CN101792180A - Preparation method of sillenite bismuth silicate microcrystal - Google Patents
Preparation method of sillenite bismuth silicate microcrystal Download PDFInfo
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- CN101792180A CN101792180A CN201010108167A CN201010108167A CN101792180A CN 101792180 A CN101792180 A CN 101792180A CN 201010108167 A CN201010108167 A CN 201010108167A CN 201010108167 A CN201010108167 A CN 201010108167A CN 101792180 A CN101792180 A CN 101792180A
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Abstract
The invention relates to a preparation method of a sillenite bismuth silicate microcrystal, which comprises the following steps: firstly, mixing and adding bismuth trioxide powder and quartz sand into a ball milling tank, adding ethanol for uniformly mixing, and then drying to obtain a mixture; then, adding the mixture into a crucible for melting; after melting, taking the crucible out of a muffle furnace, and putting the crucible outside the furnace for quickly cooling at room temperature; and when the surface of the molten glass in the crucible is supercooled and crystallized, putting the crucible into the muffle furnace again for heating, then cooling the crucible at room temperature, and repeatedly heating and cooling the crucible to obtain the bismuth silicate microcrystal. By adding raw materials at high temperature and using a process for quickly melting at high temperature, the invention avoids the influence of uneven components caused by volatilization of the bismuth trioxide at high temperature. The prepared bismuth silicate (Bi12SiO20) microcrystal has small size, high crystal purity, extremely few impurity phases, low cost of raw materials, wide sources of raw materials, lower synthesis temperature and simple preparation process, and is favorable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of bismuth silicate micro crystal, particularly a kind of preparation method of sillenite bismuth silicate microcrystal.
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).Phases such as the compound crystalline phase of finding in this system has 6: 1,1: 1 and 2: 3 have been 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.
Bismuth silicate (Bi
12SiO
20, being called for short BSO) and crystal is non-ferroelectric cube of semi-insulator of a kind of broad-band gap, high resistivity.Effects such as it has simultaneously that electric light, photoconduction, light are sold off, piezoelectricity, acousto-optic, optically-active and faraday's rotation are a kind of promising multifunctional light information materials.Utilize BSO crystalline electric light and photoconductive property, at room temperature just can realize multiple nonlinear optics conversion with low power laser.Usually the laser with wavelength X=514nm writes hologram, is that the He-Ne laser of 633nm is read with wavelength.Under an extra electric field, the BSO crystalline writes down and wipes energy and is equivalent to the high resolving power photocopy, and its time of response can reach 1～10ms, and hologram can be deposited 20～30h in the dark.As real-time body hologram recording material, the BSO crystal is one of a few photorefractive material that sensitivity is the highest, response speed is the fastest that is obtained at present.Thereby in technology such as optical information processing in real time and photometry calculation, be widely used.That incoherent/coherent light image conversion that these application comprise, optical storage, real-time interferometry, zoom and phase conjugate etc. are learned is multi-field, in addition, the detection that photo-sensor is used for electric substation's internal fault is also made with this material by Japan, has also developed the transmitter that can measure current/voltage simultaneously.
The research of BSO crystalline material is the history of existing two more than ten years so far.Initial it be used as a kind of piezoelectric and study.But in recent years, as a kind of important photorefractive material, the BSO crystal has caused various countries scientist's very big attention, annual nearly 60～80 pieces of paper publishings, research contents relate to the various optical dioptric devices that crystal growth, defective characterize, light is sold off all many-sides such as mechanism, performance and application, make with the BSO crystal at present and still are in the model phase run.Can expect, along with light being sold off the further understanding of low-light process and going deep into of applied research.The BSO optical dioptric device will enter the practical stage and become commercialized device, thereby plays a significant role in the message area in future.For adapting to the different requirements that various application propose the BSO crystal mass, researcher is to traditional BSO growing method---when crystal pulling method is updated, also trying to explore other growth method, as hydrothermal method, descent method etc.
Since the initiative work of Ballman in 1967, crystal pulling method as one of main method of BSO crystal growth, directly is subjected to people's generally attention.According to Bi
2O
3-SiO
2The phasor of system is worked as Bi
2O
3And SiO
2Mole ratio is 6: 1 o'clock, and system is 900 ℃ of left and right sides congruent meltings.To place the Pt crucible by the raw material that this stoichiometric(al) is mixed with, make the raw material fusing by radio-frequency induction heating and resistive heating, through sowing, inoculate, " necking down ", shouldering, etc. through, rapidly pull and cool off these a series of processes after, promptly finish a single crystal growing.Crystal diameter can be realized automatic control by weighting method or floating title method in the process of growth.This method technology is complicated, and influence factor is more.
Harris and Larkin etc. have reported the result of study with the Hydrothermal Growth BSO monocrystalline of seed crystal, once are used for the interior autoclave of experimental study scope of crystal growth before they adopt.Owing to contain the corrosive property (metal in the still wall can be reduced into bismuth oxide the Bi metal) of Bi compound solution, the whole growth experiment must be kept apart with autoclave, and for this reason, experiment is carried out in the Pt of sealing bushing pipe.Cutting the seed crystal that size is about 30 * 10 * 1.5mm from the BSO crystal of pulling growth, serves as to cultivate body with the BSO crystal block of the pulling growth of centimetre magnitude.4N NaOH solution is packed in the Pt bushing pipe as solvent (mineralizer), with the high-purity quartzy SiO of 5～15g
2To strengthen the composition of solubility and control solution, in the annular space of bushing pipe and autoclave, add 1.0NNaOH or 1.5M Na as additive
2SiO
3Pressure equilibrium solution.The nutrition district, bottom of autoclave remains on 390 ℃ of steady temperatures, and its seed crystal district, top remains on a lower steady temperature, and temperature stability is in thermograde about one 5 ℃, the experimentation to set up ± 0.1 ℃, pressure is at 422～844kg/cm
2In the scope, growth velocity is 0.1～0.3mm/ days, and growth cycle was generally 30～40 days, and after growth finished, system reduced to room temperature in the time more than 72 hours.
The hydrothermal growth technology has the crystalline ability in production large size and identical performance, and in case set up the growth inside condition, temperature control that only need be stable.Under the ideal growth conditions, crystalline quantity and size are cultivated amount, container size and the seed crystal limited in number of body.This method also can prevent the induct formation of phenomenon of some textural defect of often running into such as veil, bubble, precipitate and other strain in high-temperature fusant growth.But the BSO crystal with above-mentioned Hydrothermal Growth is colourless, and the yellow BSO crystalline of pulling growth absorbs shoulder and disappears fully in the BSO of hydrothermal growth crystal.Because BSO crystalline photorefractive effect is closely related with absorption heart concentration, colourless hydro-thermal BSO crystal will not have photorefractive effect.
Falling crucible method also claims vertical Bridgman method.Its growth apparatus is simple in structure, stable operation, low price, thereby is easy to realize suitability for industrialized production.Shanghai silicate this method is successfully applied to the suitability for industrialized production of oxide crystal (BGO, LBO etc.), and obtained remarkable economic efficiency.In recent years, Shanghai silicate first descent method is applied to the growth of photorefractive crystal BSO again and has obtained initial success.It is that the BSO melt is to the corrosion of Pt crucible under the high temperature that leftover problem to be solved is arranged in the BSO crystal descent method for growing technology at present, and this can cause Pt content increase in the melt and form Pt parcel or wire Pt scattering of light defective in crystal.
Wang 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 Bi1
2SiO
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, 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.CN100389071C 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 of Materials 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
12SiO
20) be a kind of superior performance, widely used material.Bibliographical information mostly around the preparation and the applied research of bi silicate crystals, do not report about preparation bismuth silicate monocrystalline by raw materials used correlative study at present.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, the high-quality sillenite bismuth silicate of a kind of preparation (Bi is provided
12SiO
20) preparation method of microcrystal.According to the sillenite bismuth silicate microcrystal 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, can be used as the high quality raw material and the high performance catalytic 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) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, and the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder got admixtion in 2 hours with the slurry insulation under 150 ℃ that obtains after 1～6 hour;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 900～950 ℃ for the first time, add remaining admixtion again behind insulation 10～30min, be warming up to 1050 ℃ with 20～30 ℃/minute, crucible cover upper cover insulation 1～6 hour was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 5～30min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind 10～60s crucible put into 930 ℃ retort furnace rapidly, insulation 10～30min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind 10～60s rapidly, insulation 10～30min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind 10～60s rapidly, insulation 10～30min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind 10～60s rapidly, insulation 10～30min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind 10～60s rapidly, behind insulation 1～24h, furnace cooling promptly gets bismuth silicate micro crystal.
The quartz sand of quartz sand of the present invention after overpickling, granularity are 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity.
The present invention adds raw material by high temperature, and the rapid melting process of high temperature has been avoided the influence of the uneven components that the volatilization of bismuthous oxide bismuth trioxide brings under the high temperature.Simultaneously, employing high temperature is put under the high temperature again and is cooled off rapidly after the insulation again after cooling off rapidly, so repeatedly the prepared bismuth silicate (Bi of intensification cooling
12SiO
20) microcrystal.Adopt the bigger condensate depression and the technology of high growth temperature, help bismuth silicate (Bi
12SiO
20) generation and the mass-producing of microcrystal shoot up.Prepared Bi (Bi
12SiO
20) crystallite dimension is little, the crystal purity height, dephasign is few, and cost of material is cheap, and the source is abundant, and synthesis temperature is lower, and preparation technology is simple, helps suitability for industrialized production.Prepared Bi (Bi
12SiO
20) crystal can be used as the preparation high-quality transparent silicic acid bismuth (Bi
12SiO
20) high quality raw material and the high performance catalytic material of monocrystalline.
Description of drawings
Fig. 1 is the sillenite bismuth silicate (Bi that makes according to preparation method of the present invention
12SiO
20) 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 sillenite bismuth silicate (Bi of embodiment 1,2 preparations
12SiO
20) photo of crystal under polarizing microscope.
Embodiment
Embodiment 1,1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder is incubated 2 hours with the slurry that obtains down in 150 ℃ after 1 hour and gets admixtion, the quartz sand of said quartz sand after overpickling, granularity is 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 900 ℃ for the first time, add remaining admixtion again behind the insulation 10min, be warming up to 1050 ℃ with 20 ℃/minute, crucible cover upper cover insulation 1 hour was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 20min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind the 15s crucible put into 930 ℃ retort furnace rapidly, insulation 10min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind the 15s rapidly, insulation 10min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind the 15s rapidly, insulation 10min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind the 15s rapidly, insulation 10min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind the 15s rapidly, behind the insulation 24h, furnace cooling promptly gets bismuth silicate micro crystal.By the Scherrer formula to the sillenite (Bi among Fig. 1
12SiO
20) the microcrystal size calculates prepared sillenite bismuth silicate (Bi
12SiO
20) size of microcrystal is 10～50nm.
Referring to accompanying drawing 1, be the higher sillenite bismuth silicate (Bi of purity at the prepared Bi crystal as can be seen
12SiO
20) the microcrystal crystalline phase.Accompanying drawing 2 (a) is prepared sillenite bismuth silicate (Bi
12SiO
20) surface topography of microcrystal under polarizing microscope.
Embodiment 2,1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder is incubated 2 hours with the slurry that obtains down in 150 ℃ after 3 hours and gets admixtion, the quartz sand of said quartz sand after overpickling, granularity is 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 950 ℃ for the first time, add remaining admixtion again behind the insulation 15min, be warming up to 1050 ℃ with 24 ℃/minute, crucible cover upper cover insulation 2 hours was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 7min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind the 40s crucible put into 930 ℃ retort furnace rapidly, insulation 20min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind the 40s rapidly, insulation 20min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind the 40s rapidly, insulation 20min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind the 40s rapidly, insulation 20min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind the 40s rapidly, behind the insulation 16h, furnace cooling promptly gets bismuth silicate micro crystal.
Referring to accompanying drawing 1, be the higher sillenite (Bi of purity at the prepared Bi crystal as can be seen
12SiO
20) the microcrystal crystalline phase.Accompanying drawing 2 (b) is prepared sillenite (Bi
12SiO
20) surface topography of microcrystal under polarizing microscope.
Embodiment 3,1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder is incubated 2 hours with the slurry that obtains down in 150 ℃ after 5 hours and gets admixtion, the quartz sand of said quartz sand after overpickling, granularity is 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 910 ℃ for the first time, add remaining admixtion again behind the insulation 30min, be warming up to 1050 ℃ with 30 ℃/minute, crucible cover upper cover insulation 5 hours was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 1min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind the 10s crucible put into 930 ℃ retort furnace rapidly, insulation 30min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind the 10s rapidly, insulation 30min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind the 10s rapidly, insulation 30min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind the 10s rapidly, insulation 30min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind the 10s rapidly, behind the insulation 20h, furnace cooling promptly gets bismuth silicate micro crystal.
Embodiment 4,1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder is incubated 2 hours with the slurry that obtains down in 150 ℃ after 2 hours and gets admixtion, the quartz sand of said quartz sand after overpickling, granularity is 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 930 ℃ for the first time, add remaining admixtion again behind the insulation 20min, be warming up to 1050 ℃ with 22 ℃/minute, crucible cover upper cover insulation 3 hours was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 30min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind the 60s crucible put into 930 ℃ retort furnace rapidly, insulation 15min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind the 60s rapidly, insulation 15min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind the 60s rapidly, insulation 15min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind the 60s rapidly, insulation 15min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind the 60s rapidly, behind the insulation 10h, furnace cooling promptly gets bismuth silicate micro crystal.
Embodiment 5,1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder is incubated 2 hours with the slurry that obtains down in 150 ℃ after 6 hours and gets admixtion, the quartz sand of said quartz sand after overpickling, granularity is 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 920 ℃ for the first time, add remaining admixtion again behind the insulation 25min, be warming up to 1050 ℃ with 28 ℃/minute, crucible cover upper cover insulation 6 hours was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 25min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind the 20s crucible put into 930 ℃ retort furnace rapidly, insulation 258min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind the 20s rapidly, insulation 25min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind the 20s rapidly, insulation 25min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind the 20s rapidly, insulation 25min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind the 20s rapidly, behind the insulation 1h, furnace cooling promptly gets bismuth silicate micro crystal.
Embodiment 6,1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder is incubated 2 hours with the slurry that obtains down in 150 ℃ after 4 hours and gets admixtion, the quartz sand of said quartz sand after overpickling, granularity is 300 orders, and it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 940 ℃ for the first time, add remaining admixtion again behind the insulation 22min, be warming up to 1050 ℃ with 26 ℃/minute, crucible cover upper cover insulation 4 hours was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 5min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind the 30s crucible put into 930 ℃ retort furnace rapidly, insulation 18min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind the 30s rapidly, insulation 18min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind the 30s rapidly, insulation 18min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind the 30s rapidly, insulation 18min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind the 30s rapidly, behind the insulation 6h, furnace cooling promptly gets bismuth silicate micro crystal.
The present invention adds raw material by high temperature, and the rapid melting process of high temperature has been avoided the influence of the uneven components that the volatilization of bismuthous oxide bismuth trioxide brings under the high temperature.Simultaneously, employing high temperature is put under the high temperature again and is cooled off rapidly after the insulation again after cooling off rapidly, so repeatedly the prepared bismuth silicate (Bi of intensification cooling
12SiO
20) microcrystal.Adopt the bigger condensate depression and the technology of high growth temperature, help bismuth silicate (Bi
12SiO
20) generation and the mass-producing of microcrystal shoot up.Prepared Bi (Bi
12SiO
20) crystallite dimension is little, the crystal purity height, dephasign is few, and cost of material is cheap, and the source is abundant, and synthesis temperature is lower, and preparation technology is simple, helps suitability for industrialized production.Prepared Bi (Bi
12SiO
20) crystal can be used as the preparation high-quality transparent silicic acid bismuth (Bi
12SiO
20) high quality raw material and the high performance catalytic material of monocrystalline.
Claims (2)
1. the preparation method of a sillenite bismuth silicate microcrystal is characterized in that:
1) at first, bismuthous oxide bismuth trioxide and quartz sand are pressed Bi
2O
3: SiO
2=6: 1 mol ratio is put into agate breast body ball grinder and is got compound, and the ethanol ball milling that adds mixture quality 40% again in agate breast body ball grinder got admixtion in 2 hours with the slurry insulation under 150 ℃ that obtains after 1～6 hour;
2) then, retort furnace high purity aluminium oxide crucible with cover is put in 30% adding of batch weight ratio in advance, charge temperature is 900～950 ℃ for the first time, add remaining admixtion again behind insulation 10～30min, be warming up to 1050 ℃ with 20～30 ℃/minute, crucible cover upper cover insulation 1～6 hour was that admixtion stirs 1min every 1 hour to the fused glass metal in the insulating process;
3) after insulation finishes, crucible cover is removed, from retort furnace, take out crucible, put into the outer room temperature of stove and cool off, treat in the crucible that fused glass metal surface crosses when beginning crystallization after cold, crucible is put into 950 ℃ retort furnace rapidly, insulation 5～30min; And then crucible taken out from retort furnace put into outside the stove room temperature and cool off, behind 10～60s crucible put into 930 ℃ retort furnace rapidly, insulation 10～30min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 900 ℃ retort furnace behind 10～60s rapidly, insulation 10～30min; Then crucible is taken out from retort furnace again and put into room temperature and cool off, again crucible is put into 950 ℃ retort furnace behind 10～60s rapidly, insulation 10～30min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible is put into 880 ℃ retort furnace behind 10～60s rapidly, insulation 10～30min; And then crucible taken out from retort furnace put into room temperature and cool off, again crucible being put into 850 ℃ retort furnace behind 10～60s rapidly, behind insulation 1～24h, furnace cooling promptly gets bismuth silicate micro crystal.
2. the preparation method of sillenite bismuth silicate microcrystal according to claim 1, it is characterized in that: the quartz sand of said quartz sand after overpickling, granularity are 300 orders, it is the pure bismuthous oxide bismuth trioxides of 200 goal analysis that bismuthous oxide bismuth trioxide adopts granularity.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105129850A (en) * | 2015-08-27 | 2015-12-09 | 安徽理工大学 | Sillenite phase Bi25VO40 cube and synthetic method thereof |
| CN112342622A (en) * | 2020-09-24 | 2021-02-09 | 彩虹集团（邵阳）特种玻璃有限公司 | High-purity single-phase Bi12SiO20Method for producing polycrystal |
-
2010
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105129850A (en) * | 2015-08-27 | 2015-12-09 | 安徽理工大学 | Sillenite phase Bi25VO40 cube and synthetic method thereof |
| CN112342622A (en) * | 2020-09-24 | 2021-02-09 | 彩虹集团（邵阳）特种玻璃有限公司 | High-purity single-phase Bi12SiO20Method for producing polycrystal |
| CN112342622B (en) * | 2020-09-24 | 2022-05-17 | 彩虹集团（邵阳）特种玻璃有限公司 | High-purity single-phase Bi12SiO20Method for producing polycrystal |
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