CN100532326C - Process for preparing tungstate nano film - Google Patents
Process for preparing tungstate nano film Download PDFInfo
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- CN100532326C CN100532326C CNB2005100266326A CN200510026632A CN100532326C CN 100532326 C CN100532326 C CN 100532326C CN B2005100266326 A CNB2005100266326 A CN B2005100266326A CN 200510026632 A CN200510026632 A CN 200510026632A CN 100532326 C CN100532326 C CN 100532326C
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Abstract
A process for preparing the tungstate nanofilm includes such steps as preparing the solutions of metal salt and tungsten source, sequential adding cyclohexane and tween-80, stirring, adding pentanol, stirring, quickly mixing both together, stirring, laying aside for 1 2hr, adding acetone for elemulsifying, centrifugal separation of deposit, washing deposit by absolute alcohol, acetone and distilled water sequentially, storing in absolute alcohol, removing supernatant, stirring, adding collodion, stirring, immersing glass substrate in it, pulling it up at 35 mm/min, drying in air, putting it in muffle furnace, holding temp at 200 deg.C for 30 min and than at 500 deg.C for /hr, and annealing.
Description
Technical field
The present invention relates to a kind of preparation method of tungstate nano film.Specifically being to adopt reverse micelle method and dipping-lift technology, is that dispersion agent and membrane-forming agent controls under hot conditions and synthesized the method for preparing tungstate nano film with the pyroxylin (e) cement.
Background technology
In recent years, the tungstate nano material since its unique photoelectric properties, structural performance have broad application prospects in industries such as optics, electronics, biology, coating, medicine, thereby caused people's attention, started the extensive studies upsurge.Many scientific researches confirm that when the normality material was machined into extremely small yardstick, very significant variation also correspondingly took place for its optics, calorifics, electricity, magnetics, mechanics and even chemical property.Because its inherent is small particle size and lower transverse scattering etc. more, the inorganic light-emitting thin-film material is compared aspect performances such as having excellent more light, electricity, magnetic, catalysis with its powder body material, can be applied at aspects such as solid-state laser, fiber optics, light-emitting flash body, accelerators.Wherein, along with the requirement of photoelectric device microminiaturization, the tungstate nano film material causes people's extensive concern day by day in the research application facet of whole novel material.Yet up to the present, the preparation method of tungstate nano film mainly contains sol-gel method, solid state reaction, sputtering method, hydro-thermal-solvent thermal synthesis method and electrochemical process.All there is the cost height in various degree in above-mentioned reaction method, and generation toxic gas, product pattern are difficult to problems such as control.And the preparation of tungstate nano film can only be a spot of as research, can not satisfy the photoelectric device demand of producing.Therefore, the scale production tungstate nano film is significant.Reverse micelle method demonstrates its unique glamour owing to stablizing particulate and control size of particles from microcosmic, can carry out scale production.So far do not see the report for preparing tungstate nano film with the reversed phase micelle system as yet, and in numerous preparation methods of nano thin-film, still number is first to prepare nano thin-film with pyroxylin (e) cement as dispersion agent and membrane-forming agent.
Summary of the invention
The objective of the invention is to disclose a kind of preparation method of tungstate nano film, with pattern, the easy control of structure of the film of this method preparation, purity height, it is convenient to handle, and is easy to industrialization.
Purpose of the present invention is achieved by the following scheme.Through studying discovery for a long period of time, the reversed phase micelle system is as a kind of sophisticated nanoparticle preparation method, compare with other wet chemical methods such as sol-gel method, coprecipitation methods, it has, and raw material is cheap, easy to prepare, reaction conditions is gentle, do not need characteristics such as special conditions such as High Temperature High Pressure, has been widely used in fields such as waste water control, extracting and separating, material preparation and chemosynthesis.The present invention utilizes the reversed phase micelle system, selects metal-salt and tungsten source prepared in reaction to go out the tungstate nano particle, and employing floods-and the technology of lifting prepares tungstate nano film.This method is difficult to obtain the nano thin-film of high compaction under normal temperature and pressure conditions, but can realize under the adding condition of pyroxylin (e) cement.Wherein, pyroxylin (e) cement has been taken on the role of the membrane-forming agent in the film process again both as dispersion agent.In this reaction system, can regulate and control product size, crystal structure degree by the control high temperature sintering time, the high temperature sintering temperature changes the pattern of product.
Concrete technology is as follows:
The first step: take by weighing the tungsten source of metal-salt and the 0.020mol of 0.020mol, then it is dissolved in metal-salt and the tungsten source solution of making concentration 0.4mol/L in the 50mL distilled water respectively.Metal-salt is oxymuriate or soluble salts such as nitrate or acetate, and there are sodium wolframate or potassium wolframate or wolframic acid in the tungsten source.
Second step: the metal salt solution of the 1mL 0.4mol/L that 28mL hexanaphthene, 3mL tween-80 and the first step are made adds in the Erlenmeyer flask successively.Rotating speed with 3000rpm fully stirs, and adds the 1mL amylalcohol again, and stir about 15 minutes to reversed phase micelle solution clarification makes metal-salt micellar solution.Replace metal salt solution with the prepared tungsten of the first step source solution, adopt identical method to obtain tungsten source micellar solution.Then two kinds of prepared micellar solutions are mixed rapidly, and stirring mixed it in 5 minutes under room temperature.Behind the question response 12 hours, add the acetone breakdown of emulsion.Centrifugal with whizzer with the rotating speed of 200rpm, supernatant liquid glue head dropper sucking-off.
The 3rd step: the precipitated product that centrifugation is obtained cleans (each is three times) with dehydrated alcohol, acetone, distilled water successively, obtain raw material of the present invention, at last raw material is kept in the dehydrated alcohol after stirring 30 minutes with the rotating speed of 3000rpm under the room temperature, add the stirring of 2mL pyroxylin (e) cement and it was mixed in 1 hour, gained is Coating Materials of the present invention.
The 4th step: with the sheet glass of standard as film plating substrate.Before the use, adopted concentrated nitric acid, acetone and ethanol supersound process respectively 20 minutes, clean with distilled water flushing again, dry standby.
The 5th step: adopt to flood-technology of lifting prepares nano thin-film.The 4th sheet glass that clean up of step is immersed in the prepared Coating Materials of the 3rd step, and control pull rate is 35mm/min, and placement 20 minutes under room temperature, makes it air-dry.Be placed on then in the retort furnace, in 200 ℃ the insulation 30 minutes after, be heated to 500 ℃ of constant temperature 1h (hour) after annealing.Reaction is closed retort furnace after finishing, and makes it slowly reduce to room temperature.Promptly obtain product of the present invention.
Use X-ray powder diffraction (XRD) and scanning electronic microscope (SEM) that the structure and the pattern of product are characterized respectively, XRD result shows product pure (consistent with the JCPDS card), SEM shows that particle diameter all in the 30-300 nanometer, is tungstate nano film of the present invention.
The present invention has the following advantages:
1. because the present invention adopts reverse micelle method, select metal-salt and tungsten source prepared in reaction to go out the tungstate nano particle, therefore answer the water oil ratio in the strict control reaction process, to obtain the nanoparticle of uniform particle diameter, pattern rule.This method is simple and reaction conditions is gentle.
2. because raw material used in the present invention is the prepared nanoparticle of reversed phase micelle system, its viscosity to glass substrate is poor, under normal temperature and pressure conditions, be difficult to obtain the nano thin-film of high compaction, but as the membrane-forming agent in dispersion agent and the film process, can under normal temperature and pressure conditions, obtain the high nano thin-film of density with pyroxylin (e) cement.
Since the present invention in preparation process, the product particle diameter is increased or reduce by increasing or reduce sintering time, can obtain the product of different-shape simultaneously by the control sintering temperature: peanut shape nanoparticle, nanometer rod etc., therefore with pattern, the easy control of structure of the film of the present invention's preparation, the purity height, it is convenient to handle, and is easy to industrialization.
4. technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is easily controlled, and is with low cost, and product pattern, size are easily controlled, and purity height, better crystallinity degree and product are handled convenient succinct, are suitable for large-scale commercial production.Whole process of production does not have any pollution simultaneously, meets the Sustainable development requirement.
5. the product of the present invention's preparation has performances such as good light, electricity: emission peak blue shift, fluorescence strengthen.
Description of drawings
Fig. 1 is the shape appearance figure that the scanning electronic microscope (SEM) of the product of embodiments of the invention 1 obtains
Fig. 2 is the structure iron that the X-ray powder diffraction (XRD) of the product of embodiments of the invention 1 obtains
Fig. 3 is the infrared absorpting light spectra of the product of embodiments of the invention 1
Fig. 4 is the fluorescence emission spectrogram of the product of embodiments of the invention 1
Embodiment
Embodiment 1:
The first step takes by weighing 0.020mol plumbic acetate (analytical pure), and the tungsten source is 0.020mol sodium wolframate (analytical pure).Respectively it is dissolved in the solution that is made into two kinds of 0.4mol/L in the 50mL distilled water.
Second step: the 1mL 0.4mol/L metal salt solution that 28mL hexanaphthene, 3mL tween-80 and the first step are made adds in the Erlenmeyer flask successively.Rotating speed with 3000rpm fully stirs, and adds the 1mL amylalcohol again, and stir about 15 minutes to reversed phase micelle solution clarification makes metal-salt micellar solution.Replace metal salt solution with the prepared tungsten of the first step source solution, adopt identical method to obtain tungsten source micellar solution.Then two kinds of prepared micellar solutions are mixed rapidly, and stirring mixed it in 5 minutes under room temperature.Behind the question response 12 hours, add the acetone breakdown of emulsion.Centrifugal with whizzer with the rotating speed of 200rpm, supernatant liquid glue head dropper sucking-off.
The 3rd step: the precipitated product that centrifugation is obtained cleans (each is three times) with dehydrated alcohol, acetone, distilled water successively, obtain raw material of the present invention, at last product is kept in the dehydrated alcohol after stirring 30 minutes with the rotating speed of 3000rpm under the room temperature, add the 2mL pyroxylin (e) cement as dispersion agent and membrane-forming agent, stir and it was mixed in 1 hour, make Coating Materials of the present invention.
The 4th step: with the sheet glass of standard as film plating substrate.Before the use, adopted concentrated nitric acid, acetone and ethanol supersound process respectively 20 minutes, clean with distilled water flushing again, dry standby.
The 5th step: adopt to flood-technology of lifting prepares nano thin-film.The sheet glass that the 4th step was cleaned up immerses in the Coating Materials of the 3rd step preparation, and the control pull rate is 35mm/min, and places 20 minutes under room temperature, makes it air-dry.Be placed on then in the retort furnace, after 30 minutes, be heated to 1 hour after annealing of 500 ℃ of constant temperature in 200 ℃ of insulations.Reaction is closed retort furnace after finishing, and makes it slowly reduce to room temperature.The scanning electronic microscope of product (SEM) observations shows PbWO
4Nanoparticle is evenly distributed on the film, and the compactness height of film, and it is shaped as peanut shape, is about 300nm, and diameter is 180nm (seeing accompanying drawing 1).Results of IR has been verified PbWO
4The existence of nanoparticle on film.From X-ray powder diffraction figure (seeing accompanying drawing 2) as can be known, this PbWO
4Nano thin-film is the stolzite of tetragonal system, and degree of crystallinity is fine, and purity is very high.Fluorescent spectroscopy is the result show, the emission maximum band of product is compared with the powder plumbous tungstate, occurs " blue shift ", show tangible quantum size effect, and product has good photoluminescence performance.
Embodiment 2:
The comparative example that does not add pyroxylin (e) cement.Other conditions and step and embodiment 1 are identical, and the product that obtains is peanut shape PbWO
4Nano thin-film.The scanning electronic microscope of product (SEM) observations shows prepared PbWO
4Nano thin-film disperses very inhomogeneous, and density is low, and it is shaped as peanut shape, is about 300nm, and diameter is 180nm.This PbWO
4Nano thin-film is the stolzite of tetragonal system, and its luminescent properties obviously is inferior to PbWO
4Nano thin-film.
Embodiment 3:
Replace the 0.020mol plumbic acetate with the 0.020mol barium acetate, other conditions and step and embodiment 1 are identical, and the product that obtains is the bar-shaped barium tungstate nanometer film of high compaction, and the nanometer rod diameter is 50nm, is about 180nm.And length, the thickness of rod are more even.This rod-like nano film is the stolzite of tetragonal system, the product purity height, and degree of crystallinity and optical property are good.
Embodiment 4:
The Comparative Examples that does not add pyroxylin (e) cement.Other conditions and step and embodiment 4 are identical, and the product that obtains is bar-shaped barium tungstate nanometer film.The scanning electronic microscope of product (SEM) observations shows prepared BaWO
4The nano thin-film density is low, and its size, shape and crystallographic system are identical with embodiment 4.The fluorescence spectrum result shows that its luminescent properties is than BaWO
4Nano thin-film is poor.
Claims (1)
1. method for preparing tungstate nano film is characterized in that:
The first step: respectively take by weighing earlier metal-salt and the tungsten source of 0.020mol, respectively it is dissolved in the solution of making 0.4mol/L in the 50mL distilled water then; Metal-salt is oxymuriate or nitrate or acetate; The tungsten source is sodium wolframate or potassium wolframate or wolframic acid;
Second step: the metal salt solution of the 1mL0.4mol/L that 28mL hexanaphthene, 3mL tween-80 and the first step are made adds in the Erlenmeyer flask successively; Rotating speed with 3000rpm fully stirs, and adds the 1mL amylalcohol again, and stir about 15 minutes to reversed phase micelle solution clarification makes metal-salt micellar solution; Replace metal salt solution with the prepared tungsten of the first step source solution, adopt identical method to obtain tungsten source micellar solution; Then two kinds of prepared micellar solutions are mixed rapidly, and stirring mixed it in 5 minutes under room temperature; Behind the question response 12 hours, add the acetone breakdown of emulsion; Centrifugal with whizzer with the rotating speed of 200rpm, supernatant liquid glue head dropper sucking-off;
The 3rd step: the precipitated product that centrifugation is obtained cleans each three times with dehydrated alcohol, acetone, distilled water successively, obtain raw material, at last raw material is kept in the dehydrated alcohol after stirring 30 minutes with the rotating speed of 3000rpm under the room temperature as product, add the stirring of 2mL pyroxylin (e) cement and it was mixed in 1 hour, gained is Coating Materials;
The 4th step: as film plating substrate, before the use, adopted concentrated nitric acid, acetone and ethanol supersound process respectively 20 minutes with the sheet glass of standard, clean with distilled water flushing again, dry standby;
The 5th step: adopt dipping one technology of lifting to prepare nano thin-film: the sheet glass that the 4th step was cleaned up immerses in the prepared Coating Materials of the 3rd step, and control pull rate is 35mm/min, and placement 20 minutes under room temperature, makes it air-dry; Be placed on then in the retort furnace, after 30 minutes, be heated to 1 hour after annealing of 500 ℃ of constant temperature in 200 ℃ of insulations; Reaction is closed retort furnace after finishing, and makes it slowly reduce to room temperature; Promptly obtain tungstate nano film.
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| CN104891572B (en) * | 2015-05-19 | 2017-01-18 | 江苏大学 | A micro-nano potassium yttrium tungstate film and a preparing method thereof |
| CN108407171B (en) * | 2018-01-19 | 2019-12-27 | 同济大学 | Method for preparing plastic scintillator film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1468934A (en) * | 2003-06-16 | 2004-01-21 | 中国科学院长春应用化学研究所 | Prepn of luminous tungstate film |
| CN1493395A (en) * | 2002-10-28 | 2004-05-05 | ���Ĵ���ѧ | Nano-titanium dioxide photocatalyst film, preparation and its application |
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| CN1493395A (en) * | 2002-10-28 | 2004-05-05 | ���Ĵ���ѧ | Nano-titanium dioxide photocatalyst film, preparation and its application |
| CN1468934A (en) * | 2003-06-16 | 2004-01-21 | 中国科学院长春应用化学研究所 | Prepn of luminous tungstate film |
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