JPH04280856A - Production of oxide superconducting sintered compact - Google Patents
Production of oxide superconducting sintered compactInfo
- Publication number
- JPH04280856A JPH04280856A JP3123301A JP12330191A JPH04280856A JP H04280856 A JPH04280856 A JP H04280856A JP 3123301 A JP3123301 A JP 3123301A JP 12330191 A JP12330191 A JP 12330191A JP H04280856 A JPH04280856 A JP H04280856A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- powder
- fired
- oxide
- density
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000843 powder Substances 0.000 claims abstract description 70
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 238000010304 firing Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000011812 mixed powder Substances 0.000 abstract description 11
- 239000012071 phase Substances 0.000 description 47
- 239000008188 pellet Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- -1 D y Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、超電導特性に優れ、特
に高密度,高臨界電流密度で大型のR−Ba−Cu−O
系(Rは希土類元素のうち少なくとも1種)の酸化物超
電導焼結体の作製方法に関するものである。[Industrial Application Field] The present invention has excellent superconducting properties, particularly high density, high critical current density, and large R-Ba-Cu-O
The present invention relates to a method for producing an oxide superconducting sintered body (R is at least one rare earth element).
【0002】0002
【従来の技術】酸化物超電導焼結体の作製方法としては
、従来から多くの方法が提案されており、その代表的な
方法としては溶融法,及び焼結法がある。しかしながら
、いずれの方法も一長一短があり、特に使用する合成粉
により作製した酸化物超電導焼結体の特性が著しく左右
される。即ち、2. Description of the Related Art Many methods have been proposed for producing oxide superconducting sintered bodies, and representative methods include a melting method and a sintering method. However, each method has advantages and disadvantages, and in particular, the properties of the oxide superconducting sintered body produced by the synthetic powder used are significantly affected. That is,
【0003】(1)溶融法の場合
Y1Ba2Cu3Oxの粉体を白金ルツボで1400℃
以上で溶融し、Y2O3分散の溶体を作り、該溶体を急
冷する。この急冷体を粉砕して粉体を製造する。あるい
は、必要に応じてBa化合物の粉とCu化合物の粉の原
料粉を所定比に混合し、これを1000℃以上で溶融さ
せた後急冷し、この急冷体を粉砕して粉体を製造する。
上記のようにして作った粉体をプレス成形し、この成形
体を約1100℃で焼成してY2Ba1Cu1Oy相の
バルクを作製した後、1000℃以下でY1Ba2Cu
3Ox相の結晶を成長させて焼結体を作製する。(1) In the case of the melting method, powder of Y1Ba2Cu3Ox is heated at 1400°C in a platinum crucible.
The above is melted to create a solution of Y2O3 dispersion, and the solution is rapidly cooled. This rapidly cooled body is pulverized to produce powder. Alternatively, if necessary, raw material powders of Ba compound powder and Cu compound powder are mixed at a predetermined ratio, melted at 1000° C. or higher, then rapidly cooled, and the rapidly cooled material is pulverized to produce powder. . The powder produced as described above was press-molded, and this compact was fired at about 1100°C to produce a bulk of Y2Ba1Cu1Oy phase, and then Y1Ba2Cu was formed at 1000°C or less.
A sintered body is produced by growing 3Ox phase crystals.
【0004】しかし、この方法では、種を使用しない限
り、単結晶もしくは結晶配向された高密度,高臨界電流
密度で大型の焼結体を作製することはできない。しかも
、プロセスが複雑で長時間を必要とし、溶融−急冷−粉
砕工程が必要であるので、作製コストが非常に高くなる
。However, with this method, unless a seed is used, it is not possible to produce a large sintered body with a single crystal or crystal orientation at high density and high critical current density. Moreover, the process is complicated and takes a long time, and requires melting, rapid cooling, and pulverization steps, so the manufacturing cost becomes extremely high.
【0005】(2)焼結法の場合
Y,Ba,Cu各化合物粉を原料として、これらを所定
比に混合し、この混合粉を850℃で仮焼し、次に95
0℃で20時間焼成した後粉砕する。更に950℃で2
0〜30時間焼成した後粉砕して、Y1Ba2Cu3O
x相の合成粉を製造する。この粉体をプレス成形して成
形体を作り、950℃で30時間焼成して焼結体を作製
する。(2) In the case of the sintering method, Y, Ba, and Cu compound powders are used as raw materials, mixed at a predetermined ratio, and this mixed powder is calcined at 850°C, and then heated at 95°C.
After baking at 0°C for 20 hours, it is ground. Further at 950℃ 2
After firing for 0 to 30 hours, it is crushed to produce Y1Ba2Cu3O.
Produce an x-phase synthetic powder. This powder is press-molded to produce a molded body, which is then fired at 950° C. for 30 hours to produce a sintered body.
【0006】しかし、この方法には、次のような欠点が
ある。
イ)微細なY1Ba2Cu3Ox相の結晶である合成粉
を使用するため、作製される焼結体もそれらの集合体と
なり、高密度化はできても、臨界電流密度は400A/
cm2程度で非常に低いものしか作製できない。
ロ)Y1Ba2Cu3Ox相合成粉の製造工程で、上記
のように所定比に配合した混合粉を850℃で仮焼した
後、950℃で20時間焼成し粉砕して、再度950℃
で20〜30時間焼成し粉砕する必要があるので、作製
コストが極めて高くなる。However, this method has the following drawbacks. b) Since synthetic powder, which is a fine crystal of Y1Ba2Cu3Ox phase, is used, the sintered body produced will also be an aggregate of these, and although high density can be achieved, the critical current density will be 400A/
Only a very low thickness of about cm2 can be manufactured. b) In the manufacturing process of Y1Ba2Cu3Ox phase synthetic powder, the mixed powder blended at a predetermined ratio as described above is calcined at 850°C, then calcined at 950°C for 20 hours, pulverized, and then heated again to 950°C.
Since it is necessary to bake and grind for 20 to 30 hours, the manufacturing cost becomes extremely high.
【0007】[0007]
【発明が解決しようとする課題】本発明は、原料粉に特
定の処理を施して、高密度,高臨界電流密度で大型の酸
化物超電導焼結体を作製することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to produce a large oxide superconducting sintered body with high density and high critical current density by subjecting raw material powder to a specific treatment.
【0008】[0008]
【課題を解決するための手段】本発明は、Rの酸化物又
は有機物の粉(Rは希土類元素であるSc,Y,Ls,
Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,D
y,Ho,Er,Tm,Yb又はLuのうち少なくとも
1種)、Baの酸化物又はその塩の粉及びCuの酸化物
又はその塩の粉を原料粉として所定比に混合し、その混
合粉を900℃以下で焼成して微細なR1Ba2Cu3
Ox相(以下、R系123相という)とR2Ba1Cu
1Oy相(以下、R系211相という)を生成させ、そ
の他BaCuO2相等を存在せしめ、その仮焼粉を微粉
砕して成形体を成形し、920〜1000℃で焼成して
R系123相を生成させた後、1050〜1200℃で
焼成してR系211相を主相として生成させ、更に該焼
成体を920〜1000℃で焼成してR系123相を成
長させることにより、高密度かつ高臨界電流密度を有す
る大型の酸化物超電導焼結体の作製方法を提供するもの
である。[Means for Solving the Problems] The present invention provides R oxide or organic powder (R is a rare earth element Sc, Y, Ls,
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
y, Ho, Er, Tm, Yb or Lu), Ba oxide or its salt powder, and Cu oxide or its salt powder are mixed at a predetermined ratio as raw material powder, and the mixed powder is prepared. is fired at 900℃ or less to form fine R1Ba2Cu3
Ox phase (hereinafter referred to as R system 123 phase) and R2Ba1Cu
1Oy phase (hereinafter referred to as R-based 211 phase) and other BaCuO2 phases are made to exist, and the calcined powder is finely pulverized to form a molded body, which is fired at 920 to 1000°C to form R-based 123 phase. After the formation, it is fired at 1050 to 1200°C to produce the R-based 211 phase as the main phase, and the fired body is further fired at 920 to 1000°C to grow the R-based 123 phase, resulting in high density and A method for producing a large oxide superconducting sintered body having a high critical current density is provided.
【0009】即ち、本発明は、(1)Rの酸化物又は有
機物の粉(ただし、Rは希土類元素であるSc,Y,L
a,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb
,Dy,Ho,Er,Tm,Yb及びLuのうち少なく
とも1種),Baの酸化物又は塩の粉,及びCuの酸化
物又は塩の粉を混合して900℃以下で焼成することに
より、微細なR1Ba2Cu3Ox相とR2Ba1Cu
1Oy相とを生成する第1工程と、(2)第1工程で得
られた焼成体を粉砕した後成形し、920〜1000℃
で焼成してR1Ba2Cu3Ox相を生成する第2工程
と、(3)第2工程で得られた焼成体を1050〜12
00℃で焼成してR2Ba1Cu1Oy相を主相とする
第3工程と、(4)第3工程で得られた焼成体を920
〜1000℃で焼成してR1Ba2Cu3Ox相を成長
させる第4工程と、からなることを特徴とする酸化物超
電導焼結体の作製方法である。以下、本発明を詳細に説
明する。That is, the present invention provides (1) R oxide or organic powder (where R is a rare earth element Sc, Y, L
a, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb
, Dy, Ho, Er, Tm, Yb and Lu), Ba oxide or salt powder, and Cu oxide or salt powder by mixing and firing at 900 ° C. or less, Fine R1Ba2Cu3Ox phase and R2Ba1Cu
(2) The sintered body obtained in the first step is crushed, then molded, and heated at 920 to 1000°C.
(3) the fired body obtained in the second step is fired at a temperature of 1050 to 12
(4) the fired body obtained in the third step is heated to
A method for producing an oxide superconducting sintered body is characterized by comprising a fourth step of growing an R1Ba2Cu3Ox phase by firing at ~1000°C. The present invention will be explained in detail below.
【0010】Rの酸化物又は有機物の粉(Rは上記同様
に希土類元素のうち少なくとも1種),Baの酸化物又
は塩の粉,及びCuの酸化物又は塩の粉から選ばれた原
料粉を所定比に混合し、900℃以下で仮焼すると、結
晶粒の小さいR系123相とR系211相及びBaとC
uの複合酸化物(BaCuO2等)が生成し、粉体の嵩
密度が向上し、従って該合成粉を用いて成形した成形体
のグリーン密度が向上する。Raw material powder selected from R oxide or organic powder (R is at least one rare earth element as above), Ba oxide or salt powder, and Cu oxide or salt powder When mixed in a predetermined ratio and calcined at 900°C or lower, R-type 123 phase and R-type 211 phase with small crystal grains and Ba and C
A complex oxide of u (BaCuO2, etc.) is generated, the bulk density of the powder is improved, and therefore the green density of a molded article formed using the synthetic powder is improved.
【0011】即ち、R系123相の結晶粒を大きく粒成
長させないように仮焼することにより、原料粉を仮焼す
ることなく直接成形した場合と比較して、成形体のグリ
ーン密度が著しく向上する。[0011] That is, by calcining the R-123 phase crystal grains to prevent large grain growth, the green density of the molded product is significantly improved compared to when the raw material powder is directly molded without calcining. do.
【0012】上記仮焼温度範囲を900℃を超えれば、
R系123相の結晶成長が進行し、R系123相の結晶
粒径が大きくなる。R系123相の粒径が大きくなると
、1050〜1200℃で焼成した時(前記第3工程)
にこのR系123相がR系211相主相とBaCuO2
,CuOヘの分解が不完全となり、バルク中にR系12
3相の微細な結晶粒が残留し、これが次の920〜10
00℃焼成(前記第4工程)でのR系123相結晶成長
過程で結晶核となり、多結晶体を生成する原因になるも
のと思料される。[0012] If the above calcination temperature range exceeds 900°C,
Crystal growth of the R-based 123 phase progresses, and the crystal grain size of the R-based 123 phase increases. When the particle size of the R-based 123 phase becomes larger, when fired at 1050 to 1200°C (the third step)
This R system 123 phase is the main phase of R system 211 phase and BaCuO2
, the decomposition into CuO is incomplete, and R system 12 is present in the bulk.
Three-phase fine crystal grains remain, which form the next 920-10
It is thought that it becomes a crystal nucleus during the R-based 123 phase crystal growth process in the 00° C. firing (the fourth step) and becomes a cause of producing polycrystals.
【0013】従って、適度な仮焼温度、即ち900℃以
下で加熱処理して微細なR系123相とR系211相と
その他複合酸化物を含有する合成粉を製造することによ
り、合成粉自体の密度が向上し、これによってこの合成
粉をプレス成形した成形体のグリーン密度も向上する。
即ち、従来の単純に混合粉をプレス成形した成形体と比
較して、そのグリーン密度は著しく向上するのである。Therefore, by producing a synthetic powder containing fine R-based 123 phase, R-based 211 phase, and other composite oxides by heat treatment at an appropriate calcination temperature, that is, 900° C. or lower, the synthetic powder itself can be improved. The density of the synthetic powder is improved, and the green density of the molded product press-molded from this synthetic powder is also improved. That is, the green density is significantly improved compared to the conventional molded product simply press-molded mixed powder.
【0014】次に、焼成過程で起こる収縮現象は本発明
法でも若干起こるが、これは仮焼処
微々たるものである。従って、本発明法によれば、焼成
過程での収縮が著しく減少するので、クラックの発生も
防止され、しかも形状の崩れも生ずることなく大型の酸
化物超電導焼結体を作製することができるのである。こ
れは、焼成過程(前記第2,3,4工程)の焼成時にバ
ルクの液相の滲み出しが抑制されるため、クラックの発
生が抑制され、従って形状の崩れが全くなくなって大型
化できるのである。[0014] Next, although the shrinkage phenomenon that occurs during the firing process occurs to some extent even in the method of the present invention, this is insignificant during the calcination process. Therefore, according to the method of the present invention, shrinkage during the firing process is significantly reduced, so cracks are prevented from occurring, and a large oxide superconducting sintered body can be produced without deformation. be. This is because the seepage of the bulk liquid phase is suppressed during the firing process (steps 2, 3, and 4), which suppresses the occurrence of cracks, which eliminates any deformation of the shape and allows for larger sizes. be.
【0015】即ち、本発明法は、所定比に配合した混合
粉を900℃以下で仮焼して、微細なR系123相とR
系211相及びBa,Cuの複合酸化物を含有する合成
粉を製造した後、成形・焼成することにより発現される
のであって、次のような特徴がある。
(イ)合成粉の嵩密度が向上し、従って成形体のグリー
ン密度が向上する。
(ロ)生成されるR系123相の結晶が微細でかつ僅少
なため、これらが核となって多結晶体になることはほと
んどない。即ち、R系123相の結晶粒径が大きいと、
これらが第3工程の1050〜1200℃焼成終了時に
も残留し、第4工程においてこれらが核となって存在す
るので多結晶体となり易く、超電導特性を著しく劣化さ
せる。
(ハ)従来のR系123相の合成粉から焼結体を作製す
る場合と比較して、本発明に係る合成粉は製造コストが
安く、しかもその合成粉から作製される焼結体の特性が
著しく優れている。
(ニ)上記のように本発明に係る合成粉から作製したR
−Ba−Cu−O系酸化物超電導焼結体は、高密度で高
臨界電流密度を有し、かつ大型化することができるので
ある。That is, in the method of the present invention, a mixed powder blended in a predetermined ratio is calcined at 900°C or lower to form a fine R-based 123 phase and an R-based 123 phase.
It is developed by producing a synthetic powder containing the system 211 phase and a composite oxide of Ba and Cu, followed by molding and firing, and has the following characteristics. (a) The bulk density of the synthetic powder is improved, and therefore the green density of the molded product is improved. (b) Since the crystals of the R-based 123 phase that are generated are fine and few, they almost never become a nucleus and become a polycrystalline body. That is, when the crystal grain size of the R-based 123 phase is large,
These remain even after the third step of firing at 1,050 to 1,200° C. and exist as nuclei in the fourth step, so that they tend to become polycrystalline, significantly deteriorating the superconducting properties. (c) Compared to the case of producing a sintered body from a conventional R-based 123-phase synthetic powder, the production cost of the synthetic powder according to the present invention is lower, and the properties of the sintered body produced from the synthetic powder are lower. is significantly superior. (d) R produced from the synthetic powder according to the present invention as described above
The -Ba-Cu-O based oxide superconducting sintered body has high density and high critical current density, and can be made large.
【0016】次に、本発明を実施例により詳細に説明す
る。Next, the present invention will be explained in detail with reference to examples.
【0017】[0017]
【実施例】実施例1
原料粉としてY2O3,BaCO3,CuOを1.6:
2.3:3.3の所定比に混合し、この混合粉を820
℃で5時間仮焼した。得られた仮焼粉をX線回折したと
ころ、Y系123相,BaCuO2相,Y系211相及
び上記原料粉が確認された。この仮焼粉を微粉砕した後
、200メッシュ篩で篩分けして−200メッシュの合
成粉体を製造した。この−200メッシュ合成粉体を2
inchφの金型により全圧20tonの条件でプレス
成形し、2inchφ×(厚さ)1cmのペレットを成
形した。このペレットのグリーン密度は4.2g/cm
3であった。[Example] Example 1 Y2O3, BaCO3, CuO as raw material powder 1.6:
Mix at a predetermined ratio of 2.3:3.3, and mix this mixed powder with 820
It was calcined at ℃ for 5 hours. When the obtained calcined powder was subjected to X-ray diffraction, a Y-based 123 phase, a BaCuO2 phase, a Y-based 211 phase, and the above raw material powder were confirmed. This calcined powder was finely pulverized and then sieved through a 200 mesh sieve to produce -200 mesh synthetic powder. This -200 mesh synthetic powder is
Press molding was performed using an inchφ mold at a total pressure of 20 tons to form pellets of 2 inchφ×(thickness) 1 cm. The green density of this pellet is 4.2g/cm
It was 3.
【0018】このペレットを20℃/分の昇温速度で9
50℃まで昇温し、950℃で3時間焼成した後、更に
1℃/分の昇温速度で1150℃まで昇温させて115
0℃で1時間焼成した。次に、20℃/分の降温速度で
960℃まで降温させて、960℃で30時間保持して
加熱処理した後、1℃/分の降温速度で20℃まで徐冷
し、目的とするY1Ba2Cu3Ox酸化物超電導焼結
体を作製した。[0018] This pellet was heated at a heating rate of 20°C/min.
After raising the temperature to 50°C and firing at 950°C for 3 hours, the temperature was further raised to 1150°C at a rate of 1°C/min to give 115
It was baked at 0°C for 1 hour. Next, the temperature was lowered to 960°C at a cooling rate of 20°C/min, held at 960°C for 30 hours for heat treatment, and then slowly cooled to 20°C at a cooling rate of 1°C/min to obtain the desired Y1Ba2Cu3Ox An oxide superconducting sintered body was fabricated.
【0019】得られた焼成ペレットは、径が45mmφ
(収縮率11.4%)となり、その密度は6.0g/c
m3であった。このペレットについて超電導特性である
臨界電流密度(JC)を測定した結果、5×103A/
cm3であった。The obtained fired pellets have a diameter of 45 mmφ.
(Shrinkage rate: 11.4%), and its density is 6.0g/c
It was m3. As a result of measuring the critical current density (JC), which is a superconducting property, for this pellet, it was found to be 5 × 103 A/
It was cm3.
【0020】実施例2
原料粉としてシュウ酸イットリウム,BaCO3,Cu
Oを1.6:2.3:3.3の所定比に混合し、この混
合粉を300℃で仮焼した後、更に850℃で10時間
仮焼した。得られた仮焼粉をX線回折したところ、Y系
123相,BaCuO2相,Y系211相及び原料粉が
確認された。この仮焼粉を微粉砕して200メッシュ篩
で篩分けして−200メッシュの合成粉体を製造した。
この−200メッシュ合成粉体を2inchφの金型に
より、全圧20tonの条件でプレス成形し、2φ×(
厚さ)1cmのペレットを成形した。このペレットのグ
リーン密度は4.3g/cm3であった。Example 2 Yttrium oxalate, BaCO3, Cu as raw material powder
O was mixed in a predetermined ratio of 1.6:2.3:3.3, and this mixed powder was calcined at 300°C, and then further calcined at 850°C for 10 hours. When the obtained calcined powder was subjected to X-ray diffraction, a Y-based 123 phase, a BaCuO2 phase, a Y-based 211 phase, and raw material powder were confirmed. This calcined powder was finely ground and sieved through a 200 mesh sieve to produce -200 mesh synthetic powder. This -200 mesh synthetic powder was press-molded using a 2-inchφ mold under conditions of a total pressure of 20 tons.
A pellet with a thickness of 1 cm was molded. The green density of this pellet was 4.3 g/cm3.
【0021】このペレットを20℃/分の昇温速度で9
50℃まで昇温し、950℃で3時間焼成した後、更に
1℃/分の昇温速度で1150℃まで昇温させて、11
50℃で1時間焼成した。次に、20℃/分の降温速度
で960℃まで降温させて、960℃で30時間保持し
て加熱処理した後,1℃/分の降温速度で20℃まで徐
冷し、目的とするY1Ba2Cu3Ox酸化物超電導焼
結体を作製した。[0021] This pellet was heated at a heating rate of 20°C/min.
After raising the temperature to 50°C and baking at 950°C for 3 hours, the temperature was further raised to 1150°C at a rate of 1°C/min.
It was baked at 50°C for 1 hour. Next, the temperature was lowered to 960°C at a cooling rate of 20°C/min, held at 960°C for 30 hours for heat treatment, and then slowly cooled to 20°C at a cooling rate of 1°C/min to obtain the desired Y1Ba2Cu3Ox. An oxide superconducting sintered body was fabricated.
【0022】得られた焼成ペレットは、径が45mmφ
(収縮率11.4%)となり、その密度は6.0g/c
m3であった。このペレットについて超電導特性である
臨界電流密度(Jc)を測定した結果、3×103A/
cm2であった。The obtained fired pellets have a diameter of 45 mmφ.
(Shrinkage rate: 11.4%), and its density is 6.0g/c
It was m3. As a result of measuring the critical current density (Jc), which is a superconducting property, for this pellet, it was found to be 3×103A/
It was cm2.
【0023】実施例3
原料粉としてY2O3,BaCO3,CuOを1.6:
2.3:3.3の所定比に混合し、この混合粉を900
℃で5時間仮焼した。得られた仮焼粉をX線回折したと
ころ、Y系123相,BaCuO2相,Y系211相及
び原料粉が確認された。この仮焼粉を微粉砕した後、2
00メッシュ篩で篩分けして−200メンシュの合成粉
体を製造した。この−200メッシュ合成粉体を2in
chφの金型により全圧20tonの条件でプレス成形
し、2inchφ×(厚さ)1cmのペレットを成形し
た。このペレットのグリーン密度は4.5g/cm3で
あった。Example 3 Y2O3, BaCO3, CuO as raw material powder at 1.6:
Mix at a predetermined ratio of 2.3:3.3, and add this mixed powder to 900
It was calcined at ℃ for 5 hours. When the obtained calcined powder was subjected to X-ray diffraction, a Y-based 123 phase, a BaCuO2 phase, a Y-based 211 phase, and raw material powder were confirmed. After finely pulverizing this calcined powder, 2
A -200 mesh synthetic powder was produced by sieving through a 00 mesh sieve. 2 inches of this -200 mesh synthetic powder
Press molding was performed using a chφ mold at a total pressure of 20 tons to form pellets of 2 inchφ×1 cm (thickness). The green density of this pellet was 4.5 g/cm3.
【0024】このペレットを20℃/分の昇温速度で9
50℃まで昇温し、950℃で3時間焼成した後、更に
1℃/分の昇温速度で1150℃まで昇温させて115
0℃で1時間焼成した。次に、20℃/分の降温速度で
960℃まで降温させ、960℃で30時間保持して加
熱処理した後、1℃/分の降温速度で20℃まで徐冷し
、目的とするY1Ba2Cu3Ox酸化物超電導焼結体
を作製した。[0024] This pellet was heated at a heating rate of 20°C/min.
After raising the temperature to 50°C and firing at 950°C for 3 hours, the temperature was further raised to 1150°C at a rate of 1°C/min to give 115
It was baked at 0°C for 1 hour. Next, the temperature was lowered to 960°C at a cooling rate of 20°C/min, held at 960°C for 30 hours for heat treatment, and then gradually cooled to 20°C at a cooling rate of 1°C/min to achieve the desired Y1Ba2Cu3Ox oxidation. A superconducting sintered body was fabricated.
【0025】得られた焼成ペレットは、径が45mmφ
(収縮率11.4%)となり、その密度は6.0g/c
m3であった。このペレットについて超電導特性である
臨界電流密度(Jc)を測定した結果、4×103A/
cm2であった。The obtained fired pellets have a diameter of 45 mmφ.
(Shrinkage rate: 11.4%), and its density is 6.0g/c
It was m3. As a result of measuring the critical current density (Jc), which is a superconducting property, for this pellet, it was found to be 4 × 103 A/
It was cm2.
【0026】比較例1(実施例1との比較)原料粉とし
てY2O3,BaCO3,CuOを1.6:2.3:3
.3の所定比に混合し、この混合粉を仮焼することなく
2inchφの金型により全圧20tonの加圧条件で
プレス成形し、2inchφ×(厚さ)1cmのペレッ
トと2inchφ×(厚さ)2cmのペレットを成形し
た。このペレットのグリーン密度は共に2.6g/cm
3であった。Comparative Example 1 (Comparison with Example 1) Y2O3, BaCO3, and CuO were used as raw material powder in a ratio of 1.6:2.3:3.
.. This mixed powder was press-molded in a 2-inch φ mold under a total pressure of 20 tons without calcining, and the powder was press-molded into 2-inch φ×(thickness) 1 cm pellets and 2-inch φ×(thickness) pellets. A 2 cm pellet was molded. The green density of these pellets is 2.6g/cm.
It was 3.
【0027】この2種のペレットを20℃/分の昇温速
度で950℃まで昇温し、950℃で3時間焼成した後
、更に1℃/分の昇温速度で1150℃まで昇温させて
1150℃で1時間焼成した。次に、20℃/分の降温
速度で960℃まで降温させ、960℃で30時間保持
して加熱処理した後、1℃/分の降温速度で20℃まで
徐冷し、Y系酸化物超電導体を作製した。[0027] These two types of pellets were heated to 950°C at a heating rate of 20°C/min, fired at 950°C for 3 hours, and then further heated to 1150°C at a heating rate of 1°C/min. The mixture was baked at 1150°C for 1 hour. Next, the temperature was lowered to 960°C at a cooling rate of 20°C/min, held at 960°C for 30 hours for heat treatment, and then slowly cooled to 20°C at a cooling rate of 1°C/min to form a Y-based oxide superconductor. The body was created.
【0028】この結果、両焼成体とも中央部に空隙が多
く見られ、その密度も5.8g/cm3程度と低く、特
にペレットの厚さ2cmの焼成体にはクラックが発生し
ており、焼成ペレットの径は37mmφ(収縮率27.
2%)であった。この焼成ペレットの臨界電流密度(J
c)を測定したところ、2×103A/cm2であった
。As a result, many voids were observed in the center of both fired bodies, and the density was as low as about 5.8 g/cm3. In particular, cracks occurred in the fired bodies with a pellet thickness of 2 cm, and The diameter of the pellet is 37mmφ (shrinkage rate 27.
2%). The critical current density (J
c) was measured and found to be 2 x 103 A/cm2.
【0029】比較例2
原料粉として平均粒径10μmのY1Ba2Cu3Ox
の合成粉を用い、2inchφの金型により全圧20t
onの加圧条件で2inchφ×(厚さ)1cmのペレ
ットを成形した。このペレットのグリーン密度は4.5
g/cm3であった。Comparative Example 2 Y1Ba2Cu3Ox with an average particle size of 10 μm as raw material powder
Using synthetic powder, the total pressure is 20t with a 2inchφ mold.
A pellet of 2 inch diameter x 1 cm (thickness) was molded under the pressurizing condition of on. The green density of this pellet is 4.5
g/cm3.
【0030】このペレット成形体を20℃/分の昇温速
度で950℃まで昇温し、950℃で3時間焼成した後
、更に1℃/分の昇温速度で1150℃まで昇温させて
1150℃で1時間焼成した。次に、20℃/分の降温
速度で960℃まで降温させ、960℃で30時間保持
して加熱処理した後、1℃/分の降温速度で20℃まで
徐冷し、Y系酸化物超電導焼結体を作成した。[0030] This pellet molded body was heated to 950°C at a heating rate of 20°C/min, fired at 950°C for 3 hours, and then further heated to 1150°C at a heating rate of 1°C/min. It was baked at 1150°C for 1 hour. Next, the temperature was lowered to 960°C at a cooling rate of 20°C/min, held at 960°C for 30 hours for heat treatment, and then slowly cooled to 20°C at a cooling rate of 1°C/min to form a Y-based oxide superconductor. A sintered body was created.
【0031】得られた焼成ペレットは、径が44mmφ
(収縮率13.4%)であり、その密度は5.5g/c
m3であった。この焼成ペレットの臨界電流密度(Jc
)を測定した結果、1×103A/cm2であった。[0031] The fired pellets obtained had a diameter of 44 mmφ.
(shrinkage rate 13.4%), and its density is 5.5g/c
It was m3. The critical current density (Jc
) was measured and found to be 1 x 103 A/cm2.
【0032】[0032]
【発明の効果】木発明法は上記のように構成され、原料
粉を所定比に混合し、その混合粉を900℃以下で仮焼
して結晶粒の微細なR系123相とR系211相を含有
する合成粉を製造することにより、合成粉自体の嵩密度
が向上すると共に、プレス成形した成形体のグリーン密
度も向上する。また、その後の成形体の焼成過程でのク
ラックの発生が防止できると共に、焼成体の収縮を小さ
くでき、焼成体の密度を向上させることができので、高
密度,高臨界電流密度で大型のR系酸化物超電導焼結体
を作製することができるのである。Effects of the Invention The wood invention method is constructed as described above, and the raw material powders are mixed in a predetermined ratio, and the mixed powder is calcined at 900°C or lower to form the R-type 123 phase with fine crystal grains and the R-type 211 phase. By producing a synthetic powder containing a phase, the bulk density of the synthetic powder itself is improved, and the green density of the press-molded body is also improved. In addition, it is possible to prevent the occurrence of cracks during the subsequent firing process of the molded body, reduce the shrinkage of the fired body, and improve the density of the fired body. Therefore, it is possible to produce a sintered oxide superconducting body.
【0033】更に、本発明法によれば 従来の溶融法
等に比べて処理工程が簡単であり、熱処理温度も低くて
済み、高品質の酸化物超電導焼結体を低コストで作製で
きる利点がある。Furthermore, the method of the present invention has the advantage that the processing steps are simpler and the heat treatment temperature can be lower than that of conventional melting methods, and high quality oxide superconducting sintered bodies can be produced at low cost. be.
Claims (1)
、Rは希土類元素のうち少なくとも1種),Baの酸化
物又は塩の粉,及びCuの酸化物又は塩の粉を混合して
900℃以下で焼成することにより、微細なR1Ba2
Cu3Ox相とR2Ba1Cu1Oy相とを生成する第
1工程、(2)第1工程で得られた焼成体を粉砕して成
形し、920〜1000℃で焼成してR1Ba2Cu3
Ox相を生成する第2工程、(3)第2工程で得られた
焼成体を1050〜1200℃で焼成してR2Ba1C
u1Oyを主相とする第3工程、(4)第3工程で得ら
れた焼成体を920〜1000℃で焼成してR1Ba2
Cu3Ox相を成長させる第4工程、からなることを特
徴とする酸化物超電導焼結体の作製方法。Claim 1: (1) A mixture of R oxide or organic powder (R is at least one rare earth element), Ba oxide or salt powder, and Cu oxide or salt powder. By firing at 900℃ or less, fine R1Ba2
A first step of generating a Cu3Ox phase and an R2Ba1Cu1Oy phase, (2) the fired body obtained in the first step is crushed and molded, and fired at 920 to 1000°C to form R1Ba2Cu3.
2nd step of generating Ox phase; (3) sintering the sintered body obtained in the 2nd step at 1050 to 1200°C to form R2Ba1C;
(4) The fired body obtained in the third step is fired at 920 to 1000°C to form R1Ba2.
A method for producing an oxide superconducting sintered body, comprising a fourth step of growing a Cu3Ox phase.
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JP12330191A JP3165921B2 (en) | 1991-03-07 | 1991-03-07 | Manufacturing method of oxide superconducting sintered body |
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JP3165921B2 JP3165921B2 (en) | 2001-05-14 |
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