CN117550798A - Alkali-free glass - Google Patents
Alkali-free glass Download PDFInfo
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- CN117550798A CN117550798A CN202311373160.6A CN202311373160A CN117550798A CN 117550798 A CN117550798 A CN 117550798A CN 202311373160 A CN202311373160 A CN 202311373160A CN 117550798 A CN117550798 A CN 117550798A
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- Prior art keywords
- alkali
- free glass
- cao
- sio
- mgo
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- 239000011521 glass Substances 0.000 title claims abstract description 95
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 50
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims description 4
- 239000006060 molten glass Substances 0.000 claims description 3
- 238000006124 Pilkington process Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 21
- 230000009477 glass transition Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to alkali-free glass. The present invention relates to an alkali-free glass satisfying both high young's modulus and high specific elastic modulus, and more particularly, to an alkali-free glass comprising, in mass% based on oxide: siO (SiO) 2 40～61、Al 2 O 3 15～23.5、MgO 2～20、CaO 0.1～40，[SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6.ltoreq.0, and [ SiO ] 2 ]+0.21×[MgO]+1.16×[CaO]‑83.0≤0。
Description
The present application is a divisional application of chinese patent application with application number 201480036486.2, 24 days of application 6, 2014.
Technical Field
The present invention relates to an alkali-free glass which contains substantially no alkali metal oxide and satisfies both high young's modulus and high specific elastic modulus, and which is suitable as a substrate glass for displays or a substrate glass for photomasks used in the production of various Flat Panel Displays (FPDs).
Background
With the progress of high definition and large size of FPDs, deformation due to self-weight deflection, and accompanying defects or board breakage may occur in the manufacturing process, and the yield may decrease. In addition, in order to sufficiently secure the practical strength of a large FPD, it is useful to improve the fracture toughness of the substrate glass.
Accordingly, various substrate glasses for display use are required to have a high specific elastic modulus for reducing the self-weight deflection and a high young's modulus for improving the fracture toughness.
On the other hand, various substrate glasses for displays, particularly those having a metal or oxide thin film formed on the surface thereof, have conventionally been required to have the following characteristics, for example, as shown in patent document 1.
(1) Has sufficient chemical durability for various chemicals used in semiconductor formation. Particularly, the resist stripping liquid has durability against alkali such as buffered hydrofluoric acid (BHF: mixed solution of hydrofluoric acid and ammonium fluoride) used for etching SiOx or SiNx, a hydrochloric acid-containing chemical solution used for etching ITO, various acids (nitric acid, sulfuric acid, etc.) used for etching metal electrodes, and a resist stripping liquid.
(2) In order to increase the rate of temperature rise and decrease in heat treatment during the production of a liquid crystal display device, thereby improving productivity or improving thermal shock resistance, it is required that the average thermal expansion coefficient of glass is small.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2001-348247
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide an alkali-free glass which is suitable as a substrate glass for a display or a substrate glass for a photomask and which satisfies both a high Young's modulus and a high specific elastic modulus.
Means for solving the problems
The present invention provides an alkali-free glass, wherein the alkali-free glass contains, in mass% based on oxides:
SiO 2 40～61、
Al 2 O 3 15～23.5、
MgO 2～20、
CaO 0.1～40，
[SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6.ltoreq.0, and
[SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0≤0。
effects of the invention
The alkali-free glass of the present invention is suitable as a substrate glass for various displays or a substrate glass for photomasks, and can be used as a glass substrate for magnetic disks, etc. However, when the glass plate is required to be large and thin, the young's modulus is high and the modulus is higher than the elastic modulus, and therefore, the glass plate is effective as a substrate glass for various displays or a substrate glass for photomasks.
Detailed description of the preferred embodiments
Next, the composition ranges of the respective components will be described. SiO (SiO) 2 Less than 40% by mass, the devitrification adhesion and acid resistance are reduced unless otherwise indicated. Preferably 45% or more, more preferably 50% or more, further preferably 53% or more, and particularly preferably 55% or more. Above 61%, young's modulus decreases. More preferably 60.5% or less, and still more preferably 60% or less.
By containing Al 2 O 3 When the Young's modulus and the specific elastic modulus are increased to more than 23.5%, the devitrification temperature is increased, and thus the production of glass becomes difficult. Preferably 23% or less, more preferably 22% or less, further preferably 21% or less, particularly preferably 20% or less. In addition, when the content is less than 15%, the devitrification temperature increases, and thus the production of glass becomes difficult. Preferably 16% or more, more preferably 17% or more, still more preferably 18% or more, and particularly preferably 19% or more.
MgO contributes to an improvement in Young's modulus and specific elastic modulus. The specific elastic modulus decreases at less than 2%. Preferably 3% or more, more preferably 6% or more, still more preferably 8% or more, and particularly preferably 10% or more. In addition, devitrification is liable to occur at more than 20%. Preferably 18% or less, more preferably 17% or less, further preferably 16% or less, particularly preferably 15% or less.
The CaO content can reduce the devitrification temperature and increase the Young's modulus, but when the content is too large, the CaO content is too much due to the SiO 2 Excessive substitution increases density and decreases specific elastic modulus. Therefore, the content is set to 40% or less. Preferably 30% or less, more preferably 25% or less, further preferably 20% or less, particularly preferably 15% or less. On the other hand, when the Young's modulus is smaller than 0.1%, the above-mentioned Young's modulus-improving effect cannot be exerted. Preferably 1% or more, more preferably 5% or more, further preferably 8% or more, and particularly preferably 10% or more.
For SiO as 2 、Al 2 O 3 As a result of examining the relationship between the composition and physical properties of the glass in detail, the inventors of the present invention have found that, in order to increase the Young's modulus and specific elastic modulus together, it is necessary to adjust the specific blending ratio according to the degree of contribution of each component. By adjusting the blending ratio to satisfy the following formulas (1) and (2), a high Young's modulus of 94.5GPa or more and 34.5GPa cm can be simultaneously achieved 3 High specific elastic modulus of not less than/g.
[SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤0 (1)
[SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0≤0 (2)
The formula (1) is a blend ratio for satisfying a Young's modulus of 94.5GPa or more, and the formula (2) is a blend ratio for satisfying a specific elastic modulus of 34.5GPa cm 3 The mixing ratio of the components is higher than/g. When the values of the above formulae (1) and (2) are out of the range, the target properties of Young's modulus and specific elastic modulus cannot be satisfied at the same time.
Other components, for example, the following components may be contained within a range that does not hinder the effects of the present invention. In order to suppress decrease in Young's modulus, the other components in this case are preferably less than 5%, more preferably less than 3%, still more preferably less than 1%, still more preferably less than 0.5%, and particularly preferably substantially free, i.e., excluding unavoidableThe free impurities are not contained. Thus, in the present invention, siO 2 、Al 2 O 3 The total content of CaO and MgO is preferably 95% or more, more preferably 97% or more, still more preferably 99% or more, and still more preferably 99.5% or more. Particularly preferably consists essentially of SiO 2 、Al 2 O 3 Constituted by CaO and MgO, i.e. SiO, except for unavoidable impurities 2 、Al 2 O 3 CaO and MgO.
To improve the chemical resistance of the glass, it may contain less than 3% of B 2 O 3 . On the other hand, due to the inclusion of B 2 O 3 The Young's modulus is reduced, and therefore the content is preferably less than 1%, more preferably less than 0.5%, and particularly preferably substantially no.
By containing ZrO 2 The Young's modulus can be increased, but the devitrification temperature is increased at the same time, so that the content is preferably less than 3%, more preferably less than 1%, still more preferably less than 0.5%, particularly preferably substantially free.
In order to improve the melting property, srO and BaO may be contained within a range not impairing the mechanical properties, specifically, young's modulus and specific elastic modulus. Preferably less than 1%, even more preferably less than 0.5%, and particularly preferably substantially free of each.
In the present invention, the glass raw material may contain ZnO and SO in an amount of less than 1%, preferably less than 0.5%, more preferably less than 0.3%, still more preferably less than 0.1%, based on the total amount, in order to improve the meltability, clarity and formability of the glass 3 、Fe 2 O 3 、F、Cl、SnO 2 。
In order to prevent deterioration of characteristics of a metal or oxide thin film provided on the surface of glass at the time of manufacturing a panel, the glass of the present invention does not contain an alkali metal oxide exceeding the impurity level (i.e., does not substantially contain an alkali metal oxide). In order to facilitate recovery of the glass, it is preferable that PbO and As are substantially not contained 2 O 3 、Sb 2 O 3 。
The Young's modulus of the alkali-free glass of the present invention is preferably 94.5GPa or more. The high young's modulus improves fracture toughness, and is therefore suitable for various display substrate glasses and photomask substrate glasses, which require an increase in size and a reduction in thickness of a glass plate.
In order to reduce the deflection by weight, the alkali-free glass of the present invention preferably has a specific elastic modulus of 34.5GPa cm 3 And/g. When the modulus is higher than the elastic modulus, the deformation due to the self-weight deflection in the manufacturing process is small, and the glass is suitable for various display substrate glasses and photomask substrate glasses, which require the glass to be large-sized and thin.
The alkali-free glass of the present invention can be produced, for example, by the following method. Raw materials of each component which are generally used are prepared into a target component, and the target component is continuously charged into a furnace, heated to 1550 to 1650 ℃ and melted. The molten glass is formed into a predetermined plate thickness by a float method, annealed, and then cut, whereby a sheet glass can be obtained.
Examples
Examples 1 to 50 and 55 to 58 are examples, and examples 51 to 54 are comparative examples. Raw materials of each component were prepared into a target composition, and melted at a temperature of 1550 to 1650 ℃ using a platinum crucible. Then, the molten glass is flowed out, formed into a plate shape, and annealed.
Tables 1 to 10 show glass compositions (unit: mass%) and densities ρ (g/cm) containing values of formulas (1), (2) 3 ) Young's modulus E (GPa) (measured by ultrasonic method), specific elastic modulus E/ρ (GPa cm) 3 /g), vickers hardness Hv, glass viscosity eta of 10 2 Temperature T at poise 2 (unit: DEG C), glass transition temperature Tg (unit: DEG C), and average thermal expansion coefficient (unit: 10) at 50 to 350 ℃ -7 /℃)。
In tables 1 to 10, the values indicated by brackets are calculated values.
TABLE 1
| Mass percent of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| SiO 2 | 60 | 50 | 54 | 60 | 60 | 59.3 |
| Al 2 O 3 | 20 | 20 | 20 | 20 | 20 | 21 |
| MgO | 10 | 13 | 14 | 14 | 12 | 11.9 |
| CaO | 10 | 17 | 12 | 6 | 8 | 7.9 |
| B 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -0.1 | -6.0 | -4.9 | -2.5 | -1.3 | -1.7 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -9.3 | -10.6 | -12.1 | -13.1 | -11.2 | -12.1 |
| Density ρ (g/cm) 3 ) | 2.60 | 2.75 | 2.69 | 2.60 | 2.60 | 2.60 |
| Young's modulus E (GPa) | 95.3 | 101.9 | 100.6 | 96.9 | 96.2 | 96.4 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 36.7 | 37.1 | 37.4 | 37.3 | 37.0 | 37.0 |
| Vickers hardness Hv | 672 | 713 | - | - | - | - |
| T 2 (℃) | 1527 | 1338 | 1397 | 1489 | 1505 | 1511 |
| Glass transition temperature Tg (. Degree. C.) | 784 | 749 | 755 | 772 | 776 | 776 |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | 44 | 58 | 52 | 44 | 44 | 44 |
TABLE 2
| Mass percent of | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| SiO 2 | 58.5 | 57.8 | 58.0 | 45 | 42 | 51.5 |
| Al 2 O 3 | 22 | 23 | 20 | 20 | 20 | 20 |
| MgO | 11.7 | 7.7 | 14 | 15.0 | 9.0 | 14.5 |
| CaO | 7.8 | 11.6 | 8 | 20 | 29 | 14 |
| B 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -2.0 | -0.1 | -3.3 | -9.2 | -6.9 | -6.2 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -13.0 | -10.2 | -12.8 | -11.7 | -5.5 | -12.2 |
| Density ρ (g/cm) 3 ) | 2.61 | 2.61 | 2.64 | 2.82 | 2.86 | 2.73 |
| Young's modulus E (GPa) | 96.9 | 94.5 | 97.6 | 104.1 | 104.7 | 103.3 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 37.2 | 36.1 | 37.0 | 37.0 | 36.6 | 37.9 |
| Vickers hardness Hv | (695) | 694 | 710 | 763 | 727 | 713 |
| T 2 (℃) | 1517 | 1524 | 1458 | 1271 | 1257 | 1354 |
| Glass transition temperature Tg (. Degree. C.) | 778 | 778 | 762 | 741 | 748 | 748 |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | 44 | 46 | 48 | 66 | 74 | 58 |
TABLE 3
| Mass percent of | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 |
| SiO 2 | 53.3 | 52.7 | 52 | 54 | 45 | 57 |
| Al 2 O 3 | 21 | 22 | 23 | 20 | 16 | 17 |
| MgO | 13.8 | 13.7 | 13.5 | 18 | 10 | 10 |
| CaO | 11.9 | 11.7 | 11.6 | 8 | 29 | 16 |
| B 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -5.3 | -5.6 | -5.9 | -7.3 | -5.6 | -0.8 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -13.0 | -13.9 | -14.8 | -15.9 | -2.3 | -5.3 |
| Density ρ (g/cm) 3 ) | 2.69 | 2.70 | 2.70 | 2.69 | 2.85 | 2.69 |
| Young's modulus E (GPa) | 100.0 | 100.5 | 100.7 | 102.1 | 101.7 | 96.4 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 37.1 | 37.3 | 37.3 | 37.9 | 35.7 | 35.9 |
| Vickers hardness Hv | (713) | (716) | (718) | (725) | (707) | (683) |
| T 2 (℃) | (1406) | (1413) | (1419) | (1369) | 1310 | 1430 |
| Glass transition temperature Tg (. Degree. C.) | 755 | 753 | 759 | (747) | 750 | 772 |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | 53 | 52 | 52 | (51) | (75) | (54) |
TABLE 4
| Mass percent of | Example 19 | Example 20 | Example 21 | Example 22 | Example 23 | EXAMPLE 24 |
| SiO 2 | 60.5 | 58.5 | 52 | 56 | 60 | 55 |
| Al 2 O 3 | 21.5 | 20 | 20 | 20 | 20 | 20 |
| MgO | 11.7 | 13 | 16 | 16 | 13 | 9 |
| CaO | 6.3 | 8.5 | 12 | 8 | 7 | 16 |
| B 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -1.1 | -2.5 | -6.9 | -5.3 | -1.9 | -1.6 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -12.7 | -11.9 | -13.7 | -14.4 | -12.2 | -7.6 |
| Density ρ (g/cm) 3 ) | 2.59 | 2.62 | 2.71 | 2.66 | 2.60 | 2.68 |
| Young's modulus E (GPa) | 96.0 | 97.1 | 101.7 | 100.1 | 97.5 | 95.7 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 37.1 | 37.0 | 37.5 | 37.7 | 37.5 | 35.7 |
| Vickers hardnessDegree Hv | (690) | (697) | (722) | (713) | (693) | (689) |
| T 2 (℃) | 1538 | (1474) | (1354) | (1413) | (1497) | (1454) |
| Glass transition temperature Tg (. Degree. C.) | 777 | (757) | (747) | (768) | (748) | (756) |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | (41) | (46) | (55) | (49) | (44) | (54) |
TABLE 5
| Mass percent of | Example 25 | Example 26 | Example 27 | EXAMPLE 28 | Example 29 | Example 30 |
| SiO 2 | 50 | 45 | 40 | 58 | 45 | 45 |
| Al 2 O 3 | 20 | 20 | 20 | 20 | 20 | 15 |
| MgO | 8 | 7 | 6 | 16 | 18 | 14 |
| CaO | 22 | 28 | 34 | 6 | 17 | 26 |
| B 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -3.0 | -4.5 | -5.9 | -4.5 | -11.0 | -7.8 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -5.8 | -4.1 | -2.3 | -14.7 | -14.5 | -4.9 |
| Density ρ (g/cm) 3 ) | 2.75 | 2.81 | 2.87 | 2.64 | 2.81 | 2.85 |
| Young's modulus E (GPa) | 97.4 | 99.1 | 100.4 | 98.6 | 105.3 | 103.8 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 35.4 | 35.2 | 35.0 | 37.4 | 37.5 | 36.4 |
| Vickers hardness Hv | (696) | (703) | (710) | (709) | (744) | 720 |
| T 2 (℃) | (1386) | (1319) | (1250) | (1343) | (1238) | (1196) |
| Glass transition temperature Tg (. Degree. C.) | (771) | (774) | (767) | (761) | (759) | (747) |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | (62) | (71) | (80) | (46) | (65) | (74) |
TABLE 6
| Mass percent of | Example 31 | Example 32 | Example 33 | Example 34 | Example 35 | Example 36 |
| SiO 2 | 55 | 50 | 45 | 50 | 55 | 60 |
| Al 2 O 3 | 15 | 15 | 18 | 18 | 18 | 18 |
| MgO | 11 | 14 | 8 | 12 | 17 | 11 |
| CaO | 19 | 11 | 29 | 20 | 10 | 11 |
| B 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -1.9 | -1.7 | -4.8 | -5.1 | -6.0 | -0.4 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -3.7 | -8.0 | -2.7 | -7.3 | -12.8 | -7.9 |
| Density ρ (g/cm) 3 ) | 2.72 | 2.64 | 2.82 | 2.75 | 2.72 | 2.61 |
| Young's modulus E (GPa) | 96.5 | 95.8 | 99.7 | 99.8 | 101.7 | 95.1 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 35.5 | 36.3 | 35.3 | 36.3 | 37.4 | 36.4 |
| Vickers hardness Hv | 688 | (706) | (703) | (707) | 706 | (682) |
| T 2 (℃) | (1361) | (1360) | (1281) | (1325) | (1361) | (1482) |
| Glass transition temperature Tg [ ]℃) | (731) | (739) | (765) | (754) | (757) | (755) |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | (60) | (54) | (73) | (63) | (53) | (47) |
TABLE 7
| Mass percent of | Example 37 | Example 38 | Example 39 | Example 40 | Example 41 | Example 42 |
| SiO 2 | 54 | 54 | 54 | 54 | 54 | 54 |
| Al 2 O 3 | 20 | 20 | 20 | 20 | 20 | 20 |
| MgO | 13.5 | 12.5 | 13.5 | 12.5 | 13.5 | 12.5 |
| CaO | 11.5 | 10.5 | 11.5 | 10.5 | 11.5 | 10.5 |
| B 2 O 3 | 1 | 3 | 0 | 0 | 0 | 0 |
| BaO | 0 | 0 | 0 | 0 | 1 | 3 |
| SrO | 0 | 0 | 1 | 3 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -5.2 | -5.8 | -5.2 | -5.8 | -5.2 | -5.8 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -12.8 | -14.2 | -12.8 | -14.2 | -12.8 | -14.2 |
| Density ρ (g/cm) 3 ) | 2.67 | 2.63 | 2.69 | 2.71 | 2.70 | 2.71 |
| Young's modulus E (GPa) | 98.7 | 95.9 | 99.1 | 97.7 | 98.9 | 97.2 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 36.9 | 36.4 | 36.8 | 36.1 | 36.6 | 35.9 |
| Vickers hardness Hv | 701 | 699 | 707 | 703 | 709 | 697 |
| T 2 (℃) | — | — | — | — | — | — |
| Glass transition temperature Tg (. Degree. C.) | — | — | — | — | — | — |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | — | — | — | — | — | — |
TABLE 8
| Mass percent of | Example 43 | Example 44 | Example 45 | Example 46 | Example 47 | Example 48 |
| SiO 2 | 54 | 54 | 54 | 54 | 54 | 54 |
| Al 2 O 3 | 20 | 20 | 20 | 20 | 20 | 20 |
| MgO | 13.5 | 12.5 | 13.5 | 12.5 | 13.5 | 12.5 |
| CaO | 11.5 | 10.5 | 11.5 | 10.5 | 11.5 | 10.5 |
| B 2 O 3 | 0.5 | 1.5 | 0.5 | 1.5 | 0 | 0 |
| BaO | 0.5 | 1.5 | 0 | 0 | 0.5 | 1.5 |
| SrO | 0 | 0 | 0.5 | 1.5 | 0.5 | 1.5 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -5.2 | -5.8 | -5.2 | -5.8 | -5.2 | -5.8 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -12.8 | -14.2 | -12.8 | -14.2 | -12.8 | -14.2 |
| Density ρ (g/cm) 3 ) | 2.61 | 2.68 | 2.67 | 2.67 | 2.70 | 2.71 |
| Young's modulus E (GPa) | 96.0 | 98.8 | 96.6 | 96.6 | 98.7 | 97.6 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | 36.8 | 36.8 | 36.1 | 36.2 | 36.6 | 36.0 |
| Vickers hardness Hv | 710 | 699 | 707 | 700 | 707 | 701 |
| T 2 (℃) | — | — | — | — | — | — |
| Glass transition temperature Tg (. Degree. C.) | — | — | — | — | — | — |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | — | — | — | — | — | — |
TABLE 9
| Mass percent of | Example 49 | Example 50 | Example 51 | Example 52 | Example 53 | Example 54 |
| SiO 2 | 54 | 54 | 59.6 | 60.6 | 61 | 64 |
| Al 2 O 3 | 20 | 20 | 17.2 | 18.8 | 17 | 20 |
| MgO | 13.5 | 12.5 | 3.2 | 4.4 | 12.6 | 8.5 |
| CaO | 11.5 | 10.5 | 3.8 | 3.9 | 0 | 7.5 |
| B 2 O 3 | 0 | 0 | 8.1 | 4.7 | 9.4 | 0 |
| BaO | 0 | 0 | 8.1 | 7.6 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 1 | 3 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -5.2 | -5.8 | * | * | * | 2.4 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -12.8 | -14.2 | * | * | * | -8.5 |
| Density ρ (g/cm) 3 ) | (2.69) | (2.70) | 2.51 | (2.56) | 2.60 | 2.54 |
| Young's modulus E (GPa) | (99) | (100) | 76.0 | (84.6) | 92.7 | 94.1 |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | (37.2) | (36.7) | 30.3 | (37.8) | 35.6 | 37 |
| Vickers hardness Hv | — | — | 580 | (726) | 762 | 663 |
| T 2 (℃) | — | — | 1669 | (1647) | (1494) | 1622 |
| Glass transition temperature Tg (. Degree. C.) | — | — | 720 | (726) | 764 | 793 |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | — | — | 38 | (38) | 47 | 40 |
* : outside the application composition range of the above (1), (2)
TABLE 10
| Mass percent of | Example 55 | Example 56 | Example 57 | Example 58 |
| SiO 2 | 60.5 | 58.5 | 58.2 | 56.6 |
| Al 2 O 3 | 21 | 18 | 22 | 21 |
| MgO | 0.4 | 0.9 | 0.9 | 2.5 |
| CaO | 12 | 12.2 | 10.6 | 12.8 |
| B 2 O 3 | 6.1 | 10.4 | 8.3 | 7.1 |
| BaO | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 |
| [SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 | -1.5 | -2.2 | -2.04 | -4.78 |
| [SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0 | -12.9 | -9.9 | -12.9 | -15.5 |
| Density ρ (g/cm) 3 ) | (2.58) | (2.62) | (2.60) | (2.60) |
| Young's modulus E (GPa) | (95.5) | (95.4) | (95.3) | (95.4) |
| Specific elastic modulus E/ρ (GPa cm) 3 /g) | (37.0) | (36.4) | (36.7) | (36.7) |
| Vickers hardness Hv | — | — | — | — |
| T 2 (℃) | (1538) | (1483) | (1519) | (1473) |
| Glass transition temperature Tg (. Degree. C.) | (773) | (756) | (773) | (751) |
| Average coefficient of thermal expansion alpha (×10) -7 /℃) | (41) | (48) | (44) | (44) |
As is clear from the results, the Young's moduli of the glasses of the examples were all 94.5GPa or more and the specific elastic moduli were all 34.5GPa cm 3 And/g.
The present invention has been described in detail with reference to specific embodiments, but it will be apparent to one skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the invention.
The present application is based on japanese patent application 2013-134752 filed on 27, 6, 2013, the contents of which are incorporated herein by reference.
Industrial applicability
The alkali-free glass of the present invention is suitable as a substrate glass for various displays or a substrate glass for photomasks, and can be used as a glass substrate for magnetic disks, etc. However, when the glass plate is required to be large and thin, the young's modulus is high and the modulus is higher than the elastic modulus, and therefore, the glass plate is effective as a substrate glass for various displays or a substrate glass for photomasks.
Claims (31)
1. An alkali-free glass, wherein the alkali-free glass contains, in mass% on an oxide basis:
SiO 2 50～61、
Al 2 O 3 18～23.5、
MgO 2～20、
CaO 0.1～29，
[SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6 is less than or equal to-1.1, and
[SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0≤-10.6，
SiO 2 、Al 2 O 3 the total content of CaO and MgO is 95% or more,
the alkali-free glass contains less than 3% of B 2 O 3 Or is substantially free of B 2 O 3 ，
The Young's modulus of the alkali-free glass is more than 94.5GPa, and the specific elastic modulus is 34.5GPa cm 3 And/g.
2. The alkali-free glass according to claim 1, wherein SiO is in mass% based on oxide 2 、Al 2 O 3 The total content of CaO and MgO is 97% or more.
3. The alkali-free glass according to claim 1, wherein SiO is in mass% based on oxide 2 、Al 2 O 3 The total content of CaO and MgO is 99% or more.
4. The alkali-free glass according to claim 1, wherein SiO is in mass% based on oxide 2 、Al 2 O 3 The total content of CaO and MgO is 99.5% or more.
5. The alkali-free glass according to any one of claims 1 to 4, wherein the content of MgO is 3% or more in mass% based on the oxide.
6. The alkali-free glass according to any one of claims 1 to 4, wherein the content of MgO is 6% or more in mass% based on the oxide.
7. The alkali-free glass according to any one of claims 1 to 4, wherein the content of MgO is 8% or more in mass% based on the oxide.
8. The alkali-free glass according to any one of claims 1 to 4, wherein the content of MgO is 10% or more in mass% based on the oxide.
9. The alkali-free glass according to any one of claims 1 to 8, wherein the content of MgO is 18% or less by mass% based on the oxide.
10. The alkali-free glass according to any one of claims 1 to 8, wherein the content of MgO is 17% or less by mass% based on the oxide.
11. The alkali-free glass according to any one of claims 1 to 8, wherein the content of MgO is 16% or less by mass% based on the oxide.
12. The alkali-free glass according to any one of claims 1 to 8, wherein the content of MgO is 15% or less by mass% based on the oxide.
13. The alkali-free glass according to any one of claims 1 to 12, wherein the content of CaO is 1% or more in mass% on an oxide basis.
14. The alkali-free glass according to any one of claims 1 to 12, wherein the content of CaO is 5% or more by mass% based on oxides.
15. The alkali-free glass according to any one of claims 1 to 14, wherein the content of CaO is 25% or less by mass% based on oxides.
16. The alkali-free glass according to any one of claims 1 to 14, wherein the content of CaO is 20% or less by mass% based on oxides.
17. The alkali-free glass according to any one of claims 1 to 14, wherein the content of CaO is 15% or less by mass% based on oxides.
18. The alkali-free glass of any one of claims 1 to 17, wherein [ SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤-1.5。
19. The alkali-free glass of any one of claims 1 to 17, wherein [ SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤-1.6。
20. The alkali-free glass of any one of claims 1 to 17, wherein [ SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤-1.9。
21. The alkali-free glass of any one of claims 1 to 17, wherein [ SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤-2.5。
22. The alkali-free glass of any one of claims 1 to 17, wherein [ SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤-3.0。
23. Such as weightThe alkali-free glass of any one of claims 1 to 17, wherein [ SiO 2 ]+0.43×[Al 2 O 3 ]+0.59×[CaO]-74.6≤-3.3。
24. The alkali-free glass of any one of claims 1 to 23, wherein [ SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0≤-11.9。
25. The alkali-free glass of any one of claims 1 to 23, wherein [ SiO 2 ]+0.21×[MgO]+1.16×[CaO]-83.0≤-12.2。
26. The alkali-free glass of any of claims 1-25, wherein the young's modulus of the alkali-free glass is 95.3GPa or greater.
27. The alkali-free glass of any of claims 1-25, wherein the young's modulus of the alkali-free glass is 96.4GPa or greater.
28. The alkali-free glass of any one of claims 1 to 27, wherein the alkali-free glass has a specific elastic modulus of 35.0GPa cm 3 And/g.
29. The alkali-free glass of any one of claims 1 to 27, wherein the alkali-free glass has a specific elastic modulus of 35.4GPa cm 3 And/g.
30. The alkali-free glass of any one of claims 1 to 27, wherein the alkali-free glass has a specific elastic modulus of 35.9GPa cm 3 And/g.
31. The alkali-free glass of any one of claims 1 to 30, wherein the alkali-free glass is manufactured by:
the raw materials of the respective components are heated to 1550 to 1650 ℃ to be melted, and the molten glass is formed by a float process and then annealed.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013134752A JP2016155693A (en) | 2013-06-27 | 2013-06-27 | Alkali-free glass |
| JP2013-134752 | 2013-06-27 | ||
| PCT/JP2014/066624 WO2014208522A1 (en) | 2013-06-27 | 2014-06-24 | Alkali-free glass |
| CN201480036486.2A CN105392743A (en) | 2013-06-27 | 2014-06-24 | Alkali-free glass |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480036486.2A Division CN105392743A (en) | 2013-06-27 | 2014-06-24 | Alkali-free glass |
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| CN117550798A true CN117550798A (en) | 2024-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480036486.2A Pending CN105392743A (en) | 2013-06-27 | 2014-06-24 | Alkali-free glass |
| CN202311373160.6A Pending CN117550798A (en) | 2013-06-27 | 2014-06-24 | Alkali-free glass |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201480036486.2A Pending CN105392743A (en) | 2013-06-27 | 2014-06-24 | Alkali-free glass |
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|---|---|
| JP (1) | JP2016155693A (en) |
| KR (1) | KR102268829B1 (en) |
| CN (2) | CN105392743A (en) |
| TW (1) | TW201509854A (en) |
| WO (1) | WO2014208522A1 (en) |
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| WO2017033246A1 (en) * | 2015-08-21 | 2017-03-02 | 日東紡績株式会社 | Glass composition for glass fibers |
| JP7448741B2 (en) | 2017-12-19 | 2024-03-13 | オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | High performance fiberglass composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3804101B2 (en) * | 1995-04-27 | 2006-08-02 | 旭硝子株式会社 | Glass substrate for magnetic disk |
| JPH1079122A (en) * | 1996-09-04 | 1998-03-24 | Hoya Corp | Method for selecting material suitable for substrate of information recording medium, material selected by using the method, and substrate and magnetic disk using the material |
| US6060168A (en) * | 1996-12-17 | 2000-05-09 | Corning Incorporated | Glasses for display panels and photovoltaic devices |
| JP2000159539A (en) * | 1998-11-25 | 2000-06-13 | Asahi Glass Co Ltd | Glass for information recording medium substrate |
| JP2001348247A (en) | 2000-05-31 | 2001-12-18 | Asahi Glass Co Ltd | Alkaline-free glass |
| JP4977965B2 (en) * | 2005-05-02 | 2012-07-18 | 旭硝子株式会社 | Alkali-free glass and method for producing the same |
| US8281618B2 (en) * | 2005-12-16 | 2012-10-09 | Nippon Electric Glass Co., Ltd. | Alkali-free glass substrate and process for producing the same |
-
2013
- 2013-06-27 JP JP2013134752A patent/JP2016155693A/en active Pending
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2014
- 2014-06-24 CN CN201480036486.2A patent/CN105392743A/en active Pending
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- 2014-06-24 CN CN202311373160.6A patent/CN117550798A/en active Pending
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| WO2014208522A1 (en) | 2014-12-31 |
| TW201509854A (en) | 2015-03-16 |
| KR102268829B1 (en) | 2021-06-25 |
| JP2016155693A (en) | 2016-09-01 |
| CN105392743A (en) | 2016-03-09 |
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