CN101318813B - Method for manufacturing monoclinic-phase celsian ceramics material - Google Patents
Method for manufacturing monoclinic-phase celsian ceramics material Download PDFInfo
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- CN101318813B CN101318813B CN200810039797A CN200810039797A CN101318813B CN 101318813 B CN101318813 B CN 101318813B CN 200810039797 A CN200810039797 A CN 200810039797A CN 200810039797 A CN200810039797 A CN 200810039797A CN 101318813 B CN101318813 B CN 101318813B
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Abstract
The invention provides a method for preparing a monoclinic phase barium feldspar ceramic material, belonging to the fluorescent material and preparation field. In the method, barium carbonate, caustic baryta or baryta, hydrafil and silicon dioxide are taken as raw materials and matched according to the chemical formula of BaAl2Si2O8 to generate a hydro-thermal precursor by the hydro-thermal reaction, and then the hydro-thermal precursor is calcined in solid phase. The method has the advantages of energy conservation, economy, simplicity and convenience, single product, and superfine powder, etc. The material can be taken as a high temperature structural ceramics and electronic ceramics to meet the requirement of the fields such as space flight, chemical engineering and energy. The material prepared by the method can be also taken as a good luminescent material applied to the fields such as illumination and display.
Description
Technical field
The present invention relates to monocline phase celsian ceramics preparation methods, belong to fluorescent material and preparation field.
Background technology
Advanced information society, the purposes of high temperature fine pottery is quite extensive, exploitation, preparation, suitability for industrialized production high temperature fine stupalith is a focus international and that home government, enterprise and learned society pay close attention to always.It is little that the celsian-felspar of monocline phase has a thermal expansivity; Fusing point is high; Chemicalstability is good, carries out fiber easily and increases advantages such as a piece of wood serving as a brake to halt a carriage reinforcement, gets into practical the popularization as excellent high-temperature 26S Proteasome Structure and Function matrix of materials at present; Be used for high temperature multilayer ceramic matrix, piezoelectric, electrician, electronics and chemical fields such as ceramic fiber is toughened and strengthened, high-temperature catalytic agent carrier.Korea S's scholar's research achievement in 2006 proves that further monocline phase celsian-felspar is the rare earth ion of matrix or the using value that doped transition metal ions fluorescent material has potential illumination, demonstration aspect.
Celsian-felspar (the BaAl of same chemical constitution formula
2Si
2O
8) there are different phases such as six sides, monocline, four directions, up till now, still there is deficiency in the synthetic monocline phase celsian-felspar method of tradition.The traditional industry working method utilizes carbonate, oxide compound etc. as raw material; Directly solid phase synthesis obtains is six sides phase or with six side's phases of a small amount of monocline phase, must these six sides phase presomas be calcined on 1400 ℃ or higher temperature for a long time and could obtain pure monocline material.This two step solid phase synthesis techniques need long heat time heating time; The production equipment that needs the above high temperature of ability 1500 degree; Keep long-time high temperature in addition and need import great amount of heat; And temperature is high more; The energy by the heat radiation waste is many more, and this huge energy resource consumption does not obviously meet the requirement of the extensive energy saving economy of advocating at present with waste.
The U.S. 1991 and 2000 to utilizing aluminum trifluoride to carry out patent protection as the solid phase method and the sol-gel method in aluminium source; These two patents also SEPARATE APPLICATION the patent protection of state such as European, still, utilize aluminum trifluoride as the aluminium source; Although drop to 900 ℃ to calcining temperature; But introduced severe corrosive, supervirulent fluorion has been run counter to the basic demand that fine ceramics is kept the safety in production.And sol-gel method building-up process cost is high, and its calcining temperature also just is reduced to 1200 ℃, and industrial applications still remains to be improved.
American-European countries developed IX-solid phase calcination two-step approach again in 2005, and its step is to utilize the barium ion in the sodium based molecular sieve and the aqueous solution to carry out IX, and then high-temperature calcination obtains product.This method calcining temperature also can drop to 1200 ℃; But the IX cycle in the sodium based molecular sieve and the aqueous solution is long; The viewpoint of being particular about efficient with industriallization is incompatible, comprises impurity such as the thorough and not remaining sodium of IX, lithium in addition in the product, is difficult to obtain high-purity celsian-felspar product.
After the development of superfine powder makes people recognize that the material grains size reduces; Performances such as agglomerating ceramic machinery intensity are with rapid enhancement; Small particle size powder (diameter is at micron, nanoscale) is one of effective means of promoting ceramic material property; Therefore exploitation can directly obtain the new ceramics preparation method of ultrafine powder granule product, can further reduce the cost of product secondary processing, and the performance of sintetics is provided.
Although country such as American-European-Japanese has carried out patent protection with regard to the preparation of monocline phase celsian-felspar, China up to the present independent intellectual property right of this respect is still blank.
Summary of the invention
The present invention provides a kind of monocline phase celsian ceramics preparation methods, and related celsian-felspar chemical formula is: BaAl
2Si
2O
8, thing is the monocline phase mutually.Than known preparation method, the present invention has following meliority, and the preparation method who the present invention relates to is raw materials used cheap and easy to get; Production process is based on the synthetic and solid phase calcination process of very sophisticated hydro-thermal in the existing industrial production; The solid phase calcination temperature is compared more than 1400 ℃ with traditional synthetic, and suitable calcining temperature is 1200 ℃, and is identical with present international most advanced level; Product is ultra-fine powder; Thing phase purity is high; Sintering is used for harsh external environment such as thermal shocking, acid and alkali corrosion as high temperature ceramic material easily; Satisfy the needs of industries such as aerospace, chemical industry, the energy; Also can be used as good luminescent material matrix and carry out light emitting ionic (such as rare earth, transition metal ion etc.) doping, obtain high light efficiency fluorescent material, be used for the fields such as image display of lighting source, optical storage, x-ray medical imaging, display instrument equipment.The preparation route that the present invention proposes is convenient to suitability for industrialized production, and meets energy-conservation, economy, environmental protection and the follow-up use leading zero of product treatment requirement, has the potential economic worth.
The industrial chemicals that the present invention adopts comprises barium carbonate, hydrated barta or barium oxide, white lake and silicon-dioxide.The purity of industrial chemicals can require to select according to product purity, and technical pure rank or above all can.
The hydro-thermal that the present invention relates to-concrete synthesis step of solid phase two-step approach is following:
One, hydro-thermal reaction is obtained the hydro-thermal presoma:
(1) with barium carbonate, hydrated barta or barium oxide, white lake and silicon-dioxide are that raw material is by chemical formula BaAl
2Si
2O
8Take by weighing, add water and mix;
(2) above-mentioned mixed solution is transferred in the autoclave;
(3) reaction kettle is sealed under 150～300 ℃ and reacts completely desciccate.
The above-mentioned reaction times is according to the control of raw material quantity, to guarantee that reaching abundant reaction gets final product.
Two, solid phase calcination obtains monocline celsian-felspar finished product
(1) above-mentioned steps (3) product is put into crucible and is reacted completely cooling at 850～1300 ℃.
The above-mentioned reaction times is according to the control of raw material quantity, to guarantee that reaching abundant reaction gets final product.
The general condensed summary of the hydro-thermal that the present invention relates to-solid phase two-step approach is following:
(1) hydro-thermal synthesis temperature scope is 200-300 ℃, and hydrothermal reaction condition is gentle, to production unit withstand voltage, corrosion-resistant require low; The hydro-thermal constant temperature time can from several hours to several days, can not change the chemical constitution and the phase of final calcinate as required; But can influence the dispersiveness and the particle size of product; It influences rule is the prolongation along with the hydro-thermal constant temperature time, and dispersiveness is good more, and granularity is more little.
(2) calcination temperature range is 850-1300 ℃, still is six sides or a small amount of monocline thing just occurs and compare, the hydro-thermal presoma that utilizes the present invention's technology to obtain at 1200 ℃ with traditional solid phase synthesis; Calcining just can obtain monocline thing phase under 900 ℃, because the general character of industrial solid phase calcination, when temperature is lower; Internal-external temperature difference is little, and heat transfer rate is slow, and solid state reaction is carried out slowly; Synthesizing needs the time long, time-consuming just more when raw material ratio is more; In addition, temperature is too high, can accelerate solid-phase reaction velocity, and calcination time can shorten, but has but improved production cost, causes energy dissipation, and too high calcining temperature there is no need.Therefore, can require to carry out the selection of thermostat temperature and the adjustment of constant temperature time according to raw material quantity and PT in the actual production.
(3) too much possibly cause at the raw material consumption and mix inhomogeneous or production unit need under lower temperature, produce the time; Take repeatedly calcining method to enhance productivity; Repeatedly method for calcinating is following: with a preceding incinerating product stirring and evenly mixing, calcine again.Because product powder exquisiteness is not lumpd, therefore easy mixing, general 2-3 calcining gets final product.
Description of drawings
Fig. 1: 900 ℃ of incomplete product powdery diffractometrys of calcination reaction of hydro-thermal presoma spectrogram shows that product mainly is the celsian-felspar of six side's phases, but considerable monocline phase (using part that square frame the irises out spectrogram as the monocline phase) occurred.
Fig. 2: 1200 ℃ of calcination reactions of hydro-thermal presoma are product powdery diffractometry spectrogram completely, shows that product is pure monocline celsian-felspar.
Embodiment
Through embodiment the present invention is described further below, but is not limited only to following embodiment.
Embodiment 1
Take by weighing analytically pure barium carbonate (BaCO respectively by the product chemical constitution formula
3), white lake (Al (OH)
3), silicon-dioxide (SiO
2) 0.987,0.780,0.601 gram, magnetic stirred about 20 minutes in deionized water, and the gained turbid solution directly is transferred in the interior cover of tetrafluoroethylene of stainless steel autoclave, and adding water is 3/4 of interior cover volume to TV; Subsequently the reaction kettle sealing is put in baking oven, is raised to 260 ℃ by room temperature, constant temperature carried out hydro-thermal reaction in 8 hours, turned off the baking oven power supply then, automatically cool to room temperature.Reaction kettle uncapped pours out product, place clarification after, outwell supernatant liquid to shorten time of drying, in loft drier, promptly get hydro-thermal presoma product after 70 ℃ of dryings of temperature control then.
Gained hydro-thermal presoma is put into the alumina crucible of 30x30 specification, then puts into retort furnace, is raised to 1200 ℃ from room temperature, and constant temperature 8 hours naturally cools to room temperature subsequently, promptly gets final product monocline phase celsian-felspar.
Embodiment 2
Take by weighing analytically pure hydrated barta (Ba (OH) respectively by the product chemical constitution formula
2), white lake (Al (OH)
3), silicon-dioxide (SiO
2) 0.857,0.780,0.601 gram, magnetic stirred about 20 minutes in deionized water, and the gained turbid solution directly is transferred in the interior cover of tetrafluoroethylene of stainless steel autoclave, and adding water is 3/4 of interior cover volume to TV; Subsequently the reaction kettle sealing is put in baking oven, is raised to 260 ℃ by room temperature, constant temperature 8 hours is turned off the baking oven power supply then, automatically cool to room temperature.Reaction kettle uncapped pours out product, place clarification after, outwell supernatant liquid to shorten time of drying, in loft drier, promptly get hydro-thermal presoma product after 70 ℃ of dryings of temperature control then.
Gained hydro-thermal presoma is put into the alumina crucible of 30x30 specification, then puts into retort furnace, is raised to 900 ℃ from room temperature; Constant temperature 6 hours naturally cools to room temperature subsequently, stirs powder more again; Secondary clacining, 900 ℃ of constant temperature promptly got final product monocline phase celsian-felspar in 6 hours.
Embodiment 3
Take by weighing analytically pure barium oxide (BaO), white lake (Al (OH) respectively by the product chemical constitution formula
3), silicon-dioxide (SiO
2) 0.767,0.780,0.601 gram, magnetic stirred about 20 minutes in deionized water, and the gained turbid solution directly is transferred in the interior cover of tetrafluoroethylene of stainless steel autoclave, and adding water is 3/4 of interior cover volume to TV; Subsequently the reaction kettle sealing is put in baking oven, is raised to 230 ℃ by room temperature, constant temperature 8 hours is turned off the baking oven power supply then, automatically cool to room temperature.Reaction kettle uncapped pours out product, place clarification after, outwell supernatant liquid to shorten time of drying, in loft drier, promptly get hydro-thermal presoma product after 70 ℃ of dryings of temperature control then.
Gained hydro-thermal presoma is put into the alumina crucible of 30x30 specification, then puts into retort furnace, is raised to 1200 ℃ from room temperature, and constant temperature 8 hours naturally cools to room temperature subsequently, promptly gets final product monocline phase celsian-felspar.
Claims (3)
1. monocline phase celsian ceramics preparation methods is characterized in that with barium carbonate, hydrated barta or barium oxide, and white lake and silicon-dioxide are that raw material is by chemical formula BaAl
2Si
2O
8Proportioning is obtained the hydro-thermal presoma with hydro-thermal reaction earlier and is carried out solid phase calcination again;
Described hydro-thermal reaction comprises the steps:
(1) raw material adds water and mixes and be transferred in the autoclave;
(2) reaction kettle is sealed under 150～300 ℃ and reacts completely desciccate;
Said solid phase calcination condition is that calcination temperature is 850～1300 ℃.
2. by the described monocline phase of claim 1 celsian ceramics preparation methods, the time that it is characterized in that said hydro-thermal reaction is according to the control of raw material quantity, to guarantee to reach abundant reaction.
3. by the described monocline phase of claim 1 celsian ceramics preparation methods, the time that it is characterized in that said solid phase calcination is according to the control of raw material quantity, to guarantee to reach abundant reaction.
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|---|---|---|---|
| CN200810039797A CN101318813B (en) | 2008-06-30 | 2008-06-30 | Method for manufacturing monoclinic-phase celsian ceramics material |
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|---|---|---|---|
| CN200810039797A CN101318813B (en) | 2008-06-30 | 2008-06-30 | Method for manufacturing monoclinic-phase celsian ceramics material |
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| CN101318813A CN101318813A (en) | 2008-12-10 |
| CN101318813B true CN101318813B (en) | 2012-10-03 |
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| CN115286374A (en) * | 2022-08-10 | 2022-11-04 | 武汉科技大学 | Monoclinic celsian ceramic material based on solid-phase synthesis method and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041400A (en) * | 1990-09-13 | 1991-08-20 | The United States Of America As Represented By The Secretary Of The Navy | Low temperature synthesis of high purity monoclinic celsian |
| US5695725A (en) * | 1989-07-18 | 1997-12-09 | Talmy; Inna G. | Method of preparing monoclinic BaO.A12 O3.2SiO2 |
| US6039929A (en) * | 1997-12-15 | 2000-03-21 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of monoclinic celsian |
-
2008
- 2008-06-30 CN CN200810039797A patent/CN101318813B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5695725A (en) * | 1989-07-18 | 1997-12-09 | Talmy; Inna G. | Method of preparing monoclinic BaO.A12 O3.2SiO2 |
| US5041400A (en) * | 1990-09-13 | 1991-08-20 | The United States Of America As Represented By The Secretary Of The Navy | Low temperature synthesis of high purity monoclinic celsian |
| US6039929A (en) * | 1997-12-15 | 2000-03-21 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of monoclinic celsian |
Non-Patent Citations (1)
| Title |
|---|
| B. Hoghooghi et al.Synthesis of celsian ceramics from zeolite precursors.《Journal of Non-Crystalline Solids》.1994,第170卷303-307. * |
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