CN111320392A - Microcrystalline glass, reinforced microcrystalline glass and preparation method thereof - Google Patents
Microcrystalline glass, reinforced microcrystalline glass and preparation method thereof Download PDFInfo
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- CN111320392A CN111320392A CN202010146594.2A CN202010146594A CN111320392A CN 111320392 A CN111320392 A CN 111320392A CN 202010146594 A CN202010146594 A CN 202010146594A CN 111320392 A CN111320392 A CN 111320392A
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- 239000011521 glass Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005342 ion exchange Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 36
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 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 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 15
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 13
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000005728 strengthening Methods 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 230000006911 nucleation Effects 0.000 claims abstract description 10
- 238000010899 nucleation Methods 0.000 claims abstract description 10
- 229910000500 β-quartz Inorganic materials 0.000 claims abstract description 10
- 239000008395 clarifying agent Substances 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000002241 glass-ceramic Substances 0.000 claims description 36
- 239000006121 base glass Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 5
- 239000006058 strengthened glass Substances 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000006025 fining agent Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 53
- 238000002834 transmittance Methods 0.000 abstract description 18
- 239000011882 ultra-fine particle Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 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 4
- 239000013081 microcrystal Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000002245 particle Substances 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
- 239000000243 solution Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 process parameters Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C03C10/0018—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 SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—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 SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
Abstract
The invention provides microcrystalline glass, reinforced microcrystalline glass and a preparation method thereof, wherein the microcrystalline glass comprises the following components in percentage by mass: SiO 2260％‑70％、Al2O318％‑24％、Li2O 3％‑5％、Na2O 0.5％‑3％、MgO 0.5％‑2％、B2O31.2％‑3％、P2O50.8％‑2％、ZnO 0.8％‑1.5％、ZrO21％‑3％、TiO21.8 to 4 percent of the total weight of the waste water, and 0.15 to 0.5 percent of clarifying agent; wherein, 83% < SiO2+Al2O3+ZrO2≤88％、4％＜Li2O+Na2O＜7％，1.5≤MgO+ZnO＜3，4％＜P2O5+TiO2+ZrO2Is less than 6 percent. Carrying out microcrystallization heat treatment on the glass, and controlling the nucleation temperature to be 670-710 ℃ and the crystallization temperature to be 760-820 ℃. By designing and heating the components of the microcrystalline glass compositionThe restriction of the processing parameters can prepare β -quartz solid solution crystals with uniform distribution, 30-60% of crystallinity and nanometer-scale ultrafine particles (10-50nm), the transmittance of 1mm thickness at a visible light wave section of more than 560nm is more than 90%, and the Vickers hardness is at least 630kgf/mm2After the post-treatment of ion exchange strengthening, the Vickers hardness is more than 700kgf/mm2The DOC value is more than 100um, and the CS-30 is more than 90 MPa. In addition, the total consumed time of the micro crystallization heat treatment process is short, the later equipment and energy consumption cost can be reduced, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the field of microcrystalline glass, in particular to microcrystalline glass with high permeability and high strength, reinforced microcrystalline glass and a preparation method thereof.
Background
For portable electronic devices such as smart phones, tablet PCs, and other optical devices, a back cover is used to protect the internal electronics. In the past, metal is generally used as a protective material for a rear cover plate, but the metal rear cover can seriously affect the signal acceptance, and with the coming of the 5G communication era and the gradual maturity of wireless charging technology, the metal rear cover is forced to be eliminated, and glass and ceramic in non-metal materials become the first choice of mobile display terminal products. At present, the rear cover material generally adopts ion-exchanged high aluminosilicate glass, and the principle is to perform ion exchange on the surface of the high aluminosilicate glass, so that a high-pressure Stress (CS for short) and an ion strengthening layer (DOL for short) with a certain Depth are formed on the surface layer of the glass, and the surface hardness, the impact resistance, the scratch resistance and the damage resistance of the glass can be improved to a certain extent. However, the glass material is brittle and has insufficient strength, so that the glass material is still limited when being used as an appearance protection material of mobile electronic equipment, and the ceramic material has the advantage of high strength, but has low transmittance, high processing difficulty and low yield, and cannot be applied in a large scale.
The nucleated glass is also called glass ceramic, and is made up by introducing nucleating agent into general glass formula or regulating oxide proportion in the formula so as to make the basic glass form one or several crystal phases in the following heat treatment process, and the crystal phase and glass phase are coexisted in the glass body to form multi-phase crystal material. Which has both the high permeability of glass and the high strength of ceramics. The average hardness, the fracture toughness and other properties of the glass can be improved; in addition, the microcrystalline phase in the microcrystalline glass can block the expansion path of the microcrack, and is beneficial to the overall improvement of the performances of scratch resistance, impact resistance, falling resistance and the like of the glass.
In addition, due to the requirement of the electronic product on the transparency of the cover glass, the selected microcrystalline glass must have higher transmittance. The transmittance of the glass-ceramic is affected by the size of the crystal grain and the refractive index ratio between the crystal phase and the glass phase, and the smaller the crystal grain size, the closer the refractive index ratio, and the greater the transmittance. Therefore, it is necessary to control the size of the crystal grain and to prepare the crystal phase composition having a refractive index close to that of the glass phase in developing the glass ceramics for the cover plate.
Patent CN110143759A provides a lithium disilicate (Li)2Si2O5) Although the strength of the glass can be improved by the method, the lithium disilicate has a dendritic crystal structure, the size of the lithium disilicate is large, and the lithium disilicate is penetrated in the glass phase in a cross mode, so that the devitrification of the glass and the non-uniformity of the crystallization of a glass body are easily caused, the difficulty of strong post-crystallization is increased, the non-uniformity of the strong post-crystallization is caused, and the performance is influenced.
Patent CN104350017A provides a transparent glass-ceramic with β -quartz as main crystal phase, which can prepare transparent colorless glass-ceramic with β -quartz crystal as main crystal phase, but the formulation does not contain Na2O and higher crystallinity, which is not convenient for the later-period ion exchange. In addition, the composition does not contain P2O5Thus, the zirconia is difficult to melt and the melting conditions are harsh.
Patent CN109867447A provides a glass-ceramic and a substrate thereof, wherein the glass-ceramic has a crystal phaseContaining β -quartz solid solution crystal, except that in the composition R2Too high content of O (alkali metal oxide) easily results in a great variety of generated crystal phases, is not beneficial to the control of the crystallization heat treatment process, and has more devitrification phenomenon in part of the components.
Disclosure of Invention
In view of the problems of the prior art, the present invention is to provide a microcrystalline glass composition having high strength and high transmittance by designing the composition of the microcrystalline glass composition to form β -quartz solid solution crystals having a crystalline phase component refractive index close to that of the glass phase and a crystal structure of ultrafine particles (10 to 50nm) under a certain heat treatment process, wherein the fine crystal particles are uniformly distributed in the glass body and ion-exchanged at a later stage.
In order to achieve the above object, in a first aspect of the present invention, there is provided a glass ceramic, characterized in that the glass ceramic comprises the following components in percentage by mass: SiO 2260％-70％、Al2O318％-24％、Li2O3％-5％、Na2O 0.5％-3％、MgO 0.5％-2％、B2O31.2％-3％、P2O50.8％-2％、ZnO 0.8％-1.5％、ZrO21％-3％、TiO21.8 to 4 percent of the total weight of the waste water, and 0.15 to 0.5 percent of clarifying agent;
wherein, 83% < SiO2+Al2O3+ZrO2≤88％、4％＜R2O(Li2O+Na2O)＜7％，1.5≤MgO+ZnO＜3，4％＜P2O5+TiO2+ZrO2＜6％。
In order to achieve the above object, according to a second aspect of the present invention, there is provided a strengthened glass ceramic obtained by ion-exchange strengthening the glass ceramic according to the first aspect of the present invention.
In order to achieve the above object, in a third aspect of the present invention, there is provided a method for producing a glass ceramics, comprising:
preparing base glass: weighing and mixing the components according to the mass percentage and the components as defined in claim 1, and then melting, forming and annealing the mixture to obtain base glass;
microcrystallization heat treatment: and (2) putting the base glass into a crystallization furnace, heating to the nucleation temperature of 670-710 ℃, preserving the heat for 60-120min, then heating to the crystallization temperature of 760-820 ℃ for crystallization time of 10-60min, annealing, cooling and taking out to obtain the microcrystalline glass.
In order to achieve the above object, in a fourth aspect of the present invention, there is provided a method for producing a strengthened glass ceramics obtained by ion-exchanging the glass ceramics according to the first aspect of the present invention.
Compared with the prior art, the invention at least has the following beneficial effects that through the design of the components of the microcrystalline glass composition and the limitation of the technological parameters of the heat treatment, the glass is subjected to microcrystallization heat treatment, the nucleation temperature is controlled to be 670-710 ℃, the crystallization temperature is controlled to be 760-820 ℃, β -quartz solid solution crystals which are uniformly distributed, have 30-60 percent of crystallinity and have nanometer ultrafine particles (10-50nm) can be prepared, the transmittance of the crystals is more than 90 percent at the thickness of 1mm at a visible light wave section of more than 560nm, and the Vickers hardness is at least 630kgf/mm2After the post-treatment of ion exchange strengthening, the Vickers hardness is more than 700kgf/mm2The DOC value is more than 100um, and the CS-30 is more than 90 MPa. In addition, the total consumed time of the micro crystallization heat treatment process is short, the later equipment and energy consumption cost can be reduced, and the industrial production is facilitated.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) chart of the microcrystalline glass of the sample of example 3,
FIG. 2 is a Scanning Electron Microscope (SEM) image of a glass-ceramic of a sample of example 3,
figure 3 is an X-ray diffraction (XRD) pattern of the microcrystalline glass of the sample of example 3,
FIG. 4 is a graph showing the transmittance at a wavelength of 380nm to 780nm of the crystallized glass of the sample in example 3.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
In a first aspect of the present invention, the present invention provides a glass ceramic, which comprises the following components by mass: SiO 2260％-70％、Al2O318％-24％、Li2O 3％-5％、Na2O 0.5％-3％、MgO0.5％-2％、B2O31.2％-3％、P2O50.8％-2％、ZnO 0.8％-1.5％、ZrO21％-3％、TiO21.8 to 4 percent of the total weight of the waste water, and 0.15 to 0.5 percent of clarifying agent;
wherein, 83% < SiO2+Al2O3+ZrO2≤88％、4％＜R2O(Li2O+Na2O)＜7％，1.5≤MgO+ZnO＜3，4％＜P2O5+TiO2+ZrO2＜6％；TiO2/ZrO2＝0.8-1.5。
The reason for numerically limiting the contents of the components is as follows:
SiO2：SiO2one of the essential components of the base glass is the main oxide of glass formation. It constitutes the main structure of the base glass and the glass ceramics, and is also the main component constituting the crystal phase. Too low a content thereof may result in a change in the composition of the crystal phase. In addition, to ensure the uniformity of crystal precipitation, it is necessary to ensure that there is a sufficiently viscous base glass, SiO2The content should not be less than 60 wt%; but higher SiO2The content of the components can cause difficulty in melting and forming, and the components also contain high aluminum and zirconium components.
Comprehensively considering the whole composition and the content of each component, mixing SiO2The content of (A) is controlled to be 60-70 wt%.
Al2O3：Al2O3With SiO2Also one of the essential components of the base glass, is a network intermediate oxide. Al (Al)2O3With four coordination in the glass [ AlO4]And octadentate [ AlO6]Two coordination states. The structure has a larger volume in glass than that of silicon-oxygen tetrahedron, and can provide strengthening channel for glass in ion strengthening process, promote base glass and micro glassAnd (4) ion strengthening of the crystal glass. In addition, high Al2O3The content can effectively control the growth speed of the crystal, and is convenient for controlling the heat treatment process so as to prepare the crystal grain size and the uniformity of the crystal grain distribution which meet the requirements.
Thus, Al in the base glass2O3The content should not be less than 18 wt%; however, Al2O3Belongs to refractory oxide, can quickly improve the high-temperature viscosity of glass, increases the difficulty of clarification and homogenization of the glass, and prevents bubble defects from being easily discharged. In addition, it is considered that the silicon content in the present composition is high and a part of the zirconium component is contained.
Taking the whole composition and the content of each component into comprehensive consideration, mixing Al2O3The content is controlled to be 18-24 wt%.
Li2O：Li2O is an optional component for improving the low-temperature melting property and the formability of the glass, and is also an essential component constituting the main crystal phase, and can lower the crystallization temperature of the glass and promote the crystallization of the glass. In addition, the glass contains Li2O may be Na+With Li+The ion exchange of (2) can obtain higher stress depth and increase the strength of the glass. Thus, Li in the base glass2The O content should not be less than 3 wt.%. But too high Li2O makes the devitrification of the glass more difficult to control and is liable to cause devitrification or inhomogeneity of the glass. Thus, Li in the base glass2The O content is not higher than 5 wt%.
Taking the whole composition and the content of each component into comprehensive consideration, and mixing Li2The content of O is controlled to be 3 to 5 weight percent.
Na2O：Na2O belongs to network exo-oxide, and can remarkably reduce the viscosity of the base glass and promote the melting and clarification of the base glass. But Na2The increase of the content of O leads to the reduction of the chemical durability of the glass, and the increase of the glass phase in the glass ceramics leads to the difficulty in controlling the glass crystallization. Thus, Na in the base glass2The O content is at most 3 wt.%. Further, K is allowed to be carried out in order to enable the microcrystalline glass to be subjected to the later stage+With Na+The ion exchange forms high compressive stress on the glass surface, and the minimum content is not less than 0.5 wt%.
Taking the overall composition and the content of each component into comprehensive consideration, adding Na2The content of O is controlled between 0.5 and 3 weight percent.
MgO: MgO is one of the components constituting the main crystal phase, and improves the chemical stability and mechanical strength of the glass, but when the content of MgO is high, the devitrification resistance is lowered. Further, MgO inhibits ion exchange to some extent, and affects the depth of the stress layer.
The MgO content is set to 0.5 wt% to 2 wt% in consideration of the whole constitution and the contents of the respective components.
B2O3：B2O3Belongs to network forming body oxide, can reduce the high-temperature melting viscosity of the glass and improve the melting characteristic. But B2O3Phase separation can be caused, and the transmittance of the crystallized glass can be influenced along with the increase of the content.
Taking the whole composition and the content of each component into comprehensive consideration, mixing B2O3The content of the components is set to be 1.2 wt% -3 wt%.
P2O5：P2O5One of the network former components belonging to the base glass, P5+The ionic field strength is greater than that of Si4+Ions are easily separated from the network by combining with alkali metal ions to form crystal nuclei, so that the phase separation of the basic glass is promoted, the nucleation activation energy is reduced, and the crystallization of the glass is facilitated; furthermore, P2O5With [ PO4 ]]The tetrahedrons are connected with each other to form a network, so that the glass network structure is in a loose state, and the network gaps are enlarged, thereby being beneficial to the mutual diffusion of ions. At the same time, P2O5Can promote ZrO2The solubility in the glass liquid is favorable for homogenizing the glass.
Taking the overall composition and the content of each component, P into comprehensive consideration2O5The content is at least 0.8 wt%. But P is2O5Too high content can cause severe phase separation of glass, affecting crystallization uniformity and permeability of glass ceramics, P2O5The content is at most 2 wt%.
ZnO: ZnO is one of the components constituting the main crystal phase, and it can improve the melting property of glass and contribute to melting. Alkali silicate glasses are mainlyWith [ ZnO4 ]]There is a role of network formation which can significantly increase the surface compressive stress after ion exchange in ion exchange, but has an adverse effect on the depth of the stress layer, and excessive ZnO can increase the grain size and decrease ZrO2The solubility in glass is not favorable for the melting of zirconium.
The ZnO component content is set to be 0.8 wt% -1.5 wt% by comprehensively considering the whole composition and the content of each component.
ZrO2：ZrO2The method is beneficial to reducing the size of crystal grains in the crystallization process, thereby improving the transmittance of the glass and rapidly improving the chemical stability of the glass. In this composition, Zr02Contribute to the stability of the main crystalline phase; if no Zr02The main crystal phase is easy to generate crystal form transformation, so that a plurality of crystal phases are generated, the integral uniformity and permeability of the glass are influenced, and the glass is devitrified.
Thus, ZrO2The minimum content of the components is not less than 1 wt%. But ZrO2Belongs to a refractory component, can quickly improve the viscosity of base glass and has overhigh ZrO content2The content may result in ZrO in the glass2An unmelted mass is present. Thus, ZrO2The content is controlled at most to 3 wt%.
Taking into account the overall composition and the contents of the components, ZrO2The content is set to 1 wt% to 3 wt%.
TiO2：TiO2Is a nucleating agent, TiO2And ZrO2The mixed usage can lead the microcrystalline glass to have a large amount of fine and uniform-sized microcrystals. Containing no or little TiO2The glass is crystallized and delaminated, and the prepared glass is yellowish due to the coloring effect of Ti, thereby affecting the transmittance.
Comprehensively considering the whole composition and the content of each component, adding TiO2The content of the components is controlled to be 1.8-4 percent.
Besides the oxides, the glass contains a chemical clarifying agent, and the clarifying agent can be decomposed at high temperature in the glass melting process, gasified to generate gas or reduce the viscosity of glass liquid, so that bubbles in the glass liquid are eliminated or dissolved and absorbed, and a better melting effect is achieved.
The integral composition and the content of each component are comprehensively considered, and the content of the clarifying agent is controlled to be 0.15-0.5%.
The inventor has found that in order to satisfy the uniformity of crystal precipitation, it is necessary to ensure a sufficiently viscous base glass and to minimize the effect on strong ion exchange, it is necessary to limit the amount of SiO to 83% < SiO2+Al2O3+ZrO2≤88％、4％＜R2O(Li2O+Na2O) < 7%; in order to control the melting performance, the main crystal phase component and the depth of the strengthening stress layer of the glass, MgO + ZnO is limited to be more than or equal to 1.5 and less than 3; in order to control the uniform crystallization of the base glass and to make the microcrystalline glass have a large number of microcrystals with nanometer size, the limitation of 4% < P2O5+TiO2+ZrO2Less than 6 percent; to avoid TiO2Introduction of the resulting coloration, TiO control being necessary2/ZrO2Approximately equal to 0.8-1.5, preferably TiO2/ZrO2≈0.8-1.0。
Preferably, the fining agent is SnO2Or CeO2One or a combination of both.
In the technical scheme of the invention, the clarifying agent does not contain Sb2O3CeO may be preferred2And SnO2One or more of (a).
Preferably, the microcrystalline glass comprises a glass phase and a microcrystalline phase, wherein the microcrystalline phase is β -quartz solid solution, the grain diameter is 10-50nm, the crystallinity is 30% -60%, and the grains are uniformly distributed in the microcrystalline phase.
The transmittance of the glass-ceramic is affected by the size of the crystal grain and the refractive index ratio between the crystal phase and the glass phase, and the smaller the crystal grain size, the closer the refractive index ratio, and the greater the transmittance.
When the diameter of the glass crystal grain reaches the nanometer level of 10-50nm, the refractive index of the microcrystalline phase is 1.53, the refractive index of the glass phase is 1.51, and the transmissivity of the microcrystalline glass is high.
The microcrystalline glass of the invention needs to limit the crystallinity of the microcrystalline phase to be more than or equal to 30 percent and less than or equal to 60 percent. Because too low crystallinity is not beneficial to the improvement of Vickers hardness, compared with base glass, the hardness of the glass is not obviously improved, and the crystallinity is not lower than 30 percent
Because the main crystal phase contains Li and Al components, when the crystallinity of the main crystal phase is higher than 60 percent, the content of Li and Al in a glass phase is reduced, the ion exchange of Na and Li is influenced, and the DOC (ion exchange depth) value is reduced;
preferably, the microcrystalline glass has a transmittance of > 90% at a visible wavelength range of greater than 560nm at a thickness of 1 mm.
Preferably, the Vickers hardness of the microcrystalline glass is more than or equal to 630kgf/mm2。
The inventor has studied that, according to the present invention, the Vickers hardness is at least 630kgf/mm when the crystallinity is about 30%2And the Vickers hardness tends to increase with the increase of the crystallinity.
In a second aspect of the present invention, the present invention provides a strengthened microcrystalline glass obtained by subjecting the microcrystalline glass according to the first aspect of the present invention to ion exchange strengthening.
Preferably, the Vickers hardness of the strengthened glass-ceramic is more than 700kgf/mm2。
Preferably, the DOC value of the strengthened glass ceramics is more than 100 um.
Preferably, the CS-30 of the strengthened glass ceramics is more than 90 MPa.
In a third aspect of the present invention, the present invention provides a method for producing a glass ceramics, the production of the glass ceramics comprising:
preparing base glass: weighing and mixing the components according to the mass percentage and the components as defined in claim 1, and then melting, forming and annealing the mixture to obtain base glass;
microcrystallization heat treatment: and (2) putting the base glass into a crystallization furnace, heating to the nucleation temperature of 670-710 ℃, preserving the heat for 60-120min, then heating to the crystallization temperature of 760-820 ℃ for crystallization time of 10-60min, annealing, cooling and taking out to obtain the microcrystalline glass.
Preferably, the microcrystallization heat treatment step includes: and (2) putting the base glass into a crystallization furnace, heating to the nucleation temperature of 670-710 ℃ at the speed of 5-10 ℃/min, preserving the heat for 60-120min, then heating to the crystallization temperature of 760-820 ℃ at the speed of 2-5 ℃/min, preserving the heat for 10-60min, annealing, cooling and taking out to obtain the microcrystalline glass.
The invention aims to meet the requirements of grain size and crystallinity by controlling the micro crystallization heat treatment process. The nucleation temperature is generally given by the empirical formula Tg +50-100 deg.C (Tg ≈ 655 deg.C). In order to control the crystallinity and control the formation of crystal nucleus, the invention sets the temperature between 670 and 710 ℃ which is lower than the empirical value, and sets the nucleation time between 60 and 120 min; the crystallization is mainly the growth of crystal grains, the selection of the crystallization temperature is generally the highest point of a DSC peak value, and the invention is to control the size of the crystal grains, not to select the peak value high point on the DSC, but to select the temperature range with smaller crystallization rate at the bottom of the peak. The invention sets the crystallization temperature between 760 ℃ and 820 ℃ and the crystallization time between 10 min and 60 min.
Preferably, the melting temperature of the base glass is 1600 ℃ to 1650 ℃.
The basic glass has high viscosity, and the melting temperature of the basic glass is set to be 1600-1650 ℃ in order to be beneficial to the elimination of glass bubbles and the uniformity of a body.
In a fourth aspect of the present invention, the present invention provides a method for preparing a strengthened microcrystalline glass, wherein the strengthened microcrystalline glass is obtained by performing ion exchange on the microcrystalline glass according to the first aspect of the present invention.
The ion exchange adopts a one-step method, which comprises the following steps: placing the microcrystalline glass in a preheating furnace at 400 ℃ for heat preservation for 30min, and then placing the microcrystalline glass in 80-100 wt% KNO3Melting salt, keeping the temperature at 450 ℃ and 540 ℃, and keeping the temperature for 4-15 h to perform ion exchange.
The ion exchange adopts a two-step method, which comprises the following steps:
ion exchange for the first time: putting the microcrystalline glass into 80-100 wt% of NaNO3In molten salt, keeping the temperature at 450-540 ℃ for 4-15 h for primary ion exchange;
secondary ion exchange: taking out the microcrystalline glass which is subjected to the first ion exchange, and placing the microcrystalline glass in 100 wt% KNO3In the molten salt, the temperature is kept at 450-540 ℃ for 0.5-6h for secondary ion exchange.
The invention is further illustrated by the following specific examples:
examples 1 to 8 of the present invention were prepared by the following method:
1. weighing and mixing the components:
the components and the mass percentage ratio according to the following table 1 comprise: SiO 2260％-70％、Al2O318％-24％、Li2O 3％-5％、Na2O 0.5％-3％、MgO 0.5％-2％、B2O31.2％-3％、P2O50.8％-2％、ZnO0.8％-1.5％、ZrO21％-3％、TiO21.8 to 4 percent of the total weight of the waste water, and 0.15 to 0.5 percent of clarifying agent; weighing corresponding raw material compounds, and uniformly mixing to obtain a meltable mixture. In weighing, the raw material compound is weighed and disposed after converting to 100% purity in consideration of the purity and moisture of the raw material compound.
2. Preparing a base glass block:
the method comprises the steps of putting a meltable mixture into a platinum or platinum-rhodium crucible, melting for 4-6 hours in an electric furnace at 1600-1650 ℃ according to the melting difficulty of glass composition, stirring for 2-3 times to make the mixture uniform, cooling to a proper temperature, casting into a mold, putting a cast and formed glass block into a 600-650 ℃ annealing furnace for annealing, cooling to normal temperature along with the furnace after annealing, and taking out to obtain a basic glass block.
3. Microcrystallization heat treatment:
and (3) putting the basic glass block into a crystallization furnace, uniformly heating to the nucleation temperature according to the parameters in the table 1, preserving the heat, slowly heating to the crystallization temperature, crystallizing, annealing, cooling and taking out to obtain the microcrystalline glass.
4. Preparing the reinforced glass ceramics:
cutting, grinding and polishing the prepared microcrystalline glass block to prepare a sheet, and then carrying out ion exchange by adopting a one-step or two-step method.
The method comprises the following steps:
a one-step method: placing the microcrystalline glass block in a preheating furnace at 400 ℃ for heat preservation for 30min, and then placing the microcrystalline glass block in the preheating furnacePutting 80-100 wt% KNO3Molten salt, ion exchange conditions set to: the temperature is 450 ℃ and 540 ℃, and the temperature is kept constant for 4-15 h; examples 4, 5, 7 used this method.
Or
A two-step method: putting the microcrystalline glass into 80-100 wt% of NaNO3In the molten salt, the ion exchange conditions were set as follows: the temperature is 450 ℃ and 540 ℃, and the temperature is kept constant for 4-15 h; taking out the glass and placing the glass in 100 wt% KNO3In the molten salt, the ion exchange conditions were set as follows: the temperature is 450 ℃ and 540 ℃, and the constant temperature is kept for 0.5-6 h; examples 1, 2, 3, 6, 8 used this method.
Placing the ion-exchanged reinforced glass-ceramic in a muffle furnace for rapid cooling; and cleaning the surface residues of the reinforced glass ceramics by using hot water to be tested.
The compositions of the raw materials and properties of the microcrystalline glass and strengthened microcrystalline glass samples prepared in examples 1-8 are shown in table 1 below:
table 1 component compositions, process parameters, and product performance test results for the microcrystals and strengthened microcrystals prepared in examples 1-8
The physical properties of examples 1-8 are defined and explained as follows:
(1) tg: glass transition temperature, using DSC test.
(2) Average grain size: and (3) measuring by using an SEM (scanning electron microscope), performing surface treatment on the microcrystalline glass in HF (hydrofluoric acid), performing chromium spraying coating on the surface of the microcrystalline glass, performing surface scanning under the SEM, observing the diameter of particles, and dividing the average diameter size of all the crystal grain sections by the number of the crystal grains in the SEM image.
(3) Crystal phase and crystallinity: comparing the XRD diffraction peak with the database map to determine the crystal phase, and calculating the proportion of the diffraction intensity of the crystal phase in the whole map intensity by a Rietveld method to obtain the crystallinity.
(4) Transmittance: and testing by using an ultraviolet-visible spectrophotometer.
(5) Vickers hardness: the loading force was 200g and the loading time was 15S as measured using a vickers hardness tester.
(6) DOC: the depth of the stress change from compression to tension in the microcrystalline glass, namely the depth of the strengthening layer, is tested by using an SLP-1000 surface stress tester.
(7) CS-30: and (3) testing the compressive stress value at the position of 30um in the microcrystalline glass by using an SLP-1000 surface stress meter.
Meanwhile, from the Differential Scanning Calorimetry (DSC) graphs of the microcrystalline glass samples of FIG. 1 and example 3, it can be seen that the Tg of the base glass is 655.54 ℃, the exothermic peak (crystallization temperature) range is 760 and 880 ℃, and the peak position is 864.79 ℃.
From FIG. 2, a Scanning Electron Microscope (SEM) picture of the microcrystalline glass of the sample of example 3, it can be seen that the average grain size is 10-50 nm.
From FIG. 3, the X-ray diffraction (XRD) pattern of the microcrystalline glass of the sample of example 3, and by phase analysis, the phase-contrast XRD phase card has the diffraction peak corresponding to the angular position of β -quartz solid solution crystal.
From FIG. 4, the transmittance from 380nm to 780nm of the microcrystalline glass of the sample in example 3 is shown, and it can be seen that the transmittance of 1mm thickness at the visible light wavelength section of more than 560nm is more than 90%.
As can be seen from Table 1 and FIGS. 1 to 4, β -quartz solid solution crystals having a uniform distribution, a crystallinity of < 60% and nano-sized ultrafine particles (10 to 50nm) can be prepared by defining the composition of the glass-ceramic composition and the parameters of the heat treatment process, and have a transmittance of > 90% at a thickness of 1mm at a visible light wavelength of more than 560nm, a Vickers hardness of at least 630kgf/mm2, and a Vickers hardness of > 700kgf/mm2, a DOC value of > 100 μm and a CS-30 of > 90MPa after the subsequent ion exchange strengthening.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (16)
1. The microcrystalline glass is characterized by comprising the following components in percentage by mass: SiO 2260％-70％、Al2O318％-24％、Li2O 3％-5％、Na2O 0.5％-3％、MgO 0.5％-2％、B2O31.2％-3％、P2O50.8％-2％、ZnO 0.8％-1.5％、ZrO21％-3％、TiO21.8 to 4 percent of the total weight of the waste water, and 0.15 to 0.5 percent of clarifying agent;
wherein, 83% < SiO2+Al2O3+ZrO2≤88％、4％＜Li2O+Na2O＜7％，1.5≤MgO+ZnO＜3，4％＜P2O5+TiO2+ZrO2＜6％，TiO2/ZrO2＝0.8-1.5。
2. The glass-ceramic according to claim 1, wherein the TiO is selected from the group consisting of2/ZrO2＝0.8-1.0。
3. The microcrystalline glass of claim 1, wherein the fining agent is SnO2Or CeO2One or a combination of both.
4. The microcrystalline glass according to claim 1, wherein the microcrystalline glass comprises a glass phase and a microcrystalline phase, wherein the microcrystalline phase is β -quartz solid solution, the grain diameter is 10-50nm, and the crystallinity is 30-60%.
5. The glass-ceramic according to claim 1, wherein the glass-ceramic has a transmission > 90% at a visible wavelength range of greater than 560nm at a thickness of 1 mm.
6. The glass-ceramic according to claim 1, wherein the glass-ceramic has a Vickers hardness of not less than 630kgf/mm2。
7. A strengthened glass ceramic obtained by subjecting the glass ceramic according to any one of claims 1 to 6 to ion exchange strengthening.
8. The strengthened microcrystalline glass of claim 7, wherein the strengthened microcrystalline glass has a vickers hardness > 700kgf/mm2。
9. The strengthened microcrystalline glass of claim 7, wherein the strengthened microcrystalline glass has a DOC of > 100 um.
10. The strengthened glass-ceramic according to claim 7, wherein CS-30 > 90 MPa.
11. The preparation method of the microcrystalline glass is characterized by comprising the following steps of:
preparing base glass: weighing and mixing the components according to the mass percentage and the components as defined in claim 1, and then melting, forming and annealing the mixture to obtain base glass;
microcrystallization heat treatment: putting the base glass into a crystallization furnace, nucleating and crystallizing the base glass to obtain microcrystalline glass, and controlling the nucleating temperature to be 670-710 ℃ and the crystallization temperature to be 760-820 ℃.
12. The method according to claim 11, wherein the microcrystallization heat treatment step comprises: and (2) putting the base glass into a crystallization furnace, heating to the nucleation temperature of 670-710 ℃ at the speed of 5-10 ℃/min, preserving the heat for 60-120min, then heating to the crystallization temperature of 760-820 ℃ at the speed of 2-5 ℃/min, preserving the heat for 10-60min, annealing, cooling and taking out to obtain the microcrystalline glass.
13. The method according to claim 11, wherein the melting temperature of the base glass is 1600 ℃ to 1650 ℃.
14. A method for preparing reinforced glass ceramics, which is characterized in that the reinforced glass ceramics are obtained by ion exchange of the glass ceramics of any one of claims 1 to 6.
15. The method for preparing a strengthened glass-ceramic according to claim 14, wherein the ion exchange is performed by a one-step method comprising the steps of: placing the microcrystalline glass in a preheating furnace at 400 ℃ for heat preservation for 30min, and then placing the microcrystalline glass in 80-100 wt% KNO3Molten salt is subjected to ion exchange at the constant temperature of 450-540 ℃ for 4-15 h.
16. The method for producing a strengthened glass-ceramic according to claim 13, wherein the ion exchange is carried out in a two-step process comprising the steps of:
ion exchange for the first time: putting the microcrystalline glass into 80-100 wt% of NaNO3In molten salt, keeping the temperature at 450-540 ℃ for 4-15 h for primary ion exchange;
secondary ion exchange: taking out the microcrystalline glass which is subjected to the first ion exchange, and placing the microcrystalline glass in 100 wt% KNO3In the molten salt, the temperature is kept at 450-540 ℃ for 0.5-6h for secondary ion exchange.
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