CN101215104B - Method for preparing IIB group tungstate nano film - Google Patents
Method for preparing IIB group tungstate nano film Download PDFInfo
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- CN101215104B CN101215104B CN2008100324560A CN200810032456A CN101215104B CN 101215104 B CN101215104 B CN 101215104B CN 2008100324560 A CN2008100324560 A CN 2008100324560A CN 200810032456 A CN200810032456 A CN 200810032456A CN 101215104 B CN101215104 B CN 101215104B
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Abstract
The invention discloses a process for preparing IIB group tungstate nano films, which comprises the steps as follows: a, respectively weighing IIB group metal salt and tungsten according to mol ratio of 1:1, laying the IIB group metal salt and tungsten in an autoclave with the temperature between 140-200DEG C to heat for 2-12 hours, b, after precipitating, centrifugating and dispersing, the IIB group metal salt and tungsten is added with ethanol and stirred, and then is added with collodion and stirred, c, film coating substrates are treated for reservation, d, insulating for 30 minutes at the temperature between 150-200DEG C after being coated by films, keeping the constant temperature of 350-500DEG C and slowly decreasing to room temperature at last, the product of the invention is obtained. The invention is the novel method of combined application of hydrothermal and collodion dispersing filming technique of nano particles, and the production rate reaches up to 90%. The prepared product is provided with fine functions of light, electricity and the like. The raw materials of the invention are easy to be obtained, the cost is low, the operation is simple and the treatment is convenient, further, the invention is easy to be industrialized.
Description
Technical field
The present invention relates to a kind of preparation method of nano thin-film, particularly relate to a kind of method for preparing the IIB group tungstate nano film that combines by hydrothermal method and collodion dispersing nanometer particle film technique.
Background technology
IIB group tungstate powder body material is because the flicker of its uniqueness and the characteristics of luminescence etc. and have broad application prospects in industries such as optics, electronics, biology, coating, medicine.Studies confirm that, when powder body material is processed to film, because thin-film material inherent small size and low characteristics such as transverse scattering, make the inorganic light-emitting thin-film material have performances such as the light excellent more, electricity, magnetic, catalysis, can be used for fields such as solid-state laser, fiber optics, light-emitting flash body, accelerator than its powder body material.Along with the requirement of photoelectric device microminiaturization, nano film material causes people's extensive concern day by day in the research application facet of whole novel material.The preparation method of the IIB group tungstate nano film of having reported so far, mainly contains: sol-gel method, sputtering method, hydro-thermal-solvent thermal synthesis method and electrochemical process.Yet above-mentioned preparation method all in various degree have a preparation cost height, easily produce toxic gas, the product pattern is difficult to problems such as control, can not satisfy the demand of producing photoelectric device.Generally speaking, hydrothermal method can have the high yield advantage again from size and the pattern that microcosmic is stablized particulate and controlled particle, can carry out scale production, yet up to the present, do not see as yet with the combine report of preparation IIB group tungstate nano film of hydrothermal system and collodion dispersing nanometer particle film technique.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method for preparing the IIB group tungstate nano film that combines by hydrothermal method and collodion dispersing nanometer particle film technique, and this method is with low cost, reaction conditions is gentle, the IIB group tungstate nano film is produced on a large scale.
The technical solution used in the present invention: the preparation method of IIB group tungstate nano film comprises the following steps:
A. take by weighing IIB family metal-salt and tungsten source respectively according to 1: 1 ratio of mol ratio, it is presented to has in the teflon-lined autoclave, in autoclave, add distilled water to autoclave volumetrical 2/3, seal autoclave then and be placed in the baking oven 140～200 ℃ of heating 2～12 hours, reaction is chilled to room temperature with the autoclave gradient after finishing, wherein said IIB family metal-salt is selected from a kind of in the metal chlorate of IIB family, nitrate or the acetate of solubility, and described tungsten source is selected from Na
2WO
4, K
2WO
4Or H
2WO
4In a kind of;
B. with after the precipitated product centrifugation in the step a autoclave, clean respectively three times with distilled water, acetone and dehydrated alcohol successively, again to the dehydrated alcohol that wherein adds 0.2～1 times of precipitated product volume, add collodion in the rotating speed stirring with 3000rpm under the room temperature after 30 minutes, collodion: the volume ratio of precipitated product is 1: 5～15, stir and it was mixed in 1 hour, standby as Coating Materials;
C. with the normal glass sheet as film plating substrate, use concentrated nitric acid, acetone and ethanol supersound process 20 minutes before the use respectively, clean with distilled water flushing again, dry standby;
D. above-mentioned standby sheet glass is immersed in the Coating Materials of step b preparation, the control pull rate is 35mm/min, and plated film finish to place under the room temperature of back 20 minutes air-dry, then the sheet glass behind the plated film is placed retort furnace, 150～200 ℃ are incubated 30 minutes, reheat to 300～500 ℃ constant temperature 1 hour is closed retort furnace at last and is made it slowly reduce to room temperature, promptly obtains product of the present invention.
The beneficial effect of the invention is as follows: the present invention is a kind of nano film material preparation method that hydro-thermal and collodion dispersing nanometer particle film technique are combined in principle, wherein hydrothermal method is as a kind of effective nano material synthetic method, is temperature and pressure with the key distinction of other wet chemical methods such as sol-gel method, hydrothermal method.Hydrothermal method (Hydrothermal), be meant in special closed reactor (autoclave), adopt the aqueous solution as reaction system, by to reaction system heating, in reaction system, produce one in temperature (100～600 ℃), highly compressed environment and a kind of effective ways of carrying out inorganic synthetic and material preparation.Collodion dispersing nanometer particle film technique is the contriver from a kind of film of wound, and in the method, collodion is used as the dispersion agent and the membrane-forming agent of film process, and institute's made membrane has that even compact, pattern are easily controlled, advantage such as convenient and simple.The present invention combines by hydrothermal system and collodion dispersing nanometer particle film technique, select the reaction of IIB family's metal-salt and tungsten source, go out IIB group tungstate nano particle by Hydrothermal Preparation, adopt collodion dispersing nanometer particle film technique series preparation IIB group tungstate nano film again.This method is difficult to obtain the nano thin-film of height even compact under normal temperature and pressure conditions, but can realize in this film preparation system.In this reaction system, can change the pattern of product by control high temperature sintering temperature, sintering time is regulated and control product size and crystal structure degree.Particularly: one, the present invention is that hydro-thermal and collodion dispersing nanometer particle film technique are in conjunction with the new preparation process of using, both utilized the induce control action kou of hydro-thermal enclosed system to the product pattern, use characteristics such as collodion dispersing nanometer particle film technique film quality height, performance are good again, can control the IIB group tungstate nano film material of the multiple good pattern of synthetic preparation; Two, the present invention can prepare productive rate up to IIB group tungstate nano film material 90%, different-shape; Three, the product of the present invention's preparation has performances such as good light, electricity, and tangible emission peak blue shift phenomenon is arranged; Four, raw material of the present invention is easy to get, and is with low cost, simple to operate, and it is convenient to handle, and is easy to industrialization, and new approach is provided for the control of IIB group tungstate nano film is synthetic.
Description of drawings
Fig. 1 is scanning electronic microscope (SEM) figure of embodiment 1 product;
Fig. 2 is X-ray powder diffraction (XRD) figure of embodiment 1 product;
Fig. 3 is the fluorescence emission spectrogram of embodiment 1 product;
Fig. 4 is the infrared spectrogram of embodiment 1 product.
Embodiment
Below by drawings and Examples the present invention is described in further detail, the preparation method of IIB group tungstate nano film comprises the following steps:
A. take by weighing IIB family metal-salt and tungsten source respectively according to 1: 1 ratio of mol ratio, it is presented to has in the teflon-lined autoclave, in autoclave, add distilled water to autoclave volumetrical 2/3, seal autoclave then and be placed in the baking oven 140～200 ℃ of heating 2～12 hours, reaction is chilled to room temperature with the autoclave gradient after finishing, wherein said IIB family metal-salt is selected from a kind of in the metal chlorate of IIB family, nitrate or the acetate of solubility, and described tungsten source is selected from Na
2WO
4, K
2WO
4Or H
2WO
4In a kind of;
B. with after the precipitated product centrifugation in the step a autoclave, clean respectively three times with distilled water, acetone and dehydrated alcohol successively, again to the dehydrated alcohol that wherein adds 0.2～1 times of precipitated product volume, add collodion in the rotating speed stirring with 3000rpm under the room temperature after 30 minutes, collodion: the volume ratio of precipitated product is 1: 5～15, stir and it was mixed in 1 hour, standby as Coating Materials;
C. with the normal glass sheet as film plating substrate, use concentrated nitric acid, acetone and ethanol supersound process 20 minutes before the use respectively, clean with distilled water flushing again, dry standby;
D. above-mentioned standby sheet glass is immersed in the Coating Materials of step b preparation, the control pull rate is 35mm/min, and plated film finish to place under the room temperature of back 20 minutes air-dry, then the sheet glass behind the plated film is placed retort furnace, 150～200 ℃ are incubated 30 minutes, reheat to 300～500 ℃ constant temperature 1 hour is closed retort furnace at last and is made it slowly reduce to room temperature, promptly obtains product of the present invention.
All can induce the end product IIB group tungstate nano film material that synthesizes different-shape and size at described hydro-thermal synthesis temperature of step a and time, and the fluorescence peak blue shift degree difference of product.The quality of forming film of the introducing ratio control end product IIB group tungstate nano film material of collodion, the i.e. homogeneity of film and compactness in the described Coating Materials of step b.In the described film plating substrate of step c purifying treatment in advance, to eliminate the pollution of film plating substrate to end product IIB group tungstate nano film material.All influence the size and the crystallization situation of end product IIB group tungstate nano film material in the described film forming sintering time of steps d and temperature.
Embodiment 1
(1) takes by weighing the HgCl of 0.010mol respectively
2With 0.010mol Na
2WO
4It is presented in the 45mL band teflon-lined autoclave, in autoclave, adds distilled water, be placed in the baking oven behind the sealing autoclave to autoclave volumetrical 2/3, in 180 ℃ of heating 3 hours, close baking oven autoclave gradient after reaction finishes and be chilled to room temperature.
(2) precipitated product in the reactor is carried out centrifugation after, clean respectively three times with distilled water acetone and dehydrated alcohol successively, add the dehydrated alcohol of 0.5 times of precipitation capacity volume.Again after stirring 30 minutes with the rotating speed of 3000rpm under the room temperature, add volume ratio (collodion: precipitation capacity) be 1: 10 collodion, stir and it was mixed in 1 hour that gained is Coating Materials of the present invention.
(3) 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.
(4) the sheet glass immersion second that the 3rd step was cleaned up goes on foot in the prepared Coating Materials, 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, in 200 ℃ the insulation 30 minutes after, 1 hour after annealing of reheat to 350 ℃ constant temperature.Reaction is closed retort furnace after finishing, and makes it slowly reduce to room temperature.Promptly obtain product of the present invention.
The product that embodiment 1 obtains uses scanning electronic microscope (SEM) and X-ray powder diffraction (XRD) that the pattern and the structure of product are characterized respectively, as shown in Figure 1, SEM result shows the surperficial even compact of film, particle diameter is all in 50～3000 nanometers, as shown in Figure 2, XRD result shows product pure (consistent with the JCPDS card).As shown in Figure 3, fluorescent spectroscopy is the result show, some products have photoluminescence performance, and the maximum absorption band of product is compared with conventional material, in a big way " blue shift " occur, shows tangible quantum size effect.As shown in Figure 4, infrared result shows that product is the wolframite structure.
Embodiment 2
Take by weighing 0.015 mole of HgCl respectively
2With 0.015 mole of K
2WO
4, then it is transferred in the 45mL band teflon-lined autoclave, in 140 ℃ of heating 10 hours.Other conditions and step and embodiment 1 are identical, and the film product that obtains surface even compact is by mean diameter 100 nanometers, be about the HgWO of 300 nanometers
4The nano bar-shape granulometric composition, the crystallographic system of product is identical with embodiment 1.The product purity height, degree of crystallinity is good.
Embodiment 3
In the step (2) of embodiment 2, add the dehydrated alcohol of 0.5 times of precipitation capacity volume.Again after stirring 30 minutes with the rotating speed of 3000rpm under the room temperature, add volume ratio (collodion: precipitation capacity) be 1: 5 collodion, other conditions and step and embodiment 1 are identical, the film product that obtains equally by about 250 nanometers of diameter, be about the bar-shaped HgWO of 800 nanometers
4Form, the crystallographic system of product is identical with embodiment 1.Compare in embodiment 1, even compact is poor slightly.
Embodiment 4
Embodiment 2 with step (1) in heating condition change 160 ℃ of heating 5 hours into, other conditions and step and embodiment 1 are identical, the film product that obtains by about 250 nanometers of diameter, be about the bar-shaped HgWO of 800 nanometers
4Form, the crystallographic system of product is identical with embodiment 1.The product purity height, degree of crystallinity and optical property are good.Compare with embodiment 1, its fluorescence peak position less blue shift occurs with respect to conventional material.
Embodiment 5
In the step (1) of embodiment 2, take by weighing 0.015 mole of ZnCl respectively
2And H
2WO
4, be placed in the 45mL band teflon-lined autoclave, in the step (4), 200 ℃ of insulations are after 30 minutes, be heated to 500 ℃ of constant temperature 1 hour, other conditions and step and embodiment 1 are identical, the film product that obtains by about 80 nanometers of diameter, be about the ZnWO of 400 nanometers
4Nanometer rod is formed, and the crystallographic system of product is identical with embodiment 1.Compare with embodiment 1, the blue shift degree of fluorescence peak is bigger.
Embodiment 6
In the step (1) of embodiment 2, with Zn (NO
3)
2Replace HgCl
2, in 200 ℃ of heating 2 hours, other conditions and step and embodiment 3 were identical, the film product that obtains by about 120 nanometers of diameter, be about the ZnWO of 600 nanometers
4Nanometer rod is formed, and the crystallographic system of product is identical with embodiment 1.The product purity height, degree of crystallinity and optical property are basic similar to embodiment 3.
Embodiment 7
In the step (1) of embodiment 2, with HgCl
2Change CdCl into
2, other conditions and step and embodiment 6 are identical, the film product that obtains by about 200 nanometers of diameter, be about the CdWO of 400 nanometers
4Nanometer rod is formed, and the crystallographic system of product is identical with embodiment 1.The product purity height, degree of crystallinity and optical property are good.Compare with embodiment 1, its fluorescence peak position tangible blue shift occurs with respect to conventional material.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1.IIB the preparation method of group tungstate nano film comprises the following steps:
A. take by weighing IIB family metal-salt and tungsten source respectively according to 1: 1 ratio of mol ratio, it is presented to has in the teflon-lined autoclave, in autoclave, add distilled water to autoclave volumetrical 2/3, seal autoclave then and be placed in the baking oven 140～200 ℃ of heating 2～12 hours, reaction is chilled to room temperature with the autoclave gradient after finishing, wherein said IIB family metal-salt is selected from a kind of in IIB family metal chloride, nitrate or the acetate of solubility, and described tungsten source is selected from Na
2WO
4, K
2WO
4Or H
2WO
4In a kind of;
B. with after the precipitated product centrifugation in the step a autoclave, clean respectively three times with distilled water, acetone and dehydrated alcohol successively, again to the dehydrated alcohol that wherein adds 0.2～1 times of precipitated product volume, add collodion in the rotating speed stirring with 3000rpm under the room temperature after 30 minutes, collodion: the volume ratio of precipitated product is 1: 5～1: 15, stir and it was mixed in 1 hour, standby as Coating Materials;
C. with the normal glass sheet as film plating substrate, use concentrated nitric acid, acetone and ethanol supersound process 20 minutes before the use respectively, clean with distilled water flushing again, dry standby;
D. above-mentioned standby sheet glass is immersed in the Coating Materials of step b preparation, the control pull rate is 35mm/min, and plated film finish to place under the room temperature of back 20 minutes air-dry, then the sheet glass behind the plated film is placed retort furnace, 150～200 ℃ are incubated 30 minutes, reheat to 300～500 ℃ constant temperature 1 hour is closed retort furnace at last and is made it slowly reduce to room temperature, promptly obtains product of the present invention.
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| CN101215104B true CN101215104B (en) | 2011-06-29 |
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| CN104261475B (en) * | 2014-09-15 | 2015-11-04 | 陕西科技大学 | A kind of thread tunnel type potassium wolframate and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| Lin J et al..Controlled synthesis of the ZnWO4 nanostructrue and effects on the photocatalytic performance.《Inorganic Chemistry》.2007,第46卷(第20期),第8372-8378页. * |
| Wang YG et al..Hydrothermal synthesis and characterization of CdWO4 nanorods.《Journal of the American Ceramic Society》.2006,第89卷(第9期),第2980-2982页. * |
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