CN100567593C - Artificial corundum crystal - Google Patents
Artificial corundum crystal Download PDFInfo
- Publication number
- CN100567593C CN100567593C CNB200480035730XA CN200480035730A CN100567593C CN 100567593 C CN100567593 C CN 100567593C CN B200480035730X A CNB200480035730X A CN B200480035730XA CN 200480035730 A CN200480035730 A CN 200480035730A CN 100567593 C CN100567593 C CN 100567593C
- Authority
- CN
- China
- Prior art keywords
- artificial corundum
- crystal
- corundum crystal
- compound
- artificial
- 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 - Fee Related
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- 239000013078 crystal Substances 0.000 title claims abstract description 473
- 239000010431 corundum Substances 0.000 title claims abstract description 335
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 335
- 238000000034 method Methods 0.000 claims abstract description 106
- 239000002994 raw material Substances 0.000 claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 claims abstract description 64
- 238000001704 evaporation Methods 0.000 claims abstract description 63
- 230000008020 evaporation Effects 0.000 claims abstract description 62
- 230000004907 flux Effects 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 130
- 229910052742 iron Inorganic materials 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 64
- 239000011651 chromium Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 51
- 229910052804 chromium Inorganic materials 0.000 claims description 50
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 44
- 229910052720 vanadium Inorganic materials 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 30
- 239000006103 coloring component Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 150000001339 alkali metal compounds Chemical group 0.000 claims description 19
- 239000005078 molybdenum compound Substances 0.000 claims description 17
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 16
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 14
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims 2
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- 239000002244 precipitate Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
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- 239000000203 mixture Substances 0.000 description 49
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 34
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- 239000004570 mortar (masonry) Substances 0.000 description 17
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- 239000002904 solvent Substances 0.000 description 7
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 3
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- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- GHCSGWDRXJEIRB-UHFFFAOYSA-N [Bi]=O.[La] Chemical compound [Bi]=O.[La] GHCSGWDRXJEIRB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 2
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- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 2
- QXOLLBTXUCQAEQ-UHFFFAOYSA-N cobalt;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Co].OC(=O)CC(O)(C(O)=O)CC(O)=O QXOLLBTXUCQAEQ-UHFFFAOYSA-N 0.000 description 2
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- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本发明目的在于提供一种能以低成本实用化的人造刚玉晶体及其制造方法。本发明提供一种人造刚玉晶体，其特征在于其具有从{113}面、{012}面、{104}面、{110}面、{101}面、{116}面、{211}面、{122}面、{214}面、{100}面、{125}面、{223}面、{131}面和{312}面中选出的至少一个晶面。而且还提供一种人造刚玉晶体的制造方法，其特征在于采用将含有原料和助熔剂的样品加热，以助熔剂的蒸发作为驱动力，使晶体析出和生长的助熔剂蒸发法，制造所述的人造刚玉晶体。
An object of the present invention is to provide an artificial corundum crystal that can be put into practical use at low cost and a method for producing the same. The present invention provides an artificial corundum crystal, which is characterized in that it has {113} plane, {012} plane, {104} plane, {110} plane, {101} plane, {116} plane, {211} plane, At least one crystal plane selected from {122} plane, {214} plane, {100} plane, {125} plane, {223} plane, {131} plane and {312} plane. Moreover, it also provides a method for manufacturing artificial corundum crystals, which is characterized in that the flux evaporation method is used to heat a sample containing raw materials and flux, and use the evaporation of flux as a driving force to precipitate and grow crystals. Synthetic corundum crystals.
Description
Technical field
The present invention relates to and to vibrate the artificial corundum crystal (corundum crystal) that uses in material, high rigidity bearing materials, the daily necessities of physical property measurement at for example laser with reference material, gem ornament and high added value.
Background technology
In recent years, naturally occurring the sort of monocrystalline with the exclusive three-dimensional shape of crystal is because of its unknown characteristic all has demand in each field.
Manufacture method as artificial corundum crystal, can enumerate (1) falls the raw material powder of corundum crystal on one side in oxyhydrogen flame, make the Verneuil method (bernoulli method) of crystal grain growth on one side, (2) raw material powder of corundum crystal is blended in uses the crucible fusion in the suitable fusing assistant (flux), separate out and grow while solution slowly being cooled off make crystal, perhaps in crucible, make crystal separate out and grow while making solution produce thermograde, perhaps while the flux method that makes the fusing assistant evaporation make crystal separate out and grow, (3) with the raw material powder fusion of crucible with corundum crystal, from the liquation pulling Czochralsk method that makes progress, (4) raw material powder of corundum crystal is shaped after, long-time heating agglomerating method etc. under the high temperature in hydrogen atmosphere.
In the Verneuil method of above-mentioned (1), because of the crystalline fast growth is difficult to obtain high-quality crystal.And in this method owing to make rhabdolith, so when in fact in the laser generation material, using, the rhabdolith of manufacturing must be cut into required shape, and because the hardness height of artificial corundum crystal has the high problem of cost.Moreover, the artificial corundum crystal of Zhi Zaoing is free from foreign meter in this way, and the Naxas emery crystal contains table impurity, thus identification easily, thereby also have as the low-down problem of the value of gem ornament.
And, the Czochralsk method of above-mentioned (3), owing to can make the high crystal of purity, so be applicable to laser generation material etc., but because this method manufacturing is rhabdolith, so when practicability as described above, rhabdolith must be cut into required shape, again because of the hardness height of artificial corundum crystal, so there is the high problem of cost.And the artificial corundum crystal made from this method is because of purity height, free from foreign meter, with natural corundum crystal very big difference arranged, so shortcoming is extremely low as the value of gem ornament.About the Czochralsk rule as being disclosed in patent documentation 1 and the patent documentation 2.
In addition, in the agglomerating method, at high temperature long-time heating needs huge energy, so there is the high problem of cost after the shaping of above-mentioned (4).Sintering method for example is disclosed in the patent documentation 3.
On the other hand, in the flux method of above-mentioned (2), use Lithium Oxide 98min-oxidation (fluoridizing) lead, sodium aluminum fluoride, Lithium Oxide 98min-Tungsten oxide 99.999-oxidation (fluoridizing) lead, bismuth oxide-lanthanum trioxide-oxidation (fluoridizing) lead etc. as fusing assistant, make crystal separate out growth while solution is slowly cooled off, can obtain platelike crystal.Yet, can only obtain lamellar crystal, thereby the high problem of cost when having practicability.Flux method for example is disclosed in non-patent literature 1 or the non-patent literature 2.
Patent documentation 1: the spy opens flat 7-277893 communique
Patent documentation 2: the spy opens flat 6-199597 communique
Patent documentation 3: the spy opens flat 7-187760 communique
Non-patent literature 1:Elwell D., Man-made gemstones, Ellis HorwoodLtd.Chichester (1979)
Non-patent literature 2:Elwell D., Scheel H.J., Crystal growth fromhigh-temperature solutions, Academic Press, London (1975)
Summary of the invention
The present invention proposes at the problems referred to above just, its purpose be to provide a kind of can be with the artificial corundum crystal and the manufacture method thereof of low-cost practicability.
For reaching above-mentioned purpose, the invention provides a kind of artificial corundum crystal, it is characterized in that it has from { 113} face, { 012} face, { 104} face, { 110} face, { 101} face, { 116} face, { 211} face, { 122} face, { 214} face, { 100} face, { 125} face, { 223} face, { 131} face and { at least one crystal face of selecting the 312} face.
According to the present invention, because artificial corundum crystal has above-mentioned crystal face, so need not to implement processing such as cutting grade when in laser generation material etc., using, even the crystal face of implementing also can utilize artificial corundum crystal of the present invention to have under the situation of processing such as cutting is processed, can be in the advantage of practicability under the low cost so have.And artificial corundum crystal of the present invention is polygonal crystal, and is approaching with the Naxas emery crystal, so also have the costly advantage as gem ornament etc.
The invention provides a kind of artificial corundum crystal, it is characterized in that it has { the advantage crystal face (dominant crystal face) beyond the 001} face.
According to the present invention, because artificial corundum crystal has { the advantage crystal face beyond the 001} face, so be not come from existing so that { the 001} face is as the crystal of the platelike crystal of advantage crystal face, need not to implement processing such as cutting grade when in laser generation material etc., using, even also can utilize the shape of artificial corundum crystal of the present invention to process under the situation of processing such as enforcement cutting, can be so have in the advantage of practicability under the low cost.And, because artificial corundum crystal of the present invention and Naxas emery crystal are approaching, so also have costly advantage as gem ornament etc.
In addition, artificial corundum crystal of the present invention preferably comes from double hexagonal pyramid shape crystal.So, can make artificial corundum crystal with regulation crystal face, thus can utilize the shape of double hexagonal pyramid shape to process when in laser generation material etc., using, have can be under low cost the advantage of practicability.And owing to be to come from double hexagonal pyramid shape crystal, so be polygonal crystal, approaching with the Naxas emery crystal, so also have costly advantage as gem ornament etc.
Among the present invention, above-mentioned artificial corundum crystal also can be colourless in addition.Perhaps, both can in above-mentioned artificial corundum crystal, add chromium, also can add iron and titanium, can also add nickel, vanadium or cobalt as coloring components.
And the present invention also provides a kind of manufacture method of artificial corundum crystal, it is characterized in that adopting the sample heating that will contain raw material and fusing assistant, with the evaporation of fusing assistant as motivating force, the fusing assistant method of evaporation that makes crystal separate out and grow, make with double hexagonal pyramid shape as basic configuration artificial corundum crystal.
According to the present invention, is the corundum crystal of basic configuration by adopting the fusing assistant method of evaporation owing to making with double hexagonal pyramid shape, need not to implement machining when in laser generation material etc., using, even implement under the situation of machining, owing to can utilize the shape of double hexagonal pyramid to process, can make can be in the advantage of the artificial corundum crystal of practicability under the low cost so have.And in the fusing assistant method of evaporation owing to can obtain the crystal approaching, so also have costly advantage as gem ornament etc. with the Naxas emery crystal.In addition, High Temperature Furnaces Heating Apparatus that uses in the fusing assistant method of evaporation and crucible etc. are simple, thereby can make the artificial corundum crystal of double hexagonal pyramid shape easily.
Among the present invention, above-mentioned fusing assistant preferably contains molybdenum compound in addition.And above-mentioned molybdenum compound aluminum oxide or add the compound that heat energy forms molybdenum oxide preferably.By using this molybdenum compound, can the selectivity manufacturing not belong to platelike crystal or needle-like crystal, and belong to the crystal of double hexagonal pyramid shape as fusing assistant.
And in foregoing invention, above-mentioned fusing assistant also can contain evaporation suppressor.So, owing to can suppress the velocity of evaporation of fusing assistant, can suppress multinuclear and produce and crystalline growth velocity, so can make high-quality artificial corundum crystal.
In this external foregoing invention, above-mentioned evaporation suppressor preferred as alkali compound.And above-mentioned alkali metal compound preferred as alkali oxide compound, perhaps add the compound that heat energy forms alkalimetal oxide.Wherein more preferably can generate Li by heating
2O, Na
2O and K
2The alkali metal compound of at least a alkalimetal oxide of selecting among the O.By using this material, can suppress the evaporation of fusing assistant effectively, can make high-quality large artificial corundum crystal.
And in foregoing invention, the mole number of alkali metal atom in the above-mentioned alkali metal compound, preferably the whole mole numbers with respect to above-mentioned sample are in 40 moles below the %.Among the present invention,, surpass under the situation of above-mentioned scope so work as the content of alkali metal compound owing to promote karyomorphism to become and crystal growth as motivating force with the evaporation of fusing assistant, might retard crystal growth.
Among the present invention, the mole number of above-mentioned raw materials preferably is in 10 moles below the % with respect to whole mole numbers of above-mentioned sample in addition.The content of raw material surpasses under the situation of above-mentioned scope, and raw material is difficult to dissolving in above-mentioned fusing assistant, might retard crystal growth.
The present invention also provides a kind of raw material that artificial corundum crystal is used of making, and it is characterized in that being used to make artificial corundum crystal, and wherein contains molybdenum compound and aluminum compound.
Use artificial corundum crystal production of raw material for use of the present invention to make under the situation of artificial corundum crystal, owing to can the selectivity manufacturing not belonging to the artificial corundum crystal that tabular or needle-like belongs to double hexagonal pyramid shape, so as mentioned above can be, and can access costly crystal as gem ornament in practicability under the low cost.
And in the present invention, above-mentioned artificial corundum crystal production of raw material for use also can contain alkali metal compound.Alkali metal compound is owing to can suppress the evaporation of above-mentioned molybdenum compound etc., so make under the situation of artificial corundum crystal when adopting artificial corundum crystal production of raw material for use of the present invention, the speed of multinuclear generation and crystal growth can be suppressed, high-quality artificial corundum crystal can be obtained.
In addition among the present invention, the preferred molybdenum oxide of above-mentioned molybdenum compound or can generate the compound of molybdenum oxide by heating.
And among the present invention, the preferred aluminum oxide of above-mentioned aluminum compound is perhaps by heating the compound that can generate aluminum oxide.
And among the present invention, above-mentioned alkali metal compound preferred as alkali oxide compound is perhaps by heating the compound that can generate alkalimetal oxide.These materials so adopt artificial corundum crystal production of raw material for use of the present invention to make under the situation of artificial corundum crystal, can access high-quality and large-scale artificial corundum crystal owing to can suppress the evaporation of fusing assistant effectively.
In addition among the present invention, above-mentioned artificial corundum crystal production of raw material for use, both can contain the chromium cpd that generates chromium ion by heating, also can contain the iron cpd that generates iron ion by heating, and by heating generate titanium ion titanium compound, by heating generate nickel ion nickel compound, generate the vanadium compound of vanadium ion, generate the cobalt compound of cobalt ion by heating by heating.
According to the present invention be the artificial corundum crystal of basic configuration owing to adopt the fusing assistant method of evaporation can make with double hexagonal pyramid shape, so in laser generation material etc. handling ease during use, can under low cost, realize practicability.And owing to can access the crystal approaching with the Naxas emery crystal, so also have as the costly advantage of gem ornament.
Description of drawings
Fig. 1 is the aspect graph of an example of expression artificial corundum crystal of the present invention.
Fig. 2 is the graphic representation of the X-ray diffraction pattern example of expression artificial corundum crystal of the present invention.
Fig. 3 is the graphic representation of another example of X-ray diffraction pattern of expression artificial corundum crystal of the present invention.
Fig. 4 is the optical microscope photograph of an example of expression artificial corundum crystal of the present invention.
Fig. 5 is the process picture sheet of expression artificial corundum crystal manufacture method example of the present invention.
The explanation of symbol
1 ... sample
1 ' ... remaining sample
2 ... artificial corundum crystal
11 ... mortar
12 ... crucible
13 ... High Temperature Furnaces Heating Apparatus
Embodiment
The present invention relates to artificial corundum crystal, its manufacture method and artificial corundum crystal production of raw material for use.Respectively it is described in detail as follows.
A. artificial corundum crystal
Artificial corundum crystal of the present invention at first is described.
Artificial corundum crystal of the present invention can be divided into two kinds of forms.As first kind of form, be to have from { 113} face, { 012} face, { 104} face, { 110} face, { 101} face, { 116} face, { 211} face, { 122} face, { 214} face, { 100} face, { 125} face, { 223} face, { 131} face and the { form of at least one crystal face of selecting the 312} face.And, be to have { the form of the advantage crystal face beyond the 001} face as second kind of form.
Respectively various forms are described as follows.
1. first kind of form
First kind of shape of artificial corundum crystal of the present invention is characterized in that wherein having from { 113} face, { 012} face, { 104} face, { 110} face, { 101} face, { 116} face, { 211} face, { 122} face, { 214} face, { 100} face, { 125} face, { 223} face, { 131} face and { at least one crystal face of selecting the 312} face.
Here will describe with regard to corundum crystal.Corundum crystal has the corundum structure that belongs to trigonal system.In this corundum structure, positively charged ion (Al) occupy regularly substantially with six sides the lattice of intensive filling hexa-coordinate (octahedron) position 2/3, with the AlO of positively charged ion (Al) as the center
6The total face of octahedra part forms the structure that connects along the Z axle.And corundum (Al
2O
3) in a part of Al generally replaced by Cr, form to add the chromium corundum crystal.
Corundum (Al
2O
3) in the aluminum oxide variform, be the most stable, have the corundum crystal of this corundum structure, about 2050 ℃ of fusing point has high rigidity (Mohs' hardness 9), and resistance to chemical reagents, wearability and weather resisteant are good.And under hot environment, also can show high electrical insulating property.Owing to have above-mentioned character, so corundum crystal is used as in the bearing, min-cutter, switching element, laser oscillation element material of instrument etc.And corundum (Al
2O
3) in a part of Al, by by displacements such as Cr or Ti and Fe, will become the different crystal of tone, these crystal are commonly referred to as ruby or sapphire, can be used as gem ornament.
And as the manufacture method of artificial corundum crystal, the past is known Czochralsk method, Verneuil method, flux method, sintering process etc.The artificial corundum crystal of Czochralsk method or Verneuil method manufacturing can be used as rhabdolith and obtains, thereby does not have complicated crystal shape.And the artificial corundum crystal of sintering process manufacturing is owing to be sintered after being shaped, so have complicated crystal shape in this case.On the other hand.Fusing assistant slow cooling method can obtain platelike crystal, so though the artificial corundum crystal that obtains has crystal face, the advantage face is { 001} a face.
Therefore since the past with the bar-shaped or tabular artificial corundum crystal that obtains, so processing such as must cut when in laser generation material etc., using to make required shape, but as mentioned above because artificial corundum crystal has high rigidity, so just produced the high rough sledding of cost.And the artificial corundum crystal that Czochralsk method and Verneuil method are made is free from foreign meter, and the Naxas emery crystal is impure, thereby distinguishes easily, be as gem ornament be worth product.
Artificial corundum crystal in the present embodiment is the crystal with regulation crystal face, and this crystal face is to come from double hexagonal pyramid shape crystal.So-called double hexagonal pyramid shape crystal for example is meant the artificial corundum crystal with shape shown in Fig. 1 (a).In the present embodiment, artificial corundum crystal is owing to come from double hexagonal pyramid shape crystal, so when laser generation material and the use of gem ornament material, need not to implement machining, even the crystal face that carries out also utilizing artificial corundum crystal of the present invention to have under the situation of machining is processed, can be with the advantage of low-cost practicability so have.
Here adopt the X-ray diffraction device respectively above-mentioned crystal and crystal face to be identified and measured.At this moment, trigonal system is decided to be a=4.759 dust, c=12.991 dust, will compares with JCPDSNo.46-1212 during evaluation.One example of the X-ray diffraction pattern of the crystal face of the artificial corundum crystal of present embodiment is shown among Fig. 2 (a) and Fig. 3 (a).And Fig. 2 (b) and Fig. 3 (b) are the X-ray patterns of pulverizing and measuring for the artificial corundum crystal of identifying present embodiment.In the present embodiment, so-called artificial corundum crystal has the crystal face of regulation, for example shown in Fig. 2 (a) and Fig. 3 (a), is meant to detect any peak that belongs to the regulation crystal face.Wherein Fig. 2 (c) and Fig. 3 (c) are the X-ray diffraction patterns of CPDSNo.46-1212, and the X-ray diffraction pattern of Fig. 2 (a)～(c) and Fig. 3 (a)～(c) is to measure with the CuK alpha-ray.
And among the present invention, for example described { 101} face, be meant with whole faces of 101} face equivalence, promptly the 101} face and the 011} face or as its multiple the 202} face, the 022} face, the 303} face, the 033} face, the 404} face, 044} face etc., about the crystal face of miscellaneous stipulations too.
The artificial corundum crystal of present embodiment by having the crystal face of regulation, and can be distinguished with the artificial corundum crystal that adopts manufacture method manufacturing in the past.For example, do not have complicated crystal shape, may be processed into crystal hardly yet with particular crystal plane even implement processing such as cutting with the artificial corundum crystal of Czochralsk manufactured.And be platelike crystal, though so that { the 001} face is as the advantage crystal face, can not be processed into usually to have the above-mentioned double hexagonal pyramid shape crystalline crystal face that comes from the artificial corundum crystal of fusing assistant slow cooling manufactured.
And artificial corundum crystal in the present embodiment, as long as come from double hexagonal pyramid shape crystal, also can have above-mentioned crystal face crystal face in addition.
Wherein what is called comes from double hexagonal pyramid shape crystal, and the artificial corundum crystal that is meant present embodiment both can be with the artificial corundum crystal of double hexagonal pyramid shape as basic configuration, also can implement machining to double hexagonal pyramid shape artificial corundum crystal.
And so-called with double hexagonal pyramid shape as basic configuration, be meant it both can is double hexagonal pyramid shape artificial corundum crystal shown in Fig. 1 (a) and Fig. 4 (a) for example, also can be for example shown in Fig. 1 (b) and Fig. 4 (b), to lack a double hexagonal pyramid shape part, the artificial corundum crystal that other crystal faces occur.In addition, Fig. 4 (a) and (b) be with opticmicroscope (キ-エ Application ス Co., Ltd. makes, VH-Z450+VH-7000C), to the optical microscope photograph of the artificial corundum crystal photography of having added Cr.
The artificial corundum crystal of present embodiment both can be colourless, also can be painted because of adding additives such as chromium, iron, titanium, nickel, vanadium, cobalt in the artificial corundum crystal.
Wherein known corundum crystal dissimilates because of the kind tone of additives such as chromium, iron, titanium, nickel, vanadium, cobalt.What for example do not have additive is colourless, and added chromium will present scarlet, redness or pink, added the blueness that presents of iron and titanium, added the yellow that presents of nickel, that has added vanadium presents the chrysoberyl look, to have added presenting of nickel and chromium or nickel, chromium and iron orange, added the yellow-green colour that presents of nickel, titanium, iron, added the purple that presents of titanium, chromium and iron.And will except that the scarlet artificial corundum crystal that has added chromium, generally be called sapphire.
The artificial corundum crystal of present embodiment, preferably by interpolation chromium, iron and titanium, nickel, vanadium, perhaps cobalt is coloured to scarlet, redness or pink respectively as the coloring components in the crystal, blueness, yellow, chrysoberyl look or green.That is to say the artificial corundum crystal of present embodiment, preferred scarlet, redness or pink artificial corundum crystal (adding the artificial corundum crystal of chromium), blue artificial corundum crystal, yellow artificial corundum crystal, chrysoberyl look artificial corundum crystal, perhaps green man-made corundum crystal.
Wherein what is called is painted to the chrysoberyl look, is meant that artificial corundum crystal has the artificial corundum crystal of discolouration, and so-called chrysoberyl look artificial corundum crystal, is meant the artificial corundum crystal with discolouration.There is no particular restriction for the zone that shows this discolouration, be to present dark blue green or darker yellow green under the spectrographic high light (for example sunlight and luminescent lamp) for example, under red colour system spectrographic high light (for example candle light and incandescent light), become and present puniceous and sorrel in blue green.
And in the present embodiment, yellow artificial corundum crystal except that nickel, can also add iron as coloring components.In this case, the example that makes up as coloring components for example can be enumerated and nickel only be arranged, the perhaps combination of nickel and iron.
Chrysoberyl look artificial corundum crystal except that vanadium, also can add at least a element of selecting as added ingredients from titanium and chromium.In this case, as the combination of coloring components, for example can enumerate only has vanadium, vanadium and iron, vanadium and titanium, vanadium and chromium, vanadium, iron and titanium, vanadium, iron and chromium, vanadium, titanium and chromium, the combination of vanadium, iron, titanium and chromium etc.
The green man-made corundum crystal except that cobalt, also can add at least a element of selecting as coloring components from iron, vanadium and nickel.In this case, as the combination of coloring components, for example can enumerate only has cobalt, cobalt and iron, cobalt and vanadium, cobalt and nickel, the combination of cobalt, vanadium and nickel etc.
And also can contain the metal beyond the above-mentioned chromium, iron, titanium, nickel, vanadium, cobalt or the compound of this metal in the artificial corundum crystal of present embodiment.
Wherein add chromium, iron, titanium, nickel, vanadium, cobalt etc., can use EPMA (electron rays micro-zone analysis), XPS (x-ray photoelectron spectrum analysis) or EDX (energy dispersion type X-ray analysis) method to confirm.
And the stoichiometric composition of colourless artificial corundum crystal can be used Al
2O
3Expression.The stoichiometric composition of scarlet, redness or pink artificial corundum crystal (adding the artificial corundum crystal of chromium) can be used Al
2O
3: Cr represents.The stoichiometric composition of blue artificial corundum crystal can be used Al
2O
3: Fe, Ti represents.Though the stoichiometric composition of yellow artificial corundum crystal is different because of the combination of above-mentioned coloring components, for example can use Al
2O
3: Ni or Al
2O
3: Ni, expressions such as Fe.Though the stoichiometric composition of chrysoberyl look artificial corundum crystal is different because of the combination of above-mentioned coloring components, for example can use Al
2O
3: V, Al
2O
3: V, Fe, Al
2O
3: V, Ti, Al
2O
3: V, Cr, Al
2O
3: V, Fe, Ti, Al
2O
3: V, Fe, Cr, Al
2O
3: V, Ti, Cr, or Al
2O
3: expressions such as V, Fe, Ti, Cr.Though the stoichiometric composition of green man-made corundum crystal is different because of the combination of above-mentioned coloring components, for example can use Al
2O
3: Co, Al
2O
3: Co, Fe, Al
2O
3: Co, V, Al
2O
3: Co, Ni, or Al
2O
3: expressions such as Co, V, Ni.
In the present embodiment, any artificial corundum crystal, composition all is not limited to also comprise with stoichiometric composition devious on the stoichiometry.The artificial corundum crystal of present embodiment preferably adopts fusing assistant method of evaporation described later manufacturing, adopts under the situation of fusing assistant method of evaporation manufacturing, can make sometimes and contain the element as impurity contained in fusing assistant in the artificial corundum crystal.Wherein to be in 1 mole usually be denier below the % to the foreign matter content in the artificial corundum crystal.
And, only can make the painted coloring components of artificial corundum crystal just not have special restriction if contain as the content of coloring components in the artificial corundum crystal, also can be denier.For example as the chromium content in above-mentioned scarlet, redness or the pink artificial corundum crystal (adding the artificial corundum crystal of chromium), only making the painted Cr of scarlet, redness or pink artificial corundum crystal just not have special restriction if contain, also can be denier.And, only make artificial corundum crystal be colored as blue iron and the just special restriction of nothing of titanium if contain as the iron in the above-mentioned blue artificial corundum crystal and the content of titanium, also can be denier.As the content of the coloring components such as nickel in the above-mentioned yellow artificial corundum crystal, only make artificial corundum crystal be coloured to the just special restriction of nothing of xanchromatic coloring components if contain, also can be denier.As the content of the coloring components such as vanadium in the above-mentioned chrysoberyl look artificial corundum crystal, just there is not special restriction if contain the coloring components that only makes artificial corundum crystal be coloured to the chrysoberyl look, also can be denier.As the content of the coloring components such as cobalt in the above-mentioned green man-made corundum crystal, only make artificial corundum crystal be coloured to the just special restriction of nothing of green coloring components if contain, also can be denier.
In the present embodiment, preferably adopt the fusing assistant method of evaporation to make artificial corundum crystal.The device that uses in the fusing assistant method of evaporation is simple High Temperature Furnaces Heating Apparatus and crucible, and double hexagonal pyramid shape artificial corundum crystal can be provided easily.And according to the difference of the fusing assistant kind of using, can optionally make and do not belong to platelike crystal or needle-like crystal, and belong to the crystal of double hexagonal pyramid shape.In addition, the artificial corundum crystal that adopts the fusing assistant method of evaporation to make as described above, owing to contain element contained in the fusing assistant sometimes as impurity, so can make the crystal that contains with the same impurity of Naxas emery crystal, approaching with natural product, so have costly advantage as gem ornament etc.
Wherein, the manufacture method about artificial corundum crystals such as fusing assistant method of evaporation is documented on " in manufacture method one hurdle of B. artificial corundum crystal " described later, so omit the explanation to it here.
And the artificial corundum crystal of present embodiment, also can be that the people is contained impurity.As mentioned above, can make the corundum crystal approaching, thereby have costly advantage as gem ornament etc. with natural product by containing impurity.
2. second kind of embodiment
Second kind of form of artificial corundum crystal of the present invention is characterized in that it has { the advantage crystal face beyond the 001} face.
Putting down in writing in top first kind of embodiment, the artificial corundum crystal that adopts existing Czochralsk method, Verneuil method or sintering process to make does not have complicated crystal shape.And adopt the available platelike crystal of fusing assistant slow cooling method, though artificial corundum crystal has crystal face, the crystal face of advantage but is { 001} a face.
Artificial corundum crystal in the present embodiment, be have the artificial corundum crystal of the advantage crystal face beyond the 001} face, this crystal face does not come from platelike crystal, and with above-mentioned first kind of embodiment be to come from double hexagonal pyramid shape crystal equally.In the present embodiment, artificial corundum crystal has { the advantage crystal face beyond the 001} face, come from double hexagonal pyramid shape crystal, so need not to implement machining when in laser generation material, gem ornament etc., using, even perhaps process at the crystal face of implementing also to utilize artificial corundum crystal of the present invention to have under the situation of machining, thereby have can be with the advantage of low-cost practicability.
Here what is called has that { the advantage crystal face beyond the 001} face is meant and does not have that { the 001} face perhaps { under the situation of 001} face, exists than belonging to { the peak that the peak intensity of 001} face is bigger having in X-ray diffraction pattern.In addition, as { the advantage crystal face beyond the 001} face is preferably any regulation crystal face of putting down in writing in above-mentioned first kind of embodiment.
Wherein, about artificial corundum crystal and other each points, because identical with first kind of embodiment and omit explanation here.
B. the manufacture method of artificial corundum crystal
The manufacture method of artificial corundum crystal of the present invention below is described.
The manufacture method of artificial corundum crystal of the present invention, it is characterized in that adopting the sample heating that will contain raw material and fusing assistant, as motivating force, the fusing assistant method of evaporation that makes crystal separate out and grow is made with the artificial corundum crystal of double hexagonal pyramid shape as basic configuration with the evaporation of fusing assistant.
Flux method is a kind of in the solution method, also can be called flux method.Adopt flux method to make when the crystal growth, mix with raw material, behind the heating and melting, form hypersaturated state, make crystal growth while make the solution slow cooling or fusing assistant is evaporated as solute with forming the salt of fusing assistant or oxide compound.Formation method difference based on this hypersaturated state can be divided into fusing assistant method of evaporation, fusing assistant slow cooling method and fusing assistant temperature gradient method substantially.
The present invention adopts the fusing assistant method of evaporation in the aforesaid method.The fusing assistant method of evaporation, be that a kind of promotion is with the nucleus formation that is evaporated to motivating force of fusing assistant and the method for crystal growth, for example shown in Fig. 5 (b), with filling contain the sample 1 of fusing assistant and raw material crucible 12 place High Temperature Furnaces Heating Apparatus 13, by heating the fusing assistant in the sample 1 is evaporated, make artificial corundum crystal 2 separate out and grow, shown in Fig. 5 (c), just can obtain containing the sample 1 ' of artificial corundum crystal 2.This remaining sample 1 ' is dissolved in the suitable medium, just artificial corundum crystal 2 can be separated.
Manufacture method as the artificial corundum crystal that adopts flux method, known following method, promptly, adopt the fusing assistant slow cooling method that the solution slow cooling is formed hypersaturated state on one side and make crystal growth, using lead such as Lithium Oxide 98min-oxidation (fluoridizing) lead, Lithium Oxide 98min-Tungsten oxide 99.999-oxidation (fluoridizing) lead or bismuth oxide-lanthanum trioxide-oxidation (fluoridizing) lead is fusing assistant, obtains platelike crystal.Yet what obtain in this way only is lamellar crystal, is difficult to make large-scale and high-quality crystal.Therefore, platelike crystal need be cut into required shape when in laser generation material etc., using, in addition because artificial corundum crystal has higher hardness, so produced the rough sledding that cost increases.
Except that this problem, make sometimes in the flux method and contain impurity element contained in the fusing assistant in the crystal, so it is different with the Czochralsk method, the artificial corundum crystal that obtains contains impurity, approaching owing to making with the Naxas emery crystal, so have the advantage that can obtain as the costly artificial corundum crystal of gem ornament.
Among the present invention, by adopting the fusing assistant method of evaporation, can make with the artificial corundum crystal of the double hexagonal pyramid shape shown in Fig. 1 (a) and 4 (a), so handling ease during practicability can provide the artificial corundum crystal of high added value with nominal price as basic configuration.And the device of fusing assistant method of evaporation employing, only be that High Temperature Furnaces Heating Apparatus 13 and crucible 12 are simple like that shown in Fig. 5 (b), in the fusing assistant method of evaporation, separate out and grow by fusing assistant being evaporated make crystal, remaining sample dissolution just can be obtained artificial corundum crystal in appropriate solvent, so manufacturing process is simple.In addition in sum, in the fusing assistant method of evaporation, artificial corundum crystal contains sometimes that contained element can obtain the artificial corundum crystal approaching with the Naxas emery crystal as impurity in the fusing assistant, so can make as costly artificial corundum crystals such as gem ornaments.
In addition in the present invention, so-called with the artificial corundum crystal of double hexagonal pyramid shape as basic configuration, not only comprise the crystal of double hexagonal pyramid shape shown in Fig. 1 (a) and Fig. 4 (a), and comprise and lack a double hexagonal pyramid shape part shown in Fig. 1 (b) and Fig. 4 (b) but crystal with other crystal faces.
Fig. 5 is the process picture sheet of expression artificial corundum crystal manufacture method one example of the present invention.As shown in Figure 5, the manufacture method of artificial corundum crystal of the present invention, comprise following operation: the sample-preparation processes (Fig. 5 (a)) that in mortar 11, fusing assistant and raw material stirring is prepared sample 1, with filling the crucible 12 of above-mentioned sample 1 place High Temperature Furnaces Heating Apparatus 13 heating, and then insulation at high temperature, make the heating evaporation operation (Fig. 5 (b)) of fusing assistant evaporation, in above-mentioned heating evaporation operation with fused sample refrigerative refrigerating work procedure (Fig. 5 (c)), with sample 1 ' remaining behind above-mentioned heating evaporation operation and the above-mentioned refrigerating work procedure is dissolved in the appropriate solvent, with artificial corundum crystal 2 isolating separation circuits (crystal recovery process) (Fig. 5 (d)).
Each operation of the manufacture method of this artificial corundum crystal below is described.
1. sample-preparation processes
In the manufacture method of artificial corundum crystal of the present invention, at first carry out fusing assistant and raw material stirring are prepared the sample-preparation processes of sample.
In this operation, as method, though, for example can adopt in mortar with fusing assistant and the well-beaten method of raw material as long as evenly stirring method does not just have special restriction with fusing assistant and raw material stirring.
The sample that the present invention uses is the sample that contains fusing assistant and raw material.Fusing assistant and raw material below are described respectively.
(1) fusing assistant
The fusing assistant that the present invention uses, though so long as can in heating evaporation operation described later, evaporate, and in separation circuit described later, be dissolved in and just do not have special restriction, preferably a molybdenum compound in the appropriate solvent.Because, can the selectivity manufacturing not be tabular or acicular artificial corundum crystal, but with the artificial corundum crystal of double hexagonal pyramid shape as basic configuration by making above-mentioned fusing assistant contain aluminum oxide.
As this molybdenum compound, can use molybdenum oxide, perhaps in heating evaporation operation described later, can generate the compound of molybdenum oxide by heating.And, for example can enumerate carbonic acid molybdenum, molybdenum trisulfate, nitric acid molybdenum, molybdenum hydroxide and hydrate thereof etc. as the compound that can generate molybdenum oxide by heating.In above-mentioned substance, preferably use molybdenum oxide among the present invention.
And among the present invention, above-mentioned fusing assistant also can contain evaporation suppressor.So, suppress the speed of multinuclear generation and crystal growth, so can make high-quality artificial corundum crystal owing to can suppress the velocity of evaporation of fusing assistant.
On the other hand, do not contain when fusing assistant under the situation of above-mentioned evaporation suppressor,, can form more multinuclear, so can make a lot of artificial corundum crystals because karyomorphism becomes speed fast.
As above-mentioned evaporation suppressor, so long as can suppress fusing assistant evaporation, and in separation circuit described later, can be dissolved in and just do not have a special restriction in the appropriate solvent, but but preferred as alkali compound in the present invention.By using alkali metal compound, can suppress the evaporation of fusing assistant effectively, make high-quality large artificial corundum crystal.
As this alkali metal compound, can use alkalimetal oxide, perhaps in heating evaporation operation described later, generate the compound of alkalimetal oxide by heating.As the above-mentioned compound that heating generates alkalimetal oxide that passes through, can enumerate alkaline carbonate, alkali metal sulfates, base metal nitrate, alkali metal hydroxide and hydrate thereof etc.Among the present invention, in above-mentioned substance, preferably can generate from Li
2O, Na
2O and K
2The compound of at least a alkalimetal oxide of selecting among the O.
And as the content of above-mentioned alkali metal compound, mole number meter according to alkali metal atom in the alkali metal compound, whole mole numbers with respect to above-mentioned sample are in 40 moles below the %, preferably are in 30 moles below the %, more preferably in the following scope of 20 moles of %.Among the present invention, owing to evaporation promotion is examined as motivating force formation and crystal growth, so under the situation of the content of alkali metal compound greater than above-mentioned scope, might hinder crystallization process with fusing assistant.
(2) raw material
The raw material that the present invention uses below is described.Among the present invention, raw material is the formation material of artificial corundum crystal, artificial corundum crystal, as above-mentioned " A. artificial corundum crystal " hurdle record, there are branch and its essentially consist of colourless artificial corundum crystal, scarlet, redness or peach artificial corundum crystal (adding the artificial corundum crystal of chromium), blue artificial corundum crystal, yellow artificial corundum crystal, chrysoberyl look artificial corundum crystal and green man-made corundum crystal different.Colourless artificial corundum crystal, scarlet, redness or peach artificial corundum crystal (adding the artificial corundum crystal of chromium), blue artificial corundum crystal, yellow artificial corundum crystal, chrysoberyl look artificial corundum crystal and green man-made corundum crystal below are described respectively.
(i) colourless artificial corundum crystal
Colourless artificial corundum crystal among the present invention has the Al of using
2O
3The essentially consist of expression is so adopt aluminum compound (Al
2O
3The source) gets final product as raw material.
As aluminum compound (Al
2O
3The source) can use aluminum oxide, perhaps in heating evaporation operation described later by adding the compound that heat energy generates aluminum oxide.Add the compound that heat energy generates aluminum oxide as above-mentioned passing through, for example can enumerate aluminium hydroxide, Tai-Ace S 150, aluminium carbonate, aluminum nitrate and hydrate thereof etc.Among the present invention, the preferred aluminum oxide that uses in these materials.
Wherein about the composition of colourless artificial corundum crystal, because of omitting explanation here with above-mentioned " A. artificial corundum crystal " hurdle record identical.
Among the present invention, as the content of above-mentioned raw materials, the mole number of raw material preferably is in 10 moles below the % with respect to the total mole number of above-mentioned sample.Under the situation of material content greater than above-mentioned scope, raw material is not easy dissolving in above-mentioned fusing assistant, might hinder crystallization.And because material content also can form crystal less, so the lower value of material content is not particularly limited.
(ii) scarlet, redness or peach the artificial corundum crystal artificial corundum crystal of chromium (add)
Among the present invention, scarlet, redness or peach artificial corundum crystal (adding the artificial corundum crystal of chromium) are owing to be to have the Al of using
2O
3: the essentially consist that Cr represents, so above-mentioned raw materials can be divided into aluminum compound (Al
2O
3The source) and chromium cpd (Cr source).
As chromium cpd (Cr source), though so long as in heating evaporation operation described later fused just do not have special restriction, preferably by heating the compound that can generate chromium ion.As the compound that can generate chromium ion by heating, for example can enumerate chromic oxide, chromium hydroxide, chromium sulphate, chromium carbonate, chromium nitrate and hydrate thereof.Among the present invention in these materials preferred chromic oxide.
Wherein about aluminum compound (Al
2O
3The source), because omission explanation here with the identical of above-mentioned colourless artificial corundum crystal one hurdle record.
As aluminum compound (Al
2O
3The source), forms required stoichiometric ratio and mix and get final product according to forming regulation with the ratio of mixture of chromium cpd (Cr source).For example when using aluminum oxide and chromic oxide to do under the situation of raw material, addition about chromic oxide, be in mode below the 5 weight % according to weight and mix and get final product,, more preferably be in the following mode of 1 weight % and mix preferably according to being in below the 2 weight % with respect to aluminum oxide.
In addition, identical about the content of raw material etc. because with the record of above-mentioned colourless artificial corundum crystal one hurdle, and about the composition of scarlet, redness or peach the artificial corundum crystal artificial corundum crystal of chromium (add), identical with the record of above-mentioned " A. artificial corundum crystal " hurdle, and omit explanation here.
(iii) blue artificial corundum crystal
Among the present invention, blue artificial corundum crystal is owing to be to have the Al of using
2O
3: the essentially consist that Fe, Ti represent gets final product so above-mentioned raw materials is aluminum compound, iron cpd and titanium compound.
As iron cpd, though so long as in heating evaporation operation described later the fused compound just do not have special restriction, preferably by heating the compound that can generate iron ion.As the compound that can generate iron ion by heating, for example can enumerate ferric oxide, ironic hydroxide, ferric sulfate, iron carbonate, iron nitrate, iron(ic) chloride, ironic citrate, tertiary iron phosphate, ferric fluoride, ferric iodide, ironic oxalate and hydrate thereof etc.The present invention preferably uses ferric oxide in these materials.In this case, the valence mumber of the iron in the above-mentioned ferric oxide both can be divalence or trivalent, also can be that divalence and tervalent iron mix existence.
As titanium compound, though so long as in heating evaporation operation described later the fused compound just do not have special restriction, preferably by heating the compound that can generate titanium ion.As the compound that can generate titanium ion by heating, for example can enumerate titanium oxide, titanium nitride, tetraisopropoxy titanium, titanous oxalate, titanium sulfide, titanium bromide, titanium chloride and hydrate thereof etc.The present invention preferably uses titanium oxide in these materials.In this case, the valence mumber of the titanium in the above-mentioned titanium oxide can be enumerated divalence, trivalent and tetravalence.The valence mumber of titanium both can be single, also can be to mix to exist.
In addition about aluminum compound, owing to the explanation of here omitting with the identical of above-mentioned colourless artificial corundum crystal one hurdle record to it.
And about the ratio of mixture between aluminum compound and iron cpd and the titanium compound, if iron cpd that adds and titanium compound can make the painted special restriction of just nothing of blue artificial corundum crystal.For example when using under aluminum oxide, ferric oxide and the situation of titanium oxide as raw material, total addition as ferric oxide and titanium oxide, reach mode below the 5 weight % according to its weight and mix and get final product, preferably mix according to being in the mode that below the 2 weight %, more preferably is in below the 1 weight % with respect to aluminum oxide.By above-mentioned ratio of mixture is in the above-mentioned scope, blue artificial corundum crystal can be coloured to bright-coloured blueness.
In addition, though the ratio of mixture between iron cpd and titanium compound is different because of the valence mumber of iron and titanium, usually according to the (Fe: Ti) reach 1: 0.05～20 mode and mix of weight ratio between elemental iron and element titanium.Wherein preferably according to reach 1: 0.07～15,1: 0.1～10 the mode of more preferably reaching is mixed.By above-mentioned ratio of mixture being in the above-mentioned scope, can accessing a kind of colour developing is the blue artificial corundum crystal of bright-coloured blueness.
Wherein about the content of raw material, identical with the record of above-mentioned colourless artificial corundum crystal one hurdle, and about the composition of blue artificial corundum crystal, identical with above-mentioned " A. artificial corundum crystal " hurdle record, thereby omit explanation here to it.
(iv) yellow artificial corundum crystal
Among the present invention, yellow artificial corundum crystal is owing to have the Al of using
2O
3: the essentially consist that Ni represents, so can use aluminum compound and nickel compound as raw material.In addition in the present invention, as the record of above-mentioned " A. artificial corundum crystal " hurdle, yellow artificial corundum crystal is owing to also having added iron as coloring components, so can also add iron cpd in aluminum compound and nickel compound as above-mentioned raw materials except that nickel.In this case, as the combination that raw material combination for example can be enumerated aluminum compound and nickel compound, the perhaps combination of aluminum compound, nickel compound and iron cpd.
Though as nickel compound so long as in heating evaporation operation described later the fused compound just do not have special restriction, preferably by heating the compound that can generate nickel ion.By heating the compound that can generate nickel ion, for example can enumerate nickelous acetate, nickelous carbonate, nickelous chloride, nickel hydroxide, nickelous iodide, nickelous nitrate, nickel oxide, nickel sulfamic acid, single nickel salt and hydrate thereof as above-mentioned.Among the present invention, the preferred nickel oxide that uses in these compounds.In this case, the valence mumber of nickel in the above-mentioned nickel oxide both can be divalence or trivalent, also can be that divalence and trivalent are mixed existence.
In addition about aluminum compound, because identical with the record of above-mentioned colourless artificial corundum crystal one hurdle,, because identical with the record of above-mentioned blue artificial corundum crystal one hurdle, and omit explanation here to it about iron cpd.
And about the ratio of mixture between aluminum compound and nickel compound, if the nickel compound that adds can make the special restriction of the painted just nothing of yellow artificial corundum crystal.In addition, when except that aluminum compound and nickel compound, also using under the situation of iron cpd,, be colored the just special restriction of nothing if add the yellow artificial corundum crystal in back as the nickel compound and the iron cpd of coloring components.
For example when using under aluminum oxide and the situation of nickel oxide as raw material, addition about nickel oxide, reach mode below the 5 weight % according to its weight and mix and get final product,, more preferably be in the following mode of 1 weight % and mix preferably according to being in below the 2 weight % with respect to aluminum oxide.By above-mentioned ratio of mixture is in the above-mentioned scope, yellow artificial corundum crystal can be coloured to bright-coloured yellow.
And when using under aluminum oxide, nickel oxide and the situation of ferric oxide as raw material, total addition about nickel oxide and ferric oxide, reaching mode below the 5 weight % according to its weight with respect to aluminum oxide mixes and gets final product, preferably, more preferably be in the following mode of 1 weight % and mix according to being in below the 2 weight %.Be because by above-mentioned ratio of mixture is in the above-mentioned scope, as mentioned above, yellow artificial corundum crystal can be coloured to bright-coloured yellow.And in this case, the ratio of mixture between nickel oxide and ferric oxide is different because of the valence mumber of nickel and iron, and the purposes of yellow artificial corundum crystal that can be constructed in accordance is suitably selected.
In addition about the content of raw material, identical with the record of above-mentioned colourless artificial corundum crystal one hurdle, and about the composition of yellow artificial corundum crystal, identical with above-mentioned " A. artificial corundum crystal " hurdle record, thereby omit explanation here to it.
(v) chrysoberyl look artificial corundum crystal
Among the present invention, chrysoberyl look artificial corundum crystal is owing to have the Al of using
2O
3: the essentially consist of expression such as V, so can use aluminum compound and vanadium compound as raw material.And in the present invention, as the record of above-mentioned " A. artificial corundum crystal " hurdle, chrysoberyl look artificial corundum crystal is owing to can also add iron, titanium or chromium etc. as coloring components except that vanadium, so except that aluminum compound and vanadium compound, can also use at least a compound of from iron cpd, titanium compound and chromium cpd, selecting as above-mentioned raw materials.
In this case, for example can enumerate the combination of aluminum compound and vanadium compound as raw material combination, aluminum compound, the combination of vanadium compound and iron cpd, aluminum compound, the combination of vanadium compound and titanium compound, aluminum compound, the combination of vanadium compound and chromium cpd, aluminum compound, vanadium compound, the combination of iron cpd and titanium compound, aluminum compound, vanadium compound, the combination of iron cpd and chromium cpd, aluminum compound, vanadium compound, the combination of titanium compound and chromium cpd, perhaps aluminum compound, vanadium compound, iron cpd, the combination of titanium compound and chromium cpd etc.
Though as vanadium compound so long as in heating evaporation operation described later fused just do not have special restriction, preferably by heating the compound that can generate vanadium ion.By heating the compound that can generate vanadium ion, for example can enumerate vanadium carbide, vanadium chloride, vanadium oxide, bisulphate vanadium, acid vanadium oxalate and hydrate thereof etc. as above-mentioned.Among the present invention, the preferred vanadium oxide that uses in these compounds.In this case, the valence mumber of vanadium in the above-mentioned vanadium oxide can be enumerated trivalent, tetravalence and pentavalent.The valence mumber of vanadium both can be single, also can be to mix to exist.
In addition about aluminum compound, because identical with above-mentioned colourless artificial corundum crystal one hurdle record, identical about chromium cpd and above-mentioned scarlet, redness or the record of pink artificial corundum crystal one hurdle, and identical about iron cpd and titanium compound and the record of above-mentioned blue artificial corundum crystal one hurdle, thereby omit explanation here to it.
And about the ratio of mixture between aluminum compound and vanadium compound, if the vanadium compound that adds makes the special restriction of the painted just nothing of chrysoberyl look artificial corundum crystal.In addition, too, after adding as the vanadium compound of coloring components and other compounds chrysoberyl look artificial corundum crystal not being colored does not just have special restriction under the situation of also using at least a compound of selecting except that aluminum compound and vanadium compound from iron cpd, titanium compound and chromium cpd.
For example when using under aluminum oxide and the situation of vanadium oxide as raw material, addition about vanadium oxide, reach mode below the 5 weight % according to its weight and mix and get final product, preferably mix according to being in the mode that below the 2 weight %, more preferably is in below the 1 weight % with respect to aluminum oxide.By above-mentioned ratio of mixture is in the above-mentioned scope, chrysoberyl look artificial corundum crystal can be coloured to the good chrysoberyl look of discolouration.
And when using under aluminum oxide, vanadium oxide and the situation of ferric oxide as raw material, total addition about vanadium oxide and ferric oxide, reaching mode below the 5 weight % according to its weight with respect to aluminum oxide mixes and gets final product, preferably, more preferably be in the following mode of 1 weight % and mix according to being in below the 2 weight %.Be because by above-mentioned ratio of mixture is in the above-mentioned scope, chrysoberyl look artificial corundum crystal can be coloured to the good chrysoberyl look of discolouration.In addition, in this case, as the ratio of mixture of vanadium oxide and ferric oxide, different because of the valence mumber of vanadium and iron, the purposes of chrysoberyl look artificial corundum crystal constructed in accordance is suitably selected to get final product.
In addition, about the content of raw material, identical with above-mentioned colourless artificial corundum crystal one hurdle record, and about the composition of chrysoberyl look artificial corundum crystal, identical with above-mentioned " A. artificial corundum crystal " hurdle record, thereby omit explanation here to it.
(vi) green man-made corundum crystal
Among the present invention, the green man-made corundum crystal for example has the Al of using
2O
3: the essentially consist of expression such as Co, so can use aluminum compound and cobalt compound as raw material.And as the record of above-mentioned " A. artificial corundum crystal " hurdle, the green man-made corundum crystal is owing to can also add vanadium or nickel etc. as coloring components except that cobalt, so except that aluminum compound and cobalt compound, can also use at least a compound of from iron cpd, vanadium compound and nickel compound, selecting as above-mentioned raw materials.
In this case, for example can enumerate the combination of aluminum compound and cobalt compound as raw material combination, the combination of aluminum compound, cobalt compound and iron cpd, the combination of aluminum compound, cobalt compound and vanadium compound, the combination of aluminum compound, cobalt compound and nickel compound, the combination of aluminum compound, cobalt compound, vanadium compound and nickel compound etc. etc.
Though as cobalt compound so long as in heating evaporation operation described later fused just do not have special restriction, preferably by heating the compound that can generate cobalt ion.By heating the compound that can generate cobalt ion, for example can enumerate cobaltous bromide, cobalt chloride, citric acid cobalt, cobaltous fluoride, glyconic acid cobalt, cobaltous hydroxide, cobaltous iodide, Xiao Suangu, cobalt oxalate, cobalt oxide, cobaltous phosphate, cobalt stearate, rose vitriol, cobaltous sulfide and hydrate thereof as above-mentioned.Among the present invention, preferred citric acid cobalt, cobaltous fluoride, glyconic acid cobalt, cobaltous hydroxide, cobaltous iodide, cobalt oxalate, cobalt oxide, cobalt stearate, the cobaltous phosphate of using more preferably uses cobalt oxide, cobaltous hydroxide, cobalt stearate, cobaltous phosphate in these compounds.In this case, the valence mumber of cobalt in the above-mentioned cobalt compound can be divalence or trivalent, also can divalence and tervalent cobalt mixing existence.
In addition, about aluminum compound, because identical with above-mentioned colourless artificial corundum crystal one hurdle record, identical about the record of iron cpd and above-mentioned blue artificial corundum crystal one hurdle, and identical about the record of nickel compound and above-mentioned yellow artificial corundum crystal one hurdle, identical about the record of vanadium compound and above-mentioned chrysoberyl look artificial corundum crystal one hurdle is so omit its explanation here.
And about ratio of mixture between aluminum compound and cobalt compound, if the cobalt compound that adds makes the special restriction of the painted just nothing of green man-made corundum crystal.In addition, except that aluminum compound and cobalt compound, also using under the situation of at least a compound of from iron cpd, vanadium compound and nickel compound, selecting, as the cobalt compound of coloring components and other compounds too, the green man-made corundum crystal is painted just not to have a special restriction if make after adding.
For example when using under aluminum oxide and the situation of cobalt oxide as raw material, addition about cobalt oxide, reach mode below the 5 weight % according to its weight and mix and get final product, preferably mix according to being in the mode that below the 2 weight %, more preferably is in below the 1 weight % with respect to aluminum oxide.Be owing to, the green man-made corundum crystal can be coloured to bright-coloured green by above-mentioned ratio of mixture is in the above-mentioned scope.
And for example when using under aluminum oxide, cobalt oxide and the situation of ferric oxide as raw material, total addition about cobalt oxide and ferric oxide, reaching mode below the 5 weight % according to its weight with respect to aluminum oxide mixes and gets final product, preferably, more preferably be in the following mode of 1 weight % and mix according to being in below the 2 weight %.Be owing to, as mentioned above, the green man-made corundum crystal can be coloured to bright-coloured green by above-mentioned ratio of mixture is in the above-mentioned scope.And in this case, the ratio of mixture between cobalt oxide and ferric oxide is different because of the valence mumber of cobalt and iron, and the purposes of green man-made corundum crystal that can be constructed in accordance is suitably selected.
Therefore, among the present invention for above-mentioned aluminum compound and cobalt compound, can be with various iron cpd, vanadium compound and the nickel compounds of being used in combination, the ratio of mixture of these compounds is different because of the valence mumber of each element, and the purposes of green man-made corundum crystal that can be constructed in accordance is suitably selected.
In addition about the content of raw material, identical with the record of above-mentioned colourless artificial corundum crystal one hurdle, and about the composition of green man-made corundum crystal, identical with above-mentioned " A. artificial corundum crystal " hurdle record is so omit its explanation here.
(3) other
Among the present invention, can contain impurity in the above-mentioned sample.So, the crystal approaching can be produced, thereby a kind of costly artificial corundum crystal can be obtained as gem ornament with natural product.
2. heat and evaporization process
Below be illustrated with regard to heating in the manufacture method of artificial corundum crystal of the present invention and evaporization process.Heating among the present invention and evaporization process are to contain the sample heating of fusing assistant and raw material, and then at high temperature keep making the operation of fusing assistant evaporation.
In this operation, the sample for preparing in the above-mentioned sample-preparation processes is put into crucible adds a cover, for example shown in Fig. 5 (b) with filling the crucible 12 of sample 1 place High Temperature Furnaces Heating Apparatus 13.Be warming up to the highest maintenance temperature then, under this temperature, keep the specified time, make the fusing assistant evaporation in the sample 1, as motivating force, promote karyomorphism to become and crystal growth with the evaporation of this fusing assistant.Can in sample 1, form artificial corundum crystal 2 like this.
As the highest maintenance temperature in this operation, so long as can make above-mentioned sample melted, the temperature of fusing assistant evaporation just there is not special restriction, specifically be 950～1300 ℃, wherein preferred 975 ℃～1250 ℃, more preferably 1000 ℃～1200 ℃.
And the heat-up rate when setting above-mentioned the highest maintenance temperature, so long as the speed of above-mentioned sample even heating just can not had special restriction.As the hold-time under the highest above-mentioned maintenance temperature,, do not limit the time that crystal is fully grown in addition so long as just having especially.
As the crucible that uses in this operation,, use platinum crucible usually so long as can tolerate the crucible of the highest above-mentioned maintenance temperature and just not have special restriction with the reactive low crucible of above-mentioned sample.
3. refrigerating work procedure
Below the explanation artificial corundum crystal of the present invention manufacture method in refrigerating work procedure.Refrigerating work procedure among the present invention is with fused sample refrigerative operation in the above-mentioned heating evaporation operation.
In this operation, for example shown in Fig. 5 (b) with filling sample 1 crucible 12 from High Temperature Furnaces Heating Apparatus 13, take out, shown in Fig. 5 (c) with filling sample 1 crucible 12 cool to room temperature.
So long as can be cooled to the method for room temperature and get final product, for example can enumerate method as method of cooling with the crucible naturally cooling.
4. separation circuit (crystal recovery process)
Below describe with regard to the separation circuit in the manufacture method of artificial corundum crystal of the present invention.Among the present invention, separation circuit be with sample dissolution remaining behind above-mentioned heating evaporation operation and the refrigerating work procedure in appropriate solvent, thus with the operation of crystal separation.
In the crucible behind above-mentioned refrigerating work procedure, shown in Fig. 5 (c), sample 1 ' surrounds crystal 2 and remaining.In this operation, by with this remaining sample dissolution in appropriate solvent, can easily only artificial corundum crystal be separated.
As the solvent used of the above-mentioned remaining sample of dissolving, so long as do not influence artificial corundum crystal, and with the remaining sample dissolution beyond the artificial corundum crystal just do not have a special restriction, for example can enumerate cold water, warm water, hot water etc.
In addition, about adopting other all points of the artificial corundum crystal that the present invention makes, identical with above-mentioned " A. artificial corundum crystal " hurdle record, and omit its explanation.
C. artificial corundum crystal production of raw material for use
The artificial corundum crystal production of raw material for use below is described.
Artificial corundum crystal production of raw material for use of the present invention is characterized in that being used to make artificial corundum crystal, wherein contains molybdenum compound and aluminum compound.
Artificial corundum crystal production of raw material for use of the present invention, be suitable for utilizing above-mentioned fusing assistant method of evaporation to make the situation of artificial corundum crystal, use this artificial corundum crystal production of raw material for use of the present invention to make under the situation of artificial corundum crystal, owing to can the selectivity manufacturing not belong to the double hexagonal pyramid shape crystal of platelike crystal or needle-like crystal, so as mentioned above can be with low-cost practicability.And can obtain as costly crystal such as gem ornaments.
And artificial corundum crystal production of raw material for use of the present invention, except that above-mentioned molybdenum compound and aluminum compound, can also contain chromium cpd, iron cpd and titanium compound, nickel compound, vanadium compound perhaps contains cobalt compound.By making the artificial corundum crystal production of raw material for use contain this compound, can be suitable for making various painted artificial corundum crystals.
For example, make the artificial corundum crystal production of raw material for use that yellow artificial corundum crystal is used, except that above-mentioned molybdenum compound, aluminum compound and nickel compound, can also contain iron cpd.
Make the artificial corundum crystal production of raw material for use that chrysoberyl look artificial corundum crystal is used, except that above-mentioned molybdenum compound and aluminum compound and vanadium compound, can also contain at least a compound in chosen from Fe compound, titanium compound and the chromium cpd.Wherein, for example can enumerate the combination of in above-mentioned " manufacture method 1. sample-preparation processes of B. artificial corundum crystal " hurdle, putting down in writing as these combination of compounds.
Make the artificial corundum crystal production of raw material for use that the green man-made corundum crystal is used, except that above-mentioned molybdenum compound, aluminum compound and cobalt compound, can also contain at least a compound of from iron cpd, vanadium compound and nickel compound, selecting.Wherein, for example can enumerate the combination of in above-mentioned " manufacture method 1. sample-preparation processes of B. artificial corundum crystal " hurdle, putting down in writing as these combination of compounds.
In addition, artificial corundum crystal production of raw material for use of the present invention can also contain alkali metal compound.Alkali metal compound is owing to can suppress the evaporation of above-mentioned molybdenum compound etc., so adopting artificial corundum crystal production of raw material for use of the present invention makes under the situation of artificial corundum crystal, can suppress multinuclear and produce and crystalline growth velocity, can obtain high-quality artificial corundum crystal.
In addition, about molybdenum compound, aluminum compound, chromium cpd, iron cpd, titanium compound, nickel compound, vanadium compound, cobalt compound and alkali metal compound, and the content of these compounds etc., since with put down in writing in above-mentioned " manufacture method 1. sample-preparation processes of B. artificial corundum crystal " hurdle identical, so explanation is omitted.
In addition, the present invention is not limited to above-mentioned embodiment.Above-mentioned embodiment only is for example, has identical in fact structure with the technological thought of putting down in writing in the claim of the present invention, and produces the technical scheme of effect same, and no matter how it changes, and all is included in the technical scope of the present invention.
Embodiment
Below enumerate embodiment and reference examples specifies the present invention
[embodiment 1]
At first weighing aluminum oxide (1.5 gram), chromic oxide (0.008 gram), molybdenum oxide (28.5 gram) and Quilonum Retard (1.5 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 5 hours under this temperature.After the insulation, from electric furnace, take out crucible, naturally cool to room temperature.The crucible that is cooled to room temperature is put into warm water, will add the artificial corundum crystal Separation and Recovery of chromium.It is the three-dimensional shape of basic configuration that the crystal that obtains has with double hexagonal pyramid shape, is scarlet and transparent.And its mean sizes, be about 1 millimeter respectively at a axle and c direction of principal axis.
[reference examples 1]
At first weighing aluminum oxide (5.2 gram), chromic oxide (0.05 gram) and plumbous fluoride (49.8 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 10 hours under this temperature.After the insulation, slowly be cooled to 600 ℃, from electric furnace, take out crucible, naturally cool to room temperature with 5 ℃ speed per hour.The crucible that is cooled to room temperature is put into warm water, will add the artificial corundum crystal Separation and Recovery of chromium.The crystal that obtains is to be the red transparent crystals of basic configuration with tabular.
[embodiment 2]
Weighing aluminum oxide (1.5 gram), titanium oxide (0.002 gram), ferric oxide (0.002 gram), molybdenum oxide (28.5 gram) and Quilonum Retard (1.5 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 5 hours under this temperature.After the insulation, from electric furnace, take out crucible, naturally cool to room temperature.The crucible that is cooled to room temperature is put into warm water, the blue artificial corundum crystal of Separation and Recovery.It is the three-dimensional shape of basic configuration that the crystal that obtains has with double hexagonal pyramid shape, is blue transparence.
[reference examples 2]
Weighing aluminum oxide (5.2 gram), titanium oxide (0.0125 gram), ferric oxide (0.0125 gram) and plumbous fluoride (49.8 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 10 hours under this temperature.After the insulation, slowly be cooled to 600 ℃, from electric furnace, take out crucible, naturally cool to room temperature with 5 ℃ speed per hour.The crucible that is cooled to room temperature is put into warm water, the Separation and Recovery artificial corundum crystal.The crystal that obtains is to be the blue transparent crystals of basic configuration with tabular.
[embodiment 3]
Weighing aluminum oxide (1.5 gram), nickel oxide (0.008 gram), molybdenum oxide (28.5 gram) and Quilonum Retard (1.5 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 5 hours under this temperature.After the insulation, from electric furnace, take out crucible, naturally cool to room temperature.The crucible that is cooled to room temperature is put into warm water, the yellow artificial corundum crystal of Separation and Recovery.It is the three-dimensional shape of basic configuration that the crystal that obtains has with double hexagonal pyramid shape, is the yellow transparent shape.
[embodiment 4]
Weighing aluminum oxide (1.5 gram), vanadium oxide (0.008 gram), molybdenum oxide (28.5 gram) and Quilonum Retard (1.5 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 5 hours under this temperature.After the insulation, from electric furnace, take out crucible, naturally cool to room temperature.The crucible that is cooled to room temperature is put into warm water, separating and recovering gold emerald color artificial corundum crystal.It is the three-dimensional shape of basic configuration that the crystal that obtains has with double hexagonal pyramid shape, is chrysoberyl look transparence.
[embodiment 5]
Weighing aluminum oxide (1.5 gram), cobalt oxide (0.008 gram), molybdenum oxide (28.5 gram) and Quilonum Retard (1.5 gram) are put into mortar.In mortar, this biased sample dry type was mixed about 20 minutes.Then biased sample is filled in the platinum crucible, cover lid is placed in the electric furnace.With 45 ℃ speed per hour electric furnace is heated to 1100 ℃, insulation is 5 hours under this temperature.After the insulation, from electric furnace, take out crucible, naturally cool to room temperature.The crucible that is cooled to room temperature is put into warm water, Separation and Recovery green man-made corundum crystal.It is the three-dimensional shape of basic configuration that the crystal that obtains has with double hexagonal pyramid shape, is the green transparent shape.
The possibility of utilizing on the industry
Artificial corundum crystal of the present invention can be practical with low cost, and as gem ornament The value height.
Claims (17)
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| CN103882520A (en) * | 2014-04-04 | 2014-06-25 | 玉溪市明珠晶体材料有限公司 | Method for growing jewelry-grade sapphire monocrystal |
| CN106966704A (en) * | 2017-02-28 | 2017-07-21 | 梧州市东麟宝石机械有限公司 | One kind synthesis ruby preparation method of dove blood |
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