CN111747645A - Aluminosilicate glass - Google Patents

Aluminosilicate glass Download PDF

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Publication number
CN111747645A
CN111747645A CN202010505352.8A CN202010505352A CN111747645A CN 111747645 A CN111747645 A CN 111747645A CN 202010505352 A CN202010505352 A CN 202010505352A CN 111747645 A CN111747645 A CN 111747645A
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zno
mgo
percent
glass
sro
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彭寿
张冲
沈玉国
曹志强
金良茂
朱明柳
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CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Bengbu Zhongguangdian Technology Co Ltd
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CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Bengbu Zhongguangdian Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to aluminosilicate glass which is characterized by being prepared from the following raw materials in percentage by weight: 55-65% of SiO216-21% of Al2O33.5-7.5% of B2O36 to 9 percent of MgO, 1 to 6 percent of CaO, 0.5 to 3 percent of SrO, 1.6 to 4 percent of ZnO and 0.5 to 2 percent of TiO20.1-0.2% of SnO2(ii) a Wherein the TiO is20.04-0.18% of (MgO + CaO + SrO + ZnO); al (Al)2O31.5-2.3% of (MgO + ZnO); (Al)2O3+SiO2)/B2O310.7-23.95%; ZnO/(MgO + CaO + SrO + ZnO) is 0.13-0.3%; (Al)2O3+B2O3) /(MgO + CaO + SrO + ZnO) is 1.2 to 2.35 percent; SiO 22/(Al2O3+B2O3) Is 2.15-3.2. The inventionThe advantages are that: the prepared glass has the characteristics of high strain point, high Young modulus, high hardness, high transmittance, low surface tension, low thermal shrinkage, high chemical stability and the like, and is suitable for industries such as photoelectric display, photos, photovoltaics and the like; the glass is an environment-friendly alkaline earth aluminosilicate glass system, does not contain any toxic substance, accords with the development trend of the flat panel display industry, is suitable for a plurality of forming modes such as a melting down-draw method and a float method, and is suitable for large-scale industrial production.

Description

Aluminosilicate glass
Technical Field
The invention belongs to the field of glass production, relates to various glass substrates for displays, and particularly relates to aluminosilicate glass.
Background
Liquid Crystal Displays (LCDs) and Organic light-emitting displays (OLEDs) are two major display products at present, from 2004 to the present, LCD display technologies are continuously updated, products are developed to be large, ultra-Thin and high-definition, the maximum size of a panel of the LCD is 2940 × 3370mm, and a Thin Film Transistor (TFT) driving circuit is converted from amorphous (a-Si) to polycrystalline silicon (p-Si), so that the circuit is finer and finer, the conductivity is better, the display opening area is larger, the color is brighter, the pixels are more miniaturized, and the image is more vivid and fine. The OLED has the characteristics of no need of backlight, higher contrast ratio, thin thickness, wide viewing angle, high reaction speed, capability of being used for flexible display and the like, and becomes a new favorite in the display industry.
The glass substrate is a key basic material of an LCD/OLED display, is mainly used for a TFT (thin film transistor) manufacturing process and a carrier plate of a CF (color film) device, and is used for carrying out circuit and manufacturing process processing on the surface of glass. Due to the requirement of improving the display effect and the screen refreshing rate, the TFT is prepared by adopting a Low Temperature Polysilicon (LTPS) technology, so that the LCD/OLED display product has the characteristics of high resolution, high reaction speed, high resolution, high stability, high brightness, increased aperture ratio and the like.
The LTPS process is a process of converting Amorphous silicon (a-Si) deposited on a surface of a glass substrate into Poly-silicon (p-Si) by heat treatment, thereby increasing an electron transfer rate by 100 times or more. However, the heat treatment temperature is as high as 600-700 ℃, and the glass substrate is affected by heat treatment to generate irreversible shrinkage deformation, so that the positions of pixel points of the upper and lower substrates are relatively deviated during laminating/box forming, permanent light leakage or black spots are generated, pixel display is not controlled, display defects are formed, and the quality of a display panel is affected, so that new technical challenges and quality requirements are provided for LTPS substrate glass, and the requirements on temperature resistance, surface quality and dimensional accuracy are more strict.
Low Temperature Polysilicon (LTPS) is the mainstream technology. Nowadays, the requirements for panel resolution, light weight, low energy consumption and the like in the market are higher and higher, especially for mobile devices such as mobile phones, tablets and wearable devices. The panel factory mainly plans G6 and the following generation production lines to produce mobile device panels, and applies G6 and above production lines (continental is mainly G8.5 production line) to produce large-size panels such as TV, monitor, etc. While the production line of large generation panels needs to improve the precision of film coating by means of the IGZO display screen technology, G6 and the production lines of the following generation of middle and small panels need to greatly improve the resolution, the traditional alpha-Si technology has been developed, and both the AM-OLED (active matrix organic light emitting diode) technology and the high-resolution high-end TFT-LCD panel need to be realized by applying the LTPS technology.
Disclosure of Invention
The invention aims to provide an aluminosilicate glass, and the aluminosilicate glass composition has a glass product with high strain point, high Young modulus, high transmittance, low surface tension, low thermal shrinkage and good surface flatness, is suitable for large-scale industrial production, and is suitable for high-generation panels.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the aluminosilicate glass is characterized by being prepared from the following raw materials in percentage by weight (calculated by oxides): 55-65% of SiO216-21% of Al2O33.5-7.5% of B2O36-9% of MgO, 1-6% of CaO and 0.5 to 3 percent of SrO, 1.6 to 4 percent of ZnO and 0.5 to 2 percent of TiO20.1-0.2% of SnO2；
Wherein the TiO is20.04-0.18% of (MgO + CaO + SrO + ZnO);
Al2O31.5-2.3% of (MgO + ZnO);
(Al2O3+SiO2)/B2O310.7-23.95%;
ZnO/(MgO + CaO + SrO + ZnO) is 0.13-0.3%;
(Al2O3+B2O3) /(MgO + CaO + SrO + ZnO) is 1.2 to 2.35 percent;
SiO2/(Al2O3+B2O3) Is 2.15-3.2.
Further, the aluminosilicate glass is characterized by being prepared from the following raw materials in percentage by weight (calculated by oxides): 57.8-65% SiO217-19.58% of Al2O33.5-7.5% of B2O36 to 8.5 percent of MgO, 1 to 5.5 percent of CaO, 1.55 to 2.5 percent of SrO, 2 to 3.5 percent of ZnO and 0.5 to 2 percent of TiO20.1-0.2% of SnO2；
Wherein the TiO is20.05 to 0.16 percent of (MgO + CaO + SrO + ZnO);
Al2O3v. (MgO + ZnO) 1.49-2.28%;
(Al2O3+SiO2)/B2O310.7-20.95%;
ZnO/(MgO + CaO + SrO + ZnO) is 0.15-0.3%;
(Al2O3+B2O3) /(MgO + CaO + SrO + ZnO) is 1.25 to 2.15 percent;
SiO2/(Al2O3+B2O3) Is 2.15-3.05.
Further, the density of the aluminosilicate glass is between 2.3 and 2.8g/cm3Has a thermal expansion coefficient of 32.8-37.5 × 10 at 50-350 deg.C-7/° C, Young's modulus of 79.7-87.1GPa, Vickers hardness of 678.6-691.6, surface tension of 279.3-295.8mN/m at 1250 ℃,the strain point is higher than 718-773 ℃, the melting temperature is lower than 1635 ℃, the thermal shrinkage rate of the material after 10min of heat preservation at 600 ℃ is 5.85-9.74ppm, the transmittance at 308nm is 70.5-78.4 percent, 10wt percent of HF acid is corroded at 20 ℃ for 20min, and the corrosion amount is 5.31-8.58mg/cm2。
In the glass composition of the present invention:
SiO in the glass composition2Is a glass former, the components constituting the glass skeleton are increased by SiO2And (3) the chemical resistance, mechanical strength and strain point are improved. If SiO2Too much, the high temperature viscosity of the glass increases, causing refractory behavior and aggravating the erosion of the refractory material. SiO 22If the content is low, glass is not easy to form, the strain point is reduced, the expansion coefficient is increased, and the acid resistance and the alkali resistance are reduced; in consideration of properties such as melting temperature, glass expansion coefficient, mechanical strength, glass frit property and the like, 55-65wt% of SiO is introduced into the glass2。
Al in the glass composition2O3Is intermediate oxide for improving the strength and strain point of glass structure, improving the chemical stability of glass, reducing the devitrification tendency of glass, and Al2O3Excessive content, difficult melting of glass, short material property, easy crystallization and Al2O3The content is low, the glass is easy to devitrify, the mechanical strength is low, and the forming is not facilitated, 16 to 21 weight percent of Al is introduced into the invention2O3。
In the glass composition B2O3The glass can be independently generated, is a good fluxing agent, can reduce the viscosity, dielectric loss and vibration loss of the glass, and can improve the brittleness, toughness and light transmittance of the glass. Having [ BO ] in glass4]Tetrahedron and [ BO3]Two structures of triangle, B under high temperature melting condition2O3Difficult to form [ BO4]Can reduce high temperature viscosity, and B can deprive free oxygen to form [ BO ] at low temperature4]The tendency of the invention leads the structure to be compact, improves the low-temperature viscosity of the glass, prevents the occurrence of crystallization, and introduces 3.5 to 7.5 weight percent of B2O3。
MgO in the glass composition has the effects of reducing high-temperature viscosity and increasing low-temperature viscosity, can increase the Young modulus of glass, reduce surface tension and inhibit the brittleness increase of the glass, and 6-9wt% of MgO is introduced.
The alkaline earth metal oxide RO (CaO, SrO, BaO) in the glass composition can improve the strain point and Young's modulus of the glass and reduce the thermal expansion coefficient. The high-temperature viscosity of the glass can be effectively reduced, so that the meltability and the formability of the glass are improved, the occurrence probability of devitrification and phase separation can be increased due to excessive content, and 1.5-8.15wt% of RO is introduced into the glass.
ZnO is introduced into the glass composition, so that the melting quality of glass is improved, the uniformity of the glass is improved, the chemical stability and the thermal stability of the glass are improved, but excessive glass is easy to crystallize, and 1.6-4wt% of ZnO is introduced into the glass composition.
The glass composition is introduced with TiO2Promoting the melting of the glass, improving the forming stability of the glass, improving the refractive index of the glass and reducing the thermal expansion coefficient, and 0.5 to 2 weight percent of TiO is introduced into the invention2。
The composition for glass of the present invention, when used for preparing aluminosilicate glass, enables the glass to have excellent overall properties mainly due to the coordination of the components in the composition, especially SiO2、Al2O3、B2O3Satisfies SiO between2/(Al2O3+B2O3) 2.15-3.05 of MgO, CaO, SrO, ZnO and TiO2Satisfies the condition of TiO20.04-0.18% of (MgO + CaO + SrO + ZnO).
The invention has the beneficial effects that:
(1) the glass prepared by the invention has the characteristics of high strain point, high Young modulus, high hardness, high transmittance, low surface tension, low thermal shrinkage, high chemical stability and the like;
(2) al in the components of the glass composition according to a specific proportion2O3/（MgO+ZnO）、(Al2O3+B2O3)/（MgO+CaO+SrO+ZnO）、SiO2/(Al2O3+B2O3) Can effectively reduce the glassThe surface tension of the glass is improved, the thermal stability of the glass is improved, the glass is easy to spread, thin and wet, the forming, thinning and widening are convenient, and particularly the glass is drawn into a high-generation large-size glass substrate (in the high-generation large-size glass substrate, the size of a G8.5 generation glass substrate is 2200 × 2500mm, the size of a G10.5 generation glass substrate is 2940 × 3370mm, the size of a G11 generation glass substrate is 3000mm × 3320mm, and the thickness of the glass substrate is less than or equal to 0.5 mm), so that the requirement of large size can be realized;
(3) the glass composition is an environment-friendly alkaline earth aluminosilicate glass system, does not contain any toxic substance, and does not contain BaCO3、As2O3、Sb2O3And the prepared glass is suitable for industries of photoelectric display, photo, photovoltaic and the like, and is particularly suitable for being used as a substrate glass substrate material of a flat panel display product and/or a substrate glass substrate material of a flexible display product.
Detailed Description
The aluminosilicate glass comprises the following specific implementation steps:
the preparation method of the aluminosilicate glass adopts the mixture ratio shown in the table 1-4, wherein SiO2、Al2O3、B2O3、MgO、CaO、SrO、ZnO、TiO2The composition contains Si-containing compound, Al-containing compound, B-containing compound, Mg-containing compound, Ca-containing compound, Sr-containing compound, Zn-containing compound and Ti-containing compound (such as carbonate, nitrate, sulfate, oxide and the like containing the elements), the composition contains a clarifying agent according to the glass preparation process, the concrete selection of the clarifying agent is not particularly limited, and the clarifying agent can be various selections commonly used in the field, and the SiO is heated2、Al2O3、B2O3、MgO、CaO、SrO、ZnO、TiO2After being mixed uniformly, the mixture is melted at high temperature (1450 and 1650 ℃), clarified, homogenized, molded and annealed to obtain the aluminoborosilicate glass substrate, and then the aluminoborosilicate glass substrate is cut, ground, polished and the like.
The density of the glass prepared by the invention is between 2.3 and 2.8g/cm3Has a thermal expansion coefficient of 32.8-37.5 × 10 at 50-350 deg.C-7The Young's modulus is 79.7-87.1GPa, the Vickers hardness is 678.6-691.6,1250 ℃, the surface tension is 279.3-295.8mN/m, the strain point is higher than 718-773 ℃, the melting temperature is lower than 1635 ℃, the heat shrinkage rate (600 ℃, 10 min) is 5.85-9.74ppm, the transmittance at 308nm is 70.5-78.4%, and the erosion amount of 10wt% HF acid erosion at 20 ℃ for 20min is 5.31-8.58mg/cm2。
In the following examples and comparative examples:
glass Density is determined in g/cm according to ASTM C-6933。
The coefficient of thermal expansion of the glass at 50-350 ℃ is measured in 10 units using a horizontal dilatometer with reference to ASTM E-228-7/℃。
The Young's modulus of glass was measured in GPa using a mechanical testing machine in accordance with ASTM C-623.
Vickers Hardness (HV) was determined using an automatic digital turret display micro vickers hardness tester, referred to GB/T4340.2-2012.
The surface tension at 1250 ℃ is measured with a high temperature surface tensiometer and has the unit of mN/m.
The annealing and strain points of the glasses were measured in degrees centigrade using a three-point tester with reference to astm c-336 and astm c-338.
The glass high temperature visco-temperature curve was determined using a rotary high temperature viscometer with reference to astm c-965, where the temperature at 200P viscosity corresponds to the melting temperature in c.
The heat shrinkage was calculated using the difference. A glass substrate without any defects, the initial length of which is marked as L0, after being subjected to heat treatment under certain conditions (for example, the heat treatment process conditions of the invention are that the glass is heated to 600 ℃ from room temperature at a heating rate of 10 ℃/min and is kept for 10min, and then the glass is cooled to room temperature at a cooling rate of 10 ℃/min), the length of the substrate is shrunk by a certain amount, the length of the substrate is measured again, the length is marked as Lt, and the heat shrinkage Yt is expressed as:
Figure RE-DEST_PATH_IMAGE001
the glass transmittance was measured using an ultraviolet-visible spectrophotometer with a glass sample thickness of 0.5mm, and the transmittance was taken in units of% at 308 nm.
The corrosion amount of the glass in a 10% hydrofluoric acid solution is detected by using a weight loss method, and the detection conditions comprise: placing defect-free glass into 10wt% hydrofluoric acid solution at 20 deg.C, eroding for 20min under oscillation state, and calculating erosion amount by using (before erosion of M sample-after erosion of M sample)/S sample surface area with unit of mg/cm2The smaller the value, the stronger the acid resistance.
Specific examples and comparative examples are given below, in weight percentages, of the components of the formulation, see tables 1, 2, 3, 4:
table 1.
The components by weight percent Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9
SiO2 55.01 55.34 55.87 56.25 56.57 56.93 57.31 57.62 57.89
Al2O3 21 20.93 20.09 20.84 20.35 19.58 19.32 18.33 19.25
B2O3 3.92 4.59 3.63 3.87 3.75 4.12 4.12 6 5.17
MgO 9 6.86 8.64 6.63 7.91 7.24 6.87 6.93 8.23
CaO 4.5 4.61 5.22 5.99 4.73 5.17 5.7 4.12 3.52
SrO 2.35 3 2.25 2.15 1.62 2.63 2.11 1.11 1.97
ZnO 2.5 2.95 2.52 2.53 3.36 3.14 2.58 3.74 3.03
TiO2 1.61 1.6 1.65 1.62 1.59 1.06 1.84 2 0.81
SnO2 0.11 0.12 0.13 0.12 0.12 0.13 0.15 0.15 0.13
TiO2/（MgO+CaO+SrO+ZnO） 0.09 0.09 0.09 0.09 0.09 0.06 0.11 0.13 0.05
Al2O3/（MgO+ZnO） 1.83 2.13 1.80 2.28 1.81 1.89 2.04 1.72 1.71
(Al2O3+SiO2)/B2O3 19.39 16.62 20.93 19.92 20.51 18.57 18.60 12.66 14.92
ZnO/（MgO+CaO+SrO+ZnO） 0.14 0.17 0.14 0.15 0.19 0.17 0.15 0.24 0.18
(Al2O3+B2O3)/（MgO+CaO+SrO+ZnO） 1.36 1.46 1.27 1.43 1.37 1.30 1.36 1.53 1.46
SiO2/(Al2O3+B2O3) 2.21 2.17 2.36 2.28 2.35 2.40 2.44 2.37 2.37
Density g/cm3 2.59 2.76 2.49 2.75 2.61 2.67 2.31 2.49 2.58
Coefficient of thermal expansion (50-350 deg.C)）10-7/℃ 37.2 33.5 36.4 35.1 37.2 36.7 32.9 35.5 36.9
Young's modulus GPa 81.6 80.4 83.5 81.9 82.2 80.7 81.4 80.9 79.7
Vickers hardness Hv 680.9 683 681.4 682.8 683.2 681.7 678.6 679.2 683.6
Surface tension mN/m at 1250 ℃ 283.7 285.5 288.6 295.8 285.3 288.5 286.8 281.9 282.4
Strain point of DEG C 730 726 734 756 741 724 731 722 735
Melting temperature T2.3℃ 1609 1613 1620 1603 1631 1619 1606 1627 1615
Heat shrinkage (600 ℃ C., 10 min) ppm 7.46 8.92 6.84 6.25 7.82 8.34 9.72 7.35 8.29
Transmittance of 308nm,%) 73.6 75.5 73.1 74.9 73.2 70.7 71.4 75.6 72.7
HF（10%,20min,20℃）mg/cm2 7.76 8.54 7.91 8.32 7.15 6.86 6.36 8.11 7.49
Table 2.
The components by weight percent Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18
SiO2 58.12 58.53 58.78 59.21 59.54 59.96 60.13 60.48 60.97
Al2O3 18.34 19.18 18.21 18.23 18.61 18.07 19.25 19.33 18.35
B2O3 4.29 3.76 3.57 5.36 4.58 5.1 5.15 6.02 6.15
MgO 7.45 6.19 8.25 7.42 8.07 7.13 6.52 7.39 6.11
CaO 5.13 5.34 4.24 3.19 3.12 3.32 4.21 3.05 2.43
SrO 2.07 2.55 1.35 2.56 1.36 1.55 1.16 0.55 1.01
ZnO 2.56 2.58 3.96 2.64 3.25 3.46 2.85 2.53 3.32
TiO2 1.9 1.71 1.49 1.24 1.34 1.28 0.58 0.53 1.54
SnO2 0.14 0.16 0.15 0.15 0.13 0.13 0.15 0.12 0.12
TiO2/（MgO+CaO+SrO+ZnO） 0.11 0.10 0.08 0.08 0.08 0.08 0.04 0.04 0.12
Al2O3/（MgO+ZnO） 1.83 2.19 1.49 1.81 1.64 1.71 2.05 1.95 1.95
(Al2O3+SiO2)/B2O3 17.82 20.67 21.57 14.45 17.06 15.30 15.41 13.26 12.90
ZnO/（MgO+CaO+SrO+ZnO） 0.15 0.15 0.22 0.17 0.21 0.22 0.19 0.19 0.26
(Al2O3+B2O3)/（MgO+CaO+SrO+ZnO） 1.31 1.38 1.22 1.49 1.47 1.50 1.66 1.88 1.90
SiO2/(Al2O3+B2O3) 2.57 2.55 2.70 2.51 2.57 2.59 2.46 2.39 2.49
Density g/cm3 2.63 2.71 2.77 2.79 2.48 2.53 2.69 2.55 2.42
Thermal expansion coefficient (50-350 deg.C) 10-7/℃ 37.1 34.7 33.9 36.4 33.7 36.6 34.5 36.8 37.2
Young's modulus GPa 82.6 81.3 80.6 82.7 83.4 85.1 82.5 83.7 82.6
Vickers hardness Hv 680.4 682.3 679.5 681.4 680.6 678.7 684.5 680.9 683.6
Surface tension mN/m at 1250 ℃ 284.5 293.7 283.1 282.8 285.6 279.4 280.7 284.5 283.6
Strain point of DEG C 719 723 737 718 734 726 747 738 757
Melting temperature T2.3℃ 1608 1611 1625 1622 1605 1618 1634 1628 1635
Heat shrinkage (600 ℃ C., 10 min) ppm 5.85 6.96 8.96 7.36 6.53 8.74 7.06 8.75 9.09
Transmittance of 308nm,%) 73.8 74.3 75.9 76.3 74.9 75.4 78.4 76.9 77.3
HF（10%,20min,20℃）mg/cm2 8.58 5.31 6.48 7.02 5.64 6.87 7.35 6.89 7.95
Table 3.
The components by weight percent Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27
SiO2 61.53 61.26 61.93 62.32 62.59 62.89 63.18 63.64 63.91
Al2O3 18.05 18.28 18.65 17.67 18.15 17.84 17.55 16.82 16.38
B2O3 6.5 6.01 5.78 7.15 6.05 5.47 4.37 7.5 4.58
MgO 6.03 6.15 7.01 6.08 7.04 7.56 6.85 6.05 7.25
CaO 2.54 2.42 1.62 2.35 1.3 1.15 2.16 1.11 1.53
SrO 0.55 0.68 1.04 0.95 1.57 1.08 2.32 0.56 1.64
ZnO 4 3.13 2.75 2.74 2.52 3.01 1.63 2.76 2.57
TiO2 0.65 1.95 1.1 0.59 0.65 0.85 1.79 1.43 1.99
SnO2 0.15 0.12 0.12 0.15 0.13 0.15 0.15 0.13 0.15
TiO2/（MgO+CaO+SrO+ZnO） 0.05 0.16 0.09 0.05 0.05 0.07 0.14 0.14 0.15
Al2O3/（MgO+ZnO） 1.80 1.97 1.91 2.00 1.90 1.69 2.07 1.91 1.67
(Al2O3+SiO2)/B2O3 12.24 13.23 13.94 11.19 13.35 14.76 18.47 10.73 17.53
ZnO/（MgO+CaO+SrO+ZnO） 0.30 0.25 0.22 0.23 0.20 0.24 0.13 0.26 0.20
(Al2O3+B2O3)/（MgO+CaO+SrO+ZnO） 1.87 1.96 1.97 2.05 1.95 1.82 1.69 2.32 1.61
SiO2/(Al2O3+B2O3) 2.51 2.52 2.53 2.51 2.59 2.70 2.88 2.62 3.05
Density g/cm3 2.67 2.47 2.65 2.44 2.52 2.56 2.49 2.54 2.72
Thermal expansion coefficient (50-350 deg.C) 10-7/℃ 36.3 32.8 35.7 37.4 34.2 36.9 35.1 34.7 37.5
Young's modulus GPa 84.9 83.3 87.1 85.4 83.2 84.3 82.9 80.4 81.2
Vickers hardness Hv 680.4 683.5 684.1 685.2 691.6 683.3 683.9 680.4 682.5
Surface tension mN/m at 1250 ℃ 286.4 295.8 279.3 285.7 283.2 284.9 281.6 283.9 285.3
Strain point of DEG C 770 763 748 752 739 740 735 732 753
Melting temperature T2.3℃ 1624 1619 1630 1621 1618 1628 1623 1633 1628
Heat shrinkage (600 ℃ C., 10 min) ppm 6.62 8.53 7.36 6.85 8.03 9.74 7.58 6.47 8.38
Transmittance of 308nm,%) 76.5 78.1 77.6 75.4 73.2 71 74.3 71.7 70.5
HF（10%,20min,20℃）mg/cm2 6.02 7.34 6.35 8.42 7.03 8.26 6.41 7.64 8.33
Table 4.
The components by weight percent Example 28 Example 29 Example 30 Example 31 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
SiO2 64.26 64.52 64.89 65 53.64 67.37 61.82 61.15
Al2O3 17.15 16.76 19.31 18.83 23.65 11.03 19.04 19.95
B2O3 4.93 3.54 3.65 3.5 8.73 1.15 6.08 7.79
MgO 6.07 8.07 6.05 6.04 10.96 4.26 6.33 6.07
CaO 2.85 2.43 1.76 1.38 0.55 6.34 3.52 2.04
SrO 1.56 0.85 0.78 0.59 0.45 3.03 1.58 1.03
ZnO 1.72 3.17 2.90 2.58 1.5 4.05 1.82
TiO2 1.31 0.52 0.55 1.93 0.37 2.62 1.48
SnO2 0.15 0.14 0.11 0.15 0.15 0.15 0.15 0.15
TiO2/（MgO+CaO+SrO+ZnO） 0.11 0.04 0.04 0.18 0.03 0.15 0.13 0.00
Al2O3/（MgO+ZnO） 2.20 1.49 2.15 2.18 1.90 1.33 3.01 2.53
(Al2O3+SiO2)/B2O3 16.51 22.96 23.07 23.95 8.85 68.17 13.30 10.41
ZnO/（MgO+CaO+SrO+ZnO） 0.14 0.22 0.26 0.24 0.11 0.23 0.00 0.17
(Al2O3+B2O3)/（MgO+CaO+SrO+ZnO） 1.81 1.40 1.99 2.11 2.41 0.69 2.20 2.53
SiO2/(Al2O3+B2O3) 2.91 3.18 2.83 2.91 1.66 5.53 2.46 2.20
Density g/cm3 2.61 2.59 2.75 2.63 2.34 2.76 2.69 2.81
Thermal expansion coefficient (50-350 deg.C) 10-7/℃ 36.2 34.9 35.6 36.1 26.85 43.11 39.08 38.67
Young's modulus GPa 80.7 81.3 82 83.5 71.34 73.45 78.73 75.06
Vickers hardness Hv 684.5 683.6 680.5 682.9 630.7 641.2 656.3 649.1
Surface tension mN/m at 1250 ℃ 284.7 280.4 290.2 287.3 382.3 390.4 378.6 369.5
Strain point of DEG C 761 744 773 729 631 648 697 683
Melting temperature T2.3℃ 1629 1617 1626 1635 1649 1598 1628 1631
Heat shrinkage (600 ℃ C., 10 min) ppm 9.63 6.95 7.23 9.28 28.45 19.72 15.89 13.51
Transmittance of 308nm,%) 73.4 76.3 75.1 73.4 57.5 55.6 68.3 69.8
HF（10%,20min,20℃）mg/cm2 8.55 7.15 8.49 8.15 16.46 10.24 9.67 11.85

Claims (3)

1. The aluminosilicate glass is characterized by being prepared from the following raw materials in percentage by weight: 55-65% of SiO216-21% of Al2O33.5-7.5% of B2O36 to 9 percent of MgO, 1 to 6 percent of CaO, 0.5 to 3 percent of SrO, 1.6 to 4 percent of ZnO and 0.5 to 2 percent of TiO20.1-0.2% of SnO2；
Wherein the TiO is20.04-0.18% of (MgO + CaO + SrO + ZnO);
Al2O31.5-2.3% of (MgO + ZnO);
(Al2O3+SiO2)/B2O310.7-23.95%;
ZnO/(MgO + CaO + SrO + ZnO) is 0.13-0.3%;
(Al2O3+B2O3)/（Mgo + CaO + SrO + ZnO) is 1.2 to 2.35 percent;
SiO2/(Al2O3+B2O3) Is 2.15-3.2.
2. The aluminosilicate glass according to claim 1, characterized by being prepared from the following raw materials in percentage by weight: 57.8-65% SiO217-19.58% of Al2O33.5-7.5% of B2O36 to 8.5 percent of MgO, 1 to 5.5 percent of CaO, 1.55 to 2.5 percent of SrO, 2 to 3.5 percent of ZnO and 0.5 to 2 percent of TiO20.1-0.2% of SnO2；
Wherein the TiO is20.05 to 0.16 percent of (MgO + CaO + SrO + ZnO);
Al2O3v. (MgO + ZnO) 1.49-2.28%;
(Al2O3+SiO2)/B2O310.7-20.95%;
ZnO/(MgO + CaO + SrO + ZnO) is 0.15-0.3%;
(Al2O3+B2O3) /(MgO + CaO + SrO + ZnO) is 1.25 to 2.15 percent;
SiO2/(Al2O3+B2O3) Is 2.15-3.05.
3. An aluminosilicate glass according to claim 1 or 2 having a density in the range 2.3-2.8g/cm3Has a thermal expansion coefficient of 32.8-37.5 × 10 at 50-350 deg.C-7The Young's modulus is 79.7-87.1GPa, the Vickers hardness is 678.6-691.6, the surface tension is 279.3-295.8mN/m at 1250 ℃, the strain point is higher than 718-773 ℃, the melting temperature is lower than 1635 ℃, the heat shrinkage rate is 5.85-9.74ppm when the temperature is kept for 10min at 600 ℃, the transmittance at 308nm is 70.5-78.4%, 10wt% HF acid corrosion is 20min at 20 ℃, and the corrosion amount is 5.31-8.58mg/cm2。
CN202010505352.8A 2020-06-05 2020-06-05 Aluminosilicate glass Withdrawn CN111747645A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105118A (en) * 2021-04-14 2021-07-13 台嘉蚌埠玻璃纤维有限公司 Glass composition with low thermal expansion coefficient and glass fiber made from same
CN115196876A (en) * 2022-08-30 2022-10-18 郑州大学 Flexible ultrathin glass and preparation method and application thereof
WO2023037951A1 (en) * 2021-09-07 2023-03-16 Ａｇｃ株式会社 Alkali-free glass

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105118A (en) * 2021-04-14 2021-07-13 台嘉蚌埠玻璃纤维有限公司 Glass composition with low thermal expansion coefficient and glass fiber made from same
WO2023037951A1 (en) * 2021-09-07 2023-03-16 Ａｇｃ株式会社 Alkali-free glass
CN115196876A (en) * 2022-08-30 2022-10-18 郑州大学 Flexible ultrathin glass and preparation method and application thereof
CN115196876B (en) * 2022-08-30 2024-02-27 郑州大学 Flexible ultrathin glass and preparation method and application thereof

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