CN117164230A - Composition for glass substrate, high-generation alkali-free glass substrate, preparation method and application thereof - Google Patents
Composition for glass substrate, high-generation alkali-free glass substrate, preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 151
- 239000000758 substrate Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 238000002834 transmittance Methods 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000010128 melt processing Methods 0.000 claims description 3
- 239000006121 base glass Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000008395 clarifying agent Substances 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Abstract
The invention relates to the field of glass, and discloses a composition for a glass substrate, a high-generation alkali-free glass substrate, a preparation method and application thereof. The glass composition includes: the composition contains 59-68wt% of SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-8wt% of B 2 O 3 2-4wt% of P 2 O 5 1-3wt% MgO, 0-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 . The high-generation alkali-free glass provided by the invention can simultaneously give consideration to higher Young modulus and strain point temperature, lower thermal shrinkage and higher light with 308nm wavelengthTransmittance.
Description
Technical Field
The invention relates to the field of glass, in particular to a composition for a glass substrate, a high-generation alkali-free glass substrate, a preparation method and application thereof.
Background
With the development of the production of glass substrates in a large-sized and thin manner, the sagging problem of the glass panel during the production process needs to be solved, and thus the substrate glass should have as low a density and as high an elastic modulus as possible.
The glass substrate for a display should have the following properties:
(1) Substantially no alkali metal oxide is contained, and if the alkali metal oxide is contained, alkali metal ions diffuse into the semiconductor material on which the film is formed, resulting in deterioration of film characteristics.
(2) In the TFT-LCD process, the glass substrate is exposed to high temperature, which causes deformation and shrinkage of the glass substrate, so that the glass substrate has a high strain point.
(3) The glass has high quality requirement, and bubbles, striae, inclusions, unmelted objects, scratches and the like cannot appear in the interior and the surface.
(4) In the production and transportation of glass substrates, the amount of bending due to the self weight is required to be high.
In addition, the substrate glass can be used as OLED carrier glass, is an important breakthrough in accordance with the development trend of the novel display, and provides powerful upstream material support for the current hot OLED panel manufacture. The heat treatment temperature of the crystallization process of the device is higher than that of a TFT-LCD, so that the heat shrinkage rate and the flatness of the substrate glass are required to be higher.
The main performance requirements of the rigid OLED substrate glass are similar to those of the TFT-LCD glass substrate, and the rigid OLED substrate glass can meet the normal use within the temperature range of 550-600 ℃ according to the OLED backboard manufacturing process. Besides meeting the high-temperature environment, the flexible OLED substrate glass also ensures higher and in-chip uniform UV light transmittance, and meets the requirement of separating the flexible substrate from the substrate glass by using a laser stripping technology.
Therefore, the ultraviolet transmittance of 308nm is particularly important, the carrier glass provides support for the flexible substrate, the carrier glass and the substrate need to be stripped by using laser after the manufacture is finished, and the stripping process has certain requirements on the ultraviolet transmittance of 308nm of the carrier glass.
The thermal shrinkage is the shrinkage deformation of the glass substrate after high-temperature heat treatment at 550-600 ℃, and the smaller the thermal shrinkage, the quality and the production efficiency of the high-definition panel can be improved.
However, with the progress of the liquid crystal display technology, curved display and advanced generation panels put new demands on the performance of the glass substrate, for example, the glass substrate can bear smaller radius of curvature requirements without cracking during bending, and the large-size substrate has the smallest sagging amount during the transmission process, which needs to improve the requirements of the glass substrate on mechanical properties.
Particularly in the case of a large-size glass substrate of a high generation, for example, the size of a G8.5 generation glass substrate is 2200×2500mm, the size of a G10.5 generation glass substrate is 2940×3370mm, and the thickness of the glass substrate is not more than 0.5mm, the production thereof becomes more difficult as the size of the glass substrate becomes larger, and the quality of the molded product is also required to be higher.
CN104211300a discloses a formula of a glass substrate with high specific modulus, wherein the glass substrate comprises the following components in mole percent: siO (SiO) 2 66％-74％，Al 2 O 3 11％-16％，B 2 O 3 2％-9.5％，MgO 1-6.5％，CaO 3-7％，SrO 0.5-4％，Y 2 O 3 0.01 to 1.5 percent of SnO 0.01 to 0.15 percent. The elastic modulus of the glass substrate is more than 82GPa, and the specific modulus is more than 34 GPa/(g/cm) 3 ) The strain point temperature is greater than 720 ℃, but the transmittance at 308nm is not studied, and the strain point temperature is not suitable for flexible OLED carrier glass.
CN109678341 publicAn alkali-free glass composition, alkali-free glass and a method for preparing the same are provided. The glass composition contains 58 to 64wt% of SiO 2 16-19wt% of Al 2 O 3 7-13wt% of B 2 O 3 +P 2 O 5 0.5 to 3.5 weight percent MgO, 4 to 8 weight percent CaO, 0.1 to 4 weight percent SrO, 0 to 2.5 weight percent BaO, 0 to 4 weight percent ZnO, and less than 0.05 weight percent R 2 O, where R 2 O is Li 2 O、Na 2 O、K 2 And the sum of the contents of O. The Young's modulus of the glass substrate is more than 72GPa, and the specific modulus is more than 30 GPa/(g/cm) 3 ) The strain point is 650-730 ℃, but is not suitable for high-quality flexible OLED panel manufacturing process, which requires a glass substrate with higher strain point and transmittance of 308nm wavelength.
Disclosure of Invention
The invention aims to provide a high-generation alkali-free glass substrate which has higher Young's modulus, higher strain point temperature, low heat shrinkage and high transmittance at 308nm wavelength.
In order to achieve the above object, the present invention provides, in one aspect, a composition for a high-generation alkali-free glass substrate, comprising 59 to 68wt% of SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-8wt% of B 2 O 3 2-4wt% of P 2 O 5 1-3wt% MgO, 0-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 ；
Wherein the weight ratio of MgO/CaO content is not less than 1.0;
the content weight ratio of SrO/CaO is not less than 2.0;
B 2 O 3 /P 2 O 5 the content weight ratio of the components is 1.8-B 2 O 3 /P 2 O 5 ≤3.0；
The SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 0.5-2:1-3.
Preferably, the composition contains 65 to 68wt% SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-7wt% of B 2 O 3 2-3wt% of P 2 O 5 1-3wt% MgO, 0.5-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 。
More preferably, the composition contains 67 to 68wt% SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-6.5wt% of B 2 O 3 2-3wt% of P 2 O 5 1 to 1.5 weight percent of MgO, 1 to 1.5 weight percent of CaO, 3 to 4 weight percent of SrO, 1 to 1.5 weight percent of ZnO and 0.1 to 0.2 weight percent of SnO 2 0.1-0.2wt% of Y 2 O 3 0.2-0.3wt% Ga 2 O 3 。
Preferably, the MgO/CaO content weight ratio satisfies 1.0.ltoreq.MgO/CaO.ltoreq.2.0.
More preferably, the MgO/CaO content weight ratio satisfies 1.0.ltoreq.MgO/CaO.ltoreq.1.2.
Preferably, the SrO/CaO content weight ratio satisfies 2.0.ltoreq.SrO/CaO.ltoreq.4.0.
More preferably, the SrO/CaO content weight ratio satisfies 3.0.ltoreq.SrO/CaO.ltoreq.3.5.
Preferably B 2 O 3 /P 2 O 5 The content weight ratio of (2) to (2) is not less than 2.0 2 O 3 /P 2 O 5 ≤3.0。
Preferably, the SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 1-1.2:2.5-3.
In a second aspect, the present invention provides a method for preparing a high generation alkali-free glass, the method being performed using the composition for a high generation alkali-free glass substrate of the first aspect, comprising:
(1) Carrying out melting treatment on a mixed material containing the composition for the high-generation alkali-free glass substrate to obtain a material I;
(2) Molding the material I to obtain a material II;
(3) And (3) annealing the material II to obtain the high-generation alkali-free glass.
Preferably, the composition for the high-generation alkali-free glass substrate is subjected to mixing treatment to obtain a mixed material before the melting treatment, and the conditions of the mixing treatment at least meet the following conditions: the stirring speed is 15-20rpm, the temperature is 20-40 ℃ and the time is 0.5-1h.
Preferably, the conditions of the melt processing include: the temperature is 1150-1750 ℃ and the time is 2-8h.
Preferably, the annealing conditions include: the temperature is 700-900 ℃ and the time is 0.5-2h.
Preferably, the melting treatment is performed by a two-stage melting method, and the operation steps of the two-stage melting method include:
(1) At a first temperature, preserving the temperature of the mixed material for a first time to obtain an intermediate material; the first temperature is 1150-1250 ℃, and the first time is 1-4h;
(2) At a second temperature, preserving the heat of the intermediate material for a second time to obtain a material I; the second temperature is 1550-1750 ℃, and the second time is 1-4h.
The third aspect of the invention provides a high-generation alkali-free glass substrate prepared by the method of the second aspect.
Preferably, the glass substrate has the following properties:
(1) Young's modulus not lower than 78.2GPa;
(2) The strain point temperature is not lower than 744 ℃;
(3) The heat shrinkage is not higher than 10ppm.
Preferably, the light transmittance of the high-generation alkali-free glass substrate at 308nm is not lower than 80%.
A fourth aspect of the invention provides the use of the high generation alkali-free glass substrate of the third aspect in a display device.
Preferably, the use of the high generation alkali-free glass substrate in an OLED display.
The invention is controlled in the presence ofPreparation of SiO 2 、Al 2 O 3 、B 2 O 3 、P 2 O 5 On the premise of the contents of MgO, caO, srO and ZnO, snO is blended 2 、Y 2 O 3 And Ga 2 O 3 The amount of the glass substrate is precisely adjusted, so that the glass substrate can be endowed with higher Young's modulus and higher strain point temperature, and meanwhile, the glass substrate is low in heat shrinkage and high in transmittance at 308nm wavelength.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, in one aspect, the present invention provides a composition for a high generation alkali-free glass substrate, comprising 59 to 68wt% of SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-8wt% of B 2 O 3 2-4wt% of P 2 O 5 1-3wt% MgO, 0-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 ；
Wherein the weight ratio of MgO/CaO content is not less than 1.0;
the content weight ratio of SrO/CaO is not less than 2.0;
B 2 O 3 /P 2 O 5 the content weight ratio of the components is 1.8-B 2 O 3 /P 2 O 5 ≤3.0；
The SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 0.5-2:1-3.
In the present invention, the composition for a high-generation alkali-free glass substrate is to be understood as the combinationNo additional alkali metal component is required to be added to the composition, which may be added in the form of any simple substance or compound containing alkali metal elements, including Li, na and/or K. It is also understood that alkali metal oxides (Li 2 O、Na 2 O、K 2 O) content is less than 0.1mol%.
The inventors of the present invention have defined the content ranges of the respective components in the composition for a high-generation alkali-free glass substrate provided by the present invention based on the following considerations:
SiO 2 the network forming body of the base glass can be independently formed into glass, belongs to one of the essential components, mainly forms a netlike main structure of the base glass and the microcrystalline glass, and endows the base glass and the microcrystalline glass with better chemical stability, mechanical property and forming property. SiO (SiO) 2 Glass is not easy to form when the content is low, the strain point is reduced, the expansion coefficient is increased, and the acid resistance and the alkali resistance are reduced; excessive SiO2 content can cause excessive melting temperature, difficult melting and aggravated corrosion of the refractory. Therefore, the inventors of the present invention have studied SiO after extensive studies 2 The content of (2) is defined as 59-68wt%.
Al 2 O 3 Is one of the essential components of the base glass, is a network intermediate oxide which has two coordination states in the glass, namely tetraligand [ AlO ] 4 ]And eight coordinated [ AlO 6 ]The method comprises the steps of carrying out a first treatment on the surface of the Al in the base glass 3+ The ion abstracts non-bridging oxygen to charge balance with the basic ions, making most alumina prone to [ AlO ] 4 ]Reconnecting the broken network, thereby forming a part of a glass network structure, improving the stability and mechanical property of the glass and reducing the crystallization tendency of the glass; al (Al) 2 O 3 Excessive content, difficult melting of glass, short material property and easy crystallization; al (Al) 2 O 3 The content is lower, and glass is easy to devitrify, and the mechanical strength is lower, so that the molding is not facilitated. Therefore, the inventors of the present invention have studied the Al in a large amount 2 O 3 The content of (2) is defined as 16-20wt%.
B 2 O 3 As a better glass melting flux, the glass melting property can be improvedThe cost of glass melting is reduced, and when the content of the glass is too low, the fluxing effect of the glass cannot be fully exerted; when B is 2 O 3 If the content of (2) is too high, the strain point of the glass tends to be lowered, and the chemical stability tends to be poor. Therefore, the inventors of the present invention have studied extensively to obtain B 2 O 3 The content of (2) is defined as 6-8wt%.
P 2 O 5 One of the network former components of the base glass, P 5+ The ions have large field intensity, strong oxygen capturing capacity and small accumulation effect; p (P) 2 O 5 Too high a content will cause the base glass to be difficult to form stable glass and cause crystallization of the base glass. Therefore, the inventors of the present invention have studied extensively to obtain P 2 O 5 The content of (2) is defined as 2-4wt%.
MgO is a glass network intermediate, can reduce the high-temperature viscosity of glass, improve the glass meltability and reduce the glass density, and if excessive MgO is contained in glass components, crystallization easily occurs in the glass, and the thermal expansion coefficient is greatly increased, so that the method is unfavorable for subsequent processes. Therefore, the inventors of the present invention have defined the content of MgO to 1-3wt% after extensive studies.
CaO is an external network oxide, can improve chemical stability and mechanical strength, mainly plays a role in stabilization, and when the content is high, the glass material becomes short, the brittleness is increased, and when the content is too high, the hydrolytic resistance is reduced. Therefore, the inventors of the present invention have defined the CaO content to be 0 to 2% by weight after extensive studies.
SrO is an external network oxide, and can improve the glass strain point, young's modulus, reduce expansion coefficient and high-temperature viscosity of the glass, so that the meltability and formability of the glass are improved, and the probability of devitrification is increased due to excessive content. Therefore, the inventors of the present invention have defined the content of SrO to 3-5wt% after extensive studies.
ZnO is a divalent metal oxide, and can improve melting of glass, improve optical properties of glass, and Zn 2+ With hexacoordinated [ ZnO ] 6 ]And four coordinated [ ZnO ] 4 ]State in which six-coordinate [ ZnO ] 6 ]The structure is compact, and four-coordination [ ZnO ] 4 ]The structure is loose, the four coordination number increases with the increase of alkali metal oxide, when four coordination [ ZnO 4 ]When the content is more, the glass network is more loose, which is beneficial to migration of ions (Na+) in the glass, thereby improving the depth of the glass ion strengthening layer, and having positive effects on improving the glass ion strengthening efficiency, strengthening depth and improving the surface strength of the glass; meanwhile, the chemical stability and refractive index of the glass are improved, and the glossiness and transmittance of the glass are improved; however, excessive amount thereof inhibits crystallization of the base glass, thereby causing non-uniform crystallization of the glass. Accordingly, the inventors of the present invention have defined the content of ZnO to be 1-2wt% after extensive studies.
SnO 2 As a clarifying agent for glass, the glass clarifying agent is beneficial to reducing the formation of gas defects in glass melt, reducing the quantity of bubbles in the melt and improving the clarifying effect, but excessive clarifying agent can lead to devitrification of a glass substrate and affect the optical performance of the glass. Therefore, the inventors of the present invention have studied SnO after extensive studies 2 The content of (2) is defined as 0.1-0.3wt%.
Y 2 O 3 The transparency and refractive index of the optical glass can be improved, the chemical stability of the glass can be improved, and the dispersion of the glass can be reduced; y is Y 3+ The field is strong, the electric charge is high, the electric charge is positioned between network gaps, when the introduced amount is small, free oxygen is provided, the network breaking effect is achieved, the network structure is destroyed, the integrity of the silicon oxygen tetrahedron network connection is reduced, and the viscosity is reduced; but when Y 2 O 3 When the addition amount is higher, Y 3+ Free oxygen can be reduced, the accumulation is mainly performed, and the viscosity is increased instead. Therefore, the inventors of the present invention have studied the Y in a large number 2 O 3 The content of (2) is defined as 0.1-0.3wt%.
Ga 2 O 3 The liquid phase temperature can be lowered, the glass melting property can be improved, and the chemical properties of the glass can be improved, but excessive addition deteriorates the devitrification resistance of the glass. Therefore, the inventors of the present invention studied Ga after extensive studies 2 O 3 The content of (2) is defined as 0.1-0.3wt%.
In addition, the inventors of the present invention have found through inventive studies that, when the components are containedThe weight ratio of MgO/CaO content is not less than 1.0, the weight ratio of SrO/CaO content is not less than 2.0, B 2 O 3 /P 2 O 5 The content weight ratio of the components is 1.8-B 2 O 3 /P 2 O 5 Not more than 3.0, and the SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 0.5-2:1-3, the Young's modulus and the strain point temperature of the glass substrate can be obviously improved, the light transmittance of 308nm wavelength is improved, and the heat shrinkage is reduced.
Preferably, the composition contains 65 to 68wt% SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-7wt% of B 2 O 3 2-3wt% of P 2 O 5 1-3wt% MgO, 0.5-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 。
More preferably, the composition contains 67 to 68wt% SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-6.5wt% of B 2 O 3 2-3wt% of P 2 O 5 1 to 1.5 weight percent of MgO, 1 to 1.5 weight percent of CaO, 3 to 4 weight percent of SrO, 1 to 1.5 weight percent of ZnO and 0.1 to 0.2 weight percent of SnO 2 0.1-0.2wt% of Y 2 O 3 0.2-0.3wt% Ga 2 O 3 . The inventors found that, in this preferred embodiment, the glass substrate provided by the present invention has a higher Young's modulus and transmittance at a wavelength of 308 nm.
Preferably, the MgO/CaO content weight ratio satisfies 1.0.ltoreq.MgO/CaO.ltoreq.2.0.
More preferably, the MgO/CaO content weight ratio satisfies 1.0.ltoreq.MgO/CaO.ltoreq.1.2.
Preferably, the SrO/CaO content weight ratio satisfies 2.0.ltoreq.SrO/CaO.ltoreq.4.0.
More preferably, the SrO/CaO content weight ratio satisfies 3.0.ltoreq.SrO/CaO.ltoreq.3.5. The inventors found that, in this preferred embodiment, the glass substrate provided by the present invention has a higher Young's modulus and transmittance at a wavelength of 308nm, while having a lower heat shrinkage.
Preferably B 2 O 3 /P 2 O 5 The content weight ratio of (2) to (2) is not less than 2.0 2 O 3 /P 2 O 5 ≤3.0。
Preferably, the SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 1-1.2:2.5-3. The inventors found that, in this preferred embodiment, the glass substrate provided by the present invention has a higher Young's modulus and transmittance at a wavelength of 308nm, while having a lower heat shrinkage.
As previously described, a second aspect of the present invention provides a method of preparing a high generation alkali-free glass using the composition for a high generation alkali-free glass substrate of the first aspect, comprising:
(1) Carrying out melting treatment on a mixed material containing the composition for the high-generation alkali-free glass substrate to obtain a material I;
(2) Molding the material I to obtain a material II;
(3) And (3) annealing the material II to obtain the high-generation alkali-free glass.
Preferably, the method further comprises: before the melting treatment, the composition for the high-generation alkali-free glass substrate is mixed to obtain a mixed material, and the conditions of the mixing treatment at least meet the following conditions: the stirring speed is 15-20rpm, the temperature is 20-40 ℃ and the time is 0.5-1h.
Preferably, the conditions of the melt processing include: the temperature is 1150-1750 ℃ and the time is 2-8h.
Preferably, the annealing conditions include: the temperature is 700-900 ℃ and the time is 0.5-2h.
In the invention, in the melting treatment, in order to achieve better clarifying homogenization effect, the melting treatment is performed by adopting a two-stage melting method, and the operation steps of the two-stage melting method comprise:
(1) At a first temperature, preserving the temperature of the mixed material for a first time to obtain an intermediate material; the first temperature is 1150-1250 ℃, and the first time is 1-4h;
(2) At a second temperature, preserving the heat of the intermediate material for a second time to obtain a material I; the second temperature is 1550-1750 ℃, and the second time is 1-4h.
Preferably, the temperature rising rate of the first temperature to the second temperature is 2-6 ℃/min.
In the present invention, in the melting process, the melting process may be performed under stirring in order to achieve a better clarifying homogenization effect. The invention is not described in detail herein, and those skilled in the art should not understand the limitation of the invention.
It should be noted that the method of the present invention may further include various post-treatment methods that are conventional in the art, for example, cutting, grinding, polishing the product obtained after the annealing treatment to obtain the high-generation alkali-free glass. The invention is not described in detail herein, and those skilled in the art should not understand the limitation of the invention.
As described above, the third aspect of the present invention provides a high-generation alkali-free glass substrate prepared by the method of the second aspect.
Preferably, the glass substrate has the following properties:
(1) Young's modulus not lower than 78.2GPa;
(2) The strain point temperature is not lower than 744 ℃;
(3) The heat shrinkage is not higher than 10ppm.
Preferably, the light transmittance of the high-generation alkali-free glass substrate at 308nm is not lower than 80%.
As previously described, a fourth aspect of the present invention provides the use of the high-generation alkali-free glass substrate of the third aspect described above in a display device.
Preferably, the use of the high generation alkali-free glass substrate in an OLED display.
The present invention will be described in detail by examples.
In the following examples, all the raw materials used are commercially available unless otherwise specified.
In the examples below, room temperature represents 25 ℃.+ -. 3, unless otherwise specified.
In the examples below, the total amount of the composition was 850g, unless otherwise specified.
In the following examples, the performance test methods involved are as follows:
(1) Young's modulus was measured with reference to ASTMC-623 standard using a materials mechanical testing machine;
(2) Determining a strain point by using an annealing point strain point tester according to an ASTMC-336 standard;
(3) Melting temperature reference astm c-965 glass height Wen Nianwen curve was measured using a rotary high temperature viscometer, melting temperature 200P viscosity corresponding temperature in degrees celsius;
(4) Heat shrinkage rate: the thermal shrinkage adopts a difference value calculation method; glass substrate without any defect, initial length marked L 0 After heat treatment under certain conditions (the heat treatment process conditions of the invention are that the glass is heated to 600 ℃ from room temperature at the heating rate of 10 ℃/min and is kept at the temperature for 10min, and then is cooled to room temperature at the cooling rate of 10 ℃/min), the length of the substrate is contracted by a certain amount, and the length of the substrate is measured again and is marked as L t Heat shrinkage Y t Expressed as: (L) t -L 0 )/L 0 *100 in ppm.
(5) Light transmittance at 308nm wavelength: the transmittance of the glass was measured using an ultraviolet-visible spectrophotometer, the thickness of the glass sample was 0.5mm, and the transmittance at a wavelength of 308nm was taken as a unit of%.
Example 1
This example illustrates the preparation of a high generation alkali-free glass substrate according to the present invention according to the formulation in table 1 and as follows.
The method for preparing the high-generation alkali-free glass substrate comprises the following steps:
(1) After uniformly stirring and mixing the components in the composition for the high-generation alkali-free glass substrate (the stirring speed is 20rpm, the temperature is 25 ℃ and the time is 40 min), placing the mixture in a platinum crucible, and preserving the temperature of the mixture for the first time at the first temperature to obtain an intermediate material; the first temperature is 1200 ℃, and the first time is 2h;
(2) At a second temperature, preserving the heat of the intermediate material for a second time to obtain a material I; the second temperature is 1635 ℃, and the second time is 2h.
(3) Pouring the material I into a cast iron mold (the size is 120mm multiplied by 60mm multiplied by 30 mm) for molding treatment to obtain a material II;
(4) And (3) annealing the material II to obtain the high-generation alkali-free glass substrate, wherein the annealing conditions are as follows: the temperature was 750℃and the time was 1h.
The remaining examples were carried out using procedures similar to those of example 1, except that the formulations used in each example were different, see in particular Table 1, unless otherwise specified.
TABLE 1
Table 1 (subsequent table)
Note that: in the table "/" indicates that no numerical value can be calculated.
Test case
The performance of the high generation alkali-free glass substrates obtained in each of the examples and comparative examples was measured by the foregoing test method, and the specific results are shown in table 2.
TABLE 2
As can be seen from the results of table 2, the high-generation alkali-free glass substrate provided by the present invention can simultaneously achieve higher young's modulus and strain point temperature, lower thermal shrinkage, and higher light transmittance at 308nm wavelength.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A composition for a high-generation alkali-free glass substrate, characterized in that the composition contains 59 to 68wt% of SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-8wt% of B 2 O 3 2-4wt% of P 2 O 5 1-3wt% MgO, 0-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 ；
Wherein the weight ratio of MgO/CaO content is not less than 1.0;
the content weight ratio of SrO/CaO is not less than 2.0;
B 2 O 3 /P 2 O 5 the content weight ratio of the components is 1.8-B 2 O 3 /P 2 O 5 ≤3.0；
The SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 0.5-2:1-3.
2. The composition according to claim 1, wherein the composition comprises 65 to 68 wt.% SiO, based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-7wt% of B 2 O 3 2-3wt% of P 2 O 5 1-3wt% MgO, 0.5-2wt% CaO, 3-5wt% SrO, 1-2wt% ZnO, 0.1-0.3wt% SnO 2 0.1-0.3wt% of Y 2 O 3 0.1-0.3wt% Ga 2 O 3 ；
Preferably, the composition contains 67 to 68wt% SiO based on the total weight of the composition 2 16-20wt% of Al 2 O 3 6-6.5wt% of B 2 O 3 2-3wt% of P 2 O 5 1 to 1.5 weight percent of MgO, 1 to 1.5 weight percent of CaO, 3 to 4 weight percent of SrO, 1 to 1.5 weight percent of ZnO and 0.1 to 0.2 weight percent of SnO 2 0.1-0.2wt% of Y 2 O 3 0.2-0.3wt% Ga 2 O 3 。
3. Composition according to claim 1 or 2, wherein the MgO/CaO content weight ratio satisfies 1.0.ltoreq.mgo/cao.ltoreq.2.0; preferably, the MgO/CaO content weight ratio satisfies 1.0.ltoreq.MgO/CaO.ltoreq.1.2;
and/or the content weight ratio of SrO/CaO is 2.0-4.0; preferably, the content weight ratio of SrO/CaO is 3.0-3.5;
and/or B 2 O 3 /P 2 O 5 The content weight ratio of (2) to (2) is not less than 2.0 2 O 3 /P 2 O 5 ≤3.0；
And/or the SnO 2 Said Y 2 O 3 And the Ga 2 O 3 The content weight ratio of (1): 1-1.2:2.5-3.
4. A method of making a high generation alkali-free glass using the composition of any one of claims 1-3, comprising:
(1) Carrying out melting treatment on the mixed material containing the composition for the high-generation alkali-free glass substrate to obtain a material I;
(2) Molding the material I to obtain a material II;
(3) And (3) annealing the material II to obtain the high-generation alkali-free glass.
5. The method of claim 4, further comprising: before the melting treatment, the composition for the high-generation alkali-free glass substrate is mixed to obtain a mixed material, and the conditions of the mixing treatment at least meet the following conditions: the stirring speed is 15-20rpm, the temperature is 20-40 ℃ and the time is 0.5-1h.
6. The method according to claim 4 or 5, wherein the conditions of the melt processing include: the temperature is 1150-1750 ℃ and the time is 2-8h;
and/or, the annealing treatment conditions include: the temperature is 700-900 ℃ and the time is 0.5-2h.
7. The method of claim 6, wherein the melting treatment is performed by a two-stage melting method, and the operating step of the two-stage melting method comprises:
(1) At a first temperature, preserving the temperature of the mixed material for a first time to obtain an intermediate material; the first temperature is 1150-1250 ℃, and the first time is 1-4h;
(2) At a second temperature, preserving the heat of the intermediate material for a second time to obtain a material I; the second temperature is 1550-1750 ℃, and the second time is 1-4h.
8. A high generation alkali-free glass substrate made by the method of any one of claims 4-7.
9. The high generation alkali-free glass substrate of claim 8, wherein the glass substrate has the following properties:
(1) Young's modulus not lower than 78.2GPa;
(2) The strain point temperature is not lower than 744 ℃;
(3) The heat shrinkage is not higher than 10ppm;
preferably, the light transmittance of the high-generation alkali-free glass substrate at 308nm is not lower than 80%.
10. Use of the high generation alkali-free glass substrate of claim 9 in a display device;
and/or, the application of the high-generation alkali-free glass substrate in an OLED display.
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