CN1033977A - Adulterated BaTiO 3 based dielectric composition powder - Google Patents
Adulterated BaTiO 3 based dielectric composition powder Download PDFInfo
- Publication number
- CN1033977A CN1033977A CN88106966A CN88106966A CN1033977A CN 1033977 A CN1033977 A CN 1033977A CN 88106966 A CN88106966 A CN 88106966A CN 88106966 A CN88106966 A CN 88106966A CN 1033977 A CN1033977 A CN 1033977A
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- CN
- China
- Prior art keywords
- symbiont
- doping
- barium titanate
- less
- particle diameter
- 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.)
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Links
- 239000000203 mixture Substances 0.000 title claims description 36
- 239000000843 powder Substances 0.000 title description 18
- 239000002245 particle Substances 0.000 claims abstract description 78
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 56
- 239000002019 doping agent Substances 0.000 claims abstract description 51
- 238000009826 distribution Methods 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 39
- 238000004458 analytical method Methods 0.000 claims description 20
- 208000035126 Facies Diseases 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000010955 niobium Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 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 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 description 49
- 239000011575 calcium Substances 0.000 description 15
- 229910052788 barium Inorganic materials 0.000 description 14
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 13
- 239000011133 lead Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000011135 tin Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052712 strontium Inorganic materials 0.000 description 7
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229940071182 stannate Drugs 0.000 description 4
- 125000005402 stannate group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 by densification Chemical compound 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- ZYCFPSLHSPMWDE-UHFFFAOYSA-N [Mn].[Nb].[Co] Chemical compound [Mn].[Nb].[Co] ZYCFPSLHSPMWDE-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012207 quantitative assay Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000012869 ethanol precipitation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical group [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
- C01G27/006—Compounds containing, besides hafnium, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The present invention is relevant various dispersible, adulterated barium titanate Symbionts, and this Symbiont comes down to spheric, has the mixed uniformly particle of submicron of narrow size distribution.The main particle diameter of this doping Symbiont is the 0.05-0.4 micron.The amount of one or more doping agent oxidation things that contain in the Symbiont is greater than 0 to 10%.No matter selected one or more doping agents, all available identical particular structure feature of all Symbionts of the present invention come fixed.
Description
The application is the partial continuous application of No. 856047, common pending application case (applying date is on April 25th, 1986) and No. 859577 (applying date is on May 5th, 1986), and No. 856047 and No. 859577 applications are examined.
The present invention relates to barium titanate-based composition, more particularly, the present invention relates to dispersible, submicron, adulterated barium titanate Symbiont, the size distribution of this Symbiont is very narrow.
In electronic industry, barium titanate-based composition is widely used in produces electrical condenser, phase modulator (Condensers) and PTCR(positive temperature coefficient of resistance) device.In electronics, barium titanate is particularly useful, and its purposes is many-sided, because its electrical property can obviously improve by blast blending and/or doping agent.Usually the additive that adopts is MAO
3Compound, wherein M is a divalent cation, A has BaTiO
3The quadrivalent cation of perovskite structure.Typical additive comprises calcium, strontium, barium and plumbous titanate, zirconate and stannate.Because one or more additives all have as BaTiO
3Crystalline structure, they generate easily a kind of sosoloid in calcining or sintering process.In general, the amount of additive is greater than BaTiO
3The 3%(mole of based component).Doping agent comprises various metal oxides.In general, dopant dose is less than BaTiO
3The 5%(mole of based component total amount).One or more used doping agents can be miscible wholly or in part in perovskite crystalline lattice, or in this lattice unmixing.The example of used doping agent comprises La, lanthanon, Y, Nb, Ta, Cu, Mo, W, Mn, Fe, Co, Ni, Zn, Al, Si, Sb and Bi.
In industrial production, barium titanate-based composition can make by desired pure titanate, zirconate, stannate are mixed with doping agent, and perhaps the oxide compound of the barium that appropriate chemical is measured, calcium, titanium etc. or the uniform mixture of their parent (as carbonate, oxyhydroxide or nitrate) are directly made desired powder through high temperature solid-state reactions.In general, pure titanate,
Zirconate, stannate etc. also make with high-temperature solid phase reaction method.
The existing method for preparing barium titanate and barium titanate-based composition by solid state reaction is fairly simple, and but, still there are some shortcomings in they.At first, the impurity of grinding steps introducing has disadvantageous effect to electrical property.The second, from microcosmic, the ununiformity of the composition that causes owing to incomplete mixing can cause generating undesirable phase, for example positive barium titanate, Ba
2TiO
4Thereby, can produce moisture-sensitive property.The 3rd, sintering phenomenon between remarkable growth of particle and particle can take place in calcination process.Therefore, be made up of erose broken aggregate through the product that grinds, its particle size distribution range is wide, is about the 0.2-10 micron.And, confirmed that the size distribution of prepared sintered compact is wide by assembling the required sintering temperature height of base substrate that the wide this powder of accumulative of size distribution generates.
Study many methods and attempted to overcome the limitation of conventional solid reacting method.Following document has been introduced the intermediate processing of adulterated oxalic acid titanyl barium, or the intermediate processing that replaces barium and partly replace the adulterated oxalic acid titanyl barium of titanium with zirconium with strontium or plumbous part: Gallagher et al., " Preparation of Semiconducting Titanates by Chemical Methods; " 46, J.Amer.Chem.Soc., 359(1963); Schrey, " Effect of PH on the Chemical Preparation of Barium-Strontium Titanate, " 48, J.Amer.chem Soc., 401(1965); And Vincenzini, " Chemical preparation of Doped BaTiO
3, " Proceedings of the Twelfth Int, l Conf., Science of Ceramics, vol.12, P 151(1983).Oxalate at high temperature decomposes the adulterated barium titanate-based composition of generation.United States Patent (USP) 3637531 has been introduced a kind of single solution of being made up of doping agent, titanium compound and alkaline earth salt and has been generated a kind of semisolid block through heating, through calcining
Become desired titanate based products.United States Patent (USP) 4537865 discloses the hydrous oxide precipitation of Ti, Zr, Sn or Pb and the hydrous oxide of doping agent has been mixed with the aqueous slurry of the carbonate deposition of Ba, Sr, Ca or Mg.Calcine this solid and can obtain desired product.People such as Kakegawa at " Synthesis of Nb-doped Barium Titanate Semiconductor by a Wet-Dry Combination Technique; " 4, J.Mat.Sci.Lets., 1266(1985) in the literary composition a kind of similar synthetic method has been described.
Mulder is ejected into the aqueous solution of the Citrate trianion of this component or formate and dewaters in the ethanol and co-precipitation, to prepare adulterated BaTiO
3And BaTiO
3Based products (" Preparation of BaTiO
3And other Ceramic Powders by Coprecipitation of Citrates in an Alcohol ", 49, Ceramic Bulletin, 990-993(1970)).The resulting product of coprecipitated powder by calcining Citrate trianion or formate mainly by densification, particle diameter is that the globule of 3-10 micron is formed.United States Patent (USP) 4061583 has been described by the nitrate of required component or chloride soln and has been added the doping BaTiO that contains the alkaline aqueous solution of hydrogen peroxide and make
3Based composition and use thereof in packaging.Contain sedimentary hydrogen peroxide and decompose about 100 ℃, the result generates a kind of unbodied BaTiO
3Based composition and use thereof in packaging.This amorphous products is calcined to about 600 ℃ can obtain crystalline powder.Unfortunately do not characterize the main particle diameter of this product.The repeated experiments of the embodiment that the present invention is listed shows that the main particle diameter of this amorphous powder is in fact less than 0.05 micron.The transmission electron micrograph of this product shows that the main particle of 600 ℃ of calcinates is accumulative.
In the above-mentioned typical existing method, finish the synthetic of the composition grain of wanting with method for calcinating.In view of the foregoing, this high-temperature operation is deleterious, because the gathering product that makes obtains the littler gathering fragment that wide particle diameter distributes that has after grinding.
United States Patent (USP) 4233282,4293534 and 4487755 has been described by molten salt reaction and has been synthesized BaTiO
3And BaTiO
3The method of based composition and use thereof in packaging in this reaction, partly replaces Ba with Sr, partly replaces Ti with Zr.Being characterized as of this product has chemical uniformity and is made up of more single dispersive submicron crystal.Adulterated BaTiO
3Based products is not a synthetic.People such as Yoon are at " Influence of the PTCR Effect in Semiconductive BaTiO
3, " 21, Mat.Res.Bul. 1429(1986), has described in the literary composition with the synthetic Ba that consists of of melting salt method
(0.900-x)Sr
0.100Sb
xTiO
3Product, wherein the x value is 0.001,0.002,0.003 and 0.004.The product of being produced by the melting salt method has bigger influence to PTCR in their resistivity-temperature characteristic, resistivity at room temperature is bigger, compare with the powder comparative sample that mixture by calcined oxide thing and oxide matrix makes, in one time of electric current characteristic, electric current changes greatly.This difference is to have used KCl owing in the melting salt synthetic method, and resulting sample particle diameter is little, the cause of narrow diameter distribution.Though fusion alkali synthesis method can obtain the submicron doped products of narrow diameter distribution, this powder is subjected to alkali-metal pollution inevitably, because melting salt is made up of an alkali metal salt.Certainly, in most of electronic application, basic metal is deleterious pollutent.
Introduce below and be used to prepare BaTiO
3And BaTiO
3Several water-based process of based composition and use thereof in packaging, wherein Ba is partly replaced by Sr, and Ti is by Sn or partly replaced by Zr if possible.United States Patent (USP) 3577487 has been described adulterated many components alkaline earth and/or Pb(II) the preparation method of titanate, stannate, zirconate and/or hafnates.In these methods, perhaps handle the hydrogel of co-precipitation with alkaline earth metal hydroxides, and by preparation BaTiO
3Used same treatment step is handled, and perhaps desired gel and alkaline earth metal hydroxides is added preformed BaTiO
3In the slurry, carry out fluid energy milling then and forge
Burn.Unfortunately this product does not have obvious characteristic before fluid energy milling.But experience shows that before grinding, this adulterated its specific surface of many components product surpasses 20m
2/ g, this main particle diameter that shows this powder is approximately less than 0.05 micron.Even when temperature out surpassed 800 °F, behind fluid energy milling, its specific surface of many components product of quoting among the embodiment surpassed 18m
2/ g.Calcining can make specific surface further reduce.In view of the foregoing, will cause assembling the generation of product.
Disclosed many components powder has following general formula in our common pending application application (No. 859577, U.S. Patent application):
Ba
(1-x-x '-x ")M
xM '
X 'M "
X "Ti
(1-y-y '-y ")A
yA '
Y 'A "
Y "O
3M is the Pb(II in the formula), M ' is the Ca(II), M " be the Sr(II); A is the Sn(IV), A ' is the Zr(IV) and A " be the Hf(IV), x, x ', x " with y, y ', y " represent the atomic fraction of divalence and quadrivalent cation respectively, respectively have independently value, its scope is 0-0.3.As long as (x+x '+x ") or (y+y '+y ") sum be no more than 0.4, has the stoichiometric product of above-mentioned nominal and can use common Hydrothermal Preparation, and this product is called as Symbiont (Coform).Various Symbionts are all with stoichiometry, dispersibility, submicron with to have narrow size-grade distribution be feature.
In No. 859577 common unsettled patent applications, do not study the doping problem of barium titanate Symbiont.Therefore, there is not any doping Symbiont of barium titanate in the prior art, comprises calcium and/or plumbous or the multiple divalence and the quadrivalent cation substituent of the submicron of dispersible, spheric and narrow diameter distribution.
Therefore, main purpose of the present invention provides a kind of dispersible, adulterated barium titanate Symbiont of submicron, its narrow diameter distribution.
Second purpose of the present invention provides various BaTiO
3Doping BaTiO
3Based composition and use thereof in packaging, its main particle diameter is the 0.05-0.4 micron.
The 3rd purpose of the present invention provides equiaxial main particulate barium titanate doping based composition and use thereof in packaging.
The 4th purpose of the present invention provides adulterated barium titanate-based composition, and said composition is non-grinding medium in fact.
The 5th purpose of the present invention provides adulterated barium titanate-based composition, and wherein the uniform particles of all components is mixed.
The present invention includes various dispersible, be essentially spheric, mixed uniformly, submicron barium titanate doping Symbiont with narrow size distribution.In the important example of the present invention, adulterated barium phthalate base Symbiont following general formula:
XBa
(1-x ')Ca
X 'OYTi
(1-y-y '-y ")Sn
yZr
Y 'Hf
Y "O
2Sum that ZD, x, y and z are coefficients in the formula, the value of x and y is 0.9-1.1, the value of z is greater than 0, less than 0.1, y, y ' and y " value be respectively 0-0.3, y+y '+y " is less than 0.4, and x ' is greater than 0, less than 0.4, and D represents one or more doping agent oxidation things.
In another important example of the present invention, adulterated barium titanate Symbiont following general formula:
XBa
(1-x)Pb
xOYTi
(1-y-y '-y ")Sn
yZr
yHf
Y "O
2Sum that x, y and z are coefficients in the ZD formula, and the value of x and y is 0.9-1.1, and the z value is greater than 0, less than 0.1, y, y ' and y " value be respectively 0-0.3, y+y '+y " is less than 0.4, and x is greater than 0, less than 0.4, and D represents one or more doping agent oxidation things.
In another important example of the present invention, barium titanate Symbiont following general formula:
X, y and z are coefficients in the formula, and the value of x and y is 0.9-1.1, and the z value is greater than 0, less than 0.1, the value of x, x ', x ", y, y ', y " respectively greater than 0, less than 0.3, " sum is less than 0.4, and " sum is less than 0.4, and D represents one or more doping agent oxidation things for y+y '+y for x+x '+x.
Various barium titanate doping base Symbiont of the present invention all has unique physicals.The main particle diameter average out to 0.05-0.4 micron of this barium titanate doping base Symbiont.And, can compare with the median size of measuring with settling process with the median size that facies analysis is measured, this proves that this Symbiont is dispersible.The quartile ratio of this doping Symbiont particle grain size distribution curve is less than or equal to 2, and this has proved the narrow diameter distribution of adulterated barium phthalate base Symbiont.In addition, it should be noted that among the present invention that any dispersible, adulterated barium titanate dielectric combination of submicron can be with a kind of simple, common Hydrothermal Preparation.
To further specify each details of the present invention and advantage thereof in conjunction with the accompanying drawings:
Fig. 1 is the transmission electron micrograph (magnification is 50000) of the compound Symbiont of make according to the present invention a kind of dispersible, the multiple doping agent of submicron, and this Symbiont has following general formula:
And
Fig. 2 is a kind of transmission electron micrograph (magnification is 50000) of composite titanic acid barium Symbiont of single doping agent, and this Symbiont has following general formula:
The structural similitude of the composite mixed Symbiont of its structure and Fig. 1 in fact.
Preferred example of the present invention is the doping Symbiont with following general formula:
In the formula, x, y and z are the cationic coefficients of divalence, tetravalence and doping agent, the value of x and y is 0.9-1.1, be preferably 0.95-1.05, the Z value is greater than 0 to 0.1, the value sum of more preferably greater than 0 to 0.05, x, x ', x " atomic fraction of expression divalent cation, it be worth respectively greater than 0 to 0.3; more preferably greater than 0 to 0.2; x+x '+x " sum is preferably 0-0.3 greater than 0 to 0.4, y, y ', y " represented the atomic fraction of quadrivalent cation; it is worth respectively greater than 0 to 0.3; more preferably greater than 0 to 0.25, y+y '+y " is greater than 0 to 0.4, and more preferably greater than 0 to 0.3.D represents the different dopant oxide compound of barium titanate Symbiont.
Thin, dispersible submicron powder preferably of the present invention is made up of a kind of adulterated barium titanate Symbiont, and wherein the replacement amount of tetravalence and divalent-metal ion is greater than 0 to 30%(mole).The divalence barium ion can partly replace with lead, calcium, strontium or its mixture.In addition, the titanic ion can partly replace with tin, zirconium, hafnium or its mixture.
This barium titanate-based composition can mix a spot of one or more different doping agents, and this doping agent comprises the oxide compound of column element down: lanthanon, cobalt, manganese, magnesium, scandium, yttrium, antimony, bismuth, zinc, cadmium, aluminium, boron, tungsten, chromium, nickel, molybdenum, iron, niobium, vanadium, tantalum, copper, silicon and composition thereof.Doping agent oxidation thing or in Symbiont the amount of contained oxide compound greater than 0 to 10%(mole), more preferably greater than 0 to 5%(mole).No matter with which kind of doping agent or mixing and doping agent, this barium titanate-based composition can only be identified with above-mentioned structural performance in the barium titanate Symbiont.Therefore, in fact the single doping agent of barium titanate or the compound Symbiont of multiple doping agent are formed by spheric, dispersible granules, and its main particle diameter is the 0.05-0.4 micron, has narrow size distribution.
The best method for preparing adulterated barium phthalate base Symbiont be with one or more doping agents with
One or more tetravalence hydrous oxide uniform mixing.A kind of method in can be is in many ways mixed.Doping agent can with the co-precipitation of tetravalence hydrous oxide.Perhaps, make doping agent generate high surface area hydrous oxide precipitation, washing, mix with the tetravalence hydrous oxide then.At last, because doping agent can contain the Ba(II) alkaline medium in precipitate, their solution (be preferably acetate, formate, nitrate or be ammonium salt) can be added in the tetravalence hydrous oxide.The slurry of hydrous oxide and doping agent oxide compound or the oxyhydroxide with lead and/or calcium under up to 200 ℃ temperature is carried out hydrothermal treatment consists.Make this slurry be cooled to 60-150 ℃ then.Be heated to 70 °-100 ℃ temperature with barium hydroxide solution or with the displaced barium hydroxide solution of strontium hydroxide part, with this solution with constant speed, in 0.1 to 12 minute, be added in the slurry of insoluble divalent cation, tetravalence hydrous oxide and doping agent.This slurry was kept 10-30 minute adding under the temperature, be heated to 120 ℃-225 ℃ then, reach needed degree with the reaction of the hydroxides of divalent cation that guarantees hydrous oxide and solubility.
No matter adulterated barium titanate Symbiont only contains a kind of doping agent, still contain several doping agents, all be the same by the main particle diameter and the size distribution of the Symbiont of Hydrothermal Preparation.This point can obviously be found out from the transmission electron micrograph of the compound Symbiont of multiple doping agent.This Symbiont is 1.02Ba among Fig. 1
0.811Pb
0.105Ca
0.081Sr
0.003OTi
0.832Sn
0.074Zr
0.942O
20.012CoO0.009MnO0.005Nb
2O
5, this shows and mainly has a kind of main particle spherical in shape in fact, and its main particle diameter is 0.2 micron, and the quartile ratio is 1.29, illustrates that thus the main size distribution of this product is very narrow.Barium titanate Symbiont (0.998Ba with the adulterated composite titanic acid barium of multiple component base Symbiont among Fig. 1 and a kind of doping agent among Fig. 2
0.792Pb
0.104Ca
0.098Sr
0.006OTi
0.831Sn
0.070Zr
0.099O
20.03CoO) transmission electron micrograph compare, the result shows that the structure of various barium titanate-based compositions is closely similar.The facies analysis result has further confirmed this point, analyzes knot
Fruit shows that its main particle diameter of product of Fig. 2 is 0.18 micron, and the quartile ratio is 1.26.
In order to measure the physics and the chemical property of barium titanate doping base Symbiont of the present invention, various laboratory tests have been carried out.All use SILVER REAGENT chemical preparations or its equivalent in the test.Used Ba(OH)
28H
2The O product contains the 1.00%(mole approximately) or the 0.3%(mole) Sr, the Sr in this product can concentrate gradually.To remain on all Ba(OH of 70 ℃-90 ℃ before using)
2Solution filters to remove any carbonate that exists.At 800 ℃ of calcining CaCO
3Can obtain CaO.When contacting with water, CaO can generate Ca(OH)
2Tungsten adds with ammonium tungstate solution.This solution is with wolframic acid, WO
3H
2O is dissolved under stirring condition in the 2M ammonia solution that has heated and preparation.The solution that makes is metastable, uses in the short duration after preparation.
TiO
2, SnO
2, ZrO
2Hydrous oxide be at room temperature, prepare with their the corresponding muriatic aqueous solution of ammoniacal liquor neutralization.This product after filtration, the washing up to using AgNO
3Measure in the filtrate till the no muriate.Hydration Nb(V) oxide compound be in passing through with similar approach and the Nb(V) fluoride aqueous solution prepare.TiO
2And SnO
2, TiO
2And Sb
2O
3Mixed hydrous oxide be to contain the Ti(V by neutralization respectively with similar approach) and the Sn(IV), the Ti(IV) and the Sb(III) chloride soln prepare.Hydration TiO
2And Bi
2O
3Co-precipitation be to prepare by the aqueous solution that neutralization contains titanium chloride (IV) and Bismuth trinitrate (III).Percent solids in 900 ℃ of calcining wet cakes that mensuration has been washed after 1 hour.In operating process of the present invention, every kind of product has all used several wet cakes.
All synthetic test all carries out in 2 liters of autoclave pressures.For preventing to stain, the parts that all are got wet in the autoclave pressure perhaps coat with teflon R all by the titanium metal manufacturing.All synthetic tests are all at no CO
2Condition under carry out.With the filtering Ba(OH that is maintained at about under 80 ℃ of temperature)
2Solution is sent in the autoclave pressure, perhaps for quick adding, sends in the autoclave pressure with high-pressure pump, perhaps will be contained in the Ba(OH in the heating steel cylinder)
2Solution is used high pressure N
2In 10 seconds, put into pressure
Still.Stir the content of autoclave pressure with the Scroll-type agitator of an English inch diameter, stirring velocity is 1000-1500 rev/min in the building-up process.After synthetic, the slurry that generates is delivered to pressure filter and must not be exposed in the air (to prevent to generate insoluble BaCO
3), after the filtration,, dry in a vacuum in 100 ℃.
Measure the main particle diameter and the main size distribution of product with facies analysis.Determine main particle diameter and main size distribution by the size of measuring 500-1000 particle in a plurality of TEM visual field, to obtain the equivalent sphere diameter of main particle.Two or more from intuitively being accumulative not, and have measured the size of each main particle in abutting connection with particle.Calculate the funtcional relationship of percentage distribution of accumulative total quality and main particle diameter with equivalent spherical diameter.With the main particle diameter of medium grain size (by weight) as sample.With higher quartile diameter divided by the lower defined quartile of quartile value (by weight) than the tolerance of QR as particle diameter distribution width.The QR value of single dispersion product is 1.0.The QR value has narrow size distribution for the product of 1.0-1.5 is categorized as; The product that the QR value is about 1.5-2.0 is categorized as has medium narrow size distribution, and the QR value is categorized as greater than 2.0 product approximately and has wide size distribution.
Experience shows, adulterated Symbiont can be categorized as with the visual examination of TEM to have narrow, medium narrow and wide size distribution.Based on this experience, utilize visual examination that the size distribution of product of the present invention is classified.Because the size distribution of most of adulterated Symbionts is very narrow among the present invention, measure the size of 20-30 particle in the Photomicrograph, just can draw the mean value of main particle diameter.Quantitatively show that with semiquantitative two kinds of grain diameter measurement methods the main particle diameter of this barium titanate doping base Symbiont is the 0.05-0.4 micron.
Also can calculate particle diameter by the determination of nitrogen adsorption surface-area.In these calculate, the density of this product by this powder form and the theoretical density of pure perovskite type component calculates.Since in the sample amount of doping agent seldom, and in general the density of density and the said uhligite of doping agent less than big difference very, so doping agent can be ignored to the influence of product density.By
This error of bringing is very little.
Should be noted that to have only concerning the monodisperse spherical powder, the particle diameter of usefulness measurement microscope and just in full accord with the particle diameter of surface area test.When size distribution broadening, when spherical degree reduction and particle surface rugosity increase, increase with the difference between the particle diameter of these two kinds of methods mensuration.Therefore, in practical systems, the particle diameter that records with microscope is generally greater than the particle diameter that is calculated by surface-area.In the present invention, differ two times between two kinds of particle diameters of mensuration, this proof fine grain size throw out relevant with these particles is a spot of.
Main particle diameter that facies analysis is measured and size distribution can be measured the dispersiveness of product with being compared by the value of settling process mensuration.Roughly consistent by this particulate StoKes diameter that settling process obtains with the equivalent spherical diameter of measuring with facies analysis.In the present invention, (Norcross Georgia) determines that according to the Stokes diameter mass accumulation percentage distributes, and calculates intermediate value Stokes diameter and QR value by the Stokes diameter to utilize the micromeritics sedigraph.
Before sedimentation, with 15-30 minute ultrasonic (Sonification) this powder is dispersed in and contains 0.12%(weight) Emphos PS-21A(Vvitoo organics Division, 520Madison Ave., New York) do in the Virahol of dispersion agent.
Owing to measure particle diameter based on different principles with settling process and facies analysis method, therefore the particle diameter that records with these two kinds of methods is not quite identical.In addition, as mentioned above, carry out facies analysis in particle, some particle may bond together, but from being depolymerization intuitively.In settling process, with adjacency with two kinds of particles of agglutinating as individual.Exist the reason of these individuals as follows: there is bonding (as necking) between some main particles thereby the indestructible bonding aggregate of generation ultrasonic method, and owing to do not reach optimum dispersion stability, thereby cause flocculation.In the present invention, differ two times of signs with facies analysis with the medium wt particle grain size that settling process is measured as this product dispersibility.In addition, can expect
The QR value that (and discovery) measured by settling process is bigger than the value of being measured by facies analysis.Supposition thus, under the dispersion condition of the best, the QR value is between the measured value of facies analysis method and settling process.In the present invention, be used to measure dispersed additional standard and be, the QR value of this powder that obtains with settling process is less than 2.0.
Also available qualitative method is measured dispersed.Experience of the present invention shows, if a large amount of main particles is to exist with single particle in the TEM visual field, then this product is dispersible.Dispersed qualitative test conforms to the quantitative criterion of above-mentioned sign dispersiveness.
Uniformity coefficient with the scanning transmission electron microscope working sample of X-ray analysis ability with energy dispersion.Having measured several main particulate forms.With particle how much, if at least 80% particle contains the component of all powder, think that then this product is uniform.In fact, carry out STEM when analyzing, always meet this standard, and the amount of each component though do not do quantitative analysis, to particle, is made comparisons (in 80%) reasonably by peak intensity based on particle.
After the sample dissolution, carry out ultimate analysis to measure the composition of product with inductively coupled plasma spectrum IPC.The analysis precision of main component is about ± and 2%.Its precision of the analytical results of minority element is worth less than this.Also available x-ray fluorescence method is measured mainly by BaTiO
3Ba(II in the sample of forming)/and the Ti(IV) atomic ratio is more more accurate with the result of liquor analysis mensuration than this atomic ratio.
Barium titanate doping Symbiont of the present invention comprises that divalence lead or calcium partly replace the Symbiont of divalence barium.This doping Symbiont comprises that also the mixture of the mixture of plumbous and calcium or lead, calcium and strontium partly replaces the Symbiont of divalence barium.The titanic positively charged ion that partly replaces with tin, zirconium and hafnium also belongs to the scope of the invention.Pointed in the common pending application application (application number is 859577) as us, the constitutional features of this barium titanate Symbiont is all identical, and is irrelevant with specific divalence or tetravalence replacement positively charged ion.Therefore, following non-restrictive example includes only more complicated
The barium titanate Symbiont, and do not want to provide the constitutional features of the doping Symbiont of relevant lead barium titanate and barium titanate calcium and quadrivalent cation modification thereof.
Embodiment 1
In about 70 minutes, the slurry of 0.64 liter of vigorous stirring is heated to 200 ℃ from room temperature, contain (in mole) 0.167TiO in this slurry
2, 0.066Sn, 0.02ZrO
2, 0.022PbO, 0.022CaO and with 0.006 dopant salt that nitrate adds, make the one group of Symbiont that contains single doping agent.This slurry is cooled to 120 ℃, and will be heated to 70-90 ℃ contain 0.21 mole of Ba(OH approximately)
20.46 liter of Ba(OH)
2Solution was added in this slurry in 3.0 ± 0.2 minutes.The gained slurry was kept about 30 minutes under 120 ℃ of temperature, then at about 30 minutes internal heating to 200 ℃.With pulpous state sample filtering, drying, measure surface-area, chemical property and structural performance then.
The concentration of doping agent and tetravalence hydrous oxide all is lower than the determination limit (1 * 10 of this instrument in the filtrate
-4Mol is following).Therefore can suppose that these metals almost enter solid phase quantitatively.The TEMS analytical results shows, this product particle comes down to spheric and submicron.Differ 2 times by the particle diameter of surface area test and particle diameter by measurement microscope, this shows that this particle does not almost have plasma.All adulterated Symbionts all belong to dispersible.The visual examination of the TEMS of cobalt doped products shows that the quartile ratio is 1.26.Check the TEMS of other product with visual method, find that it all has similar size distribution.With the settling process quantitative assay dispersiveness of manganese doped products.This method shows that the particle diameter of this product is 0.21 micron, and this value is very consistent with the particle diameter that is obtained by TEMS, and the quartile ratio of this product is 1.69.These quantitative datas confirm that this product is dispersible.
Embodiment 2
With the tetravalence hydrous oxide among the embodiment 1, alkaline-earth metal and Pb(II) cationic source and close amount thereof carry out the compound Symbiont that the hydrothermal method Processing of Preparation contains three kinds of doping agents.The amount of various nitrate doping agent is 0.002 mole, under the situation of niobium, then uses Nb(OH)
5Wet cake before hydro-oxidation barium, adds them in the tetravalence hydrous oxide slurry.After hydrothermal treatment consists, find that solid phase tetravalence and bivalent atom are more or less the same than with embodiment 1, here no longer narration.
About 50% to 60%Al(III) enter in the filtrate, therefore, the mol ratio in these doping agent oxidation things and titanium calcium ore deposit, i.e. coefficient Z is little than cobalt-niobium-manganese doping Symbiont concerning chromium-cobalt-aluminium doping Symbiont.All these products in fact all are spheric, dispersible, and have narrow size distribution.Facies analysis confirms that cobalt-niobium-its main particle diameter of manganese doping Symbiont is 0.20 micron, and the quartile ratio is 1.29.Sedimentation studies show that the particle diameter of this product is 0.26 micron, and the quartile ratio is 1.67.The quantitative assay result has confirmed the qualitative reaction result, and promptly this product is dispersible, and has narrow size distribution.Disperse
The property another sign be to differ two times between the particle diameter that calculates with the particle diameter of measurement microscope and by surface-area.The adulterated composite titanic acid barium of cobalt-niobium-manganese Symbiont is carried out STEM analyze, find that its particle all contains barium, lead, calcium, strontium, titanium, zirconium, tin, manganese, cobalt and niobium, its amount is roughly close.This STEM result confirms that its particle diameter of composite titanic acid barium Symbiont of multiple doping agent is uniform.
Mol ratio
Doping agent doping agent oxidation thing X/Y specific area particle diameter (micron)
Ratio (m with titanium calcium ore deposit
2/ g) area TEM
Co（Ⅱ）
Nb（Ⅴ）????0.031????1.035????10.0????0.10????0.20
Mn（Ⅱ）
Cr（Ⅲ）
Co（Ⅱ）????0.024????1.034????12.6????0.08????0.15
Al（Ⅲ）
Claims (18)
1, a kind of adulterated barium phthalate base Symbiont of being made up of spheroidal particle in fact has following general formula:
XBa
(1-x ')Ca
X 'OYTi (1-y-y '-y ") Sn
yZr
Y 'Hf
Y "O
2X and y value are 0.9-1.1 in the ZD formula, and the Z value is greater than 0, and less than 0.1, y, y ' and y " are independently to be worth; this value is 0-0.3, and " sum is less than 0.4, and x ' is greater than 0 for y+y '+y, less than 0.4, D is a kind of doping agent oxidation thing at least, the main particle diameter average out to 0.05-0.4 micron of the Symbiont that wherein mixes.
2, the barium titanate doping Symbiont of claim 1, wherein at least a doping agent oxidation thing D is selected from down the oxide compound of column element: lanthanon, cobalt, manganese, magnesium, yttrium, bismuth, aluminium, boron, tungsten, niobium, chromium, nickel, molybdenum, iron, antimony, vanadium, tantalum, copper, silver, zinc, cadmium, silicon and composition thereof.
3, the barium titanate doping Symbiont of claim 1 wherein differs 2 times with facies analysis with the main particle diameter that settling process is measured.
4, the barium titanate doping Symbiont of claim 1 is measured the Symbiont that wherein mixes through facies analysis and is had narrow size distribution, and the quartile ratio of the main grain size distribution curve of this doping Symbiont is less than or equal to 2.0.
5, the adulterated barium titanate Symbiont of claim 1, wherein the x/y ratio is 1.000 ± 0.015.
6, the barium titanate doping Symbiont of claim 1, wherein x/y is than being 0.95-1.1.
7, a kind of barium titanate doping base Symbiont of being made up of spheroidal particle in fact has following general formula:
XBa
(1-X)Pb
xOYTi
(1-y-y '-y ")Sn
yZr
Y 'Hf
Y "O
2X and y value are 0.9-1.1 in the ZD formula, and the z value is greater than 0, less than 0.1, yy ' and y " value be respectively 0-0.3; " sum is less than 0.4 for y+y '+y, x is greater than 0, less than 0.4, and D is at least a kind of doping agent oxidation thing, the main particle diameter average out to 0.05-0.4 micron of this doping Symbiont.
8, the barium titanate doping Symbiont of claim 7, wherein at least a doping agent oxidation thing D is selected from down the oxide compound of column element: lanthanon, cobalt, manganese, magnesium, yttrium, bismuth, aluminium, boron, tungsten, niobium, chromium, nickel, molybdenum, iron, antimony, vanadium, tantalum, copper, silver, zinc, cadmium, silicon and composition thereof.
9, the barium titanate doping Symbiont of claim 7, wherein the main particle diameter of being measured by facies analysis and settling process differs 2 times.
10, the barium titanate doping Symbiont of claim 7 is measured this doping Symbiont through facies analysis and is had narrow size distribution, and the quartile ratio of the main grain size distribution curve of this doping Symbiont is less than or equal to 2.0.
11, the barium titanate doping Symbiont of claim 7, wherein the x/y ratio is 1.000 ± 0.015.
12, the barium titanate doping Symbiont of claim 7, wherein x/y is than being 0.95-1.1.
13, a kind of barium titanate doping base Symbiont of being made up of spheroidal particle in fact has following general formula:
X and y value are 0.9-1.1 in the formula, the Z value is greater than 0, less than 0.1, x, x ', x ", y, y ' and y " respectively greater than 0, less than 0.3, " sum is less than 0.4; " sum is less than 0.4 for y+y '+y for x+x '+x, D is at least a kind of doping oxide, the main particle diameter average out to 0.05-0.4 micron of the Symbiont that wherein mixes.
14, the barium titanate doping Symbiont of claim 13, wherein at least a doping agent oxidation thing D is selected from down the oxide compound of column element: lanthanon, cobalt, manganese, magnesium, yttrium, bismuth, aluminium, boron, tungsten, niobium, chromium, nickel, molybdenum, iron, antimony, vanadium, tantalum, copper, silver, zinc, cadmium, silicon and composition thereof.
15, the barium titanate doping Symbiont of claim 13, wherein the main particle diameter of being measured by facies analysis and settling process differs 2 times.
16, the barium titanate doping Symbiont of claim 13 is measured this doping Symbiont through facies analysis and is had narrow size distribution, and the quartile ratio of the main grain size distribution curve of this doping Symbiont is less than or equal to 1.5.
17, the barium titanate doping Symbiont of claim 13, wherein the x/y ratio is 1.000 ± 0.015.
18, the barium titanate doping Symbiont of claim 13, wherein x/y is than being 0.95-1.1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8504387A | 1987-08-12 | 1987-08-12 | |
| US085,043 | 1987-08-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033977A true CN1033977A (en) | 1989-07-19 |
| CN1016962B CN1016962B (en) | 1992-06-10 |
Family
ID=22189096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88106966A Expired CN1016962B (en) | 1987-08-12 | 1988-08-12 | Doped batio3 based dielectric composition powder |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JP2532599B2 (en) |
| KR (1) | KR970004271B1 (en) |
| CN (1) | CN1016962B (en) |
| DE (1) | DE3826801C2 (en) |
| ES (1) | ES2006956A6 (en) |
| FR (1) | FR2619370B1 (en) |
| GB (1) | GB2208644B (en) |
| HK (1) | HK994A (en) |
| IE (1) | IE61487B1 (en) |
| IT (1) | IT1226738B (en) |
| MX (1) | MX169172B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054166C (en) * | 1997-11-14 | 2000-07-05 | 中国科学院固体物理研究所 | Preparing method for inlaid dimension controllable nanometre grade silver particle on barium titanate film |
| CN115872735A (en) * | 2022-11-18 | 2023-03-31 | 广东工业大学 | Zirconium tin hafnate lanthanum lead ceramic and preparation method and energy storage application thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19635406B4 (en) * | 1996-08-31 | 2005-09-01 | Philips Intellectual Property & Standards Gmbh | Capacitor and multilayer capacitor with a tungsten-containing BCZT ceramic dielectric |
| DE19744857A1 (en) * | 1997-10-10 | 1999-05-06 | Fraunhofer Ges Forschung | Nanocrystalline sensor and manufacturing process |
| JP2002519298A (en) * | 1998-07-01 | 2002-07-02 | キャボット コーポレイション | Hot water production method of barium titanate powder |
| JP4446324B2 (en) * | 2001-09-27 | 2010-04-07 | 株式会社村田製作所 | Dielectric porcelain composition and capacitor using the same |
| JP4201242B2 (en) * | 2002-03-26 | 2008-12-24 | Ｔｄｋ株式会社 | High dielectric constant dielectric ceramic composition |
| US6960546B2 (en) | 2002-09-27 | 2005-11-01 | Paratek Microwave, Inc. | Dielectric composite materials including an electronically tunable dielectric phase and a calcium and oxygen-containing compound phase |
| EP2328193B1 (en) * | 2009-11-30 | 2015-03-11 | Canon Kabushiki Kaisha | Piezoelectric ceramic, method for making the same, piezoelectric element, liquid discharge head, and ultrasonic motor |
| CN113603498B (en) * | 2020-12-30 | 2022-09-30 | 苏州金宏气体股份有限公司 | Cobalt-doped BaTiO 3 Piezoelectric ceramic, preparation method thereof and high-purity hydrogen production |
| CN112759385B (en) * | 2021-01-06 | 2021-12-14 | 中国科学院福建物质结构研究所 | Perovskite ceramic material and preparation method and application thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637531A (en) * | 1970-05-01 | 1972-01-25 | Texas Instruments Inc | Method for making ceramic titanate elements and materials therefor |
| US4061583A (en) * | 1974-03-13 | 1977-12-06 | Murata Manufacturing Co., Ltd. | Preparation of titanates |
| JPS5552211A (en) * | 1978-10-13 | 1980-04-16 | Suwa Seikosha Kk | Temperature compensating capacitor and method of manufacturing same |
| DE2941304A1 (en) * | 1978-10-13 | 1980-04-30 | Suwa Seikosha Kk | DIELECTRICAL, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE IN CAPACITORS FOR TEMPERATURE COMPENSATION PURPOSES |
| US4233282A (en) * | 1979-10-18 | 1980-11-11 | General Electric Company | Molten salt synthesis of barium and/or strontium titanate powder |
| DE3165390D1 (en) * | 1980-06-30 | 1984-09-13 | Centralab Inc | Ceramic dielectric for base metal electrode capacitors and method of manufacture |
| US4293534A (en) * | 1980-08-22 | 1981-10-06 | General Electric Company | Molten salt synthesis of alkaline earth titanates, zirconates and their solid solutions |
| DE3106136A1 (en) * | 1981-02-19 | 1982-08-19 | Draloric Electronic GmbH, 8672 Selb | Process for producing polycrystalline ceramic PTC thermistor bodies |
| US4487755A (en) * | 1982-07-01 | 1984-12-11 | General Electric Company | Preparation of large crystal sized barium and/or strontium titanate powder |
| US4537865A (en) * | 1984-07-11 | 1985-08-27 | Murata Manufacturing Co., Ltd. | Process for preparing a particulate ceramic material |
| JPS6131345A (en) * | 1984-07-25 | 1986-02-13 | 堺化学工業株式会社 | Manufacture of composition |
| JPS61111957A (en) * | 1984-11-02 | 1986-05-30 | 堺化学工業株式会社 | Composition for ceramic dielectric |
| MX172902B (en) * | 1986-05-05 | 1994-01-20 | Cabot Corp | BARIO TITANATE COFORMS |
| DE3723082C2 (en) * | 1986-07-14 | 2003-09-25 | Cabot Corp | Process for the production of submicron perovskites |
| GB2193713B (en) * | 1986-07-14 | 1990-12-05 | Cabot Corp | Method of producing perovskite-type compounds. |
-
1988
- 1988-05-24 ES ES8801633A patent/ES2006956A6/en not_active Expired
- 1988-08-06 DE DE3826801A patent/DE3826801C2/en not_active Expired - Fee Related
- 1988-08-10 MX MX012622A patent/MX169172B/en unknown
- 1988-08-10 GB GB8818969A patent/GB2208644B/en not_active Expired - Fee Related
- 1988-08-11 IE IE245088A patent/IE61487B1/en not_active IP Right Cessation
- 1988-08-11 FR FR8810833A patent/FR2619370B1/en not_active Expired - Fee Related
- 1988-08-12 KR KR1019880010295A patent/KR970004271B1/en not_active IP Right Cessation
- 1988-08-12 JP JP63201830A patent/JP2532599B2/en not_active Expired - Fee Related
- 1988-08-12 CN CN88106966A patent/CN1016962B/en not_active Expired
- 1988-08-12 IT IT8821706A patent/IT1226738B/en active
-
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054166C (en) * | 1997-11-14 | 2000-07-05 | 中国科学院固体物理研究所 | Preparing method for inlaid dimension controllable nanometre grade silver particle on barium titanate film |
| CN115872735A (en) * | 2022-11-18 | 2023-03-31 | 广东工业大学 | Zirconium tin hafnate lanthanum lead ceramic and preparation method and energy storage application thereof |
| CN115872735B (en) * | 2022-11-18 | 2024-01-16 | 广东工业大学 | Zirconium tin hafnium lanthanum lead acid ceramic, preparation method and energy storage application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8821706A0 (en) | 1988-08-12 |
| CN1016962B (en) | 1992-06-10 |
| DE3826801A1 (en) | 1989-02-23 |
| FR2619370B1 (en) | 1993-12-17 |
| MX169172B (en) | 1993-06-23 |
| KR970004271B1 (en) | 1997-03-26 |
| GB2208644B (en) | 1991-11-13 |
| GB8818969D0 (en) | 1988-09-14 |
| ES2006956A6 (en) | 1989-05-16 |
| IE882450L (en) | 1989-02-12 |
| DE3826801C2 (en) | 2003-05-15 |
| FR2619370A1 (en) | 1989-02-17 |
| KR890004359A (en) | 1989-04-21 |
| JP2532599B2 (en) | 1996-09-11 |
| IT1226738B (en) | 1991-02-05 |
| GB2208644A (en) | 1989-04-12 |
| JPH01133974A (en) | 1989-05-26 |
| HK994A (en) | 1994-01-14 |
| IE61487B1 (en) | 1994-11-02 |
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