JP2000273694A - Composition for electrolytically forming rare earth oxide - Google Patents
Composition for electrolytically forming rare earth oxideInfo
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- JP2000273694A JP2000273694A JP11081095A JP8109599A JP2000273694A JP 2000273694 A JP2000273694 A JP 2000273694A JP 11081095 A JP11081095 A JP 11081095A JP 8109599 A JP8109599 A JP 8109599A JP 2000273694 A JP2000273694 A JP 2000273694A
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- Prior art keywords
- rare earth
- earth oxide
- composition
- oxide film
- compound
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、希土類酸化物膜電
解形成用組成物、希土類酸化物膜形成方法、及び希土類
酸化物膜に関する。TECHNICAL FIELD The present invention relates to a composition for electrolytically forming a rare earth oxide film, a method for forming a rare earth oxide film, and a rare earth oxide film.
【0002】[0002]
【従来の技術】従来、希土類酸化物膜の形成方法として
は、CVD法、蒸着法、スパッタリング法などの乾式
法、スプレーパイロリシス法、ゾルーゲル法、液相成長
法などの湿式法などによって基板上に成膜する方法が試
みられている。これらの中でも、スパッタリング法によ
れば、低温で成膜でき、しかも均一な膜を形成できるた
めに、現在、希土類酸化物膜の多くはこの方法によって
作製されている。しかしながら、スパッタリング法を始
めとしたCVD法、蒸着法等の乾式法では、成膜の際
に、成膜室の減圧やガス混入、基板の加熱などの処理が
必要であり、真空排気装置、基板加熱装置、高周波電源
などを含む大規模な作製装置が必要となる。しかも、こ
れらの方法では、成膜速度が遅く、組成や膜厚の制御が
難しく、さらに、使用できる基板の面積が制限され、複
雑な形状の基板上に均一な膜を作製することが難しいな
どの欠点がある。2. Description of the Related Art Conventionally, a rare earth oxide film is formed on a substrate by a dry method such as a CVD method, a vapor deposition method or a sputtering method, a spray pyrolysis method, a sol-gel method, or a wet method such as a liquid phase growth method. A method of forming a film on a substrate has been attempted. Among them, the sputtering method can form a film at a low temperature and can form a uniform film. Therefore, at present, most rare earth oxide films are produced by this method. However, in a dry method such as a sputtering method, a CVD method, a vapor deposition method, or the like, processing such as decompression of a film formation chamber, mixing of gas, and heating of a substrate is required during film formation. A large-scale manufacturing device including a heating device, a high-frequency power supply, and the like is required. Moreover, in these methods, the film formation rate is low, the composition and the film thickness are difficult to control, the area of the substrate that can be used is limited, and it is difficult to form a uniform film on a substrate having a complicated shape. There are disadvantages.
【0003】また、スプレーパイロリシス法やゾルーゲ
ル法では、基板に成膜後、300〜900℃で加熱する
必要があるために、加熱炉が必要となり、使用できる基
板材料も制限される。Further, in the spray pyrolysis method or the sol-gel method, it is necessary to heat the substrate at 300 to 900 ° C. after forming the film on the substrate, so that a heating furnace is required and the usable substrate material is limited.
【0004】そこで、希土類酸化物膜を幅広い範囲で利
用可能とするために、真空排気装置や加熱炉などの大規
模設備を必要とせず、大面積で複雑な形状の基材上にも
形成可能であり、しかも成膜速度が速く、膜厚や組成が
均一で、その制御も容易な希土類酸化物膜の形成方法の
開発が望まれている。[0004] In order to make the rare earth oxide film usable in a wide range, large-scale equipment such as a vacuum evacuation device and a heating furnace is not required, and the film can be formed on a substrate having a large area and a complicated shape. It is desired to develop a method of forming a rare earth oxide film which has a high film forming rate, a uniform film thickness and a uniform composition, and which can be easily controlled.
【0005】[0005]
【発明が解決しようとする課題】本発明の主な目的は、
膜厚や組成が均一な希土類酸化物膜を簡単な操作によっ
て形成できる方法を提供することである。SUMMARY OF THE INVENTION The main object of the present invention is to:
An object of the present invention is to provide a method capable of forming a rare earth oxide film having a uniform thickness and composition by a simple operation.
【0006】[0006]
【課題を解決するための手段】本発明者は、上記のよう
な課題に鑑みて鋭意研究を重ねた結果、希土類化合物を
溶解し、硝酸イオン及び亜硝酸イオンから選ばれた少な
くとも一種の陰イオンが存在する水溶液中に基材を浸漬
し、基材を陰極として電解を行うことによって、水溶液
中での電解という非常に簡単な方法で、大面積の基材や
複雑な形状の基材上にも膜厚や組成が均一な希土類酸化
物膜を形成できることを見出した。そして、形成された
希土類酸化物膜を加熱処理することによって、結晶性が
向上し、基材との密着性等がより向上することを見出
し、ここに本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, have dissolved a rare earth compound and at least one kind of anion selected from nitrate ion and nitrite ion. The substrate is immersed in an aqueous solution in which is present, and electrolysis is performed using the substrate as a cathode. It has also been found that a rare earth oxide film having a uniform thickness and composition can be formed. Then, it has been found that by heating the formed rare earth oxide film, the crystallinity is improved and the adhesion to the base material and the like are further improved, and the present invention has been completed.
【0007】即ち、本発明は、下記の希土類酸化物膜電
解形成用組成物、希土類酸化物膜形成方法、及び希土類
酸化物膜を提供するものである。 1.希土類化合物を溶解した水溶液であって、硝酸イオ
ン及び亜硝酸イオンから選ばれた少なくとも一種の陰イ
オンが存在する水溶液からなる希土類酸化物膜電解形成
用組成物。 2.(i)水溶性希土類化合物、並びに(ii)硝酸イオ
ン源となる化合物及び亜硝酸イオン源となる化合物から
選ばれた少なくとも一種の化合物、を溶解した水溶液か
らなる上記項1に記載の希土類酸化物膜電解形成用組成
物。 3.希土類元素の硝酸塩を溶解した水溶液からなる上記
項1に記載の希土類酸化物膜電解形成用組成物。 4.希土類化合物が、セリウム、テルビウム、イットリ
ウム及びユーロピウムから選ばれた少なくとも一種の希
土類元素を含む化合物である上記項1〜3のいずれかに
記載の希土類酸化物膜電解形成用組成物。 5.上記項1〜4のいずれかに記載の希土類酸化物膜電
解形成用組成物中で、希土類酸化物形成用基材を陰極又
は陽極として電解を行うことを特徴とする希土類酸化物
膜の形成方法。 6.上記項5の方法で形成した希土類酸化物膜を100
〜800℃で加熱処理することを特徴とする希土類酸化
物膜形成方法。 7.上記項5又は6の方法によって基材上に形成された
希土類酸化物膜。That is, the present invention provides the following composition for forming a rare earth oxide film by electrolysis, a method for forming a rare earth oxide film, and a rare earth oxide film. 1. A rare earth oxide film electrolytic formation composition comprising an aqueous solution in which a rare earth compound is dissolved, wherein the aqueous solution contains at least one anion selected from nitrate ions and nitrite ions. 2. Item 1. The rare earth oxide according to item 1, comprising an aqueous solution in which (i) a water-soluble rare earth compound and (ii) at least one compound selected from a compound serving as a nitrate ion source and a compound serving as a nitrite ion source are dissolved. A composition for forming a membrane electrolysis. 3. Item 2. The composition for electrolytically forming a rare earth oxide film according to Item 1, which comprises an aqueous solution in which a nitrate of a rare earth element is dissolved. 4. Item 4. The composition for electrolytically forming a rare earth oxide film according to any one of Items 1 to 3, wherein the rare earth compound is a compound containing at least one rare earth element selected from cerium, terbium, yttrium, and europium. 5. Item 5. A method for forming a rare earth oxide film, comprising performing electrolysis using the rare earth oxide forming substrate as a cathode or an anode in the composition for forming an rare earth oxide film according to any one of the above items 1 to 4. . 6. Item 100 is the rare earth oxide film formed by the method of Item 5.
A method for forming a rare-earth oxide film, comprising performing a heat treatment at -800 ° C. 7. Item 7. A rare earth oxide film formed on a substrate by the method according to item 5 or 6.
【0008】[0008]
【発明の実施の形態】本発明の希土類酸化物膜電解形成
用組成物は、希土類化合物を溶解した水溶液であって、
硝酸イオン及び亜硝酸イオンから選ばれた少なくとも一
種の陰イオンが存在する水溶液である。BEST MODE FOR CARRYING OUT THE INVENTION The composition for electrolytically forming a rare earth oxide film of the present invention is an aqueous solution in which a rare earth compound is dissolved,
This is an aqueous solution containing at least one anion selected from nitrate ions and nitrite ions.
【0009】希土類化合物としては、セリウム、テルビ
ウム、イットリウム、ユーロピウム等の希土類元素を含
む水溶性化合物を用いることができる。水溶性化合物の
種類としては、硝酸塩、硫酸塩、シュウ酸塩、酢酸塩、
炭酸塩、塩化物等の各種の希土類化合物を挙げることが
できる。これらの希土類化合物は、一種単独又は二種以
上混合して用いることができる。As the rare earth compound, a water-soluble compound containing a rare earth element such as cerium, terbium, yttrium and europium can be used. Types of water-soluble compounds include nitrates, sulfates, oxalates, acetates,
Various rare earth compounds such as carbonates and chlorides can be mentioned. These rare earth compounds can be used alone or in combination of two or more.
【0010】該組成物中の希土類化合物濃度は、特に限
定的ではないが、0.0001mol/l〜0.5mo
l/l程度が好ましく、0.001〜0.1mol/l
程度がより好ましい。希土類化合物濃度が低くなりすぎ
ると電解条件を調整しても希土類酸化物膜を形成するこ
とが困難になり、一方、濃度が高くなりすぎると、水酸
化物が形成され易くなるので好ましくない。The concentration of the rare earth compound in the composition is not particularly limited, but may be 0.0001 mol / l to 0.5 mol.
about 1 / l is preferable, and 0.001 to 0.1 mol / l
The degree is more preferred. If the concentration of the rare earth compound is too low, it is difficult to form a rare earth oxide film even if the electrolysis conditions are adjusted. On the other hand, if the concentration is too high, a hydroxide is easily formed, which is not preferable.
【0011】また、本発明組成物には、硝酸イオン及び
亜硝酸イオンから選ばれた少なくとも一種の陰イオンが
存在することが必要である。本発明組成物中にこれらの
陰イオンが存在しない場合には、電解操作を行っても希
土類酸化物膜を形成することができない。硝酸イオン及
び亜硝酸イオンから選ばれた少なくとも一種の陰イオン
の存在量は、特に限定的ではないが、通常、陰イオン濃
度として、0.0001mol/l〜1.0mol/l
程度の範囲内にあることが好ましく、0.001mol
/l〜0.1mol/l程度の範囲内にあることがより
好ましい。The composition of the present invention must contain at least one anion selected from nitrate ions and nitrite ions. When these anions are not present in the composition of the present invention, a rare earth oxide film cannot be formed even by performing an electrolytic operation. The amount of at least one anion selected from nitrate ions and nitrite ions is not particularly limited, but is usually 0.0001 mol / l to 1.0 mol / l as anion concentration.
Preferably in the range of about 0.001 mol
More preferably, it is in the range of about 0.1 mol / l to about 0.1 mol / l.
【0012】本発明組成物において、硝酸イオン及び亜
硝酸イオンから選ばれた少なくとも一種の陰イオンを水
溶液中に存在させるためには、通常、硝酸イオン源とな
る化合物及び亜硝酸イオン源となる化合物から選ばれた
少なくとも一種の化合物を溶媒となる水に溶解させれば
よい。In the composition of the present invention, in order for at least one anion selected from nitrate ions and nitrite ions to be present in an aqueous solution, a compound serving as a nitrate ion source and a compound serving as a nitrite ion source are usually used. At least one compound selected from the above may be dissolved in water as a solvent.
【0013】硝酸イオン源となる化合物としては、硝
酸、水溶性硝酸塩等を用いることができる。硝酸塩の具
体例としては、硝酸アンモニウム、硝酸ナトリウム、硝
酸カリウム、硝酸リチウム、硝酸尿素等を挙げることが
できる。As a compound serving as a nitrate ion source, nitric acid, water-soluble nitrate and the like can be used. Specific examples of the nitrate include ammonium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, urea nitrate and the like.
【0014】亜硝酸イオン源となる化合物としては、水
溶性亜硝酸塩を用いることができ、その具体例として
は、亜硝酸カリウム、亜硝酸ナトリウム等を挙げること
ができる。As a compound serving as a nitrite ion source, a water-soluble nitrite can be used, and specific examples thereof include potassium nitrite and sodium nitrite.
【0015】硝酸イオン源となる化合物と亜硝酸イオン
源となる化合物は、一種単独又は二種以上混合して用い
ることができる。The compound serving as a nitrate ion source and the compound serving as a nitrite ion source can be used alone or in combination of two or more.
【0016】また、希土類化合物として希土類元素の硝
酸塩を用いる場合には、この硝酸塩自体が、硝酸イオン
源となるので、その他に、硝酸イオン源となる化合物や
亜硝酸イオン源となる化合物を配合しなくても良い。こ
の場合には、浴中に不要な成分が存在することがなく、
純度の高い希土類酸化物を広い濃度範囲で形成すること
が可能となる。When a rare earth element nitrate is used as the rare earth compound, the nitrate itself serves as a nitrate ion source. In addition, a compound serving as a nitrate ion source or a compound serving as a nitrite ion source is added. You don't have to. In this case, there is no unnecessary component in the bath,
A highly pure rare earth oxide can be formed in a wide concentration range.
【0017】本発明の組成物を用いて希土類酸化物膜を
形成するには、該組成物中に希土類酸化物膜形成用基材
を浸漬し、該基材を陰極として電解を行なえばよい。電
解方法としては、通常の電解法を採用して、無撹拌また
は撹拌下で電解を行えばよい。In order to form a rare earth oxide film using the composition of the present invention, a substrate for forming a rare earth oxide film may be immersed in the composition, and electrolysis may be performed using the substrate as a cathode. As an electrolysis method, a normal electrolysis method may be employed, and electrolysis may be performed without stirring or under stirring.
【0018】電解を行う際の陰極電位は、Ag/AgC
l電極を基準電極として、−0.2V〜−2.0V程度
とすることが好ましく、−0.5V〜−1.6V程度と
することがより好ましい。電解時の電流密度は、用いる
基材の種類によって異なるが、上記電位範囲で電解を行
う場合には、通常、0.001mA/cm2〜200m
A/cm2程度の電流密度となる。The cathode potential at the time of electrolysis is Ag / AgC
Using the 1 electrode as a reference electrode, the voltage is preferably about -0.2 V to -2.0 V, and more preferably about -0.5 V to -1.6 V. The current density at the time of electrolysis varies depending on the type of the base material to be used, but when electrolysis is performed in the above potential range, it is usually 0.001 mA / cm 2 to 200 m.
The current density becomes about A / cm 2 .
【0019】陽極としては、カーボン、白金、白金めっ
きチタン等の不溶性材料を用いることができる。陽極と
して、不溶性材料を用いる場合には、希土類化合物及び
硝酸塩の補給を行い、電解液のpHを調整することによ
って連続作業が可能となる。As the anode, an insoluble material such as carbon, platinum, and platinum-plated titanium can be used. When an insoluble material is used as the anode, a continuous operation can be performed by replenishing the rare earth compound and the nitrate and adjusting the pH of the electrolytic solution.
【0020】電解時の液温は、通常、20〜90℃程度
とすればよく、40〜70℃程度が好ましい。The temperature of the solution during the electrolysis may be usually about 20 to 90 ° C., preferably about 40 to 70 ° C.
【0021】又、電解時の液のpHが高くなりすぎる
と、沈殿が生成して希土類酸化物膜を得ることが難しく
なるので、pH1〜5程度とすることが適当であり、
2.5〜4程度とすることが好ましい。If the pH of the solution during the electrolysis is too high, it is difficult to obtain a rare earth oxide film due to the formation of a precipitate.
It is preferable to set it to about 2.5 to 4.
【0022】形成される希土類酸化物膜の膜厚は、電解
時間に応じて増加するので、電解時間を適宜設定するこ
とによって、目的とする膜厚の希土類酸化物膜を得るこ
とができる。Since the film thickness of the formed rare earth oxide film increases in accordance with the electrolysis time, a rare earth oxide film having a desired film thickness can be obtained by appropriately setting the electrolysis time.
【0023】本発明では、希土類酸化物膜を形成する基
材の種類については特に限定されず、通常の電気めっき
の対象となる全ての材料を基材とすることができる。具
体例としては、銅、鉄等の金属材料、NESAガラス、
ITOガラス等のガラス材料、セラミックス材料、プラ
スチックス材料が例示される。セラミックス材料、プラ
スチックス材料等の非導電性材料に対しては、常法に従
って、無電解めっき法等の湿式処理、PVD法等の乾式
処理等によって、導電化処理を施せばよい。基材には、
上記電解を行う前に、常法に従って、前処理を施しても
よい。また、電解後には、水洗、乾燥など通常行われて
いる操作を行ってもよい。In the present invention, the type of the substrate on which the rare earth oxide film is formed is not particularly limited, and any material that is a target of ordinary electroplating can be used as the substrate. Specific examples include metal materials such as copper and iron, NESA glass,
Glass materials such as ITO glass, ceramic materials, and plastics materials are exemplified. A non-conductive material such as a ceramic material or a plastics material may be subjected to a conductive treatment by a wet treatment such as an electroless plating method or a dry treatment such as a PVD method according to a conventional method. In the base material,
Before performing the electrolysis, a pretreatment may be performed in accordance with a conventional method. In addition, after the electrolysis, operations that are usually performed such as washing with water and drying may be performed.
【0024】本発明では、上記した電解方法によって、
希土類酸化物膜を形成した後、更に、加熱処理を行うこ
とによって、希土類酸化物膜の結晶性が向上し、基材と
の密着性が向上する。熱処理温度は、100〜800℃
程度が好ましく、200〜600℃程度がより好まし
い。熱処理の時間は、特に限定的ではなく、特性の改善
が認められる時間とすれば良いが、通常、30分〜3時
間程度とすればよい。In the present invention, by the above-described electrolysis method,
After the formation of the rare earth oxide film, by further performing a heat treatment, the crystallinity of the rare earth oxide film is improved, and the adhesion to the base material is improved. Heat treatment temperature is 100-800 ° C
Degree is preferable, and about 200 to 600 ° C. is more preferable. The time of the heat treatment is not particularly limited, and may be a time at which the improvement of the characteristics is recognized, but may be generally about 30 minutes to 3 hours.
【0025】[0025]
【発明の効果】本発明の希土類酸化物膜電解形成用組成
物によれば、水溶液からの電解という非常に簡単な方法
によって希土類酸化物膜を形成できる。この様な水溶液
からの電解法によれば、真空排気装置や加熱炉等の大規
模な装置を必要とすることなく、工業的に広く用いられ
れている電気めっき装置などの簡単な装置を使用して、
大面積の基材や複雑な形状の基材にも膜厚や組成が均一
な希土類酸化物膜を形成でき、しかも膜厚や組成を電解
条件により容易に制御できるという利点がある。According to the composition for electrolytically forming a rare earth oxide film of the present invention, a rare earth oxide film can be formed by a very simple method of electrolysis from an aqueous solution. According to the electrolysis method from such an aqueous solution, a simple apparatus such as an electroplating apparatus widely used industrially is used without requiring a large-scale apparatus such as an evacuation apparatus and a heating furnace. hand,
There is an advantage that a rare earth oxide film having a uniform film thickness and composition can be formed on a substrate having a large area or a substrate having a complicated shape, and the film thickness and composition can be easily controlled by electrolysis conditions.
【0026】形成される希土類酸化物膜は、例えば、磁
性体、強誘電体、電池材料、触媒等の各種用途について
幅広い利用が可能である。The formed rare earth oxide film can be widely used for various uses such as a magnetic material, a ferroelectric material, a battery material, and a catalyst.
【0027】[0027]
【実施例】以下に、実施例および比較例を示して、本発
明の特徴をより一層明らかにする。 実施例1〜6及び比較例1〜6 下記表1及び表2に記載の各成分を含有する水溶液から
なるセリウム酸化物膜電解形成用組成物を調製した。こ
れらの組成物中のセリウム化合物及び硝酸塩の配合量は
mol/lで示す。EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples. Examples 1 to 6 and Comparative Examples 1 to 6 A composition for electrolytic formation of a cerium oxide film comprising an aqueous solution containing the components shown in Tables 1 and 2 below was prepared. The amounts of the cerium compound and the nitrate in these compositions are shown in mol / l.
【0028】[0028]
【表1】 [Table 1]
【0029】[0029]
【表2】 [Table 2]
【0030】これらの各組成物中で、NESAガラスを
陰極とし、Pt板を陽極として電解を行なってNESA
ガラス上に電析膜を析出させた。表1及び表2に、電解
条件を記載する。電位(V)は、Ag/AgCl電極基
準で示す。In each of these compositions, NESA glass was used as a cathode, and a Pt plate was used as an anode to perform electrolysis to obtain NESA.
An electrodeposited film was deposited on the glass. Tables 1 and 2 show the electrolysis conditions. The potential (V) is shown based on the Ag / AgCl electrode.
【0031】得られた電析膜の種類をX線回折法により
調べた結果を下記表3に示す。比較例1〜6の組成物を
用いた場合には、膜を形成することはできなかった。The results of examination of the type of the obtained electrodeposited film by X-ray diffraction are shown in Table 3 below. When the compositions of Comparative Examples 1 to 6 were used, a film could not be formed.
【0032】[0032]
【表3】 [Table 3]
【0033】以上の結果より、本発明の組成物を用いる
ことによって、水溶液中での電解という簡単な方法によ
りセリウム酸化物膜を形成できることが判る。 実施例7〜12及び比較例7〜12 下記表4及び表5に記載の各成分を含有する水溶液から
なるテルビウム酸化物膜電解形成用組成物を調製した。
これらの組成物中のテルビウム化合物及び硝酸塩の配合
量はmol/lで示す。From the above results, it is understood that the cerium oxide film can be formed by using the composition of the present invention by a simple method of electrolysis in an aqueous solution. Examples 7 to 12 and Comparative Examples 7 to 12 A terbium oxide film electrolytic formation composition comprising an aqueous solution containing the components shown in Tables 4 and 5 below was prepared.
The amounts of the terbium compound and nitrate in these compositions are shown in mol / l.
【0034】[0034]
【表4】 [Table 4]
【0035】[0035]
【表5】 [Table 5]
【0036】これらの各組成物中で、NESAガラスを
陰極とし、Pt板を陽極として電解を行なってNESA
ガラス上に電析膜を析出させた。表4及び表5に、電解
条件を記載する。電位(V)は、Ag/AgCl電極基
準で示す。In each of these compositions, NESA glass was used as a cathode, and a Pt plate was used as an anode to perform electrolysis to obtain NESA.
An electrodeposited film was deposited on the glass. Tables 4 and 5 list the electrolysis conditions. The potential (V) is shown based on the Ag / AgCl electrode.
【0037】得られた電析膜の種類をX線回折法により
調べた結果を下記表6示す。比較例7〜12の組成物を
用いた場合には、膜を形成することはできなかった。The results of examination of the type of the obtained electrodeposited film by X-ray diffraction are shown in Table 6 below. When the compositions of Comparative Examples 7 to 12 were used, a film could not be formed.
【0038】[0038]
【表6】 [Table 6]
【0039】以上の結果より、本発明の組成物を用いる
ことによって、水溶液中での電解という簡単な方法によ
りテルビウム酸化物膜を形成できることが判る。 実施例13〜18及び比較例13〜18 下記表7及び表8に記載の各成分を含有する水溶液から
なるイットリウム酸化物膜電解形成用組成物を調製し
た。これらの組成物中のイットリウム化合物及び硝酸塩
の配合量はmol/lで示す。From the above results, it can be seen that a terbium oxide film can be formed by using the composition of the present invention by a simple method of electrolysis in an aqueous solution. Examples 13 to 18 and Comparative Examples 13 to 18 Yttrium oxide film electrolytic formation compositions comprising aqueous solutions containing the components shown in Tables 7 and 8 below were prepared. The amounts of the yttrium compound and the nitrate in these compositions are shown in mol / l.
【0040】[0040]
【表7】 [Table 7]
【0041】[0041]
【表8】 [Table 8]
【0042】これらの各組成物中で、NESAガラスを
陰極とし、Pt板を陽極として電解を行なってNESA
ガラス上に電析膜を析出させた。表7及び表8に、各電
解条件を記載する。電位(V)は、Ag/AgCl電極
基準で示す。実施例13〜18については、電析膜形成
後、表7に示す条件で加熱処理を行った。In each of these compositions, NESA glass was used as a cathode, and a Pt plate was used as an anode to perform electrolysis to obtain NESA glass.
An electrodeposited film was deposited on the glass. Tables 7 and 8 show the respective electrolysis conditions. The potential (V) is shown based on the Ag / AgCl electrode. In Examples 13 to 18, after the electrodeposited film was formed, heat treatment was performed under the conditions shown in Table 7.
【0043】得られた電析膜の種類をX線回折法により
調べた結果を下記表に示す。比較例13〜18の組成物
を用いた場合には、膜を形成することはできなかった。The type of the obtained electrodeposited film was examined by an X-ray diffraction method, and the result is shown in the following table. When the compositions of Comparative Examples 13 to 18 were used, a film could not be formed.
【0044】[0044]
【表9】 [Table 9]
【0045】以上の結果より、本発明の組成物を用いる
ことによって、水溶液中での電解という簡単な方法によ
りイットリウム酸化物膜を形成できることが判る。 実施例19〜24及び比較例19〜24 下記表10及び表11に記載の各成分を含有する水溶液
からなるユーロピウム酸化物膜電解形成用組成物を調製
した。これらの組成物中のユーロピウム化合物及び硝酸
塩の配合量はmol/lで示す。From the above results, it can be seen that the use of the composition of the present invention enables the formation of an yttrium oxide film by a simple method of electrolysis in an aqueous solution. Examples 19 to 24 and Comparative Examples 19 to 24 Europium oxide film electrolytic formation compositions comprising aqueous solutions containing the components shown in Tables 10 and 11 below were prepared. The amounts of the europium compound and nitrate in these compositions are shown in mol / l.
【0046】[0046]
【表10】 [Table 10]
【0047】[0047]
【表11】 [Table 11]
【0048】これらの各組成物中で、NESAガラスを
陰極とし、Pt板を陽極として電解を行なってNESA
ガラス上に電析膜を析出させた。表10及び表11に、
各電解条件を記載する。電位(V)は、Ag/AgCl
電極基準で示す。実施例19〜24については、電析膜
形成後、表10に示す条件で加熱処理を行った。In each of these compositions, the NESA glass was used as a cathode and the Pt plate was used as an anode to perform electrolysis to obtain NESA.
An electrodeposited film was deposited on the glass. In Table 10 and Table 11,
Each electrolysis condition is described. The potential (V) is Ag / AgCl
Shown on an electrode basis. In Examples 19 to 24, after forming the electrodeposited film, heat treatment was performed under the conditions shown in Table 10.
【0049】得られた電析膜の種類をX線回折法により
調べた結果を下記表に示す。比較例19〜24の組成物
を用いた場合には、膜を形成することはできなかった。The type of the obtained electrodeposited film was examined by the X-ray diffraction method, and the result is shown in the following table. When the compositions of Comparative Examples 19 to 24 were used, a film could not be formed.
【0050】[0050]
【表12】 [Table 12]
【0051】以上の結果より、本発明の組成物を用いる
ことによって、水溶液中での電解という簡単な方法によ
りユーロピウム酸化物膜を形成できることが判る。From the above results, it is understood that the europium oxide film can be formed by using the composition of the present invention by a simple method of electrolysis in an aqueous solution.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 片山 順一 京都府相楽郡精華町大字下狛小字上新庄47 −13 Fターム(参考) 4G076 AA02 AB07 AC02 BC08 BD02 BG02 CA10 DA01 DA03 DA07 DA30 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Junichi Katayama 47-13 Kamishinjo, Seika-cho, Soraku-cho, Soraku-gun, Kyoto F-term (reference) 4G076 AA02 AB07 AC02 BC08 BD02 BG02 CA10 DA01 DA03 DA07 DA30
Claims (7)
硝酸イオン及び亜硝酸イオンから選ばれた少なくとも一
種の陰イオンが存在する水溶液からなる希土類酸化物膜
電解形成用組成物。An aqueous solution in which a rare earth compound is dissolved,
A composition for electrolytically forming a rare earth oxide film, comprising an aqueous solution containing at least one anion selected from nitrate ions and nitrite ions.
硝酸イオン源となる化合物及び亜硝酸イオン源となる化
合物から選ばれた少なくとも一種の化合物、を溶解した
水溶液からなる請求項1に記載の希土類酸化物膜電解形
成用組成物。(I) a water-soluble rare earth compound, and (ii)
The composition for electrolytic formation of a rare earth oxide film according to claim 1, comprising an aqueous solution in which at least one compound selected from a compound serving as a nitrate ion source and a compound serving as a nitrite ion source is dissolved.
なる請求項1に記載の希土類酸化物膜電解形成用組成
物。3. The composition for electrolytically forming a rare earth oxide film according to claim 1, comprising an aqueous solution in which a nitrate of a rare earth element is dissolved.
イットリウム及びユーロピウムから選ばれた少なくとも
一種の希土類元素を含む化合物である請求項1〜3のい
ずれかに記載の希土類酸化物膜電解形成用組成物。4. The method according to claim 1, wherein the rare earth compound is cerium, terbium,
The composition for electrolytically forming a rare earth oxide film according to any one of claims 1 to 3, which is a compound containing at least one rare earth element selected from yttrium and europium.
化物膜電解形成用組成物中で、希土類酸化物形成用基材
を陰極として電解を行うことを特徴とする希土類酸化物
膜の形成方法。5. The rare earth oxide film according to any one of claims 1 to 4, wherein the electrolysis is performed using the rare earth oxide forming substrate as a cathode. Formation method.
を100〜800℃で加熱処理することを特徴とする希
土類酸化物膜形成方法。6. A method for forming a rare earth oxide film, comprising heating the rare earth oxide film formed by the method of claim 5 at 100 to 800 ° C.
成された希土類酸化物膜。7. A rare earth oxide film formed on a substrate by the method according to claim 5.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003013284A (en) * | 2001-06-27 | 2003-01-15 | Nkk Corp | Method for manufacturing surface-treated steel sheet superior in corrosion resistance |
JP2013500398A (en) * | 2009-07-30 | 2013-01-07 | スネクマ | Parts with a substrate carrying a ceramic coating layer |
JP2013500399A (en) * | 2009-07-30 | 2013-01-07 | スネクマ | Method for manufacturing a thermal barrier |
-
1999
- 1999-03-25 JP JP11081095A patent/JP2000273694A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003013284A (en) * | 2001-06-27 | 2003-01-15 | Nkk Corp | Method for manufacturing surface-treated steel sheet superior in corrosion resistance |
JP2013500398A (en) * | 2009-07-30 | 2013-01-07 | スネクマ | Parts with a substrate carrying a ceramic coating layer |
JP2013500399A (en) * | 2009-07-30 | 2013-01-07 | スネクマ | Method for manufacturing a thermal barrier |
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