CN100509637C - Perovskite titanium-containing composite oxide particle, production process and uses thereof - Google Patents

Abstract

The present invention provides a perovskite titanium-containing composite oxide fine particle represented by the formula: (A1<SUB>X</SUB>A2<SUB>(1-X)</SUB>)<SUB>Y</SUB>TiO<SUB>3+-delta</SUB> (wherein 0<=X<=1, 0.98<=Y<=1.02, 0<=delta<=0.05, A1 and A2 each is an atom selected from a group consisting of Ca, Sr, Ba, Pb and Mg and are different from each other), wherein the specific surface area is from 1 to 100 m<SUP>2</SUP>/g and the D2/D1 value is from 1 to 10.

Description

Perovskite titanium-containing composite oxide particle, its production method and purposes

The cross reference of related application

The application is the application of submitting to according to 35 U.S.C.111 (a), this application is according to 35 U.S.C.119 (e) (1), required regulation according to 35 U.S.C.111 (b), the U.S. provisional application sequence number of submitting on April 17th, 2,004 60/463,335 and said the right of priority of the U.S. provisional application sequence number of submitting in 17th 60/478,829 at 2003 6.

Technical field

The present invention relates to be used in perovskite titanium-containing composite oxide particle and production method thereof in electronic material such as dielectric materials, piezoelectric, thermoelectricity (pyroelectric) material, laminated ceramic capacitor and the thin-film material.

More particularly, the present invention relates to perovskite titanium-containing composite oxide particle and production method thereof, described perovskite titanium-containing composite oxide particle has the sosoloid ratio that is controlled at arbitrary value and has little granularity, narrow distribution of particle sizes, excellent dispersibility, high degree of crystallinity and less impurity.

Background technology

By formula ABO ₃The titanium-containing composite oxide of the perovskite structure of expression demonstrates excellent electric performance such as dielectricity, piezoelectricity and pyroelectricity, and therefore it is widely used as electronic material.

By (A1 _XA2 _(1-X)) _YTiO _{3 ± δ}The titanium-containing composite oxide of the perovskite structure of expression has perovskite crystal structure, and the B site is occupied by titanium so that the A site is occupied by A1 atom and A2 atom.In these cases, electrical property according to the difference of the sosoloid ratio of A1 atom pairs A2 atom and the different and titanium-containing composite oxide of perovskite structure that will have a sosoloid ratio that is controlled at arbitrary value as various electronic materials.For example, will control with those titanium-containing composite oxides the sosoloid ratio and be used for dielectric spectral filter, dielectric antenna, dielectric resonator, dielectric duplexer (dielectric duplexer), electrical condenser, phase shifter and comprise the various capacitor materials of laminated ceramic capacitor with high dielectric property; And will control to have those electrical composite oxides of high pressure the sosoloid ratio and be used for the multi-layer piezoelectric stimulator.

The method that the titanium-containing composite oxide particle of perovskite structure is formed electronic material is not particularly limited.For example, particulate and solvent are obtained slurry or paste, make it form thin-film material or porcelain by method then such as mold pressing/sintering or film-making.

In order to deal with recently requirement, need have the titanium-containing composite oxide particle of the perovskite structure of narrow distribution of particle sizes under the small particle size situation and high-crystallinity for miniaturization, weight saving and the superior performance of electronic component.

In addition, by formula (A1 _XA2 _(1-X)) _YTiO _{3 ± δ}In the titanium-containing composite oxide of perovskite structure of expression, for electrical property according to different and different to the ratio of titanium of the total amount of the sosoloid ratio of A1 atom pairs A2 atom and A1 atom and A2 atom, therefore need accurately control above-mentioned ratio.

And all impurity influences electrical property unfriendly, therefore need remove the titanium-containing composite oxide particle of the high purity perovskite structure of impurity.With regard to the method for the titanium-containing composite oxide particle of producing perovskite structure, known scorification.But the disadvantage of described method is that not only production cost becomes very high, and grinding is the unique method that obtains particulate in described method, and this causes the wide distribution of particle sizes of particulate that is obtained and differs from dispersibility.

Other example that production is used in the titanium-containing composite oxide particulate method in the electronic material comprises solid phase method, wherein will in ball mill or the like, mix, under the high temperature of about 800 ℃ or higher temperature, make its reaction produce the titanium-containing composite oxide particle then as the oxide compound or the carbonate powder of raw material; Oxalic Acid Method wherein prepares compound oxalate, then its thermolysis is obtained the titanium-containing composite oxide particle; Under high pressure make starting raw material in water solvent under high temperature reaction obtain the hydrothermal synthesis of precursor and wherein make alkoxide hydrolysis obtain precursor alkoxide method as starting raw material.

In addition, the method that the usually known hydrolysate that makes titanium compound reacts in highly basic in water-soluble barium (referring to, (JP-B-3-39014) is (as used herein for European patent 104002, term " JP-B " meaning is " Japanese patent application of examining bulletin ")) and make the method that titanium oxide sol and barium compound react in strong alkali aqueous solution (referring to, European patent 114803 (WO00/35811) and US patent application 2003/0044347A1 (W03/004416)).During the improvement of above-mentioned synthetic method is just actively carried out.

The problem that solid phase method has is, although lower production cost, the titanium-containing composite oxide particle of being produced has the macrobead degree and when abrasive grains, and the granularity distribution of particle sizes that diminishes broadens and do not improve mold pressing density.In addition, make the crystalline structure distortion and can not obtain to be suitable for perovskite titanium-containing composite oxide particle small-sized and that high-performance forms owing to grinding.

In oxalate method, although can obtain than at the medium and small particle of solid phase method, but still there is the carbonic acid group that comes from oxalic acid and exists in a large number derived from the hydroxyls that are captured in inner water, this causes electrical property to descend.Therefore, can not obtain to have the titanium-containing composite oxide particle of excellent electrical.

In hydrothermal synthesis, can obtain microgranular titanium-containing composite oxide, but described oxide compound is owing to have many defectives and be difficult to the titanium-containing composite oxide that acquisition has excellent electrical because of being captured in the inner remaining hydroxyl of water.In addition, synthesize under high-temperature and high-pressure conditions and carry out, and this needing to cause the problem of specific equipment and cost rising.

In the alkoxide method, can obtain than granular titanium-containing composite oxide thinner in hydrothermal synthesis.But, cause many particle defectiveness of producing because of being captured in the inner remaining hydroxyl of water, therefore the titanium-containing composite oxide that is difficult to obtain to have excellent electrical.In addition, another defective that the alkoxide method has is, residual in the particle of being produced have a carbonic acid group.

In European patent 104002 (JP-B-3-39014), use potassium hydroxide or sodium hydroxide as alkali, the step of therefore removing described alkali after the reaction is necessary.In above-mentioned steps, the dissolving of barium and capturing of hydroxyl take place, and be difficult to obtain to have the titanium-containing composite oxide of high-crystallinity.

And, in aforesaid method,, be difficult to the A1 atom of production solid solution and the titanium-containing composite oxide particle that the A2 atom is controlled at the perovskite structure of arbitrary ratio because starting material compound is reactive different.For example, in the barium strontium titanate compound particles of producing the barium wherein contain the solid solution under arbitrary ratio and strontium, reactivity between starting raw material barium compound and the titanium compound is different from the reactivity between starting raw material strontium compound and the titanium compound, so raw material still tends to mixture residual or barium titanate and strontium titanate and is easy to be mingled in the product.

JP-A-2-188427, JP-A-4-16513, US patent 4,677,083 (JP-A-60-155532) and JP-A-6-9219 disclose a kind of method of producing barium strontium titanate compound particles.In JP-A-2-188427, adopt to use and to control to barium with arbitrary ratio solid phase method the carbonate of strontium, and the step of therefore not only producing the carbonate with above-mentioned ratio is necessary, and since the requisite cracked distribution of particle sizes that makes unfriendly broaden.In JP-A-4-16513, not only Ang Gui titan-alkoxide is essential, and because because of being captured in the titanium-containing composite oxide that the inner residual hydroxyl crystalline texture of water has many defectives and is difficult to obtain to have excellent electrical.In US patent 4,677,083 (JP-A-60-155532) and JP-A-6-9219, the step that after producing reaction, must remove the by product of titanium compound and alkali metal hydroxide.In described step, barium or the dissolving of strontium and capturing of hydroxyl take place, and therefore barium is difficult to the titanium-containing composite oxide that is controlled at arbitrary value and is difficult to obtain have high-crystallinity to the ratio of strontium.

In addition, considering provides a kind of have the narrow distribution of particle sizes under the small particle size situation and the barium strontium titanate compound particles of higher crystallinity, and aforesaid method all needs to improve.

An example with Ti-base composite oxide of perovskite typed crystalline texture is a calcium titanate, and it is widely used in the temperature compensating ceramic capacit material.Calcium titanate also is used as the additive of specific inductivity flip-flop under Curie temperature of avoiding the high dielectric capacitor of barium phthalate base.Therefore, be similar to other Ti-base composite oxide, need that development is a kind of to have small particle size, a calcium titanate of dispersibility, high-crystallinity and excellent electric performance preferably.

In European patent 104002 (JP-A-59-45927) and JP-A-5-178617, disclose a kind of method of producing spherical calcium titanate, but required to provide a kind of have more high-crystallinity and the more calcium titanate of excellent electric performance.

For example, in using European patent 1148030 (WO00/35811) or US patent application 2003/0044347A1 (WO03/004416), during disclosed technology, under lower cost, can obtain the particulate of subparticle reduced number.But, for miniaturization, the weight that realizes electronic component reduces and high-performance, the perovskite titanium-containing composite oxide particle that need provide a kind of impurity level to reduce wherein further reduces the number of ultra-fine grain in atom solid solution on the A-site or the calcium titanate particle (0.01 μ m or still less) or agglomerating particles and guarantees to have dispersibility, high-crystallinity and excellent electric performance preferably at arbitrary ratio.

One of purpose of the present invention provides a kind of perovskite titanium-containing composite oxide particle and production method thereof, and described perovskite titanium-containing composite oxide particle has little granularity, narrow distribution of particle sizes, dispersibility, high-crystallinity and excellent electric performance preferably.

Another object of the present invention provides the perovskite titanium-containing composite oxide particle that a kind of impurity level reduces, and wherein contains atom on the A-site and calcium titanate particle at arbitrary ratio and is reducing aspect the number of ultra-fine grain or agglomerating particles and having an extremely narrow distribution of particle sizes.

Summary of the invention

That is, the present invention includes following summary of the invention.

(1) by formula: (A1 _XA2 _(1-X)) _YTiO _{3 ± δ}The perovskite titanium-containing composite oxide particle of (wherein, 0≤X≤1,0.98≤Y≤1.02,0≤δ≤0.05, and A1 and A2 are the atom that is selected from Ca, Sr, Ba, Pb and Mg and differ from one another) expression, its specific surface area is 1-100m ²/ g and D2/D1 value are 1-10.

(2) perovskite titanium-containing composite oxide particle described in above (1), it comprises the monocrystalline of perovskite titanium-containing composite oxide.

(3) perovskite titanium-containing composite oxide particle described in above (1) or (2), the shape that it has the tetragonal prism shape or is similar to tetragonal prism.

(4) perovskite titanium-containing composite oxide particle described in above (3), wherein the long limit of crystalline is 1.1-6 to the ratio of minor face.

(5) perovskite titanium-containing composite oxide particle described in above (3) or (4), wherein the long limit of crystalline extends to structure cell (010) plane.

(6) perovskite titanium-containing composite oxide particle described in each of above (1)-(5), wherein the D2/D1 value is 1-3.

(7) perovskite titanium-containing composite oxide particle described in each of above (1)-(6), wherein the D3/D2 value is 0.1-0.9.

(8) perovskite titanium-containing composite oxide particle described in each of above (1)-(7), wherein the D4/D2 value is 1.1-10.

(9) perovskite titanium-containing composite oxide particle described in each of above (1)-(8) is wherein by (A1 _XA2 _(1-X)) _YTiO _{3 ± δ}The compound of expression is CaTiO ₃And calcium carbonate content is 3 quality % or still less.

(10) perovskite titanium-containing composite oxide particle described in each of above (1)-(9), its specific surface area is 1-10m ²/ g.

(11) perovskite titanium-containing composite oxide particle described in each of above (1)-(10), wherein at 900-1, during any temperature lower calcination of 200 ℃, specific surface area reduces 8m ²/ g or still less.

(12) perovskite titanium-containing composite oxide particle described in above (1), wherein 0.2≤X≤0.8,0.99≤Y≤1.01,0≤δ≤0.03 and particulate are monocrystalline.

(13) perovskite titanium-containing composite oxide particle described in above (1), wherein A1 is that Ba and A2 are Sr.

(14) perovskite titanium-containing composite oxide particle described in each of above (1)-(13), wherein the amount of alkali metal impurity is that the amount of 0-100ppm and chlorine impurity is 0-600ppm.

(15) perovskite titanium-containing composite oxide particle described in each of above (1)-(14), wherein at 900-1, during 000 ℃ any temperature lower calcination 0.1-3 hour, the minimizing percentage of specific surface area is 90% or still less.

(16) perovskite titanium-containing composite oxide particle described in each of above (1)-(15), wherein at 900-1, shape becomes square after any temperature lower calcination 0.1-3 hour of 200 ℃.

(17) perovskite titanium-containing composite oxide particle described in each of above (1)-(16), wherein the amount of carbonate is 3 quality % or still less.

(18) perovskite titanium-containing composite oxide particle described in each of above (1)-(17), wherein when 1.5g perovskite titanium-containing composite oxide particle is immersed in the 45ml pure water, total extracted amount of per surface area A1 atom and A2 atom is 0-2 μ mol/m ²

(19) method of the perovskite titanium-containing composite oxide particle described in each of production as above (1)-(18) wherein comprises titanium oxide sol and metal-salt adding in the alkali aqueous solution of basic cpd, makes its reaction then.

(20) method of the production perovskite titanium-containing composite oxide particle described in above (19), wherein with the 10-10 of metal-salt with saturation solubility, the weight of 000 quality multiple adds in the alkaline solution.

(21) method of the production perovskite titanium-containing composite oxide particle described in above (19), wherein calcium salt is an oxyhydroxide.

(22) method of the production perovskite titanium-containing composite oxide particle described in above (19), this method comprise with regard to CO ₂The concentration of carbonic acid group controls to 500ppm or lower in the reaction soln.

(23) method of the production perovskite titanium-containing composite oxide particle described in above (19), this method comprise makes reaction system boiling 2 hours or step of longer time under 100 ℃ or higher temperature.

(24) method of the production perovskite titanium-containing composite oxide particle described in above (19), this method are included in normal pressure or decompression down, the step that by evaporation and/or thermolysis impurity is removed as gas to the temperature range of calcining temperature in room temperature.

(25) method of the production perovskite titanium-containing composite oxide particle described in above (19), wherein titanium oxide sol obtains by make the titanium compound hydrolysis in acidic solution.

(26) method of the production perovskite titanium-containing composite oxide particle described in above (19), wherein titanium oxide sol comprises brookite crystal.

(27) method of the production perovskite titanium-containing composite oxide particle described in above (19), wherein basic cpd is for becoming the material of gas by evaporation, distillation and/or thermolysis under normal pressure or decompression.

(28) method of the production perovskite titanium-containing composite oxide particle described in above (27), wherein basic cpd is an organic bases.

(29) method of the production perovskite titanium-containing composite oxide particle described in above (19), wherein basic cpd is a Tetramethylammonium hydroxide.

(30) method of production perovskite titanium-containing composite oxide particle, this method comprises makes A1 (OH) ₂And A2 (OH) ₂Under arbitrary ratio with A1 (OH) ₂And A2 (OH) ₂The titanium oxide of 0.98-1.02 mole multiple of total mole number in alkaline solution, react, described alkaline solution contains basic cpd and the pH that has is 10 or higher, wherein A1 and A2 all represent to be selected from the atom of Ca, Sr, Ba, Pb and Mg; Make reaction continue in reaction soln A1 ion and A2 ionic total concn and become 1/1 of the amount that added, 000 or still less and after reaction finishes, under normal pressure or decompression, to the temperature range of calcining temperature, basic cpd is removed as gas by evaporation, distillation and/or thermolysis in room temperature.

(31) method of the production perovskite titanium-containing composite oxide particle described in above (30), wherein A1 (OH) ₂To A2 (OH) ₂Molar ratio be 0.2-0.8.

(32) method of the production perovskite titanium-containing composite oxide particle described in above (30), this method comprise with regard to CO ₂The concentration of carbonic acid group controls to 0-500ppm in the reaction soln.

(33) method of the production perovskite titanium-containing composite oxide particle described in above (30), wherein titanium oxide comprises brookite crystal.

(34) method of the production perovskite titanium-containing composite oxide particle described in above (30), wherein titanium oxide obtains by make the titanium compound hydrolysis in acidic solution.

(35) method of the production perovskite titanium-containing composite oxide particle described in above (30), wherein basic cpd is for becoming the material of gas by evaporation, distillation and/or thermolysis under normal pressure or decompression.

(36) method of the production perovskite titanium-containing composite oxide particle described in above (30), wherein basic cpd is an organic bases.

(37) method of the production perovskite titanium-containing composite oxide particle described in above (30), wherein basic cpd is a Tetramethylammonium hydroxide.

(38) comprise the dielectric materials of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(39) comprise the paste of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(40) comprise the slurry of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(41) comprise the thin-film material of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(42) comprise the dielectric ceramic of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(43) comprise the thermoelectric ceramics of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(44) comprise the piezoelectric ceramics of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(45) comprise the electrical condenser of the dielectric ceramic described in above (42).

(46) comprise at least a electron device that is selected from the element of pottery described in the thin-film material described in above (41), above (42)-(44) and the electrical condenser described in above (45).

(47) comprise the thin-film material described in one or more above (41) or the transmitter of the pottery described in above (42)-(44).

(48) comprise the dielectric film of the perovskite titanium-containing composite oxide particle described in each of above (1)-(18).

(49) comprise the electrical condenser of the dielectric film described in above (48).

Perovskite titanium-containing composite oxide particle among the present invention is that the perovskite titanium-containing composite oxide particle that is expressed from the next is (in formula, 0≤X≤1,0.98≤Y≤1.02,0≤δ≤0.05, and A1 and A2 differs from one another and they each is selected from Ca, Sr, Ba, Pb and Mg):

(A1 _XA2 _(1-X)) _YTiO _3±δ

Wherein, specific surface area is 1-100m ²/ g and assumed average primary granule degree are that D1 and average secondary granule degree are D2, and then the D2/D1 value is 1-10.Above-mentioned perovskite titanium-containing composite oxide particulate be characterised in that have little granularity, narrow distribution of particle sizes, dispersibility, high-crystallinity and excellent electric performance preferably.

As used herein, composite oxides not merely are that the mixture and the meaning are atom solid-state dissolved sosoloid under constant ratio wherein.Crystalline texture can be determined by the X-ray diffraction method of masurement.And the ratio of A1 atom pairs A2 atom can be determined according to the peak position in the x-ray diffraction pattern in the perovskite titanium-containing composite oxide particle.

Hereinafter, described (1) especially and comprised controlled arbitrarily A1 has narrower distribution of particle sizes to the perovskite titanium-containing composite oxide particle of the sosoloid ratio of A2 and (2) under the situation that has less ultra-fine grain and less agglomerating particles calcium titanium particle (CaTiO ₃: wherein A1 is Ca, X and Y all represent 1 and δ be 0).

(1) comprises the perovskite titanium-containing composite oxide particle of controlled arbitrarily A1 to the sosoloid ratio of A2

In the perovskite titanium-containing composite oxide in the present invention, the value of the X of expression sosoloid ratio is 0≤X≤1, preferred 0.2≤X≤0.8, more preferably 0.3≤X≤0.7.Preferably sosoloid ratio X is regulated so that needed electrical property to be provided.For example, under the room temperature specific inductivity of barium titanate be about 1,600 and the specific inductivity of strontium titanate be about 260.By regulating the sosoloid ratio of barium, can obtain to be adjusted to the barium strontium titanate that demonstrates needed dielectric constant values to strontium.

The total mole number of A1 atom and A2 atom is to the ratio of the mole number of titanium, and promptly ratio (Y) can be 0.98≤Y≤1.02, preferred 0.99≤Y≤1.01, and more preferably 0.995≤Y≤1.005, and described ratio regulated so that needed electrical property to be provided.Ratio (Y) preferably approaches 1, because produce less defects and obtain higher degree of crystallinity.

The ratio of oxygen (3 ± δ) can be 0≤δ≤0.1, preferred 0≤δ≤0.05, and more preferably 0≤δ≤0.03, and described ratio regulated so that needed electrical property to be provided.δ is preferably near 0, because produce less defects and obtain higher degree of crystallinity.

In order to improve the electrical property of the perovskite titanium-containing composite oxide particle among the present invention, can add and use other compound and not produce any problem like this.

The specific surface area that perovskite titanium-containing composite oxide particle among the present invention can have is 1-100m ²/ g, preferred 5-70m ²/ g, more preferably 10-50m ²/ g.Specific surface area can be measured by the BET method.Usually, in order to make the electronic material miniaturization, the specific surface area that particle must have is 1m ²/ g or more is if but specific surface area surpasses 100m ²/ g, particle are easy to reunite and powder becomes is difficult to handle.

Perovskite titanium-containing composite oxide particle among the present invention is to have the particulate that narrow distribution of particle sizes is seldom reunited with excellent dispersibility.Herein, for the particle with regard to spherical, average primary granularity D1 can be determined by the specific surface area that obtains by the BET method according to formula (1):

D1＝6/ρS

Wherein ρ is that pellet density and S are the particulate specific surface area.

The secondary granule degree of agglomerating particles can be by being dispersed in perovskite titanium-containing composite oxide particle in the dissolving and measuring granularity by the distribution of particle sizes analyser and determine.Usually, the distribution of particle sizes analyser of Shi Heing can be selected according to measured distribution of particle sizes scope.The secondary granule degree of the perovskite titanium-containing composite oxide particle among the present invention can for example pass through centrifugal, Microtrack method, electrozone method (Coulter-counter) and light scattering method and measure, and consider the particulate good sensitivity, preferably use light scattering method to measure.Distribution of particle sizes on the weight basis of secondary granule degree can be measured and can determine the average particle size granularity of 50% place (or begun by minimum value) D2 by aforesaid method.The granularity of Que Dinging is the particle size with regard to spherical herein.

When measured primary granule and secondary granule were sphere, average secondary diameter D2 was 1 to the minimum value of the D2/D1 value of average primary granularity D1 in theory.Bigger D2/D1 value shows, primary granule reunited more and dispersibility is reduced more.The D2/D1 value that the titanium-containing composite oxide particle of the perovskite structure among the present invention can have is 1-10, preferred 1-9, more preferably 1-8.

Perovskite titanium-containing composite oxide particle among the present invention can be a monocrystalline, and this can be by determining through transmission electron microscope observation.

And the perovskite titanium-containing composite oxide particle among the present invention can have the impurity of minimizing.Alkali metal content can be 0-100ppm, preferred 0-80ppm, more preferably 0-60ppm.The amount of chlorine impurity can be 0-600ppm, preferred 0-400ppm, more preferably 0-200ppm.

In addition, the perovskite titanium-containing composite oxide particle among the present invention may less growth in calcining step, and makes the less reduction of specific surface area.Though understand its reason dully, infer it is that specific surface area surpasses 100m because the perovskite titanium-containing composite oxide among the present invention contains seldom ²/ g ultrafine particle caused.For example, when being 900-1 in temperature, calcined 0.1-3 hour down for 000 ℃ the perovskite titanium-containing composite oxide particle among the present invention, in the time of preferred 1-3 hour, the percentage that specific surface area reduces can be for 90% or still less, and preferred 80% or still less, more preferably 60% or still less.Suppose that specific surface area when dried powder is S1 and is 900-1 in temperature, 000 ℃ of calcining 0.1-3 hour down, the specific surface area after preferred 1-3 hour is S2, then the percentage that reduces of specific surface area can be determined according to following formula (2):

(S1-S2)/S1×100　　　　　(2)

The shape of the perovskite titanium-containing composite oxide particle among the present invention can be determined by observing via the amplification of scanning electronic microscope.In the present invention, for example in most cases at barium strontium titanate compound particles, shape almost is that the composition ratio (X value) of spheric and the barium in the A-site is 0-0.8, particularly during 0.35-0.65, in temperature is 900-1, and shape may become similar quadrate shape after 200 ℃ of following calcinings.Though understand alteration of form dully is the quadrate reason, infers because its high-crystallinity causes.More particularly, the atomic radius that strontium has is less than the atomic radius of barium and is easy to be reset by calcining, therefore, when the composition ratio (1-X) of strontium is 0.2-1 (that is, the X value is 0-0.8), produces square.

As used herein, the square meaning is near cubical shape.In the present invention, when the composition ratio (X value) of the barium in the A-site when being 0-0.8,50% or the particulate of more (preferred 70% or more, more preferably 80% or more) can the side's of formation shape shape.

The total amount of the carbonate that is comprised in the perovskite titanium-containing composite oxide particle is few more, and is preferred more.The content of carbonate usually can be for 3 quality % or still less, preferred 2 quality % or still less, more preferably 0-1 quality %.The content of the carbonate that is comprised in the perovskite titanium-containing composite oxide particle (for example, barium carbonate, lime carbonate, strontium titanate, lead carbonate) can be determined by measuring infrared absorption spectrum.For example, under the situation of barium strontium titanate compound particles, the amount of carbonate can by with standard barium carbonate and Strontium carbonate powder at 880cm ^-1Near peak intensity and the present invention in the peak intensity of barium strontium titanate compare definite.

When being immersed in perovskite titanium-containing composite oxide particle in the pure water, the A1 ion of the particulate of unit surface and the total extracted amount of A2 ionic can be 0-2 μ mol/m ², preferred 0-1 μ mol/m ², more preferably 0-0.5 μ mol/m ²Although be not well understood to reason, infer that perovskite titanium-containing composite oxide particle has the ionic A1 atom and the A2 atom of high-crystallinity and low levels, so the ionic amount that elution is gone in the pure water is also little.

As used herein, the ionic amount of the extraction meaning is the various ionic total amounts of perovskite titanium-containing composite oxide particle of unit surface and determines according to following formula (3):

a×L/G×S (3)

Wherein

A: the ionic concentration of after extracting test, extracting in the pure water (ppm),

L: extract the amount L (g) of the pure water that uses in the test,

G: extract the perovskite titanium-containing composite oxide particle that uses in the test weight (g) and

S: the specific surface area (m of perovskite titanium-containing composite oxide particle ²/ g).

In the process of determining the total extracted amount of various ionic, in nitrogen glove box, add the perovskite titanium-containing composite oxide particle among the present invention in the ion exchanged water and after jam-pack, thoroughly stir, isolate the upper strata stillness of night and can measure the ionic amount of extracting in the pure water by ICP shooting method, atomic absorption method or the like.Churning time is according to the difference of agitation condition and therefore difference is not particularly limited.Time point when churning time can reach capacity by the ionic quantitative value of extracting in the pure water determines that it is observed by the time interval measurement method.

Describe the method for the perovskite titanium-containing composite oxide particle among production the present invention as an example below by the situation that will produce the barium strontium titanate, still, the present invention is not limited to the barium strontium titanate.

In inert atmosphere, hydrated barta and strontium hydroxide are dissolved in the alkaline solution, described alkaline solution contains basic cpd and the pH that has is about 10 or more, and preferred about 13 or more.Subsequently, titanium oxide sol is added wherein and reaction total amount of barium and strontium in reaction soln become inlet amount 1/1,000 or still less.

After reaction finishes, under normal pressure or decompression, to the temperature range of calcining temperature, basic cpd is removed as gas, thereby produced barium strontium titanate compound particles by evaporation, distillation and/or thermolysis in room temperature.

In the process of the perovskite titanium-containing composite oxide particle in production the present invention, preferably contain the alkaline solution of basic cpd.Though understand this reason dully, infer that every kind of ion (barium ion or strontium ion in these cases) is easier to react with titanium oxide because alkalescence is high more.The pH of solution can be 10 or more, preferred 13 or more, more preferably 14 or more.Be limited to the saturation solubility of basic cpd in water on the inlet amount of basic cpd.

In the method for the perovskite titanium-containing composite oxide particle in production the present invention, the oxyhydroxide of arbitrary ratio can be used, thereby corresponding perovskite titanium-containing composite oxide particle can be produced.Under the situation of barium strontium titanate compound particles, use the hydrated barta and the strontium hydroxide of arbitrary ratio, thereby can produce the barium strontium titanate mixture of corresponding ratio.And, titanium oxide sol can be sneaked into the total amount that produces barium and strontium estimated rate titanium.Ratio between hydrated barta and the strontium hydroxide is not particularly limited.

For example, when being 5mol (hydrated barta): 5mol (strontium hydroxide) with ratio: when the hydrated barta of 10 (titanium oxide), strontium hydroxide and titanium oxide charging, can produce Ba _0.5Sr _0.5TiO ₃Compound particles, and when being 6mol (hydrated barta): 4mol (strontium hydroxide) with ratio: when the hydrated barta of 10 (titanium oxide), strontium hydroxide and titanium oxide charging, can produce Ba _0.6Sr _0.4TiO ₃Compound particles.

Then, continue reaction various ionic total concns in reaction soln become inlet amount 1/1,000 or still less, preferred 1/2,000 or still less, more preferably 1/5,000 or still less, more preferably 1/10,000 or still less.By reacting like this, can improve the speed of reaction that obtains perovskite titanium-containing composite oxide, unreacted raw material for example oxyhydroxide and titanium oxide can be reduced, and purity and degree of crystallinity can be improved.

Various ionic amounts can be by removing solids content and carrying out determining of various ionic amounts in the reaction soln by ICP shooting method, atomic absorption method or the like in the solution after the reaction.

In the present invention, various ionic amounts can be definite according to following formula (4) in the solution after the reaction:

([A1’]+[A2’])×L2/([A1]+[A2]) (4)

Wherein

[A1 '], [A2 ']: respectively be volumetric molar concentration (mol/ml) by A1 ion in the solution after the reaction or A2 ionic mass concentration are obtained after changing,

[A1], [A2]: respectively for the mole number (mol) of the oxyhydroxide that is used to react institute's charging and

L2: the amount of reaction soln (ml).

After reaction finishes, under normal pressure or decompression, to the temperature range of calcining temperature, basic cpd is removed as gas, can be avoided the perovskite titanium-containing composite oxide particulate surface wash-out of various ions from the present invention to come out thus and can improve degree of crystallinity by evaporation, distillation and/or thermolysis in room temperature.

Industrial, this reaction heating is the most under agitation carried out.Carbonic acid group in the reaction soln (comprises, as carbonic acid material, CO ₂, H ₂CO ₃, HCO ₃ ^-And CO ₃ ^2-) produce stable barium carbonate or Strontium carbonate powder with hydrated barta or strontium hydroxide reaction.Barium carbonate or Strontium carbonate powder do not remain in the perovskite titanium-containing composite oxide particle with the titanium oxide reaction and as impurity.Therefore, control the concentration of carbonic acid group in the reaction soln (with regard to CO ₂; If not indicated otherwise, suitable equally below) make it possible to stably manufactured high purity perovskite titanium-containing composite oxide particle.

With regard to CO ₂Concentration in the reaction soln can be 0-500ppm (in mass), preferred 0-200ppm (in mass), more preferably 0-100ppm (in mass).In order to reduce the concentration of carbonic acid group in the reaction soln, preferably before making basic cpd dissolving with hydrothermal treatment consists, thereby just decarboxylation between the beginning production process.And reaction soln is alkali and is easy to absorb airborne CO ₂Therefore, reaction is preferably carried out in closed system or is carried out so that reaction soln is not contacted with air when purging nitrogen.

In order to improve degree of crystallinity, preferable reaction temperature is high as far as possible.Under the situation that improves temperature of reaction, the hydro-thermal reaction that can carry out critical temperature from 100 ℃ to solution, but this may need to guarantee the equipment of autoclave security.Therefore, preferably by under normal pressure, making reaction system boiling and keep this temperature to react under 100 ℃ or higher temperature.In addition, because raw material is mixed with each other, preferred mechanical stirs.Reaction times can be 2 hours or longer time, preferred 3 hours or longer time, more preferably 4 hours or longer time usually.

The impurity that influences electrical property unfriendly also comprises trace components for example metal ion and negatively charged ion.

Trace impurity ion for example metal ion and negatively charged ion can pass through the whole bag of tricks, for example by making slurry carry out the processing that for example electrodialysis, ion-exchange, washing, pickling and permeable membrane are removed after reaction finishes.But, according to aforesaid method, barium that is comprised in the perovskite titanium-containing composite oxide particle or the like can be simultaneously with the foreign ion ionization and be partly dissolved in the slurry sometimes, and this not only makes barium and strontium with needed ratio solid solution, and cause in crystal, producing defective, and this has reduced degree of crystallinity.Therefore in addition, reaction soln is an alkalescence, and in above-mentioned processing, is easy to the carbonic acid gas in the entrained air, and the result has increased the carbonate that is comprised in the perovskite titanium-containing composite oxide ion unfriendly.

Therefore, preferably select the raw material that impurity reduces and when reaction or calcining, avoid impurity to sneak into.In addition, preferably under normal pressure or decompression, to the temperature range of calcining temperature, impurity is removed as gas by evaporation, distillation and/or thermolysis in room temperature.

Usually calcine to improve the degree of crystallinity of titanium-containing composite oxide, in calcination process, impurity is removed as gas simultaneously by evaporation, distillation and/or thermolysis.The example of removable impurity can be included in the raw material organic amine, the oxyhydroxide of ammonium salt and the organic compound of trace that for example has low carbon number as carbonate that impurity comprised or organic bases in aforesaid method.Calcining is carried out under 200 ℃ usually at 350-1.Calcination atmosphere is not particularly limited and calcines usually carries out in air or under reduced pressure.

Just reduce heat energy in when calcining or improve with regard to the degree of crystallinity, preferably calcine making slurry carry out the solid-liquid after separating.The solid-liquid separation comprises the steps: the particulate precipitation, concentrates and filters and/or dry and grinding.By precipitation, concentrated and filtration, can remove dissolved impurity in the solution.In order to change settling rate or filtering rate, can use condensing agent or dispersion agent.Under described situation, the preferred use can be used as condensing agent or the dispersion agent that gas is removed by evaporation, distillation and/or thermolysis.

In order to make moisture evaporation can carry out drying step, in this step, can the basic cpd or the impurity of some kinds partially or completely be removed simultaneously by evaporation, distillation and/or thermolysis.Drying can be by carrying out such as drying under reduced pressure, warm air drying and cryodesiccated method.Drying was carried out 1-24 hour under room temperature to 350 ℃ usually.Dry atmosphere is not particularly limited, but drying is carried out in air or rare gas element or under reduced pressure usually.Can by appropriate means make particle cracked thereafter.

Barium salt, strontium salt that is used for the present invention or the like all uses as oxyhydroxide.As long as salt is oxyhydroxide, it can be anhydrous salt or hydrate and this qualification especially.

In the process of the common titanium-containing composite oxide of synthetic perovskite structure, separate at reaction, solid-liquid, each step Chinese style of dry, calcining or the like: (A1 _XA2 _(1-X)) _YTiO _{3 ± δ}In oxygen ratio (3+ δ) change, in crystalline structure, produce defective and electrical property and tend to reduce.But, in the present invention, use aforementioned production method, thereby can make the δ value very little.

The titanium oxide sol that is used for the present invention is not particularly limited, but preferably contains the titanium oxide sol or the titanium oxide sol by titanium salt hydrolysis in acidic solution is obtained of brookite crystal.

As long as contain brookite crystal, titanium oxide sol can only comprise the brookite titanium oxide maybe can comprise rutile or anatase titanium oxide.Under the situation that contains rutile or anatase titanium oxide, the ratio of brookite titanium oxide is not particularly limited in the titanium oxide, but is generally 1-100 quality %, preferred 10-100 quality %, more preferably 50-100 quality %.This is because crystalline particle is easier to form simple particle than amorphous granular, therefore preferably uses it for and realizes that excellent dispersibility and the brookite titanium oxide of titan oxide particles in solvent is excellent especially aspect dispersibility.Though be not well understood to this reason, infer that the ζDian Shi of brookite titanium oxide that is higher than the ζDian Shi of rutile or Detitanium-ore-type for 2 times at pH plays a role.

Be used for the example of method that solid phase production comprises the titan oxide particles of brookite crystal and comprise that a kind of production method of the titan oxide particles that the thermal treatment of anatase titanium oxide particle is obtained to comprise brookite crystal and a kind of making comprise titanium compound for example titanium tetrachloride, titanous chloride, titan-alkoxide and titanium sulfate neutralization or hydrolysis obtain to have therein the liquid phase production method of the titanium oxide sol of dispersive titan oxide particles.

Beginning to produce by the titan oxide particles that comprises brookite crystal in the titanium-containing composite oxide particulate method, the preferred use comprises the particle of titanium oxide sol as titan oxide particles, because this colloidal sol has small particle size and excellent dispersibility, above-mentioned titanium oxide sol obtains by making titanium salt hydrolysis in acidic solution.More particularly, preferred a kind of with titanium tetrachloride 75 to 100 ℃ add down in the hot water and temperature be 75 ℃ in the control chlorine ion concentration, make to the temperature of the boiling point of solution titanium tetrachloride hydrolysis with obtain to contain the titan oxide particles of brookite crystal as the method for titanium oxide sol (referring to, JP-A-11-43327) and a kind of with titanium tetrachloride 75 to 100 ℃ add down in the hot water and temperature be 75 ℃ to the temperature of the boiling point of solution at the control chlorion, make in the time of the total concn of nitrate ion and phosphate anion titanium tetrachloride in the presence of one of nitrate ion and phosphate anion or both hydrolysis with obtain to contain the titan oxide particles of brookite crystal as the method for titanium oxide sol (referring to, US patent 6,627,336 (WO99/58451)).

The primary granule degree that the titan oxide particles that obtains like this has usually is 1-100nm, preferred 3-50nm, more preferably 5-20nm.If the primary granule degree surpasses 100nm, then by using titan oxide particles may make the granularity raising and not be suitable for functional material for example dielectric materials and piezoelectric as the titanium-containing composite oxide particle of starting raw material production; And if the primary granule degree is less than 1nm, then in the step of producing titan oxide particles, be difficult to handle.

Under using by the situation that makes the titanium salt titanium oxide sol that hydrolysis obtains in acidic solution, titanium oxide is not limited to crystalline form and is not limited to the brookite crystalline form.

When make titanium salt for example titanium tetrachloride and titanium sulfate in acidic solution during hydrolysis, suppressed speed of reaction more in the reaction than property in use or alkaline solution, as a result, can form particle with simple granularity and the titanium oxide sol that can obtain to have excellent dispersibility.In addition, negatively charged ion for example chlorion and sulfate ion is difficult to capture the inside of the titan oxide particles of being produced, and therefore when production titanium-containing composite oxide particle, has reduced negatively charged ion is sneaked in the particle.

On the other hand, if in neutrality or alkaline solution, be hydrolyzed, then speed of reaction may improve and may produce many nucleus in the starting stage, and granularity is little to be had the titanium oxide sol of poor dispersibility and may produce that resemble must shape accumulative particle although the possibility of result obtains.When beginning to produce the titanium-containing composite oxide particle, although the little dispersibility of going on business that shows of the particle granularity of acquisition by above-mentioned titanium oxide sol.And negatively charged ion may be easy to sneak into the inside of titan oxide particles and may be difficult to remove at negatively charged ion described in the subsequent step.

The method that makes titanium salt hydrolysis in acidic solution obtain titanium oxide sol is not particularly limited, as long as can make solution keep acid, but titanium tetrachloride as starting raw material hydrolysis and the chlorine of avoiding produce this moment in being equipped with the reactor of reflux exchanger are overflowed, thereby make keep to keep the tart method (referring to, JP-A-11-43327).

The concentration of titanium salt in acidic solution is preferably 0.01-5mol/L.If this concentration surpasses 5mol/L, the dispersibility that hydrolysis is carried out under high speed of response and the titanium salt that obtains may have big granularity and differ from then; And if this concentration is less than 0.01mol/L, the concentration and the throughput of titanium oxide that then may reduce acquisition is low.

The method that adds titanium oxide sol is not particularly limited, but, the barium strontium titanate that has excellent dispersibility for fear of the reunion and the acquisition of titanium oxide sol, preferably little by little add titanium oxide sol in the reaction soln, described reaction soln by with barium strontium salt at least with saturation solubility or more add to contain in the alkaline solution of basic cpd, heating and stirred solution obtain.The example of the method that titanium oxide sol is added gradually comprises by using method that pump etc. dropwise adds titanium oxide sol and titanium oxide sol being injected into method in the solution.

Be used for basic cpd of the present invention and be not particularly limited, but the preferred material that under normal pressure or decompression, becomes gas by evaporation, distillation and/or thermolysis.The example comprises that organic bases for example has high-dissolvability and has the organic amine of low carbon number and the oxyhydroxide of ammonium salt in ammoniacal liquor or water.

Wherein, high dissociation degree and when reaction, do not evaporate and be used as the alkaline characteristic when being dissolved in the water because of it, the preferably oxyhydroxide of ammonium salt owing to it.On the other hand, the organic amine that has high-dissolvability and have a low carbon number in ammoniacal liquor or water is very weak and be difficult to use because of its lower boiling as alkali.

The industrial known example of the oxyhydroxide of ammonium salt comprises choline and Tetramethylammonium hydroxide (TMAH), and they can be buied at a low price.Especially, in electronic industry, use Tetramethylammonium hydroxide and preferably use described compound, but and be that this compound is 135-140 ℃ of thermolysis and remove as gas down not only because the product that is purchased of this compound contains for example metal ion or the like of few impurities.

Barium strontium titanate composite oxide particle among the present invention also can still, more preferably become the basic cpd of gas by using cheap for example lithium hydroxide, sodium hydroxide and potassium hydroxide production of mineral compound.

Basic cpd is not particularly limited.Can be used alone basic cpd or also can be with two or more compounds by it mix being used with arbitrary ratio and this does not produce any problem.

(2) contain the calcium titanate particle (CaTiO of less ultrafine particle and agglomerating particles ₃)

In the perovskite titanium-containing composite oxide particle in the present invention; therein A1 be calcium, X and Y represent 1 and δ be 0 calcium titanate; the shape that it is characterized in that having perovskite crystal structure and tetragonal prism shape or be similar to tetragonal prism; be monocrystalline, the reduced number of ultrafine particle or agglomerating particles and have narrow distribution of particle sizes and excellent dispersibility.

The shape of calcium titanate can be determined by observing through the amplification of scanning electronic microscope.The calcium titanate powder that has perovskite crystal structure and tetragonal prism shape or be similar to the shape of tetragonal prism may have the column hexahedral shape, and wherein the bottom surface has near foursquare shape and side and has near rectangular shape.Each face intersects with almost right angle, but in some cases, can make at least one angle cut sth. askew, become circle or sharpening slightly.Each face with the number of particles of right angle intersection account for total powder 80% or more, preferred 90% or more, more preferably 95% or more.Under being cut sth. askew a little in the angle and becoming round situation, radius-of-curvature can be 10 μ m or more.

When the calcium titanate particle can pass through sem observation, the bond length that most of particles can have was that 0.2-0.6 μ m and long edge lengths are 0.2-1.2 μ m.Described particulate percentage can be 80% or more, preferred 85% or more, more preferably 90% or more.

Long limit to minor face ratio can each calcium titanate particulate greatly enhance the limit most and minimum minor face is measured by measuring, and the production method of the calcium titanate in according to the present invention, can stably produce long limit is the particle with square cylindricality of 1.1-6 to the ratio of minor face.The long limit of calcium titanate crystalline be to big more may the meaning of ratio of minor face, particle along the longitudinal growth of the perovskite structure of expression electrical property more and this be preferred.

Can confirm that by analysis calcium titanate is a monocrystalline and in described monocrystalline, long limit extends to structure cell (010) plane through the electron beam diffraction image of transmission electron microscope.

Monocrystalline means that degree of crystallinity is very high.The long limit that extends to structure cell (010) in-plane can illustrate that the perovskite structure of expression electrical property is longitudinally grown.Therefore, for example dielectricity, piezoelectricity and pyroelectricity are very excellent for electrical property.

The specific surface area that calcium titanate can have is 1-10m ²/ g, preferred 1-8m ²/ g, more preferably 1-6m ²/ g.Specific surface area can be measured by the BET method.In order to make the electronic material miniaturization, the specific surface area that particle can have is 1m ²/ g or more is if but specific surface area surpasses 100m ²/ g, particle are easy to reunite each other and powder may become is difficult to handle.

Calcium titanate is to have narrow distribution of particle sizes and excellent dispersibility and particulate that seldom reunite.Herein, the average primary granularity can be measured according to above-mentioned formula (1).

Distribution of particle sizes on the weight basis of secondary granule can be measured and can measure average particle size D2, begun 10% granularity D3 by minimum value and at the granularity D4 that is begun 90% by minimum value by aforesaid method.The granularity that this place is measured is the particle size with regard to spherical.

The D2/D1 ratio that calcium titanate can have is 1-3, preferred 1-2.7, more preferably 1-2.5.

The distribution of particle sizes of secondary granule can be obtained by D3/D2 ratio in the distribution of particle sizes of calcium titanate and D4/D2 ratio.Because each value is all near 1, the distribution of particle sizes of secondary granule becomes narrower and this is preferred.

In the present invention, the D3/D2 value can be 0.1-0.9, preferred 0.15-0.7, more preferably 0.2-0.5.The D4/D2 value is 1.1-10, preferred 1.2-8, more preferably 1.4-5.

The amount of the lime carbonate that is comprised in the calcium titanate can be 0-3 quality %, preferred 0-2 quality %, more preferably 0-1 quality %.The amount of the lime carbonate that is comprised in the calcium titanate can be determined by measuring infrared absorption spectrum.Specifically, the amount of lime carbonate can be by will be at 880cm ^-1Near the peak area intensity of standard lime carbonate and the peak area strength ratio of calcium titanate of the present invention are more definite.

And the calcium titanate among the present invention is characterised in that particle is less growth and the less minimizing of specific surface area in calcining step.Usually, microgranular Ti-base composite oxide is easy to grow when calcining step and specific surface area is tended to significantly reduce, but the calcium titanate among the present invention does not have above-mentioned tendency.For example, when exsiccant calcium titanate powder at 900-1,200 ℃ down during calcining, specific surface area reduces 8m ²/ g or still less, preferred 5m ²/ g or still less, more preferably 2m ²/ g or still less.

Production method among the present invention is described below.In the method for the calcium titanate in production the present invention, titanium oxide sol and calcium salt added the alkali aqueous solution that comprises basic cpd until saturation solubility or until greater concn and make its reaction to produce calcium titanate.

Industrial, react the most common heating under agitation and carry out.Carbonic acid group in the reaction soln (comprises, as carbonic acid material, CO ₂, H ₂CO ₃, HCO ₃ ^-And CO ₃ ^2-) produce stable barium carbonate or Strontium carbonate powder with barium salt or strontium reactant salt.Barium carbonate or Strontium carbonate powder do not remain in the perovskite titanium-containing composite oxide particle with the titanium oxide reaction and as impurity.Therefore, control the concentration of carbonic acid group in the reaction soln (with regard to CO ₂; If not indicated otherwise, suitable equally below) make it possible to stably manufactured high purity perovskite titanium-containing composite oxide particle.

About the concentration of carbonic acid group and control, temperature of reaction, reaction times, Impurity removal and incinerating reaction conditions almost with above-mentioned (1) perovskite titanium-containing composite oxide particulate production method is described in defined identical, but, reaction times can be 3 hours or longer time herein, preferred 4 hours or longer time, and more preferably 6 hours or longer time.

In the present invention, calcium salt can saturation solubility or is more added to comprise in the alkaline solution of at least a basic cpd.Though understand reaction mechanism dully, but infer in reaction during the starting stage, the granular calcium titanate of ultra micro is produced in the calcium salt and the titanium oxide sol reaction that are dissolved in the solution, and thereafter, the undissolved calcium salt when the starting stage of reaction of nubbin also begins dissolving gradually to produce calcium titanate with the titanium oxide sol reaction, and the calcium titanate of new generation is grown on the initial calcium titanate that produces.According to above-mentioned reaction mechanism, not only reduced ultrafine particle but also can obtain narrow distribution of particle sizes and the granularity that is suitable for small electronic component.In addition, the solubleness of calcium salt is very low and think that therefore the calcium titanate particle of new generation is becoming very little granularity and formed stable shape before production under the very low speed, and the result can obtain to have the single crystal particle of similar tetragonal prism shape.

The amount of the calcium salt that is added is not particularly limited, as long as it is a saturation solubility or more, if but the amount that is added in alkali aqueous solution is little, then be easy to the calcium titanate of sneaking into the granular calcium titanate of ultra micro and can not obtain to have narrow distribution of particle sizes.On this meaning, the concentration of calcium salt is preferably higher, if but in alkali aqueous solution the amount of institute's charging excessive, calcium salt can not evenly be sneaked in the alkali aqueous solution and the viscosity of solution uprises.

Therefore, preferably with the 10-10 of saturation solubility, 000 times weight is fed in the alkali aqueous solution calcium salt.

The calcium salt that is used for the present invention is not particularly limited, as long as it is a small amount of solvable in alkali aqueous solution, and can use oxyhydroxide, nitrate, vitriol, halogenide or with organic materials for example carboxylic acid and pure salt.Can use a kind of in the above-claimed cpd separately or also two or more compounds can be used by it is mixed with arbitrary ratio.

Especially, calcium salt is preferably oxyhydroxide, because calcium hydroxide is a small amount of solvable and solvable more on a small quantity in alkali aqueous solution in water.The favourable part of oxyhydroxide is that also the negatively charged ion in the calcium hydroxide can be used as gas and easily removes.

Not preferred and calcium forms those of stable chelate (for example compound of the calcium salt of ethylenediamine tetraacetic acid (EDTA)), because saturated solubleness uprises and may not produce calcium titanate.

In the process of the calcium titanate in production the present invention, preferably comprise the alkaline solution of basic cpd.When alkalescence was higher, calcium salt was difficult to dissolving and this is preferred.The pH of solution is preferably 13 or more, and more preferably 14 or more.The upper limit of the amount of the basic cpd that is added can be the saturation solubility of basic cpd in water.

According to the present invention,, can use those compounds that can be used in above-mentioned production (1) the perovskite titanium-containing composite oxide particulate method as the basic cpd that is used in the aforesaid method.

Unreacted calcium salt may be difficult to separate with titanium oxide sol and after reaction it be removed from calcium titanate.Therefore, can titanium oxide sol be sneaked into, promptly can after reaction is finished, can obtain the estimated rate of calcium and titanium in the calcium titanate with such consumption.

The titanium oxide sol that is used for the present invention is not particularly limited, but preferably contains the titanium oxide sol or the titanium oxide sol by titanium salt hydrolysis in acidic solution is obtained of brookite crystal.Can use those titanium oxide sols in above-mentioned production (1) perovskite titanium-containing composite oxide particulate method illustrated.

The method that adds titanium oxide sol is not particularly limited, but for fear of the calcium titanate that titanium oxide sol is reunited and acquisition has excellent dispersibility, preferably add titanium oxide sol in the reaction soln gradually, described reaction soln comprises in the alkaline solution of basic cpd by calcium salt is added with saturation solubility or more amount, and heating and stirred solution obtain.The example that adds the method for titanium oxide sol gradually comprises a kind of by using pump etc. dropwise to add method and a kind of method of titanium oxide sol being injected solution of titanium oxide sol.

So the titanate of producing can have small particle size, dispersibility, high-crystallinity and excellent electric performance preferably under narrow distribution of particle sizes, and described calcium titanate can be shaped as dielectric ceramic, thermoelectric ceramics, piezoelectric ceramics or thin-film material.Dielectric ceramic or thin-film material can be used as capacitor material or be used for transmitter.

Perovskite titanium-containing composite oxide particle among the present invention also can be used as slurry or paste by particle is sneaked in one or more solvents that comprise water, existing inorganic adhesive or existing organic binder bond separately or with additive or other combination of materials.

The electrical property of the perovskite titanium-containing composite oxide particle among the present invention can be by calcining or its molded article of sintering under proper condition, for example by with various additives for example sintering aid add in the particle and make its be shaped the disk that obtains or by various additives are added contain in this particulate slurry or the paste and make its film that obtains that is shaped after use electric impedance analyzer or the like evaluation.

Having fillers dispersed that the film of high dielectric ratio (dielectric rate) can be by will comprising the perovskite titanium-containing composite oxide particle among the present invention obtains in one or more are selected from one or more of thermoplastic resin and thermosetting resin.

Comprise in addition under the situation of the material that is different from the perovskite titanium-containing composite oxide particle among the present invention at filler, can use one or more that is selected from aluminum oxide, titanium dioxide, zirconium white and tantalum oxide.

The thermoplastic resin and the thermosetting resin that can be used among the present invention are not particularly limited, and can adopt the conventional resin that uses.The preferred embodiment of thermosetting resin comprises Resins, epoxy, polyimide resin, polyamide resin and two cyanate resin.The preferred embodiment of thermoplastic resin comprises polyolefin resin, styrene resin and polymeric amide.

Be dispersed in for the uniform filling that will comprise the perovskite titanium-containing composite oxide particle among the present invention in the resin of at least a thermoplastic resin and/or thermosetting resin, preferred in advance by fillers dispersed is prepared slurry in the mixture of solvent or solvent and above-mentioned resin combination.

Be not particularly limited by the method that fillers dispersed is prepared slurry in the mixture of solvent or solvent and above-mentioned resin combination, still, preferably this preparation method comprises the wet type fragmentation step.

Solvent is not particularly limited and can uses the conventional any solvent that uses.The example comprises methyl ethyl ketone, toluene, vinyl acetic monomer, methyl alcohol, ethanol, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone and methylcyclohexane, described solvent can use separately or use with the form of mixture its two or more.

Wherein in the process with the slurry of fillers dispersed in the mixture of solvent or solvent and resin combination, preferably sneak into coupling agent in preparation.Coupling agent is not particularly limited and can uses the conventional any coupling agent that uses.The example comprises silane coupling agent, titanate-based coupling agent and aluminate-base coupling agent.The hydrophilic radical that is comprised in the coupling agent and the lip-deep reactive with active hydrogen that is present in the filler that comprises perovskite titanium-containing composite oxide particle of the present invention to be providing top coat, thereby improved the dispersibility of filler in solvent.Suitably selecting under the situation of coupling agent, the hydrophobic grouping that is comprised in the coupling agent can improve the consistency with resin.For example, using under the situation of Resins, epoxy as resin, preferred use have functional group for example mono amino, diamino, cationic styrene base, epoxy group(ing), sulfydryl, anilino and uride silane coupling agent or have for example titanate-based coupling agent of phosphorous acid ester, amino, diamino, epoxy group(ing) and sulfydryl of functional group.In addition, using under the situation of polyimide resin, preferred use have functional group for example mono amino, diamino and anilino silane coupling agent or have for example titanate-based coupling agent of mono amino and diamino of functional group.Above-mentioned coupling agent can use separately or use with the form of mixture its two or more.

The consumption of coupling agent is not particularly limited, as long as this consumption makes coupling agent reaction to provide coating on the part of perovskite titanium-containing composite oxide particle of the present invention or whole surface.But the consumption too excessive of preferred coupling agent because the coupling agent of part remained unreacted may influence slurry unfriendly, is not measured very little and then may be reduced coupling effect.Therefore require to select the consumption of coupling agent according to the kind that comprises granularity, its specific surface area and the employed coupling agent of the filler of perovskite titanium-containing composite oxide particle of the present invention, so that make the filler can homodisperse, and the preferable range of this consumption be 0.05-20 weight %.

In order to finish hydrophilic radical in the coupling agent and to be present in reaction between the lip-deep active hydrogen of the filler that comprises perovskite titanium-containing composite oxide particle of the present invention, preferably in process of production, after the preparation slurry, heat-treat.Heating temperature and heat-up time are not particularly limited, and still, preferred thermal treatment is to carry out under 100-150 ℃ 1-3 hour in temperature.When the boiling point of solvent is 100 ℃ or still less the time, Heating temperature is adjusted to boiling point or still less and therefore prolongs heat-up time.

The accompanying drawing summary

The Ba of Fig. 1 for producing among the embodiment 1 before the calcining _0.6Sr _0.4TiO ₃The X-ray diffraction spectrum of powder particle.

The Ba of Fig. 2 for producing among the embodiment 1 before the calcining _0.6Sr _0.4TiO ₃The image that powder particle arrives by sem observation.

The Ba of Fig. 3 for producing among the embodiment 1 after the calcining _0.6Sr _0.4TiO ₃The image that powder particle arrives by sem observation.

The Ba of Fig. 4 for producing among the embodiment 1 after the calcining _0.6Sr _0.4TiO ₃The X-ray diffraction spectrum of powder particle.

The Ba of Fig. 5 for producing among the embodiment 1 after the calcining _0.6Sr _0.4TiO ₃The image that powder particle arrives by transmission electron microscope observation.

The Ba of Fig. 6 for producing among the embodiment 1 after the calcining _0.6Sr _0.4TiO ₃The image K-M of powder particle.

Fig. 7 is the Ba that produces among the embodiment 2 _0.6Sr _0.4TiO ₃The X-ray diffraction spectrum of powder particle.

Fig. 8 is the Sr that produces among the embodiment 3 ₄TiO ₃The X-ray diffraction spectrum of powder particle.

Fig. 9 is the X-ray diffraction spectrum of the calcium titanate powder of acquisition among the embodiment 8.

The image that Figure 10 arrives by sem observation for the calcium titanate powder that obtains among the embodiment 8.

Figure 11 is the X-ray diffraction spectrum of the calcium titanate powder of acquisition among the embodiment 9.

The image that Figure 12 arrives by sem observation for the calcium titanate powder that obtains among the embodiment 9.

Image and electron diffraction that Figure 13 arrives by transmission electron microscope observation for the calcium titanate powder that obtains among the embodiment 9.

The optimum implementation that carries out an invention

Describe the present invention in detail below by reference example and comparative example, but the present invention is not limited in these embodiment.

Embodiment 1:

(produced purity by Sumitomo Titanium Corporation: 99.9%) concentration is that the aqueous solution of 0.25mol/L adds in the reactor that has reflux exchanger and by being heated when avoiding chlorion to overflow keeping solution acidic near the boiling point will to have titanium tetrachloride.Solution was kept 60 minutes under this temperature, thereby make titanium tetrachloride hydrolysis obtain titanium oxide sol.The titanium oxide sol drying under 110 ℃ that obtains is also detected crystal type and finds that it is the brookite titanium oxide by the X-ray diffraction device of being made by Rigaku Corporation (RAD-B Rotor Flex).

In stream of nitrogen gas, 456g 20 quality % tetramethylammonium hydroxide aqueous solutions (TMAH) (being produced the concentration of carbonic acid group: 60ppm or lower by Sachem Showa K.K.), 75.7g barium hydroxide octahydrate and 42.5g eight hydronium(ion) oxidation strontiums are fed in the reactor that has reflux exchanger.The pH that under agitation makes acquisition is the boiling of 14 the aqueous solution and is under 7g/ minute to be that the colloidal sol of 15 quality % dropwise adds in the reactor with 213g titanium oxide concentration in speed, and described colloidal sol is by with the colloidal sol of above preparation (by the electrodialysis instrument from wherein removing chlorion until 500ppm) precipitation with concentrate acquisition.

Under agitation make boiling continue 4 hours.Subsequently, stop heating, continue simultaneously to stir and make resulting solution be cooled to 50 ℃, and then decompression is filtered down.Thereafter, be that 50ml adds in the 1g filtrate and by the ICP shooting method and measures the solution that is obtained with the consumption with 1ml concentrated nitric acid and water, the amount of barium ion is that the amount of 2ppm and strontium ion is 1ppm in the filtrate as a result.Continue reaction after reaction in the solution total concn (calculating) of barium ion and strontium ion according to formula (3) become inlet amount 1/1,000 or still less.

The filter cake that obtains was obtained dried powder down in dry 5 hours at 300 ℃.Actual output is 99.9% with the ratio of the theoretical yield that calculates according to the amount of titanium oxide that uses in the reaction and hydrated barta.

The powder particle that X-ray diffraction device (the RAD-B Rotor Flex) evaluation of dried powder being pulverized in mortar and being made by Rigaku Corporation by use is obtained.By the Rietveld analysis revealed that uses the X-ray diffraction peak to carry out, institute's powder particle that acquires is wherein to contain the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃Compound particles.Fig. 1 represents the X-ray diffraction spectrum of powder particle.

The particulate specific surface area is measured by the BET method and is found that it is 49m ²/ g.Observe shape and find that it is spherical by it is amplified via scanning electronic microscope.(referring to Fig. 2)

The average primary granularity D1 that calculates according to formula (1) is 0.022 μ m.And, be 0.17 μ m by powder particle being dispersed in the pure water and measuring determined average particle size D2 by the optical scatter degree apparatus for measuring distribution of making by Otsuka Electronics Co. (ELS-8000).Thereby D2/D1 is 7.7.

This dried powder particle of about 6mg and about 900mgKBr are ground and mix, and mixture that will about 800mg acquisition is suppressed shape in blocks.And, similarly the standard barium carbonate is suppressed shape in blocks.Then, measure infrared absorption spectrum by the FTS6000 that makes by Bio-Rad.Will be at 880cm ^-1Near the standard barium carbonate and the peak intensity of Strontium carbonate powder and the peak intensity of barium strontium titanate of the present invention compare.The barium carbonate that is comprised in the above-mentioned powder particle and the total amount of Strontium carbonate powder are 0.5 quality %.

Measure potassium (K) ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 20ppm.And, measuring chlorine (Cl) ionic amount by the anion chromatographic method, the result contains the Cl ion of 100ppm.

In nitrogen glove box, pack into 1.5g dried powder and stirring rod in the 45ml ion exchanged water and after jam-pack, use agitator thoroughly to stir 24 hours or longer time.Isolate the upper strata stillness of night and by membrane filter it filtered thereafter.Then, concentrated nitric acid and the water with 0.5ml adds in the 1ml filtrate with the amount that obtains 25ml.The amount of barium ion and strontium ion is measured by the ICP shooting method.The extracted amount that calculates according to formula (3) is 0.22 μ mol/m ²

Dried powder is placed the electric furnace (KDFP-90) made by Denken Co. and heats up and hold it in 950 ℃ after following 2 hours with speed being 20 ℃/minute, make its naturally cooling.The specific surface area of the powder that obtains is 21m ²/ g and calculate according to formula (2), the percentage that specific surface area reduces is 57%.By observe be shaped as square (referring to the Fig. 3) that determines through the amplification of scanning electronic microscope.Fig. 4 represents the X-ray diffraction spectrum of powder particle.And, observe the sample (referring to Fig. 5) of acquisition and find that by image K-M it is monocrystalline (referring to Fig. 6) by transmission electron microscope (H-9000UHR: by Hitachi, Ltd. makes).

Embodiment 2:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 50.5g barium hydroxide octahydrate and 63.8g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 48m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.4Sr _0.6TiO ₃Mixture, and be shaped as sphere.Fig. 7 represents the X-ray diffraction spectrum of powder particle.

D1 is 0.023 μ m, and D2 is 0.17 μ m, and D2/D1 is 7.4.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.4 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 10ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 80ppm.

According to the barium ion of formula (3) calculating and total extracted amount of strontium ion is 0.32 μ mol/m ²After 950 ℃ kept 2 hours down, specific surface area was 23m ²/ g calculates according to formula (2), and the percentage that specific surface area reduces is 52%, is shaped as squarely, and particle is a monocrystalline.

Embodiment 3:

By with embodiment 1 in identical operations produce the strontium titanate particulate, except using 0g barium hydroxide octahydrate and 106.3g eight hydronium(ion) oxidation strontiums.

Continue reaction concentration of strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 46m ²/ g, particle are uhligite SrTiO ₃, and be shaped as sphere.Fig. 8 represents the X-ray diffraction spectrum of powder particle.

D1 is 0.025 μ m, and D2 is 0.16 μ m, and D2/D1 is 6.4.The amount of the Strontium carbonate powder that is comprised in the described powder particle is 0.6 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 25ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 92ppm.

The ionic extracted amount that calculates according to formula (3) is 0.36 μ mol/m ²After 950 ℃ kept 2 hours down, specific surface area was 15m ²/ g calculates according to formula (2), and the percentage that specific surface area reduces is 67%, is shaped as squarely, and particle is a monocrystalline.

Embodiment 4:

By with embodiment 1 in identical operations produce barium titanate microparticles, except using 126.2g barium hydroxide octahydrate and 0g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 39m ²/ g, particle are uhligite BaTiO ₃, and be shaped as sphere.

D1 is 0.024 μ m, and D2 is 0.16 μ m, and D2/D1 is 6.4.The amount of the barium carbonate that is comprised in the described powder particle is 0.5 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 18ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 100ppm.

The ionic extracted amount that calculates according to formula (3) is 0.36 μ mol/m ²

After 950 ℃ kept 2 hours down, specific surface area was 4m ²/ g calculates according to formula (2), and the percentage that specific surface area reduces is 90%, be shaped as sphere, and particle is a monocrystalline.

Embodiment 5:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 1.3g barium hydroxide octahydrate and 105.2g eight hydronium(ion) oxidation strontiums.

Continue reaction after reaction in the solution total concn of barium ion and strontium ion become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 46m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.01Sr _0.99TiO ₃, and be shaped as sphere.

D1 is 0.025 μ m, and D2 is 0.16 μ m, and D2/D1 is 6.4.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.6 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 16ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 80ppm.

The ionic extracted amount that calculates according to formula (3) is 0.36 μ mol/m ²

After 950 ℃ kept 2 hours down, specific surface area was 16m ²/ g, the percentage that specific surface area reduces is 65%, is shaped as squarely, and particle is a monocrystalline.

Embodiment 6:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 124.9g barium hydroxide octahydrate and 1.1g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 43m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.99Sr _0.01TiO ₃, and be shaped as sphere.

D1 is 0.024 μ m, and D2 is 0.17 μ m, and D2/D1 is 7.1.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.4 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 21ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 95ppm.

The total extracted amount of ionic that calculates according to formula (3) is 0.42 μ mol/m ²

After 950 ℃ kept 2 hours down, specific surface area was 5m ²/ g, the percentage that specific surface area reduces is 88%, be shaped as sphere, and particle is a monocrystalline.

Embodiment 7:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, the anatase titanium oxide sol (STS-02 is produced by Ishihara Sangyo Kaisha Ltd.) that is purchased except use replaces synthetic brookite titanium oxide sol among the embodiment 1.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 57m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃, and be shaped as sphere.

D1 is 0.018 μ m, and D2 is 0.17 μ m, and D2/D1 is 9.4.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.5 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 20ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 60ppm.

The total extracted amount of ionic that calculates according to formula (3) is 0.53 μ mol/m ²

After 950 ℃ kept 2 hours down, specific surface area was 30m ²/ g, the percentage that specific surface area reduces is 47%, is shaped as squarely, and particle is a monocrystalline.

Comparative example 1:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, replace barium hydroxide octahydrate and 42.7g Strontium dichloride hexahydrate to replace eight hydronium(ion) oxidation strontiums except using the 58.6g barium chloride dihydrate.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 48m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃, and be shaped as sphere.

D1 is 0.022 μ m, and D2 is 0.17 μ m, and D2/D1 is 7.7.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.5 quality %.The total extracted amount of ionic that calculates according to formula (3) is 0.46 μ mol/m ²

After 950 ℃ kept 2 hours down, specific surface area was 25m ²/ g, the percentage that specific surface area reduces is 48%, is shaped as squarely, and particle is a monocrystalline.

But, when measuring the Cl ion, containing 14 with the dried powder dissolving and by the anion chromatographic method, the Cl ion/g powder of 000ppm and the barium strontium compound particles of producing by this method are not suitable for electronic material.

Comparative example 2:

In comparative example 1, after synthetic, repeat to wash and filter 10 times.Cl ionic amount is reduced to 500 μ g/g dried powders.The amount of barium is that the amount of 20ppm and strontium is 15ppm in the filtrate when the 10th time is filtered.With dried powder dissolving and measurement, titanium is 0.94 to the ratio of the total amount of barium and strontium as a result.

Comparative example 3:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, replace TMAH except using 20%KOH.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 48m ²/ g, particle are by the X-ray diffraction evaluation and find that it is wherein to contain the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃And shape observes and finds that by it is amplified through electron microscope it is spherical.

D1 is 0.022 μ m, and D2 is 0.16 μ m, and D2/D1 is 7.3.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.5 quality %.The total extracted amount of ionic that calculates according to formula (3) is 0.46 μ mol/m ²

After 950 ℃ kept 2 hours down, specific surface area was 25m ²/ g, the percentage that specific surface area reduces is 48%, is shaped as squarely, and particle is a monocrystalline.

But, when measuring the K ion, containing 5 with the dried powder dissolving and by the ICP shooting method, the K ion/g powder of 000ppm and the barium strontium compound particles of producing by this method are not suitable for electronic material.

Comparative example 4:

In comparative example 3, after synthetic, repeat to wash and filter 10 times.Make K ionic amount be reduced to the 300ppm/g dried powder.The amount of barium is that the amount of 18ppm and strontium is 12ppm in the filtrate when the 10th time is filtered.With dried powder dissolving and measurement, titanium is 0.96 to the ratio of the total amount of barium ion and strontium ion as a result.

Comparative example 5:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, replace adding TMAH except using the 368g pure water.

Continue reaction total concn of barium ion and strontium ion in reaction soln and become 2% of inlet amount.Actual output is 98% to the ratio of theoretical yield.Make in the filtrate water evaporation and by with filtrate 300 ℃ dry 5 hours down, obtain powder particle.Powder particle detects by X-ray diffraction and finds that it comprises hydrated barta and strontium hydroxide (raw material).The total extracted amount of ionic that calculates according to formula (3) is 30 μ mol/m ²

Comparative example 6:

By with comparative example 5 in identical operations produce barium strontium titanate compound particles, except constantly boiling under agitation replaced 4 hours in 12 hours.

Continue reaction total concn of barium ion and strontium ion in reaction soln and become 1.7% of inlet amount.Actual output is 98.3% to the ratio of theoretical yield.Make in the filtrate water evaporation and by with filtrate 300 ℃ dry 5 hours down, obtain powder particle.Powder particle detects by X-ray diffraction and finds that it comprises hydrated barta and strontium hydroxide (raw material).The total extracted amount of ionic that calculates according to formula (3) is 26 μ mol/m ²

Comparative example 7:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except constantly boiling under agitation replaced 4 hours in 1 hour.

Continue reaction total concn of barium ion and strontium ion in reaction soln and become 0.4% of inlet amount.Actual output is 99.6% to the ratio of theoretical yield.Make in the filtrate water evaporation and by with filtrate 300 ℃ dry 5 hours down, obtain powder particle.Powder particle detects by X-ray diffraction and finds that it comprises hydrated barta and strontium hydroxide (raw material).The total extracted amount of ionic that calculates according to formula (3) is 5 μ mol/m ²

Comparative example 8:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, (produce except making 20 quality % tetramethylammonium hydroxide aqueous solutions by Sachem Showa K.K., carbonate concentration: 60ppm or root are few) in air, leave standstill, thereby make the concentration of carbonic acid group rise to 6,000ppm.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield.Adopt with embodiment 1 in identical mode detect the powder particle of acquisition, the result, the barium carbonate that is comprised in this powder particle and the total amount of Strontium carbonate powder are 6 quality %.The total extracted amount of ionic that calculates according to formula (3) is 7 μ mol/m ²

Embodiment 8:

(produced purity by Sumitomo Titanium Corporation: 99.9%) concentration is that the aqueous solution of 0.25mol/L adds in the reactor that has reflux exchanger and by being heated when avoiding chlorion to overflow keeping solution acidic near the boiling point will to have titanium tetrachloride.Solution was kept 60 minutes under this temperature, thereby make titanium tetrachloride hydrolysis obtain titanium oxide sol.The titanium oxide sol drying under 110 ℃ that obtains is also detected crystal type and finds that it is the brookite titanium oxide by the X-ray diffraction device of being made by Rigaku Corporation (RAD-B Rotor Flex).

To 29.6g calcium hydroxide (by Wako Pure Chemical Industries, Ltd. produce, purity: 99.9%) and 213g contain the colloidal sol that titanium oxide concentration is 15 quality % (by with the colloidal sol of above-mentioned preparation precipitation with concentrate and obtain, remove dechlorination until 500ppm by the electrodialysis instrument) in, the tetramethylammonium hydroxide aqueous solution (producing the concentration of carbonic acid group: 60ppm or lower by Sachem Showa K.K.) that adds 456g 20 quality %.In having the reactor of reflux exchanger, in by small amount of nitrogen, under agitation resulting solution is heated to boiling.Under agitation make boiling continue 6 hours.Subsequently, stop heating, continue to stir and make resulting solution air cooling to 50 ℃ or still less simultaneously, then it is filtered under vacuum.The filter cake that obtains was obtained dried powder down in dry 5 hours at 300 ℃.Actual output is 99.9 quality % with the ratio of the theoretical yield that calculates according to the amount of titanium oxide that uses in the reaction and calcium hydroxide.

The X-ray diffraction of described powder particle detects by the X-ray diffraction device of being made by Rigaku Corporation (RAD-B Rotor Flex), and the powder particle that the result obtained is the uhligite calcium titanate.Fig. 9 represents the X-ray diffraction spectrum of this moment.The particulate specific surface area that is obtained is measured by the BET method and is found that it is 4.7m ²/ g.And the shape of the powder particle that is obtained is by sem observation and find that it is the shape of similar tetragonal prism, as shown in Figure 2.

The calcium titanate particle that is obtained is by transmission electron microscope observation and find that it is a monocrystalline.In addition, the electron beam photo is analyzed, the result, the long limit of the particulate of square column extends to (010) direction.

The average primary granularity D1 that calculates according to formula (1) is 0.32 μ m.Be dispersed in powder particle in the water that wherein is dissolved with 0.03% Poise 532A (producing) and the secondary granule degree of described powder particle is measured by the following method: use Shimadzu centrifugation type optical scatter degree apparatus for measuring distribution (SA-CP4L type), and impose a condition so that can be in the distribution of particle sizes of measuring to the scope of minimum value 0.03 μ m at maximum value 30 μ m on weight basis by Kao Corp. as dispersion agent.

Average particle size D2 is 0.17 μ m.Beginning 10% o'clock granularity D3 by minimum value is 0.34 μ m, and to begin 90% o'clock granularity D4 by minimum value be 1.10 μ m.In view of the above, D2/D1 is 2.2, D3/D2 be 0.48 and D4/D2 be 1.55.

Above-mentioned dried powder particle (about 6mg) and about 900mg KBr are ground and mix, and mixture that will about 800mg obtained is suppressed shape in blocks.And, similarly standard lime carbonate (is produced purity: 99.99%) suppress shape in blocks by Wako Pure Chemical Industries simultaneously.Then, measure infrared absorption spectrum by the FTS6000 that makes by Bio-Rad.Will be at 880cm ^-1Near the peak intensity of standard lime carbonate and the peak intensity of calcium titanate of the present invention compare.The amount of the lime carbonate that is comprised in the above-mentioned powder particle is 0.5 quality %.

Embodiment 9:

Adopt with embodiment 8 in identical mode obtain uhligite calcium titanate powder particle.Described powder particle was kept 2 hours down at 950 ℃, thereby it is cured.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is 3.6m for specific surface area ²The uhligite calcium titanate of/g.Figure 11 represents X-ray diffraction spectrum.Reduce 1.1m by the calcination surface-area ²/ g.Shape by sem observation calcium titanate powder and find that it is the shape of similar tetragonal prism, as shown in figure 12.And, be to analyze by the limited area electron diffraction that uses transmission electron microscope (H-9000UHR: by Hitachi, Ltd. makes) under the 300kV at acceleration voltage.The result as shown in figure 13.Find that the sample that is obtained is a monocrystalline, wherein the long edge of the particulate of square column (010) direction while minor face edge (101) direction.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.42 μ m, D2 is 1.12 μ m, D3 is that 0.28 μ m and D4 are 5.56 μ m.In view of the above, D2/D1 is 2.7, D3/D2 be 0.25 and D4/D2 be 4.96.

Embodiment 10:

By with embodiment 8 in the synthetic calcium titanate of identical operations, except with 45.6g20 quality % tetramethylammonium hydroxide aqueous solution (producing) by Sachem Showa K.K. by it being diluted to wherein adding the 410.4g pure water.Actual output is 99.7 quality % to the ratio of theoretical yield.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is 5.7m for specific surface area ²The uhligite calcium titanate of/g.Be shaped as the shape of similar tetragonal prism.And, find that described powder is a monocrystalline, wherein the long limit of the particulate of square column extends to (010) direction.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.26 μ m, D2 is 0.72 μ m, D3 is that 0.30 μ m and D4 are 1.75 μ m.In view of the above, D2/D1 is 2.8, D3/D2 be 0.42 and D4/D2 be 2.43.

Embodiment 11:

By with embodiment 8 in the synthetic calcium titanate of identical operations, the anatase titanium oxide sol (STS-02 is produced by Ishihara Sangyo Kaisha Ltd.) that is purchased except use replaces synthetic brookite titanium oxide sol among the embodiment 8.Actual output is 99.9 quality % to the ratio of theoretical yield.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is 3.9m for specific surface area ²The uhligite calcium titanate of/g.Be shaped as the shape of similar tetragonal prism.And, find that described powder is a monocrystalline, wherein the long limit of the particulate of square column extends to (010) direction.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.38 μ m, D2 is 0.69 μ m, D3 is that 0.17 μ m and D4 are 1.08 μ m.In view of the above, D2/D1 is 1.8, D3/D2 be 0.25 and D4/D2 be 1.57.

Embodiment 12:

By with embodiment 8 in the synthetic calcium titanate of identical operations, except using 0.296g calcium hydroxide.Actual output is 99.9 quality % to the ratio of theoretical yield.Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is the uhligite calcium titanate.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is 4.8m for specific surface area ²The uhligite calcium titanate of/g.Be shaped as the shape of similar tetragonal prism.And, find that described powder is a monocrystalline, wherein the long limit of the particulate of square column extends to (010) direction.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.31 μ m, D2 is 0.65 μ m, D3 is that 0.23 μ m and D4 are 1.21 μ m.In view of the above, D2/D1 is 2.1, and D3/D2 is 0.35 and D4/D2 be 1.86.

Embodiment 13:

By with embodiment 8 in the synthetic calcium titanate of identical operations, (by Wako Pure Chemical Industries, Ltd. produces, purity: 99.9%) replace calcium hydroxide except using 58.8g two hydration calcium chloride.After vacuum filtration, the filter cake that obtains is adopted the water repeated washing and filters until the Cl concentration that has is 100ppm.To by filter cake that vacuum filtration obtain at 300 ℃ descend dry 5 hour to obtain dried powder thereafter.Actual output is 99.9 quality % with the ratio of the theoretical yield that calculates according to the amount of titanium oxide that uses in the reaction and calcium hydroxide.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is 4.6m for specific surface area ²The uhligite calcium titanate of/g.Be shaped as the shape of similar tetragonal prism.And, find that described powder is a monocrystalline, wherein the long limit of the particulate of square column extends to (010) direction.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.33 μ m, D2 is 0.75 μ m, D3 is that 0.22 μ m and D4 are 1.36 μ m.In view of the above, D2/D1 is 2.3, D3/D2 be 0.29 and D4/D2 be 1.81.

Embodiment 14:

By with embodiment 8 in the synthetic calcium titanate of identical operations, replace TMAH except using KOH (by Wako Pure Chemical Industries, Ltd. produces, extra best best).After vacuum filtration, the filter cake that obtains is adopted the water repeated washing and filters until the K concentration that has is 100ppm.To by filter cake that vacuum filtration obtain at 300 ℃ descend dry 5 hour to obtain dried powder thereafter.Actual output is 99.3 quality % with the ratio of the theoretical yield that calculates according to the amount of titanium oxide that uses in the reaction and calcium hydroxide.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is 4.4m for specific surface area ²The uhligite calcium titanate of/g.Be shaped as the shape of similar tetragonal prism.And, find that described powder is a monocrystalline, wherein the long limit of the particulate of square column extends to (010) direction.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.34 μ m, D2 is 0.74 μ m, D3 is that 0.23 μ m and D4 are 1.30 μ m.In view of the above, D2/D1 is 2.2, D3/D2 be 0.31 and D4/D2 be 1.76.

Comparative example 9:

By with embodiment 8 in the synthetic calcium titanate of identical operations, (produce except making 20 quality % tetramethylammonium hydroxide aqueous solutions by Sachem Showa K.K., carbonate concentration: 60ppm or lower) in air, leaves standstill, thereby make the concentration of carbonic acid group rise to 6,000ppm.Actual output is 99.9 quality % to the ratio of theoretical yield.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is mixed with the lime carbonate of 6 quality %.The BET specific surface area is 7.2m ²/ g.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.20 μ m, D2 is 0.80 μ m, D3 is that 0.20 μ m and D4 are 2.10 μ m.In view of the above, D2/D1 is 4.0, D3/D2 be 0.25 and D4/D2 be 2.63.

Comparative example 10:

By with embodiment 8 in the synthetic calcium titanate of identical operations, except using 0.0185g calcium hydroxide.Actual output is 99.9 quality % to the ratio of theoretical yield.

Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is the uhligite calcium titanate.The particulate specific surface area that is obtained is 23m ²/ g and major part are spherical particle.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.065 μ m, D2 is 0.06 μ m, D3 is that 0.04 μ m and D4 are 11.0 μ m.In view of the above, D2/D1 is 9.2, D3/D2 be 0.06 and D4/D2 be 18.3.

Comparative example 11:

By with embodiment 8 in the synthetic calcium titanate of identical operations, replace adding TMAH except using the 368g pure water.This moment, pH was 7.1.Actual output is 99.6 quality % to the ratio of theoretical yield.Adopt with embodiment 8 in identical mode detect the powder particle that is obtained and find that it is the uhligite calcium titanate, wherein residual have residual as raw material in a large number and calcium hydroxide and titanium oxide that react.

Comparative example 12:

By with embodiment 8 in the synthetic calcium titanate of identical operations, except adding the 73g ethylenediamine tetraacetic acid (EDTA) and making calcium hydroxide dissolving and reaction.The dried powder particle that obtains was kept 2 hours down at 900 ℃, thereby ethylenediamine tetraacetic acid (EDTA) is decomposed.Adopt with embodiment 8 in identical mode detect the powder particle that is obtained, the result, discovery does not almost obtain the uhligite calcium titanate.

Comparative example 13:

By with embodiment 8 in the synthetic calcium titanate of identical operations, except changing into 1 hour the reaction times.Actual output is 99.5 quality % to the ratio of theoretical yield.The BET specific surface area of the powder particle that is obtained is 27.1m ²/ g.In X-ray diffraction spectrum, observe very faintly as the titanium oxide of raw material and the peak of calcium hydroxide, but great majority are the uhligite calcium titanate.

By the sem observation coating of particles, the result, great majority be spherical particle and square column particulate number seldom.

Adopt with embodiment 8 in identical mode measure distribution of particle sizes, the result, D1 is 0.06 μ m, D2 is 0.64 μ m, D3 is that 0.05 μ m and D4 are 11.5 μ m.In view of the above, D2/D1 is 10.6, D3/D2 be 0.08 and D4/D2 be 18.0.

Embodiment 15:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 77.2g barium hydroxide octahydrate and 43.5g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 46m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃Mixture, and be shaped as sphere.

D1 is 0.023 μ m, and D2 is 0.17 μ m, and D2/D1 is 7.4.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.5 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 10ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 100ppm.

According to the barium ion of formula (3) calculating and total extracted amount of strontium ion is 0.60 μ mol/m ²After 950 ℃ kept 2 hours down, specific surface area was 24m ²/ g calculates according to formula (2), and the percentage that specific surface area reduces is 48%, is shaped as squarely, and particle is a monocrystalline.

Embodiment 16:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 74.2g barium hydroxide octahydrate and 41.7g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 49m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃Mixture, and be shaped as sphere.

D1 is 0.022 μ m, and D2 is 0.18 μ m, and D2/D1 is 8.2.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.4 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 20ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 110ppm.

According to the barium ion of formula (3) calculating and total extracted amount of strontium ion is 0.70 μ mol/m ²After 950 ℃ kept 2 hours down, specific surface area was 21m ²/ g calculates according to formula (2), and the percentage that specific surface area reduces is 57%, is shaped as squarely, and particle is a monocrystalline.

Comparative example 14:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 79.5g barium hydroxide octahydrate and 44.6g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 46m ²/ g, although only some X-ray diffraction peaks can not be by unconfirmed, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃Mixture, and be shaped as sphere.

D1 is 0.023 μ m, and D2 is 0.20 μ m, and D2/D1 is 8.7.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.5 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 20ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 120ppm.

According to the barium ion of formula (3) calculating and total extracted amount of strontium ion is 3.3 μ mol/m ²

Comparative example 15:

By with embodiment 1 in identical operations produce barium strontium titanate compound particles, except using 71.9g barium hydroxide octahydrate and 40.4g eight hydronium(ion) oxidation strontiums.

Continue reaction total concn of barium ion and strontium ion in reaction soln become inlet amount 1/1,000 or still less.Actual output is 99.9% to the ratio of theoretical yield, and specific surface area is 51m ²/ g, particle is for wherein containing the barium of solid solution and the uhligite Ba of strontium _0.6Sr _0.4TiO ₃Mixture, and be shaped as sphere.

D1 is 0.021 μ m, and D2 is 0.19 μ m, and D2/D1 is 9.0.The barium carbonate that is comprised in the described powder particle and the total amount of Strontium carbonate powder are 0.4 quality %.

Measure K ionic amount with dried powder dissolving and by the ICP shooting method, the result contains the K ion of 30ppm.And, measuring Cl ionic amount by the anion chromatographic method, the result contains the Cl ion of 100ppm.

According to the barium ion of formula (3) calculating and total extracted amount of strontium ion is 3.9 μ mol/m ²

Industrial usability

Perovskite titanium-containing composite oxide particle among the present invention has little granularity, narrow granularity The dispersibility of distribution, excellence, high-crystallinity and excellent electrical property.

Especially, the perovskite titanium-containing composite oxide particle of small particle size can obtain by a kind of method in less impurity situation, makes A1 (OH) in described method₂And A2 (OH)₂Under arbitrary ratio with Titanium oxide reacts in comprising the aqueous slkali of alkali compounds, then can be by the evaporation through thermal decomposition etc. Alkali compounds removed and in described method two kinds of metallic atoms of A site (A1 and A2) can the arbitrary ratio solid solution.

In addition, by make titanium oxide sol and calcium salt saturation solubility or more relative superiority or inferiority comprising alkalization The character of the calcium titanate particle that reaction obtains in the aqueous alkali of compound is: distribution of particle sizes is extremely narrow, and is super The number of microparticle or agglomerated particle seldom.

Demonstrate the perovskite titanium-containing composite oxide among the present invention of excellent electrical property by use Particle, dielectric material dielectric material, piezoelectric and the thermoelectric material that can obtain to have excellent performance, For example pottery, film and dielectric film. In addition, in electronic device, use above-mentioned material so that device is little Type and reduction weight.

Claims (37)

1. by formula: (A1 _xA2 _(1-x)) _YTiO _{3 ± δ}The perovskite titanium-containing composite oxide particle of expression, it contains the monocrystalline of perovskite titanium-containing composite oxide, wherein, 0≤X≤1,0.98≤Y≤1.02,0≤δ≤0.05, and A1 and A2 respectively do for oneself and are selected from the atom of Ca, Sr, Ba, Pb and Mg and differ from one another, and its specific surface area is 1-100m ²/ g and D2/D1 value are 1-10.

2. the perovskite titanium-containing composite oxide particle of claim 1, the shape that it comprises the tetragonal prism shape or is similar to tetragonal prism.

3. the perovskite titanium-containing composite oxide particle of claim 2, wherein the long limit of crystalline is 1.1-6 to the ratio of minor face.

4. claim 2 or 3 perovskite titanium-containing composite oxide particle, wherein the long limit of crystalline extends to structure cell (010) plane.

5. each perovskite titanium-containing composite oxide particle among the claim 1-4, wherein the D2/D1 value is 1-3.

6. each perovskite titanium-containing composite oxide particle among the claim 1-5, wherein the D3/D2 value is 0.1-0.9.

7. each perovskite titanium-containing composite oxide particle among the claim 1-6, wherein the D4/D2 value is 1.1-10.

8. each perovskite titanium-containing composite oxide particle among the claim 1-7 is wherein by (A1 _xA2 _(1-x)) _YTiO _{3 ± δ}The compound of expression is CaTiO ₃And calcium carbonate content is 3 quality % or still less.

9. each perovskite titanium-containing composite oxide particle among the claim 1-8, its specific surface area is 1-10m ²/ g.

10. each perovskite titanium-containing composite oxide particle among the claim 1-9, wherein at 900-1, during any temperature lower calcination of 200 ℃, specific surface area reduces 8m ²/ g or still less.

11. the perovskite titanium-containing composite oxide particle of claim 1, wherein 0.2≤X≤0.8,0.99≤Y≤1.01,0≤δ≤0.03 and particulate are monocrystalline.

12. the perovskite titanium-containing composite oxide particle of claim 1, wherein A1 is that Ba and A2 are Sr.

13. each perovskite titanium-containing composite oxide particle among the claim 1-12, wherein the amount of alkali metal impurity is that the amount of 0-100ppm and chlorine impurity is 0-600ppm.

14. each perovskite titanium-containing composite oxide particle among the claim 1-13, wherein at 900-1, during 000 ℃ any temperature lower calcination 0.1-3 hour, the minimizing percentage of specific surface area is 90% or still less.

15. each perovskite titanium-containing composite oxide particle among the claim 1-14, wherein at 900-1, shape becomes square after 200 ℃ any temperature lower calcination 0.1-3 hour.

16. each perovskite titanium-containing composite oxide particle among the claim 1-15, wherein the amount of carbonate is 3 quality % or still less.

17. each perovskite titanium-containing composite oxide particle among the claim 1-16, wherein when being immersed in 1.5g perovskite titanium-containing composite oxide particle in the 45ml pure water, total extracted amount of per surface area A1 atom and A2 atom is 0-2 μ mol/m ²

18. produce the method for perovskite titanium-containing composite oxide particle, this method comprises makes A1 (OH) ₂And A2 (OH) ₂Under arbitrary ratio with A1 (OH) ₂And A2 (OH) ₂The titanium oxide of 0.98-1.02 mole multiple of total mole number in alkaline solution, react, described alkaline solution contains basic cpd and the pH that has is 10 or higher, wherein A1 and A2 all represent to be selected from the atom of Ca, Sr, Ba, Pb and Mg; Make reaction continue in reaction soln A1 ion and A2 ionic total concn and become 1/1 of the amount that added, 000 or still less and after reaction finishes, under normal pressure or decompression, to the temperature range of calcining temperature, basic cpd is removed as gas by evaporation, distillation and/or thermolysis in room temperature.

19. the method for the production perovskite titanium-containing composite oxide particle of claim 18, wherein A1 (OH) ₂To A2 (OH) ₂Molar ratio be 0.2-0.8.

20. the method for the production perovskite titanium-containing composite oxide particle of claim 18, this method comprise with regard to CO ₂The concentration of carbonic acid group controls to 0-500ppm in the reaction soln.

21. the method for the production perovskite titanium-containing composite oxide particle of claim 18, wherein titanium oxide comprises brookite crystal.

22. the method for the production perovskite titanium-containing composite oxide particle of claim 18, wherein titanium oxide obtains by make the titanium compound hydrolysis in acidic solution.

23. the method for the production perovskite titanium-containing composite oxide particle of claim 18, wherein basic cpd is for becoming the material of gas by evaporation, distillation and/or thermolysis under normal pressure or decompression.

24. the method for the production perovskite titanium-containing composite oxide particle of claim 18, wherein basic cpd is an organic bases.

25. the method for the production perovskite titanium-containing composite oxide particle of claim 18, wherein basic cpd is a Tetramethylammonium hydroxide.

26. comprise the dielectric materials of each perovskite titanium-containing composite oxide particle among the claim 1-17.

27. comprise the paste of each perovskite titanium-containing composite oxide particle among the claim 1-17.

28. comprise the slurry of each perovskite titanium-containing composite oxide particle among the claim 1-17.

29. comprise the thin-film material of each perovskite titanium-containing composite oxide particle among the claim 1-17.

30. comprise the dielectric ceramic of each perovskite titanium-containing composite oxide particle among the claim 1-17.

31. comprise the thermoelectric ceramics of each perovskite titanium-containing composite oxide particle among the claim 1-17.

32. comprise the piezoelectric ceramics of each perovskite titanium-containing composite oxide particle among the claim 1-17.

33. comprise the electrical condenser of the dielectric ceramic of claim 30.

34. comprise the electron device of element of the electrical condenser of the pottery of at least a thin-film material that is selected from claim 29, claim 42-44 and claim 41-44.

35. comprise the transmitter of the pottery of the thin-film material of one or more claims 29 or claim 30-32.

36. comprise the dielectric film of each perovskite titanium-containing composite oxide particle among the claim 1-17.

37. comprise the electrical condenser of the dielectric film of claim 36.

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