CN102976400A - Preparation method for tetragonal phase nano barium titanate - Google Patents
Preparation method for tetragonal phase nano barium titanate Download PDFInfo
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Abstract
The invention provides a preparation method for tetragonal phase nano barium titanate. The preparation method comprises the steps as follows: i), preparing water solutions of barium chloride and oxalic acid respectively, and mixing alcoholic solution of butyl titanate and oxalic acid solution uniformly to obtain titanium oxyoxalate complex ion solution; ii), adding titanium oxyoxalate complex ion solution obtained in the step i) into a supergravity reactor as a circulating flowing phase to control the supergravity level; and meanwhile, dropping barium chloride solution to obtain white barium titanyl oxalate precipitation suspension as a precursor of barium titanate, and keeping the pH value of the whole system at 2.5-3.5 during reaction; and iii),ageing the precipitation suspension obtained in the step ii), leaching, washing and drying to obtain white barium titanyl oxalate power. The preparation method provided by the invention has the advantages that tetragonal phase nano barium titanate can be prepared; and the particle size of the prepared power can be controlled to be within the range of 30-90 nm; the average particle size is small, and the particle size is narrow in distribution; and the degree of crystallinity is high, and the crystal formation is intact.
Description
Technical field
The present invention relates to field of inorganic nano material, be specifically related to a kind of preparation method of cubic phase nano barium titanate.
Background technology
Nano material is because its unique interfacial effect has become a study hotspot of present material science in recent years, among this, barium titanate has extensive and important application as a kind of typically ferroelectric, dielectric materials at manufacturing non-linear element such as the electronic devices and components fields such as dielectric amplifier, ceramic condenser and ferroelectric piezoelectric device.The development of barium carbonate powder starts from the forties in 20th century, and China has introduced many laminated ceramic capacitors (MLCC) production line at present, and its dielectric material mainly is barium titanate.Because the every layer thickness of laminated ceramic capacitor has reached about 3 μ m, and every layer to need effective grain boundary layer be more than 5 layers, this high pure and ultra-fine cubic phase nano barium carbonate powder that just requires to use high-quality is as its dielectric material, and the cubic phase nano barium titanate not only can improve the electrical capacity of MLCC but also can improve to resist and wear intensity in addition.Therefore prepare that particle diameter is little, good dispersity, the cubic phase nano barium carbonate powder that is evenly distributed be subject to people's common concern.Along with the development of technology, people have higher requirement to the electronic material of barium titanate series, realize that high-purity, the Tetragonal of barium carbonate powder and ultra-fine and even nanometer are one of effective measure that improve the barium titanate electronic component performance.
Yet still there are many problems in barium titanate in the process that realizes Tetragonal and ultra-fine and even Nano grade.The main method of synthesizing tetragonal barium titanate has solid phase method, sol-gel method, the precipitator method and hydrothermal method etc. at present.The powder granule particle diameter is large, the component skewness owing to preparing for solid phase method, and needs ball milling easily to introduce impurity, more and more is difficult to adapt to the demand for development of barium carbonate powder High Purity super-refinement, the existing trend that is progressively replaced by liquid phase method.Sol-gel method in the liquid phase method, although usually can make the little and finely disseminated barium titanate of particle diameter, but its raw material valency is high, and preparation barium titanate gel needs just can be converted into barium carbonate powder after the high-temperature calcination, this has not only increased energy consumption, and often causes growing up and the hard aggregation of particle of crystal grain in the high-temperature calcination process.The hydro-thermal rule needs the reaction conditions of high temperature, high pressure, and is high to equipment requirements, and operation control is also comparatively complicated and be difficult to realize serialization production, and the product of hydrothermal method preparation also can't reach the Tetragonal product of 100% purity.
China recent years has proposed the following method for preparing tetragonal-phase barium titanate, as:
Chinese patent CN1323759 discloses a kind of preparation method of nanometer grade tetragonal-phase barium titanate powder, but its preparation method is hydrothermal method, needs the reaction conditions of high temperature, high pressure, and is too high to equipment requirements, and flow process is numerous and diverse is difficult to realize serialization production.
Chinese patent CN101746814A discloses a kind of production technique for preparing tetragonal-phase barium titanate, but its preparation method is hydrothermal method, and is too high to equipment requirements, and flow process product particle numerous and diverse and that make is larger, can't make the barium carbonate powder less than 100nm.
Chinese patent CN102060325A discloses a kind of preparation method of tetragonal-phase barium titanate nanorod array, but resulting product is not tetra phase barium titanate powder, and needs two step hydro-thermal reactions, and reaction conditions is complicated, complex operation.
Chinese patent CN102584215A discloses a kind of preparation method of barium titanate ceramics material of classifying porous Tetragonal, is sintered precursor but the method need to prepare nano-hollow ball, and process complexity and calcining temperature are higher, and the product of preparation is classifying porous pottery.
Chinese patent CN1323759 discloses a kind of nanometer grade tetragonal-phase barium titanate powder and preparation method.The method adopts cheap bariumchloride, titanium tetrachloride as barium, the titanium source of hydro-thermal reaction, and to introduce sodium hydroxide be mineralizer.It comprises that in advance bariumchloride, titanium tetrachloride being made into respectively highly concentrated solution also mixes subsequently, adds sodium hydroxide again and is made into mobile extraordinary colloidal sol as the hydro-thermal reaction mixture.Heat up after inserting this mixture in the high pressure corrosion protection reactor, 240 ℃ of the temperature of reaction that makes it to reach required, keep and product is filtered behind this temperature 12h and use deionized water wash, namely prepare after drying the mean sizes of monodispersity less than the nanometer grade tetragonal-phase barium titanate powder of 100nm.
Chinese patent CN101746814A provides a kind of tetragonal-phase barium titanate production technique for preparing, and comprises the preparation pure water, produces the titanium hydroxide precipitation; Hydro-oxidation barium utilizes microwave treatment under the medium of Virahol, gets the barium titanate precipitation, by washing to get superfine high-purity Tetragonal product.
Chinese patent CN102060325 relates to a kind of tetragonal-phase barium titanate nanorod array and preparation method thereof.In order to overcome the barium titanate nano-rod array that there is no Tetragonal in the prior art and must to process by high-temperature calcination, just can make the barium-titanate material crystalline structure change the defective of Tetragonal into from Emission in Cubic, a kind of tetragonal-phase barium titanate nanorod array is provided, wherein single nanometer rod is single crystal structure, length is 200nm～10 μ m, and diameter is 50nm～250nm; A kind of method for preparing tetragonal-phase barium titanate nanorod array also is provided, namely mixing on the tindioxide conductive glass of fluorine by hydro-thermal reaction growth titanic oxide nanorod array first, by the second step hydro-thermal reaction, titanic oxide nanorod array is changed into barium titanate nano-rod array of the present invention again.
Chinese patent CN102584215A discloses a kind of preparation method of barium titanate ceramics material of classifying porous Tetragonal, the method at first prepares the nano-hollow ball of barium carbonate cladding titanium dioxide as sintered precursor, then in temperature is 900 ℃ retort furnace, this presoma of dinectly bruning has just obtained the barium titanate ceramics of layering porous Tetragonal.The generation in the nano-hollow ball sintered precursor control porous ceramics hole of barium carbonate cladding titanium dioxide, simultaneously, sintering temperature affects the size in aperture.When sintering temperature was raised to 1100 ℃ from 900 ℃, the aperture dropped to several nanometers by the hundreds of nanometer, and ceramic degree of thickening increases.
Existing liquid-phase coprecipitation and classical solid phase method all can't be prepared high-purity as can be known in sum, the tetra phase barium titanate powder of ultra-fine and even Nano grade, even prepare that tetragonal-phase barium titanate exists also that particle diameter is large, thicker, the cubic rate of particle is lower or the method is not suitable for being applied to the problem of large-scale industrial production, therefore, intensification is sought to be more suitable for industrialized technology of preparing and processing condition and could really be made the cubic phase nano barium titanate step into the epoch of commercial scale production cubic phase nano barium titanate preparation method's research.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cubic phase nano barium titanate.Cubic phase nano barium carbonate powder through method preparation of the present invention can obtain required particle diameter by regulation and control nanometer precursor size.The present invention utilizes the median size of the cubic phase nano barium titanate of microwave high-temperature calcining nanometer presoma preparation to be 30-90nm, narrow diameter distribution, degree of crystallinity height and complete in crystal formation.
For achieving the above object, the invention provides a kind of preparation method of cubic phase nano barium titanate, may further comprise the steps:
I) bariumchloride and oxalic acid are configured to the aqueous solution, then alcoholic solution and the oxalic acid solution with butyl (tetra) titanate mixes to get titanium oxyoxalate complexing ion solution;
Ii) with step I) the titanium oxyoxalate complexing ion solution that obtains adds in the supergravity reactor as circulating phase, and adults power reactor rotor speed is 500-2200rpm; Drip simultaneously barium titanate presoma barium titanium oxalate (BTO) the precipitation suspension that the barium chloride solution reaction generates white, the pH value of whole system maintains 2.5-3.5 in the reaction;
Iii) with step I i) the precipitation suspension of gained carries out ageing, then suction filtration, washing and drying, at last calcining obtains barium titanium oxalate (BTO) powder of white.
In a preparation method's of the present invention preferred embodiment, step I) bariumchloride described in: oxalic acid: the mol ratio of butyl (tetra) titanate is 1-1.05:2.2-2.5:1.
In a preparation method's of the present invention preferred embodiment, step I) the pH value of complexing ion solution is 2.5-3.5 described in.
In a preparation method's of the present invention preferred embodiment, step I ii) described ageing is at 30 ℃ of-80 ℃ of ageing 2-6h.
In a preparation method's of the present invention preferred embodiment, step I i) supergravity reactor described in is rotating packed bed or rotating bed with helix channel.
Step I ii) described ageing is at 30 ℃ of-80 ℃ of ageing 2-6h.
In a preparation method's of the present invention preferred embodiment, then step I ii) described washing uses absolute ethanol washing 1 time at first spending ionized water washing 3 times.
In a preparation method's of the present invention preferred embodiment, step I ii) described drying is 80 ℃-120 ℃ lower dry 8-24h.
In a preparation method's of the present invention preferred embodiment, step I ii) described calcining is to control temperature at 700-1200 ℃, microwave calcination 1-4h under microwave condition.
Described microwave calcination is preferably the substep microwave calcination calcining that heats up with 10 ℃/min.
The median size of the cubic phase nano barium titanate of described method preparation is 30-90nm.
Utilize hypergravity method or additive method to prepare the nanometer precursor, adopt microwave high-temperature calcining preparation cubic phase nano barium titanate.At present also not about utilizing the patent of the integrated preparation cubic phase nano of high-gravity technology and microwave technology barium titanate aspect.
The nanometer precursor can react with solution-air (G-L) under the super gravity field environment or liquid-liquid (L-L) reaction method prepares or additive method prepares.The super gravity field reactor comprises the hypergravity reaction unit of rotating packed bed (RPB), rotating bed with helix channel (RBHC) or other form.Its step is as follows:
The present invention utilizes that high-temperature calcination precursor B TO obtains the cubic phase nano barium titanate in the microwave field.Microwave heating is different from common heating, common method for calcinating be heat energy by conduction pattern by centripetal transmission of specimen surface, make the specimen surface temperature be higher than inside.For microwave calcination, sample is inner to have the ability of equal absorbing microwave with the surface, and external enwergy is simultaneously by homogeneous heating in the sample.The thermograde of sample inside is little, can make the material built-in thermal stress reduce to minimum, can stop like this reunion of particle.And microwave heating is faster than conventional heating, and save energy is pollution-free.
In sum, the present invention has following beneficial effect:
1, can provide a kind of novel method for preparing the cubic phase nano barium titanate, the tetra phase barium titanate powder size distribution that has overcome existing liquid-phase coprecipitation and classics (solid phase method) preparation is uneven, easily reunite, the shortcomings such as batch poor repeatability, can prepare the cubic phase nano barium titanate, the diameter of particle of preparing can be controlled in the 30-90nm scope, and median size is little, narrow diameter distribution, degree of crystallinity height and complete in crystal formation.
2, the preparation method of nanometer presoma of the present invention is many.This nanometer precursor can prepare with solution-air (G-L) reaction or liquid-liquid (L-L) reaction under Elevated Gravity, perhaps prepares with other method.
The size that 3, can prepare by the regulation and control of hypergravity level nanometer presoma particle diameter, thereby the controlled cubic phase nano barium titanate of preparing required particle diameter.
4, utilize microwave high-temperature calcining preparation cubic phase nano barium titanate, utilize the microwave field temperature evenly, do not have thermograde, make its not easy-sintering, avoid that particle is grown up, reunion etc.; Realize controlled preparation cubic phase nano barium titanate, operation is simple.
5, the present invention publishes or uses there are no similar structure design and method in like product and preparation method, no matter and larger improvement is all arranged on product structure, pattern, the method technique is simple, but rapid batch is produced the cubic phase nano barium titanate.
Description of drawings
Fig. 1 is the XRD figure of the cubic phase nano barium titanate of preparation among the embodiment 1
Fig. 2 is the SEM figure of the cubic phase nano barium titanate of preparation among the embodiment 1
Fig. 3 is the SEM figure of the cubic phase nano barium titanate of preparation among the embodiment 2
Fig. 4 is the SEM figure of the cubic phase nano barium titanate of preparation among the embodiment 3
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail, but scope of the present invention is not limited in following examples.
Embodiment 1
Accurately take by weighing respectively BaCl
22H
2O27.48g, H
2C
2O
42H
2O30.88g, Ti (OC
4H
9)
439.2ml, bariumchloride and oxalic acid are configured to the aqueous solution, butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed at 700 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace to be calcined, calcining manners is three sections intensification room temperatures-500 ℃ insulation 30min of temperature programming, 500 ℃-700 ℃ insulation 30min, 700 ℃-1200 ℃ insulations 4 hours, 10 ℃/min of heat-up rate, the multistep calcining, calcining temperature is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 200nm.
Embodiment 2
Accurately take by weighing respectively BaCl
22H
2O27.48g, H
2C
2O
42H
2O30.88g, Ti (OC
4H
9)
439.2ml, bariumchloride and oxalic acid are configured to the aqueous solution, butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed at 800 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 90nm.
Embodiment 3
Accurately take by weighing respectively BaCl
22H
2O142.8g, H
2C
2O
42H
2O162g, Ti (OC
4H
9)
4200ml is configured to the aqueous solution with bariumchloride and oxalic acid, and butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed degree at 800 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 90-100nm.
Embodiment 4
Accurately take by weighing respectively BaCl
22H
2O27.48g, H
2C
2O
42H
2O30.88g, Ti (OC
4H
9)
439.2ml, bariumchloride and oxalic acid are configured to the aqueous solution, butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed degree at 1000 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 80nm.
Embodiment 5
Accurately take by weighing respectively BaCl
22H
2O142.8g, H
2C
2O
42H
2O162g, Ti (OC
4H
9)
4200ml is configured to the aqueous solution with bariumchloride and oxalic acid, and butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed degree at 1000 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 70nm.
Embodiment 6
Accurately take by weighing respectively BaCl
22H
2O27.48g, H
2C
2O
42H
2O30.88g, Ti (OC
4H
9)
439.2ml, bariumchloride and oxalic acid are configured to the aqueous solution, butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed at 1200 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 60nm.
Embodiment 7
Accurately take by weighing respectively BaCl
22H
2O142.8g, H
2C
2O
42H
2O162g, Ti (OC
4H
9)
4200ml is configured to the aqueous solution with bariumchloride and oxalic acid, and butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed at 1200 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 55nm.
Embodiment 8
Accurately take by weighing respectively BaCl
22H
2O27.48g, H
2C
2O
42H
2O30.88g, Ti (OC
4H
9)
439.2ml, bariumchloride and oxalic acid are configured to the aqueous solution, butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed at 1500 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is Tetragonal that the performance of product is detected by XRD, and SEM detects granular size and is about 45nm.
Embodiment 9
Accurately take by weighing respectively BaCl
22H
2O142.8g, H
2C
2O
42H
2O162g, Ti (OC
4H
9)
4200ml is configured to the aqueous solution with bariumchloride and oxalic acid, and butyl (tetra) titanate is dissolved in an amount of ethanolic soln, then the butyl (tetra) titanate alcoholic solution is added oxalic acid solution, stir and form transparent yellow solution, regulating the pH value scope with ammoniacal liquor is 2.5-3.0, sonic oscillation 10min, the solution total amount is 2.0L.Use the rotating bed with helix channel supergravity reactor produce super gravity field super gravity field level be adults power reactor rotor speed at 1500 rev/mins, in super gravity field, react and circulate, in the super gravity field reactor, drip BaCl
22H
2O solution, liquid measure are 0.5L, and reaction generates white precipitate.With the precipitation suspension of gained through 80 ℃ of water-baths suction filtration after still aging 2 hours, with deionized water wash 3 times, absolute ethanol washing 1 time.In 80 ℃ of air dry ovens dry evenings, obtain barium titanium oxalate (BTO) powder of white.Dried presoma is put into microwave Muffle furnace calcine, calcining manners is that multistep calcining, the calcining temperature of temperature programming is controlled in the 900-1200 ℃ of scope.It is tetragonal-phase barium titanate that the performance of product is detected by XRD, and SEM detects granular size and is about 40nm.
Claims (10)
1. the preparation method of a cubic phase nano barium titanate may further comprise the steps:
I) bariumchloride and oxalic acid are configured to the aqueous solution, then alcoholic solution and the oxalic acid solution with butyl (tetra) titanate mixes to get titanium oxyoxalate complexing ion solution;
Ii) with step I) the titanium oxyoxalate complexing ion solution that obtains adds in the supergravity reactor as circulating phase, and adults power reactor rotor speed is 500-2200rpm; Drip simultaneously the barium titanate presoma titanium oxyoxalate precipitated barium suspension that the barium chloride solution reaction generates white, the pH value of whole system maintains 2.5-3.5 in the reaction;
Iii) with step I i) the precipitation suspension of gained carries out ageing, then suction filtration, washing and drying, at last calcining obtains the barium titanium oxalate powder of white.
2. method according to claim 1 is characterized in that, step I) described in bariumchloride: oxalic acid: the mol ratio of butyl (tetra) titanate is 1-1.05:2.2-2.5:1.
3. method according to claim 1 is characterized in that, step I) described in the pH value of complexing ion solution be 2.5-3.5.
4. each described method is characterized in that step I i according to claim 1-3) described in supergravity reactor be rotating packed bed or rotating bed with helix channel.
5. each described method is characterized in that according to claim 1-3, and step I ii) described ageing is at 30-80 ℃ of ageing 2-6h.
6. each described method is characterized in that according to claim 1-3, and then step I ii) described washing uses absolute ethanol washing 1 time at first spending ionized water washing 3 times.
7. each described method is characterized in that according to claim 1-3, and step I ii) described drying is 80-120 ℃ of lower dry 8-24h.
8. each described method is characterized in that according to claim 1-3, step I ii) described calcining for control temperature under 700-1200 ℃ under microwave condition microwave calcination 1-4h.
9. method according to claim 8 is characterized in that, the substep microwave calcination calcining of described microwave calcination for heating up with 10 ℃/min.
10. each described method is characterized in that according to claim 1-9, and the median size of the cubic phase nano barium titanate of described method preparation is 30-90nm.
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| CN107954469A (en) * | 2017-12-15 | 2018-04-24 | 河北工业大学 | A kind of method for preparing tetragonal phase nano barium titanate |
| CN111233463A (en) * | 2020-01-20 | 2020-06-05 | 西安理工大学 | Method for preparing tetragonal phase barium titanate powder |
| CN111762810A (en) * | 2020-07-16 | 2020-10-13 | 上海大学(浙江·嘉兴)新兴产业研究院 | Preparation method of tetragonal phase nano barium titanate |
| CN112174198A (en) * | 2020-09-30 | 2021-01-05 | 湖南先导电子陶瓷科技产业园发展有限公司 | Synthesis method of high-purity superfine nano barium strontium titanate material |
| CN112341190A (en) * | 2019-08-06 | 2021-02-09 | 广州汽车集团股份有限公司 | Barium titanate-based powder preparation method, barium titanate-based powder and supercapacitor |
| CN113603134A (en) * | 2021-08-16 | 2021-11-05 | 西安理工大学 | Batch production method of monodisperse tetragonal-phase barium titanate hollow microspheres |
| CN116443922A (en) * | 2023-04-21 | 2023-07-18 | 深圳先进电子材料国际创新研究院 | Preparation method of barium titanate with tetrabutyl titanate as titanium source |
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| CN107624788A (en) * | 2017-09-20 | 2018-01-26 | 山东星美新材料股份有限公司 | A kind of Nano composite granules, its preparation method and the application of antibacterial and mouldproof smelly eliminating |
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| CN112341190A (en) * | 2019-08-06 | 2021-02-09 | 广州汽车集团股份有限公司 | Barium titanate-based powder preparation method, barium titanate-based powder and supercapacitor |
| CN112341190B (en) * | 2019-08-06 | 2022-10-18 | 广州汽车集团股份有限公司 | Barium titanate-based powder preparation method, barium titanate-based powder and supercapacitor |
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| CN112174198A (en) * | 2020-09-30 | 2021-01-05 | 湖南先导电子陶瓷科技产业园发展有限公司 | Synthesis method of high-purity superfine nano barium strontium titanate material |
| CN113603134A (en) * | 2021-08-16 | 2021-11-05 | 西安理工大学 | Batch production method of monodisperse tetragonal-phase barium titanate hollow microspheres |
| CN116443922A (en) * | 2023-04-21 | 2023-07-18 | 深圳先进电子材料国际创新研究院 | Preparation method of barium titanate with tetrabutyl titanate as titanium source |
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