US20110152060A1 - Method of preparing ceramic powders using chelate precursors - Google Patents
Method of preparing ceramic powders using chelate precursors Download PDFInfo
- Publication number
- US20110152060A1 US20110152060A1 US13/039,530 US201113039530A US2011152060A1 US 20110152060 A1 US20110152060 A1 US 20110152060A1 US 201113039530 A US201113039530 A US 201113039530A US 2011152060 A1 US2011152060 A1 US 2011152060A1
- Authority
- US
- United States
- Prior art keywords
- acid
- primary particles
- solution
- chelate
- ion
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000000843 powder Substances 0.000 title claims abstract description 73
- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 239000013522 chelant Substances 0.000 title claims abstract description 44
- 239000002243 precursor Substances 0.000 title claims abstract description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 33
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical class [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 17
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 54
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 26
- 239000000470 constituent Substances 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 14
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052779 Neodymium Inorganic materials 0.000 claims description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 11
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052691 Erbium Inorganic materials 0.000 claims description 9
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 8
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 claims description 5
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003989 dielectric material Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims 28
- 238000010992 reflux Methods 0.000 claims 10
- 239000011575 calcium Substances 0.000 claims 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 5
- 229910052719 titanium Inorganic materials 0.000 claims 5
- 229910052788 barium Inorganic materials 0.000 claims 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 4
- 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 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000000975 co-precipitation Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 18
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- -1 rare earth metal ions Chemical class 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 5
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229960004275 glycolic acid Drugs 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 238000009700 powder processing Methods 0.000 description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- KUCWUAFNGCMZDB-UHFFFAOYSA-N 2-amino-3-nitrophenol Chemical compound NC1=C(O)C=CC=C1[N+]([O-])=O KUCWUAFNGCMZDB-UHFFFAOYSA-N 0.000 description 1
- UUNHRGSUOBTBKW-UHFFFAOYSA-M 2-hydroxypropanoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CC(O)C([O-])=O UUNHRGSUOBTBKW-UHFFFAOYSA-M 0.000 description 1
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- VZIJYSCVLOJLCI-UHFFFAOYSA-N C.C.C.C.CC.CC.CC.O.O.O.O=C(OO)OOC(=O)OOC(=O)[La][La] Chemical compound C.C.C.C.CC.CC.CC.O.O.O.O=C(OO)OOC(=O)OOC(=O)[La][La] VZIJYSCVLOJLCI-UHFFFAOYSA-N 0.000 description 1
- RZMKRWWOMKEZLQ-UHFFFAOYSA-N C.C.C.C.CC.CC.CC.O.O.O.O=C(OO)OOC(=O)OOC(=O)[Nd][Nd] Chemical compound C.C.C.C.CC.CC.CC.O.O.O.O=C(OO)OOC(=O)OOC(=O)[Nd][Nd] RZMKRWWOMKEZLQ-UHFFFAOYSA-N 0.000 description 1
- QTUJBZPDGGACKF-UHFFFAOYSA-N C.C.C.C.CC.CC.CC.O.O.O.O=C(OO)OOC(=O)OOC(=O)[Y][Y] Chemical compound C.C.C.C.CC.CC.CC.O.O.O.O=C(OO)OOC(=O)OOC(=O)[Y][Y] QTUJBZPDGGACKF-UHFFFAOYSA-N 0.000 description 1
- MWXKMXOEWPDTAX-UHFFFAOYSA-N C.C.C.C.CC.O.O.[La+3].[Mn+2].[Nd+3].[Y+3] Chemical compound C.C.C.C.CC.O.O.[La+3].[Mn+2].[Nd+3].[Y+3] MWXKMXOEWPDTAX-UHFFFAOYSA-N 0.000 description 1
- CZZRSZWWACXAFF-UHFFFAOYSA-N C.C.C.CC.CC.CC.O.O.O.O.O=C([Mn])OO Chemical compound C.C.C.CC.CC.CC.O.O.O.O.O=C([Mn])OO CZZRSZWWACXAFF-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910017504 Nd(NO3)3 Inorganic materials 0.000 description 1
- 229910017498 Nd(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229910017512 Nd2(CO3)3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTAWEKVWKJDVBY-UHFFFAOYSA-K OC(C(=O)[O-])C.[La+3].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C.OC(C(=O)[O-])C Chemical compound OC(C(=O)[O-])C.[La+3].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C.OC(C(=O)[O-])C CTAWEKVWKJDVBY-UHFFFAOYSA-K 0.000 description 1
- JQMYKSPVDWNAAH-UHFFFAOYSA-L OC(C(=O)[O-])C.[Mn+2].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C Chemical compound OC(C(=O)[O-])C.[Mn+2].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C JQMYKSPVDWNAAH-UHFFFAOYSA-L 0.000 description 1
- TUDPXELLUUOYMW-UHFFFAOYSA-K OC(C(=O)[O-])C.[Nd+3].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C.OC(C(=O)[O-])C Chemical compound OC(C(=O)[O-])C.[Nd+3].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C.OC(C(=O)[O-])C TUDPXELLUUOYMW-UHFFFAOYSA-K 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- 229910009244 Y(NO3)3.4H2O Inorganic materials 0.000 description 1
- 229910009440 Y2(CO3)3 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- RZOBLYBZQXQGFY-UHFFFAOYSA-N ammonium lactate Chemical compound [NH4+].CC(O)C([O-])=O RZOBLYBZQXQGFY-UHFFFAOYSA-N 0.000 description 1
- AZAXQLRXAXJBCG-UHFFFAOYSA-K azanium 2-hydroxypropanoate yttrium(3+) Chemical compound OC(C(=O)[O-])C.[Y+3].[NH4+].OC(C(=O)[O-])C.OC(C(=O)[O-])C.OC(C(=O)[O-])C AZAXQLRXAXJBCG-UHFFFAOYSA-K 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- KZCYIWWNWWRLBQ-UHFFFAOYSA-P diazanium 3-methanidylbutan-2-one titanium(2+) dihydrate Chemical compound [NH4+].[NH4+].O.O.[Ti++].CC([CH2-])C([CH2-])=O.CC([CH2-])C([CH2-])=O KZCYIWWNWWRLBQ-UHFFFAOYSA-P 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- JWBWFTANBHYHBC-UHFFFAOYSA-N oxozirconium(2+);dinitrate Chemical compound [Zr+2]=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JWBWFTANBHYHBC-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical compound [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 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 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- GRTBAGCGDOYUBE-UHFFFAOYSA-N yttrium(3+) Chemical compound [Y+3] GRTBAGCGDOYUBE-UHFFFAOYSA-N 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
Images
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- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
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Definitions
- the present invention relates to methods for preparing ceramic powders, and particularly to wet-chemical processes using chelate precursors.
- Ceramic powders are used in the fabrication of numerous different types of devices including specialized mechanical components, coating for mechanical components, semiconductor devices, superconducting devices, device packaging, passive electronic components such as capacitors, and more sophisticated energy storage devices.
- Numerous different techniques exist for the synthesis and fabrication of ceramic powders including solid phase synthesis such as solid-solid diffusion, liquid phase synthesis such as precipitation and coprecipitation, and synthesis using gas phase reactants.
- a host of related fabrication techniques can also be used including: spray drying, spray roasting, metal organic decomposition, freeze drying, sol-gel synthesis, melt solidification, and the like.
- the milling process generates wear debris from the ball mill itself and, the debris becomes incorporated in the powder mixture. Because of the often wide disparity in particle size among the various commercially available starting powders (and even significant variation in particle size of the same powder from lot to lot), an optimum result from ball milling rarely occurs, and a contamination-free product is never obtained.
- Solid-solid diffusion at high temperature (but below the temperature at which sintering starts) of the ball-milled powder mixture is required to form a usable and, preferably, fully reacted homogeneous single powder.
- longer times spent at high temperature e.g., the calcining temperature
- Homogeneity is improved by repeating several times the ball-milling and calcining steps in succession, each requiring several hours. Of course, this increases the amount of ball-milling wear debris added to the powder, thereby increasing the amount of contamination in the end ceramic product.
- a method is disclosed.
- a plurality of precursor materials are provided in solution.
- Each of the plurality of precursor materials in solution further comprises at least one constituent ionic species of a ceramic powder.
- At least one of the plurality of precursor materials in solution is a chelate solution.
- the plurality of precursor materials are combined in solution with a precipitant solution to cause coprecipitation of the ceramic powder in a combined solution.
- the ceramic powder is separated from the combined solution.
- a substantially contaminant free ceramic powder produced by a process includes: providing a plurality of precursor materials in solution, combining the plurality of precursor materials in solution with a nonmetal-ion-containing strong base precipitant solution to cause coprecipitation of the ceramic powder in a combined solution; and separating the ceramic powder from the combined solution.
- Each of the plurality of precursor materials in solution further comprises at least one constituent ionic species of the ceramic powder.
- At least one of the plurality of precursor materials in solution is a chelate solution.
- FIG. 1 is a flow chart illustrating ceramic powder processing techniques in accordance with the present invention.
- FIG. 2 is a flow chart illustrating chelate processing techniques in accordance with the present invention.
- high-permittivity calcined composition-modified barium titanate powders can be used to fabricate high quality dielectric devices.
- U.S. Pat. No. 6,078,494 (hereby incorporated by reference herein in its entirety) describes examples of various doped barium titanate dielectric ceramic compositions.
- the '494 patent describes a dielectric ceramic composition
- barium-calcium-zirconium-titanate compounds have a perovskite structure of the general composition ABO 3 , where the rare earth metal ions Nd, Pr, Sm and Gd (having a large ion radius) are arranged at A-sites, and the rare earth metal ions Dy, Er, Ho, Y, Yb and Ga (having a small ion radius) are arranged at B-sites.
- the perovskite material includes the acceptor ions Ag, Dy, Er, Ho, Y or Yb and the donor ions Nb, Mo, Nd, Pr, Sm and Gd at lattice sites having a different local symmetry.
- Donors and acceptors form donor-acceptor complexes within the lattice structure of the barium-calcium-zirconium-titanate according to the invention.
- the dielectric ceramic compositions described by the '494 patent are just some of the many types of ceramic compositions that can be fabricated using the processes and techniques of the present application.
- chelates are used as precursors to one or more of the constituent components of a target ceramic powder.
- chelation is the formation or presence of bonds (or other attractive interactions) between two or more separate binding sites within the same ligand and a single central atom.
- a molecular entity in which there is chelation (and the corresponding chemical species) is called a chelate.
- bidentate (or didentate), tridentate, tetradentate . . . multidentate are often used to indicate the number of potential binding sites of the ligand, at least two of which are used by the ligand in forming a chelate.
- composition-modified barium titanate For example, various wet-chemical powder preparation techniques for composition-modified barium titanate are described below.
- the methods make use of aqueous solutions for some or all reactants to form by coprecipitation the desired powders.
- the approach extends the use of one or more chelates (preferably water-soluble or water stable) as precursors to several of the component metal ions comprising the constituents of the composition-modified barium titanate.
- a nonmetal-ion-containing strong base e.g., selected from among tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide [(CH 3 ) 4 NOH] in aqueous solution is used as the precipitant for the mixture of precursors in aqueous solution.
- the tetraalkylammonium hydroxides unlike conventional strong bases, e.g., sodium and potassium hydroxides, do not introduce contamination metal ions, e.g., sodium and potassium ions, to the end product.
- contamination metal ions e.g., sodium and potassium ions
- tetraalkylammonium hydroxides as the strong base.
- tetramethylammonium hydroxide is selected for the precipitant, but various other tetraalkylammonium hydroxides can be used.
- no washing of the precipitated powder is needed to remove residual precipitant.
- a DI water washing step or some other washing step, is performed.
- a solid-solid solution of water-soluble hydrated and chelated metal-ion species in their proportioned amounts is precipitated as an oxide (the composition-modified barium titanate) by the nonmetal-ion-containing tetramethylammonium hydroxide.
- the residuals tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium 2-hydroxypropanate, ammonium hydroxide, ammonium nitrate, and ammonium 2-hydroxypropanate, are thermally decomposed and oxidized and thereby completely converted to gaseous products: H 2 O, NH 3 , CO, CO 2 , N 2 , O 2 , N 2 O, NO, and NO 2 .
- Another advantage of the use of a tetraalkylammonium hydroxide as the precipitant is the amount of DI water required for washing is reduced or, in principle, no DI water washing step is needed since the residuals are completely converted to gaseous products.
- Preparation of the high-permittivity calcined composition-modified barium titanate powder in this manner yields high purity powders with narrow particle-size distribution.
- the microstructures of ceramics formed from these calcined wet-chemical-prepared powders are uniform in grain size and can also result in smaller grain size. Electrical properties are improved so that higher relative permittivities and increased dielectric breakdown strengths can be obtained. Further improvement can be obtained by the elimination of voids within the sintered ceramic body with subsequent hot isostatic pressing.
- At least one, but not necessarily all of the precursors are chelates.
- a solution of the precursors: Ba(NO 3 ) 2 , Ca(NO 3 ) 2 .4H 2 O, Nd(NO 3 ) 3 .6H 2 O, Y(NO 3 ) 3 .4H 2 O, Mn(CH 3 COO) 2 .4H 2 O, ZrO(NO 3 ) 2 , and [CH 3 CH(O—)COONH 4 ] 2 Ti(OH) 2 is formed in deionized water.
- the Ti chelate [CH 3 CH(O—)COONH 4 ] 2 Ti(OH) 2 is used.
- the solution can be mixed and/or heated (e.g., heated to 80° C.) and is made in the proportionate amount in weight percent for each of the precursors as shown in Table 1.
- the two solutions are mixed by pumping the heated ingredient streams simultaneously through a coaxial fluid jet mixer.
- a slurry of the coprecipitated powder is produced and collected in a drown-out vessel.
- the coprecipitated powder is refluxed in the drown-out vessel at 90°-95° C. for 12 hr and then filtered, optionally deionized-water washed, and dried.
- the powder can be collected by centrifugal sedimentation, or some other technique.
- the subsequent powder is calcined under suitable conditions, e.g., at 1050° C. in air in an appropriate silica glass (fused quartz) tray or tube.
- FIG. 1 is a flow chart illustrating ceramic powder processing techniques in accordance with the present invention.
- the process begins at 100 .
- the appropriate precursor materials e.g., chelates and other precursors
- a suitable precipitant is provided ( 120 ).
- the two materials are then combined to form the desired ceramic powder via a coprecipitation reaction ( 130 ).
- the ceramic powder can be separated from the solution in which it is formed ( 140 ) using suitable separation devices and techniques.
- Other post processing steps can be employed including: washing the ceramic powder ( 150 ), drying the ceramic powder ( 160 ), and calcining the ceramic powder ( 170 ).
- the process terminates at 180 .
- the resulting ceramic powder can then be used in the fabrication of numerous different devices.
- multiple chelate precursors are used in a similar process.
- various Zr compounds can be used as precursors.
- oxozirconium(IV) nitrate (zirconyl nitrate) [ZrO(NO 3 ) 2 ] can be used.
- ZrO(NO 3 ) 2 requires a relatively low pH of about 1.5, provided by an added acid solution, e.g., nitric acid (HNO 3 ), to prevent hydrolysis.
- zirconium(IV) bis(ammonium 2-hydroxypropanato)dihydroxide [zirconium(IV) bis(ammonium lactato)dihydroxide] ⁇ [CH 3 CH(O—)COONH 4 ] 2 Zr(OH) 2 ⁇ aqueous solution, which is stable over the pH range from 6 to 8 up to 100° C.
- this compound is not readily available commercially, it can be prepared from any of the alkyl oxides of zirconium(IV).
- zirconium(IV) alkyl oxides serve as an intermediate from the zirconium tetrachloride [zirconium(IV) chloride](ZrCl 4 ) source in the preparation of all other zirconium(IV) compounds.
- zirconium(IV) alkyl oxides examples include: the ethoxide [Zr(OCH 2 CH 3 ) 4 ], the propoxide [Zr(OCH 2 CH 2 CH 3 ) 4 ], the isopropoxide ⁇ Zr[OCH(CH 3 ) 2 ] 4 ⁇ , the butoxide [Zr(OCH 2 CH 2 CH 2 CH 3 ) 4 ], and the tert-butoxide ⁇ Zr[OC(CH 3 ) 3 ] 4 ⁇ .
- zirconium(IV) isopropoxide (tetra-2-propyl zirconate) is likely to be the lowest cost because of the very large volume of 2-propanol (isopropyl alcohol) produced by several manufacturers. These alkyl oxides are all soluble in alcohols, but they all hydrolyze in the presence of moisture. However, by reaction with 2-hydroxypropanoic acid (2-hydroxypropionic acid, lactic acid) [CH 3 CH(OH)COOH], 85 wt % in aqueous solution, followed with ammonium hydroxide (NH 4 OH), 28 wt % ammonia (NH 3 ) in water, the water-stable zirconium(IV) chelate is prepared. The other reaction product is the alcohol from which the zirconium(IV) alkyl oxide was originally made in the reaction with the zirconium tetrachloride source. This alcohol is recoverable by fractional distillation, membrane per vaporization, or the like.
- titanium(IV) bis(ammonium 2-hydroxypropanato)dihydroxide [titanium(IV) bis(ammonium lactato)dihydroxide] ⁇ [CH 3 CH(O—)COONH 4 ] 2 Ti(OH) 2 ⁇ , is commercially available from, for example, DuPont with trade name Tyzor® LA. It can be prepared from any of the alkyl oxides of titanium(IV).
- titanium(IV) alkyl oxides include the following: the methoxide [Ti(OCH 3 ) 4 ], the ethoxide [Ti(OCH 2 CH 3 ) 4 ], the propoxide [Ti(OCH 2 CH 2 CH 3 ) 4 ], the isopropoxide ⁇ Ti[OCH(CH 3 ) 2 ] 4 ⁇ , the butoxide [Ti(OCH 2 CH 2 CH 2 CH 3 ) 4 ], and the tert-butoxide ⁇ Ti[OC(CH 3 ) 3 ] 4 ⁇ .
- titanium(IV) isopropoxide tetra-2-propyl titanate
- an alkyl oxide of titanium(IV) can be converted to the water-stable titanium(IV) chelate.
- Water-soluble and/or stable chelates of manganese(II), yttrium(III), lanthanum(III), neodymium(III), and several other metal ions can be prepared with the use of 2-hydroxypropanoic acid (lactic acid) and ammonium hydroxide.
- the most convenient starting compounds are commercially available water-insoluble carbonates of these metal ions, because they more readily react with 2-hydroxypropanoic acid aqueous solution to form the very stable water-soluble (ammonium 2-hydroxypropanato)metal-ion chelates.
- Water-insoluble oxides can also be used as starting compounds, although they are not as quickly reactive.
- a manganese chelate can be produced when the manganese(II) carbonate (MnCO 3 ) is converted to bis(ammonium 2-hydroxypropanato) manganese(II) (i.e., ammonium manganese (II) 2-hydroxypropanate) ⁇ Mn[CH 3 CH(O—)COONH 4 ] 2 ⁇ , as shown in the following reaction equations:
- an yttrium chelate can be produced by converting yttrium(III) carbonate[Y 2 (CO 3 ) 3 ] to tris(ammonium 2-hydroxypropanato)yttrium(III) (i.e., ammonium yttrium (III) 2-hydroxypropanate) ⁇ Y[CH 3 CH(O—)COONH 4 ] 3 ⁇ as shown in the following reaction equations:
- a lanthanum chelate can be produced by converting lanthanum(III) carbonate [La 2 (CO 3 ) 3 ] to tris(ammonium 2-hydroxypropanato)lanthanum(III) (i.e., ammonium lanthanum (III) 2-hydroxypropanate) ⁇ La[CH 3 CH(O—)COONH 4 ] 3 ⁇ as shown in the following reaction equations:
- a neodymium chelate can be produced by converting neodymium(III) carbonate[Nd 2 (CO 3 ) 3 ] to tris(ammonium 2-hydroxypropanato)neodymium(III) (i.e., ammonium neodymium (III) 2-hydroxypropanate) ⁇ Nd[CH 3 CH(O—)COONH 4 ] 3 ⁇ as shown in the following reaction equations:
- nitrate compounds have the highest solubilities in water, as concentration in moles per liter of solution at 20° C., i.e., molar, and moles per 1000 grams of water at 20° C., i.e., molal, of any salt.
- the nitrates are readily available commercially. Accordingly the first reaction of 2-hydroxypropanoic acid with the oxo-metal-ion and metal-ion species as indicated above are as follows:
- next-step reactions with ammonium hydroxide are the same as those given above.
- the more acidic hydrogen ion of the carboxyl group (COOH) splits off first to form ( 1 ) the alcohol from which the alkyl oxide was made, or (2) water and carbon dioxide.
- the hydrogen atom of the hydroxyl group (OH) splits off as a hydrogen ion to form water and the ammonium ion[(NH 4 ) + ] salt of the 2-hydroxypropanate chelate.
- the hydrogen atom of the hydroxyl group (OH) on the carbon atom (the 2-position or alpha-position) adjacent to the carbonyl group (C ⁇ O) is relatively acidic forming a hydrogen ion splitting off with sufficiently basic conditions provided by the addition of the ammonium hydroxide aqueous solution. Additionally, the presence of the hydroxyl group in the 2-position to the carboxylic acid group results in an increased acidity of the latter.
- FIG. 2 is a flow chart illustrating chelate processing techniques in accordance with the present invention.
- the process begins at 200 .
- the appropriate starting material e.g., a metal alkyl oxide or a metal-ion carbonate is selected. The material is selected based on the metal ion it will ultimately provide to a resulting ceramic powder.
- the starting material is reacted with an appropriate chelating agent ( 220 ).
- the chelating agent can be provided in aqueous solution and combined with the starting material in a suitable reaction vessel. The combined solution is also reacted with a suitable weak base ( 230 ) to complete aspects of the reaction.
- the process terminates at 240 .
- 2-hydroxypropanoic acid is a bidentate ligand, since it can bond to a central metal cation via both oxygen atoms of the five-sided ring. Since the outer cage has two or three anion groups, the total negative charge exceeds the positive charge of the central metal cation, and the chelate is an anion with the ammonium cations[(NH 4 ) + ] for charge balance Ammonium ion salts have high water solubilities at neutral and near neutral pH conditions.
- hydrolytically stable chelates in this regard is extremely versatile, even though many of the chelate precursors are not readily available commercially.
- such chelates have applicability to all the metal ions of the Periodic Table except, those of Groups IA and perhaps IIA, for coprecipitation procedures in the preparation of ceramic powders.
- Alkaline metal ions do not form complexes and alkaline earth metal ions (Group IIA) form rather weak complexes with 2-hydroxypropanoic acid.
- Table 3 illustrates an example composition modified barium titanate compound formed using the above described chelate precursors.
- the formula weight of the resulting compound is 237.24.
- the two ingredient streams one containing the aqueous solution of all the metal-ion compound precursors, and the other containing the aqueous solution of the tetramethylammonium hydroxide strong base, are reacted together simultaneously and continuously in a fluid jet column that provides a high turbulence energy environment.
- the total volume for the saturated or near-saturated commercially available and specially manufactured aqueous solutions of the precursors is typically four times that of the 25 wt % tetramethylammonium hydroxide aqueous solution.
- the resulting slurry can be refluxed as appropriate.
- the slurry is transferred to a filtration or separation device.
- the separating of the precipitate from the liquid phase and the isolation of precipitate can be carried out using a variety of devices and techniques including: conventional filtering, vacuum filtering, centrifugal separation, sedimentation, spray drying, freeze drying, or the like.
- the filtered powder can then undergo various washing, drying, and calcining steps as desired.
- a preferred chelating agent is the very water-soluble 2-hydroxypropanoic acid (i.e., lactic acid) followed by neutralization with the weak-base ammonium hydroxide aqueous solution, both of which are produced in high volume and are thus relatively low in cost.
- water-soluble chelating agents are also useful in preparing the water-soluble precursors for the coprecipitation procedure, but they are more costly than lactic acid.
- Other water-soluble alpha-hydroxycarboxylic acids can be used as will be known to those skilled in the art.
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Abstract
Wet-chemical methods involving the use of water-soluble hydrolytically stable metal-ion chelate precursors and the use of a nonmetal-ion-containing strong base can be used in a coprecipitation procedure for the preparation of ceramic powders. Examples of the precipitants used include tetraalkylammonium hydroxides. A composition-modified barium titanate is one of the ceramic powders that can be produced. Certain metal-ion chelates can be prepared from 2-hydroxypropanoic acid and ammonium hydroxide.
Description
- The present application is a continuation of U.S. patent application Ser. No. 11/369,255, filed Mar. 7, 2006, entitled “METHOD FOR PREPARING CERAMIC POWDERS USING CHELATE PRECURSORS,” naming inventors Richard D. Weir and Carl W. Nelson, which application is incorporated by reference herein in its entirety.
- The present invention relates to methods for preparing ceramic powders, and particularly to wet-chemical processes using chelate precursors.
- Ceramic powders are used in the fabrication of numerous different types of devices including specialized mechanical components, coating for mechanical components, semiconductor devices, superconducting devices, device packaging, passive electronic components such as capacitors, and more sophisticated energy storage devices. Numerous different techniques exist for the synthesis and fabrication of ceramic powders including solid phase synthesis such as solid-solid diffusion, liquid phase synthesis such as precipitation and coprecipitation, and synthesis using gas phase reactants. Moreover, a host of related fabrication techniques can also be used including: spray drying, spray roasting, metal organic decomposition, freeze drying, sol-gel synthesis, melt solidification, and the like.
- Various advantages of wet-chemical methods used in the preparation of powders for the fabrication of ceramics have been well-known since the early 1950s. Pioneering work in this area has been done at the Massachusetts Institute of Technology, the National Bureau of Standards (now the National Institute of Standards and Technology), Philips Research Laboratories, and Motorola, Inc.
- Despite the advantages of wet chemical processes, the ceramics industry largely remains reluctant to employ these techniques. Conventional methods for preparing ceramic powders entail mechanical mixing of dry powders of water-insoluble carbonates, oxides, and sometimes silicates, where each constituent of the ceramic composition is carefully selected individually. For example, if the ceramic composition has nine constituents in solid solution, then correspondingly nine starting powders are selected in accordance with the amount of each required for the end product compound. The starting powders are very likely to have different median particle sizes and different particle size distributions. In an attempt to comminute the mixture of powders to a smaller, more uniform particle size and size distribution for each component, the powder mixture is placed in a ball mill and milled for several hours. The milling process generates wear debris from the ball mill itself and, the debris becomes incorporated in the powder mixture. Because of the often wide disparity in particle size among the various commercially available starting powders (and even significant variation in particle size of the same powder from lot to lot), an optimum result from ball milling rarely occurs, and a contamination-free product is never obtained.
- Moreover, additional processing steps are still required. Solid-solid diffusion at high temperature (but below the temperature at which sintering starts) of the ball-milled powder mixture is required to form a usable and, preferably, fully reacted homogeneous single powder. The finer each powder in the mixture is, the higher the particle surface-to-volume ratio is for each. This means that there is a greater surface area per unit weight of each powder for the solid-solid diffusion to occur. Moreover, longer times spent at high temperature (e.g., the calcining temperature) produce a more satisfactory end product. Homogeneity is improved by repeating several times the ball-milling and calcining steps in succession, each requiring several hours. Of course, this increases the amount of ball-milling wear debris added to the powder, thereby increasing the amount of contamination in the end ceramic product.
- Accordingly, it is desirable to have improved wet-chemical processing techniques to prepare ceramic powders for use in the fabrication of various different devices and materials.
- It has been discovered that wet-chemical methods involving the use of water-soluble hydrolytically stable metal-ion chelate precursors and the use of a nonmetal-ion-containing strong base can be used in a coprecipitation procedure for the preparation of ceramic powders. Examples of the precipitants used include tetraalkylammonium hydroxides. A composition-modified barium titanate is one of the ceramic powders that can be produced. Certain metal-ion chelates can be prepared from 2-hydroxypropanoic acid and ammonium hydroxide.
- In one embodiment in accordance with the invention a method is disclosed. A plurality of precursor materials are provided in solution. Each of the plurality of precursor materials in solution further comprises at least one constituent ionic species of a ceramic powder. At least one of the plurality of precursor materials in solution is a chelate solution. The plurality of precursor materials are combined in solution with a precipitant solution to cause coprecipitation of the ceramic powder in a combined solution. The ceramic powder is separated from the combined solution.
- In another embodiment in accordance with the invention, a substantially contaminant free ceramic powder produced by a process is disclosed. The process includes: providing a plurality of precursor materials in solution, combining the plurality of precursor materials in solution with a nonmetal-ion-containing strong base precipitant solution to cause coprecipitation of the ceramic powder in a combined solution; and separating the ceramic powder from the combined solution. Each of the plurality of precursor materials in solution further comprises at least one constituent ionic species of the ceramic powder. At least one of the plurality of precursor materials in solution is a chelate solution.
- The foregoing is a summary and thus contains, by necessity, simplifications, generalizations and omissions of detail; consequently, those skilled in the art will appreciate that the summary is illustrative only and is not intended to be in any way limiting. As will also be apparent to one of skill in the art, the operations disclosed herein may be implemented in a number of ways, and such changes and modifications may be made without departing from this invention and its broader aspects. Other aspects, inventive features, and advantages of the present invention, as defined solely by the claims, will become apparent in the non-limiting detailed description set forth below.
- A more complete understanding of the present invention and advantages thereof may be acquired by referring to the following description and the accompanying drawings, in which like reference numbers indicate like features.
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FIG. 1 is a flow chart illustrating ceramic powder processing techniques in accordance with the present invention. -
FIG. 2 is a flow chart illustrating chelate processing techniques in accordance with the present invention. - The following sets forth a detailed description of at least the best contemplated mode for carrying out the one or more devices and/or processes described herein. The description is intended to be illustrative and should not be taken to be limiting.
- The processes and techniques described in the present application can be utilized to prepare numerous different types of ceramic powders, as will be understood to those skilled in the art. Thus, although the present application emphasizes the use of these processes and techniques in the fabrication of dielectric materials for use in electrical energy storage devices (e.g., doped or composition-modified barium titanate), the same or similar techniques and processes can be used to prepare other ceramic powders, and those ceramic powders may find application in the manufacture of various components, devices, materials, etc.
- As noted in the aforementioned '609 patent application, high-permittivity calcined composition-modified barium titanate powders can be used to fabricate high quality dielectric devices. U.S. Pat. No. 6,078,494 (hereby incorporated by reference herein in its entirety) describes examples of various doped barium titanate dielectric ceramic compositions. More specifically, the '494 patent describes a dielectric ceramic composition comprising a doped barium-calcium-zirconium-titanate of the composition (Ba1-α-μ-νAμDνCaα)[Ti1-x-δ-μ′-ν′MnδA′μ′D′ν′Zrx]zO3, where A=Ag, A′=Dy, Er, Ho, Y, Yb, or Go; D=Nd, Pr, Sm, or Gd; D′=Nb or Mo, 0.10≦x≦0.25; 0≦μ≦0.01, 0≦μ′≦0.01, 0≦ν≦0.01, 0≦ν′≦0.01, 0≦δ≦0.01, and 0.995≦z≦0≦α≦0.005. These barium-calcium-zirconium-titanate compounds have a perovskite structure of the general composition ABO3, where the rare earth metal ions Nd, Pr, Sm and Gd (having a large ion radius) are arranged at A-sites, and the rare earth metal ions Dy, Er, Ho, Y, Yb and Ga (having a small ion radius) are arranged at B-sites. The perovskite material includes the acceptor ions Ag, Dy, Er, Ho, Y or Yb and the donor ions Nb, Mo, Nd, Pr, Sm and Gd at lattice sites having a different local symmetry. Donors and acceptors form donor-acceptor complexes within the lattice structure of the barium-calcium-zirconium-titanate according to the invention. The dielectric ceramic compositions described by the '494 patent are just some of the many types of ceramic compositions that can be fabricated using the processes and techniques of the present application.
- In the present application, chelates are used as precursors to one or more of the constituent components of a target ceramic powder. In general, chelation is the formation or presence of bonds (or other attractive interactions) between two or more separate binding sites within the same ligand and a single central atom. A molecular entity in which there is chelation (and the corresponding chemical species) is called a chelate. The terms bidentate (or didentate), tridentate, tetradentate . . . multidentate are often used to indicate the number of potential binding sites of the ligand, at least two of which are used by the ligand in forming a chelate.
- For example, various wet-chemical powder preparation techniques for composition-modified barium titanate are described below. The methods make use of aqueous solutions for some or all reactants to form by coprecipitation the desired powders. Furthermore, the approach extends the use of one or more chelates (preferably water-soluble or water stable) as precursors to several of the component metal ions comprising the constituents of the composition-modified barium titanate. A nonmetal-ion-containing strong base, e.g., selected from among tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide [(CH3)4NOH] in aqueous solution is used as the precipitant for the mixture of precursors in aqueous solution. The tetraalkylammonium hydroxides, unlike conventional strong bases, e.g., sodium and potassium hydroxides, do not introduce contamination metal ions, e.g., sodium and potassium ions, to the end product. Note that there are numerous organic compounds that are basic in pH, but the tetraalkylammonium hydroxides as a group are the only organic compounds that are strong bases, e.g., as strong as common ones: NaOH and KOH, which are inorganic compound bases.
- In wet-chemical methods for the preparation of ceramic powders by coprecipitation of a mixture of precursors from solution, small amounts of precipitant will typically be included within the micropores and nanopores of the product powder. Similarly, small amounts of precipitant will also be adsorbed onto the surface of product powder. Where strong bases such as sodium hydroxide or potassium hydroxide are used as the precipitant, a very large amount of DI water is consumed (typically in several successive washings of the precipitated powder) in the attempt to rid the product of the residual precipitant. This procedure is rarely completely successful, and thus some residual precipitant remains. Subsequent calcining in air of the powder product converts the residual sodium or potassium hydroxide (which upon exposure to ambient air is first converted to the carbonate by reaction with carbon dioxide in the ambient air) to the oxide, which by solid-solid diffusion becomes incorporated within the product as a constituent. For many applications, this additional constituent is an undesirable contaminant.
- This unwanted result can be circumvented by the use of any of the tetraalkylammonium hydroxides as the strong base. In the examples below, tetramethylammonium hydroxide is selected for the precipitant, but various other tetraalkylammonium hydroxides can be used. In principle, no washing of the precipitated powder is needed to remove residual precipitant. However, in some embodiments, a DI water washing step, or some other washing step, is performed. Thus, a solid-solid solution of water-soluble hydrated and chelated metal-ion species in their proportioned amounts is precipitated as an oxide (the composition-modified barium titanate) by the nonmetal-ion-containing tetramethylammonium hydroxide.
- During calcination in air of the product powder, the residuals: tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium 2-hydroxypropanate, ammonium hydroxide, ammonium nitrate, and ammonium 2-hydroxypropanate, are thermally decomposed and oxidized and thereby completely converted to gaseous products: H2O, NH3, CO, CO2, N2, O2, N2O, NO, and NO2. Another advantage of the use of a tetraalkylammonium hydroxide as the precipitant is the amount of DI water required for washing is reduced or, in principle, no DI water washing step is needed since the residuals are completely converted to gaseous products.
- Preparation of the high-permittivity calcined composition-modified barium titanate powder in this manner yields high purity powders with narrow particle-size distribution. The microstructures of ceramics formed from these calcined wet-chemical-prepared powders are uniform in grain size and can also result in smaller grain size. Electrical properties are improved so that higher relative permittivities and increased dielectric breakdown strengths can be obtained. Further improvement can be obtained by the elimination of voids within the sintered ceramic body with subsequent hot isostatic pressing.
- In one embodiment, at least one, but not necessarily all of the precursors are chelates. A solution of the precursors: Ba(NO3)2, Ca(NO3)2.4H2O, Nd(NO3)3.6H2O, Y(NO3)3.4H2O, Mn(CH3COO)2.4H2O, ZrO(NO3)2, and [CH3CH(O—)COONH4]2Ti(OH)2, is formed in deionized water. In this example the Ti chelate [CH3CH(O—)COONH4]2Ti(OH)2 is used. As needed, the solution can be mixed and/or heated (e.g., heated to 80° C.) and is made in the proportionate amount in weight percent for each of the precursors as shown in Table 1.
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TABLE 1 Metal element Atom fraction At Wt Product Wt % Ba 0.9575 137.327 131.49060 98.52855 Ca 0.0400 40.078 1.60312 1.20125 Nd 0.0025 144.240 0.36060 0.27020 Total 1.0000 100.00000 Ti 0.8150 47.867 39.01161 69.92390 Zr 0.1800 91.224 16.42032 29.43157 Mn 0.0025 54.93085 0.13733 0.24614 Y 0.0025 88.90585 0.22226 0.39839 Total 1.0000 100.00000 - A separate solution of tetramethylammonium hydroxide, possibly in excess of the amount required, is made in deionized water free of dissolved carbon dioxide (CO2) and heated to 80°-85° C. Table 2 illustrates example calculations for the minimum amount of tetramethylammonium hydroxide needed.
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TABLE 2 Precursor FW Wt % Wt %/FW Mult. Mol of base Ba(NO3)2 261.34 48.09898 0.184048 2 0.368095 Ca(NO3)2•4H2O 236.15 1.81568 0.007689 2 0.015377 Nd(NO3)3•6H2O 438.35 0.21065 0.000481 3 0.001442 Y(NO3)3•4H2O 346.98 0.15300 0.000441 3 0.001323 Mn(CH3COO)2•4H2O 245.08 0.10806 0.000441 2 0.000882 ZrO(NO3)2 231.23 7.34097 0.031747 2 0.063495 [CH3CH(O—)COONH4]2Ti(OH)2 294.08 42.27266 0.143745 2 0.287491 Total 100.00000 0.738105 - Since the formula weight (FW) of tetramethylammonium hydroxide is 91.15, the weight of the minimum amount of tetramethylammonium hydroxide needed for 100 g of precursor mixture is (0.738105 mol)×(91.15 g/mol)=67.278 g.
- The two solutions are mixed by pumping the heated ingredient streams simultaneously through a coaxial fluid jet mixer. A slurry of the coprecipitated powder is produced and collected in a drown-out vessel. The coprecipitated powder is refluxed in the drown-out vessel at 90°-95° C. for 12 hr and then filtered, optionally deionized-water washed, and dried. Alternatively, the powder can be collected by centrifugal sedimentation, or some other technique. The subsequent powder is calcined under suitable conditions, e.g., at 1050° C. in air in an appropriate silica glass (fused quartz) tray or tube.
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FIG. 1 is a flow chart illustrating ceramic powder processing techniques in accordance with the present invention. The process begins at 100. Inoperation 110, the appropriate precursor materials, e.g., chelates and other precursors, are provided in solution (110). Next a suitable precipitant is provided (120). The two materials are then combined to form the desired ceramic powder via a coprecipitation reaction (130). Once the ceramic powder is formed, it can be separated from the solution in which it is formed (140) using suitable separation devices and techniques. Other post processing steps can be employed including: washing the ceramic powder (150), drying the ceramic powder (160), and calcining the ceramic powder (170). The process terminates at 180. The resulting ceramic powder can then be used in the fabrication of numerous different devices. - In other examples, multiple chelate precursors are used in a similar process. In the case of Zr, various Zr compounds can be used as precursors. As noted in the example above, oxozirconium(IV) nitrate (zirconyl nitrate) [ZrO(NO3)2] can be used. However, ZrO(NO3)2 requires a relatively low pH of about 1.5, provided by an added acid solution, e.g., nitric acid (HNO3), to prevent hydrolysis. An alternative approach for the precursor is the use of the hydrolytically stable chelate: zirconium(IV) bis(ammonium 2-hydroxypropanato)dihydroxide [zirconium(IV) bis(ammonium lactato)dihydroxide]{[CH3CH(O—)COONH4]2Zr(OH)2} aqueous solution, which is stable over the pH range from 6 to 8 up to 100° C. Although this compound is not readily available commercially, it can be prepared from any of the alkyl oxides of zirconium(IV). Any of these zirconium(IV) alkyl oxides serve as an intermediate from the zirconium tetrachloride [zirconium(IV) chloride](ZrCl4) source in the preparation of all other zirconium(IV) compounds. Examples of commercially available zirconium(IV) alkyl oxides include: the ethoxide [Zr(OCH2CH3)4], the propoxide [Zr(OCH2CH2CH3)4], the isopropoxide {Zr[OCH(CH3)2]4}, the butoxide [Zr(OCH2CH2CH2CH3)4], and the tert-butoxide {Zr[OC(CH3)3]4}.
- Of these examples, zirconium(IV) isopropoxide (tetra-2-propyl zirconate) is likely to be the lowest cost because of the very large volume of 2-propanol (isopropyl alcohol) produced by several manufacturers. These alkyl oxides are all soluble in alcohols, but they all hydrolyze in the presence of moisture. However, by reaction with 2-hydroxypropanoic acid (2-hydroxypropionic acid, lactic acid) [CH3CH(OH)COOH], 85 wt % in aqueous solution, followed with ammonium hydroxide (NH4OH), 28 wt % ammonia (NH3) in water, the water-stable zirconium(IV) chelate is prepared. The other reaction product is the alcohol from which the zirconium(IV) alkyl oxide was originally made in the reaction with the zirconium tetrachloride source. This alcohol is recoverable by fractional distillation, membrane per vaporization, or the like.
- The suitable water-stable titanium(IV) chelate: titanium(IV) bis(ammonium 2-hydroxypropanato)dihydroxide [titanium(IV) bis(ammonium lactato)dihydroxide]{[CH3CH(O—)COONH4]2Ti(OH)2}, is commercially available from, for example, DuPont with trade name Tyzor® LA. It can be prepared from any of the alkyl oxides of titanium(IV). Readily available commercial titanium(IV) alkyl oxides include the following: the methoxide [Ti(OCH3)4], the ethoxide [Ti(OCH2CH3)4], the propoxide [Ti(OCH2CH2CH3)4], the isopropoxide {Ti[OCH(CH3)2]4}, the butoxide [Ti(OCH2CH2CH2CH3)4], and the tert-butoxide {Ti[OC(CH3)3]4}. Of these, titanium(IV) isopropoxide (tetra-2-propyl titanate) is likely to be the least expensive. By similar preparation methods as those described above for the conversion of an alkyl oxide of zirconium(IV) to the water-stable chelate, an alkyl oxide of titanium(IV) can be converted to the water-stable titanium(IV) chelate.
- Water-soluble and/or stable chelates of manganese(II), yttrium(III), lanthanum(III), neodymium(III), and several other metal ions can be prepared with the use of 2-hydroxypropanoic acid (lactic acid) and ammonium hydroxide. The most convenient starting compounds are commercially available water-insoluble carbonates of these metal ions, because they more readily react with 2-hydroxypropanoic acid aqueous solution to form the very stable water-soluble (ammonium 2-hydroxypropanato)metal-ion chelates. Water-insoluble oxides can also be used as starting compounds, although they are not as quickly reactive.
- For example, a manganese chelate can be produced when the manganese(II) carbonate (MnCO3) is converted to bis(ammonium 2-hydroxypropanato) manganese(II) (i.e., ammonium manganese (II) 2-hydroxypropanate) {Mn[CH3CH(O—)COONH4]2}, as shown in the following reaction equations:
- Similarly, an yttrium chelate can be produced by converting yttrium(III) carbonate[Y2(CO3)3] to tris(ammonium 2-hydroxypropanato)yttrium(III) (i.e., ammonium yttrium (III) 2-hydroxypropanate) {Y[CH3CH(O—)COONH4]3} as shown in the following reaction equations:
- A lanthanum chelate can be produced by converting lanthanum(III) carbonate [La2(CO3)3] to tris(ammonium 2-hydroxypropanato)lanthanum(III) (i.e., ammonium lanthanum (III) 2-hydroxypropanate) {La[CH3CH(O—)COONH4]3} as shown in the following reaction equations:
- A neodymium chelate can be produced by converting neodymium(III) carbonate[Nd2(CO3)3] to tris(ammonium 2-hydroxypropanato)neodymium(III) (i.e., ammonium neodymium (III) 2-hydroxypropanate) {Nd[CH3CH(O—)COONH4]3} as shown in the following reaction equations:
- In general, nitrate compounds have the highest solubilities in water, as concentration in moles per liter of solution at 20° C., i.e., molar, and moles per 1000 grams of water at 20° C., i.e., molal, of any salt. Uniquely, there are no water-insoluble nitrates. Since the nitrate anion[(NO3)−] does not interfere with the formation of the chelate, the nitrates, too, can be used as starting compounds. The nitrates are readily available commercially. Accordingly the first reaction of 2-hydroxypropanoic acid with the oxo-metal-ion and metal-ion species as indicated above are as follows:
- Then with ammonium hydroxide the reaction is:
- The next-step reactions with ammonium hydroxide are the same as those given above.
- In the preparation of the hydrolytically stable chelates, at the first step of the reaction of either (1) the titanium(IV) and zirconium(IV) alkyl oxides, or (2) the metal-ion(II) and metal-ion(III) carbonates with the 2-hydroxypropanoic acid aqueous solution, the more acidic hydrogen ion of the carboxyl group (COOH) splits off first to form (1) the alcohol from which the alkyl oxide was made, or (2) water and carbon dioxide. With addition of the weak base ammonium hydroxide, the hydrogen atom of the hydroxyl group (OH) splits off as a hydrogen ion to form water and the ammonium ion[(NH4)+] salt of the 2-hydroxypropanate chelate. The hydrogen atom of the hydroxyl group (OH) on the carbon atom (the 2-position or alpha-position) adjacent to the carbonyl group (C═O) is relatively acidic forming a hydrogen ion splitting off with sufficiently basic conditions provided by the addition of the ammonium hydroxide aqueous solution. Additionally, the presence of the hydroxyl group in the 2-position to the carboxylic acid group results in an increased acidity of the latter.
-
FIG. 2 is a flow chart illustrating chelate processing techniques in accordance with the present invention. The process begins at 200. Inoperation 210, the appropriate starting material, e.g., a metal alkyl oxide or a metal-ion carbonate is selected. The material is selected based on the metal ion it will ultimately provide to a resulting ceramic powder. Next, the starting material is reacted with an appropriate chelating agent (220). For example, the chelating agent can be provided in aqueous solution and combined with the starting material in a suitable reaction vessel. The combined solution is also reacted with a suitable weak base (230) to complete aspects of the reaction. The process terminates at 240. - As a chelating agent, 2-hydroxypropanoic acid is a bidentate ligand, since it can bond to a central metal cation via both oxygen atoms of the five-sided ring. Since the outer cage has two or three anion groups, the total negative charge exceeds the positive charge of the central metal cation, and the chelate is an anion with the ammonium cations[(NH4)+] for charge balance Ammonium ion salts have high water solubilities at neutral and near neutral pH conditions.
- Use of hydrolytically stable chelates in this regard is extremely versatile, even though many of the chelate precursors are not readily available commercially. In particular, such chelates have applicability to all the metal ions of the Periodic Table except, those of Groups IA and perhaps IIA, for coprecipitation procedures in the preparation of ceramic powders. Alkaline metal ions do not form complexes and alkaline earth metal ions (Group IIA) form rather weak complexes with 2-hydroxypropanoic acid.
- In general all the water-soluble 2-hydroxycarboxylic acids (alpha-hydroxycarboxylic acids) form considerably stronger complex molecular ions with most metals ions, through bidentate chelation involving both functional donor groups, than do the corresponding simple carboxylic acids. This feature makes possible in aqueous solution at neutral and near neutral pH hydrolytically stable mixtures of these chelates involving two to nearly all metal ions and oxometal ions in any mole ratio of any one to any other. Moreover, it is important to note that the ammonium compounds: nitrates, 2-hydroxproanates, etc., thermally decompose and oxidize away as gases, so that they do not have to be washed away from the product precipitate. Numerous variations on these chelate formation techniques will be known to those skilled in the art.
- Table 3 illustrates an example composition modified barium titanate compound formed using the above described chelate precursors. In this example, the formula weight of the resulting compound is 237.24.
-
TABLE 3 Precursor FW Mol Frac. Product Wt % Ba(NO3)2 261.34 0.47875 125.116525 44.450 Ca(NO3)2•4H2O 236.15 0.02000 4.723 1.67 Nd[CH3CH(O—)COONH4]3 465.57 0.00125 0.5819625 0.207 [CH3CH(O—)COONH4]2Ti(OH)2 294.08 0.40750 119.8376 42.575 [CH3CH(O—)COONH4]2Zr(OH)2 337.44 0.09000 30.36964375 10.789 Mn[CH3CH(O—)COONH4]2 269.15 0.00125 0.3364375 0.119 Y[CH3CH(O—)COONH4]3 410.23 0.00125 0.5127875 0.182 Total 281.4779125 100.00 - In one embodiment, the two ingredient streams, one containing the aqueous solution of all the metal-ion compound precursors, and the other containing the aqueous solution of the tetramethylammonium hydroxide strong base, are reacted together simultaneously and continuously in a fluid jet column that provides a high turbulence energy environment. The total volume for the saturated or near-saturated commercially available and specially manufactured aqueous solutions of the precursors is typically four times that of the 25 wt % tetramethylammonium hydroxide aqueous solution. There are two options in this case for the jet fluid column: (1) adjust the former to a flow rate four times that of the latter, keeping the stream velocities equal by having the applied driving pressure to the two streams the same, but with the cross-sectional area of the nozzle of the former four times that of the latter; and (2) dilute one volume of the latter by three volumes of DI water, thereby lowering the concentration from 25 wt % to 6.25 wt % With equal volumes for both streams, the nozzles are alike, the flow rates are equal, and the applied driving pressure is the same. The amount of liquid processed is 60 percent greater than that of the first option, however. The first has the substantial advantage of minimizing the amount of liquid handling and the usage of DI water. There is no technical advantage in product quality of one over the other. Examples of such fluid jet column mixing techniques are described in U.S. Pat. No. 5,087,437 (hereby incorporated by reference herein in its entirety).
- In other embodiments, other techniques and devices can be used to combine the ingredient streams such as, for example: (1) pouring one solution in one vessel into the other solution in another vessel and using mechanical or ultrasonic mixing, and (2) metering the solution in one vessel at some given flow rate into the other solution in another vessel and using mechanical or ultrasonic mixing. Numerous other mixing techniques will be known to those skilled in the art.
- The resulting slurry can be refluxed as appropriate. Next, the slurry is transferred to a filtration or separation device. The separating of the precipitate from the liquid phase and the isolation of precipitate can be carried out using a variety of devices and techniques including: conventional filtering, vacuum filtering, centrifugal separation, sedimentation, spray drying, freeze drying, or the like. The filtered powder can then undergo various washing, drying, and calcining steps as desired.
- The advantages of wet-chemical methods in the preparation of powders for fabricating oxide ceramics of technical significance are enlarged in scope with the use, as precursors, of hydrolytically stable chelates of metal ions or oxometal ions at neutral and near-neutral pH, and with the use, as the strong-base precipitating agent such as a tetraalkylammonium hydroxide aqueous solution. A preferred chelating agent is the very water-soluble 2-hydroxypropanoic acid (i.e., lactic acid) followed by neutralization with the weak-base ammonium hydroxide aqueous solution, both of which are produced in high volume and are thus relatively low in cost.
- In the examples illustrated above, various compounds, solutions, temperature ranges, pH ranges, quantities, weights, and the like are provided for illustration purposes. Those having skill in the art will recognize that some or all of those parameters can be adjusted as desired or necessary. For example, other acids can be used in place of 2-hydroxypropanoic acid as a chelating agent. Alpha-hydroxycarboxylic acids having at least the same five-sided ring including the carbonyl group and having the two oxygen atoms of the ring bonding to the central metal ion or oxometal ion can be used and include:
- 2-hydroxyethanoic acid (i.e., glycolic acid, hydroxyacetic acid) [(OH)CH2COOH];
- 2-hydroxybutanedioic acid (i.e., malic acid, hydroxysuccinic acid) [HOOCCH2CH(OH)COOH];
- 2,3-dihydroxybutanedioic acid (i.e., tartaric acid) [HOOCCH(OH)CH(OH)COOH];
- 2-hydroxy-1,2,3-propanetricarboxylic acid (i.e., citric acid) [(OH)C(COOH)(CH2COOH)2];
- 2-hydroxybutanoic acid [CH3CH2CH(OH)COOH];
- 2-hydroxypentanoic acid [CH3(CH2)2CH(OH)COOH]; and
- 2-hydroxyhexanoic acid (i.e., 2-hydroxycaproic acid) [CH3(CH2)3CH(OH)COOH].
- These water-soluble chelating agents are also useful in preparing the water-soluble precursors for the coprecipitation procedure, but they are more costly than lactic acid. Other water-soluble alpha-hydroxycarboxylic acids can be used as will be known to those skilled in the art.
- Although the present invention has been described with respect to specific embodiments thereof, various changes and modifications may be suggested to one skilled in the art and it is intended that the present invention encompass such changes and modifications as fall within the scope of the appended claims.
Claims (27)
1. A method of forming a composition-modified barium titanate ceramic powder, the method comprising:
forming an aqueous solution from precursor materials comprising barium nitrate, calcium nitrate, a titanium alpha-carboxylic acid chelate, and a plurality of water-stable constituent ion chelates, each water-stable constituent ion chelate of the plurality of water-stable constituent ion chelates including an ionic species and a chelating agent, the ionic species including zirconium, manganese, yttrium, lanthanum, or neodymium, the chelating agent including 2-hydroxypropanoic acid or an alpha-hydroxycarboxylic acid selected from the group consisting of 2-hydroxyethanoic acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid;
combining the plurality of precursor materials in the aqueous solution with a precipitant solution to coprecipitate of primary particles in a combined solution, the precipitant solution comprising tetraalkylammonium hydroxide, the primary particles comprising the barium, calcium, titanium, and each ionic species of the plurality of water stable constituent ion chelates;
refluxing the coprecipitated primary particles;
separating the refluxed primary particles from the combined solution; and
calcining the separated primary particles, the primary particles forming a ceramic powder comprising composition-modified barium titanate having a perovskite structure.
2. The method of claim 1 , wherein the ionic species of the plurality of water-stable constituent ion chelates further include Pr, Sm, Gd, Dy, Er, Ho, Yb, Ga, Ag, Dy, Er, Ho, Nb, or Mo.
3. The method of claim 1 , wherein the tetraalkylammonium hydroxide is tetramethylammonium hydroxide.
4. The method of claim 1 , wherein the separating further comprises at least one of filtering the primary particles from the combined solution; centrifuging the combined solution; sedimenting the combined solution; spray drying the combined solution; or freeze drying the combined solution.
5. The method of claim 1 , further comprising at least one of washing the separated primary particles; drying the separated primary particles; or sintering the separated primary particles.
6. The method of claim 1 , wherein at least one ionic species is derived from a metal alkyl oxide.
7. The method of claim 1 , wherein at least one ionic species is derived from a metal ion carbonate.
8. The method of claim 1 , wherein the composition-modified barium titanate is barium-calcium-zirconium-titanate.
9. The method of claim 1 , wherein the composition-modified barium titanate is (Ba1-α-μ-νAμDνCaα)[Ti1-x-δ-μ′-ν′MnδA′μ′D′ν′Zrx]zO3, where A=Ag or La, A′=Dy, Er, Ho, Y, Yb, or Ga; D=Nd, Pr, Sm, or Gd; D′═Nb or Mo, 0.10≦x≦0.25; 0≦μ≦0.01, 0≦μ′≦0.01, 0≦ν≦0.01, 0≦ν′≦0.01, 0≦δ≦0.01, and 0.995≦z≦0≦α≦0.005.
10. The method of claim 1 , wherein refluxing includes refluxing at 90° C. to 95° C.
11. A method of forming a ceramic powder for use in a dielectric material, the method comprising:
for each constituent metal species selected from zirconium, manganese, yttrium, lanthanum, or neodymium:
mixing a solution comprising a constituent metal ion or oxometal ion and a solution comprising an alpha-hydroxycarboxylic acid to form a constituent metal ion chelate or an oxometal ion chelate; and
stabilizing the metal ion chelate or the oxometal ion chelate by adding ammonium hydroxide, the stabilized metal ion chelate or the stabilized oxometal ion chelate remaining in solution;
forming a solution including barium nitrate, calcium nitrate, a stabilized titanium ion chelate, and each of the stabilized metal ion chelates or the stabilized oxometal ion chelate;
precipitating primary particles by adding to the solution tetraalkylammonium hydroxide, the primary particles comprising barium, calcium, titanium, and the constituent metal species;
refluxing the primary particles; and
calcining the primary particles, the calcined primary particles forming the ceramic powder comprising composition-modified barium titanate having a perovskite structure.
12. The method of claim 11 , wherein the tetraalkylammonium hydroxide comprises tetramethylammonium hydroxide.
13. The method of claim 11 , further comprising separating the primary particles of the ceramic powder from solution prior to calcining.
14. The method of claim 11 , wherein refluxing includes refluxing at 90° C. to 95° C.
15. The method of claim 11 , wherein the alpha-hydroxycarboxylic acid is selected from the group consisting of 2-hydroxyethanoic acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid.
16. The method of claim 15 , wherein the alpha-hydroxycarboxylic acid is 2-hydroxy-1,2,3-propanetricarboxylic acid.
17. The method of claim 11 , wherein the alpha-hydroxycarboxylic acid is 2-hydroxypropanoic acid.
18. The method of claim 11 , wherein the composition-modified barium titanate is barium-calcium-zirconium-titanate.
19. The method of claim 11 , wherein the composition-modified barium titanate is (Ba1-α-μ-νAμDνCaα)[Ti1-x-δ-μ′-ν′MnδA′μ′D′ν′Zrx]zO3, where A=Ag, A′=Dy, Er, Ho, Y, Yb, or Go; D=Nd, Pr, Sm, or Gd; D′=Nb or Mo, 0.10≦x≦0.25; 0≦μ≦0.01, 0≦μ′≦0.01, 0≦ν≦0.01, 0≦ν′≦0.01, 0≦δ≦0.01, and 0.995≦z≦0≦α≦0.005.
20. A method of forming a ceramic powder for use in a dielectric material, the method comprising:
individually forming each of a plurality of stabilized metal ion chelates or stabilized oxometal ion chelates, wherein each of the stabilized metal ion chelates or oxometal ion chelates is formed from a constituent ionic species of a plurality of constituent ionic species, ammonium hydroxide, and a chelate agent, the plurality constituent ionic species including zirconium, manganese, yttrium, lanthanum, and neodymium, the chelate agent comprising 2-hydroxypropanoic acid or an alpha-hydroxycarboxylic acid selected from the group consisting of 2-hydroxyethanoic acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid;
forming a first solution from barium nitrate, calcium nitrate, a stabilized titanium ion chelate, and the plurality of stabilized metal ion chelates or oxometal ion chelates;
precipitating primary particles including barium, titanium and the plurality of constituent ionic species by adding a second solution comprising tetraalkylammonium hydroxide;
refluxing the primary particles in solution;
separating the primary particles from solution; and
calcining the primary particles, the calcined primary particles forming the ceramic powder comprising composition-modified barium titanate having a perovskite structure.
21. The method of claim 20 , wherein the tetraalkylammonium hydroxide comprises tetramethylammonium hydroxide.
22. The method of claim 20 , wherein refluxing the precipitated primary particles includes refluxing at 90° C. to 95° C.
23. The method of claim 20 , wherein the composition-modified barium titanate is barium-calcium-zirconium-titanate.
24. The method of claim 20 , wherein the composition-modified barium titanate is (Ba1-α-μ-νAμDνCaα)[Ti1-x-δ-μ′-ν′MnδA′μ′D′ν′Zrx]zO3, where A=Ag, A′=Dy, Er, Ho, Y, Yb, or Ga; D=Nd, Pr, Sm, or Gd; D′=Nb or Mo, 0.10≦x≦0.25; 0≦μ≦0.01, 0≦μ′≦0.01, 0≦ν≦0.01, 0≦ν′≦0.01, 0≦δ≦0.01, and 0.995≦z≦0≦α≦0.005.
25. A method of forming a ceramic powder for use in a dielectric material, the method comprising:
forming a first solution from barium nitrate, calcium nitrate, a stabilized titanium ion chelate, and a plurality of stabilized metal ion chelates or oxometal ion chelates, each of the stabilized metal ion chelates or oxometal ion chelates is formed from a constituent ionic species of the ceramic powder, a hydroxide, and a chelate agent, the plurality of water-stable constituent ion chelates including the ionic species zirconium, manganese, yttrium, lanthanum, and neodymium, the chelate agent comprising 2-hydroxypropanoic acid or an alpha-hydroxycarboxylic acid selected from the group consisting of 2-hydroxyethanoic acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, and 2-hydroxyhexanoic acid;
precipitating primary particles, the primary particles including barium, titanium and the constituent ionic species by adding a second solution comprising tetraalkylammonium hydroxide;
refluxing the primary particles in solution;
separating the primary particles from solution; and
calcining the primary particles, the calcined primary particles forming the ceramic powder comprising composition-modified barium titanate having a perovskite structure.
26. The method of claim 25 , wherein the composition-modified barium titanate is barium-calcium-zirconium-titanate.
27. The method of claim 25 , wherein the composition-modified barium titanate is (Ba1-α-μ-νAμDνCaα)[Ti1-x-δ-μ′-ν′MnδA′μ′D′ν′Zrx]zO3, where A=Ag, A′=Dy, Er, Ho, Y, Yb, or Go; D=Nd, Pr, Sm, or Gd; D′=Nb or Mo, 0.10≦x≦0.25; 0≦μ≦0.01, 0≦μ′≦0.01, 0≦ν≦0.01, 0≦ν′≦0.01, 0≦δ≦0.01, and 0.995≦z≦0≦α≦0.005.
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Also Published As
Publication number | Publication date |
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US20070148065A1 (en) | 2007-06-28 |
EP1999283A4 (en) | 2011-09-21 |
EP1999283A2 (en) | 2008-12-10 |
CA2643897A1 (en) | 2007-09-13 |
WO2007103421A2 (en) | 2007-09-13 |
US7914755B2 (en) | 2011-03-29 |
WO2007103421A3 (en) | 2008-06-12 |
JP2009528974A (en) | 2009-08-13 |
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