JPH0329758B2 - - Google Patents
Info
- Publication number
- JPH0329758B2 JPH0329758B2 JP62261219A JP26121987A JPH0329758B2 JP H0329758 B2 JPH0329758 B2 JP H0329758B2 JP 62261219 A JP62261219 A JP 62261219A JP 26121987 A JP26121987 A JP 26121987A JP H0329758 B2 JPH0329758 B2 JP H0329758B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- raw material
- weight
- aluminum oxide
- beryllium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000013078 crystal Substances 0.000 claims description 29
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 12
- 229910001602 chrysoberyl Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241001233037 catfish Species 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
本発明はクリソベリルキヤツツアイ単結晶を合
成する製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a manufacturing method for synthesizing chrysoberyl cateye single crystals.
本発明の目的は、キヤツチアイ効果を有するク
リソベリル単結晶を得ることにある。 An object of the present invention is to obtain a chrysoberyl single crystal having a catch's eye effect.
本発明の他の目的は、大型で、しかも安価にク
リソベリルキヤツチアイ単結晶を得ることにあ
る。 Another object of the present invention is to obtain a large-sized and inexpensive chrysoberyl catfish single crystal.
クリソベリルはBeAl2O4なる組成を持ち、天然
には猫目石、アレキサンドライトなどが宝石とし
て著名である。近年、その光物性からレーザーホ
スト材料として有望視されている。これを人工的
に製造しようとする試はPbO.PbO−PbF2系、
PbO−PbF2−B2O3系、Li2MOO4−MOO2系など
の融剤をフラツクスとして用いる方法が幾つか行
なわれてきた。しかし、これらの方法では大結晶
を得ることは難しく、又、この様な方法で作製し
た結晶は、双晶になり易く、単結晶は困難であつ
た。 Chrysoberyl has a composition of BeAl 2 O 4 , and is famous as a natural gemstone such as cat's eye stone and alexandrite. In recent years, it has been viewed as a promising laser host material due to its optical properties. Attempts to artificially produce this are PbO.PbO−PbF 2 system,
Several methods have been carried out using fluxes such as PbO--PbF 2 --B 2 O 3 system and Li 2 MOO 4 --MOO 2 system. However, it is difficult to obtain large crystals using these methods, and crystals produced by such methods tend to form twins, making it difficult to produce single crystals.
本発明者は赤外線を集光することにより得られ
る高温によりあらかじめ棒状に成型した原料中に
溶融帯を形成し、かつその溶融帯を移動せしめる
ことにより容易にクリソベリル単結晶が得られる
ことを見出した。 The present inventor has discovered that chrysoberyl single crystals can be easily obtained by forming a molten zone in a raw material that has been previously formed into a rod shape using high temperatures obtained by concentrating infrared rays, and by moving the molten zone. .
第１図にBeO−Al2O3系の状態図を示す。図か
ら明らかな如く、Al2O3の重量割合が75％から85
％の高温度にBeO.Al2O3と融液が共存する領域が
存在する。この領域から単純に冷却固化させても
3BeO.Al2O3又は、BeO.3Al2O3とBeO.Al2O3の混
晶が生成するのみで、BeO.Al2O3の単結晶は得ら
れない。しかし、本発明方法を用いることにより
容易にクリソベリル単結晶が得られた。 Figure 1 shows the phase diagram of the BeO-Al 2 O 3 system. As is clear from the figure, the weight percentage of Al 2 O 3 varies from 75% to 85%.
%, there exists a region where BeO.Al 2 O 3 and the melt coexist. Even if you simply cool and solidify from this area,
Only 3BeO.Al 2 O 3 or a mixed crystal of BeO.3Al 2 O 3 and BeO.Al 2 O 3 is generated, and a single crystal of BeO.Al 2 O 3 cannot be obtained. However, by using the method of the present invention, chrysoberyl single crystals were easily obtained.
本発明の原理を第２図に示す。 The principle of the invention is shown in FIG.
棒状原料１の部分に赤外線IRにより溶融帯２
を形成する。溶融帯２の組成からAl2O3の重量割
合が75％から85％の間にあるとする。溶融帯の温
度を1870℃以上に保ち、溶融帯を原料枠中上方に
移動せしめると、溶解帯下部は1870℃以下とな
り、BeO.Al2O3と融液が共存する領域が生成す
る。この領域に於て、BeO.Al2O3は下部原料中に
残り、融液は溶融帯を共に上方に移動する為に、
下部原料中にはBeO.Al2O3単結晶のみが残る。下
部原料棒即ち、BeO−Al2O3が育成される領域に
BeO.Al2O3の種子結晶が存在すると結晶化は容易
となり、完全なる単結晶が生成が行なわれる。 A melting zone 2 is formed on the rod-shaped raw material 1 by infrared IR.
form. It is assumed that the weight percentage of Al 2 O 3 in the composition of the melting zone 2 is between 75% and 85%. When the temperature of the melting zone is kept at 1870°C or higher and the melting zone is moved upward in the raw material frame, the lower part of the melting zone becomes lower than 1870°C, and a region where BeO.Al 2 O 3 and the melt coexist is generated. In this region, BeO.Al 2 O 3 remains in the lower raw material, and the melt moves upward along the melting zone.
Only the BeO.Al 2 O 3 single crystal remains in the lower raw material. The lower raw material rod, that is, the area where BeO−Al 2 O 3 is grown
The presence of a seed crystal of BeO.Al 2 O 3 facilitates crystallization, and a perfect single crystal is formed.
尚クリソベリル単結晶の緑色を析出させるため
に着色剤として酸化クロムを用いる。酸化クロム
は酸化ベリリウムと酸化アルミニウムの合算重量
に対して、重量比で1.54〜3.00％混入する。 Note that chromium oxide is used as a coloring agent to precipitate the green color of the chrysoberyl single crystal. Chromium oxide is mixed at a weight ratio of 1.54 to 3.00% based on the total weight of beryllium oxide and aluminum oxide.
第３図に於て、本発明を実施する装置について
説明する。 Referring to FIG. 3, an apparatus for implementing the present invention will be described.
回転楕円鏡体３内の一焦点にハロゲンランプ４
又はクセノンランプを配置し、他の焦点に棒状原
料５を配置する。棒状原料５は上部回転軸６、下
部回転軸７により支持されている。原料棒５と回
転軸６，７は透明石英管８内に密封されており雰
囲気を自由にコントロールでき、又、真空あるい
は加圧することも可能である。棒状原料５中で温
度の上るのは焦点に完全に一致した部分のみであ
り、この部分が溶融帯９である。溶融帯９は、回
転軸６，７を上下動させることにより棒状原料上
を移動させることができる。 A halogen lamp 4 is placed at one focal point within the spheroidal mirror body 3.
Alternatively, a xenon lamp is placed and the rod-shaped raw material 5 is placed at another focal point. The rod-shaped raw material 5 is supported by an upper rotating shaft 6 and a lower rotating shaft 7. The raw material rod 5 and the rotating shafts 6 and 7 are sealed in a transparent quartz tube 8, so that the atmosphere can be freely controlled, and it is also possible to apply a vacuum or pressurization. In the rod-shaped raw material 5, the temperature rises only in the part that completely coincides with the focal point, and this part is the melting zone 9. The melting zone 9 can be moved over the rod-shaped raw material by moving the rotating shafts 6 and 7 up and down.
本発明方法を用いることにより双晶のない大型
完全クリソベリル単結晶の製造が可能となつた。 By using the method of the present invention, it has become possible to produce a large perfect chrysoberyl single crystal without twins.
以下に本発明を実施例について説明する。 The present invention will be described below with reference to Examples.
実施例 １
酸化アルミニウム60ｇ、酸化ベリリウム５ｇ酸
化クロム１ｇ、酸化チタン0.5ｇをボールミル混
合し、800℃、30Kg／cm2でホツトプレス成型して
棒状とした後、赤外線集中加熱装置にセツトし、
４Kg／cm2の酸素圧下で結晶成長を行ないキヤツツ
アイ状の光条の生ずるクリソベリルを得た。Example 1 60 g of aluminum oxide, 5 g of beryllium oxide, 1 g of chromium oxide, and 0.5 g of titanium oxide were mixed in a ball mill, hot press molded at 800°C and 30 kg/cm 2 into a rod shape, and then set in an infrared concentrated heating device.
Crystal growth was carried out under an oxygen pressure of 4 kg/cm 2 to obtain chrysoberyl with cat's-eye striations.
本発明では原料棒の焼結温度を800℃以上とし
てなるが、焼結温度が800℃以下になると合成単
結晶の中に気泡が残ることがあり、光学的性質や
装飾性を著しく劣化させる。また着色剤として添
加する酸化クロムは酸化ベリリウムと酸化アルミ
ニウムの合算重量の1.54〜3.00％の添加量である
が、3.00％を超えると酸化クロムの偏析を生じ単
結晶の割れ等の惧れがあり、また1.54％より少な
いと十分な着色が得られない。 In the present invention, the raw material rod is sintered at a temperature of 800°C or higher, but if the sintering temperature is lower than 800°C, air bubbles may remain in the synthesized single crystal, significantly degrading the optical properties and decorativeness. Furthermore, the amount of chromium oxide added as a coloring agent is 1.54 to 3.00% of the total weight of beryllium oxide and aluminum oxide, but if it exceeds 3.00%, there is a risk of segregation of chromium oxide and cracking of the single crystal. , and if it is less than 1.54%, sufficient coloring cannot be obtained.
以上の如く、本発明は、酸化ベリリウム、酸化
アルミニウム、酸化チタン、及び着色剤として酸
化クロムからなる原料棒と種結晶との接触界面近
傍を部分的に加熱して溶融帯を形成し、該溶融帯
を原料棒側に移動させて単結晶を合成する製造方
法において、該原料棒中の該酸化ベリリウムと該
酸化アルミニウムの混合割合が酸化ベリリウム25
〜15重量％、酸化アルミニウム75〜85重量％であ
り、該酸化チタンは該酸化ベリリウムと該酸化ア
ルミニウムの合算重量に対して0.77重量％以下で
あり、該酸化クロムは該酸化ベリリウムと該酸化
アルミニウムの合算重量に対して1.54〜3.00重量
％であり、溶融帯の温度は1870℃以上であり、且
つ少なくとも該溶融帯の雰囲気は酸素ガスの加圧
下に保持するようにしたので、以下に示す特有の
効果を有するものである。すなわち、該原料棒中
に酸化チタンが含まれていること及び該溶融帯の
雰囲気は酸素ガスの加圧下に保持されていること
により、合成単結晶中の酸化チタンは針状結晶と
して成長し易くなり、キヤツツアイ状の光状の生
じるクリソベリル単結晶が得られる。このよう
に、溶融帯の雰囲気を加圧下に保持することによ
り、酸化チタンの針状結晶が析出し易くなる理由
は、溶融帯は加圧された酸素ガス雰囲気にさらさ
れていること、及び溶融帯は溶融状態にあるの
で、溶融帯の外表面から溶融帯内部に酸素ガスが
スムースに供給され、酸素不足の酸化チタンが全
くなくなり、酸化チタンの針状結晶が析出し易く
なるためと推測される。更に、該原料棒中の該酸
化ベリリウムと該酸化アルミニウムの混合割合が
酸化ベリリウム25〜15重量％、酸化アルミウム75
〜85重量％に、且つ酸化クロムが該酸化ベリリウ
ムと該酸化アルミニウムの合算重量に対して1.54
〜3.00重量％にし、溶融帯の温度は1870℃以上で
単結晶を合成したので、材質が均一でしかも着色
むらのない大型の単結晶を、しかも安価に提供す
ることを可能にしたものである。 As described above, the present invention involves forming a molten zone by partially heating the vicinity of the contact interface between a seed crystal and a raw material rod made of beryllium oxide, aluminum oxide, titanium oxide, and chromium oxide as a coloring agent. In a production method in which a single crystal is synthesized by moving a band toward a raw material rod, the mixing ratio of the beryllium oxide and the aluminum oxide in the raw material rod is 25% beryllium oxide.
~15% by weight, aluminum oxide is 75-85% by weight, the titanium oxide is 0.77% by weight or less based on the total weight of the beryllium oxide and the aluminum oxide, and the chromium oxide is less than 0.77% by weight based on the total weight of the beryllium oxide and the aluminum oxide. 1.54 to 3.00% by weight based on the total weight of It has the following effects. In other words, because titanium oxide is contained in the raw material rod and the atmosphere in the molten zone is maintained under pressure of oxygen gas, titanium oxide in the synthesized single crystal tends to grow as needle-shaped crystals. As a result, a chrysoberyl single crystal with a cat's eye shape is obtained. The reason why the acicular crystals of titanium oxide tend to precipitate by maintaining the atmosphere in the molten zone under pressure is that the molten zone is exposed to a pressurized oxygen gas atmosphere and Since the band is in a molten state, oxygen gas is smoothly supplied from the outer surface of the molten zone to the inside of the molten zone, and it is presumed that the oxygen-deficient titanium oxide is completely eliminated, making it easier for needle-shaped crystals of titanium oxide to precipitate. Ru. Furthermore, the mixing ratio of the beryllium oxide and the aluminum oxide in the raw material rod is 25 to 15% by weight of beryllium oxide and 75% by weight of aluminum oxide.
~85% by weight, and chromium oxide is 1.54% by weight based on the combined weight of the beryllium oxide and the aluminum oxide.
~3.00% by weight and the single crystal was synthesized at a melting zone temperature of 1870°C or higher, making it possible to provide a large single crystal with uniform material and uniform coloring at a low cost. .
第１図は本発明の原理を説明する状態図であ
る。第２図は本発明の詳細を説明する図である。
第３図は本発明に用いる赤外線集中加熱装置の説
明図である。
１……棒状原料、２……溶融帯、３……回転楕
円鏡体、４……ハロゲンランプ、５……棒状原
料、６……上部回転軸、７……下部回転軸、８…
…透明石英管、９……溶融帯。
FIG. 1 is a state diagram illustrating the principle of the present invention. FIG. 2 is a diagram illustrating details of the present invention.
FIG. 3 is an explanatory diagram of an infrared concentrated heating device used in the present invention. DESCRIPTION OF SYMBOLS 1... Rod-shaped raw material, 2... Melting zone, 3... Spheroidal body, 4... Halogen lamp, 5... Rod-shaped raw material, 6... Upper rotating shaft, 7... Lower rotating shaft, 8...
...transparent quartz tube, 9...molten zone.
Claims (1)
タン、及び着色剤として酸化クロムからなる原料
棒と種結晶との接触界面近傍を部分的に加熱して
溶融帯を形成し、該溶融帯を原料棒側に移動させ
て単結晶を合成する製造方法において、該原料棒
中の該酸化ベリリウムと該酸化アルミニウムの混
合割合が酸化ベリリウム25〜15重量％、酸化アル
ミニウム75〜85重量％であり、該酸化チタンは該
酸化ベリリウムと該酸化アルミニウムの合算重量
に対して0.77重量％以下であり、該酸化クロムは
該酸化ベリリウムと該酸化アルミニウムの合算重
量に対して1.54〜3.00重量％であり、溶融帯の温
度は1870℃以上であり、且つ少なくとも該溶融帯
の雰囲気は酸素ガスの加圧下に保持されているこ
とを特徴とするクリソベリルキヤツツアイ単結晶
の合成方法。1. Partially heating the vicinity of the contact interface between the seed crystal and the raw material rod made of beryllium oxide, aluminum oxide, titanium oxide, and chromium oxide as a coloring agent to form a molten zone, and move the molten zone toward the raw material rod side. In the production method of synthesizing a single crystal by combining the beryllium oxide and the aluminum oxide in the raw material rod, the mixing ratio of beryllium oxide and aluminum oxide is 25 to 15% by weight, aluminum oxide is 75 to 85% by weight, and the titanium oxide is The amount of chromium oxide is 1.54 to 3.00% by weight based on the total weight of beryllium oxide and aluminum oxide, and the temperature of the melting zone is 1870°C. C. or higher, and at least the atmosphere of the molten zone is maintained under pressure of oxygen gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26121987A JPS63260894A (en) | 1987-10-16 | 1987-10-16 | Synthesis method of chrysoberyl cat's eye single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26121987A JPS63260894A (en) | 1987-10-16 | 1987-10-16 | Synthesis method of chrysoberyl cat's eye single crystal |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7288185A Division JPS60260495A (en) | 1985-04-05 | 1985-04-05 | Preparation of single crystal of chrysoberyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63260894A JPS63260894A (en) | 1988-10-27 |
| JPH0329758B2 true JPH0329758B2 (en) | 1991-04-25 |
Family
ID=17358796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26121987A Granted JPS63260894A (en) | 1987-10-16 | 1987-10-16 | Synthesis method of chrysoberyl cat's eye single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63260894A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS546900A (en) * | 1977-06-17 | 1979-01-19 | Seiko Epson Corp | Production of clean beryl single crystal |
| JPS60260495A (en) * | 1985-04-05 | 1985-12-23 | Seiko Epson Corp | Preparation of single crystal of chrysoberyl |
-
1987
- 1987-10-16 JP JP26121987A patent/JPS63260894A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS546900A (en) * | 1977-06-17 | 1979-01-19 | Seiko Epson Corp | Production of clean beryl single crystal |
| JPS60260495A (en) * | 1985-04-05 | 1985-12-23 | Seiko Epson Corp | Preparation of single crystal of chrysoberyl |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63260894A (en) | 1988-10-27 |
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