JPS61251597A - Production of ruby single crystal - Google Patents

Abstract

PURPOSE:To produce a bubble-free high-quality ruby single crystal having high transparent feeling and deep scarlet -pinky red color tone, by using a raw material rod having a specific composition in floating zone method. CONSTITUTION:WO3 and/or MoO3 are added in an amount of 0.01-0.07wt% to a basic composition composed of 2-5wt% Cr2O3, 0-0.1wt% Fe2O3 and the remaining part of Al2O3, and a raw material rod made of the above mixture is used in the production of a ruby single crystal by floating zone method. A bubble-free high-quality ruby single crystal having high transparent feeling and deep scarlet - pinky red color tone can be produced by the above process. The process has considerable effect for the improvement of the quality of ruby crystal for jewery or decoration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a ruby single crystal by a floating zone method (hereinafter abbreviated as FZ method).

[Summary of the invention]

The present invention is a ruby single crystal production method using the FZ method, in which a set of raw material rods a is i! By doing so, the quality of the ruby single crystal is improved as above.

[Conventional technology]

Traditionally, the synthesis of ruby single crystals using the Pz method was developed in the 1970s.
It is manufactured using an FZ apparatus as shown in Japanese Patent Application No. 59-95145, using an FZ apparatus as shown in Japanese Patent Application No. 59-95145.

That is, the raw material powder '11 with the desired composition is combined, pressure-molded and sintered to form a raw material rod, and the light emitted from a high-temperature light source such as a halogen lamp is focused using a reflecting mirror, and the light is applied to the condensing part. The seed crystal and the raw material rod are combined with the entire molten zone to form a floating zone, and the raw material rod, the molten zone, and the seed crystal are moved to the lower blade at a constant speed for complete crystal synthesis.

[Problems and objectives to be solved by the invention] The FZ method is a type of melting method and does not use a crucible, so there is no contamination by impurities, which is a complete advantage. When chromium oxide and iron oxide are added to the crystal, the drawback that air bubbles are generated in the crystal depending on the growth rate is completely eliminated. The present invention solves all of these problems, and its purpose is to provide a ruby single crystal with excellent color tone, high transparency, and no bubbles.

[Means for solving problems]

The present invention focuses light emitted from a high-temperature light source such as a halogen lamp by using a reflecting mirror or a lens all around it, and in the condensing part, a raw material rod and a seed crystal are combined with a molten zone as an intermediary. Forming a floating zone, the raw material rod, the melting zone,
In the floating zone method, in which crystals are deposited on the seed crystal by moving the seed crystal at a constant speed, chromium oxide gold 2 to 5% by weight and iron oxide 0 to 0.1% by weight (Q
), the balance is based on the basic composition of aluminum oxide.
o, and M. All O3 alone or in combination, 0.01-0
．． Chromium oxide is the main coloring agent for ruby, but chromium oxide is the main coloring agent for ruby,
If it is less than 5%, it will not be able to give a sufficient red color, and if it is added in excess of 5%, the sinterability of the raw material rod will be lowered and bubbles will be more likely to be generated in the crystal, so the weight will be 2 to 5 times higher. Iron oxide is an auxiliary coloring agent for ruby, and if it is added in excess of 0.1%, the color will be orange to blackish red.
．． The content shall be 1% by weight or less. Furthermore, WO,,M,O, is 0.0
If it is less than 1%, no effect will be seen, and if it is added in excess of o-a7.91, the color tone will be purple-red to dark red.
01 to 0.07% by weight.

〔Example〕

Hereinafter, the present invention will be described in detail based on Examples.

FIG. 1 is a front view of the FZ device used in the present invention.

1 is a spheroidal mirror, 2 is a halogen lamp, 6 is a quartz tube,
4 is a gas inlet, 5 is a gas outlet, 6 is a raw material rod, 7 is a seed crystal, 8 is a bath melting zone, 9 is an upper shaft, 10 is a lower shaft, 11 is a lens (including prism), 12 is a screen be.

A raw material rod 6 is set on the upper shaft 9, and a seed crystal 7fc is set on the lower shaft 10. Slightly halogen rung 2
The power of the halogen lamp is increased and the spheroidal mirror τ focuses the light from the halogen lamp onto the center of the quartz tube 3. At this time, all of the atmospheric gas is introduced through the gas inlet 4, and the atmospheric gas is discharged through the gas exhaust port 5.

In the light condensing section, the tip of the raw material rod 6 and the tip of the seed crystal 7 are brought into molten contact to form a molten gold band 8.

At this time, the upper shaft 9 and the lower shaft 10 are rotated in the same direction or in opposite directions, and the upper and lower shafts are simultaneously moved downward to grow crystals. The growth status of the crystal is constantly monitored on the screen 12 via the lens 11.
Feedback to lamp power.

10,000 raw material rods are manufactured using the following process.

Weigh all the raw material powder to the specified composition, add Daiflon,
Perform thorough wet mixing. After drying and removing Daiflon,
Pack the raw material powder into a rubber tube, remove the air inside the tube with a vacuum pump, and use a laharless to produce 1 to 3 tons/-.
A rod-shaped raw material of approximately 10 mm x 100 mt was formed by pressure molding at a pressure of
Sinter at a temperature of

All specific examples regarding raw material composition are shown below [Example-1] An example regarding the basic composition, where only chromium oxide is used as a coloring agent (at composition ■ 98.2% At, O, -t 8% Or, 03■ 9
8.0%ht, o Hatake-2.0%Or, 03%. 5%
At, o, -t 5%C! r, 03■ 95.0%
AtI OH-S, OXCr, O20948%A4
,0B-5,2XOr! 01 ('l: +l W formation conditions Seed crystal Ruby growth rate tO proverb/H Rotation direction Vertical rotation Speed Up and down 20 rpm Atmosphere Air flow rate 40 L/am Synthesis time 80 hours (C1 results are pinkish red in both cases) A crystal of approximately 10■φ can be seen.

[Example-2] Similar to Example-1, this is an example regarding the basic composition, in which chromium oxide and iron oxide are used as coloring agents (al composition ■ 9 &, 08% At, 03-18% Or, 01-0
．． 12%Fe, OB ■ 9Z97%ht! OB-10%Or, 0B-0.
03%Fe, OB ■ 9&45%az, os-t 5%Or, 0B-
O,OS%Fe,01 ■ 94.91%az,os -a O%Or,03
-0.09%Pa, OB @9468%Mu'ton-5-2%Or, 01-
0.12% Fe, 0.1 min) Growth conditions were the same as in Example-1 (cl) Results: Approximately 9.5 yen φX 80 mL of crystals were obtained, but had a solid color tone.

■ is extremely orange red, ■ ~ ■ is bright red to red, 0
was dark red.

In the above examples, when the growth rate was varied with the compositions of ■ to ■ and ■ to Bubbles were observed, LO■/Htl
- Bubbles could be observed with the naked eye when crossing the line.

[Example-3] When adding WOs%M60x'e to the basic composition (
al Composition @97.99%Az, os -2,0%0r20B-〇, 01%WO.

097. %%At, Og -10%Or20g-0,
04%M003 ◎ 9Z93%A 40m-2, OXOr 203-0
．． 07%WO5 09&47%At, 03-2L5%Or, OB-O,O
3%Won 9%. 44%At, On &5%Or, 01-0.
06%M, 0゜0 94%%A40m -5,0%Or, OB-0,0
4% WO.

◎ 94.93% At, O, -5.0% Or, OB-0
,07%M003 @97.97%ht,o, -2.0%0rlO@-0,
02%E'e, O@ -0,01%won097.91
%az, ox -2t O%Or, 03-0.08 X
Fe, 03-0.01%M, Oj@%. 45% Mu'ton &5%Or, OB-0,03%Fe, 0
1-0.02% WO.

@%. 37%A t, Os -L 5%Or, 0
3-0.1%? θ,O,−0,′05%MoO.

@9490%az, ol-a O%Or! 01-
O,OS%We,O,-0,05%Won0 94.
83Xxz, 03-5.0%Cr203-0.1%Fa
, 03-0.07% MoO.

897.98%A40m-2.0%Or, 01-0.0
]%WO5-0,01%MoO.

@9 & 45%Az, os -&' 5%Or, OB
-O,OS%WO,-0,02%M,Os0 949
5%”gos-5b 0%0rlO1-0,04%M
o5s-0,0S%WO.

@97. %%ALxOa 2.0%QrlOB-0
,02%Fe,01-0.01%wol-0,01%M
001 @ 9442% A't, O, - & 5%0rlOH
-0,05%Fe, 0B-0,05%woB-0,02
%MoO.

9 94.88%”tos &O%Or, OB-
O,OS%Fθ,0. -0. Mouth 4% WO,--0,03
%M,Ox@94.83%At,O,-&0XOr20g
-〇, 1%Fe, 01-0.04%MoO3--O,O
S%WO.

(t)l Growth conditions Same as Example-1 (cl) Crystals of approximately 10+++g+φX80sIA were obtained, and a good color tone of bright red to pinkish red that could not be obtained with chromium oxide and iron oxide alone was obtained. When the growth rate was changed depending on the composition of ◎~[strain], almost no bubbles were observed at tO~λOvm/H, and 1 at 2.0~50 baskets/H.
Bubbles were observed under a 0x magnifying glass.

[Comparative Example-1] When the amount of wo, , Moo, added is more than the range of the present invention (Koshi) Composition @97.9? %At,O,-2,0%Or,ox-0
,08%Won @9&42%At1os-&5%Or@OH-0,
08%M, Os! 9492%A40m-&OX0rlO1-〇, 08%No.

897.92%az, os-z 0XOr, OB-0
,04%Won G, 04 XMnOs@9&
42%Mut, o, -s, 5%Or, OB-0,06%w
os-o, 02%M00s@94.92
XA4. Ox-&O%Or, 01-0.06%M,O,
-Q, 02%WaS@197.90%At,O,-1
0%0r20B-〇, 02%IPe, OB -0,
08%Won@%. 37%At, os 15%0
rlO1-O, OS%Fe, 01-108%M001@
94.84% At! os 5-0%Or20g-
〇, 08%Pa, 01-0.08%No.

997.89%ht,o,-λ0%Or,O@-0,(
15%Fe, 01-os 05%was --0,03
%M, Ox 0%. 56%ht, OB-L 5XOr, Ox-
0,06% Fe, OB -0,04% M, O.

-〇, 0 4% WO low @ 94.82%ht, o, -a o%Or, OB
-〇, 1%Fe, 01-0.06%MoO,--0,0
2%No.

tb+ Growth conditions Same as Example-1 (cl) Crystals of approximately 10 mm x 80 mt were obtained, but fine bubbles were generated in both cases.

In particular, continuous spherical or pipe-shaped bubbles were observed in the crystals of [phase], [phase], [phase], and O.

〔Effect of the invention〕

As described above, according to the present invention, in the Fz method, chromium oxide is contained in an amount of 2 to 5% by weight, and iron oxide is contained in an amount of 0 to 0.1% by weight (
(Ol-), the balance is based on the basic composition of aluminum oxide, WO2 and M. By using a raw material rod containing 0.01 to 0.07% by weight of 01, the color is a deep bright red.
A ruby single crystal with a pinkish-red color tone and no bubbles and high transparency can be obtained, and it has a great effect on improving the quality of ruby crystals for gemstones and jewelry.

[Brief explanation of the drawing]

W, Figure 1 is a front view of the FZ@ placement used in the present invention. that's all

Claims (1)

[Claims] A mirror that reflects light emitted from a high-temperature light source such as a halogen lamp,
Alternatively, the light is focused using a lens, and in the light focusing section, the raw material rod and the seed crystal are combined with the melting zone as an intermediary to form a floating zone, and the raw material rod, the melting zone, and the seed crystal are moved at a constant speed. In the floating zone method, in which crystals are deposited on a seed crystal by moving the chromium oxide
~5% by weight, 0 to 0.1% by weight (including 0) of iron oxide,
A method for producing a ruby single crystal, characterized by using a raw material rod to which 0.01 to 0.07% by weight of WO_2 and M_0O_3 are added alone or in combination to the basic composition of aluminum oxide.