CN101096270A - Method of manufacturing complex metal oxide powder and amorphous complex metal oxide - Google Patents
Method of manufacturing complex metal oxide powder and amorphous complex metal oxide Download PDFInfo
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- CN101096270A CN101096270A CNA200710111496XA CN200710111496A CN101096270A CN 101096270 A CN101096270 A CN 101096270A CN A200710111496X A CNA200710111496X A CN A200710111496XA CN 200710111496 A CN200710111496 A CN 200710111496A CN 101096270 A CN101096270 A CN 101096270A
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Abstract
A method of manufacturing a complex metal oxide powder, the method including: preparing a raw material composition for forming a complex metal oxide; mixing an oxidizing solution including an oxidizing substance into the raw material composition to produce complex metal oxide particles to obtain a liquid dispersion of the particles; and separating the particles from the liquid dispersion to obtain a complex metal oxide powder. The complex metal oxide is shown by a general formula AB 1-x C x O 3 , an element A including at least Pb, an element B including at least one of Zr, Ti, V, W, and Hf, and an element C including at least one of Nb and Ta. The raw material composition includes: at least one of a thermally-decomposable organometallic compound including the element A, the element B, or the element C, a hydrolyzable organometallic compound including the element A, the element B, or the element C, and a partial hydrolyzate and/or a polycondensate of the hydrolyzable organometallic compound; at least one of a polycarboxylic acid and a polycarboxylic acid ester; and an organic solvent.
Description
Technical field
The present invention relates to the manufacture method of complex metal oxide powder and the Powdered amorphous complex metal oxide that obtains by this manufacture method.
Background technology
As one of preparation method of complex metal oxide powder, known have a coprecipitation method.For example, the lead titanate-zirconate manufacturing method of power that adopts coprecipitation method is disclosed in the Japanese patent laid-open 8-277113 communique.In this manufacture method, as sequestering agent (solution stabilizer) use is hydrogen peroxide.In zirconium solution and titanium solution, add this sequestering agent respectively, thereby form the ionic complex of zirconium and titanium, its ionic concn-pH curve is moved in the pH scope of prerequisite scope, generate the uniform lead titanate-zirconate of component.But, in this coprecipitation method, must come obtain solution by in zirconium solution and titanium solution, adding hydrogen peroxide respectively, the adjustment of solution is comparatively miscellaneous, in addition, also exists sedimentation speed to wait problem more slowly.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method, and pass through the Powdered amorphous complex metal oxide that this manufacture method obtains by extremely simple method acquisition complex metal oxide powder.
Manufacture method according to complex metal oxide powder of the present invention comprises: preparation is used to form the operation of the feedstock composition of complex metal oxides; Mixing contains the oxidizing solution of oxidizing substance, the particle of the described complex metal oxides of generation forms the operation of this dispersion of particles liquid; And separate the operation that described particle forms pulverous described complex metal oxides from described dispersion liquid.Described complex metal oxides general formula AB
1-xC
xO
3Expression, wherein, the A element comprises Pb at least, the B element comprises that at least a among Zr, Ti, V, W and the Hf, C element comprise at least a among Nb and the Ta.Described feedstock composition comprises: the pyrolytic organometallic compound that contains described A element, described B element or described C element, the water-disintegrable organometallic compound that contains described A element, described B element or described C element, at least a in its partial hydrolystate and/or the polycondensate; At least a in poly carboxylic acid and the polycarboxylate; And organic solvent.
According to the manufacture method of complex metal oxides of the present invention, can obtain to have the complex metal oxide powder of good characteristic by simple method.
In manufacture method of the present invention, described complex metal oxides can be that described B element is the niobium lead titanate-zirconate that Zr and Ti, described C element are Nb.
In manufacture method of the present invention, described organic solvent can be an alcohol.
In manufacture method of the present invention, described niobium lead titanate-zirconate can use chemical formula Pb (Zr, Ti)
1-xNb
xO
3Expression, in this chemical formula, 0.05≤x≤0.3.
In manufacture method of the present invention, described niobium lead titanate-zirconate can also comprise more than or equal to the Si of 0.5 mole of % or Si and Ge.
In manufacture method of the present invention, the pH of described oxidizing solution preferably is adjusted at greater than 7 and smaller or equal in 13 the scope, more preferably more than or equal to 10 and smaller or equal to 13 scope in, also more preferably more than or equal to 10 and smaller or equal to 11 scope in.
In manufacture method of the present invention, described oxidizing solution can be solution mixing and the acquisition with the solution of oxidizing substance and alkaline matter.
In manufacture method of the present invention, described oxidizing substance can be a hydrogen peroxide.
In manufacture method of the present invention, described complex metal oxides can be non-crystal.
The amorphous complex metal oxide that the present invention relates to is the Powdered amorphous complex metal oxide that obtains by manufacture method of the present invention, uses general formula AB
1-xC
xO
3Expression, wherein, described A element comprises Pb at least, described B element comprises that at least a among Zr, Ti, V, W and the Hf, described C element comprise at least a among Nb and the Ta.
Description of drawings
Fig. 1 is the schema that the manufacture method of block PZT is shown.
Fig. 2 is XRD result's the figure that the sample of embodiment 1 is shown.
Fig. 3 is XRD result's the figure that the sample of embodiment 2 is shown.
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are elaborated.
1. the manufacture method of complex metal oxide powder
The manufacture method of the complex metal oxide powder that embodiments of the present invention relate to comprises: preparation is used to form the operation of the feedstock composition of complex metal oxides; In feedstock composition the mixed oxidization material, generate the particle of complex metal oxides and form the operation of this dispersion of particles liquid; And from dispersion liquid, separate the operation that described particle forms pulverous described complex metal oxides.
The manufacture method of present embodiment can comprise following operation:
(1) preparation of feedstock composition
The feedstock composition that present embodiment relates to can be used for the generation of complex metal oxide powder.Herein, complex metal oxides can be with general formula AB
1-xC
xO
3Expression, wherein, the A element can comprise Pb at least, the B element can comprise that at least a among Zr, Ti, V, W and the Hf, C element can comprise at least a among Nb and the Ta.
Described feedstock composition comprises: the pyrolytic organometallic compound that contains described A element, described B element or described C element, the water-disintegrable organometallic compound that contains described A element, described B element or described C element, at least a in its partial hydrolystate and/or the polycondensate; At least a in poly carboxylic acid and the polycarboxylate; And organic solvent.
Mix according to the mode that metal reaches desirable mol ratio containing the organometallic compound of formation metal of composite metal oxide material or its partial hydrolystate and/or polycondensate respectively, again with organic solvents such as alcohol with its dissolving or dispersion, thereby can make feedstock composition.Organometallic compound preferably is used in material stable under the solution state.
In the present embodiment,, generate and obtain from this metal-organic metal oxide by hydrolysis or oxidation as spendable organometallic compound, can from the alkoxide of each metal, organometallic complex, and organic acid salt etc. selection.
As the pyrolytic organometallic compound of the formation metal that contains complex metal oxides respectively, for example, can use the organometallic compound of metal alkoxide, organic acid salt, beta diketone complex compound etc.Water-disintegrable organometallic compound as the formation metal that contains complex metal oxides respectively can use organometallic compounds such as metal alkoxide.Example as organometallic compound can be exemplified below.
As the B element, promptly contain the organometallic compound of Zr, Ti, V, W or Hf, can be example with their alkoxide, acetate, octyl group hydrochlorate etc.
As the A element, promptly contain the organometallic compound of Pb, can be example with plumbic acetate, lead octoate 36.
As the C element, promptly contain the organometallic compound of Nb, can be example with sad niobium, lead octoate 36 niobium.The Nb of sad niobium is with two atom covalence bondings, and other parts are the structures with octyl group.As the C element, promptly contain the organometallic compound of Ta, can be example with sad tantalum.
In the feedstock composition of present embodiment, can use alcohol as organic solvent.When using alcohol, can dissolve organometallic compound and poly carboxylic acid or polycarboxylate well as solvent.Do not have specific limited as alcohol, but can be example with monohydroxy-alcohols such as butanols, methyl alcohol, ethanol, propyl alcohol or polyvalent alcohol.As this alcohol, for example can be exemplified below:
Unary alcohol:
As propyl alcohol (propyl group alcohol) 1-propyl alcohol (97.4 ℃ of boiling points), 2-propyl alcohol (82.7 ℃ of boiling points) are arranged;
As butanols (butyl alcohol) 1-butanols (11 7 ℃ of boiling points), 2-butanols (100 ℃ of boiling points), 2-methyl isophthalic acid-propyl alcohol (108 ℃ of boiling points), 2-methyl-2-propyl alcohol (25.4 ℃ of fusing points, 83 ℃ of boiling points) are arranged;
As amylalcohol (amyl group alcohol) 1-amylalcohol (137 ℃ of boiling points), 3-methyl isophthalic acid-butanols (131 ℃ of boiling points), 2-methyl-1-butene alcohol (128 ℃ of boiling points), 2 are arranged, 2 dimethyl-1-propyl alcohol (113 ℃ of boiling points), 2-amylalcohol (119 ℃ of boiling points), 3-methyl-2-butanols (112.5 ℃ of boiling points), 3-amylalcohol (117 ℃ of boiling points), 2-methyl-2-butanols (102 ℃ of boiling points)
Polyalcohols:
Ethylene glycol (fusing point-11.5 ℃, boiling point 197.5 ℃), glycerol (17 ℃ of fusing points, 290 ℃ of boiling points).
In feedstock composition of the present invention, poly carboxylic acid or polycarboxylate can be for more than or equal to binary.As the used poly carboxylic acid of the present invention, be exemplified below: as the ternary poly carboxylic acid, can enumerate anti--equisetic acid, trimesic acid, as the quaternary poly carboxylic acid, can enumerate pyromellitic acid, 1,2,3,4-encircles penta tetracarboxylic acid etc.In addition, as polycarboxylate, can enumerate dimethyl succinate, diethyl succinate, dibutyl oxalate, dimethyl malonate, dimethyl adipate, dimethyl maleate, the DEF of binary, ternary tributyl citrate, 1,1,2-second tricarboxylic acid triethyl, 1 of quaternary, 1,2,2-tetraethyl ethanetetraearboxylate, 1,2,4-benzene tricarbonic acid trimethyl etc.
In feedstock composition of the present invention, as the polycarboxylate of binary, that preferably can select from succinate, maleic acid ester and malonic ester is at least a.As the specific examples of these esters, can enumerate: dimethyl succinate, dimethyl maleate, dimethyl malonate.
Poly carboxylic acid or polycarboxylate can have the boiling point higher than organic solvent.Because the boiling point of poly carboxylic acid or polycarboxylate is higher than organic solvent, so can more promptly carry out the reaction of feedstock composition as described later.
The molecular weight of described polycarboxylate can be smaller or equal to 150.Excessive when the molecular weight of polycarboxylate, easily film is caused damage when ester volatilizees in thermal treatment, thereby can not obtain fine and close film.
Described polycarboxylate can at room temperature be a liquid.When polycarboxylate at room temperature was solid, the gelation of liquid may take place.
The complex metal oxides that utilizes the feedstock composition of present embodiment to obtain preferably can contain Nb with the scope of 0.05≤x＜1, more preferably with the scope of 0.1≤x≤0.3.In addition, described complex metal oxides can preferably contain more than or equal to 0.5mol%, more preferably more than or equal to 0.5mol% and smaller or equal to Si or Si and the Ge of 5mol%.And described B element can be Zr and Ti.That is, in the present embodiment, complex metal oxides can be that Nb is entrained in Pb (Zr, Ti, Nb) O on the Ti position
3(PZTN).
The size of Nb and Ti be (its ionic radius is approaching, atomic radius is identical) much at one, and its weight is the twice of Ti, even be subjected to the interatomic bump that lattice vibration produces, atom also is difficult to escape from lattice.And valence is stable+5 valencys, even Pb escapes, can utilize Nb
5+Replenish the valence mumber that Pb escapes.And when crystallization, escape even Pb takes place, compare with the disengaging of large-size O, the Nb of reduced size is more prone to enter.
In addition, owing to Nb also exists+4 valencys, so can carry out Ti fully
4+Substitute.And in fact the covalent linkage of Nb is very strong, can think that Pb also is difficult to escape (H.Miyazawa, E.Natori, S.Miyashita; Jpn.J.Appl.Phys.39 (2000) 5679).
Utilize the complex metal oxides of the feedstock composition acquisition of present embodiment, especially the complex metal oxides that utilizes PZTN to obtain, by comprising Nb,, and has good Combination Control so it has elimination because of the vacant detrimentally affect that produces of Pb with specific ratio.Consequently, compare with common PZT, PZTN has extremely good hysteresis characteristic, sews characteristic, (for example, being willing to 2005-344700 number with reference to Japanese publication is special) such as resistance to reduction, piezoelectricity and insulativity.
So far, doping Nb carries out in the rhombus crystalline region of rich Zr in PZT, and its amount is 0.2～0.025mol% (J.Am.Ceram.Soc, 84 (2001) 902; Phys.Rev.Let, 83 (1999) 1347), this is extremely few amount.This major cause that can not mix Nb in a large number is to consider: when for example adding 10mol%Nb, crystallized temperature may rise to more than 800 ℃.
In the present embodiment, complex metal oxides contains Si or Si and Ge with the ratio of for example 0.5～5mol%, thereby can reduce the crystal energy of PZTN.That is, when using PZTN,, can realize the reduction of the crystallized temperature of PZTN by when adding Nb, adding Si or Si and Ge as the material of complex metal oxides.The present inventor confirms: Si constitutes a crystalline part as A position ion after working as agglutinant.That is, when in lead titanate, adding silicon, in A position ionic Raman vibration modes E (1TO), found variation.In addition, situation about find changing on the Raman vibration modes is that the Si addition is during smaller or equal to 8mol%.Therefore, by adding Si, can confirm that Si is present in the A position of uhligite with specified proportion.
In the present invention, can use Ta to replace Nb, perhaps use Nb and Ta jointly.When using Ta, the tendency identical with above-mentioned Nb arranged also.
The usage quantity of poly carboxylic acid or polycarboxylate depends on the composition of complex metal oxides.For example be used to form the total mole ionic concn of metal of complex metal oxides and the mole ionic concn of poly carboxylic acid (ester) and can be preferably (the mole ionic concn of poly carboxylic acid (ester))/(the total mole of the metal of material solution ionic concn)≤1.
Herein, the mole number of so-called poly carboxylic acid or polycarboxylate is exactly first number (valence mumber).That is, if the poly carboxylic acid of binary or polycarboxylate, making poly carboxylic acid or polycarboxylate with respect to metal 1mol in the material solution is 0.5mol, and then the above-mentioned mole ion concentration of the poly carboxylic acid of 1 molecule or polycarboxylate is 1: 1.
(2) preparation of oxidizing solution
Preparation contains the oxidizing solution of oxidizing substance.Oxidizing solution contains oxidizing substance at least.For example, oxidizing solution can by with the solution of oxidizing substance and the solution of alkaline matter (below be also referred to as " alkaline solution "), should the necessary water equal solvent that uses mix and obtain.Can make the mixed solution of water or water and alcohol etc. as the solvent of solution, alkaline solution and the oxidizing solution of oxidizing substance.Oxidizing solution can preferably be formulated in pH greater than 7 and smaller or equal in 13 the scope by adding alkaline solution, more preferably pH more than or equal to 10 and smaller or equal to 13 scope in, also more preferably pH more than or equal to 10 and smaller or equal to 11 scope in.
As oxidizing substance (acidic substance), can use for example mineral acid such as organic acid such as hydrogen peroxide, citric acid and hydrochloric acid.As oxidizing substance, preferred hydrogen peroxide.The oxidation rate of hydrogen peroxide is fast, can generate the particle of complex metal oxides at short notice.
As alkaline matter, can use known alkaline matter.As this alkaline matter, can use for example ammoniacal liquor, dimethylamino methyl alcohol, diethylin methyl alcohol, dimethylaminoethanol, diethylaminoethanol etc.
By oxidizing solution being adjusted to above-mentioned pH scope, the non-ferroelectric phase (pyrochlore) that forms in the time of can reducing the complex metal oxide powder crystallization, and then can obtain the good crystal of reproducibility in ratio of components etc.When using hydrogen peroxide as oxidizing substance, alkaline matter plays the effect as the catalyzer of hydrogen peroxide.
In addition, comprise oxidizing substance and alkaline matter in advance and to be adjusted at oxidizing solution in the particular pH range by using, can in the mixed processes of subsequent processing (3), generate more stablize, the particle of amorphous complex metal oxide that reproducibility is good.
(3) mixing of feedstock composition and oxidizing solution
In feedstock composition, mix the oxidizing solution that is adjusted into specific pH that obtains by above-mentioned (2).After in feedstock composition, adding oxidizing solution in this wise, generate the particle of non-crystal complex metal oxides.For example, when adding oxidizing solution in the feedstock composition of using at PZTN, can obtain to separate out noncrystal PZTN is arranged (the dispersion of particles liquid of α-PZTN).For example, in using the oxidizing solution of hydrogen peroxide, in several seconds short period of time, can generate the particle of complex metal oxides as oxidizing substance.
The usage quantity of oxidizing solution can suitably be selected according to the concentration of oxidizing substance, the pH value of oxidizing solution etc.For example, with respect to feedstock composition, oxidizing solution can preferred 100 volume % to 1000 volume %, are more preferably 200 volume % to 600 volume %.
(4) recovery of particle
The dispersion of particles liquid of the complex metal oxides that obtains from the operation by above-mentioned (3) reclaims and drying particulate.Can obtain complex metal oxide powder by this operation.As the recovery method of particle, can use filtration etc. known from liquid the method for separate solid.The particle of Huo Deing has for example particle diameter of 100nm to 500nm according to the difference of condition like this.
For example when the feedstock composition that uses PZTN to use, can obtain the powder of α-PZTN.The powder of this α-PZTN can directly be used as agglomerated material, in case of necessity also can be with its further pulverizing.
Can adopt following form in the present embodiment.
Though what use in the operation of above-mentioned (3) is the oxidizing solution that comprises oxidizing substance and alkaline matter in advance and adjusted pH in above-mentioned operation (2), the mixing of feedstock composition and oxidizing substance is not limited to this.For example, can at first add alkaline solution in the feedstock composition and add the water equal solvent in case of necessity, and after the pH that adjusts mixed solution, in this mixed solution, add the solution of oxidizing substance.
The complex metal oxide powder that obtains by above method has following feature:
This complex metal oxides is owing to being non-crystal, so can carry out crystallization by thermal treatments such as sintering.The crystalline complex metal oxides has the less good crystallinity of the non-ferroelectric phase of generation.
2. the application of complex metal oxide powder
Utilize the manufacture method of present embodiment can obtain pulverous complex metal oxides.This pulverous complex metal oxides can be directly form complex metal oxides behind the sintering separately, also can with other complex metal oxides mix particles and sintering after form the crystallization complex metal oxides.
To the application examples of the complex metal oxides that obtains by present embodiment be described below.That is, the method for using the α-PZTN powder that obtains by present embodiment to form block lead zirconate titanate is described with reference to Fig. 1.
(1) weighing of raw material and mixing
At first, (Pb (Zr, Ti) O3) powder (PZT) and the powder of α-PZTN of obtaining with present embodiment make both reach predetermined amount (step S1) to the lead zirconate titanate that weighing obtains with known methods such as sintering processs.Then, PZT powder and α-PZTN powder mixes are obtained raw material powder (step S2).The powder diameter of PZT and α-PZTN is not particularly limited, and for example can be 1 μ m to 100 μ m.
α-PZTN is to be used for for example ratio of 5 weight % to 25 weight % with respect to raw material powder.When the ratio of α-PZTN is in this scope, do not use organic adhesive can obtain to have the block PZT of superperformance.That is, α-PZTN can be described as the softish state that is in, so the crystalline powder of PZT is had the effect of binding agent because its atom moves easily.And because PZTN has the perovskite structure identical with PZT, and α-PZTN is in easy initiation crystallinity and carry out the crystalline state, so can the sintering temperature when using α-PZTN be reduced to the sintering temperature that is lower than when using the PZTN monomer.And, because PZTN has good piezoelectric property, ferroelectric properties, insulativity, thus the characteristic of block PZT there is not detrimentally affect, and can increase more excellent characteristic.When using existing organic adhesive, be difficult to remove fully this organic adhesive, and have the possibility that block PZT is made any difference, but work as caking agent owing to α-PZTN in the method, so do not produce this problem.
(2) sintering
Then, raw materials for sintering powder.Sintering can use known method.For example, raw material powder can be added in the mould, carry out sintering with vacuum hot-pressing.Sintering can carry out under 800 ℃ to 1200 ℃.Can obtain block PZT like this.
According to aforesaid method, the mixture that can use PZT powder and α-PZTN powder is as raw material powder, and organic adhesive such as polyvinyl alcohol can obtain block PZT thereby for example do not use.This bulk PZT does not contain impurity such as organic adhesive, and has the good piece characteristic that crystallizes into.And block PZT contains the PZTN with good piezoelectric property, ferroelectric properties, insulativity etc., compares with the PZT monomer to have good characteristic.
This bulk PZT can be used for various uses, for example, can suitably be used in piezoelectricity engine, SAW device, gyrostat etc.
3. embodiment
The sample of embodiment can be obtained by following method.
(1) embodiment 1
The feedstock composition that is used for obtaining α-PZTN powder is by containing first to the 3rd at least a material solution of Pb, Zr, Ti and Nb, mixing as the dimethyl succinate of polycarboxylate with as the propyl carbinol of organic solvent and obtain.Mixed solution is collosol and gel raw material and Succinic acid dimethylester to be dissolved in the propyl carbinol in 1: 1 ratio form.
As first material solution, use be to be used to form the PbZrO that comprises Pb and Zr
3Uhligite crystalline polycondensate is dissolved in the solution of n-butanols solvent with anhydrous state.
As second material solution, use be to be used to form the PbTiO that comprises Pb and Ti
3Uhligite crystalline polycondensate is dissolved in the solution of n-butanols solvent with anhydrous state.
As the 3rd material solution, use be to be used to form the PbNbO that comprises Pb and Nb
3Uhligite crystalline polycondensate is dissolved in the solution of n-butanols solvent with anhydrous state.
Use above-mentioned first, second, and the 3rd material solution form by PbZr
0.33Ti
0.47Nb
0.2O
3During the ferroelectric layer that (PZTN) constitutes, with (first material solution): (second material solution): the mixed of (the 3rd material solution)=33: 47: 20.Then, be purpose with the crystallized temperature that reduces ferroelectric layer, will be used to form PbSiO
3The solution that the crystalline polycondensate is dissolved in n-butanols solvent with anhydrous state adds in the above-mentioned mixed solution with the ratio of 2mol% as the 4th material solution, obtains feedstock composition.
Then, 20% the aqueous solution, pure water with 30% the aqueous solution of hydrogen peroxide, ammoniacal liquor is mixed with oxidizing solution after mixing.The pH of this oxidizing solution is adjusted to 13.Then, in above-mentioned feedstock composition, during with the above-mentioned oxidizing solution of mixed of 600 volume %, in mixed solution, there is particle to separate out.Reclaim this particle and dry, obtain powder.The median size of this powder particle is about 100 μ m.And, when resolving the powder that is obtained, can confirm that powder is α-PZTN by xrd method.
And, at 600 ℃ of Powdered α-PZTN that following sintering obtained, obtain crystallization PZTN.The XRD result who in Fig. 2, represents this crystallization PZTN with symbol c.Can confirm from Fig. 2: the PZTN that obtains by present embodiment has the less well-crystallized of non-ferroelectric phase that generation is represented with symbol P.
And, except the pH with oxidizing solution is adjusted into 11 or 9, carry out same as the above-mentioned methodly, thus the sample of acquisition crystallization PZTN.The XRD result of these samples is shown in Figure 2.The pH that the data of representing with symbol b illustrate oxidizing solution is 11 example, and the pH that the data of representing with symbol a illustrate oxidizing solution is 9 example.Can confirm that from Fig. 2 along with the reduction of the pH of oxidizing solution, the peak value of the non-ferroelectric phase of crystallization PZTN has trend of rising.Can infer: along with the pH of the oxidizing solution side shifting to alkali, the diffusion of lead ion in feedstock composition is suppressed, and the generation of the non-ferroelectric phase that is caused by lead reduces.
(2) embodiment 2
Change the hydrogen peroxide in the oxidizing solution and the ratio of ammoniacal liquor, the pH of oxidizing solution is adjusted into about 10, and, except the addition that changes oxidizing solution, use three kinds of oxidizing solutions to obtain three kinds of α-PZTN in the same manner with embodiment 1.Use 30% aqueous solution as hydrogen peroxide, use 29% aqueous solution as ammonia soln.
First oxidizing solution be with aqueous hydrogen peroxide solution and ammonia soln with about 1: 2.5 mixed, add pure water and pH is adjusted into 10 forms.Second oxidizing solution be with aqueous hydrogen peroxide solution and ammonia soln with about 2: 1 mixed, add pure water and pH is adjusted into 10 forms.The 3rd oxidizing solution be with aqueous hydrogen peroxide solution and ammonia soln with about 3: 1 mixed, add pure water and pH is adjusted into 10 forms.
Then, in feedstock composition, add oxidizing solution in the same manner with embodiment 1 with the ratio of about 230 volume %.Like this, in mixed solution, separate out powder.During the powder that obtained by the xrd method analysis, can confirm that powder is α-PZTN.
And, with embodiment 1 in the same manner at 600 ℃ of following sintering α-PZTN, obtain crystallization PZTN sample.When each sample is asked for XRD, can obtain result shown in Figure 3.In Fig. 3, the data of representing with symbol a are to use the situation of first oxidizing solution, and the data of representing with symbol b are to use the situation of second oxidizing solution, and the data of representing with symbol c are to use the situation of the 3rd oxidizing solution.The peak value of representing with symbol P is the peak value of non-ferroelectric phase.
As can be seen from Figure 3, along with the increase of the ratio of hydrogen peroxide, the peak value of non-ferroelectric phase also raises.Can infer that this is because when hydrogen peroxide is more, because the diffusion of lead ion in feedstock composition is more, so the generation of non-ferroelectric phase is more.
In addition, the present invention is not limited to above-mentioned embodiment, and various distortion can be arranged.For example, the present invention includes and the identical formation (for example, function, method and the formation that comes to the same thing, the perhaps identical formation of purpose and effect) of formation essence that illustrates in an embodiment.And the present invention also comprises the formation of the non-intrinsically safe part of changing in the formation that illustrates among the embodiment.And, the present invention also comprise obtain with embodiment in the formation same function effect that illustrates formation or reach the formation of identical purpose.In addition, the present invention also comprises the formation of adding known technology in the formation of explanation in an embodiment.
Claims (12)
1. the manufacture method of a complex metal oxide powder comprises:
Preparation is used to form the operation of the feedstock composition of complex metal oxides;
In described feedstock composition, mix the oxidizing solution contain oxidizing substance, generate the particle of described complex metal oxides and form the operation of described dispersion of particles liquid; And
The operation of from described dispersion liquid, separating described particle, the pulverous described complex metal oxides of formation,
Described complex metal oxides general formula AB
1-xC
xO
3Expression, wherein, the A element comprises Pb at least, the B element comprises that at least a among Zr, Ti, V, W and the Hf, C element comprise at least a among Nb and the Ta,
Described feedstock composition comprises: contain at least a in the pyrolytic organometallic compound of described A element, described B element or described C element, the water-disintegrable organometallic compound that contains described A element, described B element or described C element, its partial hydrolystate and/or the polycondensate; At least a in poly carboxylic acid and the polycarboxylate; And organic solvent.
2. the manufacture method of complex metal oxide powder according to claim 1, wherein, described complex metal oxides is that described B element is the niobium lead titanate-zirconate that Zr and Ti, described C element are Nb.
3. the manufacture method of complex metal oxide powder according to claim 1, wherein, described organic solvent is an alcohol.
4. the manufacture method of complex metal oxide powder according to claim 2, wherein, described niobium lead titanate-zirconate with chemical formula Pb (Zr, Ti)
1-XNb
XO
3Expression, in the described chemical formula, 0.05≤x≤0.3.
5. the manufacture method of complex metal oxide powder according to claim 2, wherein, described niobium lead titanate-zirconate comprises more than or equal to the Si of 0.5 mole of % or Si and Ge.
6. according to the manufacture method of each described complex metal oxide powder in the claim 1 to 5, wherein:
The pH of described oxidizing solution is adjusted into greater than 7 and smaller or equal to 13.
7. the manufacture method of complex metal oxide powder according to claim 6, wherein,
The pH of described oxidizing solution is adjusted into more than or equal to 10 and smaller or equal to 13.
8. the manufacture method of complex metal oxide powder according to claim 6, wherein,
The pH of described oxidizing solution is adjusted into more than or equal to 10 and smaller or equal to 11.
9. according to the manufacture method of each described complex metal oxide powder in the claim 1 to 5, wherein,
Described oxidizing solution is the solution of the solution of oxidizing substance and alkaline matter is mixed and to obtain.
10. according to the manufacture method of each described complex metal oxide powder in the claim 1 to 5, wherein,
Described oxidizing substance is a hydrogen peroxide.
11. according to the manufacture method of each described complex metal oxide powder in the claim 1 to 5, wherein,
Described complex metal oxides is noncrystal.
12. an amorphous complex metal oxide is the Powdered amorphous complex metal oxide that obtains by each described manufacture method in the claim 1 to 5, uses general formula AB
1-xC
xO
3Expression, wherein,
Described A element comprises Pb at least,
Described B element comprises at least a among Zr, Ti, V, W and the Hf,
Described C element comprises at least a among Nb and the Ta.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006177788 | 2006-06-28 | ||
| JP2006177788 | 2006-06-28 | ||
| JP2007117642 | 2007-04-26 |
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