JPH02208208A - Production of oxide superconductor precursor film - Google Patents
Production of oxide superconductor precursor filmInfo
- Publication number
- JPH02208208A JPH02208208A JP1029143A JP2914389A JPH02208208A JP H02208208 A JPH02208208 A JP H02208208A JP 1029143 A JP1029143 A JP 1029143A JP 2914389 A JP2914389 A JP 2914389A JP H02208208 A JPH02208208 A JP H02208208A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- oxide superconductor
- acid
- material solution
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 40
- 239000002243 precursor Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000012159 carrier gas Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001473 noxious effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004020 conductor Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は酸化物超電導体前駆物質膜の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an oxide superconductor precursor film.
最近、周知のように液体窒素温度で使用できる酸化物超
電導体が見出され、この新超電導体の応用研究が内外で
活発になされている。Recently, as is well known, an oxide superconductor that can be used at liquid nitrogen temperatures has been discovered, and research into the application of this new superconductor is being actively conducted both at home and abroad.
ところで、このような酸化物超電導体は脆いため、線材
等に加工するのが難しく、粉末焼結法等の特殊な加工法
が研究されている。しかしながらこの粉末焼結法は製造
工程が長く、又長尺材の製造が困難であった。However, since such oxide superconductors are brittle, it is difficult to process them into wire rods, etc., and special processing methods such as powder sintering are being researched. However, this powder sintering method requires a long manufacturing process, and it is difficult to manufacture long materials.
このようなことから、酸化物超電導体の原料物質を溶媒
に溶かし、この原料溶液を超音波噴霧器に入れて霧状原
料溶液となして火炎中に供給し、火炎により化学反応せ
しめて酸化物超電導体の前駆物質となし、これを火炎前
方に配置した基体上に膜状に付着させてなる噴霧加熱反
応法が提案されている。For this reason, the raw material for oxide superconductor is dissolved in a solvent, and this raw material solution is put into an ultrasonic atomizer to form a mist raw material solution and supplied into a flame, and the flame causes a chemical reaction. A spray-heating reaction method has been proposed in which a precursor material for the oxidizing agent is deposited in the form of a film on a substrate placed in front of a flame.
この方法は、工程が短く又反応速度が速いので生産性に
冨み、更に基体を走行させこれに酸化物超電導体前駆物
質を連続的に付着させるようにすると長尺材が容易に製
造し得るという利点がある。This method has short steps and a high reaction rate, so it is highly productive. Furthermore, by running the substrate and continuously depositing the oxide superconductor precursor on it, it is possible to easily produce long materials. There is an advantage.
しかしながらこの製造方法によると、特に長尺材を製造
する場合に、得られる酸化物超電導体前駆物質膜は特性
が経時的に劣化するという問題があった。However, according to this manufacturing method, there is a problem in that the characteristics of the obtained oxide superconductor precursor film deteriorate over time, especially when manufacturing a long material.
〔課題を解決するための手段及び作用〕本発明はかかる
状況に鑑み鋭意研究を行い、噴霧加熱反応法により製造
される酸化物超電導体前駆物質膜の特性が経時的に劣化
する原因は、第２図に示したように超音波噴霧器２の霧
状原料溶液３の出口近傍内壁１５に霧状原料溶液３が付
着して濃縮し、これが外部から熱を受けて固形物１６と
なって原料溶液１中に落下し沈澱して発振子１７上に堆
積して超音波発振子１７の機能を低下させ、その結果霧
状原料溶液３の発生量が低減して霧状原料溶液３による
火炎温度の低下が少なくなり、この高温のために酸化物
超電導体前駆物質膜の組成が適正値を外れる為に起きる
ことを突きとめ、更に研究を重ねた結果、使用する原料
溶液中に酸を添加してやることにより前述の如き現象が
緩和できることを見出し本発明を達成するに到ったもの
である。[Means and effects for solving the problem] In view of the above situation, the present invention has conducted extensive research and has determined that the causes of deterioration over time of the properties of the oxide superconductor precursor film produced by the spray heating reaction method are as follows. As shown in Fig. 2, the atomized raw material solution 3 adheres to the inner wall 15 near the outlet of the atomized raw material solution 3 of the ultrasonic atomizer 2 and is concentrated, which receives heat from the outside and becomes a solid substance 16, and becomes the raw material solution. 1, the atomized raw material solution 3 is deposited on the oscillator 17, and the function of the ultrasonic oscillator 17 is deteriorated. After further research, we discovered that this was caused by the composition of the oxide superconductor precursor film deviating from the appropriate value due to this high temperature. The present invention has been achieved by discovering that the above-mentioned phenomenon can be alleviated by using the above method.
即ち本発明は、酸化物超電導体となし得る原料物質を所
定量溶媒に溶解し、この原料溶液を超音波噴霧器内に入
れて霧状化し、この霧状原料溶液をキャリアガスにのせ
てバーナを介して火炎中に連続供給して上記霧状原料溶
液を化学反応せしめ、生成した酸化物超電導体前駆物質
を火炎前方に配置した基体上に付着せしめる酸化物超電
導体前駆物質膜の製造方法において、使用する原料溶液
に酸が添加されていることを特徴とする酸化物超電導体
前駆物質膜の製造方法である。That is, in the present invention, a predetermined amount of a raw material that can be made into an oxide superconductor is dissolved in a solvent, this raw material solution is put into an ultrasonic atomizer to atomize it, and this atomized raw material solution is placed on a carrier gas and a burner is turned on. In a method for producing an oxide superconductor precursor film, the atomized raw material solution is chemically reacted by being continuously supplied into a flame through a flame, and the produced oxide superconductor precursor is deposited on a substrate placed in front of the flame, This is a method for producing an oxide superconductor precursor film, characterized in that an acid is added to the raw material solution used.
本発明方法は、超音波噴霧器の霧状原料溶液出口近傍壁
に霧状原料溶液が付着し、濃縮固化して固形物となって
原料溶液中に落下して超音波発振子上に堆積し発振子の
機能を低下させることに対し、原料溶液に酸を添加する
ことにより、上記固形物は原料溶液中で溶解して、上記
発振子を正常に作動させ、霧状原料溶液の発生量の低減
を防止できるものである。In the method of the present invention, the atomized raw material solution adheres to the wall near the atomized raw material solution outlet of the ultrasonic atomizer, becomes concentrated and solidified, becomes a solid, falls into the raw material solution, and deposits on the ultrasonic oscillator, causing oscillation. By adding acid to the raw material solution, the above-mentioned solids are dissolved in the raw material solution, allowing the above-mentioned oscillator to operate normally, and reducing the amount of atomized raw material solution generated. can be prevented.
上記において、固形物は、主に酸化物超電導体の構成元
素からなる金属化合物で、酢酸のような弱酸の溶液にも
容易に溶解するものであり、酸の添加量も原料溶液の酸
濃度が固形物が比較的短時間に溶解する濃度以上であれ
ば特に限定するものではない。しかしながら酸の濃度は
、３容量％未満では、固形物の溶解に時間がかかる為実
用的でなく、又１５容量％を超えると固形物の溶解能力
が飽和してしまうので、３〜１５容量％の範囲にするの
が好ましいものである。In the above, the solid substance is a metal compound mainly composed of constituent elements of the oxide superconductor, and is easily dissolved in a solution of a weak acid such as acetic acid, and the amount of acid added depends on the acid concentration of the raw material solution. There is no particular limitation as long as the concentration is higher than that at which solids can be dissolved in a relatively short period of time. However, if the concentration of acid is less than 3% by volume, it is not practical because it takes time to dissolve solids, and if it exceeds 15% by volume, the ability to dissolve solids will be saturated, so 3 to 15% by volume. It is preferable to set it within the range of .
本発明方法において、原料溶液に添加する酸としては、
酸化物超電導体となし得る原料物質が酢酸塩からなる場
合は酢酸、又硝酸塩からなる場合は硝酸というように原
料物質と同じ酸を用いるのが、原料溶液への固形物の溶
解が迅速になされ、また前駆物質中に有害物質が混入す
るようなことがなく好ましいものである。In the method of the present invention, the acid added to the raw material solution is
The use of the same acid as the raw material, such as acetic acid when the raw material that can be made into an oxide superconductor consists of acetate, or nitric acid when it consists of nitrate, allows the solids to quickly dissolve in the raw material solution. Moreover, it is preferable because no harmful substances are mixed into the precursor.
尚、原料溶液に添加する酸に塩酸や弗酸を用いた場合は
、得られる酸化物超電導体前駆物質中に（ｌやＦ等のハ
ロゲン元素が混入して超電導特性を低下させるので、塩
酸や弗酸の使用は避けた方がよい。In addition, when hydrochloric acid or hydrofluoric acid is used as the acid added to the raw material solution, halogen elements such as It is best to avoid using hydrofluoric acid.
本発明方法において、酸は、溶媒に予め添加しておいて
も、又溶媒に原料物質を溶解した後添加してもよい。In the method of the present invention, the acid may be added to the solvent in advance, or may be added after the raw material is dissolved in the solvent.
本発明方法において、基体には原料物質と加熱接触して
実質的に有害とならない程度に非反応性であり、且つ耐
熱性に富む材料、例えばＡｇ、Ａｕ、Ｐｔ等の貴金属又
はＭ ｇ Ｏ，Ｚ ｒ Ｏｘ 、Ｂ ａＡ４４．Ｏ，、
ＢａＺｒＯｓ等のセラミックス或いはＡｇ等の金属、Ｍ
ｇＯ等のセラミックスを被覆したＦｅ、Ｎｉ、Ｃｏやこ
れらの合金例えばステンレススチール（ＳＵＳ）、Ｆｅ
−Ｎｉ系、ＮｉＣｕ系、Ｎｉ−Ｃｒ−Ｆｅ系等の合金、
又はＡｌｚｏｓ、ガラス、ＡＩＮ、ＢＮ、Ｓ ｉ Ｃ，
Ｃ等の材料が用いられる。In the method of the present invention, the substrate is made of a material that is non-reactive to the extent that heating contact with the raw material does not cause substantial harm and is highly heat resistant, such as a noble metal such as Ag, Au, or Pt, or a material such as M g O, Z r Ox , B aA44. O,,
Ceramics such as BaZrOs or metals such as Ag, M
Fe, Ni, Co and alloys of these coated with ceramics such as gO, such as stainless steel (SUS), Fe
- Alloys such as Ni-based, NiCu-based, Ni-Cr-Fe-based, etc.
Or Alzos, Glass, AIN, BN, S i C,
A material such as C is used.
本発明方法において、酸化物超電導体となし得る原料物
質としては、例えばＹ−Ｂａ−Ｃｕ−０系酸化物超電導
体について示すと、上記酸化物超電導体の各々の構成元
素の酢酸塩や硝酸塩等をＹ：Ｂａ：Ｃｕの原子比で１＝
２：３になるように配合した任意の物質が用いられる。In the method of the present invention, raw materials that can be used as oxide superconductors include, for example, for Y-Ba-Cu-0-based oxide superconductors, acetates and nitrates of each constituent element of the oxide superconductor. The atomic ratio of Y:Ba:Cu is 1=
Any material in a 2:3 ratio may be used.
父上記原料物質を溶液となし霧状化して火炎により加熱
して得られる酸化物超電導体前駆物質とは、これを酸素
含有雰囲気中で所定の加熱処理を施すことにより、０２
の補給並びに結晶構造の調整がなされて酸化物超電導体
となるものである。The oxide superconductor precursor obtained by turning the above raw material into a solution, atomizing it, and heating it with a flame can be obtained by subjecting it to a predetermined heat treatment in an oxygen-containing atmosphere.
It becomes an oxide superconductor through replenishment and adjustment of the crystal structure.
以下に本発明方法を実施例により第１図に示した装置を
参照して詳細に説明する。The method of the present invention will be explained in detail below by way of example with reference to the apparatus shown in FIG.
実施例１
出発原料にＹ、、Ｂａ及びＣｕの酢酸塩を用いて各々の
酢酸塩をＹ：Ｂａ：Ｃｕがｉ：２：３になるように秤量
し混合して、これを水にＹ、ＢａｚＣｕ３の組成で０．
０４モル／！溶解してこれを原料水となし、更にこれに
種々量の酢酸を添加して原料溶液１となした。次いでこ
の原料溶液１を超音波噴霧器２に入れて霧状原料溶液３
となし、これを流速０．６０Ｉ！、／ｍｉｎのＮ２ガス
流にのせて噴霧火炎反応装置４内のバーナ５に供給し、
上記バーナ５により形成される酸水素火炎６にて所定温
度に加熱して酸化物超電導体前駆物質に化学反応せしめ
、更に上記前駆物質をアンコイラ１３から供給され火炎
６前方を１０ｍｍ／ｍｉｎの速度で走行する図示しない
加熱炉にて９００°Ｃに加熱された基体７上に厚さ１０
０戸の膜状に付着させて酸化物超電導体前駆物質膜８を
形成した。上記において基体７には０．２ ｍｍ’ Ｘ
５ ｍｍ’のｐｔテープを用いた。Example 1 Using acetates of Y, Ba, and Cu as starting materials, each acetate was weighed and mixed so that Y:Ba:Cu was i:2:3, and this was added to water with Y, Ba, and Cu acetates. The composition of BazCu3 is 0.
04 mol/! This was dissolved and used as raw material water, and various amounts of acetic acid were added to this to prepare raw material solution 1. Next, this raw material solution 1 is put into an ultrasonic atomizer 2 to form an atomized raw material solution 3.
Assuming this, the flow rate is 0.60I! , /min to the burner 5 in the spray flame reactor 4,
The oxyhydrogen flame 6 formed by the burner 5 heats the oxide superconductor precursor to a predetermined temperature to cause a chemical reaction, and the precursor is further supplied from the uncoiler 13 and moves in front of the flame 6 at a speed of 10 mm/min. A film with a thickness of 10°C is placed on the substrate 7 heated to 900°C in a moving heating furnace (not shown).
The oxide superconductor precursor film 8 was formed by depositing it in the form of a single film. In the above, the base 7 has a diameter of 0.2 mm'
5 mm' PT tape was used.
而して上記基体７上に形成した酸化物超電導体前駆物質
膜８を４００°Ｃに加熱した０□気流雰囲気の加熱反応
炉９にて酸化物超電導導体１０に反応せしめた。The oxide superconductor precursor film 8 formed on the substrate 7 was reacted with the oxide superconductor 10 in a heating reactor 9 heated to 400°C and in a 0□ air flow atmosphere.
次いで」二記酸化物超電導導体１０に溶融樹脂槽１１並
びに焼付炉１２に通して樹脂を被覆して防湿処理を施し
たのち、コイラー１４に巻取った。Next, the oxide superconducting conductor 10 was passed through a molten resin tank 11 and a baking furnace 12 to be coated with a resin for moisture-proofing treatment, and then wound around a coiler 14.
このようにして連続３時間操業してＹ系酸化物超電導導
体を１．８ｍ製造した。In this way, the operation was continued for 3 hours to produce 1.8 m of Y-based oxide superconducting conductor.
実施例２
出発原料に、Ｂｉ、Ｓｒ、Ｃａ、Ｃｕの硝酸塩を用い、
各々Ｂｉ：Ｓｒ：Ｃａ：Ｃｕが原子比で２：２：１；２
．０５になるように秤量して混合し、この混合体を２％
硝酸水にＢ１□Ｓ ｒ ２ Ｃａ Ｃｕ２、。５の組成
で０．０１モル／℃溶解し、更にこれに種々量の硝酸を
添加した原料溶液を用いた他は実施例１と同様の方法に
よりＢｉ系酸化物超電導導体を製造した。Example 2 Using nitrates of Bi, Sr, Ca, and Cu as starting materials,
The atomic ratio of Bi:Sr:Ca:Cu is 2:2:1; 2, respectively.
．． Weigh and mix so that the amount is 0.05, and add this mixture to 2%
B1□S r 2 Ca Cu2 in nitric acid water. A Bi-based oxide superconducting conductor was produced in the same manner as in Example 1, except that a raw material solution having the composition No. 5 dissolved at 0.01 mol/° C. and various amounts of nitric acid added thereto was used.
比較例１
実施例１において、原料水に酢酸を添加せずに原料溶液
として用いた他は実施例１と同様の方法によりＹ系酸化
物超電導導体を製造した。Comparative Example 1 A Y-based oxide superconducting conductor was produced in the same manner as in Example 1 except that acetic acid was not added to the raw water and used as a raw material solution.
比較例２
実施例２において、混合体を水に溶解し、そのまま硝酸
を添加せずに原料溶液として用いた他は、実施例２と同
様の方法によりＢｉ系酸化物超電導導体を製造した。Comparative Example 2 A Bi-based oxide superconducting conductor was produced in the same manner as in Example 2, except that the mixture was dissolved in water and used as a raw material solution without adding nitric acid.
斯くの如くして得られた各々の酸化物超電導導体につい
て、長手方向に３ケ所サンプリングして、臨界温度（Ｔ
、）及び臨界電流密度（Ｊ、）を測定した。結果は主な
条件等を併記して第１表に示した。For each oxide superconducting conductor obtained in this way, three locations were sampled in the longitudinal direction, and the critical temperature (T
, ) and critical current density (J, ) were measured. The results are shown in Table 1 along with the main conditions.
第１表より明らかなように本発明方法品（実施例１．２
）は全長に亘りＴｃ、Ｊｃが高い値を示した。As is clear from Table 1, the method of the present invention (Example 1.2
) showed high values of Tc and Jc over the entire length.
これに対し比較方法品（比較例１，２）は経時的にＴｃ
、Ｊｃが低下した。これは超音波噴霧器内の原料溶液に
固形物めく次第に沈澱しそれにつれて振動子の機能が低
下して霧状原料溶液の発生量が減少し、その結果酸水素
火炎により上記霧状原料溶液が所定温度以上に加熱され
、得られた酸化物超電導体前駆物質の組成が適正値を外
れた為である。In contrast, the comparative method products (Comparative Examples 1 and 2) showed Tc over time.
, Jc decreased. This solid substance gradually settles in the raw material solution in the ultrasonic atomizer, and as a result, the function of the vibrator deteriorates and the amount of atomized raw material solution generated decreases.As a result, the oxyhydrogen flame causes the atomized raw material solution to be This is because the composition of the obtained oxide superconductor precursor material deviated from the appropriate value due to heating above the temperature.
上記実施例では、Ｙ系又はＢｉ系酸化物超電導体につい
て説明したが、本発明方法はＬａ−３ｒ−Ｃｕ−０系や
Ｔｊ２−Ｂａ−Ｃａ−Ｃｕ−０系等の他の酸化物超電導
体にも適用し得るものである。In the above embodiments, Y-based or Bi-based oxide superconductors were explained, but the method of the present invention can be applied to other oxide superconductors such as La-3r-Cu-0-based and Tj2-Ba-Ca-Cu-0-based. It can also be applied to
又原料溶液に添加する酸も酢酸や硝酸の他修酸や乳酸な
ど出発原料組成又は生成する固形物の組成に応じて任意
に選択できるものである。Further, the acid added to the raw material solution can be arbitrarily selected from acetic acid, nitric acid, oxalic acid, lactic acid, etc. depending on the composition of the starting raw material or the composition of the solid product to be produced.
以上述べたように本発明方法によれば、全長に亘り高品
質の酸化物超電導体前駆物質膜が得られ、この前駆物質
膜は酸素含有雰囲気中で所定の加熱処理を施すことによ
り、Ｔｃ、Ｊｃ等の超電導特性に優れた酸化物超電導導
体となし得るもので、工業上顕著な効果を奏するもので
ある。As described above, according to the method of the present invention, a high-quality oxide superconductor precursor film can be obtained over the entire length, and this precursor film can be heated in an oxygen-containing atmosphere to form Tc, Tc, It can be made into an oxide superconductor having excellent superconducting properties such as Jc, and has a remarkable industrial effect.
第１図は本発明方法を実施する装置の一例を示す要部説
明図、第２図は霧状原料溶液の発生量が低減する原因の
説明図である。
１・・・原料溶液、 ２・・・超音波噴霧器、 ３・・
・霧状原料溶液、 ４・・・噴霧加熱反応装置、 ５・
・・バーナ、 ６・・・酸水素火炎、 ７・・・基体、
８・・・酸化物超電導体前駆物質膜、 ９・・・加熱
反応炉、１０・・・酸化物超電導導体、 １７・・・
超音波発振子。FIG. 1 is an explanatory view of essential parts showing an example of an apparatus for carrying out the method of the present invention, and FIG. 2 is an explanatory view of the cause of the reduction in the amount of atomized raw material solution generated. 1... Raw material solution, 2... Ultrasonic atomizer, 3...
- Atomized raw material solution, 4... Spray heating reaction device, 5.
... Burner, 6... Oxyhydrogen flame, 7... Substrate,
8... Oxide superconductor precursor film, 9... Heating reactor, 10... Oxide superconductor conductor, 17...
Ultrasonic oscillator.
Claims (1)
し、この原料溶液を超音波噴霧器内に入れて霧状化し、
この霧状原料溶液をキャリアガスにのせてバーナを介し
て火炎中に連続供給して上記霧状原料溶液を化学反応せ
しめ、生成した酸化物超電導体前駆物質を火炎前方に配
置した基体上に付着せしめる酸化物超電導体前駆物質膜
の製造方法において、使用する原料溶液に酸が添加され
ていることを特徴とする酸化物超電導体前駆物質膜の製
造方法。A predetermined amount of a raw material that can be made into an oxide superconductor is dissolved in a solvent, and this raw material solution is placed in an ultrasonic atomizer to atomize it,
This atomized raw material solution is placed on a carrier gas and continuously fed into a flame via a burner to cause a chemical reaction in the atomized raw material solution, and the generated oxide superconductor precursor is deposited on a substrate placed in front of the flame. A method for producing an oxide superconductor precursor film, characterized in that an acid is added to the raw material solution used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1029143A JPH02208208A (en) | 1989-02-08 | 1989-02-08 | Production of oxide superconductor precursor film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1029143A JPH02208208A (en) | 1989-02-08 | 1989-02-08 | Production of oxide superconductor precursor film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02208208A true JPH02208208A (en) | 1990-08-17 |
Family
ID=12268054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1029143A Pending JPH02208208A (en) | 1989-02-08 | 1989-02-08 | Production of oxide superconductor precursor film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208208A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0681989A1 (en) * | 1994-05-13 | 1995-11-15 | MERCK PATENT GmbH | Process for the preparation of multi-element metal oxide powders |
-
1989
- 1989-02-08 JP JP1029143A patent/JPH02208208A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0681989A1 (en) * | 1994-05-13 | 1995-11-15 | MERCK PATENT GmbH | Process for the preparation of multi-element metal oxide powders |
| AU696353B2 (en) * | 1994-05-13 | 1998-09-10 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Process for the preparation of multi-element metal oxide powders |
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