CN1059179C - 金属铌酸盐和／或钽酸盐，它们的制备和由它们形成的钙钛矿 - Google Patents
金属铌酸盐和／或钽酸盐，它们的制备和由它们形成的钙钛矿 Download PDFInfo
- Publication number
- CN1059179C CN1059179C CN95119973A CN95119973A CN1059179C CN 1059179 C CN1059179 C CN 1059179C CN 95119973 A CN95119973 A CN 95119973A CN 95119973 A CN95119973 A CN 95119973A CN 1059179 C CN1059179 C CN 1059179C
- Authority
- CN
- China
- Prior art keywords
- metal
- pmn
- iii
- additive
- oxide
- 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.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims description 18
- 239000010955 niobium Substances 0.000 claims description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 6
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical group [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 claims description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 46
- 239000000919 ceramic Substances 0.000 description 19
- 238000005245 sintering Methods 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- BJXXCWDIBHXWOH-UHFFFAOYSA-N barium(2+);oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ta+5].[Ta+5].[Ta+5].[Ta+5] BJXXCWDIBHXWOH-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- PYLYNBWPKVWXJC-UHFFFAOYSA-N [Nb].[Pb] Chemical compound [Nb].[Pb] PYLYNBWPKVWXJC-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
- C01B13/185—Preparing mixtures of oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
-
- 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
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
通式为Me(Ⅱ)A2O6或Me(Ⅲ)AO4的高活性金属铌酸盐和/或金属钽酸盐，及其制备方法，以及对它们进一步处理以形成通式为X(B′B″O3)的钙钛矿的方法以及由本发明所提供的这些钙钛矿，式中X代表Pb和/或Ba，B′代表Mg，Fe，Co，Ni，Cr，Mn，Cd，Ti，Zr和/或Zn，B″代表Nb和/或Ta。向该铌酸盐/钽酸盐中提供0.1-20mol%的Li，Na和/或K的添加剂。
Description
本发明涉及通式为Me(II)A2O6或Me(III)AO4的高活性金属铌酸盐和/或金属钽酸盐，其中A代表Nb和/或Ta，Me(II)代表二价的Mg，Fe，Co，Ni，Cr，Mn，Cd和/或Zn，Me(III)代表III价的Fe，Co，Cr和/或Mn，涉及它们的制备方法，还涉及对它们进行处理以形成通式为X(B′B″)O3的钙钛矿的方法以及这些钙钛矿，其中X代表Pb和或/Ba，B′代表Mg，Fe，Co，Ni，Cr，Mn，Cd，Ti，Zr和/或Zn，B″代表Nb和/或钽。
金属铌酸盐和/或金属钽酸盐的应用包括它们作为制备多元钙钛矿的原料，多元钙铁矿可用作电子陶瓷的原料。由于它们的介电常数高，电致伸缩系数大而且品质极高—特别是在钽酸盐的情况下一金属铌酸铅或金属铌酸钡和/或钽酸钡在电子陶瓷中起到越来越重要的作用，这些作用包括它们是生产陶瓷电容器，电致伸缩陶瓷(致动器)，压电陶瓷和微波陶瓷(例如，共振器)的主要原料。这类具有钙钛矿结构的化合物对应于通式X(B′B′)O3，式中X代表Ba和Pb，B′代表Mg，Fe，Co，Ni，Cr，Mn，Cd，Cu，Zn，B″代表Nb和Ta(Appl.phys.lett.，10(5)，163-165 1967)。
已知有好几种方法可用于制备含有VB族过渡金属(Ta和Nb)的多元铁电钙钛矿。
从J.Amer.Ceram.Soc.71(5)，C-250到c-251(1988)中已知将氧化物混合，而后在很高的烧结温度下进行固相反应。应用该陶瓷方法，制备含有大于80％的钙钛矿相的纯相钙钛矿是极困难的。在这一固相反应期间，必然出现稳定的烧绿石相，它明显损害所产生的电子陶瓷的性能。
J Ceram Soc.67(5)311-314(1984)公开了在固相反应中Nb2O5与例如Mgo的一个初始反应，在随后与PbO的反应中获得了几乎是纯相的钙钛矿，该过程按下列方程式进行：
(I)
(II)
由于在初始的形成铌铁矿的反应中的高温，在1000℃下从上述混合氧化物仅获得一般活性的铌酸镁，这样与Pbo的后序反应只有在较高温度下(大于800℃)才会获得成功。在进一步处理过程中，该用陶瓷方法制备的钙钛矿粉末只能在更高温度下烧结。为了同时获得好的介电性能，此时的烧结温度必须至少为1,200℃。
已证明用湿化学方法制备钙钛矿是有好处的。因而在J.Amceram.soc 72(8).1335-1357(1989)中描述了醇盐混合物水解，在公开的欧洲专利申请294991中描述了从酒精草酸溶液中共沉淀。从advances in ceramics，Vol.21，91-98(1987)中可以获知对凝胶的煅烧过程，而该凝胶是通过加入H2O2和柠檬酸从NbCl2或Nb(OR)5和金属盐预先制得的。通常，湿化学方法产生活性很高的中间产物，它们甚至在低温下也会反应形成所期望的钙钛矿。此外，与用陶瓷方法制备的粉末相比，这些很细的粉末的烧结性能也明显改善。但是为了在用湿化学方法制备的这些粉末中也获得高的介电常数，不得不在1000℃以上的高温下进行烧结。此外，这些湿化学方法是很不经济的。因此，例如，醇盐法具有制备和处理原料很困难的缺点。
为了获得低温烧结(但仍然为1,000℃)同时室温介电常数高的材料，人们已经开发了一系列配方，这些配方除了主要材料PMN外，还含有伴随的各种其它化合物。因而在US4287075中公开了一个由铌酸铅铁，铌酸铅镁和钨酸铅镁组成的配方，该配方中如果有必要还含有另外的添加剂，比如铌酸铅镁，氧化锂、氧化铬，和/或氧化铈。公开的日本专利申请57-208004描述了一种由铌酸铅镁，钛酸镉，钨酸铅铁组成的组合物，该组合物还含有添加剂氧化镁，氧化铈，氧化铬和/或氧化钴。根据US5011803，除了铌酸铅镁以及进一步的添加剂，比如氧化隔，氧化钛，氧化铈和/或氧化锰外，也使用了铌酸铅铁和钨酸铅铁。向该总物料中加入另外2％的烧结剂。所有上述材料都是主要材料PMN的存在量少于95％(重量)的陶瓷组合物。
添加剂，如其它钙钛矿化合物，掺杂剂和/或烧结剂或多或少地改变了纯钙钛矿化合物，如铌酸铅镁，或钽酸钡镁的性能。因而，例如，上述添加剂能大大地改变材料的居里温度和工作温度。化合物，如铌酸铅铁会导致耐绝缘性的降低而钨酸铅镁和烧结剂会降低介电常数，与此同时除了所期望的钙钛矿外还可能出现杂质相。向纯钙钛矿系统提供的添加剂数量越多，为了获得均匀的混合物所消耗的物力就变得越费劲和越大。所有这些统统会导致介电性能变次，所以纯材料的潜在性能并没有得到充分利用。
因此，本发明的目的是提供高活性的金属铌酸盐和/或金属钽酸盐，它们可以进一步被处理以获得介电性能良好的低温烧结陶瓷。
已发现了满足所有这些要求的产物。它们是高活性的金属铌酸盐和/或金属钽酸盐，其通式为Me(II)A2O6或Me(III)AO4，式中A代表Nb或Ta，MC(II)代表二价的Mg，Fe，Co，Ni，Cr，Mn，Cd，和/或Zn，Me(III)代表三价的Fe，Co，Cr和/或Mn。这些产物含有比例为0.1-20mol-％的Li，Na，和/或K添加剂。在铌酸镁的情况下，该添加剂优选地由铌酸锂组成。
本发明也提供了一种制备本发明产物的方法。该方法是一种通过将相应的金属氧化物与铌组分和/或钽组分在一起湿混、干燥，和煅烧来制备金属铌酸盐和/或金属钽酸盐的方法，其中所用的铌组分和/或钽组分是水合氧化铌和/或水合氧化钽的形式。
可预先和/或在湿混期间引入该添加剂。用在这方面的Li，Na，和/或K优选地以它们的盐，氢氧化物，和/或氧化物的形式加入，它们可以单独一种或混合几种加入。加入铌酸锂和/或钽酸锂特别有好处，以盐，氢氧化物和/或氧化物的形式加入锂，以水合氧化铌和/或水合氧化钽的形式加入铌组分和/或钽组分。
利用上述方法，通过搅拌器，无需研磨工艺就能很容易地制备其中非常均匀地分布掺杂剂的均匀混合物。特别适用的是湿混5-90分钟。当所用的金属组分和掺杂剂是碳酸盐，碳酸氢盐，氢氧化物和/或氧化物时，附加的干扰阴离子不会污染最终产物。在400℃-1200℃，优选地是500℃-1,000℃的温度下煅烧干燥混合物15分钟-6小时。
本发明也提供了对金属铌酸盐和/或金属钽酸盐进一步的处理，以形成通式为X(B′B″)O3的钙钛矿相，式中，X代表Pb和/或Ba，B′代表Mg，Fe，Co，Ni，Cr，Mn，Cd，Ti，Zr和/或Zn，B″代表Nb和/或Ta。
令人惊奇的是，发现甚至在很低的温度下本发明的掺杂的金属铌酸盐和/或金属钽酸盐也能与铅组分反应。因此，例如，向其中加入了Li，Na，和/或K的铌酸镁，在与铅组分(Pbo或Pb3O4)混合后，在600℃就已经反应形成了所期望的钙钛矿。在650℃的煅烧温度下钙钛矿相的比例已经达到90％。根据资料，至今人们还不知道在如此低的温度下，达到钙钛矿转化率如此高的粉末。因而本发明的粉末的活性甚至优于用湿化学方法制备的粉末。
表1
煅烧时间：*4小时或更长，**2小时
| 制备PMN(铌酸铅镁) | 下列在温度下煅烧后钙钛矿比例％ | ||||||
| 组合物 | 方法 | 600℃ | 650℃ | 700℃ | 800℃ | 900℃ | 1000℃ |
| P+M+N* | 直接合成(1)现有技术 | - | - | - | 68.4 | 74 | 76.3 |
| P+M+N* | 溶胶凝胶(2)现有技术 | - | - | 9 | 98 | - | - |
| P+M+N | 溶胶凝胶(3)现有技术 | -45 | -60 | -80 | -95 | -98 | - |
| P+MN* | 铌铁矿(1)本发明 | - | - | - | 98.9 | 98.5 | 98.2 |
| P+MN** | 本发明 | 3.4 | 90 | 94 | 99 | - | - |
P＝铅(Ld)，
M＝镁
N＝铌
MN＝铌酸镁。(1)J.Am ceram.soc，67(5)311-315(1984)(2)Ceram.Trans.1，182-189(1988)(3)Advances in ceramics，21，91-98(1987)
由于煅烧温度低，所获得的钙钛矿具有特别细的颗粒，所以它们能直接进一步作处理。在所有到目前为止的其它已知方法中，钙钛矿粉末在进一步处理成陶瓷之前都要研磨一定时间。在这一期间，外来物质会再次污染该粉末，这样又损害了烧结和介电性能。
令人惊奇的是，本发明的金属铌酸盐和/或金属钽酸盐的高活性还会转移到在反应后所获得的钙钛矿粉末上。这样，例如，在极低的温度下就能烧结铌酸铅镁获得致密陶瓷。在850℃/2小时下已达到大于95％的密度。令人吃惊的是，在这些极低的烧结温度下，PMN陶瓷介电常数很高。在检测频率为100KHz时，例如，在850℃下烧结的PMN陶瓷体，其介电常数在25℃时为9,000以上。
用溶胶-凝胶法也能制备活性烧结粉末。然而只有在大于1,000℃的烧结温度下，用溶胶-凝胶法制得的陶瓷才表现出可接受的介电性能。在加压下烧结溶胶凝胶粉末也能改善介电性能。但在介电性能方面这些粉末无法与本发明粉末相比，这样就首次获得了含有大于95％，优选地大于98％的主要成分的活性烧结铅钙钛矿粉末，并且该钙钛矿粉末在明显低于1,000℃的温度下进行烧结形成具有极好介电性能的致密陶瓷。(见表3-5)
下面用实施例来解释本发明，但并不意味任何限制。
实施例1
将8kg Nb含量为24.4％的水合氧化铌(因过滤而潮湿的)用31水稀释并向其中加入980g碳酸镁氢氧化物，在Thyssen-Henschel搅拌机中均化该悬浮液15分钟，该搅拌机在2,000转/分钟下操作。分离出所获得的浆体，再对部分浆体均化15分钟。
表2
(1)J.Am.Ceram.Soc.，67，311-315(1984)(4)Ferroelectrics Letters，11，137-144(1990)(5)J.Mater.Res.，5，2902-2909(1990)向另一个部分浆体中加入0.5％重量(指最终的煅烧产物)的金属组分，并且在Thyssen-Henschel搅拌机中对该混合物再均化15分钟。在105℃下干燥该浓缩的混合物(-掺杂和未掺杂的)，然后在1,000℃下煅烧2小时。之后向铌酸镁中加入相应化学计量数量的Pb3O4，然后加入水，在球磨机中均化该混合物2小时。
| 组合物 | 方法 | 最大介电常数 | 烧结条件 | 检测频率 |
| PMN | 铌铁矿(1) | 14000 | 1270℃ | 100kHz |
| PMN | 铌铁矿(1) | 15900 | 1270℃ | 100kHz |
| PMN | 铌铁矿(1) | 18200 | 1270℃ | 100kHz |
| PMN | 铌铁矿(1) | 16400 | 1300℃ | 100kHz |
| PMN单晶 | 15900 | 60kHz | ||
| PMN | 溶胶凝胶(4) | 2992 | 900℃ | 1kHz |
| PMN | 溶胶凝胶(4) | 9369 | 1000℃ | 1kHz |
| PMN | 溶胶凝胶(4) | 14550 | 1100℃ | 1kHz |
| PMN | 溶胶凝胶(4) | 15374 | 1200℃ | 1kHz |
| PMN | 溶胶凝胶(4) | 15885 | 1250℃ | 1kHz |
| PMN(5) | 热压25MPa | 6400 | 825℃ | 1kHz |
| PMN(5) | 热压18MPa | 11200 | 890℃ | 1kHz |
| PMN | (5) | 11200 | 900℃ | 1kHz |
| PMN | (5) | 15400 | 950℃ | 1kHz |
| PMN | (5) | 16600 | 1050℃ | 1kHz |
在105℃下干燥后，在不同的温度下煅烧该混合物。用X-射线衍射分析能确定在600℃下已形成了所期望的钙钛矿。在650℃/2小时下，不管选择什么添加剂，钙钛矿的比例已经达到90％。(见表1)。
对在800℃下获得的钙钛矿加压形成圆片(直径10mm/厚1.5mm)并于标准大气压下在不同温度下进行烧结2h.测量这些陶瓷的介电性能。对于所有烧结样品，介电损耗因子tanδ都低于200-10-1。对于所进行的所有实验，居里温度均是类似的。在下面的表中给出了介电常数。
表3PMN和Li2O-PMN陶瓷(加入10mol-％)的介电性能
PMN理论密度：8.12g/cm2
| 烧结条件 | 25℃时介电常数PMN | 密度[g/cm3]PMN | 25℃时介电常数PMN+Li2O | 密度[g/cm3]PMN+Li2O |
| 2h/8502h/10002h/1200 | 72719946 | 多孔8.027.96 | 862195248206 | 7.77.87.5 |
表4PMN和LiNbO3-PMN陶瓷(加入0.5mol％)的介电性能
PMN理论密度：8.12g/cm2
| 烧结条件 | 25℃时介电常数PMN | 密度[g/cm3]PMN | 25℃时介电常数PM+LN | 密度[g/cm3]PMN+LN |
| 2h/8502h/9002h/10002h/11002h/1200 | 86651125111194 | 多孔多孔8.08.07.88 | 1246112942132551288011807 | 7.97.917.967.957.83 |
表5PMN和K2O-PMN陶瓷(加入2mol-％)的介电性能
PMN理论密度：8.12g/cm2
| 烧结条件 | 25℃时介电常数PMN | 密度[g/cm3]PMN | 25℃时介电常数PMN+K2O | 密度[g/cm3]PMN+K2O |
| 2h/8502h/10002h/1200 | 940411865 | 多孔7.937.90 | 895596328893 | 7.887.917.73 |
Claims (10)
1.通式为Me(II)Nb2O6或Me(III)NbO4的金属铌酸盐，其中Me(II)代表选自Mg，Fe，Co，Ni，Cr，Mn，Cd和Zn的(II)价金属，Me(III)代表选自于Fe，Co，Cr和Mn的III价金属，其特征在于它们含有0.1-20mol％的选自Li，Na和K的一种元素。
2.权利要求1的金属铌酸盐，其特征在于该铌酸盐是含Li的铌酸镁，该Li是铌酸锂形式的。
3.通式为Me(II)Ta2O6或Me(III)TaO4的金属钽酸盐，其中Me(II)代表选自Mg，Fe，Co，Ni，Cr，Mn，Cd和Zn的(II)价金属，Me(III)代表选自Fe，Co，Cr和Mn的III价金属，其特征在于它们含有0.1-20mol％的选自Li，Na和K的一种元素。
4.通过将相应的金属氧化物与氧化铌和/或氧化钽和添加剂湿混，干燥和煅烧来制备权利要求1、2或3中任意一个所述的金属铌酸盐和/或金属钽酸盐的方法，其特征在于所用的氧化铌和/或氧化钽分别是水合氧化物的形式以及所述的添加剂为至少一种含有选自Li、Na和K的一种元素的化合物。
5.权利要求4的方法，其特征在于所提供的添加剂是选自Li、Na和K的一种元素的盐、氢氧化物和氧化物中的至少一种化合物的形式。
6.权利要求4的方法，其特征在于添加剂选自铌酸锂和钽酸锂。
7.权利要求4的方法，其特征在于添加剂的量是0.1-20mol％。
8.权利要求4的方法，其特征在于湿混进行5分钟-90分钟，并且煅烧在400℃-1200℃的温度下进行15分钟-6小时。
9.权利要求8的方法，其特征在于在500℃-1,000℃下进行煅烧。
10.使用根据权利要求4制造的金属铌酸盐和/或钽酸盐来形成通式为X(B′B″)O3的钙钛矿的用途，式中X代表选自于Pb或Ba的一种金属，B′代表选自于Mg，Fe，Co，Ni，Cr，Mn，Cd.Ti，Zr和Zn的一种金属，B″代表选自Nb和Ta的一种金属。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4436392A DE4436392C2 (de) | 1994-10-12 | 1994-10-12 | Metallniobate und/oder Tantalate, Verfahren zu ihrer Herstellung sowie deren Weiterverarbeitung zu Perowskiten |
| DEP4436392.3 | 1994-10-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130155A CN1130155A (zh) | 1996-09-04 |
| CN1059179C true CN1059179C (zh) | 2000-12-06 |
Family
ID=6530540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95119973A Expired - Fee Related CN1059179C (zh) | 1994-10-12 | 1995-10-12 | 金属铌酸盐和／或钽酸盐，它们的制备和由它们形成的钙钛矿 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5721182A (zh) |
| JP (1) | JP4057072B2 (zh) |
| CN (1) | CN1059179C (zh) |
| DE (1) | DE4436392C2 (zh) |
| NL (1) | NL1001399C2 (zh) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69738011D1 (de) * | 1996-10-25 | 2007-09-27 | Ngk Spark Plug Co | Dielektrisches Material, Verfahren zu dessen Herstellung und dieses Material enthaltende dielektrische Resonatorvorrichtung |
| KR100199301B1 (ko) * | 1997-04-09 | 1999-06-15 | 김병규 | 유전체 세라믹 조성물 |
| US6136229A (en) * | 1998-10-15 | 2000-10-24 | Alliedsignal Inc. | Method for the mechanochemical preparation of high performance ceramics |
| EP1431423A1 (de) * | 2002-12-16 | 2004-06-23 | Basf Aktiengesellschaft | Verfahren zur Herstellung eines Lithiumionenleiters |
| ATE348204T1 (de) * | 2002-12-16 | 2007-01-15 | Basf Ag | Verfahren zur gewinnung von lithium |
| US20050136292A1 (en) * | 2003-08-14 | 2005-06-23 | Mariani Robert D. | Thin film dielectrics with perovskite structure and preparation thereof |
| JP5044902B2 (ja) * | 2005-08-01 | 2012-10-10 | 日立電線株式会社 | 圧電薄膜素子 |
| ES2634440T3 (es) * | 2006-05-17 | 2017-09-27 | Dow Global Technologies Llc | Procedimiento de polimerización de polietileno en disolución a alta temperatura |
| CN100462307C (zh) * | 2007-04-23 | 2009-02-18 | 山东大学 | 一种制备铌酸锌纳米材料的方法 |
| CN101774812B (zh) * | 2010-02-02 | 2012-05-09 | 天津大学 | 溶胶凝胶技术制备钽酸镁微波陶瓷粉体的方法 |
| JP6016333B2 (ja) * | 2011-05-27 | 2016-10-26 | キヤノン株式会社 | ニオブ酸ナトリウム粉末、ニオブ酸ナトリウム粉末の製造方法、板状粒子、板状粒子の製造方法、配向セラミックスの製造方法 |
| CN103157458B (zh) * | 2013-04-01 | 2015-04-15 | 桂林理工大学 | 可见光响应的钽酸盐光催化剂LiMTa3O9及其制备方法 |
| US10035914B2 (en) * | 2014-09-22 | 2018-07-31 | Council Of Scientific And Industrial Research | Inorganic blue pigments from cobalt doped magnesium having transition element oxides and a process for the preparing the same |
| CN104386750B (zh) * | 2014-10-31 | 2016-08-17 | 渤海大学 | 一种钪钽酸钡粉体的制备方法 |
| CN114452983B (zh) * | 2021-11-18 | 2024-06-21 | 杭州同晨环保科技有限公司 | 一种钙钛矿与尖晶石复合型臭氧分解催化剂 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS585804A (ja) * | 1981-07-02 | 1983-01-13 | Toshiba Corp | プロセスコントロ−ラ |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3607752A (en) * | 1970-06-30 | 1971-09-21 | Ciba Ltd | Process for the culture of large monocrystals of lithium niobate |
| US4287075A (en) * | 1978-04-17 | 1981-09-01 | Tdk Electronics Co., Ltd. | High dielectric constant type ceramic composition consisting essentially of Pb(Fe1/2 Nb1/2)O3 -Pb(Mg1/3 Nb2/3)O3 -Pb(Mg1/2 W1/2)O3 |
| US4550088A (en) * | 1984-04-13 | 1985-10-29 | Union Carbide Corporation | Ceramic composition for dielectric in multilayer capacitors |
| JPH0233654B2 (ja) * | 1985-07-26 | 1990-07-30 | Kagaku Gijutsucho Mukizaishitsu Kenkyushocho | Ta2o5*nh2oryushinoseizohoho |
| EP0294991A3 (en) * | 1987-06-10 | 1989-08-16 | Nippon Steel Corporation | Readily sinterable powder of perovskite type oxide containing group va element and laminated element obtained therefrom |
| JPH0629140B2 (ja) * | 1988-08-31 | 1994-04-20 | 秩父セメント株式会社 | 圧電素子材料及びその製造方法 |
| FR2644779A1 (fr) * | 1989-03-22 | 1990-09-28 | Centre Nat Rech Scient | Composition ceramique a constante dielectrique elevee |
| JPH0798680B2 (ja) * | 1989-11-13 | 1995-10-25 | 堺化学工業株式会社 | 鉛系ペロブスカイト型セラミックスの原料粉末の製造方法 |
| US5011803A (en) * | 1990-01-10 | 1991-04-30 | Kemet Electronics Corporation | Lead magnesium niobate ceramic dielectrics having low sintering temperatures |
| US5051280A (en) * | 1990-10-01 | 1991-09-24 | Eastman Kodak Company | Low temperature synthesis of alkali metal niobates and tantalates |
| DE4141648C2 (de) * | 1990-12-17 | 1997-01-09 | Toshiba Kawasaki Kk | Keramischer Kondensator |
| US5229101A (en) * | 1991-01-09 | 1993-07-20 | Munetoshi Watanabe | Process for producing a powder of perovskite-type double oxide |
| JP2692448B2 (ja) * | 1991-10-01 | 1997-12-17 | 株式会社村田製作所 | 誘電体磁器組成物 |
| DE4217817C2 (de) * | 1992-05-29 | 1994-06-16 | Starck H C Gmbh Co Kg | Verfahren zur Herstellung von Blei-Perowskiten |
| DE4217819C1 (zh) * | 1992-05-29 | 1993-09-16 | H.C. Starck Gmbh & Co Kg, 3380 Goslar, De | |
| JPH06144837A (ja) * | 1992-11-10 | 1994-05-24 | Mizusawa Ind Chem Ltd | コロンバイト型ニオブ酸塩の合成法及びそれを用いるペロブスカイト型化合物の合成法 |
| US5461014A (en) * | 1994-01-13 | 1995-10-24 | Tam Ceramics, Inc. | Lead perovskite based ceramic compositions without any free lead oxide |
-
1994
- 1994-10-12 DE DE4436392A patent/DE4436392C2/de not_active Expired - Lifetime
-
1995
- 1995-09-28 US US08/535,847 patent/US5721182A/en not_active Expired - Lifetime
- 1995-10-06 JP JP28441495A patent/JP4057072B2/ja not_active Expired - Fee Related
- 1995-10-11 NL NL1001399A patent/NL1001399C2/nl not_active IP Right Cessation
- 1995-10-12 CN CN95119973A patent/CN1059179C/zh not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS585804A (ja) * | 1981-07-02 | 1983-01-13 | Toshiba Corp | プロセスコントロ−ラ |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4436392A1 (de) | 1996-04-18 |
| JP4057072B2 (ja) | 2008-03-05 |
| JPH08301618A (ja) | 1996-11-19 |
| CN1130155A (zh) | 1996-09-04 |
| DE4436392C2 (de) | 2002-10-31 |
| US5721182A (en) | 1998-02-24 |
| NL1001399A1 (nl) | 1996-04-12 |
| NL1001399C2 (nl) | 1997-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1059179C (zh) | 金属铌酸盐和／或钽酸盐，它们的制备和由它们形成的钙钛矿 | |
| US5453262A (en) | Continuous process for production of ceramic powders with controlled morphology | |
| DE69932244T2 (de) | Verfahren zur herstellung von metalloxiden, und metalloxide mit einer perovskitischen oder perovskitartigen kristallstruktur | |
| US9227876B2 (en) | High dielectric constant material | |
| JPH04502303A (ja) | 化学量及び粒子の大きさが制御されているペロブスカイト化合物のサブミクロンセラミック粉末を製造する方法 | |
| EP1831107B1 (de) | Feinteilige bleizirkonattitanate und zirkoniumtitanate und verfahren zu deren herstellung unter verwendung von titanoxidhydratpartikeln | |
| US4696810A (en) | Wet process for the production of a readily sinterable powder material of perovskite or its solid solution | |
| Takahashi et al. | Occurrence of Dielectric 1: 1: 4 Compound in the Ternary System BaO—Ln2O3—TiO2 (Ln= La, Nd, and Sm): I, An Improved Coprecipitation Method for Preparing a Single‐Phase Powder of Ternary Compound in the BaO—La2O3—TiO2 System | |
| JPS6214489B2 (zh) | ||
| Lal et al. | Piezoelectric characteristics of spray-dried PZT ceramics modified by isovalent, supervalent and subvalent substitutions | |
| DE69010178T2 (de) | Verfahren zur herstellung von pulverförmigen perovskiteverbindungen. | |
| CN1765826A (zh) | 钕掺杂钛酸铋超细粉体的制备方法 | |
| CN1051106A (zh) | 铁电陶瓷 | |
| JPH04505912A (ja) | 制御された化学量論的組成及び粒子寸法をもつ高結晶性均質でドーピングされまたはされないミクロン以下の圧電性セラミック粉末の製造方法 | |
| JPH0159967B2 (zh) | ||
| JP2841347B2 (ja) | 圧電体セラミックスの製造方法 | |
| KR100264229B1 (ko) | 금속 니오베이트 및(또는) 탄탈레이트, 그의 제조 방법 및 그의 용도 | |
| CN1027634C (zh) | 正温度系数热敏电阻陶瓷超细粉的制造方法 | |
| JPS63218514A (ja) | ジルコニウムを含むペロブスカイトセラミツクス粉末の製造方法 | |
| JP2865975B2 (ja) | 鉛のペロブスキー型化合物の製造法 | |
| JPH0873219A (ja) | セラミック粉体の製造方法 | |
| JP3243692B2 (ja) | 圧電体セラミックスの製造方法 | |
| Spagnol et al. | Effect of barium titanate seed particles on the sintering and lattice parameters in PbMg1/3Nb2/3O3 ceramics | |
| JP3393157B2 (ja) | 多結晶半導体繊維およびその製造方法 | |
| JPS6325223A (ja) | セラミツク原料粉末の製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CI02 | Correction of invention patent application |
Correction item: Second lines and third characters Correct: K2O False: Li2O Page: 13 Correction item: Eleventh lines and nineteenth characters Correct: 2 h False: ? Page: 10 Correction item: Thirteenth lines and fourteenth characters Correct: Bei False: Qin Page: 1 Correction item: Sixteenth lines and fifth characters Correct: delete False: / Page: 1 Correction item: Sixteenth lines and second characters Correct: Ceram False: Cerama Page: 2 Correction item: Fifth lines and second columns Correct: PMN False: blank Page: 11 Correction item: Fifth lines and second columns Correct: PMN False: blank Page: 12 Correction item: Second lines and eleventh characters Correct: 2 False: 10 Page: 13 Correction item: The last word of the twelfth line Correct: Cd False: CD Page: Claim 2 |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: LINE 2, PARAGRAPH 11, THE WORD; FROM: 10 TO: 2 Free format text: CORRECT: ARTICLE 13, PARAGRAPH 14 LINE CHARACTER; FROM: QIN TO: BEI Free format text: CORRECT: ARTICLE 16, PARAGRAPH 5, WORD LINE; FROM: / TO: DELETION Free format text: CORRECT: ARTICLE 16 PARAGRAPH 2 LINE CHARACTER; FROM: CERAMA TO: CERAM Free format text: CORRECT: ARTICLE 11, PARAGRAPH 9, THE WORD LINE TO: 2H Free format text: CORRECT: ARTICLE 5, PARAGRAPH 2 LINE; FROM: NULL TO: PMN Free format text: CORRECT: RIGHT-CLAIMING DOCUMENT FINALLY THE FIRST WORD LINE 12; FROM: CD TO: CD Free format text: CORRECT: LINE 2, PARAGRAPH 3 THE WORD; FROM: LI2O TO: K2O |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: H C STAACK CO., LTD. Free format text: FORMER OWNER: H.C. STARCH GMBH + CO. KG Effective date: 20090403 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090403 Address after: German Goslar Co-patentee after: Fraunhofer Ges Forschung Patentee after: H.C. STARCK GmbH Address before: German Goslar Co-patentee before: Fraunhofer Ges Forschung Patentee before: H.C. STARCK Inc. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20001206 Termination date: 20141012 |
|
| EXPY | Termination of patent right or utility model |