JPH01141805A - Production of metal oxide - Google Patents
Production of metal oxideInfo
- Publication number
- JPH01141805A JPH01141805A JP62299068A JP29906887A JPH01141805A JP H01141805 A JPH01141805 A JP H01141805A JP 62299068 A JP62299068 A JP 62299068A JP 29906887 A JP29906887 A JP 29906887A JP H01141805 A JPH01141805 A JP H01141805A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- carboxylic acid
- mixture
- water
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 33
- 150000002894 organic compounds Chemical class 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 229920002472 Starch Polymers 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract description 2
- 239000008107 starch Substances 0.000 abstract description 2
- 235000019698 starch Nutrition 0.000 abstract description 2
- 239000002562 thickening agent Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 33
- 239000000843 powder Substances 0.000 description 29
- 239000011259 mixed solution Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- -1 alkaline earth metal salts Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- RIPRKTVEBCPYNQ-UHFFFAOYSA-L manganese(2+);pentanoate Chemical compound [Mn+2].CCCCC([O-])=O.CCCCC([O-])=O RIPRKTVEBCPYNQ-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
し産業上の利用分野］
本発明は金属酸化物の製造方法に関する。本発明の方法
は、複数種の金属酸化物が分子オーダーで均一に混り合
った金属酸化物の混合物、特に粉末混合物を得るのに特
に好適である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing metal oxides. The method of the present invention is particularly suitable for obtaining a metal oxide mixture, particularly a powder mixture, in which multiple types of metal oxides are uniformly mixed on a molecular order.
し従来の技術］
複数種の金属酸化物を機械的粉砕を含むいかなる手段で
混合しても、これらの金属酸化物が分子オーダーで混り
合った金！ｌ！酸化物の粉末混合物を得ることは従来困
難であった。[Prior art] Even if multiple types of metal oxides are mixed by any means including mechanical crushing, gold is produced in which these metal oxides are mixed in the molecular order! l! It has heretofore been difficult to obtain powder mixtures of oxides.
ところで、最近報告が多い、イツトリウム、バリウム、
銅、ランタンなどを用いた超伝導セラミックスは、これ
ら金属の酸化物の混合物を焼結することにより得られて
いるが、従来法で得られる混合物では、複数種の金属酸
化物が分子オーダーで均一に混り合っておらず、混合状
態が不十分であるため、超伝導を示す結晶が、それぞれ
が単一金ｉ酸化物のみからなる比鞍的粒子径の大きな、
異種金属酸化物粉末間の界面でのみ成長し、その結果、
得られたセラミックスの物性、例えば超伝導セラミック
スの臨界温度、臨界電流密度等の物性を向上させること
ができないという欠点があった。By the way, there have been many reports recently about yztrium, barium,
Superconducting ceramics using copper, lanthanum, etc. are obtained by sintering mixtures of oxides of these metals, but in mixtures obtained by conventional methods, multiple types of metal oxides are uniform on the molecular order. Because the crystals exhibiting superconductivity are not mixed with each other, and the mixing state is insufficient, the crystals exhibiting superconductivity are composed of only a single gold i oxide, each having a comparatively large particle size.
It grows only at the interface between dissimilar metal oxide powders, resulting in
There was a drawback that the physical properties of the obtained ceramics, such as the critical temperature and critical current density of superconducting ceramics, could not be improved.
［発明の解決しようとする問題点］
上述の如〈従来の方法では複数種の金属酸化物が分子オ
ーダーで均一に混り合った金属酸化物の粉末混合物が得
られなかったため、該金属酸化物の粉末混合物を焼結す
ることにより得られたセラミックスの物性も不十分であ
った。[Problems to be Solved by the Invention] As mentioned above, it is not possible to obtain a powder mixture of metal oxides in which multiple types of metal oxides are uniformly mixed on a molecular order. The physical properties of the ceramics obtained by sintering the powder mixture were also insufficient.
本発明は、このような問題点乃至欠点を除去するために
なされたものであり、その目的は複数種の金属酸化物が
分子オーダーで均一に混り合った金属酸化物の製造法を
提供することである。The present invention was made to eliminate these problems and drawbacks, and its purpose is to provide a method for producing metal oxides in which multiple types of metal oxides are uniformly mixed on a molecular order. That's true.
［間厘点を解決するための手段］
本発明は上記目的を達成するためになされたものであり
、本発明の金属酸化物の製造法は、一般式
％式％）
［式中、Ｍは金属であり、ｍは金属Ｍの配位数であり、
ｎは１〜６の整数であるコ
で表わされる、異なる金属からなるカルボン酸金属塩の
複数種と水溶性有機化合物と溶媒とを含有する混合液を
乾燥して固体を得、次いでこの固体を前記カルボン酸金
属塩の酸化温度以上の温度に加熱することを特徴とする
。[Means for Solving the Interference Point] The present invention has been made to achieve the above object, and the method for producing a metal oxide of the present invention is based on the general formula %) [where M is is a metal, m is the coordination number of the metal M,
A mixed solution containing multiple types of carboxylic acid metal salts made of different metals, a water-soluble organic compound, and a solvent, where n is an integer from 1 to 6, is dried to obtain a solid, and then this solid is It is characterized by heating to a temperature equal to or higher than the oxidation temperature of the carboxylic acid metal salt.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の方法は、第１の工程として、複数種の−ｍ式（
Ｉ）のカルボン酸金属塩と水溶性有機化合物と溶媒とを
含有する混合液を先ず調製し、次いでこれを乾燥して固
体を得るものである。The method of the present invention includes, as a first step, a plurality of types of -m formulas (
A mixed solution containing the carboxylic acid metal salt of I), a water-soluble organic compound, and a solvent is first prepared, and then this is dried to obtain a solid.
−最大（Ｉ）のカルボン酸金属塩において、金属成分で
あるＭは、周期律表１ａ、［ａ、 ■ｂ。- In the maximum (I) carboxylic acid metal salt, the metal component M is in Periodic Table 1a, [a, 2b.
ＩＶｂ、Ｖｂ、Ｖｌｂ、■ｂ、■、 ■ｂ、ｌＪｂ、ｌ
ｌ［ａ。IVb, Vb, Vlb, ■b, ■, ■b, lJb, l
l[a.
ＩＶａ、Ｖａ族の第２周期から第６周期にある金属元素
であるのが好ましく、例えば、Ａｊｊ、Ｂａ。Preferably, it is a metal element in the second to sixth period of the IVa and Va groups, such as Ajj and Ba.
Ｂｅ、Ｂｊ、Ｃｄ、Ｃａ、Ｃｅ、Ｃｓ、Ｃｒ。Be, Bj, Cd, Ca, Ce, Cs, Cr.
Ｃｏ、Ｃ，ｕ、Ｄｙ、Ｅｒ、Ｂｕ、Ｇｄ、Ｇａ。Co, C, u, Dy, Er, Bu, Gd, Ga.
Ａｕ、Ｉｎ、Ｉｒ、Ｆｅ、Ｌａ、Ｐｂ、Ｌｉ。Au, In, Ir, Fe, La, Pb, Li.
Ｍｇ、Ｍｎ、Ｈｇ、Ｎｄ、Ｎｉ、Ｐｄ、に、Ｐｒ。Mg, Mn, Hg, Nd, Ni, Pd, Pr.
Ｒａ、Ｒｈ、Ｒｂ、Ｓｍ、Ｓｃ、Ａｇ、Ｎａ。Ra, Rh, Rb, Sm, Sc, Ag, Na.
Ｓｒ、Ｔ矛、Ｔｈ、Ｓｎ、Ｕ、Ｙｂ、Ｙ、Ｚｎ。Sr, T, Th, Sn, U, Yb, Y, Zn.
Ｚｒ、Ｔｂなどが挙げられる。まな−最大（１）のカル
ボン酸金属塩において、カルボン酸成分である［Ｃ，Ｈ
２，，１Ｃｏｏ］ （ｎ＝１〜６の整数）は、炭素数
が多くなると、後記するように溶媒である水に対する溶
解性が徐々に低下するので、ｎが１〜３である、酢酸残
基［ＣＨ３ＣＯＯ］、プロピオン酸残基［Ｃ２Ｈ５ＣＯ
Ｏ］及び酪酸残基［Ｃ３Ｈ７ＣＯＯコが特に好ましく、
ｎが１〜３であるカルボン酸の金属塩の場合、金属成分
がアルカリ金属やアルカリ土類金属である場合だけでな
く、他の金属である場合にもカルボン酸金属塩は水に溶
解する。Examples include Zr and Tb. Mana - In the carboxylic acid metal salt of maximum (1), the carboxylic acid component [C,H
2,,1Coo] (n = an integer of 1 to 6) is an acetic acid residue where n is 1 to 3, because as the number of carbon atoms increases, the solubility in water, which is a solvent, gradually decreases as described later. group [CH3COO], propionic acid residue [C2H5CO
O] and butyric acid residues [C3H7COO] are particularly preferred;
In the case of a carboxylic acid metal salt where n is 1 to 3, the carboxylic acid metal salt dissolves in water not only when the metal component is an alkali metal or alkaline earth metal, but also when it is other metal.
またｎが４〜６であるカルボン酸くすなわち、吉草酸、
カプロン酸、エナント酸）の場合もそのアルカリ金属又
はアルカリ土類金属塩は水に溶解する。また吉草酸マン
ガン等も水に溶解する。しかしカルボン酸中の炭素数が
増加するに従って、当該カルボン酸の金属塩の水に対す
る溶解度は徐々に低下するので、水に難溶又は不溶の場
合には、溶媒として水とともに有機溶媒を加えたり、可
溶化剤を加えたりしてカルボン酸金属塩の溶解性を向上
させることが行なわれる。Also, carboxylic acids in which n is 4 to 6, i.e. valeric acid,
In the case of caproic acid, enanthic acid), their alkali metal or alkaline earth metal salts are also soluble in water. Also, manganese valerate and the like are dissolved in water. However, as the number of carbon atoms in the carboxylic acid increases, the solubility of the metal salt of the carboxylic acid in water gradually decreases, so if it is poorly soluble or insoluble in water, an organic solvent may be added together with water as a solvent. The solubility of the carboxylic acid metal salt is improved by adding a solubilizing agent.
本発明の方法においては、−最大（１）のカルボン酸金
属塩として、異なる金属からなるカルボン酸金属塩を複
数種使用する。この場合、同一カルボン酸の異なる金属
の塩を２種以上用いるのが一般的であるが、異なるカル
ボン酸の異なる金属の塩を２種以上用いても良いことは
もちろんである。In the method of the present invention, - as the maximum (1) carboxylic acid metal salt, a plurality of carboxylic acid metal salts made of different metals are used. In this case, it is common to use two or more salts of the same carboxylic acid with different metals, but it goes without saying that two or more salts of different metals with different carboxylic acids may be used.
本発明の方法において、前記のカルボン酸の金属塩とと
もに用いられる水溶性有機化合物としては、増粘剤とし
て用いられているものが通常使用され、その例として、
でんぷん、ゴム、にかわ、ゼラチン、カゼイン、コラー
ゲン、ビスコース、セルロース等の天然高分子化合物や
、ポリビニルピロリドン、ポリビニルアルコール、ポリ
エチレンオキシド、ポリアクリル酸ナトリウム等の合成
高分子化合物や、エチレングリコール、グリセリン等の
低分子化合物が挙げられる。In the method of the present invention, as the water-soluble organic compound used together with the metal salt of carboxylic acid, those used as thickeners are usually used, and examples thereof include:
Natural polymer compounds such as starch, rubber, glue, gelatin, casein, collagen, viscose, cellulose, etc., synthetic polymer compounds such as polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, ethylene glycol, glycerin, etc. Examples include low molecular weight compounds.
前記のカルボン酸金属塩と水溶性有機化合物を溶解する
ために用いられる溶媒としては、上述の如く水を用いる
のが好ましいが、カルボン酸金属塩の溶解性を増すため
に必要に応じて有機溶媒を併用することができる。これ
らの有機溶媒としては以下のものが挙げられる。As the solvent used to dissolve the carboxylic acid metal salt and the water-soluble organic compound, water is preferably used as described above, but an organic solvent may be used as necessary to increase the solubility of the carboxylic acid metal salt. Can be used together. Examples of these organic solvents include the following.
・アルコールとして、メタノール、エタノール、プロパ
ツール等
・エーテルとして、エチルエーテル、プロピルエーテル
等
・ケトンとして、アセトン、プロピルケトン等・エステ
ルとして、ギ酸メチル、ギ酸エチル、ギ酸プロピル、酢
酸メチル、酢酸エチル、酢酸プロピル、プロピオン酸メ
チル、プロピオン酸エチル等
・多価アルコールとして、エチレングリコール等・その
他として、ピリジン、フェノール等カルボン酸金属塩及
び水溶性有機化合物を溶媒中に溶解して得た混合液は、
カルボン酸金属塩や、得られる金属酸化物の性質を損な
わないものであれば、他の添加剤を含有することができ
る。これらの添加剤としては酸又はアルカリが挙げられ
る。・Alcohols include methanol, ethanol, propatool, etc. ・Ethers include ethyl ether, propyl ether, etc. ・Ketones include acetone, propyl ketone, etc. ・Esters include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, acetic acid A mixed solution obtained by dissolving propyl, methyl propionate, ethyl propionate, etc. as a polyhydric alcohol, ethylene glycol, etc. as others, carboxylic acid metal salts such as pyridine and phenol, and a water-soluble organic compound in a solvent,
Other additives may be included as long as they do not impair the properties of the carboxylic acid metal salt or the resulting metal oxide. These additives include acids or alkalis.
得られた混合液の乾燥は、常温常圧下、加熱常圧下、常
温減圧下、加熱減圧下、低温減圧下、極低温減圧下、高
温高圧下等の通常の手段により行なわれる。Drying of the obtained liquid mixture is carried out by conventional means such as normal temperature and normal pressure, heating and normal pressure, normal temperature and reduced pressure, heating and reduced pressure, low temperature and reduced pressure, extremely low temperature and reduced pressure, and high temperature and high pressure.
前記水溶性有機化合物を用いずに複数種のカルボン酸金
属塩を単に溶媒に溶解して得た溶液を乾燥すると、カル
ボン酸金属塩が結晶化し、複数種のカルボン酸金属塩が
分子オーダーで均一に混り合った混合物を得ることがで
きないが、本発明において用いられる混合液は、前記水
溶性有機化合物を含み、この水溶性有機化合物が過飽和
状態時にカルボン酸金属塩の分子間に隈無く存在してカ
ルボン酸金属塩の結晶化を防止するので、この水溶性有
機化合物含有混合物を乾燥すると複数種のカルボン酸金
属塩が分子オーダーで均一に分散した固体が得られる。When a solution obtained by simply dissolving multiple types of carboxylic acid metal salts in a solvent without using the above-mentioned water-soluble organic compound is dried, the carboxylic acid metal salts crystallize, and the multiple types of carboxylic acid metal salts become uniform on the molecular order. However, the liquid mixture used in the present invention contains the above-mentioned water-soluble organic compound, and this water-soluble organic compound is present throughout the molecules of the carboxylic acid metal salt in a supersaturated state. This prevents crystallization of the carboxylic acid metal salt, and therefore, when this water-soluble organic compound-containing mixture is dried, a solid in which a plurality of types of carboxylic acid metal salts are uniformly dispersed on a molecular order is obtained.
この固体はそのままの形で次の加熱工程に送っても良い
が、適当な大きさに粉砕しても良い。なお、混合液を噴
震乾燥して、直接粉末を得ても良いことはもちろんであ
る。This solid may be sent as it is to the next heating step, or it may be pulverized to an appropriate size. It goes without saying that the mixed solution may be spun-dried to directly obtain a powder.
本発明の方法は、第２の工程として、第１の工程で得ら
れた固体を、前記−最大（Ｉ）のカルボン酸金属塩の酸
化温度以上の温度に少なくとも１度加熱するものである
。カルボン酸金属塩の酸化温度はカルボン酸金属塩の種
類により異なり、個々の場合に、必要な加熱保持温度が
決定される。In the method of the present invention, in the second step, the solid obtained in the first step is heated at least once to a temperature equal to or higher than the oxidation temperature of the carboxylic acid metal salt (I). The oxidation temperature of the carboxylic acid metal salt varies depending on the type of carboxylic acid metal salt, and the necessary heating and holding temperature is determined in each case.
本発明では酸化温度が異なる複数種のカルボン酸金属塩
を用いるので、加熱麺屑は、複数種のカルボン酸金属塩
のうちで最も高い酸化温度以上の温度にする必要がある
。この加熱により、カルボン酸金属塩はカルボン酸とし
て、または水と炭酸ガスとなって揮散し、最終的に金属
酸化物の混合物が生成される。In the present invention, since a plurality of types of carboxylic acid metal salts having different oxidation temperatures are used, the heated noodle scraps need to be heated to a temperature equal to or higher than the highest oxidation temperature among the plurality of types of carboxylic acid metal salts. By this heating, the carboxylic acid metal salt is volatilized as a carboxylic acid or as water and carbon dioxide gas, and finally a mixture of metal oxides is produced.
このようにして生成された金属酸化物の混合物は、複数
種のカルボン酸金属塩が分子オーダーで均一に分散した
固体を加熱処理して得られたものであるので、当然のこ
ととして、複数種の金属酸化物が分子オーダーで均一に
混り合った固体混合物である。The mixture of metal oxides produced in this way is obtained by heat-treating a solid in which multiple types of carboxylic acid metal salts are uniformly dispersed on the molecular order, so it is natural that multiple types of metal oxides are mixed together. It is a solid mixture of metal oxides uniformly mixed on the molecular order.
この金属酸化物の固体混合物は、前記の加熱処理により
水溶性有機化合物が酸化除去された箇所が空隙となって
いるため、非常にもろく、乳鉢等により極めて簡便に粉
末化し得るという利点があり、得られた粉末は、後述す
るように、例えばセラミックス材料の製造にそのまま用
いられるという利点がある。This solid mixture of metal oxides has voids where the water-soluble organic compounds have been oxidized and removed by the heat treatment, so it is very brittle and has the advantage of being extremely easy to powder in a mortar or the like. The obtained powder has the advantage that it can be used as it is, for example, in the production of ceramic materials, as will be described later.
また本発明の方法では使用し得るカルボン酸金属塩の範
囲が広いので、複数種の金属酸化物が分子オーダーで均
一に混り合った混合物が多数得られ、これらのうちのあ
るものを焼結することにより臨界温度、臨界電流密度等
の物性が向上した超伝導セラミックスを製造し得るとい
う利点がある。In addition, since the method of the present invention has a wide range of metal carboxylates that can be used, a large number of mixtures in which multiple types of metal oxides are uniformly mixed on the molecular order can be obtained, and some of these can be sintered. This has the advantage that superconducting ceramics with improved physical properties such as critical temperature and critical current density can be manufactured.
この超伝導セラミックスの製造について更に詳しく述べ
ると、例えば（Ｙ−Ｂａ−Ｃｕ−０）、（Ｅｒ−Ｂａ−
Ｃｕ−０）、（Ｌａ−８ｒ−Ｃｕ−０）、（Ｌａ−Ｂａ
−Ｃｕ−０）等からなる複数種の金属酸化物の粉末混合
物を加圧プレス法により円板にしたり、チューブに詰め
て線材にした後、焼結すると、各粒子内において複数種
の金属酸化物が分子オーダーで混り合っているために結
晶化が各粒子の界面だけではなく、各粒子の内部でも起
り、その結果、得られた超伝導セラミックスの臨界電流
密度が著しく向上する。このことは、複数種の金属酸化
物の粉末を単に混合して得た金属酸化物の粉末混合物を
焼結する従来の超伝導セラミックス製造法では、結晶化
が、複数種の金属酸化物が互いに接触し得る唯一の場で
ある各粒子間の界面でのみ起り、その結果、得られた超
伝導セラミックスの臨界を流密塵が低いことと好対照を
なすものであり、本発明により得られる特別の効果であ
る。To explain in more detail the production of this superconducting ceramic, for example, (Y-Ba-Cu-0), (Er-Ba-
Cu-0), (La-8r-Cu-0), (La-Ba
When a powder mixture of multiple types of metal oxides such as -Cu-0) is made into a disk by pressure pressing or packed into a tube to make a wire rod and then sintered, multiple types of metal oxides are oxidized within each particle. Because the substances are mixed on a molecular order, crystallization occurs not only at the interface of each particle but also inside each particle, and as a result, the critical current density of the obtained superconducting ceramic is significantly improved. This means that in the conventional superconducting ceramic manufacturing method in which a metal oxide powder mixture obtained by simply mixing multiple types of metal oxide powders is sintered, crystallization occurs, and multiple types of metal oxides interact with each other. This occurs only at the interface between each particle, which is the only place where they can come into contact, and as a result, the criticality of the obtained superconducting ceramics is in good contrast with the low flow dust, and the special This is the effect of
［実施例Ｊ
以下、実施例を挙げて本発明を更に説明するが、本発明
はこれらの実施例に限定されるものではない。[Example J Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.
実施例Ｉ
Ｙ （ＣＨ３ＣＯＯ） ３ ・４ Ｈ２０とＢａ（ＣＨ
３ＣＯＯ）２とＣｕ （ＣＨ３Ｃｏｏ）２ ・Ｈ２Ｏと
をＹ対Ｂａ対Ｃｕが１対２対３となる様に混合した試薬
の１ｇを、水Ｌｏｇとポリビニルピロリドン３ｇとを混
合した溶液中に加えて混合液とした。Example I Y (CH3COO) 3 ・4 H20 and Ba(CH
Add 1 g of a reagent obtained by mixing 3COO)2 and Cu (CH3Coo)2 ・H2O so that the ratio of Y to Ba to Cu is 1:2:3 to a solution containing Log of water and 3 g of polyvinylpyrrolidone. A mixed solution was prepared.
上記混合液を６０℃の恒温槽中で１週間乾燥を行なって
固体を得た。この固体の一部を採取し粉砕して得た粉末
を透過型電子顕微鏡で観察しなところ、結晶の存在は認
められず、３種の酢酸金属塩がポリビニルピロリドンを
介して均一に分散していることがｉ認された。The mixture was dried for one week in a constant temperature bath at 60°C to obtain a solid. When a part of this solid was collected and pulverized and the resulting powder was observed with a transmission electron microscope, no crystals were observed, indicating that the three types of acetic acid metal salts were uniformly dispersed through polyvinylpyrrolidone. It was recognized that there was.
次にこの固体を９５０℃で３０Ｍ間加熱して金属酸化物
の混合物を得た後、これを粉砕して粉末を得た。この粉
末は第１図にそのＸ線回折図を示すように、（ＹＩ Ｂ
ａ２ Ｃｕ３０．）の超伝導結晶を含むＹ、Ｂａ、Ｃｕ
の酸化物粉末であることをｆｌ認しな。Next, this solid was heated at 950° C. for 30M to obtain a mixture of metal oxides, which was then ground to obtain a powder. As shown in the X-ray diffraction pattern of this powder in FIG.
a2 Cu30. ) Y, Ba, Cu including superconducting crystals
Please note that it is an oxide powder.
なお、比較のため水溶性有機化合物くポリビニルピロリ
ドン）を用いずに、３種の酢酸金属塩を単に水に溶解し
た溶液を調製し、６０’Ｃの恒温槽中で１週間乾燥を行
なった所、最大１偲の結晶が成長していた。For comparison, a solution of three metal acetates simply dissolved in water was prepared without using a water-soluble organic compound (polyvinylpyrrolidone), and the solution was dried for one week in a constant temperature bath at 60'C. , up to 1 crystal was growing.
次に上記方法で作製した金属酸化物の粉末混合物をプレ
ス加工しディスクとした後、９５０’Ｃで３５時間焼結
して、超伝導セラミックスを製造したところ、この超伝
導セラミックスは８３にで電気抵抗値が零となった。ま
た温度７７にで臨界電流密度は２５００ Ａ／＆であっ
た。Next, the metal oxide powder mixture produced by the above method was pressed into a disk, and then sintered at 950'C for 35 hours to produce superconducting ceramics. The resistance value became zero. Further, at a temperature of 77, the critical current density was 2500 A/&.
なお、比較のため、酸化イツトリウム、炭酸バリウム、
酸化銅をＹ対Ｂａ対Ｃｕ対Ｏが１対２対３対ｙとなる様
に乳鉢で混合粉砕して得た混合物について、９５０℃で
３０時間加熱保持、室温への冷却、乳鉢での再粉砕、プ
レス機によるディスク形成の一連の工程を実施し、得ら
れたディスクを９５０℃で３５時間加熱保持して得た従
来の超伝導セラミックスについて同様に測定したところ
、温度７７にでの臨界電流密度は９０ＯＡ／−であった
。For comparison, yttrium oxide, barium carbonate,
A mixture obtained by mixing and pulverizing copper oxide in a mortar so that the ratio of Y to Ba to Cu to O was 1:2:3:y was heated and held at 950°C for 30 hours, cooled to room temperature, and re-milled in the mortar. Similar measurements were made on conventional superconducting ceramics obtained by carrying out a series of processes of pulverization and disk formation using a press, and heating and holding the obtained disk at 950°C for 35 hours. The density was 90OA/-.
実施例２
実施例１のポリビニルピロリドン３ｇをポリビニルアル
コール０．６ｇに変えた以外は実施例１と同様の実験を
行ない同様の結果を得た。Example 2 The same experiment as in Example 1 was carried out, except that 3 g of polyvinylpyrrolidone in Example 1 was replaced with 0.6 g of polyvinyl alcohol, and the same results were obtained.
実施例３
Ｌａ （ＣＨ３Ｃ００）３ ・ ３／２ Ｈ２０とＢａ
（ＣＨ３Ｃ００）２とＣｕ （ＣＩＩ３ Ｃ００）
２−Ｈ２ＯとをＬａ対Ｂａ対Ｃｕが１対１対１となる様
に混合した試薬の１ｇを、水１０ｇとポリビニルピロリ
ドン３ｇとを混合した溶液中に加えて混合液とした。Example 3 La (CH3C00)3 3/2 H20 and Ba
(CH3C00)2 and Cu (CII3 C00)
1 g of a reagent prepared by mixing 2-H2O in a 1:1:1 ratio of La: Ba: Cu was added to a mixed solution of 10 g of water and 3 g of polyvinylpyrrolidone to prepare a mixed solution.
上記混合液を６０°Ｃの恒温槽中で１週間乾燥を行なっ
た後、９５０℃で３０時間加熱保持して、金属酸化物の
混合物を得た後、これを粉砕して粉末を得た。The above mixture was dried in a constant temperature bath at 60°C for one week, then heated and held at 950°C for 30 hours to obtain a mixture of metal oxides, which was then ground to obtain a powder.
この粉末はＸ線回折分析によりＬａ、Ｂａ。This powder was found to contain La and Ba by X-ray diffraction analysis.
Ｃｕの酸化物粉末であることを確認した。It was confirmed that it was Cu oxide powder.
実施例４
実施例３のポリビニルピロリドン３ｇをポリビニルアル
コール０．６ｆに変えた以外は実施例３と同様の実験を
行ない、同様の結果を得た。Example 4 The same experiment as in Example 3 was conducted, except that 3 g of polyvinylpyrrolidone in Example 3 was replaced with 0.6 f of polyvinyl alcohol, and similar results were obtained.
実施例５
実施例１〜４の水と水溶性有機化合物（ポリビニルピロ
リドン又はポリビニルアルコール）との混合溶液にメタ
ノールを１ｇ加えた以外は実施例１〜４と同様にして行
ない、それぞれ同様の結果を得た。Example 5 The same procedure as in Examples 1 to 4 was carried out except that 1 g of methanol was added to the mixed solution of water and a water-soluble organic compound (polyvinylpyrrolidone or polyvinyl alcohol) in Examples 1 to 4, and the same results were obtained in each case. Obtained.
実施例６
Ｌａ（ＣＨ３ＣＯＯ）３・ ３／２Ｈ２０とＳｒ （Ｃ
Ｈ３Ｃｏｏ）２とＣｕ （ＣＨ３ＣＯＯ） ２・Ｈ２Ｏ
をＬａ対Ｓｒ対Ｃｕが１８対２対１となる様に混合した
試薬の１ｇを、水Ｌｏｇとポリビニルピロリドン３ｇを
混合した溶液に加え混合液とした。Example 6 La(CH3COO)3.3/2H20 and Sr(C
H3Coo)2 and Cu (CH3COO)2・H2O
1 g of a reagent mixed in a ratio of La: Sr: Cu of 18:2:1 was added to a mixed solution of water Log and 3 g of polyvinylpyrrolidone to form a mixed solution.
上記混合液を９０℃の恒温槽中で１週間乾燥を行なった
後、９５０℃で３０時間加熱保持して金属酸化物の混合
物を得た後、これを粉砕して粉末を得た。The mixture was dried for one week in a constant temperature bath at 90°C, then heated and held at 950°C for 30 hours to obtain a mixture of metal oxides, which was then pulverized to obtain powder.
この様にして得られた粉末は、Ｘ線回折分析の結果Ｌａ
、Ｓｒ、Ｃｕの酸化物粉末であることを確認した。As a result of X-ray diffraction analysis, the powder obtained in this way has a La
, Sr, and Cu oxide powder.
実施例７
Ｙｂ （ＣＨ３Ｃｏｏ）３ ・４Ｈ２０と Ｅｒ（ＣＨ
３ＣＯＯ）３・４Ｈ２０とＤ ｙ （ＣＨ３ＣＯＯ）３
・４Ｈ２０とＢａ （ＣＨ３Ｃｏｏ）２とＣｕ （ＣＨ
３Ｃｏｏ）２ ・Ｈ２０とをモル比で１対１対１対１対
１の比で混合した試薬１ｇを、水Ｌｏｇとポリビニルア
ルコール０．６ｇを混合した溶液に加え混合液とした。Example 7 Yb (CH3Coo)3 ・4H20 and Er(CH
3COO)3・4H20 and D y (CH3COO)3
・4H20 and Ba (CH3Coo)2 and Cu (CH
1 g of a reagent prepared by mixing 3Coo)2 .H20 in a molar ratio of 1:1:1:1:1 was added to a mixed solution of water Log and 0.6 g of polyvinyl alcohol to form a mixed solution.
上記混合液をフリーズドライ法により乾燥させた後、１
０００℃で１５時間加熱保持して、金属酸化物の混合物
を得な後、これを粉砕して粉末を得た。After drying the above mixed solution by freeze drying method, 1
After heating and holding at 000° C. for 15 hours to obtain a mixture of metal oxides, this was pulverized to obtain a powder.
この様にして得られた粉末はｘ１ｉ回折分析によりＹｂ
、Ｅｒ、Ｄｙ、Ｂａ、Ｃｕの酸化物粉末であることを確
認した。The powder obtained in this way was determined by x1i diffraction analysis to show that Yb
, Er, Dy, Ba, and Cu oxide powder.
実施例８
Ｓ （ＣＨＣ００）・３Ｈ２０とＢａ
（ＣＨ３Ｃｏｏ）２とＣｕ（ＣＨ３ＣＯＯ）２・Ｈ２Ｏ
をモル比で１対１対１の比で混合した試薬１ｇを、水Ｌ
ｏｇとポリビニルアルコール０．６ｇを混合した溶液に
加えて混合液とした。Example 8 S (CHC00)・3H20 and Ba (CH3Coo)2 and Cu(CH3COO)2・H2O
1 g of the reagent mixed in a molar ratio of 1:1:1 was added to 1 liter of water.
A mixed solution was prepared by adding 0.6 g of polyvinyl alcohol and 0.6 g of polyvinyl alcohol.
上記混合液をエバポレーターを用い６０℃の加熱下に乾
燥を行なった後、１１００℃で３０時間加熱保持して、
金属酸化物の混合物を得た後、これを粉砕して粉末を得
た。The above mixed solution was dried using an evaporator at 60°C, and then heated and held at 1100°C for 30 hours.
After obtaining the metal oxide mixture, it was ground to obtain a powder.
この様にして得られた粉末はＸ線回折分析の結果Ｓｍ、
Ｂａ、Ｃｕの酸化物粉末であることを確認した。The powder obtained in this way was analyzed by X-ray diffraction, and Sm.
It was confirmed that it was Ba and Cu oxide powder.
実施例９
実施例１〜４、実施例６〜８の水と水溶性有機化合物（
ポリビニルピロリドンスはポリビニルアルコール）との
混合溶液にエチ゛ルエーテルを１．ｒ加えて同様の実験
を行ない、実施例１〜４、実施例６〜８と同様の結果を
得た。Example 9 Water and water-soluble organic compounds of Examples 1 to 4 and Examples 6 to 8 (
For polyvinyl pyrrolidone, add ethyl ether to a mixed solution of polyvinyl alcohol). In addition, similar experiments were conducted, and results similar to Examples 1 to 4 and Examples 6 to 8 were obtained.
［発明の効果］
本発明の方法は、複数種の金属酸化物が分子オーダーで
均一に混合された金属酸化物の混合物を安価に簡単に得
ることができるため、その技術的意義は極めて大である
。[Effects of the Invention] The method of the present invention has extremely great technical significance because it is possible to easily and inexpensively obtain a mixture of metal oxides in which multiple types of metal oxides are uniformly mixed on a molecular order. be.
第１図は、本発明の実施例１で得られた金属酸化物の粉
末混合物のｘ＆１回折図である。FIG. 1 is an x&1 diffraction pattern of the metal oxide powder mixture obtained in Example 1 of the present invention.
Claims (1)
）［式中、Ｍは金属であり、ｍは金属Ｍの配位数であり
、ｎは１〜６の整数である］ で表わされる、異なる金属からなるカルボン酸金属塩の
複数種と水溶性有機化合物と溶媒とを含有する混合液を
乾燥して固体を得、次いでこの固体を前記カルボン酸金
属塩の酸化温度以上の温度に加熱することを特徴とする
金属酸化物の製造法。(1) General formula M[C_nH_2_n_+_1COO]_m...(I
) [where M is a metal, m is the coordination number of the metal M, and n is an integer of 1 to 6] Multiple types of carboxylic acid metal salts made of different metals and water-soluble A method for producing a metal oxide, which comprises drying a liquid mixture containing an organic compound and a solvent to obtain a solid, and then heating the solid to a temperature equal to or higher than the oxidation temperature of the metal carboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62299068A JPH01141805A (en) | 1987-11-27 | 1987-11-27 | Production of metal oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62299068A JPH01141805A (en) | 1987-11-27 | 1987-11-27 | Production of metal oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01141805A true JPH01141805A (en) | 1989-06-02 |
Family
ID=17867784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62299068A Pending JPH01141805A (en) | 1987-11-27 | 1987-11-27 | Production of metal oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01141805A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008521591A (en) * | 2004-11-26 | 2008-06-26 | ソウル ナショナル ユニバーシティー インダストリー ファンデーション | New mass production method of monodisperse nanoparticles |
-
1987
- 1987-11-27 JP JP62299068A patent/JPH01141805A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008521591A (en) * | 2004-11-26 | 2008-06-26 | ソウル ナショナル ユニバーシティー インダストリー ファンデーション | New mass production method of monodisperse nanoparticles |
| JP2011224558A (en) * | 2004-11-26 | 2011-11-10 | Seoul National Univ Industry Foundation | New process for large-scale production of monodisperse nanoparticles |
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