to form a specified blocky glass product, annealing the glass product in an annealing furnace for 2 hours, and turning off a power supply and cooling to 25 ℃ along with the furnace. Cutting, grinding and polishing the glass product, and then cleaning with deionized water and drying to obtain a glass finished product with the thickness of 0.7 mm. The various properties of each glass product were measured separately and the results are shown in tables 1-7.
TABLE 1 measurement of various properties of the glass products obtained in examples 1-6
TABLE 2 measurement of various Properties of the finished glass products obtained in examples 7 to 12
TABLE 3 measurement of various properties of the finished glass products obtained in examples 13-18
TABLE 4 measurement of various properties of the finished glass products obtained in examples 19-24
TABLE 5 measurement results of various properties of the respective glass end products obtained in examples 25 to 30
TABLE 6 measurement results of various properties of the respective glass end products obtained in examples 31 to 36
TABLE 7 measurement of various properties of the glass products obtained in comparative examples 1 to 6
As can be seen from the performance test results of tables 1 to 7, the high aluminosilicate glass provided in this example has a dielectric constant of 4.85 to 6.38 and a dielectric loss of 4.3X10 at room temperature at a frequency of 3GHz -3 ～7.2×10 -3 Young's modulus of 74Gpa or more and Vickers hardness of 550kgf/mm or more before strengthening 2 . After being treated by a proper strengthening system, the Vickers hardness is more than or equal to 620kgf/mm 2 The four-point bending strength is over 650MPa, the drop height of the 180-mesh sand paper is over 160cm, the compressive stress (CS_30) at the depth of 30 mu m from the surface of the glass is over 160MPa, the compressive stress (CS_50) at the depth of 50 mu m from the surface of the glass is over 110MPa, and the central tensile stress is less than or equal to 100MPa. The high-alumina silicate glass prepared by the invention has low dielectric constant and low dielectric loss, can reduce the loss of 5G high-frequency signals, has excellent mechanical property after strengthening, can well protect 5G communication equipment, and has low liquidus temperature and production process matching degreeHigh advantage.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.
The foregoing has outlined a detailed description of a low dielectric constant and low dielectric loss high alumina silicate glass provided by the present invention, wherein specific examples are provided herein to illustrate the principles and embodiments of the present invention and to assist in understanding the method and core concepts of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. A high aluminosilicate glass, wherein the high aluminosilicate glass comprises, in mole percent: 55mol% to 72mol% of SiO 2 8mol% to 25mol% of Al 2 O 3 0.1mol% to 10mol% of B 2 O 3 3 to 15mol% of Na 2 O,3mol% to 15mol% of Li 2 O,0mol% to 5mol% of K 2 O, mgO+CaO+SrO+BaO in an amount of 0-15 mol%, znO in an amount of 0-5mol%, and P in an amount of 0.01-5 mol% 2 O 5 ；
Wherein, the mole percentage of each component is substituted into a formula to calculate and obtain a dielectric factor Y= (SiO) 2 +B 2 O 3 )/(Na 2 O+Li 2 O+K 2 O+P 2 O 5 ) X (MgO+ZnO) and satisfies 0.5.ltoreq.Y.ltoreq.5.5.
2. The high aluminosilicate glass according to claim 1, wherein the massage is performedThe mole percentages of the components are substituted into a formula to calculate and obtain a production factor X= (Na) 2 O+Li 2 O+K 2 O)×P 2 O 5 /(SiO 2 +Al 2 O 3 ) And X is more than or equal to 0.1 and less than or equal to 0.6.
3. The high aluminosilicate glass according to claim 1, wherein the molar percentage of each component calculated by substitution formula is 1.ltoreq.Li 2 O+Na 2 O+K 2 O)/Na 2 O≤3，20≤(SiO 2 +Al 2 O 3 )/P 2 O 5 ≤160。
4. The high aluminosilicate glass according to claim 1, wherein the high aluminosilicate glass has a strengthening parameter Z in the range of 1.5 to 8.2 in mole percent;
Z＝(Al 2 O 3 +B 2 O 3 +P 2 O 5 )/(RO+ZnO)/Na 2 o, where ro=
MgO+CaO+SrO+BaO。
5. The high aluminosilicate glass of claim 1, wherein the high aluminosilicate glass further comprises a fining agent; the clarifying agent is present in an amount of no greater than 1 mole percent.
6. The high aluminosilicate glass according to claim 4, wherein the fining agent is at least one of a sulfate, a nitrate, a halide, tin oxide, and stannous oxide.
7. The high aluminosilicate glass of any one of claims 1-6, wherein the lithium aluminosilicate glass has a dielectric loss of 4.3 x 10 at room temperature at a frequency of 3GHz -3 ～7.2×10 -3 The dielectric constant is 4.85-6.38.
8. According to claim1-6, wherein after strengthening, the glass has a surface compressive stress of 850MPa or more and a Vickers hardness of 620kgf/mm or more 2 。
9. A method of making the high aluminosilicate glass according to any one of claims 1 to 8, comprising:
fully stirring and mixing the raw materials according to the formula proportion to obtain a batch mixture;
melting the batch mixture at a high temperature;
casting the melted mixture into a mould, and annealing to obtain a glass raw sheet;
carrying out mechanical processing treatment on the glass raw sheet to obtain a glass product;
and carrying out chemical strengthening treatment on the glass product.
10. Use of the high aluminosilicate glass according to any one of claims 1 to 8, wherein the high aluminosilicate glass is applied to cover glass of an electronic product.
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