CN1126801C - 类钙钛石型高温磁致冷工质材料 - Google Patents
类钙钛石型高温磁致冷工质材料 Download PDFInfo
- Publication number
- CN1126801C CN1126801C CN96117013A CN96117013A CN1126801C CN 1126801 C CN1126801 C CN 1126801C CN 96117013 A CN96117013 A CN 96117013A CN 96117013 A CN96117013 A CN 96117013A CN 1126801 C CN1126801 C CN 1126801C
- Authority
- CN
- China
- Prior art keywords
- working medium
- combination
- temperature magnetic
- perovskite
- gets
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- 229910052692 Dysprosium Inorganic materials 0.000 abstract 1
- 229910052693 Europium Inorganic materials 0.000 abstract 1
- 229910052689 Holmium Inorganic materials 0.000 abstract 1
- 229910052765 Lutetium Inorganic materials 0.000 abstract 1
- 229910052779 Neodymium Inorganic materials 0.000 abstract 1
- 229910052772 Samarium Inorganic materials 0.000 abstract 1
- 229910052771 Terbium Inorganic materials 0.000 abstract 1
- 229910052769 Ytterbium Inorganic materials 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 229910052701 rubidium Inorganic materials 0.000 abstract 1
- 229910052706 scandium Inorganic materials 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 0.000 abstract 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 nitrate Chemical class 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910002180 La0.8Ca0.2MnO3 Inorganic materials 0.000 description 1
- 229910017034 MnSn Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- ZPDRQAVGXHVGTB-UHFFFAOYSA-N gallium;gadolinium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Gd+3] ZPDRQAVGXHVGTB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/017—Compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/016—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on manganites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Abstract
一种高温磁致冷工质材料，其特征是具有如下类钙钛石化合物的化学通式：R1-xAxMO3-δ其中：R为稀土族元素La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y，Sc等以及组合；A为碱土金属元素及大离子半径低价元素，Ca、Sr、Ba、Pb、Na、K、Rb等及其组合；M为Mn或Mn与其它铁族元素(Fe、Ni、Co等)的组合；O为氧，其含量(3-δ)取决于工艺，X取0.2-0.6，R、A、M三类元素的配比接近正分比例。
Description
一、技术领域
本发明涉及类钙钛石型高温磁致冷工质材料及其制作。
二、背景技术
磁致冷是一种经济有效、无污染节能的制冷方式，与通常的气体压缩原理的致冷机相比，它不含有对环境有影响的氟里昂气体，不需要气体压缩机，因此可以小型化轻量化与微机控制，早在30年代，人们就采用顺磁盐类作为致冷工质成功的获得毫K量级极低温，将磁致冷应用于高温(20-300K)，尤其是室温是人们多年来追求的目标，要使高温磁致冷实用化，关键是研制一类能在永磁材料所产生的磁场下(1-1.5T)具有大磁熵变的材料，通常是利用铁磁性—顺磁性相变居里点的磁熵变化，目前所报导的钆镓石榴石、RAl、RNi仅适用于40K以下，室温磁致冷工质目前尚以金属钆及其合金最合适，而其它的如Mn3AlC、Ni2MnSn等化合物和FeZr等非晶材料的磁熵变仅为金属钆的一半，然而金属钆的化学稳定性差，物稀价昂，而且调节和控制一定居里点、温度范围的组方也比较困难，由于以上不足，因此距实用较远。目前普遍采用气体氟里昂致冷剂，由于国际上已经禁用氟里昂，开发无害的致冷工质和致冷方式已势在必行，磁致冷是无污染、高效率的制冷方式，关键是要合适的磁致冷工质。
三、发明内容
本发明的目的是这样实现的：一种类钙钛石型高温磁致冷工质材料，其特征是具有如下类钙钛石化合物的通式：R1-xAxMO3
其中R为稀土族元素La、Pr、Gd以及组合，A为碱土金属元素Ca、Sr、Ba及其组合，M为Mn或Mn与铁族元素Fe、Ni、Co等的组合，O为氧，x取0.1-0.9，尤其取0.2-0.6，R、A、M三类元素的配比接近正分比例R∶A∶M＝(1-x)∶x∶1±10％。该化合物可以采用溶胶-凝胶工艺、化学共沉淀工艺以及氧化物陶瓷工艺制备而成。具体而言：R取La、也取La与Pr的混合物以及La与Gd的混合物。A取Ca，M取Mn。
本发明的特点是：类钙钛石型高温磁致冷工质材料在室温附近的磁熵变可超过金属钆，并且化学稳定性远优于金属钆，价格低廉，居里温度可以通过成分变化进行人为控制改变。因此是一类目前较理想的高温磁致冷工质材料，可以应用于20-400K温区。
四、附图说明
图1为La0.8Ca0.2MnO3及Gd磁熵变随温度的变化关系曲线
图2为La0.67Ca0.33MnO3磁熵变随温度的变化关系曲线
图3为La0.62Gd0.05Ca0.33MnO3磁熵变随温度的变化关系曲线
图4为La1-xRxMnO3R(Ca Sr Ba)居里温度(纵座标表示绝对温度)与X(横座标)之间的关系曲线
图5为La0.7-YPrYSr0.3MnO3居里温度(纵座标表示绝对温度)与Y(横座标)之间的关系曲线
五、具体实施方式
按化学式进行配比，采用硝酸盐、硫酸盐等盐类，溶胶—凝胶工艺，200℃左右分解，300-600℃空气气氛中烧结8小时，其典型的磁熵变ΔSM与温度的关系见图2，在居里温度260K附近，磁熵变ΔSM＝4.3(J/KgK)，测量磁场为1.5T，
另一种类钙钛石型高温磁致冷工质材料的制作工艺是用共沉淀工艺，用R，A，M的草酸盐或硝酸盐按配比同时沉淀，沉淀介质为乙醇，其用量为10-20倍，PH值为6-7。至于氧化物陶瓷工艺是用相应的氧化物按相应的比例混和球磨后烧结而成。实施例1材料如图1所示、磁熵变ΔSM＝4.2(J/KgK)，居里温度293K附近，样品的制备方法同上，其典型的磁熵变ΔSM与温度的关系见图1。在居里温度230K附近，磁熵变ΔSM＝5.5(J/KgK)，测量磁场1.5T，而金属钆的磁熵变在相同条件下，ΔSM＝4.2(J/KgK)，居里温度293K。
实施例2如图2给出，在居里温度260K附近，磁熵变ΔSM＝4.3(J/KgK)，测量磁场1.5T，
实施例3如图3给出，在居里温度260K附近，磁熵变ΔSM＝4.3(J/KgK)，测量磁场1.5T，
实施例4：为了得到所需工作温区的磁工质，一方面可以用其它离子替代类钙钛石型中的离子A或改变A的含量来调节居里点，见图4，另一方面可以通过其它稀土离子部分或全部替代R来调节居里点，见图5。另一实施例如图3所示。
Claims (4)
1、一种类钙钛石型高温磁致冷工质材料，其特征是具有如下类钙钛石化合物的通式：R1-xAxMO3其中R为稀土族元素La、Pr、Gd以及组合，A为碱土金属元素Ca、Sr、Ba及其组合，M为Mn或Mn与铁族元素Fe、Ni、Co的组合，O为氧，x取0.2-0.6，R、A、M三类元素的配比接近正分比例。
2、由权利要求1所述的高温磁致冷工质材料，其特征是R取La，A取Ca，M取Mn。
3、由权利要求1或2所述的高温磁致冷工质材料，其特征是R取La与Pr的混合物。
4、由权利要求1或2所述的高温磁致冷工质材料，其特征是R取La与Gd的混合物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117013A CN1126801C (zh) | 1996-07-12 | 1996-07-12 | 类钙钛石型高温磁致冷工质材料 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117013A CN1126801C (zh) | 1996-07-12 | 1996-07-12 | 类钙钛石型高温磁致冷工质材料 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1170749A CN1170749A (zh) | 1998-01-21 |
| CN1126801C true CN1126801C (zh) | 2003-11-05 |
Family
ID=5123957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117013A Expired - Fee Related CN1126801C (zh) | 1996-07-12 | 1996-07-12 | 类钙钛石型高温磁致冷工质材料 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1126801C (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364923C (zh) * | 2003-11-13 | 2008-01-30 | 同济大学 | 一种温致发射率可逆变化材料 |
| WO2010003926A1 (en) * | 2008-07-08 | 2010-01-14 | Technical University Of Denmark | Magnetocaloric refrigerators |
| CN102134749A (zh) * | 2010-01-22 | 2011-07-27 | 中国科学院福建物质结构研究所 | 一种镝离子激活的钆镓石榴石新型激光晶体 |
| CN103014631B (zh) * | 2012-12-19 | 2014-08-20 | 河北师范大学 | 一种彩色Pr(Sr0.1Ca0.9)2Mn2O7薄膜的制备方法 |
| CN105112025B (zh) * | 2015-09-10 | 2018-04-06 | 南通大学 | 一种固体磁制冷材料、制备方法及磁制冷器 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6240241A (ja) * | 1985-08-12 | 1987-02-21 | 船井電機株式会社 | パンの製造方法 |
| CN1090313A (zh) * | 1993-01-20 | 1994-08-03 | 北京科技大学 | 磁致冷机用磁性致冷材料 |
-
1996
- 1996-07-12 CN CN96117013A patent/CN1126801C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6240241A (ja) * | 1985-08-12 | 1987-02-21 | 船井電機株式会社 | パンの製造方法 |
| CN1090313A (zh) * | 1993-01-20 | 1994-08-03 | 北京科技大学 | 磁致冷机用磁性致冷材料 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1170749A (zh) | 1998-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4804649A (en) | Alkaline oxalate precipitation process for forming metal oxide ceramic superconductors | |
| US20110126550A1 (en) | Magnetocaloric refrigerators | |
| CN100403461C (zh) | 永磁体及其制造方法 | |
| US11945753B2 (en) | Low loss power ferrites and method of manufacture | |
| CN1126801C (zh) | 类钙钛石型高温磁致冷工质材料 | |
| Huang et al. | Large magnetic entropy change in La0. 67− xGdxCa0. 33Mno3 | |
| Leccabue et al. | Magnetic and mössbauer study of rare-earth-substituted M-, W-and X-type hexagonal ferrites | |
| CN110218087B (zh) | 负温度系数热敏电阻材料的制备方法 | |
| EP0330214A2 (en) | High-Tc oxide superconductor and method for producing the same | |
| EP0498613A1 (en) | Regenerative materials | |
| JP2001135512A (ja) | フェライト磁石粉末および該磁石粉末を用いた磁石およびそれらの製造方法 | |
| Jiang et al. | Aging phenomenon of stabilized bismuth oxides | |
| US7135161B2 (en) | Method of producing nanosized oxide powders | |
| Sagar et al. | Cation distribution in germanium-substituted magnesium ferrites | |
| US5036044A (en) | R-Tl-Sr-Ca-Cu-O superconductors | |
| US5863867A (en) | Fine-particle bi-sr-ca-cu-o having high phase purity made by chemical precipitation and low-pressure calcination method | |
| Miyayama et al. | Oxygen ion conduction in fcc Bi2O3 doped with ZrO2 and Y2O3 | |
| JPH11307331A (ja) | フェライト磁石 | |
| Steblevskaya et al. | Synthesis and Magnetic Resonance of Lanthanum Manganites Doped with Potassium Ions | |
| Khalyavin et al. | Phase Relations in the Systems Ln 1–x Ba x CoO 3–δ (0< x≤ 0.66; Ln= Nd, Sm) | |
| CN118546659A (zh) | 一种基于三价铕离子掺杂的镧系钙钛矿近室温磁制冷材料、制备方法及其应用 | |
| Almodovar et al. | Magnetic characterization of SrFe2Fe16O27 ferrite prepared by chemical coprecipitation method | |
| Meng et al. | Investigation of the electrical and magnetic properties of YSr2− xCaxV3O9− y | |
| JPS63230523A (ja) | 超伝導性材料 | |
| JPH02153822A (ja) | 酸化物超電導体組成物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |