CN101709508B - Preparation method of bismuth-containing eulytite bismuth silicate crystals - Google Patents
Preparation method of bismuth-containing eulytite bismuth silicate crystals Download PDFInfo
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- CN101709508B CN101709508B CN2009102188989A CN200910218898A CN101709508B CN 101709508 B CN101709508 B CN 101709508B CN 2009102188989 A CN2009102188989 A CN 2009102188989A CN 200910218898 A CN200910218898 A CN 200910218898A CN 101709508 B CN101709508 B CN 101709508B
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Abstract
The invention relates to a preparation method of bismuth-containing eulytite bismuth silicate crystals, which comprises the following steps: mixing bismuth trioxide powder and quartz glass powder into a batch mixture; putting the batch mixture into a high purity alumina crucible; and firing according to the following technical system: ascending from room temperature to 550 DEG C at a heating rate of 5 DEG C/minute and insulating for 30 minutes; ascending the temperature from 550 DEG C to 880-920 DEG C at the heating rate of 10-12 DEG C/minute and insulating for 6-24 hours; then rapidly taking the crucible out of a muffle furnace and putting the crucible in running water, so that the sample is cooled to room temperature at a cooling rate of 400 DEG C/minute; after cooling, taking out the water-quenched sample; and finally, drying and ball milling the sample to obtain the bismuth-containing eulytite bismuth silicate crystal powder. In the invention, high purity amorphous quartz glass is used as a raw material, thereby avoiding reacting with bismuth trioxide at low temperature. The prepared bismuth silicate crystals feature high purity, very few impurities, low cost and rich sources of raw materials, and simple preparation processes.
Description
Technical field
The present invention relates to a kind of preparation method of bismuthiferous silicate crystal, particularly a kind of bismuthiferous eulytite Bi
4SiO
12The preparation method of bi silicate crystals.
Background technology
Seeking new functional crystal is international crystalline material FRONTIER IN SCIENCE, and the research of aspects such as the prediction of new functional crystal, feedstock production, crystallization behavior, crystal growth is the basis of new functional crystal research.Discovered in recent years Bi
2O
3-SiO
2System is the system that further researching value is arranged very much.Because elements Si and Ge belong to same main group, similar performance, so Bi in the periodic table of chemical element
2O
3-SiO
2System and Bi
2O
3-GeO
2System has on structure and performance learns heterogeneous seemingly part.At present to Bi
2O
3-GeO
2Systematic research is comparatively ripe, and to Bi
2O
3-SiO
2Systematic research seem not enough (Fei Yiting, Journal of Inorganic Materials, 1997,12:469～476).The compound crystalline phase of finding in this system has phases such as 6:1,1:1 and 2:3, has found out Bi
12SiO
20Crystal has performances such as electric light, photoconduction, light are sold off, piezoelectricity, acousto-optic, optically-active, Bi
4Si
3O
12Crystal has performances such as electric light, flicker.But, except to Bi
12SiO
20Aspects such as near facies relationship forming and crystalline growth thereof, character, application have outside the more detailed research, the most of zone of this system lacks careful and research in depth basically, a reason is that other crystal is difficult to synthesize in this system's composition, and be easy to produce dephasign in the building-up process, this is bigger to prepared monocrystalline performance impact, therefore prepares the basis that highly purified crystal raw material is the high-quality transparent single crystal body of preparation.
Bi
4Si
3O
12Be a kind of novel scintillation crystal, become scintillator Bi with its favorable mechanical and chemical stability, good photoelectricity, thermoluminescence etc.
4Ge
3O
12One of best substitute.Although people are familiar with eulytite (Bi
4Si
3O
12) there be more than 170 year, but up to people (Philipsborn H V.J.Crystal Growth such as Philipsborn in 1971,1971,11:348) just utilize Czochralski grown to go out its monocrystalline, in recent years, Shanghai Inst. of Silicate, Chinese Academy of Sciences utilizes falling crucible method also to grow monocrystalline (Fan Shiji, et al.The Eleventh Inter-national Conference onCrystal Growth, Advance Program, 1995.30).
Bi
4Si
3O
12Crystal belongs to isometric system, the I43d spacer,
Z=4.Its structure can be regarded as by [SiO
4] tetrahedron and [BiO
6] octahedra formation.Bi
4Si
3O
12Crystal all is transparent in visible light and near infrared range.
At present, Bi
4Si
3O
12Synthetic method mainly be solid-phase synthesis and sol-gel method.(Ishi IM, Harda K, Sengutuvan N, et al.Journal of CrystalGrowth, 1999,205 (1-2): 191-195) utilize Bridgman-Stockbarge method for growing to go out large-sized Bi such as Ishi IM in 1997
4Si
3O
12Monocrystalline.(the Fei Y T such as Fei Yiting of Shanghai Inst. of Silicate, Chinese Academy of Sciences in 2000, Fan SJ, Sun R Y, et al.Progress in Crystal Growth and Vharacterizationof Materials, 2000,40 (1-4): 189-194) also utilize this method high-quality Bi that grown
4Si
3O
12Monocrystalline.(Zhang Zhengguang, Wang Xiufeng, field clear spring such as Zhang Zhengguang.Silicate circular, 2009,28 (3): 454-458) under normal pressure, prepared and have the Bi that height has sequential structure with sintering process
4Si
3O
12Crystallite.And analyzed generation crystalline thing mutually and microscopic appearance.The result shows that prepared is the Bi of cube phase
4Si
3O
12Crystal, Bi
4Si
3O
12Crystal grain always distributes in pairs, and is arranged in rows, thereby forms high orderly brilliant array structure.But, generate middle mutually dephasign and be difficult to eliminate.People such as Bai Chaohui (Bai Chaohui, Ba Xuewei, Jia Ru, Chinese Journal of Inorganic Chemistry, 2006,22:1327～1329) utilize Prepared by Sol Gel Method Bi
4Si
3O
12In the process of nano-powder, having obtained principal crystalline phase in the time of 550～650 ℃ is Bi
2SiO
5And Bi
2O
3The mixing crystalline phase, along with the rising of temperature of reaction, Bi
2SiO
5And Bi
2O
3Constantly reaction has generated the target product Bi of principal crystalline phase for cube crystalline phase in the time of 750 ℃
4Si
3O
12Wang Yan etc. (Wang Yan, Wang Xiufeng is in Cheng Long. inorganic chemicals industry, 2007,39:38～40; Wang Yan, Wang Xiufeng is in Cheng Long. silicate circular, 2007,26:378～381) use Bi
2O
3And SiO
2Be raw material, according to amount of substance than n (Bi
2O
3): n (SiO
2The sample of the about 60g of)=1: 1 preparation.Wet mixing 1.5h in the ethanol is poured in test earlier into, and it is even to guarantee sample to grind the dried 0.5h of mixing after the infrared oven dry again.750 ℃ of roasting 1h, Bi at this moment
12SiO
20And Bi
2SiO
5The diffraction peak of XRD stronger, soaking time lengthening, Bi
2SiO
5The diffraction peak of XRD weaken Bi
12SiO
20Diffraction peak further strengthen.In addition, give the differential thermal analysis curve of test in the literary composition, as can be seen, sample is at 579.6 ℃ from differential thermal analysis curve, and 744.3 ℃, 829.3 ℃, 879.2 ℃ all have exothermic peak to occur.This component produces the crystalline kind in temperature-rise period more, prepares single crystal preparation technology and be difficult to control.Jenni etc. are by ALD (atomic layer deposition) method (Jenni Harjuoja, Samuli Vayrynen, Matti Putkonen.Journal ofCrystal Growth, 2006,286:376～383), at N
2When the Bi-Si-O of Si (100) carries out 800 ℃ of anneal on the MgO snubber under the atmosphere, obtained Bi
2SiO
5Film.It is raw material that above bi silicate crystals synthetic all adopted silicon-dioxide, and synthetic method is very complicated, and if does not adopt high-temperature melting method all can not obtain pure bi silicate crystals.
Relevant with bismuth silicate both at home and abroad patent seldom, patent CN200510046593.6 discloses and has a kind ofly contained the metal oxide of various active components such as molybdenum, iron, nickel, samarium and be the catalyzer that carrier is formed with silicon-dioxide, aluminum oxide or its mixture, can be used for third rare, isobutene ammonia oxidizing and prepares higher selection row third rare nitrile etc.CN10038071C provides a kind of preparation high purity silicic acid bismuth nano-powder, at first bismuth salt is dissolved in the organic solvent, forming the bismuth salt concn is the bismuth-containing solution of 0.5～5M, at Bi: Si=12 in molar ratio: 1 joins silicoorganic compound in the bismuth-containing solution, fully stir, form uniform solution, colloidal sol is adopted atmospheric evaporation or negative pressure evaporation, obtain exsiccant precursor powder, at last in the environment of aerobic, the precursor powder is carried out sintering, the bismuth silicate nano powder of preparation place purity and better crystallinity degree in lower temperature and short time.In addition, document (Journal ofMaterials Science Letters 1999,18:1871～1874) discloses a kind of method that adopts the prepared by mechanical alloy bismuth silicate nano powder.This method is with Bi
2O
3And SiO
2Powder (crystal) is a raw material, directly prepare bismuth silicate nano powder through high-energy ball milling, be characterized in utilizing the mechanical alloying reaction that two kinds of powders take place in collision and crushing process repeatedly to synthesize target product, thereby do not need extra high-temperature heat treatment, can obtain bismuth silicate nano powder.Thereby can avoid the shortcoming of above-mentioned solid phase reaction sintering.But mechanical alloying method required time is longer, and production efficiency is lower, is not suitable as a kind of method of batch process bismuth silicate nano powder of practicality.And, produce pollution owing in long high-energy ball milling process, can from grinding system (comprise grinding container and grind spheroid), introducing impurity inevitably, thereby be difficult to obtain highly purified bismuth silicate nano powder.This is very disadvantageous for bismuth silicate in the application of photoelectron and photocatalysis field.
In sum, bismuth silicate (Bi
4Si
3O
12) be a kind of superior performance, widely used material.Raw materials used in the document of publishing at present is analytical pure, or chemical pure, the silicon-dioxide of purity such as spectroscopically pure and bismuthous oxide bismuth trioxide.Wherein three oxidations and bismuth purity is higher generally can reach 4～5N, and price is relatively low, and used silicon-dioxide purity is lower, generally can reach 2～4N, and purity are high more, and price is high more.In addition, above literature research finds that impurities in raw materials is bigger to prepared crystal property influence, and high-purity raw material helps preparing the bismuth silicate monocrystalline of superior performance.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, it is the high-quality bismuthiferous eulytite bismuth silicate (Bi of feedstock production that a kind of silica glass with amorphous phase is provided
4Si
3O
12) the crystalline preparation method.According to the eulytite bi silicate crystals purity height that preparation method of the present invention makes, dephasign is few, and cost of material is cheap, and the source is abundant, and preparation technology is simple, is the high quality raw material of the high-quality transparent silicic acid bismuth single crystal of preparation.
For achieving the above object, the technical solution used in the present invention is:
1) with behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder, then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder and fused silica powder put into agate breast body ball grinder ball milling 30～60min get admixtion at=1: 1;
2) admixtion is put into the high purity aluminium oxide crucible, the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 880～920 ℃ and be incubated 6～24 hours with 10～12 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
SiO in the silica glass of the present invention
2Content be 99.99%～99.9999% (4～6N); The purity of bismuthous oxide bismuth trioxide is 99.99%.
The present invention prepares bi silicate crystals with the non-crystalline state silica glass, because silica glass temperature of fusion higher (greater than 1700 ℃) has been avoided being and the bismuthous oxide bismuth trioxide reaction generation of minimizing dephasign at low temperatures.Prepared Bi crystal purity height, dephasign is few, and cost of material is cheap, and the source is abundant, and preparation technology is simple.Prepared eulytite bi silicate crystals can be used as the high quality raw material of the high-quality transparent silicic acid bismuth single crystal of preparation.
Description of drawings
Fig. 1 is the eulytite bismuth silicate (Bi that makes according to preparation method of the present invention
4Si
3O
12) the diffraction photo that detects at X-ray diffractometer of crystal, wherein X-coordinate be diffraction angle 2 θ/(°), ordinate zou is a diffracted intensity.
Fig. 2 (a) and (b) are respectively the eulytite bismuth silicate (Bi of embodiment 1,2 preparations
4Si
3O
12) photo of crystal under scanning electronic microscope.
Embodiment
Embodiment 1, at first, behind the silica glass cleaning, drying, puts into ball grinder ball milling to 300 order, makes fused silica powder; Then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder (content be 99.99%) and fused silica powder put into agate breast body ball grinder ball milling 30min get admixtion at=1: 1; Admixtion is put into the high purity aluminium oxide crucible, and the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 900 ℃ and be incubated 6 hours with 10 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
Referring to accompanying drawing 1, be the higher eulytite Bi of purity at the prepared Bi crystal as can be seen
4Si
3O
12Crystalline phase.Accompanying drawing 2 (a) is prepared eulytite bismuth silicate (Bi
4Si
3O
12) the crystalline pattern.
Embodiment 2, at first, behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder; Then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder (content be 99.99%) and fused silica powder put into agate breast body ball grinder ball milling 30min get admixtion at=1: 1; Admixtion is put into the high purity aluminium oxide crucible, and the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 920 ℃ and be incubated 12 hours with 10 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
Referring to accompanying drawing 1, be the higher Bi of purity at the prepared Bi crystal as can be seen
4Si
3O
12Crystalline phase.Accompanying drawing 2 (b) is prepared eulytite bismuth silicate (Bi
4Si
3O
12) crystal grinds the growth morphology of a certain direction.
Embodiment 3, at first, behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder; Then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder (content be 99.99%) and fused silica powder put into agate breast body ball grinder ball milling 40min get admixtion at=1: 1; Admixtion is put into the high purity aluminium oxide crucible, and the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 890 ℃ and be incubated 16 hours with 12 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
Embodiment 4, at first, behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder; Then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder (content be 99.99%) and fused silica powder put into agate breast body ball grinder ball milling 40min get admixtion at=1: 1; Admixtion is put into the high purity aluminium oxide crucible, and the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 920 ℃ and be incubated 18 hours with 11 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
Embodiment 5, at first, behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder; Then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder (content be 99.99%) and fused silica powder put into agate breast body ball grinder ball milling 50min get admixtion at=1: 1; Admixtion is put into the high purity aluminium oxide crucible, and the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 880 ℃ and be incubated 21 hours with 10 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
Embodiment 6, at first, behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder; Then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder (content be 99.99%) and fused silica powder put into agate breast body ball grinder ball milling 60min get admixtion at=1: 1; Admixtion is put into the high purity aluminium oxide crucible, and the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 910 ℃ and be incubated 24 hours with 12 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bismuth silicate (Bi
4Si
3O
12) crystal powder.
The present invention is a raw material with high-purity non-crystalline state silica glass, prepared Bi crystal purity height, and dephasign is few, and cost of material is cheap, and the source is abundant, and preparation technology is simple.Bi silicate crystals according to preparation method's preparation of the present invention can be used as the high quality raw material of producing high-quality transparent silicic acid bismuth single crystal.
Claims (1)
1. the preparation method of a bismuthiferous eulytite bi silicate crystals is characterized in that:
1) with behind the silica glass cleaning, drying, put into ball grinder ball milling to 300 order, make fused silica powder, then according to mol ratio Bi
2O
3: SiO
2Mix bismuthous oxide bismuth trioxide powder and fused silica powder put into agate breast body ball grinder ball milling 30～60min get admixtion at=1: 1;
2) admixtion is put into the high purity aluminium oxide crucible, the crucible that will be placed with admixtion is then put into retort furnace, burns till according to following process system: rise to 550 ℃ with 5 ℃/minute temperature rise rates from room temperature and be incubated 30 minutes down; Rise to 880～920 ℃ and be incubated 6～24 hours with 10～12 ℃/minute temperature rise rate from 550 ℃ again; Rapidly crucible is taken out from retort furnace then and put into mobile water, make sample be cooled to room temperature, take out the sample of shrend after cooling with 400 ℃/minute, last, the sample drying ball milling is promptly obtained bismuthiferous eulytite bi silicate crystals powder;
SiO in the described silica glass
2Content be 4～6N (99.99%～99.9999%);
The purity of described bismuthous oxide bismuth trioxide is 99.99%.
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|---|---|---|---|---|
| CN102351205B (en) * | 2011-07-06 | 2012-12-19 | 陕西科技大学 | Preparation method of scintillation bismuth silicate powder |
| CN102351204A (en) * | 2011-07-06 | 2012-02-15 | 陕西科技大学 | Method for preparing scintillation bismuth silicate powder by molten salt method |
| CN103643293B (en) * | 2013-12-25 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | A kind of Bismuth silicate scintillation crystal and its preparation method and application |
| CN106948006B (en) * | 2017-02-28 | 2019-04-16 | 上海应用技术大学 | A kind of High Light Output Bismuth silicate scintillation crystal and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072221A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院上海硅酸盐研究所 | The Bridgman-Stockbarge method for growing of bismuth silicate (BSO) monocrystalline |
| CN1821088A (en) * | 2006-03-09 | 2006-08-23 | 上海交通大学 | Process for preparing bismuth silicate nano powder and use |
| CN101157026A (en) * | 2007-11-08 | 2008-04-09 | 北京师范大学 | A preparation method of bismuth silicate powder photocatalyst |
| CN101229510A (en) * | 2008-01-31 | 2008-07-30 | 福州大学 | Synthesis and applications of silicate containing Bi |
-
2009
- 2009-11-10 CN CN2009102188989A patent/CN101709508B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072221A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院上海硅酸盐研究所 | The Bridgman-Stockbarge method for growing of bismuth silicate (BSO) monocrystalline |
| CN1821088A (en) * | 2006-03-09 | 2006-08-23 | 上海交通大学 | Process for preparing bismuth silicate nano powder and use |
| CN101157026A (en) * | 2007-11-08 | 2008-04-09 | 北京师范大学 | A preparation method of bismuth silicate powder photocatalyst |
| CN101229510A (en) * | 2008-01-31 | 2008-07-30 | 福州大学 | Synthesis and applications of silicate containing Bi |
Non-Patent Citations (1)
| Title |
|---|
| JP昭62-70296A 1987.03.31 |
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