JPH0250052B2 - - Google Patents
Info
- Publication number
- JPH0250052B2 JPH0250052B2 JP9888987A JP9888987A JPH0250052B2 JP H0250052 B2 JPH0250052 B2 JP H0250052B2 JP 9888987 A JP9888987 A JP 9888987A JP 9888987 A JP9888987 A JP 9888987A JP H0250052 B2 JPH0250052 B2 JP H0250052B2
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- present
- oxide
- double oxide
- tellurium
- 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 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 4
- -1 oxygen ion Chemical class 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 15
- 239000013078 crystal Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002775 capsule Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910000953 kanthal Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
Description
産業上の利用分野
本発明は酸素のイオン伝導材料として有用であ
る新規化合物の４ビスマス３ストロンチウム５テ
ルル複酸化物及びその製造法に関する。
従来技術
従来、酸素のイオン伝導体としてZrO2−CaO
系、Zr2−Y2O3系が知られており、酸素センサー
等に使用されている。
しかしながら、これらの物質は比較的低い温度
（約500℃以下）では酸素のイオン伝導率が著しく
低下する。
低温度において比較的高い酸素イオン伝導性を
示す物質として、Bi2O3を主成分とし、これに他
の金属イオンを添加した次のようなものが知られ
ている。
(イ) 欠陥ホタル石型ビスマス酸化物
Bi1-XMXO1.5+Y（ただし、Ｍは希土類、Te、
Nb、Ｗ、Ｘ＝0.15〜0.5、Ｙ＝０〜0.2を表わ
す）
(ロ) 菱面体晶系で層状構造を有し、化学式
Bi1-XMXO1.5-X/2（ただし、ＭはCa、Sr、Ba、
Ｘ＝0.11〜0.27を表わす）あるいは
Bi1-XYXO1.5（ただし、Ｘ＝0.11〜0.12を表わ
す）
で示される複酸化物が知られている。
しかしながら、これらの物質はいずれもイオン
伝導性が十分に高いとはいえず、未だ実用材料に
は至つていない。
発明の目的
本発明の目的は、酸素の超イオン伝導材料とし
て有用な新規化合物を提供し、これにより酸素セ
ンサー等への材料設計において、より広い選択性
をもたせることにある。
発明の構成
本発明の新規化合物は化学式Bi4Sr3Te5O19で
示される化合物で、これはBi2O3、SrCO3、TeO2
の各紛末をモル比で２：３：５の割合に混合し、
これを800℃付近で焼成することにより製造され
る。この化合物は菱面体晶系に属し、層状の結晶
製造を有するもので、前記(ロ)の結晶構造と同形で
ある。
この構造型を有する化合物の格子定数と本発明
の新規化合物の格子定数を比較すると次の第１表
の通りである。
INDUSTRIAL APPLICATION FIELD The present invention relates to a novel compound 4-bismuth-3-strontium-5-tellurium double oxide useful as an oxygen ion conductive material and a method for producing the same. Conventional technology Conventionally, ZrO 2 −CaO was used as an ionic conductor of oxygen.
The Zr 2 -Y 2 O 3 system is known and is used in oxygen sensors, etc. However, the ionic conductivity of these materials for oxygen decreases significantly at relatively low temperatures (below about 500° C.). As a material that exhibits relatively high oxygen ion conductivity at low temperatures, the following material is known, which has Bi 2 O 3 as its main component and to which other metal ions are added. (a) Defected fluorite-type bismuth oxide Bi 1-X M X O 1.5+Y (M is rare earth, Te,
Nb, W, X=0.15-0.5, Y=0-0.2) (b) Rhombohedral crystal system with layered structure, chemical formula Bi 1-X M X O 1.5-X/2 (However, M is Ca, Sr, Ba,
Bi 1-X Y X O 1.5 (where X is 0.11 to 0.12) or Bi 1-X Y However, none of these substances can be said to have sufficiently high ionic conductivity, and has not yet been developed into a practical material. Purpose of the Invention The purpose of the present invention is to provide a novel compound useful as a superionic conductive material for oxygen, thereby providing wider selectivity in material design for oxygen sensors and the like. Structure of the Invention The novel compound of the present invention is a compound represented by the chemical formula Bi 4 Sr 3 Te 5 O 19 , which is a compound of Bi 2 O 3 , SrCO 3 , TeO 2
Mix each powder in a molar ratio of 2:3:5,
It is manufactured by firing this at around 800℃. This compound belongs to the rhombohedral crystal system, has a layered crystal structure, and has the same crystal structure as (b) above. A comparison of the lattice constants of compounds having this structural type and the lattice constants of the novel compounds of the present invention is shown in Table 1 below.
【表】
を金属原子と酸素原子の比で表わした化学
式である。
従来公知の化合物はBi原子を主成分とするに
対して、本発明の新規化合物は他の金属原子の割
合が多いのが特徴である。また、酸素の原子数も
公知の化合物では最大1.5であるに対して本発明
の新規化合物は1.583と大きい。
結晶構造上では空間群R3mが想定され、単位
の菱面体格子中に金属原子が３個含まれる。本発
明の新規化合物の結晶構造の概念図を示すと第１
図の通りである。
同図に示すように、金属原子の構造中に占める
位置には２種類あり、その内の１種（M1）に１
個、他（M2）を２個が占める。本発明の新規化
合物ではM1の位置をビスマス原子が占め、M2の
位置を３：５の比率で、ストロンチウム原子とテ
ルル原子が占めており、化学式との対応が成り立
つ。
CuKα線を用いて測定した紛末Ｘ線回析データ
ならびに格子定数を示すと第２表の通りである。[Table] is a chemical formula expressed in terms of the ratio of metal atoms to oxygen atoms.
While conventionally known compounds have Bi atoms as their main component, the novel compound of the present invention is characterized by a high proportion of other metal atoms. Furthermore, the number of oxygen atoms in the novel compound of the present invention is as large as 1.583, while the maximum number of oxygen atoms in known compounds is 1.5. The space group R3m is assumed in the crystal structure, and three metal atoms are included in the unit rhombohedral lattice. The conceptual diagram of the crystal structure of the new compound of the present invention is shown in Fig. 1.
As shown in the figure. As shown in the figure, there are two types of positions in the structure of metal atoms, one of which (M 1 )
2 occupies the other (M 2 ). In the novel compound of the present invention, the M 1 position is occupied by a bismuth atom, and the M 2 position is occupied by a strontium atom and a tellurium atom in a ratio of 3:5, which corresponds to the chemical formula. Table 2 shows powder X-ray diffraction data and lattice constants measured using CuKα rays.
【表】
この表では面指数を菱面体晶系から六方晶系に
変換して示す。
面指数のパラメータhk1間に−ｈ＋ｋ＋１＝3n
（ｎ＝０、１、２、…）の関係が成立しているこ
とが菱面体晶系であることを示している。
本新規複酸化物は、これと同一の結晶構造を持
つ前述(ロ)の複酸化物と同様に、酸素のイオン伝導
性を示す。第２図に本新規化合物の電気伝導度を
温度との関係について示す。同図には前述(イ)、(ロ)
の複酸化物についても同様に示してある。実線、
Ｐ，ａ，ｂ，ｃ，ｄはそれぞれ、
Ｐ：本発明の新規複酸化物
（Bi4Sr3Te5O19
ａ：Bi0.75Y0.25O1.5（欠陥ホタル石型）
ｂ：Bi0.65Sr0.235O1.3825
ｃ：Bi0.802Ca0.198O1.401
ｄ：Bi0.775Y0.225O1.5
である。本発明の新規複酸化物の電気伝導度は
500℃付近で10-2Ω-1cm-1の桁であり、他のビス
マスを主成分とした同構造型複酸化物と同程度で
ある。
実施例
純度99.9％以上の酸化ビスマス（Bi2O3）粉末
と純度99.9％以上の炭酸ストロンチウム
（SrCO3）粉末及び純度99.9％以上の酸化テルル
（TeO2）粉末をモル比２：３：５の比率に秤量
し、メノウ乳鉢中でエタノールを加えて充分に混
合し、平均粒径44μ以下微粉末の混合物を得た。
当該混合物を白金ルツボに入れ、ロジウムを20
％含む白金線発熱体たて型電気炉中に静置し、当
該ルツボを750℃にて24時間保持した。ルツボを
電気炉から取り出し、ルツボ内容物が室温に達し
たのち、内容物をメノウ乳鉢を用いて再び平均粒
径が44μ以下になるように粉砕した。当該粉砕物
を白金ルツボに入れ、前述の電気炉中に静置し、
800℃にて24時間保持した。その後、当該ルツボ
を電気炉から取り出し、再びメノウ乳鉢を用いて
粉砕し、当該新規複酸化物Bi4Sr3Te5O19を製造
した。当該新規複酸化物の粉末Ｘ線回析線は全て
菱面体晶型の六方晶系で指数付けが可能であり、
他の相に対応する回析線は含まれないことを確認
した。
また、当該最終紛砕物を炭化タングステン製金
型に入れ、油圧式静水発生装置中にて加圧成型
し、直径16mm、厚さ４mmの円板状成型物を作製し
た。当該成型物を白金ルツボに挿入し、前述の電
気炉中にて800℃で24時間保持し、その後、当該
ルツボを取り出し、室温まで自然冷却し、円板状
焼結体を得た。
次に、当該円板状焼結体をダイヤモンドブレー
ドを使用した精密切断機で切断し、一辺が３mm正
方で長さが13mmの角柱状の試料片を作成した。こ
の試料片の両端面に金ペーストを塗布し角柱の中
央に0.1mm径の金線を幅７mm間隔で２箇所巻き付
け、４端子法による電導度測定用の電極とした。
当該試料片を横型カンタル線発熱体電気炉に配置
し、400℃て試料に付着している金ペースト中の
有機成分を揮発・燃焼させ、その後に0.1Hzの三
角波交流を用い、印加電圧に対する電流特性を調
べ、オームの法則が成立していることを確認しつ
つ電導度を300℃から650℃の温度範囲で測定し
た。第２図の実線Ｐは当該焼結体の電気伝導度の
温度依存性を示したものである。
当該新規複酸化物の微粉末約１ｇを示差熱分析
用の白金カプセル中に入れ、示差熱分析を行つた
結果を第３図に示す。当該新規複酸化物は熱力学
的には約800℃から860℃の範囲で安定でありそれ
以下の温度では不安定であるが約600℃以下では
準安定に存在し得る。また、融点は約900℃であ
る。[Table] This table shows the plane indices converted from rhombohedral system to hexagonal system. -h+k+1=3n between surface index parameters hk1
The fact that the relationship (n=0, 1, 2, . . . ) holds indicates that it is a rhombohedral crystal system. The present new multiple oxide exhibits oxygen ion conductivity similarly to the aforementioned multiple oxide (b) having the same crystal structure. FIG. 2 shows the electrical conductivity of the novel compound as a function of temperature. In the same figure, the above-mentioned (a) and (b)
The same is shown for the double oxide. solid line,
P, a, b, c, and d are respectively: P: New composite oxide of the present invention (Bi 4 Sr 3 Te 5 O 19 a: Bi 0.75 Y 0.25 O 1.5 (defect fluorite type) b: Bi 0.65 Sr 0.235 O 1.3825 c: Bi 0.802 Ca 0.198 O 1.401 d: Bi 0.775 Y 0.225 O 1.5.The electrical conductivity of the novel double oxide of the present invention is
It is on the order of 10 -2 Ω -1 cm -1 at around 500°C, which is comparable to other bismuth-based double oxides with the same structure. Example Bismuth oxide (Bi 2 O 3 ) powder with a purity of 99.9% or more, strontium carbonate (SrCO 3 ) powder with a purity of 99.9% or more, and tellurium oxide (TeO 2 ) powder with a purity of 99.9% or more in a molar ratio of 2:3:5. ethanol was added in an agate mortar and thoroughly mixed to obtain a fine powder mixture with an average particle size of 44 μm or less. Place the mixture in a platinum crucible and add 20% rhodium.
% in a vertical electric furnace containing a platinum wire heating element, and the crucible was maintained at 750°C for 24 hours. The crucible was taken out from the electric furnace, and after the contents of the crucible reached room temperature, the contents were ground again using an agate mortar so that the average particle size was 44 μm or less. The pulverized material is placed in a platinum crucible and placed in the aforementioned electric furnace,
It was held at 800°C for 24 hours. Thereafter, the crucible was taken out of the electric furnace and ground again using an agate mortar to produce the new double oxide Bi 4 Sr 3 Te 5 O 19 . The powder X-ray diffraction lines of the new complex oxide are all rhombohedral hexagonal and can be indexed.
It was confirmed that diffraction lines corresponding to other phases were not included. Further, the final pulverized material was placed in a tungsten carbide mold and press-molded in a hydraulic static water generator to produce a disc-shaped molded product with a diameter of 16 mm and a thickness of 4 mm. The molded product was inserted into a platinum crucible and held at 800° C. for 24 hours in the electric furnace described above, and then the crucible was taken out and naturally cooled to room temperature to obtain a disc-shaped sintered body. Next, the disk-shaped sintered body was cut with a precision cutter using a diamond blade to create a prismatic sample piece with a side of 3 mm square and a length of 13 mm. Gold paste was applied to both end faces of this sample piece, and gold wires with a diameter of 0.1 mm were wound around the center of the prism at two locations with a width of 7 mm, thereby forming an electrode for measuring conductivity using the four-terminal method.
The sample piece was placed in a horizontal Kanthal wire heating element electric furnace, and the organic components in the gold paste adhering to the sample were volatilized and burned at 400°C.Then, using a 0.1Hz triangular wave alternating current, the current was adjusted to the applied voltage. The electrical conductivity was measured in a temperature range of 300°C to 650°C while examining the characteristics and confirming that Ohm's law holds true. A solid line P in FIG. 2 shows the temperature dependence of the electrical conductivity of the sintered body. About 1 g of fine powder of the new double oxide was placed in a platinum capsule for differential thermal analysis, and the results of differential thermal analysis are shown in FIG. Thermodynamically, the new double oxide is stable in the range of about 800°C to 860°C, is unstable at lower temperatures, but can exist metastablely at temperatures below about 600°C. Furthermore, the melting point is approximately 900°C.
第１図は本発明の新規複酸化物Bi4Sr3Te5O19
の結晶構造の概念図である。（101）面への投影図
である。第２図は各種酸化ビスマス系の超イオン
伝導性複酸化物及び本発明の新規複酸化物
Bi4Sr3Te5O19の電気伝導度の温度依存性を示し
たものである。
Ｐ：本発明における新規複酸化物
（Bi4Sr3Te5O19）、ａ：Bi0.75Y0.25O1.5（欠陥ホタル
石型）、ｂ：Bi0.65Sr0.235O1.3825、ｃ：Bi0.802
Ca0.198O1.401、ｄ：Bi0.775Y0.225O1.5
第３図は本発明の新規複酸化物Bi4Sr3Te5O19
の示差熱分析結果を示したものである。
Figure 1 shows the novel double oxide Bi 4 Sr 3 Te 5 O 19 of the present invention.
FIG. 2 is a conceptual diagram of the crystal structure of This is a projection onto the (101) plane. Figure 2 shows various bismuth oxide-based superionically conductive double oxides and the novel double oxide of the present invention.
This figure shows the temperature dependence of the electrical conductivity of Bi 4 Sr 3 Te 5 O 19 . P: New multiple oxide in the present invention (Bi 4 Sr 3 Te 5 O 19 ), a: Bi 0.75 Y 0.25 O 1.5 (defect fluorite type), b: Bi 0.65 Sr 0.235 O 1.3825 , c: Bi 0.802
Ca 0.198 O 1.401 , d: Bi 0.775 Y 0.225 O 1.5 Figure 3 shows the novel double oxide of the present invention Bi 4 Sr 3 Te 5 O 19
This shows the results of differential thermal analysis.
Claims (1)
３ストロンチウム５テルル複酸化物。 ２ Bi2O3、SrCO3、TeO2の紛末をモル比で２：
３：５の比率に混合した混合紛末を焼成すること
を特徴とする４ビスマス３ストロンチウム５テル
ル複酸化物の製造法。 ３ 化学式Bi4Sr3Te5O19で示される４ビスマス
３ストロンチウム５テルル複酸化物からなる酸素
のイオン伝導材料。[Claims] 1. A 4-bismuth- 3 -strontium-5-tellurium double oxide represented by the chemical formula Bi 4 Sr 3 Te 5 O 19 . 2 Bi 2 O 3 , SrCO 3 , TeO 2 powder in a molar ratio of 2:
A method for producing 4-bismuth-3-strontium-5-tellurium double oxide, which comprises firing a mixed powder mixed at a ratio of 3:5. 3 An oxygen ion conductive material consisting of 4 bismuth 3 strontium 5 tellurium double oxide represented by the chemical formula Bi 4 Sr 3 Te 5 O 19 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9888987A JPS63265821A (en) | 1987-04-22 | 1987-04-22 | 4-bismuth-3-strontium-5-tellurium double oxide, its production method, and oxygen ion conductive material made from the double oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9888987A JPS63265821A (en) | 1987-04-22 | 1987-04-22 | 4-bismuth-3-strontium-5-tellurium double oxide, its production method, and oxygen ion conductive material made from the double oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63265821A JPS63265821A (en) | 1988-11-02 |
| JPH0250052B2 true JPH0250052B2 (en) | 1990-11-01 |
Family
ID=14231705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9888987A Granted JPS63265821A (en) | 1987-04-22 | 1987-04-22 | 4-bismuth-3-strontium-5-tellurium double oxide, its production method, and oxygen ion conductive material made from the double oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63265821A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022266613A1 (en) * | 2021-06-15 | 2022-12-22 | Wisconsin Alumni Research Foundation | Oxygen ion transport materials and related devices |
-
1987
- 1987-04-22 JP JP9888987A patent/JPS63265821A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022266613A1 (en) * | 2021-06-15 | 2022-12-22 | Wisconsin Alumni Research Foundation | Oxygen ion transport materials and related devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63265821A (en) | 1988-11-02 |
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| EXPY | Cancellation because of completion of term |