CN109336380A - A kind of ultra-clear glasses and its production method and special equipment - Google Patents
A kind of ultra-clear glasses and its production method and special equipment Download PDFInfo
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- CN109336380A CN109336380A CN201811473203.7A CN201811473203A CN109336380A CN 109336380 A CN109336380 A CN 109336380A CN 201811473203 A CN201811473203 A CN 201811473203A CN 109336380 A CN109336380 A CN 109336380A
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- Prior art keywords
- glass
- ultra
- raw material
- clear glasses
- sio
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Links
- 239000011521 glass Substances 0.000 title claims abstract description 296
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 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 41
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 34
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 34
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 31
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 31
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 31
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 22
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002184 metal Substances 0.000 claims description 61
- 238000000137 annealing Methods 0.000 claims description 53
- 238000005352 clarification Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000009991 scouring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- -1 Ta Nb tailings Substances 0.000 claims 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 239000005401 pressed glass Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 20
- 238000005496 tempering Methods 0.000 abstract description 9
- 239000005329 float glass Substances 0.000 abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 46
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 45
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 38
- 239000000292 calcium oxide Substances 0.000 description 23
- 239000000395 magnesium oxide Substances 0.000 description 23
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 22
- 239000011787 zinc oxide Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000008395 clarifying agent Substances 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007495 chemical tempering process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
- C03B13/04—Rolling non-patterned sheets continuously
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/04—Annealing glass products in a continuous way
- C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
- C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/04—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in tank furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of ultra-clear glasses and its production method and special equipment, the raw material composition of the ultra-clear glasses includes: SiO243%-65%, Al2O35%-11%, CaO 14%-17%, MgO 2%-4%, Na2O 5%-10%, K2O 1%-3%, B2O32%-5%, ZnO 0.2%-2%, Li2O 2%-3%, MnO 0.1%-0.5%, CeO20.7%-1.8%, Na2Sb2O70.9%-2.3%.Ultra-clear glasses of the invention will have higher intensity after more common float glass chemical tempering after chemical tempering, it is suitble to the product for requiring thin and strong degree high to use, it is able to maintain high-caliber intensity, machining property is good simultaneously, can be widely applied in the products form such as liquid crystal display and wrist-watch, mobile phone, flat-panel monitor, camera.
Description
Technical field
The present invention relates to the processing technique fields of glass, more particularly to the side of a kind of ultra-clear glasses, production ultra-clear glasses
Method and the special equipment for producing ultra-clear glasses.
Background technique
Ultra-clear glasses are a kind of super transparent low iron glasses, and basis is shown in Table 1, are a kind of high-quality, multi-functional new
Type high-grade glass, light transmittance generally 91% or more, have glittering and translucent, elegant characteristic, there is glass family " crystal king
The title of son ".Ultra-clear glasses are mainly characterized by Fe2O3Content is lower, in 0.01% (100ppm) hereinafter, so to original when preparing
Material type, chemical component, particle composition, moisture, weighing accuracy etc. have strict requirements, if the sandstone powder in raw material is in ingredient
Upper requirement: SiO2>=99.10 ± 0.3%, Al2O3≤ 0.6 ± 0.1%, Fe2O3≤ 0.01 ± 0.001%, TiO2≤0.1±
0.001%；Require in granularity: particles more than>20 mesh is particle≤10 of 0,<150 mesh；Moisture≤5%；And in technique
On need the introducing of strict control machinery iron.Ultra-clear glasses have superior physics, machinery and optical property, can be as other high-quality
Float glass equally carries out various deep processings, such as tempering, plated film, colored glaze, hot bending, doubling, hollow.
The basis of 1 ultra-clear glasses of table
| Ingredient | SiO2 | Al2O3 | CaO | MgO | Na2O+K2O | Fe2O3 |
| Content (wt%) | 71-73 | 0.1-2.0 | 8.0-10.0 | 1.5-5.0 | 13.0-15.0 | ≤0.01 |
Currently, the preparation method of ultra-clear glasses has: float glass process and rolling process, process flow are respectively as follows:
Floating process process: ingredient → → clarification → tin groove forming → annealing → defects detection → crosscutting longitudinal sectional → glass is melted
Glass raw sheet detection → packaging → storage；
Rolling process process flow: ingredient → be melted → clarification → compression moulding → annealing → cutting → inspection → is packed → is entered
Library.
The ultra-clear glasses of both methods production at present have the following problems:
1. the clarification of ultra-clear glasses
Since iron content is low in ultra-clear glasses, thermal coefficient is 3-4 times of simple glass, so that diathermancy is good, viscosity is low,
Upper and lower temperature difference is relatively small, and convection current is reduced, and bubble is not easy to be discharged when clarification, causes clarification difficult.In addition, the forming ring side of flowing down
Reflowed glass liquid temperature during advance constantly rises, and microbubble is easily raised in the stream of surface, leads to number of bubbles in glass metal
Amount is obvious to be risen, and qualification rate reduces, and seriously reduces production efficiency.
2. the mildew of ultra-clear glasses
Weathering of glass is alkali metal ion (Na+And K+) diffusion and extraneous ion swap as a result, alkali metal (Na+
And K+) content is higher, mouldy tendency is more serious.Since alkali metal ion content measured is higher in ultra-clear glasses, glass is easy to cause to send out
It is mould.In addition, bivalent metal oxide (CaO and MgO) content is less in ultra-clear glasses, weaken to alkali metal ion (Na+And K+)
Suppression, cause glass to be easier to mouldy.
3. the consistency of ultra-clear glasses
For ultra-clear glasses due to radiation transmission height, bulk absorption heat is few, cannot float with common in annealing kiln leading portion heating zone
Method glass absorbs same heat, therefore vitreum is relatively colder, shortens its cooling procedure of annealing, will lead in glass in this way
Portion's structural stress remains more (ultra-clear glasses cold conditions stress value is higher by 18% than common float glass), affects glass structure
Consistency makes its strength reduction, Glass breadks easily is caused easily to burst, and also brings difficulty to subsequent processing.
Summary of the invention
The purpose of the present invention is being directed to technological deficiency existing in the prior art, in a first aspect, providing a kind of bubble-free, low
The ultra-clear glasses of stress, raw material composition includes: SiO243%-65%, Al2O35%-11%, CaO 14%-17%, MgO
2%-4%, Na2O 5%-10%, K2O 1%-3%, B2O32%-5%, ZnO 0.2%-2%, Li2O 2%-3%, MnO
0.1%-0.5%, CeO20.7%-1.8%, Na2Sb2O70.9%-2.3%.
Its raw material composition includes: SiO250%-58%, Al2O36%-10%, CaO 15%-16%, MgO 2.5%-
3.5%, Na2O 6%-9%, K2O 1.5%-2.5%, B2O33%-4%, ZnO 0.4%-1.6%, Li2O 2.2%-
2.8%, MnO 0.2%-0.4%, CeO20.9%-1.5%, Na2Sb2O71.1%-2.0%；It preferably includes: SiO2
53.5%, Al2O38%, CaO 15.6%, MgO 3%, Na2O 7.5%, K2O 2%, B2O33.5%, ZnO 1.0%,
Li2O 2.5%, MnO 0.3%, CeO21.2%, Na2Sb2O71.5%.
Its raw material is by Ta Nb tailings and SiO2、Al2O3、CaO、MgO、Na2O、K2O、B2O3、ZnO、Li2It is a kind of in O and MnO
Or several compositions.
The addition quality of the Ta Nb tailings is the 32.7%-72.0%, preferably 39.3%- of the total mass of raw material
65.5%, more preferable 52.4%.
Second aspect, the present invention provide a kind of special equipment for producing above-mentioned ultra-clear glasses, including sequentially connected glass
Melting furnaces, cooling bay, shaping area, an annealing kiln and double annealing kiln.
The glass melter, which is used to mix glass raw material, is melting into glass metal, and is clarified to remove in glass metal
Visible bubble in bubble；
The cooling bay be used to the glass metal after clarification is homogenized and is cooled down, with guarantee glass raw material be uniformly mixed,
It is cooled to forming temperature；
The shaping area is used to for the uniformly mixed glass metal of melting being pressed into certain thickness glass tape, including
Two of setting symmetrical above and below formings to roller, molding to there is gap between roller, glass metal by molding to gap between roller when
It is pressed into glass tape.
Annealing kiln is cold wind annealing kiln, including being arranged in the porous barrier above glass tape, porous barrier with
The air duct for being passed through cold wind is connected, so that cold wind is equably blown in ribbon surfaces；The double annealing kiln is free convection air
Kiln, for the temperature of glass tape to be dropped to 100-120 DEG C.
The third aspect, the present invention provide a kind of production method of above-mentioned ultra-clear glasses, use above-mentioned special equipment, including tantalum
The pretreatment of niobium tailing, melted and clarification, the homogenizing of glass metal and the cooling of glass metal, molding, is once moved back at the mixing of raw material
Fiery, double annealing and etc..
The pretreatment of the Ta Nb tailings specifically: Ta Nb tailings are passed sequentially through into the works such as classification, scouring, magnetic separation, pickling
Sequence obtains Fe2O3Content less than 0.01% (100ppm), partial size 0.1-1.5mm, Ta Nb tailings sample of the water content less than 5%
Product；Or
Preferably, the mixing of the raw material specifically:
By SiO2、Al2O3、CaO、MgO、Na2O、K2O、B2O3、ZnO、Li2It is one or more of and Ta Nb tailings in O and MnO
Obtained Ta Nb tailings sample mixing is pre-processed, is obtained comprising SiO243%-65%, Al2O35%-11%, CaO 14%-
17%, MgO 2%-4%, Na2O 5%-10%, K2O 1%-3%, B2O32%-5%, ZnO 0.2%-2%, Li2O 2%-
3%, MnO 0.1%-0.5%, CeO20.7%-1.8%, Na2Sb2O7The glass raw material of 0.9%-2.3%；Glass raw material is excellent
Choosing includes SiO250%-58%, Al2O36%-10%, CaO 15%-16%, MgO 2.5%-3.5%, Na2O 6%-
9%, K2O 1.5%-2.5%, B2O33%-4%, ZnO 0.4%-1.6%, Li2O 2.2%-2.8%, MnO 0.2%-
0.4%, CeO20.9%-1.5%, Na2Sb2O71.1%-2.0%；It more preferably include SiO253.9%, Al2O38%, CaO
15.6%, MgO 3%, Na2O 7.5%, K2O 2%, B2O33.5%, ZnO 1.0%, Li2O 2.5%, MnO 0.3%,
CeO21.2%, Na2Sb2O71.5%；Or
Preferably, the melted and clarification of the glass metal specifically:
Mixed glass raw material is fused into glass metal at 1580-1620 DEG C, temperature of glass liquid is maintained at 1600-
1650 DEG C down toward there is no bubbles to emerge；Or
Preferably, the homogenizing and cooling of the glass metal specifically:
Temperature of glass liquid after clarification is maintained at 1570-1605 DEG C, until glass metal is after mixing by glass metal temperature
Degree is down to 1020-1280 DEG C；Or
Preferably, the molding specifically:
Glass metal is pressed into required thickness to roller by molding at a temperature of 1020-1280 DEG C by glass metal after cooling
With the glass tape of size.
The primary annealing specifically:
Glass tape after molding is subjected to the 1.5-4h that once anneals with cold wind at 630-720 DEG C；The cold wind temperature be-
10-20 DEG C, wind pressure 20-50Pa, flow 130-280Nm3/h；
The double annealing specifically:
Glass tape after primary annealing is subjected to double annealing 3-6h with free convection air at 580-650 DEG C, until glass
Glass band temperature is 100-120 DEG C, obtains the ultra-clear glasses；The free convection air themperature is 15-40 DEG C, wind pressure 7-
18Pa, flow 200-350Nm3/h；
Preferably, primary annealing and double annealing is no less than 5h total time.
Compared with prior art, the beneficial effects of the present invention are:
(1) alumina content is higher in ultra-clear glasses provided by the invention, Al2O3Belong to the intermediate oxide of glass, energy
The crystallization tendency for reducing glass, improves chemical stability, thermal stability, mechanical strength, hardness and the refractive index of glass.
(2) ingredient of ultra-clear glasses of the present invention be well suited for carry out chemical tempering (chemical tempering is that glass is placed on high temperature
In fused salt, the potassium ion in the sodium ion and fused salt of glass surface swaps between each other, in fused salt large radius ionic potassium from
Son (K+'s) displace the sodium ion (Na of small radii in glass+'s).Due to big ion occupy compared with
Small " gap " and generate " jammed " phenomenon on surface, to generate compression in glass surface, center generates tensile stress, thus
Achieve the effect that enhancing, also known as ion tempering).Al2O3Acceleration is played in ion exchange, reason is [AlO4]
Molecular volume is 41cm3/ mol, and [SiO4] molecular volume be 27.24cm3/ mol, Al2O3Replace SiO2Afterwards, molecular volume increases
Greatly, structural network void enlargement is conducive to basic ion diffusion；Another party and, volume increase, be also beneficial to absorb large volume K+
Ion promotes ion exchange.
(3) contain potassium oxide, sodium oxide molybdena, lithia and boron oxide in glass raw material of the invention, the molten of glass can be promoted
Change, reduce the viscosity of glass, accelerates the exclusion of micro-bubble in glass metal；Alumina content is high in glass raw material, and contains
Boron oxide and manganese oxide the structure of glass can be made even closer, intensity is higher.
(4) thermal stress issues of the invention in order to reduce glass are solved in ultra-clear glasses production using double annealing
The excessively high problem of stress, can reduce glass cut with bursting in application process, promoted yield rate, reduce cost.The present invention
The task equipment of offer can steady production ultra-clear glasses, the ultra-clear glasses of production facilitate the chemical tempering process of glass.
Detailed description of the invention
Fig. 1 show the special equipment structural schematic diagram of present invention production ultra-clear glasses；
1 glass melter, 2 glass metals, 3 cooling bays, 4 shaping areas, 5 glass tapes, 6 moldings are to roller, No. 7 annealing kilns, and 8 two times
Annealing kiln, 9 porous barriers, 10 air ducts.
Specific embodiment
Yichuan Ta Nb tailings be from the lithium spectra containing tantalum niobium rare metal, after selected tantalum niobium remaining tail
Ore in sand form., in the future can be increasingly severe to the pollution of environment if Ta Nb tailings are not utilized rationally, be for local government
Urgent need to solve the problem.Hair is also all indicated from " economizing energy law ", " environment impact assessment ordinance " and " Renewable Energy Law " etc.
Open up the requirement of circular economy related fields.
Local raw material and geographical advantage can be made full use of using Ta Nb tailings preparation ultra-clear glasses, for enterprise and is worked as
Ground government forms new productivity growth point.Through Al in ore dressing analysis Ta Nb tailings sample2O3It is higher, therefore ultrawhite can be introduced by it
Al needed for glass2O3, while can also introduce least a portion of Na2O advantageously reduces the production of glass to reduce soda ash dosage
Cost, by determining that the chemical component in Ta Nb tailings is shown in Table 2 after beneficiation test.
Ta Nb tailings sample chemical component after 2 beneficiation test of table
| Oxide | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | K2O | Na2O | Li2O | MnO | IL |
| Content (wt%) | 75.12 | 15.27 | 0.010 | 0.39 | 0.040 | 1.75 | 5.33 | 0.20 | 0.070 | 0.13 |
Ultra-clear glasses have high elasticity modulus, low thermal expansion coefficient, high chemical stability and strain point, are a kind of
It is bordering on the high-quality float flat glass of colourless high transmission.It it requires alumina content height, improve chemical stability, the heat of glass
Stability and mechanical strength etc..Simultaneously in toughening process, Al2O3Acceleration, Al are played in ion exchange process2O3Replace SiO2
Afterwards, molecular volume increases, structural network void enlargement, is conducive to basic ion diffusion；Another party and, volume increase, be also beneficial to
Absorb the K of large volume+Ion promotes ion exchange.Physical and chemical performance requirement based on this glass, selecting includes SiO2、Al2O3、
CaO、MgO、Na2O、K2O、B2O3It is formed with ZnO etc. as the raw material of ultra-clear glasses of the present invention.It is mainly formed in glass and in height
Effect played in intensity ultra-clear glasses is as follows:
Silica SiO2It is the main body that glass forms skeleton, the SiO in soda lime glass2The heat of glass can be reduced
The coefficient of expansion improves thermal stability, chemical stability, softening temperature, hardness and the mechanical strength of glass.
Aluminium oxide Al2O3Belong to the intermediate oxide of glass, the crystallization tendency of glass can be reduced, improve the chemistry of glass
Stability, thermal stability, mechanical strength, hardness and refractive index mitigate erosion of the glass to refractory material.Ultrawhite glass of the invention
Al in glass2O3Content is 5%-11%, and Al in general ultra-clear glasses2O3Content is no more than 4%, this is because the present invention is sent out
Existing alumina content is high, ultra-clear glasses product be not easy it is mouldy, to environment ginseng when deep processing directly apply and carried out to glassware
Number require it is low, and facilitate glass carry out chemical tempering, be conducive to being widely applied for product.
Sodium oxide molybdena Na2O is glass network modifier oxides, can reduce the viscosity of glass, and glass is made to be easy to melt, and is glass
The good fluxing agent of glass.Na2O can increase the thermal expansion coefficient of glass, reduce thermal stability, chemical stability and the machinery of glass
Intensity.
Potassium oxide K2O is also glass network modifier oxides, its effect and Na in glass2O is similar.Potassium ion (K+)
Radius ratio sodium ion (Na+) it is big, the viscosity of potash glass is bigger than soda-lime glass, can reduce the tendency towards devitrification of glass, increases glass
Transparency and gloss etc..
Calcium oxide CaO is the glass network modifier oxides of divalent.Its main function is stabilizer, that is, increases the change of glass
Learn stability and mechanical strength.When content is high, the crystallization tendency of glass will increase.
Magnesia MgO is network modifying oxide in soda lime glass.With 3.5% MgO generation below in glass
For part CaO, the setting rate of glass can be made slack-off, reduce the tendency towards devitrification of glass, improve glass chemical stability and
Mechanical strength.
Boron oxide B2O3It is also network former.The coefficient of expansion that glass can be reduced, improve glass thermal stability,
Chemical stability increases the refractive index of glass, improves the gloss of glass, improves the mechanical performance of glass.
Zinc oxide ZnO is glass intermediate oxide.The thermal expansion coefficient that glass can be reduced improves the thermostabilization of glass
Property, chemical stability, increase the refractive index of glass.
B in ultra-clear glasses of the present invention2O3It is glass intermediate with ZnO, keeps glass structure finer and close, can speed up simultaneously
The fusing of glass at high temperature, MnO can promote the fusing of glass, and generate mangano-manganic oxide at high temperature, belong to spinelle
Structure keeps glass structure close.
In glass melting process, since a large amount of gas can be precipitated in the decomposition and the volatilization of Volatile Colstituent etc. of batch each component
Body.Until still have small part of gas that cannot escape completely from glass metal after glass forming process finishes, it is residual in the form of bubbles
It stays in glass metal.Therefore, in order to obtain pure uniform high-quality glass metal, CeO is added in glass batch2With
Na2Sb2O7As clarifying agent, to promote the exclusion of bubble in glass metal.The present invention selects CeO2And Na2Sb2O7As clarifying agent,
Compared to sulfate clarifying agent, both clarifying agents will not generate the secondary bubble of sulfate, while dirt will not be generated in flue gas
Contaminate object SO2, be conducive to mitigate flue gas desulfurization and denitrification load, reduce ultra-clear glasses production cost.
CeO2And Na2Sb2O7As clarifying agent, actually a kind of oxidant, working principle specifically: CeO2In high temperature
It is decomposed under the conditions of (1400 DEG C or more) and obtains Ce2O3And oxygen, Na2Sb2O7It decomposes under the high temperature conditions and obtains Sb2O3And oxygen,
Clarifying agent decompose generate oxygen can will not from glass metal, complete escaping gas is taken out of, to reach fining glass liquid
Purpose.However ultra-clear glasses are to Fe2+It is very sensitive, this is because Fe2+Colorability is strong, Fe2+Presence can make the ultra-clear glasses be in
It is light blue, it is unable to satisfy the requirement of colour consistency.After clarifying agent of the invention is added, even if there is Fe in glass metal2+In the presence of,
Fe can be oxidized to3+, Fe3+Colorability is poor, will not influence the colour consistency of ultra-clear glasses.
What clarifying agent was selected in the preparation process of existing ultra-clear glasses is antimony oxide and sodium nitrate, its working principle is that: oxygen
Change antimony Sb2O3Sb is oxidized under the action of 800-900 DEG C or so in sodium nitrate2O5, as temperature is increased to 1500-1600
DEG C, Sb2O5Decomposition obtains Sb2O3And oxygen, to play the role of fining glass liquid.However problem is, ultra-clear glasses are melted
Temperature can reach 1600 DEG C or more, that is to say, that before the temperature of glass smelting does not reach also, Sb2O5With regard to decomposing, generation
Oxygen just has been drained off in melted early period, can not be left to the melted later period for the complete escaping gas band not from glass metal
Out, clear effect is not just had yet.
The present invention prepares high-intensitive ultra-clear glasses as raw material using Ta Nb tailings, and the glass sample performance of preparation is stablized,
And Ta Nb tailings can be comprehensively utilized, reduce the pollution to environment.
The ultra-clear glasses that the present invention is prepared are high-intensitive, however intensity is high, it is meant that Al in glass ingredient itself2O3Contain
Amount is higher, and also therefore there are both sides technical problems in production: first is that glass melting temperature is higher, regular fuel melting furnaces are not easy
Reach, second is that clarifying and homogenizing is relatively difficult.When using pure oxygen combustion technology, glass viscosity is reduced, meanwhile, all-oxygen combustion flame is steady
Fixed, no commutation, burning gases are long in kiln residence time, and kiln inner pressure is stable and lower, these be all conducive to glass fusing,
Clarification, reduces intravitreous bubble, blub and striped, promotes the quality of glass.
Below in conjunction with specific embodiment, the content of the present invention will be explained in more detail, and the present invention is further elaborated, but
These embodiments limit the invention absolutely not.
Batch is formed into uniform, bubble-free by high-temperature heating and meets the process of the glass metal of forming requirements, is claimed
For being melted for glass.Glass melting process is the important link in glass production.Many defects (such as bubble, calculus, the item of glass
Line etc.) be all the glass metal in melting process it is uneven caused by.The yield and quality of glass, qualification rate, production cost, combustion
Material consumption and melted tank furnace service life etc. all have substantial connection with the melted of glass.Therefore, reasonable glass smelting is carried out, is
Entire production process is smooth, and efficiently produces the important guarantee of high-quality glassware.
The present invention is used as high intensity display and fire prevention glass by largely having determined to be used to produce by Ta Nb tailings
The raw material composition of the ultra-clear glasses of glass, the ultra-clear glasses includes: SiO243%-65%, Al2O35%-11%, CaO 14%-
17%, MgO 2%-4%, Na2O 5%-10%, K2O 1%-3%, B2O32%-5%, ZnO 0.2%-2%, Li2O 2%-
3%, MnO 0.1%-0.5%, CeO20.7%-1.8%, Na2Sb2O70.9%-2.3%；
It is preferred that:
SiO250%-58%, Al2O36%-10%, CaO 15%-16%, MgO 2.5%-3.5%, Na2O 6%-
9%, K2O 1.5%-2.5%, B2O33%-4%, ZnO 0.4%-1.6%, Li2O 2.2%-2.8%, MnO 0.2%-
0.4%, CeO20.9%-1.5%, Na2Sb2O71.1%-2.0%；
It is more preferable:
SiO253.5%, Al2O38%, CaO 15.6%, MgO 3%, Na2O 7.5%, K2O 2%, B2O33.5%,
ZnO 1.0%, Li2O 2.5%, MnO 0.3%, CeO21.2%, Na2Sb2O71.5%.
In the raw material of production ultra-clear glasses, the best introducing mass percentage of Ta Nb tailings is glass raw material gross mass
32.7%-72.0%, preferably 39.3%-65.5%, more preferable 52.4%.
The present invention also provides a kind of special equipment for producing above-mentioned ultra-clear glasses, the equipment be the equipment based on rolling process into
Capable transformation, structure is as shown in Figure 1, include sequentially connected glass melter 1, cooling bay 3,7 and of annealing kiln of shaping area No. 4, one times
Double annealing kiln 8.Wherein:
Glass melter 1 is used to mixed glass raw material being melting into glass metal 2, and removes the visible bubble in bubble in glass metal.
The process of removal visible bubble in bubble is known as the clarification of glass metal, i.e. the clarification of glass raw material being melted with glass metal is molten in glass
It is carried out in kiln 1.
Cooling bay 3 is used to that the glass metal after clarification is homogenized and is cooled down, and adjusts the viscosity of glass metal, even if melting
Glass raw material be uniformly mixed, adjustment glass metal viscosity and be cooled to forming temperature, the molding for subsequent glass metal provides guarantor
Card；
Shaping area 4 is used to the uniformly mixed glass metal of melting being suppressed into the glass system with fixed geometry
Product, shaping area 4 include upper and lower two formings to roller 6, glass metal by forming to roller 6 when be pressed into glass tape 5, completion at
Type can obtain the glass tape 5 of different-thickness to the gap compression moulding of roller 6 by adjusting forming.
Annealing stage is in order to eliminate the stress after molding in certain thickness glass tape 5, using twice annealing, the
It once is annealed into black annealing, is annealed into smart annealing for the second time.Annealing for the first time uses an annealing kiln 7, and is annealed using cold wind,
Cold wind temperature is -10-20 DEG C, wind pressure 20-50Pa, flow 130-280Nm3/h.Annealing kiln 7 is arranged more above glass tape
Hole partition 9, porous barrier 9 are connected with air duct 10, and cold wind is beaten on porous barrier 9 after being passed through by air duct 10, to reduce cold sky
Uneven cold shock of the gas to glass tape, falls in cold wind equably on ribbon surfaces.Glass tape after once annealing
It anneals into carrying out second in double annealing kiln 8, double annealing kiln 8 is annealed using free convection air, free convection
The temperature of air is 15-40 DEG C, wind pressure 7-18Pa, flow 200-350Nm3/h.When glass tape temperature drops to 100-120 DEG C,
Second of annealing is completed.
The present invention also provides the production method of above-mentioned ultra-clear glasses, process flow includes the pretreatment of Ta Nb tailings, original
The mixing of material, glass metal be melted and clarification, the homogenizing of glass metal and cooling, molding, primary annealing, double annealing；
Each step carries out in the special equipment of above-mentioned production ultra-clear glasses, specifically:
1), the pretreatment of Ta Nb tailings:
Ta Nb tailings are passed sequentially through into the processes such as classification, scouring, magnetic separation, pickling and obtain the tantalum niobium for being suitble to production ultra-clear glasses
Tailing sample, Fe in Ta Nb tailings sample2O3Content less than 0.01% (100ppm), partial size 0.1-1.5mm, water content is small
In 5%.
2), the mixing of raw material:
After detecting the chemical composition in Ta Nb tailings sample, by calculating, by SiO2、Al2O3、CaO、MgO、Na2O、K2O、
B2O3、ZnO、Li2It is one or more of in O and MnO to be mixed with the Ta Nb tailings sample that step 1) obtains, it obtains comprising SiO2
43%-65%, Al2O35%-11%, CaO 14%-17%, MgO 2%-4%, Na2O 5%-10%, K2O 1%-3%,
B2O32%-5%, ZnO 0.2%-2%, Li2O 2%-3%, MnO 0.1%-0.5%, CeO20.7%-1.8%,
Na2Sb2O7The glass raw material of 0.9%-2.3%；In general industry production, SiO2From silica sand, Al2O3From feldspar,
CaO is from lime stone, MgO from magnesite, Na2O is from soda ash, K2O is from potassium carbonate, B2O3From boric acid
Or borax, Li2O is from lithium carbonate.
Preferably contain SiO in glass raw material250%-58%, Al2O36%-10%, CaO 15%-16%, MgO 2.5%-
3.5%, Na2O 6%-9%, K2O 1.5%-2.5%, B2O33%-4%, ZnO 0.4%-1.6%, Li2O 2.2%-
2.8%, MnO 0.2%-0.4%, CeO20.9%-1.5%, Na2Sb2O71.1%-2.0%；More preferably contain SiO2
53.9%, Al2O38%, CaO 15.6%, MgO 3%, Na2O 7.5%, K2O 2%, B2O33.5%, ZnO 1.0%,
Li2O 2.5%, MnO 0.3%, CeO21.2%, Na2Sb2O71.5%.
3), glass metal is melted:
The glass raw material that step 2) mixes is melted into glass metal at 1580-1620 DEG C, is generally required left for 24 hours
It is right；
4), the clarification of glass metal:
The temperature of glass liquid that step 3) is obtained is maintained at 1600-1650 DEG C and (generally requires down toward emerging there is no bubble
8h or so, to carry out enough clarifications), clarification terminates；
5), the homogenizing and cooling of glass metal:
Temperature of glass liquid after step 4) clarification is maintained at 1570-1605 DEG C, until each section of glass metal is in chemistry
Reach uniformity on composition, homogenizing terminates, and homogenizing is to eliminate the striped and heterogeneous body in glass metal；By glass after homogenizing
The temperature of glass liquid is down to 1020-1280 DEG C；
6) it, forms:
Glass metal is pressed into institute to roller by molding at a temperature of 1020-1280 DEG C by the glass metal after step 5) homogenizing
Need the glass tape of thickness and size；
7), primary annealing:
Glass tape after molding is subjected to the 1.5-4h that once anneals with cold wind at 630-720 DEG C；Cold wind temperature is -10-
20 DEG C, wind pressure 20-50Pa, flow 130-280Nm3/h。
8), double annealing:
Glass tape after primary annealing is subjected to double annealing 3-6h with free convection air at 580-650 DEG C, twice
5h cannot be less than total time by annealing, until glass tape temperature is 100-120 DEG C, annealing terminates to obtain ultra-clear glasses of the invention；From
The temperature of right convected air is 15-40 DEG C, wind pressure 7-18Pa, flow 200-350Nm3/h。
Use Ta Nb tailings preferable as the melted obtained glass metal uniformity of a part of glass raw material, no calculus, nothing
Refractory compound, without striped under high temperature, modest viscosity, good fluidity, processability is preferable, and thus obtained glassware intensity is high,
Defect is less, and glass colour is whiter, and light transmittance is preferable, illustrates that Ta Nb tailings can be used for the raw material of ultra-clear glasses.
It is super according to the above production using the special equipment of the above production ultra-clear glasses and containing the glass raw material of Ta Nb tailings
The ultra-clear glasses of embodiment 1- embodiment 7 are prepared in the method for white glass.The ultra-clear glasses of production example 1- embodiment 7
Parameter and raw material composition are shown in Table 1.
The raw material of the ultra-clear glasses of 1 embodiment 1- embodiment 7 of table forms and manufacturing parameter
Experiment:
The bending strength for the glass that measurement embodiment 1-7 and comparative example 1-4 is obtained, by glass specimen through cutting, grinding, throwing
The strip of 80 × 10 × 10mm is made after light, using three-point bending method, test equipment is DKZ-5000 type electric bending testing
Machine.The performance test results are shown in Table 2.
The performance test results of table 2 embodiment 1-7 and comparative example 1-4 glass
As it can be seen that ultra-clear glasses of the invention to have after more common float glass chemical tempering after chemical tempering it is higher
Intensity, the product for being suitble to require thin and strong degree high uses, be able to maintain high-caliber intensity, while machining property is good,
It can be widely applied in the products form such as liquid crystal display and wrist-watch, mobile phone, flat-panel monitor, camera.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also the contents of the present invention be should be regarded as.
Claims (10)
1. a kind of ultra-clear glasses, which is characterized in that its raw material composition includes: SiO243%-65%, Al2O35%-11%, CaO
14%-17%, MgO 2%-4%, Na2O 5%-10%, K2O 1%-3%, B2O32%-5%, ZnO 0.2%-2%, Li2O
2%-3%, MnO 0.1%-0.5%, CeO20.7%-1.8%, Na2Sb2O70.9%-2.3%.
2. ultra-clear glasses according to claim 1, which is characterized in that its raw material composition includes: SiO250%-58%, Al2O3
6%-10%, CaO 15%-16%, MgO 2.5%-3.5%, Na2O 6%-9%, K2O 1.5%-2.5%, B2O33%-
4%, ZnO 0.4%-1.6%, Li2O 2.2%-2.8%, MnO 0.2%-0.4%, CeO20.9%-1.5%, Na2Sb2O7
1.1%-2.0%；It preferably includes: SiO253.5%, Al2O38%, CaO 15.6%, MgO 3%, Na2O 7.5%, K2O
2%, B2O33.5%, ZnO 1.0%, Li2O 2.5%, MnO 0.3%, CeO21.2%, Na2Sb2O71.5%.
3. ultra-clear glasses according to claim 1 or claim 2, which is characterized in that its raw material is by Ta Nb tailings and SiO2、Al2O3、
CaO、MgO、Na2O、K2O、B2O3、ZnO、Li2One or more of compositions in O and MnO.
4. ultra-clear glasses according to claim 3, which is characterized in that the addition quality of the Ta Nb tailings is that the raw material is total
The 32.7%-72.0% of quality, preferably 39.3%-65.5%, more preferable 52.4%.
5. a kind of special equipment for producing any ultra-clear glasses of claim 1-4, which is characterized in that including sequentially connected
Glass melter, cooling bay, shaping area, an annealing kiln and double annealing kiln.
6. special equipment according to claim 5, which is characterized in that the glass melter, which is used to mix glass raw material, to be melted
At glass metal, and clarified to remove the visible bubble in bubble in glass metal；
The cooling bay is used to that the glass metal after clarification is homogenized and is cooled down, to guarantee that glass raw material is uniformly mixed, cooling
To forming temperature；
The shaping area is used to for the uniformly mixed glass metal of melting being pressed into certain thickness glass tape, including upper and lower
Symmetrically arranged two formings to roller, molding to there is gap between roller, glass metal by molding to gap between roller when pressed
Glass tape is made.
7. according to the special equipment of claim 5 or 6, which is characterized in that an annealing kiln is cold wind annealing kiln, including
Porous barrier above glass tape is set, and porous barrier is connected with the air duct for being passed through cold wind, so that cold wind is equably blown in glass
Glass belt surface；The double annealing kiln is free convection air kiln, for the temperature of glass tape to be dropped to 100-120 DEG C.
8. a kind of production method of any ultra-clear glasses of claim 1-4, which is characterized in that appointed using claim 5-7
One special equipment, the mixing of pretreatment, raw material including Ta Nb tailings, glass metal be melted and clarification, glass metal it is equal
Change and cooling, molding, primary annealing, double annealing.
9. production method according to claim 8, which is characterized in that the pretreatment of the Ta Nb tailings specifically: by tantalum niobium
Tailing passes sequentially through the processes such as classification, scouring, magnetic separation, pickling and obtains Fe2O3Content less than 0.01% (100ppm), partial size is
0.1-1.5mm, Ta Nb tailings sample of the water content less than 5%；Or
Preferably, the mixing of the raw material specifically:
By SiO2、Al2O3、CaO、MgO、Na2O、K2O、B2O3、ZnO、Li2One or more of pre- places with Ta Nb tailings in O and MnO
Obtained Ta Nb tailings sample mixing is managed, is obtained comprising SiO243%-65%, Al2O35%-11%, CaO 14%-17%,
MgO 2%-4%, Na2O 5%-10%, K2O 1%-3%, B2O32%-5%, ZnO 0.2%-2%, Li2O 2%-3%,
MnO 0.1%-0.5%, CeO20.7%-1.8%, Na2Sb2O7The glass raw material of 0.9%-2.3%；Glass raw material preferably wraps
Containing SiO250%-58%, Al2O36%-10%, CaO 15%-16%, MgO 2.5%-3.5%, Na2O 6%-9%, K2O
1.5%-2.5%, B2O33%-4%, ZnO 0.4%-1.6%, Li2O 2.2%-2.8%, MnO 0.2%-0.4%, CeO2
0.9%-1.5%, Na2Sb2O71.1%-2.0%；It more preferably include SiO253.9%, Al2O38%, CaO 15.6%, MgO
3%, Na2O 7.5%, K2O 2%, B2O33.5%, ZnO 1.0%, Li2O 2.5%, MnO 0.3%, CeO21.2%,
Na2Sb2O71.5%；Or
Preferably, the melted and clarification of the glass metal specifically:
Mixed glass raw material is fused into glass metal at 1580-1620 DEG C, temperature of glass liquid is maintained at 1600-1650
DEG C down toward there is no bubbles to emerge；Or
Preferably, the homogenizing and cooling of the glass metal specifically:
Temperature of glass liquid after clarification is maintained at 1570-1605 DEG C, until glass metal after mixing drops temperature of glass liquid
To 1020-1280 DEG C；Or
Preferably, the molding specifically:
Glass metal is pressed into required thickness and ruler to roller by molding at a temperature of 1020-1280 DEG C by glass metal after cooling
Very little glass tape.
10. production method according to claim 8 or claim 9, which is characterized in that the primary annealing specifically:
Glass tape after molding is subjected to the 1.5-4h that once anneals with cold wind at 630-720 DEG C；The cold wind temperature is -10-
20 DEG C, wind pressure 20-50Pa, flow 130-280Nm3/h；
The double annealing specifically:
Glass tape after primary annealing is subjected to double annealing 3-6h with free convection air at 580-650 DEG C, until glass tape
Temperature is 100-120 DEG C, obtains the ultra-clear glasses；The free convection air themperature is 15-40 DEG C, wind pressure 7-18Pa, stream
Measure 200-350Nm3/h；
Preferably, primary annealing and double annealing is no less than 5h total time.
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| CN109336380B (en) | 2023-11-28 |
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