JPH0483798A - Removal of residue in crucible - Google Patents
Removal of residue in crucibleInfo
- Publication number
- JPH0483798A JPH0483798A JP19551890A JP19551890A JPH0483798A JP H0483798 A JPH0483798 A JP H0483798A JP 19551890 A JP19551890 A JP 19551890A JP 19551890 A JP19551890 A JP 19551890A JP H0483798 A JPH0483798 A JP H0483798A
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- residue
- lanthanum aluminate
- single crystal
- melt
- 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
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- -1 lanthanum aluminate Chemical class 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 abstract description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract 2
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ランタンアルミネート（ＬａＡ１０３）単結
晶を引き上げ法によって製造した後、るつぼ内の融液残
渣を効果的に除去する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for effectively removing melt residue in a crucible after producing a lanthanum aluminate (LaA103) single crystal by a pulling method.
［従来の技術１
ランタンアルミネート単結晶は、高Ｔｃ（臨界温度）超
伝導体用基板材料として、最近注目されている物質であ
る。[Prior Art 1 Lanthanum aluminate single crystal is a substance that has recently attracted attention as a substrate material for high Tc (critical temperature) superconductors.
ランタンアルミネートのような複合酸化物の単結晶は、
ベルヌーイ法により育成されることが多いが、るつぼ内
に原料を融解させ、融液に種結晶を浸して引き上げる、
結晶引き上げ法（−船釣にはチョクラルスキー法）によ
っても育成されている。Single crystals of complex oxides such as lanthanum aluminate are
It is often grown using the Bernoulli method, which involves melting the raw material in a crucible, dipping a seed crystal in the melt, and pulling it up.
It is also grown by the crystal pulling method (-Czochralski method for boat fishing).
結晶引き上げ法では、通常、融液量の２０〜８０重量％
の単結晶を育成させた後、融液から単結晶を弓き離し、
冷却した後、単結晶を取り出す。その結果、るつぼ内に
は残渣が残る。In the crystal pulling method, usually 20 to 80% by weight of the melt amount
After growing a single crystal, the single crystal is separated from the melt,
After cooling, the single crystal is taken out. As a result, a residue remains inside the crucible.
残渣は、その物性に応じて、再度溶解したり、機械的加
工と酸洗浄を組み合わせたりすることにより除去されて
いる。Depending on its physical properties, the residue is removed by redissolving or by a combination of mechanical processing and acid cleaning.
また、結晶引き上げ法に使用するるつぼとしては、育成
したい結晶の融解温度より融点が高いこと、原料融液と
反応しないこと等を考慮して、複合酸化物結晶を育成す
る場合は白金やイリジウム等の貴金属が一般に用いられ
ており、ランタンアルミネートの場合は融解温度が約２
０８０°Ｃと非常に高温であるため、通常、イリジウム
製のるつぼが使用されている。これらの材料は、非常に
高価であるために、通常１０〜３０回繰り返し使用した
後、改鋳に供される。In addition, when growing composite oxide crystals, the crucible used for the crystal pulling method should be made of platinum, iridium, etc. Noble metals are commonly used, and in the case of lanthanum aluminate, the melting temperature is approximately 2
Since the temperature is extremely high at 080°C, an iridium crucible is usually used. Since these materials are very expensive, they are usually used 10 to 30 times before being recast.
［発明が解決しようとする課題］
ランタンアルミネートの融液残渣を再溶解により除去す
る方法は、ランタンアルミネートの融解温度が非常に高
温であるため、イリジウム製るつぼの融解、破損、イリ
ジウムの酸化・蒸発によるるつぼの寿命短縮等の原因と
なる。[Problems to be Solved by the Invention] The method of removing the lanthanum aluminate melt residue by remelting the lanthanum aluminate has a very high melting temperature, so the iridium crucible may be melted, damaged, and the iridium may be oxidized. - May cause shortening of crucible life due to evaporation.
また、機械加工と酸洗浄を組み合わせる方法も、イリジ
ウムが脆い材料であるためにるつぼの破損・劣化、除去
工程が複雑化する等の問題がある。Furthermore, the method of combining machining and acid cleaning has problems such as damage and deterioration of the crucible and complication of the removal process because iridium is a brittle material.
したがって、高価で脆いイリジウム製るつぼの破損・劣
化を防止することができ、且つ効率的にるつぼ内残渣を
除去することができる方法が望まれていた。Therefore, there has been a desire for a method that can prevent damage and deterioration of the expensive and brittle iridium crucible and efficiently remove the residue inside the crucible.
［課題を解決するための手段］
本発明は、イリジウム製るつぼからランタンアルミネー
ト残渣を除去する方法について鋭意検討した結果、ラン
タンアルミネートの融液から多結晶を育成した後、水溶
液中に浸すことにより、るつぼの破損・劣化を起こすこ
となくるつぼ内のランタンアルミネート残渣を容易に除
去できることを見出し、本発明に到着した。[Means for Solving the Problems] As a result of intensive studies on a method for removing lanthanum aluminate residue from an iridium crucible, the present invention proposes a method for growing polycrystals from a lanthanum aluminate melt and then immersing them in an aqueous solution. It was discovered that the lanthanum aluminate residue inside the crucible can be easily removed without causing damage or deterioration of the crucible, and the present invention was arrived at.
即ち、本発明の要旨は、ランタンアルミネート単結晶を
引き上げ法によって育成した後、るつぼ内の融液残渣を
多結晶質に凝固させた後、凝固した融液残渣を含むるつ
ぼを温度０〜１０００℃、水の含有量１０〜１００％の
水溶液中に３分間以上浸すことを特徴とするるつぼ内の
残渣除去方法に存する。That is, the gist of the present invention is to grow a lanthanum aluminate single crystal by a pulling method, solidify the melt residue in the crucible into a polycrystalline state, and then heat the crucible containing the solidified melt residue at a temperature of 0 to 1000. C., and immersing the crucible in an aqueous solution having a water content of 10 to 100% for 3 minutes or more.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
通常、チョクラルスキー法等の結晶引き上げ法において
は、単結晶を育成させた後、融液から単結晶を引き離し
、冷却した後、単結晶を取り高す。Usually, in a crystal pulling method such as the Czochralski method, after growing a single crystal, the single crystal is separated from the melt, cooled, and then raised.
本発明においては、育成させたランタンアルミネート単
結晶にボイド、クラック等が発生しないように、かつ、
るつぼ内のランタンアルミネート融液残渣が多結晶質に
凝固するように、育成した単結晶及び融液残渣を緩かに
冷却するのが好ましく、通常、１０〜５０時間かけて一
１０〜５０°Ｃの温度まで冷却する。In the present invention, it is necessary to prevent voids, cracks, etc. from occurring in the grown lanthanum aluminate single crystal, and
In order to solidify the lanthanum aluminate melt residue in the crucible into a polycrystalline state, it is preferable to slowly cool the grown single crystal and the melt residue, usually at a temperature of -10 to 50 degrees over a period of 10 to 50 hours. Cool to temperature C.
次いで、多結晶質に凝固した融液残渣を含むるつぼを温
度０〜１０００℃、水の含有量１０〜１００％の水溶液
中に３分間以上放置する。通常は、室温の水中に浸すこ
とにより、ランタンアルミネート多結晶の微粉末化が起
こり、るつぼから完全に垂離するため、容易に残渣を除
去することができる。また、水溶液中の温度を高くする
ことにより、微粉末化の速度を早くすることができる。Next, the crucible containing the polycrystalline solidified melt residue is left in an aqueous solution with a temperature of 0 to 1000°C and a water content of 10 to 100% for 3 minutes or more. Normally, lanthanum aluminate polycrystals are pulverized by immersion in water at room temperature and are completely separated from the crucible, so that the residue can be easily removed. Further, by increasing the temperature in the aqueous solution, the speed of pulverization can be increased.
ランタンアルミネート単結晶では、上記のような微粉末
化は認められない。ランタンアルミネート多結晶の微粉
末化は吸湿によるものと思われるが、ランタンアルミネ
ート本来の物性によるものとは考えにくく、おそらく原
料中の不純物あるいはＬａ −ＡＩ −０系の異質層が
関与しているものと思われる。In the lanthanum aluminate single crystal, the above-mentioned pulverization is not observed. The pulverization of lanthanum aluminate polycrystals is thought to be due to moisture absorption, but it is unlikely that this is due to the inherent physical properties of lanthanum aluminate, and impurities in the raw material or a heterogeneous layer of the La-AI-0 system are probably involved. It seems that there are.
［実施例］
以下に実施例により、本発明を更に詳細に説明するが、
本発明はその要旨を越えない限り実施例に限定表れるも
のではない。[Example] The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to the examples unless it goes beyond the gist thereof.
実施例１
１１０ＫＨｚの高周波加熱炉内に、直径５０ｍｍ、高さ
５０ｍｍ、厚さ１．５ｍｍのイリジウム（Ｉｒ）製るつ
ぼを設置し、その中に純度９９．９９％の酸化ランタン
（Ｌａ２０ａ ）５０モル％、酸化アルミニウム（Ａｌ
２Ｏ３）５０モル％からなる原料を３２０ｇ入れ、窒素
ガス雰囲気中で融解した。融液を融点近くまで降温しで
ランタンアルミネート（ＬａＡ１０ａ ）の種結晶を浸
し、２５ｒｐｍで回転させながら、約２ｍｍ／時間の引
き上げ速度、結晶径２５ｍｍで結晶を育成した。結晶を
１８０ｇ育成した後、融液から切り離し、約２日かけて
冷却し結晶を取り出した。Example 1 An iridium (Ir) crucible with a diameter of 50 mm, a height of 50 mm, and a thickness of 1.5 mm was placed in a 110 KHz high-frequency heating furnace, and 50 moles of lanthanum oxide (La20a) with a purity of 99.99% was placed in the crucible. %, aluminum oxide (Al
320 g of a raw material consisting of 50 mol% of 2O3) was added and melted in a nitrogen gas atmosphere. The temperature of the melt was lowered to near its melting point, and seed crystals of lanthanum aluminate (LaA10a) were immersed therein, and crystals were grown at a pulling rate of about 2 mm/hour and a crystal diameter of 25 mm while rotating at 25 rpm. After growing 180 g of crystals, they were separated from the melt, cooled for about 2 days, and then taken out.
育成結晶は、透明で淡褐色をした双晶を含む配向性の強
い物質であり、一部にボイドを含む物であった。融液残
渣は、るつぼに付着した形で塊状に多結晶で凝固してお
り、そのままでは、るつぼからの除去は不可能であった
。The grown crystals were transparent, light brown, highly oriented substances containing twin crystals, and some contained voids. The melt residue was solidified in the form of polycrystals attached to the crucible, and could not be removed from the crucible as it was.
凝固した融液残渣を含むるつぼを温度２５°Ｃの水中に
１日放置したところ、残渣表面から塊状に臂開している
のが認められた。更に、１日放置した後、残渣部を軽く
叩くことにより、容易に残渣をるつぼから取り出すこと
ができた。When the crucible containing the solidified melt residue was left in water at a temperature of 25°C for one day, it was observed that the residue was bulging out from the surface. Further, after leaving it for one day, the residue could be easily removed from the crucible by tapping the residue.
［発明の効果］
本発明によると、高価なイリジウムるつぼを破損、劣化
させることなく、イリジウムるつぼ内に残ったランタン
アルミネート残渣を容易に除去することができる。また
、その結果、単結晶育成に要する費用を低減することが
できるため、工業的に有用である。[Effects of the Invention] According to the present invention, the lanthanum aluminate residue remaining in the iridium crucible can be easily removed without damaging or deteriorating the expensive iridium crucible. Moreover, as a result, the cost required for single crystal growth can be reduced, which is industrially useful.
Claims (1)
て育成した後、るつぼ内の融液残渣を多結晶質に凝固さ
せた後、凝固した融液残渣を含むるつぼを温度０〜１０
００℃、水の含有量１０〜１００％の水溶液中に３分間
以上浸すことを特徴とするるつぼ内の残渣除去方法。(1) After growing a lanthanum aluminate single crystal by the pulling method, the melt residue in the crucible is solidified into a polycrystalline state, and then the crucible containing the solidified melt residue is heated to a temperature of 0 to 10°C.
A method for removing residue in a crucible, the method comprising immersing the crucible in an aqueous solution containing 10 to 100% water at 00°C for 3 minutes or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19551890A JPH0483798A (en) | 1990-07-24 | 1990-07-24 | Removal of residue in crucible |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19551890A JPH0483798A (en) | 1990-07-24 | 1990-07-24 | Removal of residue in crucible |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0483798A true JPH0483798A (en) | 1992-03-17 |
Family
ID=16342420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19551890A Pending JPH0483798A (en) | 1990-07-24 | 1990-07-24 | Removal of residue in crucible |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0483798A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009203150A (en) * | 2008-02-01 | 2009-09-10 | Hitachi Chem Co Ltd | Method for removing aluminum oxide from inside surface of crucible and method for regenerating crucible |
-
1990
- 1990-07-24 JP JP19551890A patent/JPH0483798A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009203150A (en) * | 2008-02-01 | 2009-09-10 | Hitachi Chem Co Ltd | Method for removing aluminum oxide from inside surface of crucible and method for regenerating crucible |
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