CN103205812B - Compound boron rubidiurn sulfate and boron rubidiurn sulfate crystal and preparation method - Google Patents

Compound boron rubidiurn sulfate and boron rubidiurn sulfate crystal and preparation method Download PDF

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CN103205812B
CN103205812B CN201310151075.5A CN201310151075A CN103205812B CN 103205812 B CN103205812 B CN 103205812B CN 201310151075 A CN201310151075 A CN 201310151075A CN 103205812 B CN103205812 B CN 103205812B
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boron
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rubidiurn sulfate
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CN103205812A (en
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潘世烈
董凌云
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The present invention relates to a kind of compound boron rubidiurn sulfate and boron rubidiurn sulfate crystal and preparation method, the chemical formula of this compound is Rb 5bS 4o 16, molecular weight is 822.40, and the chemical formula of this compound boron rubidiurn sulfate crystal is Rb 5bS 4o 16, molecular weight is 822.40, belongs to tetragonal system, and spacer is <i>P</iGreatT.Gr eaT.GT4 32 12, does is unit cell parameters <i>a</iGreatT.Gr eaT.GT = 10.148 (4) <i>c</iGreatT.Gr eaT.GT = 16.689 (14) <i>Z </i>= 4, <i>V </i>= 1718.8 (17) 3solid reaction process is adopted to obtain boron rubidiurn sulfate compound, again this compound is adopted flux method growing crystal, can obtain boron rubidiurn sulfate crystal, made crystal has the large size of at least centimetre-sized, this crystal has through wide waveband, preparation speed is fast, and simple to operate, growth cycle is short, good mechanical property, is easy to the advantages such as processing.

Description

Compound boron rubidiurn sulfate and boron rubidiurn sulfate crystal and preparation method
Technical field
The present invention relates to a kind of compound boron rubidiurn sulfate and boron rubidiurn sulfate crystal and preparation method.
Background technology
To the further investigation of photoelectric field and the development of type material, photoelectric crystal is made all to have extremely important effect and huge potential application in various fields.These research and apply propose higher materialization requirement to photoelectric crystal, people are explored have the photoelectric crystal material of multi-functional group.
A kind of crystal has boron oxygen groups simultaneously and sulphur oxygen groups may become the functional materials with new capability.So far, the growth of the functional materials boron rubidiurn sulfate and large size boron rubidiurn sulfate monocrystalline simultaneously with boron oxygen groups and sulphur oxygen groups seldom sees report.Therefore, a kind of method of synthesizing boron rubidiurn sulfate and growing large-size boron rubidiurn sulfate crystal is needed.
Summary of the invention
The object of the invention is to provide a kind of compound boron rubidiurn sulfate and boron rubidiurn sulfate crystal and preparation method, and wherein the chemical formula of this compound is Rb 5bS 4o 16, molecular weight is 822.40, adopts solid phase method preparation; The chemical formula of this crystal is Rb 5bS 4o 16, molecular weight is 822.40, does not have symmetry centre, belongs to tetragonal system, spacer P4 32 12, unit cell parameters is z=4,
Another object of the present invention is the preparation method providing a kind of compound boron rubidiurn sulfate crystal.
A kind of compound boron rubidiurn sulfate of the present invention, is characterized in that the chemical formula of this compound is Rb 5bS 4o 16, molecular weight 822.40, adopts solid reaction process preparation.
A kind of compound boron rubidiurn sulfate crystal, the chemical formula of this crystal is Rb 5bS 4o 16, molecular weight 822.40, belongs to tetragonal system, and spacer is P4 32 12, unit cell parameters is z=4,
The preparation method of described compound boron rubidiurn sulfate crystal, adopt solid reaction process and high temperature solution method growing crystal, concrete operations follow these steps to carry out:
A, adopt solid reaction process, Rb:B:S=5:1:4 takes containing rubidium compound in molar ratio, sulfocompound and boron-containing compound put into mortar, corundum crucible is put into after grinding evenly, corundum crucible is placed in retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, crucible is taken out after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtain boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent,
B, compound boron rubidiurn sulfate prepared by step a and fusing assistant PbO, H 3bO 3or PbO-H 3bO 3mix in crucible, be heated to 480-600 DEG C with the temperature rise rate of temperature 1-80 DEG C/h, constant temperature 12-100 hour, obtains mixed molten liquid;
Or directly take in molar ratio containing rubidium compound, sulfocompound and boric acid and fusing assistant PbO, H 3bO 3or PbO-H 3bO 3mix in crucible, be heated to 480-500 DEG C of constant temperature 12-24 hour with the temperature rise rate of temperature 1-80 DEG C/h, obtain mixed molten liquid;
C, the mixed molten liquid obtained by step b are cooled to 440 DEG C-550 DEG C, seed rod is stretched into below liquid level, with the speed of temperature 0.5-5 DEG C/h slowly decline 10-30 DEG C, seed rod is proposed liquid level, seed rod has aggregation, be down to room temperature with the speed of temperature 1-80 DEG C/h again, obtain boron rubidiurn sulfate seed crystal;
D, mixed molten liquid obtained for step b is cooled to 430-540 DEG C, the seed crystal obtained by step c is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 5-60 minute, then seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid, constant temperature 5-60 minute, fast cooling is to 420-530 DEG C;
E, again with the speed slow cooling of temperature 0.1-3 DEG C/day, the growth of crystal is carried out with 0-100rpm rotating speed rotary seed crystal rod, arrive after required yardstick until single crystal growing, by crystal lift-off mixed molten liquid surface, and be down to room temperature with temperature 1-80 DEG C/h speed, then crystal is taken out from burner hearth, i.e. obtained boron rubidiurn sulfate crystal.
Compound containing rubidium in step a is Rb 2sO 4, Rb 2cO 3, Rb 2o, RbNO 3, or RbOH; The compound R b of sulfur-bearing 2sO 4or (NH 4) 2sO 4; The compound of boracic is H 3bO 3or B 2o 3.
The mol ratio boron rubidiurn sulfate of step b fusing assistant and boron rubidiurn sulfate: fusing assistant is 1:1-6.
Fusing assistant PbO-H 3bO 3in system, PbO and H 3bO 3mol ratio be 1-2:1-5.
Compound boron rubidiurn sulfate crystal of the present invention and preparation method, in principle, adopt general chemical synthesis process can prepare compound boron rubidiurn sulfate, existing preferred solid reaction process, this compound is by the following chemical equation that typically can obtain boron rubidiurn sulfate compound:
(1)5Rb 2SO 4+3(NH 4) 2SO 4+2H 3BO 3→2Rb 5BS 4O 16+6NH 3↑+6H 2O↑
(2)5Rb 2O+8(NH 4) 2SO 4+2H 3BO 3→2Rb 5BS 4O 16+16NH 3↑+11H 2O↑
(3)20RbNO 3+16(NH 4) 2SO 4+4H 3BO 3→4Rb 5BS 4O 16+20NO 2↑+22H 2O↑+32NH 3↑+5O 2↑
(4)5Rb 2CO 3+8(NH 4) 2SO 4+2H 3BO 3→2Rb 5BS 4O 16+16NH 3↑+11H 2O↑+5CO 2↑
(5)5RbOH+4(NH 4) 2SO 4+H 3BO 3→Rb 5BS 4O 16+8NH 3↑+8H 2O↑
(6)5Rb 2SO 4+3(NH 4) 2SO 4+B 2O 3→2Rb 5BS 4O 16+6NH 3↑+3H 2O↑
(7)5Rb 2O+8(NH 4) 2SO 4+B 2O 3→2Rb 5BS 4O 16+16NH 3↑+8H 2O↑
(8)20RbNO 3+16(NH 4) 2SO 4+2B 2O 3→4Rb 5BS 4O 16+20NO 2↑+16H 2O↑+32NH 3↑+5O 2↑
(9)5Rb 2CO 3+8(NH 4) 2SO 4+B 2O 3→2Rb 5BS 4O 16+16NH 3↑+8H 2O↑+5CO 2↑
(10)10RbOH+8(NH 4) 2SO 4+B 2O 3→2Rb 5BS 4O 16+16NH 3↑+13H 2O↑
Compound boron rubidiurn sulfate of the present invention and boron rubidiurn sulfate crystal and preparation method, the chemical formula of this compound is Rb 5bS 4o 16, molecular weight is 822.40, adopts solid phase method preparation; This compound boron rubidiurn sulfate crystal, this crystal-chemical formula is Rb 5bS 4o 16, not there is symmetry centre, tetragonal system, spacer P4 32 12, unit cell parameters is z=4,
The invention provides compound R b 5bS 4o 16the preparation method of crystal, adopts flux method growing crystal, easily obtains large-sized Rb 5bS 4o 16, it is high that this crystal has product purity, and the speed of growth is very fast, and hardness is moderate, is easy to the advantages such as processing.
Accompanying drawing explanation
Fig. 1 is Rb of the present invention 5bS 4o 16x-ray diffraction pattern.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
By reaction formula: 5Rb 2sO 4+ 3 (NH 4) 2sO 4+ 2H 3bO 3→ 2Rb 5bS 4o 16+ 6NH 3↑+6H 2o ↑ employing solid reaction process synthesis Rb 5bS 4o 16compound;
A, by Rb 2sO 4, (NH 4) 2sO 4and H 3bO 35:3:2 puts into mortar in molar ratio, and mixing is also carefully ground, and then loads in the opening corundum crucible of Φ 100mm × 100mm, put into retort furnace, be slowly warming up to 400 DEG C, constant temperature 12 hours, crucible is taken out after cooling, by sample grinding evenly, then be placed in crucible, retort furnace be warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtain boron rubidiurn sulfate compound single-phase polycrystal powder, then X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidiurn sulfate in reaction formula can use rubidium oxide, rubidium nitrate, rubidium hydroxide and rubidium carbonate to replace, and boric acid can be replaced by boron oxide.
B, by synthesis compound boron rubidiurn sulfate and fusing assistant PbF 2-H 3bO 31:5 carries out mixture in molar ratio, wherein PbF 2with H 3bO 3mol ratio be 1:1, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 600 DEG C with the temperature rise rate of temperature 80 DEG C/h, constant temperature 48 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 550 DEG C, under seed rod is stretched into liquid level fast, slowly declines 30 DEG C with the speed of temperature 1 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then be down to room temperature with the speed of 80 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 535 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 5 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 5 minutes, fast cooling to 530 DEG C;
E, again with the speed of temperature 2 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 5rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 80 DEG C/h, then crystal taken out from burner hearth, the Rb being of a size of 10mm × 12mm × 15mm can be obtained 5bS 4o 16crystal.
Embodiment 2:
By reaction formula: 5Rb 2cO 3+ 8 (NH 4) 2sO 4+ 2H 3bO 3→ 2Rb 5bS 4o 16+ 16NH 3↑+11H 2o ↑+5CO 2↑ synthesis Rb 5bS 4o 16compound;
A, by Rb 2cO 3, (NH 4) 2sO 4and H 3bO 35:8:2 puts into mortar mixing and carefully grinding in molar ratio, then loads in the opening corundum crucible of Φ 100mm × 100mm, puts into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidium carbonate in reaction formula can use rubidium oxide, rubidium nitrate, rubidium hydroxide and rubidiurn sulfate to replace, and boric acid can be replaced by boron oxide.
B, by synthesis compound boron rubidiurn sulfate and fusing assistant H 3bO 31:4 carries out mixture in molar ratio, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 580 DEG C with the temperature rise rate of temperature 25 DEG C/h, constant temperature 24 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 530 DEG C, under seed rod is stretched into liquid level fast, slowly declines 20 DEG C with the speed of temperature 0.5 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then is down to room temperature with the speed of 50 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 525 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 10 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 10 minutes, fast cooling to 520 DEG C;
E, again with the speed of temperature 1 DEG C of/day cooling, with the rotating speed non rotating seed rod of 0rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 50 C/h, then crystal taken out from burner hearth, the Rb being of a size of 13mm × 13mm × 14mm can be obtained 5bS 4o 16crystal.
Embodiment 3:
By reaction formula: 5Rb 2o+8 (NH 4) 2sO 4+ B 2o 3→ 2Rb 5bS 4o 16+ 16NH 3↑+8H 2o ↑ synthesis Rb 5bS 4o 16compound;
By Rb 2o, (NH 4) 2sO 4and H 3bO 35:8:1 directly takes raw material in molar ratio, by the raw material that takes and fusing assistant PbO-H 3bO 31:4 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 1:3, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 480 DEG C with the temperature rise rate of temperature 1 DEG C/h, constant temperature 12 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
Mixed molten liquid is cooled to 440 DEG C, under seed rod is stretched into liquid level fast, slowly declines 30 DEG C with the speed of temperature 1 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then be down to room temperature with the speed of temperature 10 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
Growing crystal in compound liquation: the mixed molten liquid obtained is cooled to 435 DEG C, by the Rb obtained 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 30 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 30 minutes, and fast cooling is to temperature 430 DEG C;
Again with the speed slow cooling of temperature 0.5 DEG C/day, with the rotating speed rotary seed crystal rod of 30rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 10 DEG C/h speed, then crystal taken out from burner hearth, the Rb being of a size of 12mm × 13mm × 17mm can be obtained 5bS 4o 16crystal.
Embodiment 4:
By reaction formula: 5RbOH+4 (NH 4) 2sO 4+ H 3bO 3→ Rb 5bS 4o 16+ 8NH 3↑+8H 2o ↑ synthesis Rb 5bS 4o 16compound;
A, by RbOH, (NH 4) 2sO 4and H 3bO 35:4:1 puts into mortar mixing and carefully grinding in molar ratio, then loads in the opening corundum crucible of Φ 100mm × 100mm, puts into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidium hydroxide in reaction formula can use rubidium oxide, rubidium nitrate, rubidium carbonate and rubidiurn sulfate to replace, and boric acid can be replaced by boron oxide.
B, by the compound boron rubidiurn sulfate of synthesis and fusing assistant PbO in molar ratio 1:1 carry out mixture, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 570 DEG C with the temperature rise rate of temperature 40 DEG C/h, constant temperature 50 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 520 DEG C, under seed rod is stretched into liquid level fast, slowly declines 30 DEG C with the speed of temperature 5 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then be down to room temperature with the speed of 20 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 510 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 60 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 60 minutes, fast cooling to 505 DEG C;
E, again with the speed of temperature 3 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 10rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 20 DEG C/h, then crystal taken out from burner hearth, the Rb being of a size of 11mm × 16mm × 19mm can be obtained 5bS 4o 16crystal.
Embodiment 5:
By reaction formula: 5Rb 2o+8 (NH 4) 2sO 4+ 2H 3bO 3→ 2Rb 5bS 4o 16+ 16NH 3↑+11H 2o ↑ synthesis Rb 5bS 4o 16compound;
A, by Rb 2o, (NH 4) 2sO 4and H 3bO 35:8:2 puts into mortar mixing and carefully grinding in molar ratio, then loads in the opening corundum crucible of Φ 100mm × 100mm, puts into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidium oxide in reaction formula can use rubidium hydroxide, rubidium nitrate, rubidium carbonate and rubidiurn sulfate to replace, and boric acid can be replaced by boron oxide.
B, by synthesis compound boron rubidiurn sulfate and fusing assistant PbO-H 3bO 31:6 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 2:5, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 480 DEG C with the temperature rise rate of temperature 60 C/h, constant temperature 20 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 445 DEG C, under seed rod is stretched into liquid level fast, slowly declines 30 DEG C with the speed of temperature 3 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then be down to room temperature with the speed of 15 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 440 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 15 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 15 minutes, fast cooling to 430 DEG C;
E, again with the speed of temperature 1 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 50rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 15 DEG C/h, then crystal taken out from burner hearth, the Rb being of a size of 10mm × 15mm × 17mm can be obtained 5bS 4o 16crystal.
Embodiment 6:
By reaction formula: 5Rb 2sO 4+ 3 (NH 4) 2sO 4+ B 2o 3→ 2Rb 5bS 4o 16+ 6NH 3↑+3H 2o ↑ synthesis Rb 5bS 4o 16compound;
By Rb 2sO 4, (NH 4) 2sO 4and H 3bO 35:3:1 directly takes raw material in molar ratio, by the raw material that takes and fusing assistant PbO-H 3bO 31:3 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 1:5, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 490 DEG C with the temperature rise rate of temperature 10 DEG C/h, constant temperature 15 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
Mixed molten liquid is cooled to 450 DEG C, under seed rod is stretched into liquid level fast, with the speed slow cooling 25 DEG C of temperature 1 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, be down to room temperature with the speed of temperature 1 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
Growing crystal in compound liquation: the mixed molten liquid obtained is cooled to 445 DEG C, by the Rb obtained 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 20 minutes, then seed crystal is carried out melt back down to mixed molten liquid liquid level, constant temperature 20 minutes, fast cooling to 435 DEG C;
Again with the speed slow cooling of temperature 0.8 DEG C/day, with the rotating speed rotary seed crystal rod of 70rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 1 DEG C/h speed, then crystal taken out from burner hearth, the Rb being of a size of 17mm × 18mm × 22mm can be obtained 5bS 4o 16crystal.
Embodiment 7:
By reaction formula: 20RbNO 3+ 16 (NH 4) 2sO 4+ 4H 3bO 3→ 4Rb 5bS 4o 16+ 20NO 2↑+22H 2o ↑+32NH 3↑+5O 2↑ synthesis Rb 5bS 4o 16compound;
A, by RbNO 3, (NH 4) 2sO 4and H 3bO 35:4:1 puts into mortar mixing and carefully grinding in molar ratio, then loads in the opening corundum crucible of Φ 100mm × 100mm, puts into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidium nitrate in reaction formula can use rubidium hydroxide, rubidium oxide, rubidium carbonate and rubidiurn sulfate to replace, and boric acid can be replaced by boron oxide.
B, by synthesis compound boron rubidiurn sulfate and fusing assistant PbO-H 3bO 31:2 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 4:3, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 530 DEG C with the temperature rise rate of temperature 70 C/h, constant temperature 36 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 485 DEG C, under seed rod is stretched into liquid level fast, slowly declines 25 DEG C with the speed of temperature 1.5 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then is down to room temperature with the speed of 35 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 475 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 40 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 20 minutes, fast cooling to 470 DEG C;
E, again with the speed of temperature 0.5 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 25rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 35 DEG C/h, then crystal taken out from burner hearth, the Rb being of a size of 12mm × 13mm × 16mm can be obtained 5bS 4o 16crystal.
Embodiment 8:
By reaction formula: 5Rb 2cO 3+ 8 (NH 4) 2sO 4+ B 2o 3→ 2Rb 5bS 4o 16+ 16NH 3↑+8H 2o ↑+5CO 2↑ synthesis Rb 5bS 4o 16compound;
By Rb 2cO 3, (NH 4) 2sO 4and H 3bO 35:8:1 directly takes raw material in molar ratio, by the raw material that takes and fusing assistant PbO-H 3bO 33:5 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 1:2, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 500 DEG C with the temperature rise rate of temperature 5 DEG C/h, constant temperature 12 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
Mixed molten liquid is cooled to 460 DEG C, under seed rod is stretched into liquid level fast, with the speed slow cooling 15 DEG C of temperature 3 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, be down to room temperature with the speed of temperature 10 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
Growing crystal in compound liquation: the mixed molten liquid obtained is cooled to 455 DEG C, by the Rb obtained 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 40 minutes, then seed crystal is carried out melt back down to mixed molten liquid liquid level, constant temperature 30 minutes, fast cooling to 450 DEG C;
Again with the speed slow cooling of temperature 1.5 DEG C/day, with the rotating speed rotary seed crystal rod of 20rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 10 DEG C/h speed, then crystal taken out from burner hearth, the Rb being of a size of 14mm × 15mm × 19mm can be obtained 5bS 4o 16crystal.
Embodiment 9:
By reaction formula: 10RbOH+8 (NH 4) 2sO 4+ B 2o 3→ 2Rb 5bS 4o 16+ 16NH 3↑+13H 2o ↑ synthesis Rb 5bS 4o 16compound;
A, by RbOH, (NH 4) 2sO 4and H 3bO 35:4:1 puts into mortar mixing and carefully grinding in molar ratio, then loads in the opening corundum crucible of Φ 100mm × 100mm, puts into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidium hydroxide in reaction formula can use rubidium nitrate, rubidium oxide, rubidium carbonate and rubidiurn sulfate to replace, boron oxide can boric acid by replacing.
B, by synthesis compound boron rubidiurn sulfate and fusing assistant PbO-H 3bO 32:5 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 1:5, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 500 DEG C with the temperature rise rate of temperature 35 DEG C/h, constant temperature 60 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 465 DEG C, under seed rod is stretched into liquid level fast, slowly declines 30 DEG C with the speed of temperature 2 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then be down to room temperature with the speed of 25 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 460 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 25 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 30 minutes, fast cooling to 450 DEG C;
E, again with the speed of temperature 1 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 15rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 25 DEG C/h, then crystal taken out from burner hearth, the Rb being of a size of 15mm × 16mm × 22mm can be obtained 5bS 4o 16crystal.
Embodiment 10:
By reaction formula: 20RbNO 3+ 16 (NH 4) 2sO 4+ 2B 2o 3→ 4Rb 5bS 4o 16+ 20NO 2↑+16H 2o ↑+32NH 3↑+5O 2↑ synthesis Rb 5bS 4o 16compound;
A, by RbOH, (NH 4) 2sO 4and H 3bO 35:4:1 puts into mortar mixing and carefully grinding in molar ratio, then loads in the opening corundum crucible of Φ 100mm × 100mm, puts into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
Rubidium nitrate in reaction formula can use rubidium hydroxide, rubidium oxide, rubidium carbonate and rubidiurn sulfate to replace, boron oxide can boric acid by replacing.
B, by synthesis compound boron rubidiurn sulfate and fusing assistant PbO-H 3bO 34:5 carries out mixture in molar ratio, wherein PbO and H 3bO 3mol ratio be 1:2, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 540 DEG C with the temperature rise rate of temperature 50 C/h, constant temperature 48 hours, obtain boron rubidiurn sulfate Rb 5bS 4o 16mixed molten liquid;
C, again mixed molten liquid is cooled to 490 DEG C, under seed rod is stretched into liquid level fast, slowly declines 25 DEG C with the speed of temperature 1.5 DEG C/h, seed rod is proposed liquid level, seed rod has aggregation, then is down to room temperature with the speed of 40 DEG C/h, obtain boron rubidiurn sulfate seed crystal;
D, in compound liquation growing crystal: the mixed molten liquid obtained by step b is cooled to 480 DEG C, by step c obtain Rb 5bS 4o 16seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 50 minutes, then seed crystal is carried out melt back in mixed molten liquid, constant temperature 30 minutes, fast cooling to 475 DEG C;
E, again with the speed of temperature 2.5 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 75rpm, after crystal growth terminates, by crystal lift-off mixed molten liquid surface, be down to room temperature with the speed of temperature 40 DEG C/h, then crystal taken out from burner hearth, the Rb being of a size of 17mm × 19mm × 25mm can be obtained 5bS 4o 16crystal.

Claims (4)

1. a compound boron rubidiurn sulfate crystal, is characterized in that the chemical formula of this crystal is Rb 5bS 4o 16, molecular weight 822.40, belongs to tetragonal system, and spacer is p4 32 12, unit cell parameters is a=10.148 (4), c=16.689 (14), z=4, v=1718.8 (17) 3.
2., according to the preparation method of the compound boron rubidiurn sulfate crystal described in claim 1, it is characterized in that adopting solid reaction process and high temperature solution method growing crystal, concrete operations follow these steps to carry out:
A, employing solid reaction process, Rb:B:S=5:1:4 takes containing rubidium compound is in molar ratio Rb 2sO 4, Rb 2o, RbNO 3, Rb 2cO 3, or RbOH; Sulfocompound is Rb 2sO 4or (NH 4) 2sO 4be H with boron-containing compound 3bO 3or B 2o 3put into mortar, put into corundum crucible after grinding evenly, corundum crucible is placed in retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, takes out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into the careful grinding of mortar and obtained boron rubidiurn sulfate compound single-phase polycrystal powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and Rb 5bS 4o 16monocrystalline last X-ray spectrogram of pulverizing is consistent;
B, compound boron rubidiurn sulfate prepared by step a and fusing assistant PbO, H 3bO 3or PbO-H 3bO 3mix in crucible, be heated to 480-600 DEG C with the temperature rise rate of temperature 1-80 DEG C/h, constant temperature 12-100 hour, obtains mixed molten liquid;
Or directly take in molar ratio containing rubidium compound, sulfocompound and boric acid and fusing assistant PbO, H 3bO 3or PbO-H 3bO 3mix in crucible, be heated to 480-500 DEG C of constant temperature 12-24 hour with the temperature rise rate of temperature 1-80 DEG C/h, obtain mixed molten liquid;
C, the mixed molten liquid obtained by step b are cooled to 440 DEG C-550 DEG C, seed rod is stretched into below liquid level, with the speed of temperature 0.5-5 DEG C/h slowly decline 10-30 DEG C, seed rod is proposed liquid level, seed rod has aggregation, be down to room temperature with the speed of temperature 1-80 DEG C/h again, obtain boron rubidiurn sulfate seed crystal;
D, mixed molten liquid obtained for step b is cooled to 430-540 DEG C, the seed crystal obtained by step c is fixed on seed rod, seed crystal from crystal growing furnace top, first by seed crystal preheating 5-60 minute, then seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid, constant temperature 5-60 minute, fast cooling is to 420-530 DEG C;
E, again with the speed slow cooling of temperature 0.1-3 DEG C/day, the growth of crystal is carried out with 0-100rpm rotating speed rotary seed crystal rod, arrive after required yardstick until single crystal growing, by crystal lift-off mixed molten liquid surface, and be down to room temperature with temperature 1-80 DEG C/h speed, then crystal is taken out from burner hearth, i.e. obtained boron rubidiurn sulfate crystal.
3., according to the method described in claim 2, it is characterized in that the mol ratio boron rubidiurn sulfate of step b fusing assistant and boron rubidiurn sulfate: fusing assistant is 1:1-6.
4., according to method described in claim 2, it is characterized in that fusing assistant PbO-H 3bO 3in system, PbO and H 3bO 3mol ratio be 1-2:1-5.
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