CN107226483A - 一种混晶材料及制备方法 - Google Patents
一种混晶材料及制备方法 Download PDFInfo
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- CN107226483A CN107226483A CN201710475757.XA CN201710475757A CN107226483A CN 107226483 A CN107226483 A CN 107226483A CN 201710475757 A CN201710475757 A CN 201710475757A CN 107226483 A CN107226483 A CN 107226483A
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- Prior art keywords
- mixed
- crystal
- titanium
- alkali metal
- titanate
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000013078 crystal Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- -1 alkali metal titanate Chemical class 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- 150000001340 alkali metals Chemical group 0.000 claims description 19
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 16
- 150000002602 lanthanoids Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011734 sodium Chemical group 0.000 claims description 3
- 229910052708 sodium Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910009815 Ti3O5 Inorganic materials 0.000 description 1
- 229910010411 TiO1.75 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/043—Titanium sub-oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开一种混晶材料,选自以下a)或b)或c)中的任意一种:a)由亚氧化钛晶体与二氧化钛晶体通过化学键混杂结合在一起,其中亚氧化钛晶体被金属元素参杂;b)由亚氧化钛晶体与碱金属钛酸盐晶体通过化学键混杂结合在一起;c)由亚氧化钛晶体与碱金属钛酸盐晶体通过化学键混杂结合在一起,其中亚氧化钛晶体被金属元素参杂。本发明所述的混晶材料,不仅可克服现有导电钛酸盐增强材料生产和应用中存在的缺点,而且还可进一步提高钛酸盐增强材料的耐腐蚀性和耐磨损性,在导电、耐磨和耐蚀复合材料的应用中具体巨大前景,甚至可以开发出新型高效催化剂产品。
Description
技术领域
本发明属于新材料领域,特别涉及到一种混晶材料及制备方法。
背景技术
碱金属钛酸盐,特别是钛酸钠和钛酸钾,是一类新兴材料,近十多年应用范围不断被扩展。如作为增强材料添加在POM,PA,PTFE等塑料中,用于制造各自精密零件;添加在橡胶中,提高弹性和抗老化性。作为摩擦材料,替代石棉应用于刹车片中;此外,还可用于增强涂层。
然而,现代工业对这类钛酸盐材料提出更高要求,如增强塑料或陶瓷基体的同时能防静电或导电,因此需要研发具有导电功能的钛酸盐增强材料。专利(公开号CN1786050)开发了一种聚苯胺包覆的导电钛酸盐;专利(公开号:CN106567128A)用锡盐、锑盐和五氧化二铌包覆的钛酸盐材料。这一类方法是属于物理包覆,也就是将导电材料包覆在钛酸盐表面,实现导电功能,但该类方法并没有真正实现钛酸盐材料的导电功能,而且制备中对包覆过程要求高,控制难,最终在应用中产品导电性能往往不尽人意。
另一方面,亚氧化钛是一种全新的环保无毒材料,具有优良的导电性能,高的耐腐蚀性和耐磨损性。亚氧化钛往往采用二氧化钛与还原剂高温反应来制备,如专利(CN106241861A)利用碳质还原剂与氧化钛反应制备出Ti4O7、Ti3O5等亚氧化钛粉体。专利(CN104661962B)中利用焦炭还原氧化钛,制备出Ti5O9和Ti6O11或两者的混合物的熔融颗粒;该专利还提到初始混合物中含有不同于二氧化钛的无机物质,如氧化硅、五价氧化物以及一些碱或碱土金属氧化物,而最终的颗粒可以包含其它相,如二氧化硅,或者其它元素,它们基本以氧化物形式与一种或多种亚氧化钛的固溶体形式存在;该专利反应在高于1500℃的温度下进行,属于高能耗技术。
发明内容
本发明针对现有钛酸盐材料应用中的不足,提供一种混晶材料及制备方法。本发明开发出一种混晶材料,不仅可克服现有导电钛酸盐增强材料生产和应用中存在的缺点,而且还可进一步提高钛酸盐增强材料的耐腐蚀性和耐磨损性,在导电、耐磨和耐蚀复合材料的应用中具体巨大前景,甚至可以开发出新型高效催化剂产品。
本发明的目的之一是提供一种混晶材料,选自以下a)或b)或c)中的任意一种:
a)由亚氧化钛晶体与二氧化钛晶体通过化学键混杂结合在一起,其中亚氧化钛晶体被金属元素参杂;
b)由亚氧化钛晶体与碱金属钛酸盐晶体通过化学键混杂结合在一起;
c)由亚氧化钛晶体与碱金属钛酸盐晶体通过化学键混杂结合在一起,其中亚氧化钛晶体被金属元素参杂。
作为一种优选,亚氧化钛晶体被过渡金属元素或镧系金属元素参杂。
作为一种优选,本发明所述的混晶材料,其化学式为(nM2O·TiO2)@(Ti1-xTmxO2-y),式中n范围为0-0.3,M为碱金属,O为氧,Ti为钛,@表示混晶结构,x范围为0-0.5,Tm为过渡金属元素或镧系金属元素,y范围为0-0.3;进一步优选的,式中n范围为0-0.25,M为钾或钠,y范围为0.01-0.25;更进一步优选x范围为0-0.2。
作为一种优选,本发明所述的混晶材料,其中任意一种晶体形式含量不低于1wt%。
本发明所述的过渡金属元素可以为钒、铬、锰、铁、钴、镍、铜、锌、锆、铌、钽、钼或钨中的任意一种或几种;本发明所述的镧系金属可以为镧、铈、钕或铕中任意一种或几种。
本发明的目的之二在于提供一种混晶材料的制备方法,步骤如下:
1)将钛源材料与含碱金属元素的材料均匀混合,或者将钛源材料、含碱金属元素的材料与含过渡金属元素的材料或含镧系金属元素的材料均匀混合,得到混合物;即步骤1)可以为以下①-④任意一种情况:①将钛源材料与含碱金属元素的材料均匀混合,得到混合物;②将钛源材料、含碱金属元素的材料与含过渡金属元素的材料均匀混合,得到混合物;③将钛源材料、含碱金属元素的材料与含镧系金属元素的材料均匀混合,得到混合物;④将钛源材料、含碱金属元素的材料、含过渡金属元素的材料和含镧系金属元素的材料均匀混合,得到混合物;
2)将步骤1)的混合物在温度500-1300℃下,烧结1-7小时,优选600-1200℃下,烧结2-6小时,冷却形成烧结物;或者按混合物和水体积比1:5-10混合,在140-230℃下12-50小时,优选140-220℃下12-48小时,冷却形成水热产物;
3)将步骤2)的烧结物或水热产物用酸性溶液进行洗涤,使洗涤后产物的pH值稳定在2-8之间;
4)将洗涤后的产物,置于还原氛围中在4500-1250℃下进行烧结1-7小时,优选500-1200℃下进行烧结2-6小时,冷却,得到最终产物。
作为一种优选,本发明方法中所述的钛源材料为二氧化钛粉体、偏钛酸、金属钛粉、钛酸四丁酯或异丙醇钛中的一种或多种。
作为一种优选,本发明方法中所述的含碱金属元素的材料可以为碱金属、碱金属氧化物、含碱金属的氢氧化物或碱金属盐中的任意一种或多种,如氢氧化钠、氢氧化钾、氧化钠、氧化钾、硫酸钠、硫酸钾、硝酸钠、硝酸钾、碳酸钠、碳酸钾、碳酸氢钠或碳酸氢钾中的一种或几种。
作为一种优选,本发明方法中的过渡金属元素,可以为钒、铬、锰、铁、钴、镍、铜、锌、锆、铌、钽、钼或钨。
作为一种优选,本发明方法中的含过渡金属元素的材料可以为过渡金属氧化物或亚氧化物中的一种或多种,如五氧化二钒、氧化铁、氧化锰、氧化钴、氧化铜、氧化锌、氧化钨、氧化铌等。
作为一种优选,本发明方法中的镧系金属可以为镧、铈、钕或铕。
作为一种优选,本发明方法中的含镧系金属元素的材料可以为镧系金属氧化物或亚氧化物中的一种或多种,如氧化镧、氧化铈、氧化钕等。
本发明的原料中钛源材料和含碱金属元素的材料,其折合成二氧化钛和碱金属氧化物的摩尔比范围为(8~1):1;含过渡金属元素的材料或含镧系金属元素的材料之间的配比可以根据需要进行调整。
作为一种优选,本发明方法步骤3)中的酸性溶液可以为工业中常用的酸性溶液,如盐酸溶液,硫酸溶液,硝酸溶液,醋酸溶液中的一种或几种。
作为一种优选,本发明方法步骤4)中的还原氛围为氢气氛围、一氧化碳氛围或氨气氛围中的一种或几种。
本发明中的冷却方法从节约成本的角度考虑,自然冷却即可。
本发明的有益效果:
1.本发明所述的材料,其中亚氧化钛晶体或参杂亚氧化钛晶体在混晶表面,二氧化钛晶体或碱金属钛酸盐晶体在内部,各化学元素均通过化学力结合,不是混合物或者以氧化物形式存在,这使得材料不仅具有原有钛酸盐材料的性能,还具有了亚氧化钛的性能,在应用中性能体现更佳。特别是,过渡元素或镧系金属参杂进入晶格Ti的位置,进一步提高了导电性。
2.钛酸盐材料有纤维状,棒状,颗粒状,片状,本发明的制备方法可以保留原有材料的形貌。
3.本发明的制备方法可通过pH值来调控混晶材料中两种晶体的质量比,可根据实际市场需求,生产不同比例性能的混晶材料。
4.本发明反应温度低相对较低,最高不超过1200℃,可实现工业节能。
附图说明
图1为600℃氢气气氛下样品XRD图;
图2为600℃氢气气氛下样品SEM图。
具体实施方式
本发明的一些方面和实施方案可以通过以下的具体实施例加以进一步说明。下面有代表性的例子旨在帮助阐述本发明,而不是有意也不应该被解释为限制本发明的范围。
实施例1
二氧化钛与氢氧化钾摩尔比3:1,混合均匀后,800℃下进行烧结4小时,自然冷却,在醋酸水溶液中洗涤,并最终稳定在pH3,过滤后在氢氛围中600℃下4小时,得到(0.08K2O·TiO2)@(TiO1.75)混晶材料,见图1,XRD表征结果,其中亚氧化钛晶体占40wt%,形貌为棒状(见图2),电导率约为15S·cm-1;在98wt%的浓硫酸溶液中浸48小时,质量损失小于0.5wt%,而单纯的六钛酸钾同样实验条件下质量损失率达到5wt%以上,说明耐酸性提高10倍;填充PTFE树脂中,耐磨损性比六钛酸钾填充提高4倍。
实施例2-8
具体如表1所示,其他条件同实施例1.
表1实施例2-8
Claims (10)
1.一种混晶材料,其特征在于,选自以下a)或b)或c)中的任意一种:
a)由亚氧化钛晶体与二氧化钛晶体通过化学键混杂结合在一起,其中亚氧化钛晶体被金属元素参杂;
b)由亚氧化钛晶体与碱金属钛酸盐晶体通过化学键混杂结合在一起;
c)由亚氧化钛晶体与碱金属钛酸盐晶体通过化学键混杂结合在一起,其中亚氧化钛晶体被金属元素参杂。
2.根据权利要求1所述的混晶材料,其特征在于,所述亚氧化钛晶体被过渡金属元素或镧系金属元素参杂。
3.根据权利要求1所述的混晶材料,其特征在于,所述的混晶材料,其化学式为(nM2O·TiO2)@(Ti1-xTmxO2-y),式中n范围为0-0.3,M为碱金属,O为氧,Ti为钛,@表示混晶结构,x范围为0-0.5,Tm为过渡金属元素或镧系金属元素,y范围为0-0.3;优选的,式中n范围为0-0.25,M为钾或钠,y范围为0.01-0.25;更优选x范围为0-0.2。
4.根据权利要求1所述的混晶材料,其特征在于,其中任意一种晶体形式含量不低于1wt%。
5.一种混晶材料的制备方法,其特征在于,步骤如下:
1)将钛源材料与含碱金属元素的材料均匀混合,或者将钛源材料、含碱金属元素的材料与含过渡金属元素的材料或含镧系金属元素的材料均匀混合,得到混合物;
2)将步骤1)的混合物在温度500-1300℃下,烧结1-7小时,冷却形成烧结物;或者按混合物和水体积比1:5-10混合,在140-230℃下12-50小时,冷却形成水热产物;
3)将步骤2)的烧结物或水热产物用酸性溶液进行洗涤,使洗涤后产物的pH值稳定在2-8之间;
4)将洗涤后的产物,置于还原氛围中在4500-1250℃下进行烧结1-7小时,优选500-1200℃下进行烧结2-6小时,冷却,得到最终产物。
6.根据权利要求5所述的方法,其特征在于,步骤1)所述的钛源材料为二氧化钛粉体、偏钛酸、金属钛粉、钛酸四丁酯或异丙醇钛中的一种或多种。
7.根据权利要求5所述的方法,其特征在于,步骤1)所述的含碱金属元素的材料可以为碱金属、碱金属氧化物、含碱金属的氢氧化物或碱金属盐中的任意一种或多种。
8.根据权利要求5所述的方法,其特征在于,步骤1)所述的含过渡金属元素的材料为过渡金属氧化物或亚氧化物中的一种或多种;步骤1)所述的含镧系金属元素的材料为镧系金属氧化物或亚氧化物中的一种或多种。
9.根据权利要求5所述的方法,其特征在于,步骤3)中的酸性溶液为盐酸溶液,硫酸溶液,硝酸溶液,醋酸溶液中的一种或几种。
10.根据权利要求5所述的方法,其特征在于,步骤4)中的还原氛围为氢气氛围、一氧化碳氛围或氨气氛围中的一种或几种。
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