JPS59141493A - Preparation of star corundum - Google Patents

Preparation of star corundum

Info

Publication number
JPS59141493A
JPS59141493A JP58013335A JP1333583A JPS59141493A JP S59141493 A JPS59141493 A JP S59141493A JP 58013335 A JP58013335 A JP 58013335A JP 1333583 A JP1333583 A JP 1333583A JP S59141493 A JPS59141493 A JP S59141493A
Authority
JP
Japan
Prior art keywords
corundum
powder
star
titanium oxide
sintered
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
Application number
JP58013335A
Other languages
Japanese (ja)
Inventor
Hitoshi Miyasaka
均 宮坂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seiko Epson Corp
Suwa Seikosha KK
Original Assignee
Seiko Epson Corp
Suwa Seikosha KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Seiko Epson Corp, Suwa Seikosha KK filed Critical Seiko Epson Corp
Priority to JP58013335A priority Critical patent/JPS59141493A/en
Publication of JPS59141493A publication Critical patent/JPS59141493A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B13/00Single-crystal growth by zone-melting; Refining by zone-melting
    • C30B13/16Heating of the molten zone
    • C30B13/22Heating of the molten zone by irradiation or electric discharge
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B13/00Single-crystal growth by zone-melting; Refining by zone-melting
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/16Oxides
    • C30B29/20Aluminium oxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

PURPOSE:To prepare star corundum having transparent and clear star inexpensively, by using a raw material rod obtained by molding and sintering mixed powder of TiO2-Al2O3 solid solution powder and Cr2O3 powder, synthesizing a crystal from it, annealing the crystal. CONSTITUTION:TiO2-Al2O2 Solid solution powder is blended with Cr2O3 powder as a colorant to give mixed powder, which is packed into a rubber tube, molded into a cylindrical rod by rubber press, and sintered in an electric furnace at 1,200-1,600 deg.C. The sintered rod is used as a raw material, corundum or a sintered rod of corundum is utilized as a seed crystal, a crystal is grown preferably in a reducing atmosphere by condensing floating zone method, it is annealed, to give red star corundum. The use of TiO2 and Fe2O3 as a colorant provides blue star corundum. The solid solution contains preferably 0.1-0.5wt% TiO2, the annealing is carried out at 1,100-1,600 deg.C and needle-like crystal of TiO2 is preferably precipitated.

Description

【発明の詳細な説明】 コランダムの色は、添加する発色剤により異なる。例え
ば酸化クロムを添加すれば赤色となシ、酸化チタン及び
酸化第2鉄を添加すれば青色となる。これらコランダム
の原料に酸化チタンを添加して、従来のB’ Z法やベ
ルヌーイ法によシ結晶を合成するとスターコランダムの
原石が得られる。
DETAILED DESCRIPTION OF THE INVENTION The color of corundum varies depending on the coloring agent added. For example, if chromium oxide is added, the color will be red, and if titanium oxide and ferric oxide are added, the color will be blue. When titanium oxide is added to these corundum raw materials and crystals are synthesized by the conventional B'Z method or Bernoulli method, raw star corundum is obtained.

これをアニールすることによシ、C軸方向にカボツショ
ンに研暦するとC軸を中心として互いに60゜の角度で
放射状に線が表われ、これがスター状に見える。しかし
、従来の集光F、Z法やベルヌーイ法によシ合成された
スターコランダムは、透明性や、スターの明瞭さにおい
て、天然のものに比べかなり劣る。
By annealing this, when the cabochon is polished in the C-axis direction, lines appear radially at an angle of 60 degrees to each other around the C-axis, which looks like a star. However, star corundum synthesized by the conventional condensing F, Z method or the Bernoulli method is considerably inferior to natural corundum in terms of transparency and star clarity.

これは、酸化アルミニウム中に酸化チタンが均一に固溶
しないためである。このため、本発明はあらかじめ酸化
アルミニウムー酸化チタン固溶体を作製し、その粉末を
酸化クロム等の発色剤と混合し原料粉末にすることにし
た。また育成雰囲気を還元雰囲気とすることにした。こ
れKよシコランダム中に酸化チタンを均一に固溶するこ
とができた。以下合成方法を詳細に述べる。
This is because titanium oxide is not uniformly dissolved in aluminum oxide. Therefore, in the present invention, an aluminum oxide-titanium oxide solid solution is prepared in advance, and the powder is mixed with a coloring agent such as chromium oxide to obtain a raw material powder. In addition, it was decided that the growth atmosphere would be a reducing atmosphere. With this K, titanium oxide could be uniformly dissolved in cicorundum. The synthesis method will be described in detail below.

原料とする酸化アルミニウムー酸化チタン固溶体は、イ
リジウムルツボに所望の酸化アルミニウムと酸化チタン
を入れ窒素又はアルゴン算囲気で2100℃で加熱溶融
し、急冷固化させることによジ得られる。このとき、酸
化チタンの量が全量に対し−T: 0.IW% 〜0.
5W% トする1゜こhは、0.1W%より少ない場合
は、スターコランダムを合成シたとき、スターが明瞭に
出ない。0.5W%より多い場合、合成恐に偏析を起こ
すため不適である。上記で得られた酸化アルミニウムー
酸化チタン固溶体粉末に発色剤として酸イヒクロム殻を
添加する。これを十分混合し、ゴムチューブに詰め、ラ
バーブレス法により円柱状の棒に成形する。この棒を1
200℃〜1600℃で電気炉中で焼結する。このとき
1200℃以下では焼結が不十分であり、1600℃以
上では焼結度に差がない。これを原料とし、種子結晶に
コランダムの結晶又は、焼結体を用いて公知の集光F、
Z法により合成を行なう。このとき育成雰囲気はアルゴ
ン−水素の還元雰囲気とする。また水素濃度1rili
t ppM −11000ppとする。1000 pp
M以上では、着色剤が抜けて色が辿くなシネ適である。
The aluminum oxide-titanium oxide solid solution used as a raw material is obtained by placing desired aluminum oxide and titanium oxide in an iridium crucible, heating and melting the mixture at 2100° C. in a nitrogen or argon atmosphere, and rapidly cooling and solidifying. At this time, the amount of titanium oxide is -T: 0. IW% ~0.
If 5W% of 1° is less than 0.1W%, stars will not appear clearly when star corundum is synthesized. If it is more than 0.5 W%, it is unsuitable because it causes segregation during synthesis. Acid hichrome shells are added as a coloring agent to the aluminum oxide-titanium oxide solid solution powder obtained above. This is thoroughly mixed, packed into a rubber tube, and formed into a cylindrical rod using the rubber press method. This stick is 1
Sinter in an electric furnace at 200°C to 1600°C. At this time, sintering is insufficient below 1200°C, and there is no difference in the degree of sintering above 1600°C. Using this as a raw material and using a corundum crystal or sintered body as a seed crystal, a well-known light focusing F,
Synthesis is performed using the Z method. At this time, the growth atmosphere is an argon-hydrogen reducing atmosphere. Also, the hydrogen concentration is 1rili
tppM -11000pp. 1000pp
At M or higher, the colorant does not come out and the color does not trace, making it suitable for cinema.

](] ppM以下でに′i酸化チタンの固溶を促進し
ない。次に合成されたコランダムを1100℃〜160
0℃で電気炉中でアニールする。このとき1100℃よ
シ低い温度又は1600℃よ)高い温度では酸化チタン
(ルチル)の針状結晶の析出が起らないため不適である
](] The solid solution of titanium oxide is not promoted below ppM. Next, the synthesized corundum is heated at 1100°C to 160°C.
Anneal in an electric furnace at 0°C. At this time, temperatures as low as 1100°C or as high as 1600°C are unsuitable because needle-like crystals of titanium oxide (rutile) do not precipitate.

またアニールを行なった後熱ひすみ等によるクラックの
発生を防ぐため毎分5℃〜毎分H112で徐冷を行なう
必要がある。
Further, after annealing, it is necessary to perform slow cooling at a rate of 5° C./min to H112/min to prevent cracks from occurring due to thermal distortion or the like.

以上よシ、本発明は天然と遜色違わないスターコランダ
ムを安価に一般に提供することを可能とした。オた本発
明の効果をよりはっきりさせるため〈実施例〉を以下に
示す。
In summary, the present invention has made it possible to provide star corundum, which is comparable to natural star corundum, to the general public at a low cost. In order to make the effects of the present invention clearer, <Examples> are shown below.

〈実施例1〉 ・原料棒作製方法 酸化アルミニウム99’、9Fと酸化チタン0.12を
アルミナ乳げちに取ル、十分混合する。こilをイリジ
ウムルツボに入れ、窒素雰囲気中で高周波加熱によp溶
融し、急冷固化された。これを粉砕し粉末とした。この
粉末を201と酸化クロム0.62をアルミナ乳ばちで
十分混合する。これをゴムチューブに詰め、チューブ内
の空気抜きを行なう。
<Example 1> - Raw material rod production method Aluminum oxide 99', 9F and titanium oxide 0.12 are placed in an alumina chute and mixed thoroughly. The mixture was placed in an iridium crucible, melted by high-frequency heating in a nitrogen atmosphere, and rapidly solidified. This was crushed into powder. This powder is thoroughly mixed with 201 and 0.62 of chromium oxide using an alumina pestle. Pack this into a rubber tube and remove the air inside the tube.

次にラバープレス法により 3000 抜髄”の圧力で
ブレスL 12 ms [φlX100ma−の棒とし
た。これを1600℃で4時間電気炉中で焼結し原料棒
とした。
Next, by a rubber press method, a rod of 12 ms [φl×100 ma-] was obtained using a pressure of 3000 mm. This was sintered in an electric furnace at 1600° C. for 4 hours to obtain a raw material rod.

命育成方法 ニチデン機械製赤外線集中加熱車結晶製造装置を用いて
下記の条件で性力う。
Method for growing crystals Using an infrared concentrated heating wheel crystal manufacturing device manufactured by Nichiden Machinery Co., Ltd., the crystals were grown under the following conditions.

種 子 結 晶 ホワイトザファイア 成  長  方  向  (001) シャフトの回転数 上、下共に3Orpmで逆回転 雰   囲   気  Hg、ArH2濃度(iooo
ppM)成長速度2間/H 育 成 時 間 40時間 ・アニール条件 温   度   1600℃ 時   間   12時間 徐冷速度  毎分5℃ ・結果 白濁した赤色の結晶となった。これを0面を上にしてカ
ボッションにカットすると明瞭なスターが表われた。
Seed Crystal White Zaphire Growth Direction (001) Shaft rotation speed Upper and lower rotations are 3 orpm and reverse rotation atmosphere Hg, ArH2 concentration (iooo
ppM) Growth rate: 2 hours/H Growth time: 40 hours・Annealing condition temperature: 1600°C Time: 12 hours Slow cooling rate: 5°C/min・Results were cloudy red crystals. When this was cut into a cabochon with the zero side facing up, a clear star appeared.

〈実施例2〉 ・原料棒作製 酸化アルミニウム99゜52と酸化チタンo、52をア
ルミナ乳ばちに取シ十分混合する。以下〈実施例1〉と
同様の操作を行なう。
<Example 2> - Preparation of raw material rod Aluminum oxide 99°52 and titanium oxide O,52 are taken into an alumina milk and thoroughly mixed. Hereinafter, the same operations as in <Example 1> are performed.

・育成方法 育成雰囲気ガス中の水累濃度を10 p7yMとする。・Cultivation method The cumulative concentration of water in the growth atmosphere gas is set to 10 p7yM.

その他は〈実施例1〉に従う。The rest follows <Example 1>.

・アニール条件 温   度   1100℃ 時   間   30時間 徐冷速度  毎分HJ ℃ ・結果 白濁した赤色の結晶となった。これを0面を上にし7て
カボツションにカットすると明瞭なスターが表われた。
・Annealing condition temperature: 1100°C Time: 30 hours Annealing rate: HJ°C per minute ・Result: cloudy red crystals were obtained. When this was cut into a cabochon with the 0 side facing up, a clear star appeared.

〈実施例3〉 ・原料棒作製 酸化アルミニウム99゜51と酸化チタン0.57をア
ルミナ乳ばちに取シ十分混合する。これをイリジウムル
ツボに入れ、アルゴン雰囲気中で高周波加熱により溶融
し、急冷固化させた。これを粉砕し粉末とした。この粉
末2Orと酸化チタン27と酸化第2鉄62をアルミナ
の乳ばちに取り、十分混合する。以下の操作は〈実施例
1〉に従う。
<Example 3> - Preparation of raw material rod Aluminum oxide 99.51 and titanium oxide 0.57 are taken into an alumina milk and thoroughly mixed. This was placed in an iridium crucible, melted by high frequency heating in an argon atmosphere, and rapidly solidified. This was crushed into powder. This powder 2Or, titanium oxide 27, and ferric oxide 62 are placed in an alumina mortar and mixed thoroughly. The following operations follow <Example 1>.

・育成方法 〈実施例1〉に従う。・Cultivation method According to <Example 1>.

・アニール条件 〈実施例1〉に従う。・Annealing conditions According to <Example 1>.

・結果 白濁した青色の結晶が合成された。これを0面を上にし
てカボッ7ヨンにカットすると明瞭なスターが表われた
・As a result, cloudy blue crystals were synthesized. When this was cut with the zero side facing up, a clear star appeared.

以   上 出願人 株式会社識訪精工舎that's all Applicant: Shikiwa Seikosha Co., Ltd.

Claims (1)

【特許請求の範囲】 【11酸化チタン−酸化アルミニウム固溶体粉末に発色
剤として酸化クロム粉末または、酸化チタン、激化第2
鉄粉末を加える。この粉末を混合し、仁れをゴムチュー
ブに詰め、ラバープレス法によシ円柱状の棒に成形する
。仁の棒を1200℃〜1600℃で電気炉中で焼結す
る。 この焼結棒を原料とし、種子結晶としてコランダムまた
はコランダムの焼結棒を用いて、公知の集光フローブイ
フグゾーン法(以下集光F、Z法)により合成しアニー
ルすることを特徴とするスターコランダムの製造方法。 (2)  特許請求の範囲第1項において、酸化チタン
−酸化アルミニウム固溶体中の酸化チタンが全量に対し
て0.1 W%〜0.5W%とするととよすする同項記
載のスタ〜コヲンダムの製造方法。 (3)特許請求の範囲第1項において、育成雰囲気を還
元雰囲気とすることを特徴とする同項記載のスターコラ
ンダムの製造方法。 (4)特許請求の範囲第1項において、育成した結晶中
に酸化チタン(ルチル)の針状結晶を析出させるため1
100℃〜1600℃でアニールを行なうことを特徴と
する同項記載のスターコランダムの製造方法。
[Claims] [11 Titanium oxide-aluminum oxide solid solution powder, chromium oxide powder or titanium oxide as a coloring agent,
Add iron powder. This powder is mixed, the core is packed into a rubber tube, and it is formed into a cylindrical rod by a rubber press method. The kernel bar is sintered in an electric furnace at 1200°C to 1600°C. Using this sintered rod as a raw material, using corundum or a sintered corundum rod as a seed crystal, it is characterized by being synthesized and annealed by the known condensing flow buifugu zone method (hereinafter referred to as condensing F, Z method). How to make star corundum. (2) The star powder according to claim 1, wherein the titanium oxide in the titanium oxide-aluminum oxide solid solution is 0.1 W% to 0.5 W% with respect to the total amount. manufacturing method. (3) A method for producing star corundum according to claim 1, characterized in that the growth atmosphere is a reducing atmosphere. (4) In claim 1, for precipitating needle-like crystals of titanium oxide (rutile) in the grown crystals, 1
The method for producing star corundum according to the above item, characterized in that annealing is performed at 100°C to 1600°C.
JP58013335A 1983-01-28 1983-01-28 Preparation of star corundum Pending JPS59141493A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58013335A JPS59141493A (en) 1983-01-28 1983-01-28 Preparation of star corundum

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58013335A JPS59141493A (en) 1983-01-28 1983-01-28 Preparation of star corundum

Publications (1)

Publication Number Publication Date
JPS59141493A true JPS59141493A (en) 1984-08-14

Family

ID=11830253

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58013335A Pending JPS59141493A (en) 1983-01-28 1983-01-28 Preparation of star corundum

Country Status (1)

Country Link
JP (1) JPS59141493A (en)

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