CN116002980B - Microcrystalline glass and preparation method and application thereof - Google Patents
Microcrystalline glass and preparation method and application thereof Download PDFInfo
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- CN116002980B CN116002980B CN202211702085.9A CN202211702085A CN116002980B CN 116002980 B CN116002980 B CN 116002980B CN 202211702085 A CN202211702085 A CN 202211702085A CN 116002980 B CN116002980 B CN 116002980B
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- 239000011521 glass Substances 0.000 title claims abstract description 172
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 73
- 238000002425 crystallisation Methods 0.000 claims abstract description 60
- 230000008025 crystallization Effects 0.000 claims abstract description 59
- 238000002844 melting Methods 0.000 claims abstract description 51
- 230000008018 melting Effects 0.000 claims abstract description 51
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000010899 nucleation Methods 0.000 claims abstract description 22
- 230000006911 nucleation Effects 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006059 cover glass Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 19
- 238000005266 casting Methods 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 53
- 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 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910011763 Li2 O Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 2
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 229910052637 diopside Inorganic materials 0.000 description 2
- 229910000174 eucryptite Inorganic materials 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000013081 microcrystal Substances 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
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- -1 impact resistance Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005398 lithium aluminium silicate glass-ceramic Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Glass Compositions (AREA)
Abstract
The invention relates to the field of glass, and discloses microcrystalline glass and a preparation method and application thereof. The glass raw material composition is subjected to high-temperature melting treatment and low-temperature melting treatment in sequence, casting molding treatment, annealing treatment, nucleation treatment and crystallization treatment in sequence, and the microcrystalline glass is obtained. The preparation method provided by the invention overcomes the defect of easy crystallization in the preparation process of the glass ceramics, improves the yield of the glass ceramics, and the prepared glass ceramics has the advantages of high visible light transmittance and high mechanical strength.
Description
Technical Field
The invention relates to the field of glass, in particular to microcrystalline glass and a preparation method and application thereof.
Background
The microcrystalline glass can cause bending and passivation of crack tips based on crystal grains therein, and increase breaking energy, so that cracks can be slowed down or even prevented from passing through crystal phases and possible interfaces, and the mechanical properties of the glass such as impact resistance, drop resistance, scratch resistance and the like are improved, and the microcrystalline glass can be widely applied to the field of screen protection of mobile terminal display equipment with ultra-thin, high-transparency, super-strong requirements and the like. In the glass production process flow of the microcrystalline glass, glass is required to be melted, clarified and stirred and then conveyed to glass forming equipment for forming, in the forming process, the microcrystalline glass has long residence time in a crystallization zone due to slow heat dissipation of the microcrystalline glass, the vitrification of the microcrystalline glass is easy to be caused, and the production efficiency of the microcrystalline glass is greatly reduced.
The crystal forms of the glass ceramics have important influence on the strength and the light transmittance of the glass ceramics, different crystal forms have different properties, common crystal forms in the LAS glass ceramics have crystal structures of lithium monosilicate, lithium disilicate, spodumene, eucryptite, lithium diopside and the like, wherein the crystals with the main crystal phase of lithium disilicate (Li 2Si2O5) can be uniformly distributed in the matrix of the glass, the special interlocking microstructure characteristics can prevent and limit the further expansion of cracks, so that the glass ceramics has good mechanical properties, the anti-falling performance of the glass ceramics is improved, and meanwhile, the light refraction coefficient (optical refractiveindex) of the lithium disilicate crystal is close to that of the glass matrix, so that the glass ceramics with the main crystal phase of lithium disilicate is expected to be obtained in the crystallization process of the glass ceramics.
A mobile phone screen applied to a portable electronic device such as a smart phone or a tablet PC is required to have high visible light transmittance. In order to make these devices durable in more severe environments, a higher mechanical strength is required for the cover plate of the mobile phone, and the transmittance and drop strength of the glass ceramics are closely related to the glass frit composition and crystallization process.
CN1122939435A discloses a glass ceramics and its production method and application, the basic principle is that a crystallization furnace is added at the back end of the float line to realize seamless connection between the float line and the crystallization furnace, the method avoids the operation difficulty caused by crystallization on the float line and the bad phenomena such as warpage, etc., and the method is a method for producing glass ceramics by float glass, but there is still a certain problem for large-scale and large-yield production of glass ceramics and the connection between the yield of float line and the yield of crystallization furnace.
Therefore, a need exists for a glass-ceramic production method which can overcome the crystallization problem of glass when used for preparing glass-ceramic, improve the production efficiency of the glass-ceramic, and simultaneously has the advantages of high light transmittance, high mechanical strength and the like
Disclosure of Invention
The invention aims to overcome the defect that glass crystallization easily occurs in the preparation process of glass ceramics in the prior art, and the prepared glass ceramics cannot have the problems of high light transmittance and high mechanical strength.
In order to achieve the above object, according to one aspect of the present invention, there is provided a glass ceramic comprising SiO2、Li2O、Al2O3、ZrO2、P2O5、Na2O、K2O、TiO2, parts by weight of SiO 2, 8 parts by weight to 20 parts by weight of Li 2 O, 6 parts by weight to 18 parts by weight of Al 2O3, 4 parts by weight to 12 parts by weight of ZrO 2, 0.01 parts by weight to 4 parts by weight of P 2O5, 0.1 parts by weight to 3 parts by weight of Na 2 O, 0 parts by weight to 1.5 parts by weight of K 2 O, and 0 parts by weight to 2 parts by weight of TiO 2, relative to 100 parts by weight of SiO 2;
and the weight part relation of the components in the microcrystalline glass meets the following conditions:
SA＝0.63*wt(Na2O)+0.52*wt(K2O)+0.75*wt(Li2O)-0.01*wt(Al2O3)*wt(Al2
O3)，7.5≤SA≤12.5；
SB＝wt(ZrO2)+wt(TiO2)，4≤SB≤12；
SC＝wt(Na2O)+wt(K2O)，0.1≤SC≤4。
preferably, the crystallinity of the glass ceramics is not less than 10wt%;
The main crystal phase of the microcrystalline glass is Li 2Si2O5, and the crystallite size of the main crystal phase is not more than 50nm.
Preferably, the visible light transmittance of the glass ceramics at 560nm is not lower than 85% under the condition of 0.7mm thickness.
The second aspect of the invention provides a preparation method of microcrystalline glass, which comprises the following steps:
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
s2: pouring and molding the glass liquid to obtain blank glass;
S3: sequentially carrying out annealing treatment, nucleation treatment and crystallization treatment on the blank glass to obtain the microcrystalline glass;
Wherein the glass raw material composition comprises: a substance capable of providing SiO 2, a substance capable of providing Li 2 O, a substance capable of providing Al 2O3, a substance capable of providing ZrO 2, a substance capable of providing Na 2 O, a substance capable of providing K 2 O, a substance capable of providing TiO 2;
The glass raw material composition is used in an amount such that the content of Li 2 O is 8 to 20 parts by weight, the content of Al 2O3 is 6 to 18 parts by weight, the content of ZrO 2 is 4 to 12 parts by weight, the content of P 2O5 is 0.01 to 4 parts by weight, the content of Na 2 O is 0.1 to 3 parts by weight, the content of K 2 O is 0 to 1.5 parts by weight, and the content of TiO 2 is 0 to 2 parts by weight, based on 100 parts by weight of SiO 2 in the glass ceramic;
The following conditions are satisfied in terms of the parts by weight of the components in the glass raw material composition, in terms of oxides:
SA＝0.63*wt(Na2O)+0.52*wt(K2O)+0.75*wt(Li2O)-0.01*wt(Al2O3)*wt(Al2
O3)，7.5≤SA≤12.5；
SB＝wt(ZrO2)+wt(TiO2)，4≤SB≤12；
SC＝wt(Na2O)+wt(K2O)，0.1≤SC≤4。
Preferably, in step S1, the high-temperature melting treatment is performed to obtain a glass liquid intermediate, the viscosity LogP 1 of the glass liquid intermediate is 1.5-1.7, the viscosity LogP 2 of the glass liquid is 1.7-2.0, and the LogP 1 is less than the LogP 2.
Preferably, the temperature T 1 of the high-temperature melting treatment is 1560-1650 ℃, the treatment time is 4-8 h, the temperature T 2 of the low-temperature melting treatment is 1490-1560 ℃, the treatment time is 0.5-2h, and the T 1 is more than the T 2.
Further preferably, the temperature difference between the temperature T 1 and the temperature T 2 is not lower than 60 ℃.
Further preferably, the step S1 further includes: and clarifying the glass liquid intermediate, and then carrying out low-temperature melting treatment to obtain the glass liquid.
Preferably, in the step S3, the temperature of the nucleation treatment is 480-560 ℃, the constant temperature treatment is 2-8 h, the temperature of the crystallization treatment is 590-620 ℃, and the constant temperature treatment is 0.3-4 h.
Further preferably, the temperature rising rate before reaching the temperature of the nucleation treatment is 2 ℃/min-15 ℃/min, and the temperature rising rate before reaching the temperature of the crystallization treatment is 2 ℃/min-15 ℃/min.
Preferably, in step S2, the target thickness of the casting process is 5cm to 25cm.
The third aspect of the invention provides the microcrystalline glass provided by the first aspect and/or the application of the microcrystalline glass prepared by the preparation method provided by the fourth aspect in the field of cover plate glass
The glass ceramic provided by the invention has the advantages of high visible light transmittance and high mechanical strength.
The preparation method provided by the invention overcomes the defect of easy crystallization in the preparation process of the glass ceramics, improves the yield of the glass ceramics, and the prepared glass ceramics has the advantages of high visible light transmittance and high mechanical strength.
The glass ceramic provided by the invention is used as cover plate glass, is applied to electronic products such as mobile phones, computers, televisions and the like, and has the advantages of high color rendering degree, high mechanical strength and difficult abrasion.
Drawings
FIG. 1 is a schematic diagram showing the temperature rise of a nucleation-crystallization process according to a preferred embodiment of the present invention;
FIG. 2 is an XRD pattern of glass ceramics prepared in example 5 of the present invention;
FIG. 3 is a TEM image of the glass ceramic obtained in example 5 of the present invention.
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.
Herein, wt represents parts by weight/weight, and illustratively, wt (Na 2 O) represents parts by weight of Na 2 O; 10wt% means 10 wt%.
Herein, "x" means mathematical operation symbol "multiply" and, illustratively, 0.63 x wt (Na 2 O) means a weight part value of 0.63 times Na 2 O.
The first aspect of the present invention provides a glass ceramic, wherein the glass ceramic contains SiO2、Li2O、Al2O3、ZrO2、P2O5、Na2O、K2O、TiO2, parts by weight of SiO 2, 8 parts by weight to 20 parts by weight of Li 2 O, 6 parts by weight to 18 parts by weight of Al 2O3, 4 parts by weight to 12 parts by weight of ZrO 2, 0.01 part by weight to 4 parts by weight of P 2O5, 0.01 part by weight to 3 parts by weight of Na 2 O, 0 part by weight to 1.5 parts by weight of K 2 O, and 0 part by weight to 2 parts by weight of TiO 2, relative to 100 parts by weight of SiO 2;
and the weight part relation of the components in the microcrystalline glass meets the following conditions:
SA＝0.63*wt(Na2O)+0.52*wt(K2O)+0.75*wt(Li2O)-0.01*wt(Al2O3)*wt(Al2
O3)，7.5≤SA≤12.5；
SB＝wt(ZrO2)+wt(TiO2)，4≤SB≤12；
SC＝wt(Na2O)+wt(K2O)，0.01≤SC≤4。
SiO 2 is a skeleton structure for forming microcrystalline glass, is also a basis for forming lithium disilicate crystals, is excessively low in content, is unfavorable for forming lithium disilicate crystals, further influences the strength of the microcrystalline glass, and is excessively high in content, so that the viscosity of the glass is increased, and the difficulty of melting treatment is increased.
Li 2 O is an essential component for forming lithium disilicate in glass ceramics, is also an essential component for ion exchange, has a content too low to be beneficial to the formation of crystalline lithium disilicate, and has a molar ratio of Li 2 O to SiO 2 of 1:2 and a mass ratio of 0.25 according to the composition of Li 2Si2O5 crystal, so that in order to produce a crystal having lithium disilicate as a main crystal phase during production, the content of Li 2 O should be at least 8 parts by weight relative to 100 parts by weight of SiO 2; on the other hand, if the Li 2 O content is too high, the acid resistance and stability of the glass are lowered, and therefore the Li 2 O content is generally not more than 20 parts by weight.
Al 2O3 is a component for improving ion exchange performance and weather resistance (applied to outdoor weather resistance, such as comprehensive damage caused by illumination, cold and hot, wind and rain, bacteria and the like, and the tolerance capacity is called weather resistance) in microcrystalline glass. If the content of A1 2O3 is too low, for example, when the content of A1 2O3 is less than 6 parts by weight with respect to 100 parts by weight of SiO 2, formation of the second crystalline phase liaalsi 4O10 is not favored, whereas liaalsi 4O10 is a monoclinic crystal having a three-dimensional framework structure and having a layered structure that is a dense structure formed by Li and A1 tetrahedrally connected folded crystals, liaalsi 4O10 is too small, glass is poorly weather-resistant, easily damaged, or easily broken after slight damage; when the content of A1 2O3 is more than 18 parts by weight, on one hand, the increase of the viscosity of the glass is brought, which is unfavorable for production, on the other hand, the crystallization capacity of the glass is greatly increased, and the produced crystal particles are too large, which is unfavorable for controlling the size of the microcrystal.
ZrO 2 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, the influence on the optical performance caused by overlarge crystal size is avoided, and the chemical stability of matrix glass or microcrystalline glass can be improved. However, when the content of ZrO 2 is too high, the melting temperature of the glass raw material composition is increased, the difficulty of melting treatment is increased, and crystallization control is difficult, so that the production is not facilitated; when the content of ZrO 2 is too low, zrO 2 cannot function as a crystal nucleus agent, and crystal grain formation is difficult.
TiO 2 is used as a crystal nucleus agent, and has the main effects of reducing the crystallization temperature and nucleation temperature of microcrystalline glass and reducing the grain size when the crystal nucleus agent is used, but the content of TiO 2 is too high, the color of the microcrystalline glass is gradually changed into brown, and the microcrystalline glass is unfavorable for being used as cover plate glass in electronic products such as mobile phones, computers and the like, so that the content of TiO 2 needs to be controlled while the TiO 2 is used as the crystal nucleus agent, and the content of the TiO 2 is generally controlled to be 0-2 parts by weight.
The simultaneous use of ZrO 2 and TiO 2 can form a large amount of crystallites under low temperature conditions, since excessive incorporation of TiO 2 can cause glass to be colored, the contents of TiO 2 and ZrO 2 must be controlled, and the inventors of the present invention found that when the content of (ZrO 2+TiO2) is 4 to 12 parts by weight, that is, SB=wt (ZrO 2)+wt(TiO2), 4.ltoreq.SB.ltoreq.12, the glass crystallites will not appear brown or yellow in color, and the grain size of the glass crystallites is within a qualified range, and the devitrification state is easy to control, relative to 100 parts by weight of the SiO 2.
P 2O5 can effectively lower the melting temperature of the glass raw material composition and can effectively increase the solubility of ZrO 2 in the glass system, and the two are inseparable as composite nucleating agents. However, too much P 2O5 can easily cause the phase separation of the matrix glass, devitrification during crystallization and decrease the mechanical properties of the glass ceramics, so that the invention controls P 2O5 to 0-4 parts by weight relative to 100 parts by weight of SiO 2.
Na 2 O and K 2 O are favorable for glass fusion forming and strengthening ion exchange in the later preparation stage of glass ceramics, na 2 O is taken as an outer body of a glass network, mainly plays a role of breaking the network to provide free oxygen, has stronger crystal precipitation inhibition capability, generally, the low content of Na 2 O in glass ceramics is favorable for controlling crystallization, but when the content of Na 2 O in glass ceramics is too low, the content of Na ions and K ions is insufficient during ion exchange in glass ceramics, the surface compression stress is reduced, and the mechanical strength of the glass surface is influenced, so that the minimum content of Na 2 O is 0.01 weight part; when the glass contains excessive Na 2 O and K 2 O, the expansion coefficient of the glass becomes large, the thermal stability becomes poor, the difficulty of annealing treatment is increased, the risk of glass explosion is easy to generate, and the formation of crystals can play a role in inhibiting, so that the mechanical strength of the microcrystalline glass is reduced. The inventors of the present invention found that when the total content of SiO 2,(Na2O+K2 O) is controlled to 1 to 3 parts by weight relative to 100 parts by weight, that is, SC=wt (Na 2O)+wt(K2 O), SC.ltoreq.0.1 is not more than 4, the Na 2 O content in the glass ceramic is favorable for ion exchange, and the glass stability is good.
SA＝0.63*wt(Na2O)+0.52*wt(K2O)+0.75*wt(Li2O)-0.01*wt(Al2O3)*wt(
Al 2O3), SA is more than or equal to 7.5 and is less than or equal to 12.5. The SA value represents the correlation between the fluxing factor and the refractory factor, and the inventor finds that the SA value is controlled between 7.5 and 12, and can effectively solve the problems that the melting is difficult and the molding is difficult because the glass viscosity reaches 10 dPa.s or the glass viscosity reaches 10 dPa.s due to the high content of SiO 2 and Al 2O3.
In some preferred embodiments of the present invention, the glass-ceramic has a crystallinity of not less than 10wt%, that is, the glass-ceramic has a content of all crystals of not less than 10wt% based on the total weight of the glass-ceramic.
In some preferred embodiments of the present invention, the glass-ceramic has a predominant crystalline phase of Li 2Si2O5. The common crystal forms in the glass ceramics are crystal structures such as lithium monosilicate, lithium disilicate, spodumene, eucryptite, lithium diopside and the like, wherein the crystals with the main crystal phase of lithium disilicate (Li 2Si2O5) can be uniformly distributed in the matrix of the glass, and the special interlocking microstructure characteristics can prevent and limit further expansion of cracks, so that the glass ceramics has good mechanical properties, and the anti-falling performance of the glass ceramics is improved, and meanwhile, the light refraction coefficient of the lithium disilicate crystal is close to that of the glass matrix, so that the glass ceramics is ideal for preparing the high-transparency glass ceramics, and the expected crystal is the glass ceramics with the lithium disilicate as the main crystal phase in the crystallization process of the glass ceramics.
In some preferred embodiments of the invention, the crystallite size of the predominant crystalline phase of the glass-ceramic is no greater than 50nm. The microcrystalline glass in the size range has good morphology and high visible light transmittance
In some preferred embodiments of the present invention, the glass ceramic has a 560nm visible light transmittance of not less than 85% at a thickness of 0.7 mm.
The second aspect of the invention provides a preparation method of microcrystalline glass, which comprises the following steps:
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
s2: pouring and molding the glass liquid to obtain blank glass;
S3: sequentially carrying out annealing treatment, nucleation treatment and crystallization treatment on the blank glass to obtain the microcrystalline glass;
Wherein the glass raw material composition comprises: a substance capable of providing SiO 2, a substance capable of providing Li 2 O, a substance capable of providing Al 2O3, a substance capable of providing ZrO 2, a substance capable of providing Na 2 O, a substance capable of providing K 2 O, a substance capable of providing TiO 2;
The glass raw material composition is used in an amount such that the content of Li 2 O is 8 to 20 parts by weight, the content of Al 2O3 is 6 to 18 parts by weight, the content of ZrO 2 is 4 to 12 parts by weight, the content of P 2O5 is 0.01 to 4 parts by weight, the content of Na 2 O is 0.1 to 3 parts by weight, the content of K 2 O is 0 to 1.5 parts by weight, and the content of TiO 2 is 0 to 2 parts by weight, based on 100 parts by weight of SiO 2 in the glass ceramic;
The following conditions are satisfied in terms of the parts by weight of the components in the glass raw material composition, in terms of oxides:
SA＝0.63*wt(Na2O)+0.52*wt(K2O)+0.75*wt(Li2O)-0.01*wt(Al2O3)*wt(Al2
O3)，7.5≤SA≤12.5；
SB＝wt(ZrO2)+wt(TiO2)，4≤SB≤12；
SC＝wt(Na2O)+wt(K2O)，0.1≤SC≤4。
The inventor of the invention discovers that the glass raw material composition is subjected to two-step melting treatment, and is subjected to high-temperature melting treatment firstly and then to low-temperature melting treatment, so that the problem of easy crystallization in the preparation process of glass ceramics can be effectively solved, the preparation yield of the glass ceramics is further improved, and the production efficiency is improved.
In some preferred embodiments of the present invention, in step S1, the high-temperature melting treatment is performed to obtain a glass liquid intermediate, the viscosity LogP 1 of the glass liquid intermediate is 1.5-1.7, the viscosity LogP 2 of the glass liquid is 1.7-2.0, and the LogP 1 is less than the LogP 2.
In some preferred embodiments of the invention, the high temperature melt treatment temperature T 1 is 1560 ℃ to 1650 ℃ and the treatment time is 4 hours to 8 hours. The high-temperature melting treatment is performed in this temperature range, on the one hand, in consideration of the economical efficiency of the melting apparatus and, on the other hand, also to maximize melting and homogenization of the glass raw material composition.
The method of high-temperature melting treatment is not limited in the present invention, and the high-temperature melting treatment may be performed by using an electric melting furnace or an electric mixing melting furnace, for example.
In some preferred embodiments of the invention, the low temperature melt treatment temperature T 2 is 1490 ℃ to 1560 ℃ and the treatment time is 0.5 to 2 hours. The low-temperature melting treatment is used for preparing pouring molding. Further preferably, the step S1 further includes: and clarifying the glass liquid intermediate, and then carrying out low-temperature melting treatment to obtain the glass liquid. Carrying out low-temperature melting treatment after high-temperature homogenization and clarification, wherein the viscosity of the glass is adjusted to be in a viscosity range suitable for molding; secondly, the temperature of the glass liquid is reduced before pouring and forming, so that part of heat of the glass liquid can be emitted to play a role in preventing crystallization, but the temperature of the glass liquid cannot be reduced too low, otherwise, the viscosity of the glass is too high, and the pouring and forming and subsequent cutting-off treatment of the glass liquid are not facilitated.
The method of the low-temperature melting treatment is not limited in the present invention, and the low-temperature melting treatment of the glass intermediate may be performed using a single platinum crucible, for example.
In some preferred embodiments of the present invention, said T 1 > said T 2, further preferably, the temperature difference between said temperature T 1 and said temperature T 2 is not less than 60 ℃.
In some preferred embodiments of the present invention, in step S3, the nucleation treatment is performed at a temperature of 480 ℃ to 560 ℃ for a constant temperature treatment time of 2h to 8h, the crystallization treatment is performed at a temperature of 590 ℃ to 620 ℃ for a constant temperature treatment time of 0.3h to 4h. The main crystal phase of the microcrystalline glass prepared under the nucleation treatment condition and the crystallization treatment condition is Li 2Si2O5, the mechanical strength is high, the crystallinity is high, and the visible light transmittance of the microcrystalline glass is high.
According to the process of forming microcrystalline glass grains, the microcrystalline grains form the prior crystal nucleus, then the crystal nucleus grows and forms the crystal grains, so that in order to make the crystal grains in the glass more, the formed crystal nucleus should also be more, and therefore, constant temperature treatment is carried out between 480 ℃ and 560 ℃ formed by the crystal nucleus, and the temperature is kept constant for 3h to 8h so as to form more crystal nuclei. The crystal nucleus grows up at 590-620 ℃, constant temperature treatment is needed at the crystallization temperature for 0.3-4 h, and in the constant temperature period, crystal grains with the grain size smaller than 50nm can be formed in the glass, and if the crystallization treatment is carried out for too long, the grain size can be larger, the light transmittance of the glass is affected, and even the phenomenon of porcelain possibly occurs.
In some preferred embodiments of the present invention, the rate of temperature rise before reaching the nucleation treatment temperature is 2 ℃/min to 15 ℃/min, and the rate of temperature rise before reaching the crystallization treatment temperature is 2 ℃/min to 15 ℃/min. The heating rate before nucleation and crystallization has an influence on the crystallization temperature of the glass ceramics, the lower the heating rate is, the lower the crystallization peak temperature is, the higher the heating rate is, and the crystallization peak temperature is higher. The microcrystalline glass prepared by the temperature rising rate in the range has no obvious crystallization phenomenon, the main crystal phase is Li 2Si2O5, and the microcrystalline glass has high visible light transmittance and high mechanical strength.
In some preferred embodiments of the present invention, the nucleation and crystallization process of the present invention is performed at a temperature elevated as shown in fig. 1, and the nucleation and crystallization process are exemplarily performed as follows:
Heating the annealed blank glass to 480-560 ℃ at the heating rate of 2-15 ℃/min, and maintaining the temperature for 2-8 h to fully nucleate to form crystal nuclei; then, the temperature is increased to 590-620 ℃ at the temperature increasing rate of 2-15 ℃ per minute, and the temperature is kept for 0.3-4 hours for full crystallization to form microcrystals.
In some preferred embodiments of the present invention, in step S2, the casting process has a target thickness of 5cm to 25cm. The microcrystalline glass with the thickness range prepared by the preparation method has no crystallization visible point, and the microcrystalline glass has high visible light transmittance and high mechanical strength.
The present invention will be described in detail by examples. In the following examples, the raw materials of the glass raw material composition were respectively selected from the prepared raw glass/glass ceramics as the respective components of the respective analytically pure.
The 560nm visible light transmittance means that after the glass-ceramic is cut to a thickness of 0.7mm, the glass-ceramic is measured for the spectral transmittance of 380 to 780nm visible light at 0.7mm by using an Shimadzu UV-2600 i-type spectrophotometer, and then the 560nm visible light transmittance of the glass-ceramic is obtained.
Preparation example 1: preparation of blank glass
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
S2: and pouring and forming the glass liquid to obtain blank glass.
The glass raw material composition is prepared from the following raw materials in proportion by weight:
The content of SiO 2,Li2 O was 15.1 parts by weight, the content of Al 2O3 was 11.35 parts by weight, the content of ZrO 2 was 6.89 parts by weight, the content of P 2O5 was 3.42 parts by weight, and the content of Na 2 O was 0.51 parts by weight, relative to 100 parts by weight of SiO 2,Li2 O.
Wherein, the specific parameters in the blank glass preparation step are shown in table 1.
The crystallization grades of the blank glasses obtained are shown in table 1.
Preparation examples 2 to 9: preparation of blank glass
The glass raw material composition and the preparation procedure were the same as in example 1.
The specific parameters of the preparation steps and the crystallization grade of the prepared blank glass are shown in table 1.
Comparative preparation examples 1 to 9: preparation of blank glass
The glass raw material composition and the production process were the same as in example 1, except that in step S1, only one melting treatment was performed.
The specific parameters of the preparation steps and the crystallization grade of the prepared blank glass are shown in table 1.
TABLE 1
The crystallization grade in table 1 is shown below:
level 1 represents a devitrification-free visible point; level 2 represents visible punctiform crystallization, not connected into a line; the level 3 represents local curve crystallization, the degree is light, and the line is linear; level 4 represents local curve crystallization, with the most severe degree.
As can be seen from table 1, when casting thinner blank glass by a one-step melting method, no crystallization phenomenon exists, but when the casting thickness is continuously increased, the crystallization degree is more and more obvious; the invention has little crystallization phenomenon when casting blank glass with different thickness and size through two steps of high-temperature melting and low-temperature melting treatment, so the preparation method of the microcrystalline glass can effectively overcome the crystallization problem in the preparation process of the microcrystalline glass, and has great advantages for improving the yield of the microcrystalline glass.
Examples 1to 9: preparation of microcrystalline glass
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
s2: pouring and molding the glass liquid to obtain blank glass;
s3: and carrying out annealing treatment, nucleation treatment and crystallization treatment on the blank glass in sequence to obtain the microcrystalline glass.
Wherein, the raw material dosage proportion, the treatment temperature and the time of the high-temperature melting treatment and the low-temperature melting treatment of the glass raw material composition are respectively the same as those of preparation example 1, the annealing treatment is carried out in a mode of naturally cooling to room temperature, the other step parameters are shown in table 2, and the performance parameters of the prepared glass ceramics are shown in table 2.
TABLE 2
Typically, fig. 2 is an XRD pattern of the glass-ceramics prepared in example 5 of the present invention, and fig. 3 is a TEM pattern of the glass-ceramics prepared in example 5 of the present invention, and it can be seen from fig. 2 and 3 that the main crystal phase of the glass-ceramics is Li 2Si2O5 and the crystallite size is less than 50nm.
As can be seen from Table 2, the glass raw material compositions with the same component content have different casting thicknesses and different specific control parameters of nucleation treatment and crystallization treatment, but in the preferred technological parameter range of the invention, the main crystal phases of the prepared glass ceramics are Li 2Si2O5, the mechanical strength of the glass ceramics is high, the size of the glass ceramics is less than 50nm, and the visible light transmittance is high.
Examples 10 to 17: preparation of microcrystalline glass
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
s2: pouring and molding the glass liquid to obtain blank glass;
s3: and carrying out annealing treatment, nucleation treatment and crystallization treatment on the blank glass in sequence to obtain the microcrystalline glass.
The processing temperatures and times of the high-temperature melting process and the low-temperature melting process are the same as those of preparation example 1, and the specific parameters of the raw material dosage proportion, the casting thickness, the nucleation process and the crystallization process of the glass raw material composition, and the various performance parameters of the prepared glass ceramics are shown in table 3.
TABLE 3 Table 3
Comparative examples 1to 6: preparation of microcrystalline glass
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
s2: pouring and molding the glass liquid to obtain blank glass;
s3: and carrying out annealing treatment, nucleation treatment and crystallization treatment on the blank glass in sequence to obtain the microcrystalline glass.
The processing temperatures and times of the high temperature melting process and the low temperature melting process are the same as those of preparation example 1, and the specific parameters of the raw material dosage proportion, the casting thickness, the nucleation process and the crystallization process of the glass raw material composition, and the various performance parameters of the prepared glass ceramics are shown in table 4.
TABLE 4 Table 4
The SA values of comparative examples 1 and 2 are different from the present invention, the SB values of comparative examples 3, 4 and 5 are different from the present invention, and the crystallization temperatures of comparative example 3 are different from the present invention, and the SA, SC and nucleation times of comparative example 6 are different from the present invention, and it can be seen in combination with tables 2, 3 and 4 that the glass ceramics prepared in the examples of the present invention have various properties significantly superior to those of the glass ceramics prepared in the comparative examples.
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 (4)
1. The preparation method of the glass ceramics is characterized by comprising the following steps:
S1: sequentially carrying out high-temperature melting treatment and low-temperature melting treatment on the glass raw material composition to obtain glass liquid;
s2: pouring and molding the glass liquid to obtain blank glass;
S3: sequentially carrying out annealing treatment, nucleation treatment and crystallization treatment on the blank glass to obtain the microcrystalline glass;
Wherein the glass raw material composition comprises: a substance capable of providing SiO 2, a substance capable of providing Li 2 O, a substance capable of providing Al 2O3, a substance capable of providing ZrO 2, a substance capable of providing Na 2 O, a substance capable of providing K 2 O, a substance capable of providing TiO 2;
The glass raw material composition is used in an amount such that the content of Li 2 O is 8 to 20 parts by weight, the content of Al 2O3 is 6 to 18 parts by weight, the content of ZrO 2 is 4 to 12 parts by weight, the content of P 2O5 is 0.01 to 4 parts by weight, the content of Na 2 O is 0.1 to 3 parts by weight, the content of K 2 O is 0 to 1.5 parts by weight, and the content of TiO 2 is 0 to 2 parts by weight, based on 100 parts by weight of SiO 2 in the glass ceramic;
The following conditions are satisfied in terms of the parts by weight of the components in the glass raw material composition, in terms of oxides:
SA=0.63×wt(Na2O)+0.52×wt(K2O)+0.75×wt(Li2O)-0.01×wt(Al2O3)×wt(Al2O3),7.5≤SA≤12.5;
SB=wt(ZrO2)+wt(TiO2)，4≤SB≤12；
SC=wt(Na2O)+wt(K2O)，0.1≤SC≤4；
In the step S1, the high-temperature melting treatment is performed to obtain a glass liquid intermediate, the viscosity LogP 1 of the glass liquid intermediate is 1.5-1.7, the viscosity LogP 2 of the glass liquid is 1.7-2.0, and the LogP 1 is less than the LogP 2;
The temperature T 1 of the high-temperature melting treatment is 1560-1650 ℃, the treatment time is 4-8 h, the temperature T 2 of the low-temperature melting treatment is 1490-1560 ℃, the treatment time is 0.5-2h, and the T 1 is more than the T 2; the temperature difference between the temperature T 1 and the temperature T 2 is not lower than 60 ℃;
In the step S2, the target thickness of the pouring molding treatment is 5cm-25cm;
in the step S3, the temperature of the nucleation treatment is 480-560 ℃, the constant temperature treatment is 2-8 h, the temperature of the crystallization treatment is 590-620 ℃ and the constant temperature treatment is 0.3-4 h.
2. The method according to claim 1, wherein the step S1 further comprises: and clarifying the glass liquid intermediate, and then carrying out low-temperature melting treatment to obtain the glass liquid.
3. The production method according to claim 1, wherein a temperature rise rate before reaching the temperature of the nucleation treatment is 2 ℃/min-15 ℃/min, and a temperature rise rate before reaching the temperature of the crystallization treatment is 2 ℃/min-15 ℃/min.
4. Use of the glass-ceramic produced by the production process according to any one of claims 1 to 3 in the field of cover glass.
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| CN115490428A (en) * | 2022-09-16 | 2022-12-20 | 四川虹科创新科技有限公司 | Transparent glass ceramics with ultrahigh drop strength and preparation method thereof |
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