JPH0448487B2 - - Google Patents
Info
- Publication number
- JPH0448487B2 JPH0448487B2 JP2199084A JP2199084A JPH0448487B2 JP H0448487 B2 JPH0448487 B2 JP H0448487B2 JP 2199084 A JP2199084 A JP 2199084A JP 2199084 A JP2199084 A JP 2199084A JP H0448487 B2 JPH0448487 B2 JP H0448487B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- oxygen
- porous substrate
- composite
- 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
Links
- 229910052760 oxygen Inorganic materials 0.000 claims description 151
- 239000001301 oxygen Substances 0.000 claims description 150
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 135
- 239000010409 thin film Substances 0.000 claims description 120
- 239000000758 substrate Substances 0.000 claims description 89
- 239000002131 composite material Substances 0.000 claims description 86
- 239000012530 fluid Substances 0.000 claims description 45
- 230000010220 ion permeability Effects 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- -1 oxygen ions Chemical class 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 description 32
- 239000007787 solid Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000007784 solid electrolyte Substances 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000012466 permeate Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001886 ciliary effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Description
本発明は、酸素イオン透過性を有する複合体と
この複合体の製造方法に関するものであり、特に
本発明は、酸素を含有する気体中の酸素を分離す
ること、含酸素化合物を含む流体中から酸素を分
離すること、酸素を含有する気体中の酸素を検知
すること、もしくは酸素を含有する気体中の酸素
をポンプすることのなかから選ばれる何れか少な
くとも１つを行なうことのできる酸素イオン透過
性を有する複合体とこの複合体の製造方法に関す
るものである。
酸素イオン透過性を有する複合体を利用した固
定電解質酸素センサが従来知られているが、特に
下記のようなセンサが広く用いられている。
ジルコニア（ZrO2）に８〜10molのCaO，
Y2O3，ThO2などのアルカリ土類金属、希土類金
属の酸化物を固溶化させた螢石形の結晶構造を有
する安定化ジルコニアの焼結層の両側面にガス透
過性の多孔質白金電極をそれぞれ設け、400℃以
上の高温に保持した状態で酸素分圧の異なる系を
分離すると、カソード側の酸素がイオンの状態で
固体電解質であるZrO2中を移動してアノード側
に至り、ここで電子を放出して酸素となり、これ
によりアノード側からカソード側へ電流が流れ、
この際生ずる起電力Emfは酸素分圧の対数に比例
することを利用した固体電解質酸素センサであ
り、このセンサは自動車の空燃比（Ａ／Ｆ）検出
センサとしても広く使用されている。
しかしながら、ジルコニア焼結層の厚さは通常
１〜５mm程度であり、応答性を迅速にするために
は例えば850℃のような高温で測定することが必
要である。このためセンサ寿命は短かくなるばか
りでなく、また信頼性も低下するという欠点があ
る。
このような欠点を改善するには、ジルコニア焼
結層の厚さを１mmよりできるだけ薄くして酸素イ
オンが層中を移動する時間を短かくすれば測定温
度も低下させることができると共に、寿命の長期
化にもよい影響を及ぼすが、ジルコニア焼結層の
厚さを１mmより薄くすることは焼結層の機械的強
度の点から実質的に制限される。
ところで特開昭57−145068号には、ストロンチ
ウム、ビスマスおよびコバルトの主酸化物を主体
とする、電子導電性および酸素イオン導電性を有
する金属酸化物複合体および酸素の分離方法が開
示されており、その金属酸化物複合体の層の厚さ
は通常10-3〜10+4μｍであると記載されている。
また上記金属酸化物複合体を製造する方法は、上
記公報によれば、ストロンチウム、ビスマス、コ
バルトの各々の金属原子を含む化合物を焼成して
酸化物に転換し得る化合物、例えば酸化ストロン
チウム、酸化ビスマス、酸化コバルトの如き酸化
物あるいは好ましくは硝酸塩、炭酸塩であるが、
他に硫酸塩、リン酸塩等の無機酸塩、酢酸塩、シ
ユウ酸塩等の有機酸塩、塩化物、臭化物、ヨウ化
物等のハロゲン化物、あるいは水酸化物、オキシ
ハロゲン化物を所望の割合で混合し焼成する方
法、また上記記載のそれぞれの金属の塩の混合水
溶液を、アンモニア水等のアルカリ水溶液で加水
分解するいわゆる共沈澱法により調製した後焼成
する方法が開示されている。さらにまた上記公報
によれば、金属酸化物複合体を酸素分離用として
用いる場合には層状にして、なかでも膜として使
用することが好ましく、前記記載の調製方法によ
つて得られた金属酸化物複合体の成膜と成膜を重
ねる方法としては、例えばペレツト、シート状等
の固形物を切断、研磨等の機械的加工により成膜
してもよく、粉末状のものを加圧成形あるいはペ
ースト状にして多孔性支持体上に塗布し、焼結さ
せるなどの方法があると開示されている。さら
に、真空蒸着法、アセチレン溶射法、プラズマジ
エツト法、反応性スパツタリング法、化学気相蒸
着法、化学スプレー法、合金メツキの酸化等の成
膜方法があり、前記多孔性支持体としてはステン
レス、ブロンズ等の多孔性金属板または焼結体な
らびにそれらの複合体、多孔性シリカアルミナ、
多孔性アルミナ、多孔性マグネシア等の多孔性酸
化物焼結体、窒化ホウ素等の窒化物焼結体、炭化
ケイ素等の炭化物焼結体等があると開示されてい
る。
このように上記公報に記載の金属酸化物複合体
が単体で用いられる場合には機械的強度の点から
望ましい薄い厚みの膜状とするには限度があり、
一方望ましい薄い厚みの膜状で用いるためには先
述のように多孔性支持体上に複合体粉末ペースト
を塗布、焼成するか、真空蒸着法で多孔性支持体
上に複合体膜を形成するかしており、何れにして
も同公報記載の発明の金属酸化物複合体は複合体
単体もしくは多孔性支持体の表層部に担持された
電子導電性および酸素イオン導電性を有する金属
酸化物の膜を有する複合体の態様で酸素の分離に
用いられている。
さて、酸素あるいは含酸素化合物を含有する流
体中の酸素が固体電解質中を透過するのは下記の
諸過程を逐次経由して行われると考えられてい
る。
(1) 膜界面への拡散。
(2) 膜界面への吸着、酸素含酸素化合物分子の解
離による酸素原子の生成、さらに酸素原子が電
子を受取ることによるイオン化。
(3) 酸素イオンの膜内拡散。
(4) 酸素イオンの膜界面での電子放出、酸素分子
への結合、さらに膜界面よりの酸素分子の脱
離、あるいは酸素と反応性流体との反応による
脱離。
(5) 膜界面外への酸素あるいは上記反応による生
成物の拡散。
いま酸素が固体電解質中を効率よく透過するた
めには、上記(1)〜(5)の過程が均衡して進行する必
要がある。
ところで従来の厚膜にあつては、上記過程(3)に
おける固体電解質中の拡散過程が律速となるた
め、固体電解質膜を薄くすることが望まれていた
が、従来充分満足される固体電解質薄膜であつて
使用中充分な強度を有するものは開発されていな
かつた。
例えば前記特開昭57−145068号においても、前
述のように金属酸化物複合体を単体で用いる場合
の厚さを薄くすることを目的として、酸素透過性
を有する金属酸化物複合体薄膜を多孔性支持体上
に形成させるため、前記複合体粉末ペーストを塗
布、焼成する方法、真空蒸着させる方法等が考え
られると記載されているが、これらの考えは何れ
も多孔性支持体の表面層に前記金属酸化物複合体
薄膜を形成させようとするものである。しかしな
がら多孔性支持体の表面に塗布、焼成されて形成
される薄膜は膜厚が不均一であるばかりでなく、
膜厚を薄くするため塗布量を少なくすると多孔性
支持体の表面が露出する部分が生ずるか、あるい
はいわゆるピンホールが生じ分離特性が著しく低
下する恐れが生ずる。また前記薄膜は多孔性支持
体の表面層に形成されているため、取扱いならび
に使用中に外力を受けると機械的歪により欠落す
るなどの恐れが生ずる。また前記公報に示唆され
ている真空蒸着法によつて多孔性支持体の表面層
に複合体薄膜を形成することは、前記ペーストを
塗布、焼成する方法よりも膜厚の調整は困難であ
るばかりでなく膜厚を薄くしようとするとピンホ
ールが生じる恐れがあると考えられ、さらにまた
前記塗布、焼成する方法と同様に薄膜は多孔性支
持体の表面層に形成されているため、取扱いなら
びに使用中に外力を受けると機械的歪により欠落
するなどの恐れが生ずることは避けられないと考
えられる。
本発明は、従来の酸素イオン透過性を有する複
合体とその製造方法に見られる欠点を除去、改善
することのできる複合体とその製造方法を提供す
ることを目的とし、特許請求の範囲記載の酸素イ
オン透過性を有する複合体とこの複合体の製造方
法を提供することによつて前記目的を達成するこ
とができる。
すなわち本発明は、多孔質基体と前記基体内の
多孔質部の少なくとも一部に形成された薄膜とを
有する複合体であつて、前記薄膜は前記基体内に
おいて化学反応により形成された薄膜であり、か
つ基体と前記薄膜との何れか少なくとも１つは酸
素イオン透過性を有することを特徴とする酸素イ
オン透過性を有する複合体とその製造方法に関す
る。
次に本発明を詳細に説明する。
本発明の複合体は、多孔質基体の内部において
化学反応により形成された薄膜を有する複合体で
あり、第１図はこの複合体円板を厚さ方向に切つ
た縦断面拡大説明図であり、１は複合体、２は複
合体の多孔質基体の多孔質部、３は多孔質基体の
固体部に担持されている薄膜である。この薄膜３
は化学反応により生成された薄膜である。前記化
学反応を生起させるには多孔質基体２を例えば第
２図に示すように円盤状に成形してムライト管４
内に該管を閉塞するように挿入し、該管の両端か
ら細い管５をそれぞれ挿入してそれらの先端が多
孔質基体板近傍に達するようにさせて、それぞれ
の細い管より反応性流体Ａ，Ｂをそれぞれ導入す
る。そうすると流体Ａ，Ｂは多孔質基体内部にお
いて接触して流体Ａ，Ｂ内にそれぞれ含有される
反応性物質ａ，ｂが化学反応を生起して反応生成
物が薄膜として多孔質基体板内に析出する。
第３図は本発明の複合体の１部の多孔質基体と
薄膜の相関的配列構造をミクロ的に示す縦断面説
明図であり、１は本発明の複合体、２１は多孔質
基体の固体部、３１は前記多孔質基体の固体部２
１に担持されている薄膜、４１，５１はそれぞれ
多孔質基体の固体部２１中の細孔であつて、４１
は薄膜３１の左側に形成されている細孔、５１は
薄膜３１の右側に形成されている細孔である。
いま酸素を含有する流体が薄膜３１の左側の細
孔４１を経て複合体１内に流入すると、流体分子
の移動は細孔を通じて速やかに行われる。従つて
細孔部分における透過機構は多孔質基体の固体部
の酸素透過性の有無にかかわらず、いわゆる細孔
内拡散であると考えることができる。第３図にお
いて・印は酸素分子であり、Γ印は酸素以外の気
体の分子であり、薄膜の右側の細孔５１内ならび
に複合体１の外方には酸素分子が存在している状
態が示されている。
なお本発明の複合体のマクロ的構造は、多孔質
基体を構成する固体ならびに前記基体内部に担持
される薄膜がそれぞれ酸素イオンに対する透過性
が有るか無いかによつて下記の表に示す如きａ，
ｂ，c3種の態様がある。
The present invention relates to a composite having oxygen ion permeability and a method for producing the composite.In particular, the present invention relates to a composite having oxygen ion permeability and a method for producing the composite. Oxygen ion permeation capable of performing at least one of the following: separating oxygen, detecting oxygen in an oxygen-containing gas, or pumping oxygen in an oxygen-containing gas The present invention relates to a composite material having properties and a method for producing the composite material. Fixed electrolyte oxygen sensors using composites having oxygen ion permeability are conventionally known, and the following sensors are particularly widely used. 8 to 10 mol of CaO in zirconia (ZrO 2 ),
Gas-permeable porous platinum is placed on both sides of the sintered layer of stabilized zirconia, which has a fluorite-shaped crystal structure in which oxides of alkaline earth metals and rare earth metals such as Y 2 O 3 and ThO 2 are dissolved. When systems with different oxygen partial pressures are separated by providing electrodes and maintaining the temperature at a high temperature of 400°C or higher, the oxygen on the cathode side moves in the form of ions through ZrO 2 , which is a solid electrolyte, and reaches the anode side. Here, electrons are released and become oxygen, which causes current to flow from the anode side to the cathode side.
This solid electrolyte oxygen sensor utilizes the fact that the electromotive force Emf generated at this time is proportional to the logarithm of the oxygen partial pressure, and this sensor is also widely used as an air-fuel ratio (A/F) detection sensor for automobiles. However, the thickness of the zirconia sintered layer is usually about 1 to 5 mm, and it is necessary to measure at a high temperature, for example, 850° C., in order to achieve rapid response. This not only shortens the sensor life, but also reduces reliability. In order to improve these drawbacks, the measurement temperature can be lowered by reducing the thickness of the zirconia sintered layer to be as thin as possible below 1 mm to shorten the time it takes for oxygen ions to move through the layer. Although it has a positive effect on the long-term use, reducing the thickness of the zirconia sintered layer to less than 1 mm is substantially limited in terms of the mechanical strength of the sintered layer. By the way, JP-A-57-145068 discloses a metal oxide composite mainly composed of strontium, bismuth, and cobalt oxides, which has electronic conductivity and oxygen ion conductivity, and a method for separating oxygen. , the thickness of the metal oxide composite layer is generally stated to be between 10 −3 and 10 +4 μm.
According to the above-mentioned publication, the method for producing the metal oxide composite includes a compound that can be converted into an oxide by firing a compound containing metal atoms of strontium, bismuth, and cobalt, such as strontium oxide and bismuth oxide. , oxides such as cobalt oxide or preferably nitrates, carbonates,
In addition, inorganic acid salts such as sulfates and phosphates, organic acid salts such as acetates and oxalates, halides such as chlorides, bromides, and iodides, or hydroxides and oxyhalides in desired proportions. A method in which a mixed aqueous solution of each of the metal salts described above is hydrolyzed with an alkaline aqueous solution such as aqueous ammonia by a so-called coprecipitation method and then calcined is disclosed. Furthermore, according to the above-mentioned publication, when the metal oxide composite is used for oxygen separation, it is preferable to use it in a layered form, especially as a membrane, and the metal oxide composite obtained by the preparation method described above is preferably used as a layer. As a method for forming composite films one after another, for example, a solid material such as a pellet or sheet may be formed by mechanical processing such as cutting or polishing, or a powder material may be formed by pressure molding or a paste. It is disclosed that there is a method in which the material is coated on a porous support and sintered. Furthermore, there are other film forming methods such as vacuum evaporation, acetylene spraying, plasma jetting, reactive sputtering, chemical vapor deposition, chemical spraying, and oxidation of alloy plating. , porous metal plates or sintered bodies such as bronze, and composites thereof, porous silica alumina,
It is disclosed that there are porous oxide sintered bodies such as porous alumina and porous magnesia, nitride sintered bodies such as boron nitride, and carbide sintered bodies such as silicon carbide. In this way, when the metal oxide composite described in the above-mentioned publication is used alone, there is a limit to how thin a film can be formed from the viewpoint of mechanical strength.
On the other hand, in order to use it in the form of a film with a desirable thin thickness, it is necessary to apply a composite powder paste on a porous support as described above and bake it, or to form a composite film on a porous support using a vacuum evaporation method. In any case, the metal oxide composite of the invention described in the same publication is a composite alone or a metal oxide film having electronic conductivity and oxygen ion conductivity supported on the surface layer of a porous support. It is used for the separation of oxygen in the form of a complex with Now, it is thought that oxygen in a fluid containing oxygen or an oxygen-containing compound permeates through a solid electrolyte through the following processes sequentially. (1) Diffusion to the membrane interface. (2) Generation of oxygen atoms through adsorption to the membrane interface and dissociation of oxygen-containing compound molecules, and ionization when oxygen atoms receive electrons. (3) Diffusion of oxygen ions within the membrane. (4) Electron emission of oxygen ions at the membrane interface, bonding to oxygen molecules, and further desorption of oxygen molecules from the membrane interface, or desorption due to reaction between oxygen and reactive fluid. (5) Diffusion of oxygen or products from the above reaction outside the membrane interface. In order for oxygen to efficiently permeate through the solid electrolyte, the above processes (1) to (5) need to proceed in a balanced manner. By the way, in the case of conventional thick films, since the diffusion process in the solid electrolyte in step (3) above is rate-determining, it has been desired to make the solid electrolyte membrane thinner. However, no material with sufficient strength during use has been developed. For example, in the above-mentioned Japanese Patent Application Laid-Open No. 57-145068, a metal oxide composite thin film having oxygen permeability was made with a porous layer in order to reduce the thickness when the metal oxide composite was used alone as described above. In order to form the composite powder paste on the porous support, it is stated that methods such as coating and baking the composite powder paste, vacuum deposition method, etc. can be considered. The purpose is to form the metal oxide composite thin film. However, the thin film formed by coating and baking on the surface of a porous support not only has uneven thickness;
If the coating amount is reduced in order to reduce the film thickness, the surface of the porous support may be exposed in some areas, or so-called pinholes may occur, which may significantly reduce the separation properties. Furthermore, since the thin film is formed on the surface layer of the porous support, there is a risk that it may break off due to mechanical strain if external force is applied during handling or use. Furthermore, forming a composite thin film on the surface layer of a porous support by the vacuum evaporation method suggested in the above publication is more difficult to adjust the film thickness than the method of applying and baking the paste. If you try to make the film thinner than the above, there is a risk of pinholes forming.Furthermore, like the coating and baking method described above, the thin film is formed on the surface layer of the porous support, so handling and use may be difficult. It is considered inevitable that if an external force is applied to the inside, there will be a risk of breakage due to mechanical strain. An object of the present invention is to provide a composite having oxygen ion permeability and a method for producing the same that can eliminate and improve the drawbacks found in conventional composites having oxygen ion permeability and methods for producing the same. The above object can be achieved by providing a composite having oxygen ion permeability and a method for producing the composite. That is, the present invention provides a composite body having a porous substrate and a thin film formed on at least a portion of a porous portion within the substrate, the thin film being a thin film formed within the substrate by a chemical reaction. The present invention relates to a composite having oxygen ion permeability, and a method for producing the same, wherein at least one of the substrate and the thin film has oxygen ion permeability. Next, the present invention will be explained in detail. The composite of the present invention is a composite having a thin film formed by a chemical reaction inside a porous substrate, and FIG. 1 is an enlarged longitudinal cross-sectional view of this composite disk cut in the thickness direction. , 1 is a composite, 2 is a porous portion of a porous substrate of the composite, and 3 is a thin film supported on a solid portion of the porous substrate. This thin film 3
is a thin film produced by a chemical reaction. In order to cause the chemical reaction, the porous substrate 2 is formed into a disk shape as shown in FIG. 2, and a mullite tube 4 is formed.
The thin tubes 5 are inserted into the tube so as to be closed, and the thin tubes 5 are inserted from both ends of the tube so that their tips reach the vicinity of the porous substrate plate. , B are introduced respectively. Then, fluids A and B come into contact inside the porous substrate, and the reactive substances a and b contained in fluids A and B, respectively, cause a chemical reaction, and the reaction products are deposited as a thin film inside the porous substrate plate. do. FIG. 3 is a vertical cross-sectional view microscopically showing the relative arrangement structure of the porous substrate and the thin film in a part of the composite of the present invention, where 1 is the composite of the present invention, 21 is the solid of the porous base. part, 31 is the solid part 2 of the porous substrate.
The thin films 41 and 51 supported on 1 are pores in the solid part 21 of the porous substrate, respectively.
51 is a pore formed on the left side of the thin film 31, and 51 is a pore formed on the right side of the thin film 31. When the oxygen-containing fluid now flows into the composite 1 through the pores 41 on the left side of the thin film 31, the fluid molecules move quickly through the pores. Therefore, the permeation mechanism in the pores can be considered to be so-called intra-pore diffusion, regardless of whether or not the solid portion of the porous substrate has oxygen permeability. In FIG. 3, the * mark is an oxygen molecule, and the Γ mark is a molecule of a gas other than oxygen, and oxygen molecules are present inside the pore 51 on the right side of the thin film and outside the composite 1. It is shown. The macroscopic structure of the composite of the present invention is as shown in the table below, depending on whether the solid constituting the porous substrate and the thin film supported inside the substrate are permeable to oxygen ions.
There are three types, b and c.
【表】
態様ａの場合には第４図ａに示すように含酸素
流体中の酸素分子は細孔４１中を拡散して薄膜３
１の左側に到達し、イオンの状態で薄膜３１中を
透過して薄膜３１の右側の細孔５１に到達し、細
孔５１中を拡散して複合体１より流出する。
さて薄膜３１は酸素イオン透過性を有する薄膜
であり、基体の固体部２１は酸素イオン透過性を
有しないから酸素イオンは薄膜３１の中だけを透
過して細孔５１中に拡散する。
態様ｂの場合には第４図ｂに示すように多孔質
基体の固体部２１は酸素イオンに対する透過性が
あり、薄膜３１は酸素イオンに対する透過性がな
いから、含酸素流体中の酸素分子は細孔４１中を
拡散して薄膜３１の左側に到達し、ここで多孔質
基体を構成する固体２１内を透過して薄膜３１の
右側の細孔５１内に出て、細孔５１を経て複合体
１の外へ流出する。
態様ｃの場合には第４図ｃに示すように多孔質
基体の固体部２１、薄膜３１はともに酸素イオン
に対する透過性を有しているので、含酸素流体中
の酸素分子は細孔４１中を拡散して薄膜３１の左
側に到達し、ここで固体２１と薄膜３１の何れを
も透過して薄膜３１の右側の細孔５１に到達し、
細孔中を拡散して複合体１より流出する。この際
酸素分子が固体２１、薄膜３１のどちらをより優
先的に透過するかは固体２１と薄膜３１との酸素
イオン透過能の大きい方をより多く透過すること
になる。
なお本発明の酸素イオン透過性を有する複合体
中の薄膜は、本発明の前記複合体の製造方法につ
いて詳しく説明されている如く、通常の平膜とは
異なり、薄膜の両側表面は薄膜の幾何学的断面積
よりもはるかに広い表面積すなわち多数の皺ある
いは繊毛状突起を有しているため、従来の複合体
に比し極めて効率的な機能を発揮することでき
る。
また、上記薄膜両側の広い表面の少なくともい
ずれか一面に、酸素あるいは含酸素化合物より原
子状酸素に解離するための触媒を含浸することに
よつて一層効率を高めることができる。
また、ポンプあるいは酸素センサーとして使用
するために電極が必要とされる場合には、この広
い両側表面に電極成分を含浸させてとりつければ
いわゆる過電圧の小さい優れた電極となる。
ところで本発明の複合体は、多孔質体の一部分
を閉塞させたものである。一般に、多孔質体を通
じての輸送は多孔質体の細孔部分を通じての拡散
によつてなされ、多孔質体の厚さ△Ｌに対して着
目成分の濃度差が△Ｃである時、単位断面積当り
の輸送の速度Ｆは次式で与えられる。
Ｆ＝De△Ｃ／△Ｌ
Deは有効拡散係数と呼ばれ、多孔質体の種類
によつて決まる定数である。Deは化学種にも依
存するが、特定成分のみを透過させるというよう
な機能は通常は期待できず、この意味で非選択的
な透過機構と言える。
本発明の複合体の薄膜担持部分の両側において
は、それぞれ上に示した機構で化学種の輸送がな
される。薄膜部分では、基体、薄膜の少なくとも
いずれか一方が酸素のみを選択的に透過し得る。
したがつて、複合体としては酸素のみを選択的に
透過することになるのである。
次に、定常的に、複合体の一面から他の面に向
けて酸素の輸送が行われ濃度Co2，１の含酸素流
体から濃度Co2，２の純酸素を得ている時の酸素
濃度の、酸素輸送の方向における分布の例を第５
図に示す。
定常操作における酸素の透過速度Ｆ（酸素モル
数／膜面積・時間）は
Ｆ＝DeCo2，１−Co2，ｉ／△L1＝DmCo2，ｍ−Co2，m
′／△Lm＝DeCo2′，ｉ−Co2，２／△L2
Dmは、酸素イオン透過性の固体電解質中の酸
素の拡散係数であるが、通常、多孔質体の有効拡
散係数DeはDmより５ケタ以上も大きい。したが
つて、上式のように定常操作の場合には酸素の濃
度勾配△Ｃ／△Ｌはほとんど薄膜部に存在するこ
とになり、さらに、多孔質部の厚さ△L1，△L2
が、薄膜部の厚さ△Lmに比較してDeとDmの比
近くまで厚くならない限り、多孔質部の濃度差
Co2，１−Co2，ｉ、Co2′，ｉ−Co2，２はCo2，
ｍ−Co2，m′に比して無視できることになる。し
たがつてこのような時、薄膜の両側の多孔質部は
酸素透過に対してほとんど抵抗とならず薄膜部へ
の機械的強度賦与のみに寄与することになる。
Co2，ｍは、薄膜部分の固体電解質中の酸素濃
度を表わすが、この値は接触している多孔質部の
流体中の酸素濃度Co2，ｉとの化学平衡で決まる
値よりも小さい。この原因は、流体中の酸素分子
が固体に吸着し原子に解離して、電子を受け取り
イオン化する過程の速度が有限であるためで、こ
のために酸素の透過能が低下することになる。上
記過程が十分早い場合に、Co2，ｍがCo2，ｉと
の化学平衡値となり、もつとも効率が大きくな
る。同様にして、Co2′，ｍは一般にはCo2′，ｉと
化学平衡にある濃度よりも大きく、電子の放出、
酸素原子の合一、酸素分子の脱離が十分に早い時
にCo2′，ｍがCo2′，ｉと化学平衡に達し、透過能
を増大させることができる。
したがつて、本複合体をより効果的に利用する
ための条件は、膜厚さ△Lmを小さくするととも
に膜の両端に電子の授受、酸素分子の解離や合一
などを十分速やかに行わせるための、固体電解
質、触媒、電極、含酸素流体の同時接触面を十分
に存在させることである。このために、細孔径が
小さい、好ましくは1μ以下、より好ましくは
1000Å以下、さらに好ましくは100Å以下の平均
細孔径を有する多孔質基体の使用が重要である。
このように細孔径が小さい多孔質基体を使用す
ることが重要であることの理由を以下に説明す
る。
後述するように、本発明の複合体の製造方法に
よれば、多孔質基体の両側よりそれぞれ反応性成
分ａ，ｂを拡散侵入させ、ａ，ｂ両成分間の反応
による固体生成物を細孔中に析出させる。上記反
応の反応速度はａ，ｂ濃度の積に比例する。
ａ，ｂ濃度の積は多孔質基体の内部において、
多孔質基体両側に向かつて減少する分布となる。
したがつて、固体生成物析出による薄膜が生成さ
れる過程は第６図に示すように、先ず薄膜が化学
反応により析出し始める初期は同図Ａに示す如く
析出物３１が細孔壁に析出し、同図Ｂに示す如く
析出物３１の厚さが増して細孔の通路は次第に細
くなり、最終的には同図Ｃに示す如く析出物３１
で通路が完全に閉塞される。その後は流体Ａ，Ｂ
を細孔の両側から流入させても成分ａ，ｂの接触
は薄膜３１の存在によりはばまれるので接触反応
による析出は生起しない。
このような薄膜製造機構から、製造される薄膜
３１の閉塞部分の厚さ、すなわち薄膜の有効厚さ
はほぼ多孔質基体の細孔径の大きさと相等しい程
度のものになるし、また膜両側の表面積は細孔径
に反比例して増大することになる。したがつて薄
い膜でその両側に広い流体、固体の接触面を有す
る複合体を得るためには細孔径の小さい多孔質基
体を用いることが必要である。
本発明の複合体において、多孔質基体であつて
酸素イオン透過性を有しない基体はSc，Ｙ，希
土類元素、Ti，Zr，Hf，Ｖ，Nb，Ta，Zn，
Ga，Sn，Sb，Bi，Mo，Ｗ；前記元素のなかか
ら選ばれる何れか２種以上からなる合金；前記金
属あるいは合金の窒化物、炭化物、硼化物；
Mg，Ca，Sr，Ba，Cr，Mn，Fe，Co，Ni，
Cu，Al，Si，Pb；前記元素のなかから選ばれる
何れか２種以上からなる合金；前記元素あるいは
合金の酸化物、窒化物、炭化物、硼化物：の何れ
か少なくとも１つからなる基体である。
上記酸素イオン透過性を有しない基体中電気抵
抗率が103Ω・cm以下のものは金属、合金からな
る基体が多く、これら金属、合金とこれら金属、
合金の酸化物、窒化物、炭化物、硼化物のなかか
ら選ばれる何れか少なくとも１種よりなるサーメ
ツト系基体を用いるとき、金属、合金の配合割合
を変えることによつて電気抵抗を調整することが
できる。
本発明の複合体において、多孔質基体であつて
酸素イオン透過性を有するものとしては、Sc，
Ｙ，希土類元素、Ti，Zr，Hf，Ta，Zn，Ga，
Sn，Sb，Biのなかから選ばれる何れか少なくと
も１種の酸化物がある。前記酸化物であつて電気
抵抗率が103Ω・cmより大きい基体には、例えば
Ti，Zr，Bi等の酸化物があり、一方電気抵抗率
が103Ω・cm以下の基体には、例えばGa，Sn，Zn
などの酸化物がある。
また電気抵抗率は上記種々の酸化物の配合割合
を変えることによつて調整することができる。
本発明の複合体において、薄膜であつて酸素イ
オン透過性を有するものとしてはSc，Ｙ，希土
類元素、Ti，Zr，Hf，Ta，Zn，Ga，Sn，Sb，
Biのなかから選ばれる何れか少なくとも１種の
酸化物がある。
前記酸化物であつて電気抵抗率が103Ω・cmよ
り大きい薄膜には、例えばTi，Zr，Bi等の酸化
物があり、一方電気抵抗率が103Ω・cm以下の薄
膜には例えばGa，Sn，Zn等の酸化物がある。
本発明の複合体において、上述のように多孔質
基体と薄膜の電気抵抗率の大・小により、第２表
に示す如き用途がある。[Table] In the case of embodiment a, as shown in FIG.
1, passes through the thin film 31 in the form of ions, reaches the pores 51 on the right side of the thin film 31, diffuses through the pores 51, and flows out of the composite 1. Now, the thin film 31 is a thin film having oxygen ion permeability, and since the solid portion 21 of the base does not have oxygen ion permeability, oxygen ions permeate only through the thin film 31 and diffuse into the pores 51. In the case of embodiment b, as shown in FIG. 4b, the solid portion 21 of the porous substrate is permeable to oxygen ions, and the thin film 31 is not permeable to oxygen ions, so that the oxygen molecules in the oxygen-containing fluid are It diffuses through the pores 41 and reaches the left side of the thin film 31, where it passes through the solid 21 constituting the porous substrate, exits into the pores 51 on the right side of the thin film 31, and passes through the pores 51 to form a complex. It flows out of the body 1. In the case of embodiment c, as shown in FIG. diffuses and reaches the left side of the thin film 31, where it passes through both the solid 21 and the thin film 31 and reaches the pore 51 on the right side of the thin film 31,
It diffuses through the pores and flows out from the complex 1. At this time, whether oxygen molecules preferentially permeate through the solid 21 or the thin film 31, the oxygen molecules permeate more through the solid 21 or the thin film 31, which has a larger oxygen ion permeability. Note that the thin film in the oxygen ion-permeable composite of the present invention is different from a normal flat film, as described in detail in the manufacturing method of the composite of the present invention, in that both surfaces of the thin film have a geometric shape. Because it has a much larger surface area than its biological cross-sectional area, that is, it has many wrinkles or ciliary projections, it can function extremely efficiently compared to conventional composites. Further, the efficiency can be further improved by impregnating at least one of the large surfaces on both sides of the thin film with a catalyst for dissociating oxygen or an oxygen-containing compound into atomic oxygen. Furthermore, if an electrode is required for use as a pump or an oxygen sensor, an excellent electrode with low overvoltage can be obtained by impregnating electrode components on both wide surfaces and attaching the electrode. By the way, the composite of the present invention is a porous body partially occluded. Generally, transport through a porous body is achieved by diffusion through the pores of the porous body, and when the concentration difference of the component of interest is ΔC with respect to the thickness ΔL of the porous body, the unit cross-sectional area is The transport speed F per unit is given by the following equation. F=De△C/△L De is called an effective diffusion coefficient and is a constant determined depending on the type of porous body. Although De depends on the chemical species, it cannot normally be expected to have the function of transmitting only a specific component, and in this sense it can be said to be a non-selective permeation mechanism. On both sides of the thin film-supported portion of the composite of the present invention, chemical species are transported by the mechanism shown above. In the thin film portion, at least one of the substrate and the thin film can selectively permeate only oxygen.
Therefore, only oxygen selectively permeates through the complex. Next, the oxygen concentration when oxygen is constantly transported from one side of the complex to the other and pure oxygen with a concentration of Co2.2 is obtained from an oxygen-containing fluid with a concentration of Co2.1 . An example of the distribution in the direction of oxygen transport is shown in the fifth example.
As shown in the figure. The oxygen permeation rate F (number of oxygen moles/membrane area/time) in steady operation is F=DeCo 2 , 1−Co 2 , i/△L 1 = DmCo 2 , m−Co 2 , m
′/△Lm=DeCo 2 ′, i−Co 2 , 2/△L 2 Dm is the diffusion coefficient of oxygen in a solid electrolyte permeable to oxygen ions, but the effective diffusion coefficient De of a porous body is usually It's more than 5 digits bigger than Dm. Therefore, in the case of steady operation as shown in the above equation, the oxygen concentration gradient △C/△L will mostly exist in the thin film part, and furthermore, the thickness of the porous part △L 1 , △L 2
However, unless the thickness becomes close to the ratio of De and Dm compared to the thickness △Lm of the thin film part, the concentration difference in the porous part will be
Co2,1 - Co2 ,i, Co2 ',i- Co2,2 is Co2 ,
This means that it can be ignored compared to m-Co 2 and m'. Therefore, in such a case, the porous portions on both sides of the thin film provide little resistance to oxygen permeation and only contribute to imparting mechanical strength to the thin film portion. Co 2 ,m represents the oxygen concentration in the solid electrolyte in the thin film portion, but this value is smaller than the value determined by chemical equilibrium with the oxygen concentration Co 2 ,i in the fluid in the porous portion with which it is in contact. The reason for this is that the speed of the process in which oxygen molecules in the fluid adsorb to a solid, dissociate into atoms, receive electrons, and become ionized is finite, which results in a decrease in oxygen permeability. If the above process is fast enough, Co 2 ,m reaches a chemical equilibrium value with Co 2 ,i, and the efficiency increases. Similarly, Co 2 ′,m is generally higher in concentration than is in chemical equilibrium with Co 2 ′,i, and electron emission,
When the combination of oxygen atoms and the desorption of oxygen molecules are sufficiently rapid, Co 2 ',m reaches chemical equilibrium with Co 2 ',i, and the permeability can be increased. Therefore, the conditions for using this complex more effectively are to reduce the film thickness △Lm and to ensure that electron transfer and dissociation and coalescence of oxygen molecules occur sufficiently quickly at both ends of the film. Therefore, there should be sufficient contact surfaces for the solid electrolyte, catalyst, electrode, and oxygen-containing fluid at the same time. For this purpose, the pore size is small, preferably less than 1μ, more preferably
It is important to use a porous substrate with an average pore size of less than 1000 Å, more preferably less than 100 Å. The reason why it is important to use a porous substrate with such a small pore diameter will be explained below. As described later, according to the method for producing a composite of the present invention, the reactive components a and b are diffused into the porous substrate from both sides, and the solid product resulting from the reaction between the components a and b is absorbed into the pores. Precipitate inside. The reaction rate of the above reaction is proportional to the product of a and b concentrations. The product of a and b concentrations inside the porous substrate is
The distribution decreases toward both sides of the porous substrate.
Therefore, the process in which a thin film is formed by precipitation of solid products is as shown in Figure 6. At the initial stage when a thin film begins to precipitate due to a chemical reaction, precipitates 31 are deposited on the pore walls as shown in Figure A. However, as shown in Figure B, the thickness of the precipitate 31 increases, and the passage of the pores gradually becomes narrower, and finally, as shown in Figure C, the precipitate 31 increases.
The passage is completely blocked. After that, fluids A and B
Even if components a and b are allowed to flow in from both sides of the pore, contact between components a and b is prevented by the presence of the thin film 31, so that no precipitation occurs due to contact reaction. Due to such a thin film manufacturing mechanism, the thickness of the closed portion of the thin film 31 to be manufactured, that is, the effective thickness of the thin film, is approximately equal to the size of the pores of the porous substrate, and Surface area will increase inversely with pore size. Therefore, it is necessary to use a porous substrate with a small pore size in order to obtain a thin film composite having a wide fluid-solid contact surface on both sides. In the composite of the present invention, the porous substrate having no oxygen ion permeability includes Sc, Y, rare earth elements, Ti, Zr, Hf, V, Nb, Ta, Zn,
Ga, Sn, Sb, Bi, Mo, W; an alloy consisting of two or more of any of the above elements; nitrides, carbides, borides of the above metals or alloys;
Mg, Ca, Sr, Ba, Cr, Mn, Fe, Co, Ni,
A substrate consisting of at least one of the following: Cu, Al, Si, Pb; an alloy consisting of two or more of the above elements; an oxide, nitride, carbide, or boride of the above elements or alloys; be. The substrates that do not have oxygen ion permeability and have an electrical resistivity of 10 3 Ω・cm or less are often made of metals or alloys;
When using a cermet base made of at least one selected from alloy oxides, nitrides, carbides, and borides, the electrical resistance can be adjusted by changing the blending ratio of metals and alloys. can. In the composite of the present invention, the porous substrate having oxygen ion permeability includes Sc,
Y, rare earth elements, Ti, Zr, Hf, Ta, Zn, Ga,
There is at least one oxide selected from Sn, Sb, and Bi. For the substrate which is an oxide and has an electrical resistivity greater than 10 3 Ω·cm, for example,
There are oxides such as Ti, Zr, and Bi, while substrates with electrical resistivity of 10 3 Ω・cm or less include, for example, Ga, Sn, and Zn.
There are oxides such as Further, the electrical resistivity can be adjusted by changing the blending ratio of the various oxides mentioned above. In the composite of the present invention, thin films having oxygen ion permeability include Sc, Y, rare earth elements, Ti, Zr, Hf, Ta, Zn, Ga, Sn, Sb,
There is at least one oxide selected from Bi. Examples of thin films of oxides with electrical resistivities greater than 10 3 Ω·cm include oxides of Ti, Zr, Bi, etc., while thin films with electrical resistivities of 10 3 Ω·cm or less include, for example. There are oxides of Ga, Sn, Zn, etc. The composite of the present invention has various uses as shown in Table 2, depending on the electrical resistivity of the porous substrate and the thin film as described above.
【表】
次に酸素イオン透過性薄膜を酸素分離膜として
利用することのできる機構、すなわち酸素ポンプ
機構について説明する。
安定化ジルコニアの如く電子伝導性が酸素イオ
ン透過性に比して小さい場合、酸素は透過の上流
側で電子を受け取つてイオン化し、下流側で電子
を放出する。従つて下流に電子が蓄積する。連続
的に酸素が輸送される時には、下流より上流へ向
けての電子の流れと上流から下流への酸素イオン
の流れがつり合うことになり、究極的には透過速
度は電子伝導速度によつて律せられる。
さて外部回路を通じて下流より上流への電子の
流れを生じさせれば酸素の透過は速やくなり、さ
らに下流に正、上流に負となるように電圧を印加
すれば透過速度は一層速やくなり、さらに下流酸
素濃度を上流のそれより大きくすることができる
ので酸素ポンプを構成することができる。すなわ
ち本発明の複合体は膜厚が薄く、しかも膜の両面
に大きな界面面積を有するためにこのような酸素
ポンプを実用化させることができる。
他の１つの態様として電圧を印加することはで
きないが、下流より上流への速かな電子のフイー
ドバツクにより酸素の透過速度を高めることを目
的とする場合には、多孔質基体、薄膜の何れか少
なくとも一方に十分な電子伝導性を付与するこ
と、すなわち多孔質基体、薄膜の何れか少なくと
も１つとして電気抵抗率103Ω・cm以下、より好
ましくは13Ω・cm以下のものを用いることによつ
て前記目的を達成することができる。本発明の複
合体のこのような態様にあつては、複合体内に電
位差が発生しないため酸素センサとして用いるこ
とはできず、また酸素ポンプ機能をも有しない
が、例えば空気を20気圧に圧縮して複合体の一方
側面に供給することにより４気圧の酸素分圧とな
ることを利用して、他方側面に４気圧以下の圧力
を有する純酸素を得ることができるので、本発明
の複合体をこのような目的のため効果的に使用す
ることができる。
本発明の目的は、酸素分子の分離・濃縮に限定
されない。すなわち、流体中の含酸素化合物を解
離して原子状酸素を発生させることによつて酸素
のみを系外にとり出すためにも使用できる。例え
ば、薄膜両面に存在する広い界面積を有する、流
体と酸素透過能を有する固体電解質との接触面に
触媒を担持させる。触媒としてNiを担持させた
本発明複合体の一面に一酸化炭素と水素とを流通
させ、他の面ではN2等の不活性ガスを流し、場
合によつてはさらに両面の間に電圧を印加してや
れば、省エネルギー的で安全なメタン製造反応器
となる。これをさらに説明する。
一酸素炭素と水素とよりメタンを製造する方法
は、次の化学量論式に基いて進行することが知ら
れている。
CO＋3H2→CH4＋H2O
この反応では、３モルの水素のうち１モルは水
となつて燃焼してしまうために、無駄に水素が消
費されるばかりでなく、その反応に伴う大きな発
熱が反応装置の熱的暴走を引き起しかねないな
ど、取り扱い操作上の困難をも提供しているので
ある。一方、この触媒反応はCO分子からＣ原子
とＯ原子への解離反応を経由して進行することが
知られている。したがつて、Ｏ原子を反応系外へ
取り出してやれば、水素の無駄な消費を伴わない
省エネルギー的で、しかも発熱がはるかに抑制さ
れるために安全なメタン製造反応器となるのであ
る。
さらにまた、現在麻酔剤として大量に使用さ
れ、医療従事者への悪影響の懸念されている
N2Oの安全な処理のためにも有利に使用し得る。
例えば、本発明複合体の薄膜の両側界面に白金触
媒を担持させる。白金はN2OよりＯを解離させ
る反応、ＯとH2よりH2Oを生成する反応いずれ
に対しても優れた触媒となる。そこで、手術室の
N2Oで汚染された空気を本発明複合体の一方の
面に、H2を他の面に流すことによりN2OをN2と
して手術室に戻すことができる。もしも室内の空
気とH2を直接白金触媒と接触させてN2O＋H2→
N2＋H2Oなる反応でN2Oを除去したとすると、
未反応のH2が室内に導入されて危険であるため
に、こうした方法はとれないのであり、こうた例
は数多く本発明の適用の範囲は非常に広い。
含酸素化合物に対してもこのように広い用途が
あるのは、本発明の複合体が、膜厚が薄いと同時
に、膜両面に広い流体と酸素イオン透過性を有す
る固体との接触面積を持つという特長に由来して
いるのである。
次に本発明の酸素イオン透過性を有する複合体
の製造方法について説明する。
多孔質基体円板を例えばムライト管内に嵌装
し、管の両端から細いチユーブを前記円板の近傍
に先端が到達するまで挿入して、反応性成分ａ，
ｂを含有する流体Ａ，Ｂをそれぞれのチユーブか
ら流入すると、多孔質基体内部において成分ａ，
ｂが接触して化学反応が生起し、これによつて反
応生成物が固体状で析出する。固体の析出で薄膜
が生成する過程は、第６図で模式的に示した通り
であるが、こうした製造方法は３つの大きな原理
的な特長を有している。すなわち第１に膜の厚さ
が製膜時間に依存しないこと、第２にピンホール
が生じないこと、第３に薄膜の両端に酸素イオン
透過能を有する固体電解質と流体との接触の場を
提供する広い界面が生成することである。
以下、上記３つの点について順次説明する。
第１に多孔質基体の両側から侵入する反応性成
分間の接触は第６図析出物３１の閉塞、すなわち
薄膜の完成とともに妨げられてそれ以上固体析出
物の析出は進行しないのであるからである。この
点は蒸着法などの製膜では、蒸着時間の厳密な制
御が膜厚の制御のために必要であることを考える
と本発明の製造方法の重要な利点であることが明
らかである。
第２のピンホールが生じないという点も本発明
の極めて重要な利点である。
固体薄膜は、高い選択透過性、省エネルギー等
の潜在的利点を有しているが、ピンホールが生ず
ると選択性が急激に低下するために実用化には困
難が伴つていた。多孔質体の両側から侵入する化
学種間の反応は閉塞が完了するまで反応が続くと
いう本発明の製造法の特徴からして、原理的に分
子レベルでピンホールは存在し得ない。この点は
他の製造方法に比べて類を見ない特長であると言
うことができる。
第３の薄膜両側の酸素透過能を有する固体と流
体との広い接触面に関して説明する。
多孔質基体の構造は実際には極めて複雑であ
り、固体部、細孔部それぞれが連続体であつて、
固体部の表面積は小さいものでも１m2／ｇ程度、
細孔径の小さい活性炭などでは1500m2／ｇにも達
するものがある。こうした多孔質基体の細孔中に
薄膜を担持させた、薄膜部分、第１図薄膜３の構
造は現実には極めて複雑なものとなる。例えてみ
れば、２種類の細い線を用いてより線を作り、さ
らにより線をより合わせたような複合体であつ
て、２種類のうちの１種類が多孔質基体を構成す
る固体、他の１種類が反応により析出した固体
で、線間の空隙が流体との接触部分であるような
構造と言えよう。したがつて、２種の固体の少な
くとも一方である酸素透過能を有する固体と流体
とは薄膜の両側に広い接触面積を有するのであ
る。
本発明の特徴の１つは膜厚が極めて薄いことに
あり、このため固体電解質を通じての固相拡散の
拡散抵抗が減少し、透過速度が著しく増大するた
めに、酸素あるいは含酸素分子の解離、電子受授
等の界面過程が律速となる。この界面過程の進行
のためには、固体電解質、酸素分子の解離、再結
合の触媒、電子授受のための電極および酸素分子
あるいは含酸素分子を含有する流体の同時接触面
（４相あるいは触媒が電極機能を兼ねる場合には
３相のいわゆる多相接触面）を十分に形成させる
必要がある。本発明によれば、例えば触媒および
電極を兼ねることができるPt，Ag等の金属を薄
膜両面に担持させることにより、前記の酸素透過
能を有する固体と流体との広い接触面が多相接触
面となるため、上記多相接触面を十分に形成させ
ることができる。
金属を薄膜面に担持させるには硝酸銀、塩化白
金酸溶液などを含浸させる担持触媒の製造方法を
用いることができる。
本発明の製造方法において、薄膜であつて酸化
物状態で酸素イオン透過性を有する薄膜を基体内
に形成させるには、Sc，Ｙ，希土類元素、Ti，
Zr，Hf，Ｖ，Nb，Ta，Zn，Ga，Sn，Sb，Bi，
Mo，Ｗのなかから選ばれる何れか少なくとも１
種の元素の塩化物等のハロゲン化物、硝酸塩、炭
酸塩、リン酸塩、硝酸塩等の無機酸塩類、酢酸
塩、シユウ酸塩等の有機酸塩類、アルコキシド、
アセトネート、オキソ化合物等の有機金属化合物
のなかから選ばれる何れか少なくとも１種を含む
流体を多孔質基体の１つの側面に、酸化剤、還元
剤、塩基、酸、アルコール、水のなかから選ばれ
るいずれか少なくとも１種を含有する流体を前記
多孔質基体の他の側面に導入して、両側面にそれ
ぞれ導入される流体の接触反応により析出する析
出物よりなる薄膜を多孔質基体内に生成させ、前
記析出物薄膜が酸化物薄膜でないときにはさらに
前記薄膜が生成された多孔質基体を焼成して前記
薄膜を酸化物薄膜とすることができる。
また前記酸化剤としては例えば酸素、二酸化塩
素等を用いることができ、前記還元剤としては例
えばH2，C2H4等を用いることができ、前記酸と
しては例えば硝酸、酢酸等を用いることができ、
また前記アルコールとしては例えばメタノール等
を有利に用いることができる。
一方本発明の製造方法において、薄膜であつて
酸素イオン透過性を有しない薄膜を基体内に形成
させるには、例えば、いわゆる気相析出法により
SiO2，Si3N4，BN，AlNをを薄膜状に析出させ
れば良い。
次に本発明を実施例について説明する。
実施例 １
Bi2O391部、ErO29部よりなる市販の粉末を混
合して乳鉢中で十分に粉砕、混合した後、るつぼ
中に装入し850℃に加熱溶融して固溶体となし、
冷却後この固溶体を乳鉢中で充分に粉砕して粒度
0.1〜0.3μｍの範囲内で平均粒度0.2μｍの粉末を得
た。この粉末を型内に入れ1.5t／cm2の圧力で直径
10mmφ厚さ６mmの円板に成型した後、800℃で20
時間焼結した。このようにして得た焼結体は気孔
率が25％の多孔質体であつた。この焼結体の両側
に10mmφ、10cmのムライト管を接着、円板側面の
シールも同時に行つた。
上記の試料に、第７図に示すようなガス導入管
５、ガス排出管６を両側に取りつけ、長さ８cmの
管状電気炉中央に多孔質体２１が位置するように
設置した。焼結体近傍温度を200℃に維持し両端
よりそれぞれ４塩化チタン（７mmHg）を含むHe
ガス、H2O（４mmHg）を含有するH2ガスを流入
させた。Heガス中のH2をガスクロマトグラフイ
ーにて分析したところ、ガス流通後約12分程で
H2が検知されなくなり、TiO2の薄膜が生成した
ことが明らかになつた。
次に、電気炉より取り出し、多孔質体部に
AgNO3飽和水溶液を含浸させ450℃で焼成する操
作を２回繰返した。これによつてAg粒子が生成
した。さらに、白金線を多孔質複合体の両面に銀
ペーストによつて固定し、再び同図のごとくガス
の導入、排出部を設置、電気炉内に設置した。操
作温度400℃、板両端間に5.0Vの印加電圧を与
え、一方より活性炭、シリカゲルで精製した空
気、他方よりHeガスをそれぞれ10ml／minで流
入させたところ、He中の酸素濃度は32％であつ
た。
上記実施例によれば、4.7ml／minの酸素が空
気からHe中に濃縮・分離されたことになり、表
面積当り6.0ml／min・cm2という大きな透過速度
が、400℃という低温度で得られていることがわ
かる。
実施例 ２
実施例１で製造した複合体を、実施例１で用い
た装置を使い、複合体の１面を純酸素、他の１面
にヘリウムで希釈した酸素を接触させて、測定温
度400℃とし、実施例１で説明した両面の白金線
間に生ずる電位差を測定したところ、ヘリウム中
の酸素濃度と電位差との間に表３に示すような対
応関係が得られた。この結果は本発明の複合体が
400℃程度の温度で酸素センサーとして使用し得
ることを示している。[Table] Next, the mechanism by which the oxygen ion permeable thin film can be used as an oxygen separation membrane, that is, the oxygen pump mechanism will be explained. When the electron conductivity is lower than the oxygen ion permeability, such as in stabilized zirconia, oxygen receives electrons and is ionized on the upstream side of the permeation, and releases electrons on the downstream side. Therefore, electrons accumulate downstream. When oxygen is transported continuously, the flow of electrons from downstream to upstream is balanced by the flow of oxygen ions from upstream to downstream, and ultimately the transmission rate is determined by the electron conduction rate. be given Now, if we create a flow of electrons from downstream to upstream through an external circuit, the permeation of oxygen will be faster, and if we apply a positive voltage to the downstream and negative voltage to the upstream, the permeation rate will become even faster. Furthermore, since the downstream oxygen concentration can be made higher than that in the upstream, an oxygen pump can be constructed. That is, since the composite of the present invention has a thin film thickness and a large interfacial area on both sides of the film, such an oxygen pump can be put into practical use. Another embodiment is that a voltage cannot be applied, but if the purpose is to increase the oxygen permeation rate by rapid electron feedback from downstream to upstream, it is possible to use at least one of a porous substrate and a thin film. To provide sufficient electron conductivity to one side, that is, to use at least one of the porous substrate and the thin film with an electrical resistivity of 10 3 Ω·cm or less, more preferably 1 3 Ω·cm or less. Therefore, the above objective can be achieved. Such an embodiment of the composite of the present invention cannot be used as an oxygen sensor because no potential difference is generated within the composite, and it does not have an oxygen pump function, but it can be used to compress air to 20 atmospheres, for example. By utilizing the fact that oxygen partial pressure is 4 atm by supplying it to one side of the complex, it is possible to obtain pure oxygen having a pressure of 4 atm or less on the other side. It can be effectively used for such purposes. The purpose of the present invention is not limited to the separation and concentration of oxygen molecules. That is, it can also be used to extract only oxygen from the system by dissociating oxygen-containing compounds in the fluid and generating atomic oxygen. For example, a catalyst is supported on the interface between a fluid and a solid electrolyte having oxygen permeability, which has a large interfacial area on both sides of the thin film. Carbon monoxide and hydrogen are passed through one side of the composite of the present invention on which Ni is supported as a catalyst, and an inert gas such as N2 is passed through the other side, and in some cases, a voltage is further applied between both sides. If applied, it becomes an energy-saving and safe methane production reactor. This will be explained further. It is known that the method for producing methane from monooxygen carbon and hydrogen proceeds based on the following stoichiometric formula. CO＋3H 2 →CH 4 +H 2 O In this reaction, 1 mole out of 3 moles of hydrogen becomes water and burns, so not only is hydrogen wasted, but also a large amount of heat is generated due to the reaction. It also poses handling difficulties, such as the possibility of thermal runaway in the reactor. On the other hand, this catalytic reaction is known to proceed via a dissociation reaction from CO molecules into C atoms and O atoms. Therefore, if O atoms are taken out of the reaction system, it becomes an energy-saving reactor that does not involve wasteful consumption of hydrogen, and is also safe because heat generation is much suppressed. Furthermore, it is currently used in large quantities as an anesthetic, and there are concerns about its negative effects on medical personnel.
It can also be used advantageously for the safe disposal of N 2 O.
For example, a platinum catalyst is supported on both interfaces of the thin film of the composite of the present invention. Platinum is an excellent catalyst for both reactions that dissociate O from N 2 O and reactions that generate H 2 O from O and H 2 . Therefore, in the operating room
By flowing N 2 O-contaminated air to one side of the composite and H 2 to the other side, the N 2 O can be returned to the operating room as N 2 . If indoor air and H 2 are brought into direct contact with a platinum catalyst, N 2 O + H 2 →
Assuming that N 2 O is removed by the reaction N 2 + H 2 O,
This method cannot be used because unreacted H 2 is dangerous to introduce into the room, and there are many examples of this, and the scope of application of the present invention is very wide. The reason why the composite of the present invention has such a wide range of applications for oxygen-containing compounds is that it has a thin film thickness and a large contact area between the fluid and the solid that is permeable to oxygen ions on both sides of the film. This is due to this feature. Next, a method for producing a composite having oxygen ion permeability according to the present invention will be explained. The porous substrate disk is fitted into, for example, a mullite tube, and thin tubes are inserted from both ends of the tube until the tips reach the vicinity of the disk, and the reactive components a,
When fluids A and B containing components a and b flow in from their respective tubes, components a and
When b comes into contact, a chemical reaction occurs, whereby a reaction product is precipitated in solid form. The process of forming a thin film by precipitation of a solid is as schematically shown in FIG. 6, and this manufacturing method has three major fundamental features. Firstly, the thickness of the membrane does not depend on the film forming time, secondly, pinholes do not occur, and thirdly, there is no place for contact between the solid electrolyte, which has oxygen ion permeability, and the fluid at both ends of the thin membrane. Provided is that a wide interface is generated. The above three points will be sequentially explained below. First, the contact between the reactive components entering from both sides of the porous substrate is blocked by the blockage of the precipitate 31 in Figure 6, that is, as the thin film is completed, and the precipitation of the solid precipitate does not proceed any further. . This point is clearly an important advantage of the manufacturing method of the present invention, considering that in film formation such as vapor deposition, strict control of the vapor deposition time is necessary to control the film thickness. The absence of secondary pinholes is also a very important advantage of the present invention. Although solid thin films have potential advantages such as high permselectivity and energy savings, they have been difficult to put into practical use because the selectivity decreases rapidly when pinholes occur. Considering the characteristic of the production method of the present invention that the reaction between chemical species entering from both sides of the porous body continues until the blockage is completed, pinholes cannot exist at the molecular level in principle. This point can be said to be a unique feature compared to other manufacturing methods. The wide contact surface between the solid having oxygen permeability and the fluid on both sides of the third thin film will be explained. The structure of a porous substrate is actually extremely complex, with the solid part and pore part each being a continuum.
Even if the surface area of a solid part is small, it is about 1 m 2 /g.
Some activated carbons with small pore diameters reach up to 1500 m 2 /g. In reality, the structure of the thin film portion, the thin film 3 in FIG. 1, in which the thin film is supported in the pores of such a porous substrate, is extremely complicated. For example, it is a composite material in which two types of thin wires are used to create a stranded wire, and the strands are then twisted together, one of which is a solid that constitutes a porous substrate, and another. One type of solid is a solid precipitated by a reaction, and it can be said that the structure is such that the void between the lines is the part that comes in contact with the fluid. Therefore, at least one of the two solids, the solid having oxygen permeability, and the fluid have a large contact area on both sides of the thin film. One of the features of the present invention is that the film thickness is extremely thin, which reduces the diffusion resistance of solid-state diffusion through the solid electrolyte and significantly increases the permeation rate, thereby reducing the dissociation of oxygen or oxygen-containing molecules. Interfacial processes such as electron transfer are rate-determining. In order for this interfacial process to proceed, a solid electrolyte, a catalyst for the dissociation and recombination of oxygen molecules, an electrode for electron transfer, and a fluid containing oxygen molecules or oxygen-containing molecules are required to be in simultaneous contact (four-phase or catalyst). If it also serves as an electrode function, it is necessary to sufficiently form a three-phase so-called multiphase contact surface. According to the present invention, by supporting metals such as Pt and Ag that can serve as catalysts and electrodes on both surfaces of the thin film, a wide contact surface between the solid having oxygen permeability and the fluid can be formed into a multiphase contact surface. Therefore, the multiphase contact surface can be sufficiently formed. In order to support the metal on the surface of the thin film, a method for producing a supported catalyst can be used in which the thin film is impregnated with a solution of silver nitrate, chloroplatinic acid, or the like. In the manufacturing method of the present invention, in order to form a thin film having oxygen ion permeability in an oxide state within a substrate, Sc, Y, rare earth elements, Ti,
Zr, Hf, V, Nb, Ta, Zn, Ga, Sn, Sb, Bi,
At least one selected from Mo, W
Halides such as chlorides of species elements, inorganic acid salts such as nitrates, carbonates, phosphates, nitrates, organic acid salts such as acetates and oxalates, alkoxides,
A fluid containing at least one selected from organometallic compounds such as acetonate and oxo compounds is placed on one side of the porous substrate, and a fluid selected from oxidizing agents, reducing agents, bases, acids, alcohols, and water is placed on one side of the porous substrate. A fluid containing at least one of the above is introduced into the other side of the porous substrate, and a thin film consisting of a precipitate is formed in the porous substrate by a contact reaction between the fluids introduced to both sides. When the precipitate thin film is not an oxide thin film, the porous substrate on which the thin film is formed can be further fired to make the thin film an oxide thin film. Further, as the oxidizing agent, for example, oxygen, chlorine dioxide, etc. can be used, as the aforementioned reducing agent, for example, H2 , C2H4 , etc. can be used, and as the aforementioned acid, for example, nitric acid, acetic acid, etc. can be used. is possible,
Further, as the alcohol, for example, methanol or the like can be advantageously used. On the other hand, in the manufacturing method of the present invention, in order to form a thin film that does not have oxygen ion permeability within the substrate, for example, a so-called vapor phase deposition method is used.
SiO 2 , Si 3 N 4 , BN, and AlN may be deposited in a thin film. Next, the present invention will be explained with reference to examples. Example 1 Commercially available powders consisting of 91 parts of Bi 2 O 3 and 9 parts of ErO 2 were mixed and thoroughly ground and mixed in a mortar, then charged into a crucible and heated and melted at 850°C to form a solid solution. ,
After cooling, this solid solution is thoroughly ground in a mortar to determine the particle size.
A powder with an average particle size of 0.2 μm in the range 0.1-0.3 μm was obtained. Put this powder into a mold and apply a pressure of 1.5t/cm 2 to
After molding into a disk with a diameter of 10 mm and a thickness of 6 mm, it was heated at 800℃ for 20
Sintered for hours. The sintered body thus obtained was a porous body with a porosity of 25%. Mullite tubes of 10 mmφ and 10 cm were glued to both sides of this sintered body, and the sides of the disk were also sealed at the same time. A gas inlet pipe 5 and a gas discharge pipe 6 as shown in FIG. 7 were attached to both sides of the above sample, and the porous body 21 was placed in the center of a tubular electric furnace having a length of 8 cm. The temperature near the sintered body was maintained at 200℃, and He containing titanium tetrachloride (7 mmHg) was heated from both ends.
Gas, H 2 gas containing H 2 O (4 mmHg) was introduced. Analysis of H2 in He gas using gas chromatography revealed that approximately 12 minutes after gas flow,
It became clear that H 2 was no longer detected and a thin film of TiO 2 had formed. Next, take it out of the electric furnace and place it in the porous body.
The operation of impregnating with AgNO 3 saturated aqueous solution and firing at 450°C was repeated twice. This produced Ag particles. Furthermore, platinum wires were fixed on both sides of the porous composite with silver paste, and the gas introduction and exhaust sections were installed again as shown in the same figure, and the composite was placed in an electric furnace. The operating temperature was 400℃, a voltage of 5.0V was applied between both ends of the plate, and air purified with activated carbon and silica gel was flowed in from one side at a rate of 10ml/min, and He gas was flowed from the other side at a rate of 10ml/min. The oxygen concentration in He was 32%. It was hot. According to the above example, 4.7 ml/min of oxygen was concentrated and separated from air into He, and a large permeation rate of 6.0 ml/min cm 2 per surface area was obtained at a low temperature of 400°C. I can see that it is being done. Example 2 Using the apparatus used in Example 1, the composite produced in Example 1 was brought into contact with pure oxygen on one side of the composite and oxygen diluted with helium on the other side at a measurement temperature of 400 ml. ℃, and measured the potential difference generated between the platinum wires on both sides as described in Example 1. As a result, a correspondence relationship as shown in Table 3 was obtained between the oxygen concentration in helium and the potential difference. This result shows that the complex of the present invention
This shows that it can be used as an oxygen sensor at temperatures around 400℃.
【表】
実施例 ３
実施例１と同様の方法で、Bi2O391部とErO29
部とよりなる同様の多孔質円板を製造した。次に
この円板を硝酸銀飽和水溶液に含浸させ450℃で
焼成した。この操作によつてAg粒子が、多孔質
基体細孔中に生成した。次にこの多孔質体に、実
施例１と同様に、両面にムライト管およびガス導
入用のパイレツクス製細管を設置し、管状電気炉
に設置し、200℃にて両端より４塩化チタンを含
むHeガス、H2Oを含有するH2ガスを注入して、
TiO2薄膜を生成した。次に、この複合体部分を
約400℃に維持し、一面より純酸素を100ml／
min、他の一面よりHeを5.0ml／minで流通させ
て、He気流中の酸素分圧をガスクロマトグラフ
イーにより測定したところ、10.3％であつた。こ
のときHe気流中の窒素の濃度は0.05％以下であ
つて、空気などの実験流路へのもれ込みはほとん
ど無視できるので、Ag粒子によつて電子伝導性
が生じたため電圧を印加しない条件で、0.66ml／
min・cm2という大きな透過速度が得られたことに
なる。
以上本発明の複合体は酸素を含有する気体中の
酸素を分離すること、含酸素化合物を含む流体中
から酸素を分離すること、酸素を含有する気体中
の酸素を検知すること、酸素を含有する気体中の
酸素をポンプすること等の種々の用途に使用する
ことのできる、従来の前記用途に使用される複合
体に比して極めて効率よく、かつ耐久性のある複
合体である。[Table] Example 3 In the same manner as in Example 1, 91 parts of Bi 2 O 3 and 9 parts of ErO 2
A similar porous disk consisting of Next, this disk was impregnated with a saturated silver nitrate aqueous solution and fired at 450°C. By this operation, Ag particles were generated in the pores of the porous substrate. Next, similar to Example 1, mullite tubes and Pyrex thin tubes for gas introduction were installed on both sides of this porous body, and the porous body was placed in a tubular electric furnace. Injecting gas, H2 gas containing H2O ,
A TiO2 thin film was produced. Next, this complex part is maintained at approximately 400℃, and 100ml/100ml of pure oxygen is applied from one side.
He was passed through the other side at a rate of 5.0 ml/min, and the oxygen partial pressure in the He gas stream was measured by gas chromatography and found to be 10.3%. At this time, the concentration of nitrogen in the He gas flow is less than 0.05%, and the leakage of air and other substances into the experimental flow path can be almost ignored. So, 0.66ml/
This means that a large permeation rate of min cm 2 was obtained. As described above, the complex of the present invention can be used to separate oxygen in a gas containing oxygen, to separate oxygen from a fluid containing an oxygen-containing compound, to detect oxygen in a gas containing oxygen, and to detect oxygen in a gas containing oxygen. It is a highly efficient and durable composite that can be used in a variety of applications, such as pumping oxygen in gases, and is much more efficient and durable than conventional composites used in such applications.
第１図は本発明の複合体を厚さ方向に切つた縦
断面拡大説明図、第２図は本発明の複合体を製造
するのに用いられる装置の１つの態様を示す縦断
面図、第３図は本発明の複合体の一部の多孔質基
体と薄膜との相関的配列構造をミクロ的に示す縦
断面説明図、第４図ａ，ｂ，ｃは前記第３図の配
列構造において、第１表の態様ａ，ｂ，ｃをそれ
ぞれミクロ的に示す縦断面説明図、第５図は定常
的に複合体の一面から他の面に向けて酸素の輸送
が行われる時の酸素濃度の酸素輸送の方向におけ
る分布の例を示す説明図、第６図Ａ，Ｂ，Ｃは薄
膜生成過程中析出初期、析出中期、析出完了期を
それぞれ示す図、第７図は実施例１において用い
た複合体の製造装置の縦断面図である。
１…複合体、２，２１…複合体の多孔質基体の
多孔質部、３，３１…多孔質基体の固体部に担持
されている薄膜、４…ムライト管、５…ガス導入
管、６…ガス排出管、４１，５１…細孔。
FIG. 1 is an enlarged vertical cross-sectional view of the composite of the present invention cut in the thickness direction; FIG. 2 is a vertical cross-sectional view showing one embodiment of the apparatus used to manufacture the composite of the present invention; FIG. 3 is a longitudinal cross-sectional view microscopically showing the relative arrangement structure of a part of the porous substrate and thin film of the composite of the present invention, and FIGS. 4 a, b, and c show the arrangement structure of FIG. , a vertical cross-sectional explanatory diagram microscopically showing aspects a, b, and c in Table 1, and Figure 5 shows the oxygen concentration when oxygen is constantly transported from one side of the complex to the other side. An explanatory diagram showing an example of the distribution in the direction of oxygen transport. Figures 6A, B, and C are diagrams showing the initial stage, middle stage, and completion stage of precipitation during the thin film formation process, respectively. FIG. DESCRIPTION OF SYMBOLS 1... Composite, 2, 21... Porous part of the porous base of the composite, 3, 31... Thin film supported on the solid part of the porous base, 4... Mullite tube, 5... Gas introduction tube, 6... Gas exhaust pipe, 41, 51...pore.
Claims (1)
とも一部に形成された薄膜とを有する複合体であ
つて、前記薄膜は前記基体内において化学反応に
より形成された薄膜であり、かつ前記基体と前記
薄膜との何れか少なくとも１つは酸素イオン透過
性を有することを特徴とする酸素イオン透過性を
有する複合体。 ２ 前記薄膜は前記基体の両側の１つの側より前
記基体内に浸入する流体と他の側より前記基体内
に浸入する前記流体と異なる種類の流体とが前記
基体内部において接触して化学反応により形成さ
れる酸素イオン透過性を有する薄膜であり、前記
多孔質基体は酸素イオン透過性を有しない多孔質
基体であることを特徴とする特許請求の範囲第１
項記載の複合体。 ３ 前記薄膜は前記基体の両側の１つの側より前
記基体内に浸入する流体と他の側より前記基体内
に浸入する前記流体と異なる種類の流体とが前記
基体内部において接触して化学反応により形成さ
れる酸素イオン透過性を有しない薄膜であり、前
記多孔質基体は酸素イオン透過性を有する多孔質
基体であることを特徴とする特許請求の範囲第１
項記載の複合体。 ４ 前記薄膜は前記基体の両側の１つの側より前
記基体内に浸入する流体と他の側より前記基体内
に浸入する前記流体と異なる種類の流体とが前記
基体内部において接触して化学反応により形成さ
れる酸素イオン透過性を有する薄膜であり、前記
多孔質基体は酸素イオン透過性を有する多孔質基
体であることを特徴とする特許請求の範囲第１項
記載の複合体。 ５ 前記基体と前記薄膜との巨視的境界面積に対
して、前記薄膜の両側において酸素の授受が行わ
れる実質的境界面積はそれぞれ少なくとも10倍で
ある特許請求の範囲第１項記載の複合体。 ６ 前記基体と前記薄膜との巨視的境界面積に対
して、前記薄膜の両側において酸素の授受が行わ
れる実質的境界面積はそれぞれ少なくとも100倍
である特許請求の範囲第５項記載の複合体。 ７ 前記酸素イオン透過性を有する薄膜は、Sc，
Ｙ、希土類元素、Ti，Zr，Hf，Ta，Zn，Ga，
Sn，Sb，Biのなかから選ばれる何れか少なくと
も１種の酸化物よりなることを特徴とする特許請
求の範囲第２あるいは４項記載の複合体。 ８ 前記酸素イオン透過性を有する多孔質基体は
Sc，Ｙ，希土類元素、Ti，Zr，Hf，Ta，Zn，
Ga，Sn，Sb，Biのなかから選ばれる何れか少な
くとも１種の酸化物よりなることを特徴とする特
許請求の範囲第３あるいは４項記載の複合体。 ９ 前記基体、薄膜のうち何れか少なくとも一方
が103Ω・cm以下の電気抵抗率を有する特許請求
の範囲第１項記載の複合体。 １０ 前記基体、薄膜のうち何れか少なくとも一
方が1Ω・cm以下の電気抵抗率を有する特許請求
の範囲第９項記載の複合体。 １１ 前記基体および薄膜はそれぞれ103Ω・cm
以上の電気抵抗率を有する特許請求の範囲第１項
記載の複合体。 １２ 前記基体および薄膜はそれぞれ106Ω・cm
以上の電気抵抗率を有する特許請求の範囲第１１
項記載の複合体。 １３ 酸化物状態において酸素イオン透過性を有
する化合物のなかから選ばれる何れか少なくとも
１種を含有する流体を多孔質基体の１つの側面
に、前記流体と接触したとき接触反応により析出
物を生成させることのできる流体を前記多孔質基
体の他の側面に導入して、多孔質基体内に析出物
よりなる薄膜を生成させ、前記析出物よりなる薄
膜が酸化物薄膜でないときにはさらに前記薄膜が
生成された多孔質基体を焼成して前記薄膜を酸化
物薄膜となすことを特徴とする酸素イオン透過性
を有する複合体の製造方法。 １４ 酸化物状態で酸素イオン透過性を有する
Sc，Ｙ、希土類元素、Ti，Zr，Hf，Ｖ，Nb，
Ta，Zn，Ga，Sn，Sb，Bi，Mo，Ｗのなかから
選ばれる何れか少なくとも１種の元素の塩化物等
のハロゲン化物、硝酸塩、炭酸塩、リン酸塩、硫
酸塩等の無機塩類、酢酸塩、シユウ酸塩等の有機
酸塩類、アルコキシド、アセトネート、オキソ化
合物等の有機金属化合物のなかから選ばれる何れ
か少なくとも１種を含む流体を多孔質基体の１つ
の側面に、酸化剤、還元剤、塩基、酸、アルコー
ル、水のなかから選ばれるいずれか少なくとも１
種を含有する流体を前記多孔質基体の他の側面に
導入して、両側面にそれぞれ導入される流体の接
触反応により析出する析出物よりなる薄膜を多孔
質基体内に生成させ、前記析出物よりなる薄膜が
酸化物薄膜でないときにはさらに前記薄膜が生成
された多孔質基体を焼成して前記薄膜を酸化物薄
膜となすことを特徴とする特許請求の範囲第１３
項記載の方法。 １５ 前記酸化剤は酸素、二酸化塩素等であり、
前記環元剤はH2、C2H4等であり、前記塩基は
NH3，NaOH等であり、前記酸は硝酸、酢酸等
であり、また前記アルコールはメタノール等であ
る特許請求の範囲第１４項記載の方法。 １６ Sc，Ｙ，希土類元素、Ti，Zr，Hf，Ｖ，
Nb，Ta，Zn，Ga，Sn，Sb，Bi，Mo，Ｗのな
かから選ばれる何れか少なくとも１つの酸素イオ
ン透過性を有する酸化物よりなる多孔質基体の両
側面からそれぞれ流体を多孔質基体内に導入し
て、前記それぞれの流体の接触反応により酸素非
透過性析出物薄膜を多孔質基体内に生成させるこ
とを特徴とする特許請求の範囲第１３項記載の方
法。 １７ Sc，Ｙ，希土類元素、Ti，Zr，Hf，Ｖ，
Nb，Ta，Zn，Ga，Sn，Sb，Bi，Mo，Ｗ；前
記元素のなかから選ばれる何れか２種以上からな
る合金；前記金属あるいは合金の窒化物、炭化
物、硼化物；Mg，Ca，Sr，Ba，Cr，Mn，Fe，
Co，Ni，Cu，Al，Si，Pb；前記元素のなかから
選ばれる何れか２種以上からなる合金；前記元素
あるいは合金の酸化物、窒化物、炭化物、硼化
物：の何れか少なくとも１つからなる酸素イオン
非透過性多孔質基体の両側面からそれぞれ流体を
多孔質基体内に導入して、前記それぞれの流体の
接触反応により酸素イオン透過性析出物よりなる
薄膜を多孔質基体内に生成させることを特徴とす
る特許請求の範囲第１３項記載の方法。[Scope of Claims] 1. A composite body comprising a porous substrate and a thin film formed on at least a portion of a porous portion within the substrate, wherein the thin film is a thin film formed within the substrate by a chemical reaction. A composite having oxygen ion permeability, wherein at least one of the substrate and the thin film has oxygen ion permeability. 2. The thin film is formed by a chemical reaction caused by a chemical reaction caused by a fluid entering the substrate from one side of the substrate and a fluid of a different type from the fluid entering the substrate from the other side. Claim 1, characterized in that a thin film is formed that has oxygen ion permeability, and the porous substrate is a porous substrate that does not have oxygen ion permeability.
Complexes described in Section. 3. The thin film is formed by a chemical reaction caused by a chemical reaction caused by a fluid entering the substrate from one side of the substrate and a fluid of a different type from the fluid entering the substrate from the other side. Claim 1, characterized in that a thin film is formed that does not have oxygen ion permeability, and the porous substrate is a porous substrate that has oxygen ion permeability.
Complexes described in Section. 4. The thin film is formed by a chemical reaction caused by a chemical reaction caused by a fluid entering the substrate from one side of the substrate and a fluid of a different type from the fluid entering the substrate from the other side. 2. The composite according to claim 1, wherein the composite is a thin film that is permeable to oxygen ions, and the porous substrate is a porous substrate that is permeable to oxygen ions. 5. The composite according to claim 1, wherein the substantial boundary area where oxygen is exchanged on both sides of the thin film is at least 10 times as large as the macroscopic boundary area between the substrate and the thin film. 6. The composite according to claim 5, wherein substantial boundary areas where oxygen is exchanged on both sides of the thin film are at least 100 times larger than the macroscopic boundary area between the substrate and the thin film. 7 The thin film having oxygen ion permeability is Sc,
Y, rare earth elements, Ti, Zr, Hf, Ta, Zn, Ga,
5. The composite according to claim 2 or 4, characterized in that the composite is made of at least one oxide selected from Sn, Sb, and Bi. 8 The porous substrate having oxygen ion permeability is
Sc, Y, rare earth elements, Ti, Zr, Hf, Ta, Zn,
The composite according to claim 3 or 4, characterized in that it is made of at least one oxide selected from Ga, Sn, Sb, and Bi. 9. The composite according to claim 1, wherein at least one of the substrate and the thin film has an electrical resistivity of 10 3 Ω·cm or less. 10. The composite according to claim 9, wherein at least one of the substrate and the thin film has an electrical resistivity of 1 Ω·cm or less. 11 The substrate and thin film each have a resistance of 10 3 Ω・cm
The composite according to claim 1, which has an electrical resistivity of at least 10%. 12 The substrate and thin film each have a resistance of 10 6 Ω・cm
Claim 11 having an electrical resistivity of
Complexes described in Section. 13 A fluid containing at least one selected from compounds having oxygen ion permeability in an oxide state is applied to one side of the porous substrate, and when the fluid comes into contact with the fluid, a precipitate is generated by a contact reaction. introducing a fluid capable of forming a precipitate into the other side of the porous substrate to generate a thin film of precipitates within the porous substrate, and further forming a thin film when the thin film of precipitates is not an oxide thin film. 1. A method for producing a composite having oxygen ion permeability, the method comprising: baking a porous substrate to form the thin film into an oxide thin film. 14 Oxygen ion permeability in oxide state
Sc, Y, rare earth elements, Ti, Zr, Hf, V, Nb,
Inorganic salts such as halides such as chlorides, nitrates, carbonates, phosphates, and sulfates of at least one element selected from Ta, Zn, Ga, Sn, Sb, Bi, Mo, and W , an oxidizing agent, an oxidizing agent, At least one selected from reducing agents, bases, acids, alcohols, and water
A fluid containing seeds is introduced to the other side of the porous substrate to form a thin film of precipitates within the porous substrate by a contact reaction of the fluids introduced to both sides, and the precipitates are deposited in the porous substrate. Claim 13, characterized in that when the thin film made of the above is not an oxide thin film, the porous substrate on which the thin film is formed is further fired to form the thin film into an oxide thin film.
The method described in section. 15 The oxidizing agent is oxygen, chlorine dioxide, etc.
The cyclic agent is H 2 , C 2 H 4 , etc., and the base is
15. The method according to claim 14, wherein the acid is NH3 , NaOH, etc., the acid is nitric acid, acetic acid, etc., and the alcohol is methanol, etc. 16 Sc, Y, rare earth elements, Ti, Zr, Hf, V,
Fluid is applied to the porous substrate from both sides of the porous substrate made of at least one oxide selected from Nb, Ta, Zn, Ga, Sn, Sb, Bi, Mo, and W that has oxygen ion permeability. 14. The method according to claim 13, wherein a thin film of oxygen-impermeable precipitate is formed in the porous substrate by a catalytic reaction of the respective fluids upon introduction into the body. 17 Sc, Y, rare earth elements, Ti, Zr, Hf, V,
Nb, Ta, Zn, Ga, Sn, Sb, Bi, Mo, W; Alloy consisting of two or more of the above elements; Nitride, carbide, boride of the above metal or alloy; Mg, Ca , Sr, Ba, Cr, Mn, Fe,
Co, Ni, Cu, Al, Si, Pb; An alloy consisting of two or more of the above elements; At least one of the following: oxides, nitrides, carbides, and borides of the above elements or alloys Fluids are introduced into the porous substrate from both sides of an oxygen ion impermeable porous substrate made of 14. The method according to claim 13, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2199084A JPS612548A (en) | 1984-02-10 | 1984-02-10 | Composite body having oxygen ion permeability and manufacture of said composite body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2199084A JPS612548A (en) | 1984-02-10 | 1984-02-10 | Composite body having oxygen ion permeability and manufacture of said composite body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS612548A JPS612548A (en) | 1986-01-08 |
| JPH0448487B2 true JPH0448487B2 (en) | 1992-08-06 |
Family
ID=12070458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2199084A Granted JPS612548A (en) | 1984-02-10 | 1984-02-10 | Composite body having oxygen ion permeability and manufacture of said composite body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS612548A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828588A (en) * | 1988-04-01 | 1989-05-09 | University Of Cincinnati | Process for preparation of heterogeneous polysiloxane membrane and membrane produced |
| US4902307A (en) * | 1988-11-18 | 1990-02-20 | California Institute Of Technology | Synthesis of SiO2 membrane on porous support and method of use of same |
| DE3921390A1 (en) * | 1989-06-29 | 1991-01-17 | Merck Patent Gmbh | METHOD AND DEVICE FOR PRODUCING PURE OXYGEN |
| US5261932A (en) * | 1992-09-01 | 1993-11-16 | Air Products And Chemicals, Inc. | Process for recovering oxygen from gaseous mixtures containing water or carbon dioxide which process employs ion transport membranes |
| US5240473A (en) * | 1992-09-01 | 1993-08-31 | Air Products And Chemicals, Inc. | Process for restoring permeance of an oxygen-permeable ion transport membrane utilized to recover oxygen from an oxygen-containing gaseous mixture |
| US5269822A (en) * | 1992-09-01 | 1993-12-14 | Air Products And Chemicals, Inc. | Process for recovering oxygen from gaseous mixtures containing water or carbon dioxide which process employs barium-containing ion transport membranes |
| US5240480A (en) * | 1992-09-15 | 1993-08-31 | Air Products And Chemicals, Inc. | Composite mixed conductor membranes for producing oxygen |
| AU706663B2 (en) * | 1994-09-23 | 1999-06-17 | Standard Oil Company, The | Oxygen permeable mixed conductor membranes |
| US6235417B1 (en) * | 1999-04-30 | 2001-05-22 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Two-phase hydrogen permeation membrane |
-
1984
- 1984-02-10 JP JP2199084A patent/JPS612548A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS612548A (en) | 1986-01-08 |
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