CN109704583A - A kind of devitrified glass and its production method - Google Patents
A kind of devitrified glass and its production method Download PDFInfo
- Publication number
- CN109704583A CN109704583A CN201910137180.0A CN201910137180A CN109704583A CN 109704583 A CN109704583 A CN 109704583A CN 201910137180 A CN201910137180 A CN 201910137180A CN 109704583 A CN109704583 A CN 109704583A
- Authority
- CN
- China
- Prior art keywords
- glass
- crystallization
- tailings
- raw material
- devitrified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 273
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 67
- 238000002425 crystallisation Methods 0.000 claims description 57
- 230000008025 crystallization Effects 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 38
- 238000000465 moulding Methods 0.000 claims description 33
- 230000007704 transition Effects 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 18
- 238000005352 clarification Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 230000006911 nucleation Effects 0.000 claims description 5
- 238000010899 nucleation Methods 0.000 claims description 5
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910004883 Na2SiF6 Inorganic materials 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 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
- 230000009471 action Effects 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 4
- 201000004569 Blindness Diseases 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- 239000000395 magnesium oxide Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000005245 sintering Methods 0.000 description 17
- 239000000292 calcium oxide Substances 0.000 description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 14
- 238000006124 Pilkington process Methods 0.000 description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 12
- 239000002667 nucleating agent Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 7
- 238000005034 decoration Methods 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007667 floating Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002241 glass-ceramic Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008395 clarifying agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 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
- 239000005361 soda-lime glass Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- -1 Ta Nb tailings Substances 0.000 description 1
- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 description 1
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 238000005422 blasting Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 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
- 239000004579 marble Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000006132 parent glass Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940072033 potash Drugs 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
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000005401 pressed glass Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006017 silicate glass-ceramic Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing 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
- 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
- C03C10/0036—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 a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
-
- 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
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- 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
- C03C10/0063—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 waste materials, e.g. slags
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of devitrified glass and its production method, raw material composition includes: SiO243%-49.8%, Al2O310.2%-16%, CaO 5.5%-9.9%, MgO 1.2%-9.8%, Na2O 3.1%-6.5%, K2O 2.3%-7.7%, BaO 4.2%-8.8%, ZnO 4.5%-10%, Sb2O30.2%-2%, nitrate 0.8%-8%, P2O50.3%-1.8%, ZrO20.2%-1.5%, fluoride 0.1%-0.7%, TiO20.7%-3.5%.Devitrified glass of the invention is prepared using Ta Nb tailings, and the blindness exploitation to lithotome can be greatly reduced, improve the comprehensive utilization ratio of Ta Nb tailings, turn waste into wealth.The devitrified glass bubble that the method for the present invention obtains is few, intensity is high, and yield rate and final product quality all have a big promotion；And idle Ta Nb tailings are utilized in production in itself, have saved resource.
Description
Technical field
The present invention relates to the processing technique fields of glass, more particularly to a kind of devitrified glass and produce devitrified glass
Method.
Background technique
Devitrified glass, using certain controlled coring and crystallization process, is passed through using natural inorganic material as primary raw material
A kind of glass of special crystallite crystal phase is precipitated in the glass metal of special composition, basis is shown in Table 1.
The basis of 1 devitrified glass of table
| Ingredient | CaO | Al2O3 | SiO2 | Sb2O3 | ZnO+MgO | Na2O |
| Content/% | 16-22 | 3-10 | 50-70 | 1-3 | 4-9 | 1-6 |
Devitrified glass has the advantages that the triple of glass, ceramics and lithotome, such as with the optics passability and table of glass
Face optical property, mechanical and surface crystallization performance, the surface anisotropic with lithotome and dicoration etc. with ceramics,
It is better than lithotome and ceramics again simultaneously, performance is relatively shown in Table 2.
The properties of 2 devitrified glass of table and ceramics, lithotome compare
From Table 2, it can be seen that devitrified glass (is reflected, because of water absorption rate and heat expansion in dimensional stability with water absorption rate
Coefficient is related, the big material of water absorption rate is easily deformed, i.e., coefficient of thermal expansion is big, poor dimensional stability), frost resistance, glossiness hold
Long property (i.e. the weatherability and durability of material is embodied by acid resistance, the alkali resistance in table 2), intensity (flexural strength, pressure resistance
Degree) etc. be superior to ceramics, natural marble and granite.Therefore, devitrified glass can be used as the inner-outer wall and ground of all kinds of buildings
Plate ornament materials, the ideal material of platen of even more washing one's face, hygienic platen.Devitrified glass is in addition to can be used as external wall and indoor height
Shelves decoration, can also do mechanical structure, such as the insulating materials on electronics, electrician, baseboard material, the micro-wave oven of large scale integrated circuit
Flameproof ware, chemical industry and anti-corrosion material and mine wear-resistant material etc., purposes is extremely wide.
The production technology of existing devitrified glass is mainly sintering process, and through molten sintering twice.Sintering process includes melting water
Particle at small particle, is then attached to by sintering process of quenching and direct sintering, melt water quenching sintering process by water quenching after glass melting
Carry out coring and crystallization in mold, specific process include: mixture preparation → glass smelting → water quenching prepare pellet → molding →
Dominated crystallization → cold working etc.；The process of direct sintering include: mixture preparation → grinding mixing → forming and sintering → cold plus
Work etc..
As Publication No. CN 1868946A Chinese patent application in disclose a kind of waste residue microcrystal glass and its preparation side
Method.The preparation method of the devitrified glass is the melt water quenching sintering process in sintering process.Not only production energy consumption occupies height not to this method
Under, it can also make the devitrified glass superficial layer densification depths (the microcrystalline coating thickness formed) of production 2nm more shallow than direct sintering
Left and right, microcrystalline coating thickness is thinner, illustrates that controlled micro crystallization degree is insufficient, and obtained devitrified glass properties are poorer, glass particle
Between bubble be difficult to exclude, lead to that rough surface, the porosity are high, are also easy to produce deformation, the fireproof die used when to subsequent forming
High temperature resistant, pressure-resistant performance and to be not easy deformation nature requirement high, it is also necessary to the processes such as secondary operation are carried out to devitrified glass surface,
Because secondary operation can further result in the production energy consumption and cost raising of devitrified glass again.While due to magnesia and calcium oxide
It is advantageous using the adjustment for capableing of viscosity and temperature performance to glass, and magnesia is not used in the devitrified glass, use height
The calcium oxide of content, this can make glass embrittlement, then adjust glass melting temperature using the relatively high boron oxide of price, promote
Into the fusing of devitrified glass, the production cost of devitrified glass can be promoted again in this way.
Direct sintering crystal phase ratio when preparing devitrified glass depends on the whole crystallization ability of parent glass, this just leads
Crystallization Process is caused to be difficult to control, and whole crystallization time length, production efficiency and yield rate are low.
Rolling process can also be used to production devitrified glass at present, such as the Chinese patent application of Publication No. CN 106746681A
In disclose it is a kind of using trade waste prepare wear-resistant glass-ceramics.The devitrified glass is prepared through rolling process, system
Standby process includes mixture preparation → glass smelting → calendering formation → annealing → nucleus crystallization → cold working etc..Rolling process is to adopt
Rotate pressed glass molding forward with double roller, glass waits have contraction at the time of molding, simultaneously because roller table surface is coarse, can all make
It is rough at glass surface, therefore also need to be processed by shot blasting after forming, process flow is increased, yield rate is reduced, is mentioned
High cost.Contain copper sulphate, nickel sulfide, magnesium diboride in the raw material composition of the devitrified glass, and is used to the Nucleating Agent of crystallization
What is selected is chrome green；Wherein, copper sulphate can make glass coloration au bleu, Cr2O3Middle Cr3+It is to belong to heavy metal ion,
It can generate pollution of chromium and intoxicating phenomenon, it is dangerous, not environmentally, use should be avoided in industry.
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
Devitrified glass, raw material composition includes: SiO243%-49.8%, Al2O310.2%-16%, CaO 5.5%-9.9%, MgO
1.2%-9.8%, Na2O 3.1%-6.5%, K2O 2.3%-7.7%, BaO 4.2%-8.8%, ZnO 4.5%-10%,
Sb2O30.2%-2%, nitrate (preferably NaNO3And/or KNO3) 0.8%-8%, P2O50.3%-1.8%, ZrO2
0.2%-1.5%, fluoride (preferably CaF2And/or Na2SiF6) 0.1%-0.7%, TiO20.7%-3.5%.
Its raw material composition includes: SiO245%-47%, Al2O311%-14%, CaO 6%-8%, MgO 3%-8%,
Na2O 4%-5%, K2O 3%-6%, BaO 5%-7%, ZnO 5%-8%, Sb2O30.5%-1.5%, nitrate 2%-
6%, P2O50.6%-1.5%, ZrO20.5%-1.1%, fluoride 0.2%-0.5%, TiO21.2%-2.9%；It is preferred that
It include: SiO246%, Al2O312.5%, CaO 7%, MgO 5.5%, Na2O 4.5%, K2O 4.5%, BaO 6%, ZnO
6.5%, Sb2O30.8%, nitrate 2.8%, P2O50.8%, ZrO20.7%, fluoride 0.4%, TiO22%.
The raw material includes Ta Nb tailings.
The addition quality of the Ta Nb tailings is 25%-40%, the preferably 30%-35% of the total mass of raw material, more excellent
Select 33%.
Second aspect, the present invention provide a kind of production method of above-mentioned devitrified glass, sequentially the mixing including raw material, glass
Liquid be melted and clarification, the homogenizing of glass metal and cooling, glass molding, glass coring, glass crystallization and annealing, it is described
Glass is shaped to float tin groove molding, and the glass coring includes a transition cooling and coring, and the glass crystallization includes two
Secondary transition heating and crystallization.
Transition cooling and coring specifically:
The transitional product obtained after tin groove forming is adjusted into temperature and carries out core to coring molten tin bath after 600-660 DEG C, is entered back into
Change, nucleation temperature is 580-640 DEG C, nucleation time 30min-3h, obtains a transitional product.
The secondary transition heating and crystallization specifically:
Transitional product is adjusted into temperature to after 740-950 DEG C, crystallization molten tin bath is entered back into and carries out crystallization, crystallization temperature is
730-940 DEG C, crystallization time 2-8.5h obtains secondary transitional product.
The tin groove forming specifically:
Homogenizing and glass metal after cooling enter molding molten tin bath in is formed under the action of edge machine, obtain with a thickness of
The transitional product of 2-15mm, the inlet temperature for forming molten tin bath is 1250-1320 DEG C, and molding molten tin bath temperature is 750- after the completion of molding
930℃。
It further include the preprocessing process of the Ta Nb tailings before raw material mixing, the pretreatment of the Ta Nb tailings specifically: will
Ta Nb tailings pass sequentially through the processes such as classification, scouring, magnetic separation, pickling and obtain Fe2O3Content less than 0.01% (100ppm), grain
Diameter is 0.1-1.5mm, Ta Nb tailings sample of the water content less than 5%.
The melted and clarification of the glass metal and the homogenizing and cooling of glass metal specifically: by mixed glass raw material
It is fused into glass metal at 1600-1660 DEG C, and there is no bubbles to emerge, temperature of glass liquid is then maintained at 1620-1670
DEG C to glass metal be uniformly mixed；Or
Optionally, the annealing specifically: secondary transitional product after crystallization at 600-700 DEG C continuous annealing 2-8h or
To 100 DEG C hereinafter, obtaining the devitrified glass.
Compared with prior art, the present invention prepares devitrified glass using floating process, impact strength, compressive resistance,
The indexs such as water absorption rate (i.e. dimensional stability) are superior to the devitrified glass of current sintering process preparation, and physicochemical property and decorative effect
The devitrified glass that current sintering process preparation can be reached is horizontal, is conducive to application.Simultaneously using Ta Nb tailings preparation building dress
The blindness exploitation to lithotome can be greatly reduced in decorations devitrified glass, improve the comprehensive utilization ratio of Ta Nb tailings, become
Waste be changed into values.
Glass raw material is melt into glass metal using pure oxygen combustion technology during preparing devitrified glass by the present invention, can
Accelerate glass metal fusing and clear process, advantageously reduces the generation of the bubble, striped plethora of glass, reduce the inside of glass
With the defect on surface.
In addition, the present invention uses secondary forming process at the time of molding, form glass metal in molten tin bath to uniform, flat
Plate glass transitional product whole, with certain thickness and width, outside molten tin bath to transitional product carry out temperature adjustment after again
Nucleus crystallization is carried out into molten tin bath, obtained devitrified glass bubble is few, intensity is high, and yield rate and final product quality have significantly
Promotion；And idle Ta Nb tailings are utilized in production in itself, have saved resource, the K contained in Ta Nb tailings2O、Na2O、
Rb2O、PbO、Li2The meltable oxide such as O generates eutectic effect, reduces fusion temperature, reduces when devitrified glass produces
Energy consumption is effectively protected resource environment.
Detailed description of the invention
Fig. 1 show the profilograph of the special equipment structure of present invention production devitrified glass；
Fig. 2 show the structure top view of the special equipment of present invention production devitrified glass；
1 glass melter, 2 glass metals, 3 cooling bays, 4 upper spaces, 5 molding molten tin baths, 6 glass tapes, 7 First Transition roller tables, 8
Roller, 9 coring molten tin baths, 10 second transition roller tables, 11 crystallization molten tin baths, 12 check aprons, 13 annealing kilns, 14 all-oxygen combustion spray guns, 15 meltings
Tin liquor, 16 edge machines.
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 by preparing devitrified glass using Ta Nb tailings, for enterprise and be worked as
Ground government forms new productivity growth point.Through Al in ore dressing analysis Ta Nb tailings sample2O3It is higher, therefore building can be introduced into
The decoration preparation of devitrified glass, provides Al needed for preparing devitrified glass2O3；Least a portion of Na can be also introduced simultaneously2O is to subtract
Few soda ash dosage；The P of introducing portion2O5, ZrO2, fluoride and TiO2It can be used as Nucleating Agent, to reduce the dosage of Nucleating Agent, have
Conducive to the production cost for reducing glass, by determining that the chemical component in Ta Nb tailings is shown in Table 3 after beneficiation test.
Ta Nb tailings sample chemical component after 3 beneficiation test of table
Include SiO with research repeatedly, the basis composition for finally selecting devitrified glass of the present invention by largely testing2、
Al2O3、CaO、MgO、Na2O、K2O and ZnO etc..In glass mainly composition and the effect played in high strength micro-crystalline glass such as
Under:
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.Crystallite glass of the invention
Al in glass2O3Content is 10.2%-16%, and Al in general devitrified glass2O3Content is no more than 10%, this is because this hair
When bright discovery alumina content is high, devitrified glass can have [AlO4] and [AlO6] two kinds of structures, glassware directly apply and into
When row deep processing to environmental parameter require it is low, and facilitate glass carry out chemical tempering, be conducive to product be widely applied and
Using.
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., can also be with Na2O generates mixed alkali effect, is conducive to the fusing of glass.
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.It is replaced in glass with 10% MgO below
Part CaO can make the setting rate of glass slack-off, reduce the tendency towards devitrification of glass, improve the chemical stability and machine of glass
Tool intensity.
Barium monoxide BaO is also glass network modifier oxides, can increase refractive index, density gloss and the chemical stabilization of glass
Property, also the material of glass can be made elongated, a small amount of barium monoxide can also accelerate fusing and the crystallization of glass.
Zinc oxide ZnO is glass intermediate oxide, keeps glass structure finer and close, can reduce the thermal expansion system of glass
Number, improves thermal stability, the chemical stability of glass, increases the refractive index of glass, while can speed up glass at high temperature
Fusing, split-phase and crystallization.
Phosphorus pentoxide P2O5It is network former, it is with phosphorus oxygen tetrahedron [PO4] formed phosphate glass structure
Network improves glass abbe number and the ability by ultraviolet light, can be as the Nucleating Agent in devitrified glass preparation process.
Zirconium dioxide ZrO2It is intermediate oxide, viscosity, hardness, elasticity, refractive index, the chemical stabilization of glass can be improved
Property, the thermal expansion coefficient of glass is reduced, can be used as the nucleating agent of devitrified glass.
Fluoride is common fluxing agent and opacifiers in glass industry, also can be used as the Nucleating Agent of devitrified glass, mainly
Select CaF2And Na2SiF6。
Titanium dioxide TiO2It is intermediate oxide, the refractive index and chemical stability of glass can be improved, increases and absorb X
The ability of ray and ultraviolet light can be used as the Nucleating Agent of Aluminous Silicate Glass-Ceramics.
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, three oxidations two are added in glass batch
Antimony (Sb2O3) and nitrate (generally sodium nitrate and potassium nitrate) be used as clarifying agent, to promote the exclusion of bubble in glass metal.Phase
Than in sulfate clarifying agent, the present invention selects Sb2O3The secondary bubble of sulfate will not be generated as clarifying agent with nitrate, simultaneously
Pollutant SO will not be generated in flue gas2, be conducive to mitigate flue gas desulfurization and denitrification load, reduce being produced into for devitrified glass
This.Nano-titanium dioxide (TiO is added in glass raw material simultaneously2), phosphorus pentoxide (P2O5), fluoride and nanometer titanium dioxide
Zirconium (ZrO2) it is used as Nucleating Agent, accelerate coring and the crystallization process of glass, accelerate the generation of crystallite and grow up, is i.e. acceleration vitreum
It, can be by particle aggregation small around together, to promote the discharge of bubble in glass metal to the process of crystalline transformation.
The present invention uses Ta Nb tailings for primary raw material, the devitrified glass produced using floating process, shock resistance
The indexs such as intensity, compressive resistance are superior to the devitrified glass that sintering process obtains.However devitrified glass of the invention is because of itself glass
Al in glass ingredient2O3Content is higher, and there is both sides technical problem with float process: first is that glass melting temperature is high, clarification is equal
Change difficult；Second is that controlled micro crystallization control is difficult, this is because producing devitrified glass, fusion temperature and forming temperature using floating process
Between the temperature difference it is big, while coring and crystallization temperature are also different, are difficult to be controlled in molten tin bath.For problem one, the present invention
Using pure oxygen combustion technology, the viscosity of glass metal is reduced, solves the problems, such as clarifying and homogenizing difficulty, can also reduce in glass metal
Bubble, blub and striped.For problem two, the present invention in Ta Nb tailings by adding P2O5, ZrO2, fluoride and TiO2
Equal Nucleating Agents, and tin groove forming is first carried out to glass metal, left after molding molten tin bath to transition roller table adjust after temperature again into
Enter the production method that molten tin bath carries out coring and crystallization, so that glass-ceramic process is controllable, prevents the generation of defect, guarantee crystallization process
Stabilization, realize continuous production, high-efficient, at low cost target obtains the Expectation of Glass-Ceramics Used as Decorated Materials of quality qualification.
Although the present invention is using float process devitrified glass, not similar with float process simple glass.Float process
Simple glass is that the glass metal after fusing is made to flow into tin groove forming, cooling by transition roller table after molding, subsequently into annealing kiln
Annealing.
And the present invention using float process devitrified glass be the glass metal that will have been melted flow into molding molten tin bath form, at
Enter coring molten tin bath after type and crystallization molten tin bath carries out coring and crystallization respectively, enters annealing kiln after gradually cooling down in crystallization molten tin bath
It anneals, to eliminate the stress of glass.When annealing, glass tape is heated by certain temperature curve, soaking, heat preservation, Xu Leng
With rapid cooling etc., making to form the inner-stress value generated in cooling procedure is reduced, to reach the standard for meeting cutting and quality requirement.
Devitrified glass of the invention due to using floating process to prepare, also referred to as float glass process devitrified glass, be with
Natural inorganic material is made through processes such as crushing, ingredient, fusing, float glass process molding, crystallization, annealing.The float glass process devitrified glass has
The good characteristic for the devitrified glass that sintering process obtains: such as without radiate, do not absorb water, not burn into do not aoxidize, colour-fast, no color differnece, no
Deformation, intensity height, glossiness height etc.；In addition, also additionally having, bubble-free, decorative pattern is naturally beautiful, physicochemical property is more preferable, product rule
Lattice can ultra-thin ultra-wide, imporosity is easy to clean, yield is big, high yield rate, it is at low cost the advantages that.The float glass process devitrified glass can be used as height
Grade building decoration materials, have extraordinary flatness, surface gloss and excellent physical and chemical performance, alternative natural flowers
Gang Yan is for the inner-outer wall of various buildings, ground and table top decoration.The popularization and application of float glass process devitrified glass will will form new warp
Ji growth point, is gone to the world with the advantage of high-performance mass, low production cost, large-scale production.Furthermore float glass process devitrified glass is raw
Primary raw material (such as: Ta Nb tailings, gold ore tailing) can be done using industrial residue in production, belong to environment-friendly type project, and floating
The preferred new product that method glass enterprise adjustment structure is increased economic efficiency.
The present invention prepares float glass process devitrified glass as raw material using Ta Nb tailings, and the glass properties of preparation is stablized, using wide
It is general, be conducive to the application of the kind devitrified glass, and can accelerate to promote Ta Nb tailings comprehensive utilization, reduce the dirt to environment
Dye.
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.
Ta Nb tailings are used to produce Expectation of Glass-Ceramics Used as Decorated Materials by the present invention by largely having determined, the crystallite
The raw material composition of glass presses mass percentage, comprising: SiO243%-49.8%, Al2O310.2%-16%, CaO
5.5%-9.9%, MgO 1.2%-9.8%, Na2O 3.1%-6.5%, K2O 2.3%-7.7%, BaO 4.2%-8.8%,
ZnO 4.5%-10%, Sb2O30.2%-2%, nitrate 0.8%-8%, P2O50.3%-1.8%, ZrO20.2%-
1.5%, fluoride 0.1%-0.7%, TiO20.7%-3.5%；Wherein P2O5, ZrO2, fluoride and TiO2As compound nucleus
Agent；
It is preferred that:
SiO245%-47%, Al2O311%-14%, CaO 6%-8%, MgO 3%-8%, Na2O 4%-5%, K2O
3%-6%, BaO 5%-7%, ZnO 5%-8%, Sb2O30.5%-1.5%, nitrate 2%-6%, P2O50.6%-
1.5%, ZrO20.5%-1.1%, fluoride 0.2%-0.5%, TiO21.2%-2.9%.
It is more preferable:
SiO246%, Al2O312.5%, CaO 7%, MgO 5.5%, Na2O 4.5%, K2O 4.5%, BaO 6%,
ZnO 6.5%, Sb2O30.8%, nitrate 2.8%, P2O50.8%, ZrO20.7%, fluoride 0.4%, TiO22%.
In the raw material of production devitrified glass, the best introducing mass percentage of Ta Nb tailings is glass raw material gross mass
25%-40%, preferably 30%-35%, more preferable 33%.The introducing ratio is guaranteeing that devitrified glass forms stable situation
Under, Ta Nb tailings can be maximally utilised, while being contained in tailing part microelement such as Li2O、Rb2O, PbO, NiO etc.,
Also help the fusing and clarification of glass.
The present invention also provides a kind of special equipments for producing above-mentioned devitrified glass, and structure is as depicted in figs. 1 and 2, including according to
Glass melter 1, cooling bay 3, molding molten tin bath 5, First Transition roller tables 7, coring molten tin bath 9, the second transition roller table 10, crystalline substance of secondary connection
Tin dissolving slot 11 and annealing kiln 13.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, it may be assumed that makes to melt
The glass raw material melted is uniformly mixed, adjusts the viscosity of glass metal and be cooled to forming temperature, and the molding for subsequent glass metal provides
Guarantee；
Molding molten tin bath 5 is used to the uniformly mixed glass metal of melting pulling into the glassware with fixed geometry,
Molding molten tin bath 5 includes the symmetrical 6-12 that is arranged in pairs of two sides to edge machine 16, and glass metal 2 floats after entering molding molten tin bath 5
In the tin liquor 15 of melting, under the pulling force of the molding symmetrically arranged edge machine 16 in 5 two sides of molten tin bath, glass metal 2 is pulled into glass
Band 6 completes molding.
First Transition roller tables 7 is used to adjust the temperature of glass tape 6 after molding to 600-660 DEG C, is then conveyed
To coring molten tin bath 9；Roller 8 in First Transition roller tables 7 is made of quartz-ceramics.
The tin liquor 15 of melting is loaded in coring molten tin bath 9, glass tape 6 floats on 15 surface of tin liquor of melting, melting after entering
Tin liquor 15 temperature of glass tape 6 is adjusted to 580-640 DEG C of progress coring；Coring molten tin bath 9 and the difference of molding molten tin bath are
Two sides are not provided with edge machine 16.
Second transition roller table 10 is used to adjust the temperature of the glass tape 6 after coring to 740-950 DEG C, is then conveyed
To crystallization molten tin bath 11；Roller 8 in second transition roller table 10 is made of quartz-ceramics.
The tin liquor 15 of melting is loaded in crystallization molten tin bath 11, glass tape 6 floats on 15 surface of tin liquor of melting, melting after entering
Tin liquor 15 temperature of glass tape 6 is adjusted to 730-940 DEG C of progress crystallization；Crystallization molten tin bath 11 and the difference of molding molten tin bath are
Two sides are not provided with edge machine 16.
It forms and fills nitrogen and hydrogen in the upper space 4 of molten tin bath, coring molten tin bath, crystallization molten tin bath, prevent tin liquor from aoxidizing；Glass
The coring of glass and crystallization are all to adjust glass to a certain temperature range is just automatic to occur, Nucleating Agent when glass raw material is added just
It is uniformly mixed with other raw materials, when fusing is evenly distributed on again at high temperature in the glass metal of melting, reaches coring and crystallization
Temperature after, Nucleating Agent promotes the formation of nucleus in glass, and crystal is made to grow up, and forms devitrified glass.
Annealing kiln 13 is in order to eliminate the stress after molding in certain thickness glass tape 6, by the temperature of glass tape
Degree is continuously down to 100 DEG C or less；It is separated between annealing kiln 13 and crystallization molten tin bath 11 by check apron 12.
The present invention also provides the production method of above-mentioned devitrified glass, 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, tin groove forming, a transition cooling and coring, secondary transition
Heating with crystallization, annealing and etc.；Each step carries out in the special equipment of above-mentioned production devitrified glass, 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 devitrified glass
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%-49.8%, Al2O310.2%-16%, CaO 5.5%-9.9%, MgO 1.2%-9.8%, Na2O 3.1%-
6.5%, K2O 2.3%-7.7%, BaO 4.2%-8.8%, ZnO 4.5%-10%, Sb2O30.2%-2%, nitrate
0.8%-8%, P2O50.3%-1.8%, ZrO20.2%-1.5%, fluoride 0.1%-0.7%, TiO20.7%-3.5%
Glass raw material；In general industry production, SiO2From silica sand, Al2O3Come from feldspar, CaO from lime stone, MgO
From in magnesite, Na2O is from soda ash, K2O is from potassium carbonate.
Preferably contain SiO in glass raw material245%-47%, Al2O311%-14%, CaO 6%-8%, MgO 3%-
8%, Na2O 4%-5%, K2O 3%-6%, BaO 5%-7%, ZnO 5%-8%, Sb2O30.5%-1.5%, nitrate
2%-6%, P2O50.6%-1.5%, ZrO20.5%-1.1%, fluoride 0.2%-0.5%, TiO21.2%-2.9%；
More preferably contain SiO246%, Al2O312.5%, CaO 7%, MgO 5.5%, Na2O 4.5%, K2O 4.5%, BaO 6%,
ZnO 6.5%, Sb2O30.8%, nitrate 2.8%, P2O50.8%, ZrO20.7%, fluoride 0.4%, TiO22%.
3), the melted and clarification of glass metal:
The glass raw material that step 2) mixes is melted into glass metal at 1600-1660 DEG C, is generally required left for 24 hours
It is right；When obtained glass metal emerges there is no bubble and (12-25h or so generally required, to carry out enough clarifications), clarification terminates；
4), the homogenizing and cooling of glass metal:
Temperature of glass liquid after clarification is maintained at 1620-1670 DEG C, until each section of glass metal reaches in chemical composition
To uniformity (generally requiring 7-16h), homogenizing terminates, and homogenizing is to eliminate the striped and heterogeneous body in glass metal；Glass
Glass liquid is cooled down during flow forward, is cooled to 1350-1400 DEG C；
5), tin groove forming:
Step 4) homogenizing and glass metal after cooling, which enter in molten tin bath, to be formed, and makes glass molding is uniform, smooth to have one
Determine the plate glass transitional product of thickness and width, with a thickness of 2-15mm, width is generally wide with molten tin bath, the inlet temperature of molten tin bath
For 1250-1320 DEG C (forming temperature in existing method is 1050-1100 DEG C), molten tin bath temperature is 750-930 DEG C after the completion of molding.
6), a transition cooling and coring:
Transitional product after molding enter First Transition roller tables adjust temperature to after 600-660 DEG C, be again introduced into molten tin bath into
Row coring, nucleation temperature are 580-640 DEG C, nucleation time 30min-3h, obtain a transitional product.
7), secondary transition heating and crystallization:
A transitional product after coring enters the second transition roller table and adjusts temperature to after 740-950 DEG C, is again introduced into tin
Slot carries out crystallization, and crystallization temperature is 730-940 DEG C, and crystallization time 2-8.5h obtains secondary transitional product.
8) it, anneals:
Secondary transitional product after crystallization used at 600-700 DEG C continuation mode annealing 2-8h or to 100 DEG C hereinafter, with
The stress for eliminating glass, obtains devitrified glass of the invention.
It is micro- according to producing above using the special equipment of the above production devitrified glass and containing the glass raw material of Ta Nb tailings
The devitrified glass of embodiment 1- embodiment 7 is prepared in the method for crystal glass.The devitrified glass of production example 1- embodiment 7
Parameter and raw material composition are shown in Table 4.
The raw material of the devitrified glass of 4 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 5.
As it can be seen that devitrified glass of the invention has higher intensity compared with the devitrified glass that sintering process obtains, it is suitable as wanting
High-intensitive building decoration materials are sought, while machining property is good, can be widely applied.
The performance test results of table 5 embodiment 1-7 and comparative example 1-4 glass
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 devitrified glass, which is characterized in that its raw material composition includes: SiO243%-49.8%, Al2O310.2%-
16%, CaO 5.5%-9.9%, MgO 1.2%-9.8%, Na2O 3.1%-6.5%, K2O 2.3%-7.7%, BaO
4.2%-8.8%, ZnO 4.5%-10%, Sb2O30.2%-2%, nitrate (preferably NaNO3And/or KNO3) 0.8%-
8%, P2O50.3%-1.8%, ZrO20.2%-1.5%, fluoride (preferably CaF2And/or Na2SiF6) 0.1%-0.7%,
TiO20.7%-3.5%.
2. devitrified glass according to claim 1, which is characterized in that its raw material composition includes: SiO245%-47%, Al2O3
11%-14%, CaO 6%-8%, MgO 3%-8%, Na2O 4%-5%, K2O 3%-6%, BaO 5%-7%, ZnO
5%-8%, Sb2O30.5%-1.5%, nitrate 2%-6%, P2O50.6%-1.5%, ZrO20.5%-1.1%, fluorination
Object 0.2%-0.5%, TiO21.2%-2.9%；It preferably includes: SiO246%, Al2O312.5%, CaO 7%, MgO
5.5%, Na2O 4.5%, K2O 4.5%, BaO 6%, ZnO 6.5%, Sb2O30.8%, nitrate 2.8%, P2O5
0.8%, ZrO20.7%, fluoride 0.4%, TiO22%.
3. devitrified glass according to claim 1 or claim 2, which is characterized in that the raw material includes Ta Nb tailings.
4. devitrified glass 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 25%-40% of quality, preferably 30%-35%, more preferable 33%.
5. a kind of production method of any devitrified glass of claim 1-4, which is characterized in that sequentially mixed including raw material
Close, glass metal be melted and clarification, the homogenizing of glass metal and cooling, glass molding, glass coring, glass crystallization and annealing etc. walk
Suddenly, the glass is shaped to float tin groove molding, and the glass coring includes a transition cooling and coring, the glass crystallization
Including secondary transition heating and crystallization.
6. production method according to claim 5, which is characterized in that a transition cooling and coring specifically:
The transitional product obtained after tin groove forming is adjusted into temperature and carries out coring, core to coring molten tin bath after 600-660 DEG C, is entered back into
Changing temperature is 580-640 DEG C, nucleation time 30min-3h, obtains a transitional product.
7. according to the production method of claim 5 or 6, which is characterized in that the secondary transition heating and crystallization specifically:
Transitional product is adjusted into temperature to after 740-950 DEG C, crystallization molten tin bath is entered back into and carries out crystallization, crystallization temperature 730-
940 DEG C, crystallization time 2-8.5h obtains secondary transitional product.
8. according to any production method of claim 5-7, which is characterized in that the tin groove forming specifically:
Homogenizing and glass metal after cooling enter in molding molten tin bath to be formed under the action of edge machine, is obtained with a thickness of 2-
The transitional product of 15mm, the inlet temperature for forming molten tin bath is 1250-1320 DEG C, and molding molten tin bath temperature is 750- after the completion of molding
930℃。
9. according to any production method of claim 5-8, which is characterized in that further include the Ta Nb tailings before raw material mixing
Preprocessing process, the pretreatment of the Ta Nb tailings specifically: Ta Nb tailings are passed sequentially through into classification, scouring, magnetic separation, pickling etc.
Process obtains Fe2O3Content less than 0.01% (100ppm), partial size 0.1-1.5mm, Ta Nb tailings of the water content less than 5%
Sample.
10. according to any production method of claim 5-9, which is characterized in that the melted and clarification of the glass metal and glass
The homogenizing and cooling of glass liquid specifically: mixed glass raw material is fused into glass metal at 1600-1660 DEG C, and there is no
Bubble is emerged, and temperature of glass liquid is then maintained at 1620-1670 DEG C and is uniformly mixed to glass metal；Or
Optionally, the annealing specifically: secondary transitional product after the crystallization continuous annealing 2-8h or extremely at 600-700 DEG C
100 DEG C hereinafter, obtain the devitrified glass.
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| CN201910137180.0A CN109704583A (en) | 2019-02-25 | 2019-02-25 | A kind of devitrified glass and its production method |
| PCT/CN2020/076571 WO2020173425A1 (en) | 2019-02-25 | 2020-02-25 | Glass ceramics, and production method and dedicated device therefor |
| US17/411,908 US20210387900A1 (en) | 2019-02-25 | 2021-08-25 | Glass Ceramics, and Production Method and Dedicated Device Therefor |
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