CN114671616A - High-strength transparent microcrystalline glass and preparation method thereof - Google Patents
High-strength transparent microcrystalline glass and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 21
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 14
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 5
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 46
- 239000002241 glass-ceramic Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 239000006112 glass ceramic composition Substances 0.000 claims description 5
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 claims description 5
- 238000009749 continuous casting Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000006124 Pilkington process Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 13
- 238000013461 design Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 description 24
- 230000008025 crystallization Effects 0.000 description 24
- 239000011734 sodium Substances 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000004031 devitrification Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000006132 parent glass Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000006121 base glass Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical group [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical group [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Chemical group 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
Images
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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of microcrystalline glass, and provides high-strength transparent microcrystalline glass which comprises the following components in percentage by mass: SiO 22：55％‑75％、Al2O3：4％‑10％、Li2O：8％‑14％、Na2O：5.1％‑8％、P2O5：1.5％‑5％、ZrO2：2％‑10％、Sb2O3：0.2％‑0.8％、CeO2: 0.2 to 1.0 percent. According to the invention, through component design and microcrystallization process regulation and control, the obtained microcrystalline glass material has excellent mechanical property and optical property, can be further chemically strengthened to improve the mechanical property, and is suitable for electronic equipment or display equipment.
Description
Technical Field
The invention relates to the technical field of microcrystalline glass, in particular to high-strength transparent microcrystalline glass and a preparation method thereof.
Background
As a transparent material with excellent mechanical properties and optical properties, a glass material is widely applied to mobile intelligent terminal devices, such as mobile phones, smart watches, tablets, personal computers and other portable electronic devices, and in addition, glass is also used to protect internal electronic components of vehicle-mounted display automobiles, aviation instrument displays and the like. However, the glass material may be scratched or damaged by impact when contacted by a hard object, which requires that the glass has excellent mechanical properties to prevent damage during use and protect equipment. In the past, chemical strengthening is often required as glass for protecting mobile portable intelligent electronic equipment, display cover plates for automobiles and the like, but the glass is easy to generate cracks vertical to the surface of the glass, and when the mobile portable intelligent electronic equipment is dropped, the glass is often damaged, and normal use is affected.
Compared with the conventional glass, the microcrystalline glass has more excellent mechanical properties such as high hardness, high toughness and high elastic modulus, has obvious advantages in scratch resistance, falling resistance and the like compared with the conventional glass, and can be chemically strengthened to further improve the mechanical properties. At present, the microcrystalline glass on the market is not easy to be chemically strengthened, or the performance of the microcrystalline glass after being chemically strengthened is difficult to meet the requirement of being applied to display equipment or electronic equipment. Therefore, a microcrystalline glass material having excellent mechanical properties and optical properties and suitable for display devices or electronic devices needs to be developed to better protect the mobile portable intelligent electronic devices.
Patent CN 112592065A provides a glass-ceramic product, and the present invention provides a glass-ceramic product, the components of the glass-ceramic product expressed by weight percentage contain: SiO 22：45～70％；Al2O3：8～18％；Li2O：10～25％；ZrO2：5～15％；P2O5：2～10％；Y2O3: greater than 0 but not greater than 8%. Through reasonable component arrangementThe microcrystalline glass and the microcrystalline glass product have excellent mechanical property and optical property, and the crystalline phase of the microcrystalline glass product contains lithium monosilicate and/or lithium phosphate and is suitable for electronic equipment or display equipment.
Patent CN 112919810A provides a glass-ceramic containing a crystalline phase of lithium metasilicate and quartz solid solution, the total content of lithium metasilicate and quartz solid solution having a higher mass percentage than the other crystalline phases, wherein Li is defined2The content of O is 15-25%, and the total alkali metal content (Li)2O+Na2O+K2O) is 21.5 to 30%, which is higher than Li of the invention2O and total alkali content, and the lithium disilicate crystalline phase having high fracture toughness provided by the present invention is not obtained.
Disclosure of Invention
The invention provides high-strength transparent glass ceramics and a preparation method thereof, which solve the problems that the glass ceramics in the prior art are not easy to be chemically strengthened or the mechanical property and the optical property after chemical strengthening can not meet the requirements of electronic equipment or display equipment.
The technical scheme of the invention is as follows:
the high-strength transparent glass ceramic comprises the following components in percentage by mass: SiO 22：55％-75％、Al2O3：4％-10％、Li2O：8％-14％、Na2O：5.1％-8％、P2O5：1.5％-5％、ZrO2：2％-10％、Sb2O3：0.2％-0.8％、CeO2：0.2％-1.0％。
As a further technical scheme, the microcrystalline glass also comprises K2O：0-0.5％、MgO：0-1.5％、ZnO：0-1.5％、BaO：0-2％、CaO：0-3％、B2O3：0-4％、Ln2O3：0-8％。
As a further technical scheme, the microcrystalline glass comprises the following components in percentage by mass: SiO 22：68％-75％、Al2O3：4％-8％、Li2O：8％-13％、Na2O：5.1％-7.8％、P2O5：1.5％-4.5％、ZrO2：2％-8％、Sb2O3：0.2％-0.8％、CeO2：0.2％-1.0％、MgO：1％-1.5％、ZnO：1％-1.5％、BaO：1％-2％、CaO：0-2％、B2O3：0.5％-4％、Ln2O3：0-6％。
As a further technical scheme, the content of each component meets the following requirements: li2O+Na2O：10-21％，Na2O/Li2O：1/3-2/3，(P2O5+ZrO2)/(Li2O+Na2O)：1/4-3/4。
As a further technical scheme, the content of each component meets the following requirements: (MgO + ZnO)/(SiO)2+Al2O3): 1/50-1/25; and Ln2O3/(SiO2+Al2O3) 1/10 or less, more preferably 1/15 or less.
As a further technical solution, the Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3、Sm2O3One or more of (a).
As a further technical solution, the total amount of crystals contained is 60% to 85%, wherein lithium disilicate accounts for 60% or more, preferably 65% or more, more preferably 75% or more of the total crystal content, and lithium monosilicate accounts for 40% or less, preferably 20% or less, more preferably 15% or less of the total crystal content.
In a further aspect, the crystallite glass material has a crystal size of 80nm or less, preferably 70nm or less, more preferably 60nm or less, and even more preferably 50nm or less.
As a further technical scheme, the fracture toughness of the microcrystalline glass material is 1.1 MPa.m1/2Above, preferably 1.2MPa · m1/2More preferably 1.3MPa · m or more1/2The above; and/or a Vickers hardness of 600kgf/mm2Above, preferably 700kgf/mm2Above, 760kgf/mm is more preferable2The above; and/or an elastic modulus of 90GPa or more, preferably 95GPaThe above is preferably 100GPa or more.
As a further technical scheme, the polished sheet with the thickness of less than 1mm of the microcrystalline glass material has the visible light transmittance of more than 89%, preferably more than 90%, and more preferably more than 91%.
As a further technical proposal, the surface stress of the microcrystalline glass material after chemical strengthening is above 650MPa, preferably above 700MPa, and more preferably above 800 MPa; and/or the depth of the ion exchange layer is 80 μm or more, preferably 90 μm or more, and more preferably 100 μm or more.
The invention also provides a preparation method of the high-strength transparent microcrystalline glass, which is prepared by one forming process of rolling, pulling down, continuous casting, micro-floating method or overflow method.
As a further technical scheme, after the microcrystalline glass material is formed into a base glass sheet with the thickness less than 1mm by rolling, or pulling down, or micro-floating, or overflowing, the base glass sheet enters a continuous crystallization heat treatment furnace to nucleate for 1-12h at the temperature rising rate of 3 ℃/min to 550-650 ℃, and then the temperature rises to crystallize for 1-6h at the temperature rising rate of 5 ℃/min to 650-800 ℃.
As a further technical scheme, when a continuous casting method is adopted, continuous flow forming is adopted, a blocky glass belt with the width of 23-30cm and the thickness of 20-30mm enters a continuous crystallization heat treatment furnace and nucleates for 1-12h at the temperature of 550 ℃ and 650 ℃ at the heating rate of 3 ℃/min, and then the temperature is raised to crystallize for 1-6h at the temperature of 650 ℃ and 800 ℃ at the temperature of 5 ℃/min.
The invention has the beneficial effects that:
1. the invention enables the microcrystalline glass to have high enough transparency and strength through composition design and microcrystallization control, and Li in the composition2Less O content, Na2The content of O is high, so that the raw material cost is reduced, the exchange of K-Na can be met, larger surface compression stress is obtained, and the mechanical property is greatly improved.
2. The invention provides the microcrystalline glass with the simultaneous existence of the lithium metasilicate and the lithium disilicate, which has higher transparency and mechanical property, is suitable for chemical strengthening and is suitable for electronic equipment or display equipment.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a diffraction pattern of a crystallized glass of example 8 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
The microcrystalline glass material is a composite material with a crystal phase and a glass phase, the crystal phase of the microcrystalline glass material can be analyzed through X-ray diffraction, and the crystal morphology is measured through SEM. Through continuous experiments and researches, the inventor of the invention generates a crystalline phase with a specific proportion specified as a specific value by controlling a crystallization process on specific compositions of the microcrystalline glass material, and obtains the microcrystalline glass material of the invention at a lower cost.
The ranges of the respective components of the mother glass and the glass ceramics material of the present invention will be explained. In the present specification, the contents of the respective components are all expressed by weight percent of oxides, if not specifically stated. In the present specification, the term "glass" refers to a matrix glass before crystallization, and the term "glass-ceramic" after crystallization.
SiO2Is an essential component of the glass of the present invention, and is one of the main components forming crystals after heat treatment, if SiO2When the content of (A) is 55% or less, the glass forming property of the glass is deteriorated, the chemical stability is deteriorated, and phase separation is easy. Thus, SiO2The lower limit of the content is preferably 65%, preferably 68%. If SiO2The content is more than 75 percent, the melting temperature is high, the clarification and homogenization are difficult, the chemical strengthening of the glass is not facilitated, and the impact and drop resistance of the strengthened microcrystalline glass material can be reduced.
Al2O3The glass is an essential component for forming a glass network structure, is very favorable for improving the glass structure and chemical stability, can refine crystal grains in heat treatment, controls the crystallization speed, is favorable for improving the ion exchange capacity of the microcrystalline glass by chemical strengthening, but is very unfavorable for crystallization if the content of the glass is less than 4 percent, is difficult to control the crystallization speed, and increases the crystal size. Thus, Al2O3The lower limit of the content is 4%, preferably 6%, more preferably 8%. On the other hand, if Al2O3When the content of (b) exceeds 10%, the glass is difficult to melt, and precipitation of target crystals is inhibited, thereby lowering the strength of the glass-ceramic material. Thus Al2O3The upper limit of the content is 10%, preferably 8%. In some embodiments, about 4%, 5%, 6%, 7%, 8%, 9%, 10% Al may be included2O3。
Li2O is a composition necessary for forming crystals and is a component which lowers the viscosity of the mother glass and promotes the formation of crystals, and is also a main component in the ion exchange process, and is substituted with sodium and potassium ions, and the depth of the chemically strengthened compressive stress can be increased, but if the content is less than 8%, on the one hand, the effect of melting the glass is unfavorable, and on the other hand, the kind of precipitation of crystals is difficult to control, and therefore, Li is a component which makes it difficult to control the kind of precipitation of crystals2The lower limit of the O content is 8%, and the preferable lower limit is 10%. If Li is contained excessively2O, the chemical stability of the glass becomes poor, and it becomes difficult to control at the time of crystallization, and it is difficult to obtain the main crystal phase of lithium monosilicate of the present invention. Thus, Li2The upper limit of the O content is 14%, preferably 13%, and more preferably 12%. In some embodiments, about 8%, 9%, 10%, 11%, 12%, 13%, 14% Li may be included2O。
Na2O is an essential component in the present invention, and is low in Na content in general glass ceramics2O content is significantly different, Na2O is used as the outer body of the glass network, mainly plays the role of breaking the network to provide free oxygen and strongly inhibits the crystal precipitation, and the common microcrystalline glass Na2The low content of O is favorable for crystallization, and Na is used in the invention if2When the O content is low, it is separatedThe obtained crystal is petalite crystal, and Na is added2O is too low, and Na in the glass-ceramic is contained when ion exchange is performed+Ion and K+Insufficient ion exchange content, low surface compressive stress value, influence strength, so Na2The lower limit of the O content is 5.1%, and the preferable lower limit is 5.5%. Excessive content of Na in glass2O, Na, which has a large coefficient of expansion and poor thermal stability, is difficult to anneal and is liable to cause a risk of explosion, and also inhibits the precipitation of crystals and fails to crystallize the lithium monosilicate and lithium disilicate crystals required in the present invention, thereby lowering the strength of the glass-ceramic material, therefore Na is used as a material for producing a glass-ceramic2The upper limit of the O content is 8%, and the preferable upper limit is 7.8%. In some embodiments, about 5.1%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Na may be included2O。
The inventor finds that the Na is controlled by a large amount of experimental research2O and Li2The introduction of O in a certain proportion can influence the precipitation of the crystalline phase of the glass-ceramic, in particular Li2O+Na 210 to 21% of O, and Na2O/Li2The O is 1/3-2/3, so that the mother glass or the microcrystalline glass has a proper thermal expansion coefficient, a large crystal content and a proper crystal size are obtained after crystallization, the hardness and the fracture toughness of the microcrystalline glass are improved, and in some embodiments, Na is preferred2O/Li2O is 1/2 to 2/3. In some embodiments, the fracture toughness is 1.1 MPa-m1/2Above, preferably 1.2MPa · m1/2More preferably 1.3 MPa.m1/2The above.
ZrO2The invention is an essential component, and the functions of the invention are mainly as follows: the glass is used as a crystal nucleus agent, so that the glass is uniformly crystallized, the precipitation of crystals and the size of the crystals can be effectively controlled, and the influence of overlarge crystal size on optical performance is avoided; and secondly, the chemical stability of the parent glass or the glass ceramics can be improved under the condition of higher Li content. In the course of experimental research, it was found that ZrO2The risk of devitrification of the parent glass during the forming process can be effectively reduced. In order to attain the effect of the present invention, ZrO2The lower limit of the content is preferably 2%, more preferably 3%, andthe first step is preferably 4 percent; but if ZrO is contained excessively2The melting temperature of the glass is increased to make melting difficult, and the precipitation of the target crystal phase is inhibited to make the precipitation uncontrollable, so that ZrO2The upper limit of the content is 10%, preferably 8%, more preferably 5%. In some embodiments, ZrO may be included at about 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%2。
P2O5Is an essential component of the composition of the invention, can effectively reduce the melting temperature and increase ZrO2The two substances are inseparable as a composite crystal nucleus agent, and have an interaction effect. P2O5The lower limit of the content is preferably 1.5%, more preferably 1.8%, and further preferably 2.0%; but if it contains P excessively2O5Therefore, phase separation is easily generated in the mother glass, the devitrification is not controllable in the crystallization process, and the mechanical property of the microcrystalline glass is reduced. Thus, P2O5The upper limit of the content is 5%, preferably 4.5%, more preferably 3%. In some embodiments, about 1.5%, 1.8%, 2.0%, 2.2%, 2.5%, 3%, 4%, 5% P may be included2O5。
ZrO as nucleating agent2And P2O5And the alkali metal oxide has a certain proportion relation, and experimental research shows that (P) is (P) when the microcrystalline glass of the invention is obtained2O5+ZrO2) When the amount is less than 1/4, crystals are hard to grow, the crystallization temperature is high, crystals are not found when the glass is translucent by XRD, and even surface crystallization may occur (P)2O5+ZrO2) When the amount is more than 3/4, the crystallization of the glass by heat treatment is not controlled, and more lithium disilicate is formed, resulting in opacity. In a limited content interval, the set crystal type and content can be better obtained by combining with the heat treatment crystallization, and the high-transparency high-mechanical-property high-transparency high-crystalline silicon glass has high transparency and mechanical property. Preferably (P)2O5+ZrO2)/(Li2O+Na2O): 3/8-3/4, most preferably 1/2-3/4.
MgO is an optional component of the composition of the present invention, and contributes to improving the glass frit property, lowering the melting temperature, suppressing crystallization in the forming stage, preventing the effect of causing difficulty in production in the process of crystallization, and also refining the crystal grains in the crystallization heat treatment stage to improve the optical performance effect. The lower limit is preferably 1.0%, and the content is too high, so that other crystals can affect the mechanical property and the optical property after crystallization. Therefore, the upper limit of the MgO content is preferably 1.4%, and the upper limit is preferably 1.2%. In some embodiments, MgO may be included at about 0%, 0.5%, 1%, 1.5%.
ZnO is an optional component in the invention, improves the material property and the thermal property of parent glass, is beneficial to refining crystal grains in the crystallization process and improves the optical property of the glass ceramics, the preferred lower limit is 1.0%, and other crystals can be obtained after the content is too high and influence the mechanical property and the optical property. Therefore, the upper limit of the ZnO content is preferably 1.4%, and the preferred upper limit is 1.2%. In some embodiments, about 0%, 0.5%, 1%, 1.5% ZnO may be included.
In the invention, ZnO and MgO are used as optional components, but too much ZnO and MgO can obtain other crystals after crystallization to influence the mechanical property and the optical property, and the invention strictly limits (MgO + ZnO)/(SiO)2+Al2O3) Less than 1/25, more preferably less than 1/40, it is found through a lot of previous experiments that if the proportional relation is more than 1/25, an unfavorable crystalline phase quartz phase is easy to appear in the crystallization process, the transparency of the glass is greatly influenced, the haze is increased, and the optical performance is influenced; meanwhile, if the proportional relation is less than 1/50, the glass quality is obviously adversely affected and defects are easily caused.
BaO improves the optical and mechanical properties of the glass and also lowers the melting temperature, and when the content exceeds 2%, the risk of devitrification of the glass increases and the corrosion of the refractory material becomes severe, which causes unfavorable defects to the glass, so that the content of BaO is preferably controlled to 2% or less, more preferably 1% or less in the present invention. In some embodiments, it is preferred not to incorporate BaO. In some embodiments, BaO may be included at about 0%, 0.5%, 1%, 1.5%, 2%.
CaO is effective in reducing the high-temperature viscosity of the glass and improving the batch property, and when the content exceeds 3%, the glass is at risk of crystallization, so that the content of CaO is preferably controlled to be less than 3%, more preferably less than 2% in the present invention. In some embodiments, it is preferred not to incorporate CaO. In some embodiments, CaO may be included at about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%.
B2O3As a glass network former, a structure of a triangle and a tetrahedron can be formed in glass and a good fluxing effect can be obtained, and when the content is too high, the chemical stability of the mother glass is lowered, so that B2O3The content is 4% or less, preferably B2O3In an amount of 0.5-4%, in some embodiments, about 0%, more than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% of B may be included2O3。
Ln2O3Is an optional component for increasing the hardness and elastic modulus of the matrix glass, but if the content is too large, the melting temperature of the matrix glass is likely to increase, and precipitation of crystals is suppressed, and the content is 8% or less, preferably 6% or less. In some embodiments, more than two lns are preferred2O3Combined, in some embodiments without introducing Ln2O3. In some embodiments, about 0%, greater than 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% Ln may be included2O3. In the present invention, Ln is strictly controlled2O3/(SiO2+Al2O3) The ratio of (B)/(A) is preferably not more than 1/10, more preferably not more than 1/15.
The crystalline phase of the microcrystalline glass material comprises lithium metasilicate and lithium disilicate which exist simultaneously, and the weight percentage of the crystalline phase in the microcrystalline glass material is 60-85%; in some embodiments, the weight percentage ranges from 65 to 75%.
The test method adopted by the embodiment of the invention is as follows
(1) Total amount of crystals and crystal grain size:
the measurement was carried out by FESEM scanning electron microscope. Firstly, acid corrosion surface treatment is carried out in HF, gold spraying treatment is carried out on the surface of glass, and finally, the total amount of crystals and the size of crystal grains are determined by utilizing a scanning electron microscope.
(2) Refractive index:
the refractive index (nd) was measured by Abbe refractometer WAY-2S according to the method prescribed in GB/T7962.1-2010.
(3) Fracture toughness:
the measurement was performed using a vickers hardness tester SCV-50A/T, and the sample was processed to a 50 x 1mm specification, ground flat, and polished to complete the preparation. Placing the sample under a Vickers hardness tester microscope to select a proper position, applying a certain force on the sample by using a Vickers hardness pressure head, maintaining the pressure head for 30S, and calculating according to the national standard GB/T37900-plus 2019 after an indentation is formed.
(4) Vickers hardness:
the Vickers hardness of the sample was measured using a Vickers hardness tester SCV-50A/T. And pressing the Vickers indenter into the surface of the sample by using test force, removing the test force after keeping for a specified time, measuring the length of the diagonal line of the indentation on the surface of the sample, and calculating according to the national standard GB/T37900-.
(5) Modulus of elasticity:
the sample is processed into a specification of 40 multiplied by 8 multiplied by 2mm (the error of the proportion range is not more than 3 percent), and the elastic modulus is measured by a glass material intrinsic analyzer.
(6) Visible light transmittance:
a sample is processed to a thickness of 0.75mm, and the opposing faces are polished in parallel, and an average light transmittance of 400 to 800nm and a transmittance at 550nm are measured by a Hitachi U-41000 type spectrophotometer.
(7) Surface stress and ion exchange layer depth:
measuring the surface stress of glass sodium-potassium exchange and the depth of an ion exchange layer by adopting a glass surface stress meter FSM-6000 LE;
the surface stress of the glass lithium-sodium exchange and the depth of the ion exchange layer were measured using a glass surface stress meter SLP-2000.
Specific examples are shown in Table 1
TABLE 1 microcrystalline glass composition
TABLE 2 microcrystalline glass Property parameters
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-strength transparent glass ceramic is characterized by comprising the following components in percentage by mass: SiO 22：55％-75％、Al2O3：4％-10％、Li2O：8％-14％、Na2O：5.1％-8％、P2O5：1.5％-5％、ZrO2：2％-10％、Sb2O3：0.2％-0.8％、CeO2：0.2％-1.0％。
2. The high-strength transparent glass-ceramic according to claim 1, further comprising K2O：0-0.5％、MgO：0-1.5％、ZnO：0-1.5％、BaO：0-2％、CaO：0-3％、B2O3：0-4％、Ln2O3：0-8％。
3. The high-strength transparent glass-ceramic according to claim 2, wherein the glass-ceramic comprises the following components by mass percent: SiO 22：68％-75％、Al2O3：4％-8％、Li2O：8％-13％、Na2O：5.1％-7.8％、P2O5：1.5％-4.5％、ZrO2：2％-8％、Sb2O3：0.2％-0.8％、CeO2：0.2％-1.0％、MgO：1％-1.5％、ZnO：1％-1.5％、BaO：1％-2％、CaO：0-2％、B2O3：0.5％-4％、Ln2O3：0-6％。
4. The high-strength transparent glass-ceramic according to claim 1, wherein the content of each component satisfies: li2O+Na2O: 10-21%, and Na2O/Li2O: 1/3-2/3, and (P)2O5+ZrO2)/(Li2O+Na2O)：1/4-3/4。
5. The high-strength transparent glass-ceramic according to claim 1, wherein the content of each component satisfies: the content of each component satisfies: (MgO + ZnO)/(SiO)2+Al2O3) 1/50-1/25; and Ln2O3/(SiO2+Al2O3) 1/10 or less, more preferably 1/15 or less.
6. The high-strength transparent glass-ceramic according to claim 1, wherein the total amount of crystals contained is 60% to 85%, wherein lithium disilicate accounts for 60% or more of the total crystal content, and lithium monosilicate accounts for 40% or less of the total crystal content.
7. The high-strength transparent glass-ceramic according to claim 1, wherein the glass-ceramic material has a crystal size of 80nm or less.
8. The high-strength transparent glass-ceramic according to claim 1, wherein the glass-ceramic material has a fracture toughness of 1.1 MPa-m or more1/2And/or Vickers hardness of more than or equal to 600kgf/mm2And/or the elastic modulus is more than or equal to 90GPa and/or the thickness of the microcrystalline glass material is less than 1mmThe light transmission rate is more than or equal to 89 percent.
9. The high-strength transparent glass-ceramic according to claim 1, wherein the surface stress of the glass-ceramic material after chemical strengthening is 650MPa or more, preferably 700MPa or more, and more preferably 800MPa or more; and/or the depth of the ion exchange layer is 80 μm or more, preferably 90 μm or more, and more preferably 100 μm or more.
10. The method for preparing high-strength transparent glass-ceramic according to any one of claims 1 to 9, characterized in that it is prepared by one of the forming processes of rolling, drawing down, continuous casting, micro-float method or overflow method.
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