JPS6128637B2 - - Google Patents
Info
- Publication number
- JPS6128637B2 JPS6128637B2 JP12706778A JP12706778A JPS6128637B2 JP S6128637 B2 JPS6128637 B2 JP S6128637B2 JP 12706778 A JP12706778 A JP 12706778A JP 12706778 A JP12706778 A JP 12706778A JP S6128637 B2 JPS6128637 B2 JP S6128637B2
- Authority
- JP
- Japan
- Prior art keywords
- star
- raw material
- oxide
- material rod
- ruby
- 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
Links
- 239000002994 raw material Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- 239000010979 ruby Substances 0.000 claims description 6
- 229910001750 ruby Inorganic materials 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052594 sapphire Inorganic materials 0.000 claims description 5
- 239000010980 sapphire Substances 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- -1 ammonium aluminum carbonate hydroxide Chemical compound 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 15
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/16—Heating of the molten zone
- C30B13/22—Heating of the molten zone by irradiation or electric discharge
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
本発明はあらかじめ焼結した原料棒に赤外線を
集光して結晶化を行なうスタールビー及びスター
サフアイアの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing star ruby and star sapphire in which crystallization is performed by concentrating infrared rays on a raw material rod that has been sintered in advance.
本発明の目的は大型高品質のスタールビー及び
スターサフアイアを得ることにある。 The object of the present invention is to obtain large-sized, high-quality star rubies and star sapphires.
本発明の他の目的は容易に歩留りよくスタール
ビー及びスターサフアイアを得ることにある。 Another object of the present invention is to easily obtain star ruby and star sapphire with good yield.
スタールビー及びスターサフアイアの主要組成
は酸化アルミニウムで、若干の酸化クローム、酸
化鉄、酸化ニツケル等が含まれたコランダムであ
る。この中に酸化チタン（ルチル）の針状結晶が
混入しているとカポツシヨン型に研磨した場合に
６条の星彩線が現われる。これがスタールビー、
スターサフアイアと呼ばれている。コランダムは
六方晶である為に針状微結晶が六角柱面に平行に
分布しており柱面の両対面に平行な三方向に並ん
でいる。従つて互いに120度に交差している為に
点光源が当ると６条のスターが現われる。これは
人工的にも作られている。通常はベルタイ法と呼
ばれる方法で作られる。これは普通のルビー、サ
フアイアの合成に用いられる方法である。粉末原
料を酸水素炎中に落下させながら溶融し、結晶成
長を行なうものである。この場合の粉末はガンマ
アルミナと酸化チタンの混合物が用いられる。ス
ターの生成は結晶育成後熱処理を行なうことによ
りコランダム結晶中の酸化チタンを微結晶化する
ことにより行なわれる。この方法は水素の燃焼熱
を利用する為に2050度以上の高温が容易に得ら
れ、コランダムと酸化チタンの固溶も比較的容易
に行なわれる。しかし原料粉末を落下させ、溶融
させる方法である為にコランダム中への酸化チタ
ンの固溶がややもすると不均一となつてしまう。
従つてコランダム中に生成する針状微結晶の分布
が不均一となる為に６条の星彩線が必らずしも彩
やかに現われず、濃い部分、淡い部分あるいは濃
い線、薄い線となつたり星彩線の中には欠けてし
まうものも現われてくる。即ち完全なスターはベ
ルヌイ法ではなかなか得られなかつた。これを完
全なものにする為に酸化チタンを均一に含有した
コランダムの焼結棒を作製し赤外線で溶融結晶化
させる方法が考えられた。第１図に焼結原料棒を
用いる方法について説明する。回転楕円面鏡１内
の焦点にハロゲンランプ２あるいはキヤノンアー
クランプを設置し、それから発する赤外線を集光
せしめて溶融帯３を形成し、徐々に原料棒４を降
下させて結晶５を得る。原料棒４は上回転軸に保
持され、結晶５は下回転軸に保持され、上回転軸
と下回転軸は逆方向に回転する。得られた結晶を
更に熱処理することにより針状微結晶を生成させ
る。この方法によりほぼ完全なスターの生じるス
タールビー及びスターサフアイアを得ることがで
きる。 The main composition of star ruby and star sapphire is aluminum oxide, and corundum containing some chromium oxide, iron oxide, nickel oxide, etc. If needle-like crystals of titanium oxide (rutile) are mixed in, six star lines will appear when polished into a capsule shape. This is Star Ruby
It is called Star Saphia. Since corundum is a hexagonal crystal, the acicular microcrystals are distributed parallel to the hexagonal cylindrical surface and arranged in three directions parallel to both sides of the cylindrical surface. Therefore, since they intersect with each other at 120 degrees, a six-striped star appears when a point light source hits them. It is also created artificially. It is usually made using a method called the Bertai method. This is the method used to synthesize common rubies and sapphires. Powdered raw materials are melted while falling into an oxyhydrogen flame to grow crystals. The powder used in this case is a mixture of gamma alumina and titanium oxide. Stars are formed by microcrystallizing titanium oxide in corundum crystals by heat treatment after crystal growth. Since this method uses the combustion heat of hydrogen, it is easy to obtain a high temperature of 2050 degrees or more, and solid solution of corundum and titanium oxide is relatively easily achieved. However, since the method involves dropping raw material powder and melting it, the solid solution of titanium oxide in corundum becomes uneven.
Therefore, because the distribution of needle-like microcrystals generated in corundum is uneven, the six star lines do not necessarily appear colorfully, and there are dark parts, pale parts, dark lines, and thin lines. As the stars fade, some things that are missing appear in the star lines. In other words, it was difficult to obtain a perfect star using the Bernoulli method. In order to perfect this, a method was devised in which a sintered bar of corundum uniformly containing titanium oxide was prepared and then melted and crystallized using infrared rays. A method using a sintered raw material rod will be explained in FIG. A halogen lamp 2 or a Canon arc lamp is installed at the focal point within the spheroidal mirror 1, and the infrared rays emitted from the lamp are focused to form a molten zone 3, and the raw material rod 4 is gradually lowered to obtain a crystal 5. The raw material rod 4 is held on the upper rotating shaft, the crystal 5 is held on the lower rotating shaft, and the upper rotating shaft and the lower rotating shaft rotate in opposite directions. The obtained crystals are further heat-treated to produce needle-like microcrystals. By this method, star rubies and star sapphires with almost perfect stars can be obtained.
しかしながら原料棒４の作製が完全に行なわれ
ていないと酸化チタンが均一に分布せず、又原料
棒の焼結が十分に行なわれていないと溶融帯３中
に泡を発生させ溶融帯３が不完全となり結晶化が
損われたり、結晶中に気泡が発生してしまう。こ
れを防ぐには原料がポイントとなる。特に主成分
である酸化アルミニウムの性質が非常に重要であ
る。 However, if the raw material rod 4 is not completely manufactured, the titanium oxide will not be distributed uniformly, and if the raw material rod is not sintered sufficiently, bubbles will be generated in the molten zone 3. The crystallization may become incomplete, resulting in impaired crystallization or the generation of air bubbles in the crystal. The key to preventing this is the raw material. In particular, the properties of aluminum oxide, the main component, are very important.
ベルヌイ法に用いられる粉末は必ずしも本方法
に有効とは限らない。通常焼結に用いられる酸化
アルミニウムは主としてバイヤー法により得られ
る水酸化アルミニウムを出発原料として焼成し、
脱アルカリ、粉砕などの処理を経て作られたアル
フア酸化アルミニウムが用いられる。しかし粉砕
処理は特殊工程となり不純物が入り易く本発明目
的に特に適しているとは言い難い。本発明者はア
ルミニウムカーボネートハイドロオキシサイドア
ンモニウム（NH4AlCO3（OH）2）を焼成して得た
酸化アルミニウムが本発明目的に合致した原料粉
末であることを見出した。アルミニウムカーボネ
ートハイドロオキサイドアンモニウムは、
NH4Alo（OH）HCO3とも記し、炭酸水素アンモ
ニウムとアンモニウム明バンを反応させると得ら
れる。 Powders used in the Bernoulli method are not necessarily effective for this method. Aluminum oxide, which is normally used for sintering, is mainly produced by firing aluminum hydroxide obtained by the Bayer method as a starting material.
Alpha aluminum oxide, which is made through processes such as dealkalization and pulverization, is used. However, the pulverization process is a special process and is easily contaminated with impurities, so it cannot be said that it is particularly suitable for the purpose of the present invention. The present inventor has discovered that aluminum oxide obtained by calcining ammonium aluminum carbonate hydroxide (NH 4 AlCO 3 (OH) 2 ) is a raw material powder that meets the purpose of the present invention. aluminum carbonate hydroxide ammonium
Also written as NH 4 Alo(OH)HCO 3 , it is obtained by reacting ammonium bicarbonate with ammonium alum.
8NH4HCO3＋（NH4）2Al2（SO4）4→2NH4AlCO3
（OH）2＋４（NH4）2SO4＋6CO2＋2H2Oこれを焼
成するとガンマ酸化アルミニウムを経てアルフア
酸化アルミニウムが得られる。この酸化アルミニ
ウム粒子が非常に微細であり、この微細粒子が凝
集し難く、２次粒子はすべり易い為に非常に焼結
し易い。この原料を用いることにより原料棒は低
温で高密度に焼結でき酸化クロム、酸化第二鉄、
酸化ニツケル、酸化チタン等を均一に固溶するこ
とができ、溶融帯中に気泡を生ずることもなく結
晶中に気泡を含有することもなく完全な結晶を得
ることができ、完全なスターの生じるスタールビ
ー及びスターサフアイアを得ることができる。第
２図ａは従来のスター、第２図ｂは本発明のスタ
ーの例を示す。以下に実施例について本発明を説
明する。 8NH 4 HCO 3 + (NH 4 ) 2 Al 2 (SO 4 ) 4 →2NH 4 AlCO 3
(OH) 2 +4(NH 4 ) 2 SO 4 +6CO 2 +2H 2 O When this is fired, alpha aluminum oxide is obtained via gamma aluminum oxide. These aluminum oxide particles are very fine, and these fine particles are difficult to aggregate, and the secondary particles are easy to slip, so they are very easy to sinter. By using this raw material, the raw material rod can be sintered with high density at low temperatures, including chromium oxide, ferric oxide,
Nickel oxide, titanium oxide, etc. can be uniformly dissolved in solid solution, and perfect crystals can be obtained without creating bubbles in the melting zone or in the crystal, resulting in perfect stars. Star Ruby and Star Sapphire can be obtained. FIG. 2a shows an example of a conventional star, and FIG. 2b shows an example of a star of the present invention. The invention will be explained below with reference to examples.
実施例
アルミニウムカーボネートハイドロオキサイド
アンモニウムを1280℃で１時間焼成して得た酸化
アルミニウムに酸化クロム及び酸化チタンを乳鉢
で混合した後ゴム製袋に充填し2000Kg/cm2の静水
圧で棒状に成型した。この棒状原料を、1600℃で
２時間焼結した。この原料棒を回転楕円面鏡内に
セツトし赤外線を集中して単結晶化した。得られ
た単結晶を1300℃で２時間熱処理して完全なスタ
ーの生じるスタールビーを得た。Example Chromium oxide and titanium oxide were mixed in a mortar with aluminum oxide obtained by baking ammonium aluminum carbonate hydroxide at 1280°C for 1 hour, then the mixture was filled into a rubber bag and molded into a rod shape under a hydrostatic pressure of 2000 Kg/cm 2 . This rod-shaped raw material was sintered at 1600°C for 2 hours. This raw material rod was set in a spheroidal mirror and infrared rays were concentrated to form a single crystal. The obtained single crystal was heat-treated at 1300°C for 2 hours to obtain a star ruby with a complete star.
第１図は本発明の基本原理を説明する図であ
る。第２図は本発明の効果を説明する図である。
１……回転楕円面鏡、２……ハロゲンランプ、
３……溶融帯、４……原料棒、５……結晶。
FIG. 1 is a diagram explaining the basic principle of the present invention. FIG. 2 is a diagram illustrating the effects of the present invention. 1...Spheroidal mirror, 2...Halogen lamp,
3...Melting zone, 4...Raw material rod, 5...Crystal.
Claims (1)
し又上下動しうる上回転軸と下回転軸、及び加熱
ランプを有する赤外線加熱炉を用いたスタールビ
ー及びスターサフアイアの製造方法において、酸
化クローム、酸化鉄、酸化ニツケルの１種もしく
は複数種の粉末と、アルミニウムカーボネイトハ
イドロオキサイドアンモニウムを焼成して得られ
た酸化アルミニウム粉末と、星彩線を形成する酸
化チタンの粉末とを混合し、前記混合粉末を棒状
に圧縮成形した後焼結して原料棒を形成し、前記
原料棒を前記上回転軸に固着し、前記下回転軸に
前記原料棒端部の溶融帯部を接着し、次いで前記
上下回転軸を下方向に移動させることにより前記
下回転軸上に単結晶を形成して成るスタールビー
及びスターサフアイアの製造方法。1. A method for producing star ruby and star sapphire using an infrared heating furnace having a spheroidal mirror body, upper and lower rotating shafts that rotate in opposite directions and can move up and down, and a heating lamp. , one or more powders of chromium oxide, iron oxide, and nickel oxide, aluminum oxide powder obtained by firing ammonium aluminum carbonate hydroxide, and titanium oxide powder that forms star lines are mixed. , the mixed powder is compression-molded into a rod shape and then sintered to form a raw material rod, the raw material rod is fixed to the upper rotating shaft, and the molten band at the end of the raw material rod is adhered to the lower rotating shaft. A method for producing star ruby and star sapphire, which comprises forming a single crystal on the lower rotation axis by then moving the vertical rotation axis downward.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12706778A JPS5556100A (en) | 1978-10-16 | 1978-10-16 | Production of star ruby or star sapphire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12706778A JPS5556100A (en) | 1978-10-16 | 1978-10-16 | Production of star ruby or star sapphire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5556100A JPS5556100A (en) | 1980-04-24 |
| JPS6128637B2 true JPS6128637B2 (en) | 1986-07-01 |
Family
ID=14950758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12706778A Granted JPS5556100A (en) | 1978-10-16 | 1978-10-16 | Production of star ruby or star sapphire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5556100A (en) |
-
1978
- 1978-10-16 JP JP12706778A patent/JPS5556100A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5556100A (en) | 1980-04-24 |
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