CN114127013A - Me element-substituted organic acid barium titanium oxide, method for producing same, and method for producing titanium perovskite ceramic raw material powder - Google Patents

Me element-substituted organic acid barium titanium oxide, method for producing same, and method for producing titanium perovskite ceramic raw material powder Download PDF

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CN114127013A
CN114127013A CN202080051268.1A CN202080051268A CN114127013A CN 114127013 A CN114127013 A CN 114127013A CN 202080051268 A CN202080051268 A CN 202080051268A CN 114127013 A CN114127013 A CN 114127013A
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松下晃
村田智春
国枝武久
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Nippon Chemical Industrial Co Ltd
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Abstract

The invention provides Me element-substituted organic acid barium titanyl oxide powder, which is characterized by comprising the following components in parts by weight: the barium titanyl organic acid powder is prepared by replacing a part of Ba positions with Me element (Me represents at least 1 selected from Ca, Sr and Mg), the molar ratio of the total of Ba and Me element to Ti ((Ba + Me)/Ti) is more than 0.980 and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is more than 0.001 and less than 0.250.

Description

Me element-substituted organic acid barium titanium oxide, method for producing same, and method for producing titanium perovskite ceramic raw material powder
Technical Field
The present invention relates to an organic acid barium titanyl oxide obtained by substituting a part of barium element useful as a raw material of a functional ceramic such as a dielectric, a piezoelectric body, an optoelectronic material, a semiconductor, a sensor, or the like with another element, and a method for producing the same.
Background
The dielectric layer of a multilayer ceramic chip capacitor (MLCC) is generally in the form of a multi-component system composed of barium titanate as a main raw material and a trace amount of additives. For example, although calcium is a component that is commonly used as an additive, it is known that calcium has an effect of acting as an inhibitor for smoothing the temperature characteristics of the relative permittivity of a dielectric substance by substituting and dissolving a barium site in barium titanate, and can be used as a glass component that is a sintering aid.
The barium titanate in the form of a multicomponent system can be obtained by adding a trace amount of components by using a conventionally known solid phase method, oxalate method, hydrothermal synthesis method, alkoxide method, or the like. Among these, the oxalate method is a production method of synthesizing barium titanate by heat-treating a wet-synthesized oxalate precursor and then removing oxalic acid. The oxalate method is characterized in that stoichiometric barium titanate can be obtained at a high grade depending on the composition ratio (Ba/Ti) of barium to titanium in the precursor crystal.
As for the oxalate method, several processes have been reported, and industrially, a method of adding a mixed solution of titanium chloride and barium chloride to an aqueous oxalic acid solution to carry out a reaction is generally used. A method for producing barium titanyl oxalate by replacing a part of barium element with another metal element by the oxalate method is proposed.
For example, patent document 1 describes a method in which a mixed solution of titanium chloride and barium chloride is added to an oxalic acid aqueous solution so as to contain other substituted alkaline earth metal compounds. However, it is difficult to quantitatively perform the reaction, and thus there is a disadvantage that it is industrially disadvantageous.
Therefore, in order to quantitatively perform the reaction, patent document 2 describes: when a solution containing titanium tetrachloride and oxalic acid is added to a solution containing a barium compound and a compound containing the other element to be substituted, the reactivity is improved, and barium titanyl oxalate having a high substitution rate of barium with the other element to be substituted can be obtained.
Patent document 3 describes: the ceramic raw material fine powder having good dispersibility and excellent uniformity of the alkaline earth metal such as barium and calcium and titanium can be obtained by dropping and mixing a first aqueous solution containing oxalic acid and titanium into a second aqueous solution containing ammonia and at least 1 selected from calcium, barium and strontium.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-212543
Patent document 2: japanese laid-open patent publication No. 2006-188469
Patent document 3: japanese laid-open patent publication No. 4-292455
Disclosure of Invention
Technical problem to be solved by the invention
However, the method described in cited document 2 has a problem that, although other elements such as calcium can be substituted at the barium site with high probability, it is difficult to uniformly distribute the substitution element in the entire barium titanyl oxalate because the reactivity is too high.
Further, although the examples of cited document 3 describe that a product having a composition corresponding to the additive composition can be obtained, there is no evaluation about uniformity, and it cannot be said that the pH adjustment using ammonia is industrially advantageous.
The object of the invention is therefore: there are provided a Me element-substituted barium titanyl organic acid powder and a barium titanate powder, which are barium titanyl organic acid powders and barium titanate powders in which a part of the Ba site is substituted with other elements (Me element) and in which the substitution elements are uniformly distributed in the entirety of the barium titanyl organic acid powder or the entirety of the barium titanate powder without being segregated, and a method for industrially advantageously producing the barium titanyl organic acid powder or the barium titanate powder.
Technical solution for solving technical problem
In view of the above circumstances, the present inventors have made extensive studies and found that a barium titanyl organic acid powder with less segregation can be obtained by setting the molar ratio of the total of Ba and Me elements of the barium titanyl organic acid to Ti to 0.980 to 0.999 within a range of slightly less than 1 and setting the molar ratio of Me element to Ba within a range of 0.001 to 0.200, and have completed the present invention.
That is, the present invention (1) provides a Me element-substituted barium titanyl organic acid powder characterized by: wherein a part of Ba site is replaced by Me element (Me represents at least 1 selected from Ca, Sr and Mg) to replace organic acid barium titanium oxide,
the molar ratio of the total of Ba and Me elements to Ti ((Ba + Me)/Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is 0.001 or more and 0.250 or less.
Further, the present invention (2) provides Me element-substituted barium titanyl organic acid powder (1), characterized in that: in Electron Probe Microanalyzer (EPMA) analysis, the Me element was uniformly distributed in particles of the Me element-substituted barium titanate powder obtained by firing the Me element-substituted organic acid barium titanyl powder.
Further, the present invention (3) provides Me element-substituted barium titanyl organic acid powder (1), characterized in that: on the surface of the green compact of Me element-substituted barium titanate obtained by firing the Me element-substituted organic acid barium titanyl powder, mapping analysis of 256 points in vertical and horizontal directions was performed at 0.8 μm intervals within a square having a side length of 205 μm by analysis with an Electron Probe Microanalyzer (EPMA), and the CV value (standard deviation/average value) of Ca in the obtained image analysis was 0.4 or less.
Further, the present invention (4) provides a method for producing barium titanyl Me-substituted organic acid powder, comprising: mixing a barium compound, a Me element compound and a titanium compound in water to obtain an aqueous solution (solution A), adding the aqueous solution (solution A) to an organic acid aqueous solution (solution B) to obtain Me element-substituted barium titanyl organic acid,
in the solution A, the molar ratio of Me element to Ba (Me/Ba) is 0.020 to 5.000 in terms of atomic conversion, the molar ratio of Ba to Ti (Ba/Ti) is 0.300 to 1.200, and the mixing temperature of the solution A and the solution B is 10 to 50 ℃.
Further, the present invention (5) provides the Me element-substituted barium titanyl organic acid powder production method of (4), characterized in that: the barium compound is at least 1 selected from the group consisting of barium chloride, barium carbonate and barium hydroxide.
Further, the present invention (6) provides the Me element-substituted barium titanyl organic acid powder production method of (4) or (5), characterized in that: the Me compound is at least 1 selected from the group consisting of a chloride of Me element, a carbonate of Me element and a hydroxide of Me element.
Further, the present invention (7) provides a method for producing a Me element-substituted barium titanyl organic acid powder according to any one of (4) to (6), comprising: the titanium compound is at least 1 selected from titanium tetrachloride and titanium lactate.
Further, the present invention (8) provides a method for producing a Me element-substituted barium titanyl organic acid powder according to any one of (4) to (7), comprising: the organic acid is at least 1 selected from oxalic acid, citric acid, malonic acid and succinic acid.
Further, the present invention (9) provides a method for producing a titanium perovskite ceramic raw material powder, comprising: the Me-substituted barium titanyl titanate powder of any one of (1) to (3) is fired to obtain Me-substituted barium titanate.
Further, the present invention (10) provides a method for producing a titanium perovskite ceramic raw material powder, comprising: the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the Me element-substituted barium titanyl organic acid powder according to any one of (4) to (8) is fired to obtain the Me element-substituted barium titanate powder.
Effects of the invention
The present invention can provide a Me element-substituted organic acid titanyl barium powder and barium titanate powder, which are organic acid titanyl barium and barium titanate in which a part of Ba site is substituted with other element (Me element), and the substitution elements are uniformly distributed in the whole organic acid titanyl barium powder or the whole barium titanate powder without segregation, and can provide a method for industrially advantageously producing the organic acid titanyl barium or the barium titanate powder.
Drawings
Fig. 1 shows the results of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 1.
FIG. 2 shows XRD analysis results of barium calcium titanyl oxalate obtained in examples 1 to 5 and comparative examples 1 to 2.
Fig. 3 shows the results of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 2.
Fig. 4 shows the results of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 3.
Fig. 5 shows the results of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 4.
Fig. 6 shows the results of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 5.
Fig. 7 shows the results of EPMA mapping analysis of Ca atoms in barium calcium titanate powder obtained in comparative example 1.
Fig. 8 shows the results of EPMA mapping analysis of Ca atoms in barium calcium titanate powder obtained in comparative example 2.
Detailed Description
The Me element-substituted organic acid barium titanyl oxide powder is characterized in that: wherein a part of Ba site is replaced by Me element (Me represents at least 1 selected from Ca, Sr and Mg) to replace organic acid barium titanium oxide,
the molar ratio of the total of Ba and Me elements to Ti ((Ba + Me)/Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is 0.001 or more and 0.250 or less.
The Me element-substituted barium titanyl organic acid powder of the present invention is a powdery aggregate of particles of barium titanyl organic acid in which a portion of the Ba site is substituted with Me element.
In the Me element-substituted barium titanyl organic acid powder of the present invention, the Me element that substitutes for a part of the Ba site of barium titanyl organic acid is at least 1 element selected from Ca, Sr and Mg, preferably Ca, Sr, and particularly preferably Ca. Me may be 1 species or 2 or more species.
In the Me element-substituted organic acid titanyl barium powder of the present invention, the organic acid is at least 1 selected from oxalic acid, citric acid, malonic acid and succinic acid, and oxalic acid and citric acid are preferred, and oxalic acid is particularly preferred.
The molar ratio ((Ba + Me)/Ti) of the total of Ba and Me elements in the Me element-substituted barium titanyl organic acid powder of the present invention to Ti is 0.980 or more and less than 0.999. Preferably 0.983 to 0.998, and particularly preferably 0.985 to 0.997. When (Ba + Me)/Ti is in the above range, a Me element-substituted organic acid barium titanyl powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained, and a Me element-substituted barium titanate powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained by firing. On the other hand, when (Ba + Me)/Ti is less than the above range, Me element-substituted barium titanate having desired characteristics is difficult to obtain, and when it exceeds the above range, Me element segregation is likely to occur.
The molar ratio (Me/Ba) of Me element to Ba element in the Me element-substituted barium titanyl organic acid powder of the present invention is 0.001 to 0.250, preferably 0.005 to 0.150. When Me/Ba is in the above range, the Me element-substituted barium oxotitanate organic acid having Me elements uniformly distributed in the entire powder and less segregated to Me elements can be obtained, and the Me element-substituted barium titanate having Me elements uniformly distributed in the entire particles and less segregated to Me elements can be obtained by firing. On the other hand, when the ratio Me/Ba is less than the above range, it is difficult to obtain Me element-substituted barium titanate having desired characteristics, and when it exceeds the above range, segregation of Me element is likely to occur.
Among the Me element-substituted barium titanyl oxalate powders of the present invention, examples of the organic acid which is oxalic acid include a Me element-substituted barium titanyl oxalate powder represented by the following general formula (1).
(Ba1－pMep)qTiO(C2O4)2·nH2O (1)
(wherein Me represents at least 1 element selected from Ca, Sr and Mg, p is 0.001. ltoreq. p.ltoreq.0.200, q is 0.980. ltoreq. q.ltoreq.0.999, and n is an integer of 1 to 8.)
In the general formula (1), Me is at least 1 element selected from Ca, Sr and Mg, preferably Ca, Sr, and particularly preferably Ca. Me may be 1 species or 2 or more species. That is, the Me element represented by the general formula (1) replaces a part of the Ba site of the barium titanyl oxalate powder with 1 or 2 or more species selected from Ca, Sr and Mg.
In the general formula (1), the value of q corresponds to the molar ratio ((Ba + Me)/Ti) of the total of Ba and Me elements in terms of atoms to Ti. q is 0.980 or more and less than 0.999, preferably 0.983 or more and 0.998 or less, and particularly preferably 0.985 or more and 0.997 or less. When q is within the above range, the Me element-substituted barium titanyl oxalate powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained, and the Me element-substituted barium titanate powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained by firing. On the other hand, if q is less than the above range, it is difficult to obtain Me element-substituted barium titanate having desired characteristics, and if q exceeds the above range, Me element segregation tends to occur.
In the general formula (1), p corresponds to a molar ratio of Me element to Ba (Me/Ba) in terms of atoms. P is 0.001 to 0.200, preferably 0.005 to 0.150. When p is in the above range, the Me element-substituted barium titanyl oxalate in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained, and the Me element-substituted barium titanate in which the Me element is uniformly distributed in the entire particle and segregation of the Me element is small can be obtained by firing. On the other hand, if p is less than the above range, it is difficult to obtain Me element-substituted barium titanate having desired characteristics, and if p exceeds the above range, Me element segregation tends to occur.
In the general formula (1), n is an integer of 1 to 8. n is preferably an integer of 3 to 7.
The molar ratio of the Me element substituted for each atom of Ti, Ba, and Me in barium titanyl oxalate represented by general formula (1) can be calculated based on the measured value of a fluorescence X-ray analyzer (ZSX 100e, manufactured by kogaku corporation). In addition, regarding the molar ratio of each atom of Ti, Ba, Me in the Me element-substituted barium titanyl oxalate represented by the general formula (1), the Me element-substituted barium titanyl oxalate can be fired, and the obtained Me element-substituted barium titanate can be measured by a fluorescent X-ray analyzer (ZSX 100e, manufactured by kokushi corporation) and calculated based on the obtained value.
The average particle diameter of the Me element-substituted barium titanyl organic acid powder of the present invention is not particularly limited, but is preferably 0.1 to 300. mu.m, and particularly preferably 0.5 to 200. mu.m. In the present invention, the average particle diameter of the Me element-substituted barium titanyl organic acid refers to a particle diameter of 50% by volume in a particle size distribution obtained by a laser diffraction-scattering method (D50).
The fired product obtained by firing the Me element-substituted organic acid barium titanyl powder of the present invention at 600 to 1200 ℃, preferably 650 to 1100 ℃, is a titanium-based perovskite-type composite oxide, and is barium titanate obtained by substituting a part of Ba sites with Me element. That is, the fired product of the Me element-substituted barium titanyl organic acid powder of the present invention is a Me element-substituted barium titanate powder represented by the following general formula (2).
(Ba1－xMex)yTiO3 (2)
In the general formula (2), Me is at least 1 selected from the group consisting of Ca, Sr and Mg. x is 0.001. ltoreq. x.ltoreq.0.200, preferably 0.010. ltoreq. x.ltoreq.0.150. Y is 0.980. ltoreq. y < 0.999, preferably 0.983. ltoreq. y.ltoreq.0.998, and particularly preferably 0.985. ltoreq. y.ltoreq.0.997.
In the Me element-substituted barium titanate powder obtained by firing the Me element-substituted organic acid barium titanyl powder of the present invention at 600 to 1200 ℃, preferably 650 to 1100 ℃, the Me element is uniformly distributed in each particle. In the present invention, the uniform distribution of the Me element in the particles of the Me element-substituted barium titanate means that: on the surface of the green compact containing barium titanate substituted with Me element, mapping analysis of 256 points in length and width was performed at 0.8 μm intervals in the range of a square having a side length of 205 μm by using an Electron Probe Microanalyzer (EPMA), and the CV value (standard deviation/average value) of Ca was calculated in the obtained image analysis and was 0.4 or less.
The method for preparing Me element-substituted organic acid barium titanyl oxide powder is characterized in that: a barium compound, a Me element compound (Me represents at least 1 selected from the group consisting of Ca, Sr and Mg), and a titanium compound are mixed in water to obtain an aqueous solution (solution A), and the aqueous solution (solution A) is added to an organic acid aqueous solution (solution B), thereby obtaining Me element-substituted barium oxotitanate, wherein the molar ratio of the Me element to Ba (Me/Ba) in the solution A is 0.020 or more and 5.000 or less in terms of atoms, the molar ratio of Ba to Ti (Ba/Ti) in terms of atoms is 0.300 or more and 1.200 or less in terms of atoms, and the rate of addition of the solution A to the solution B is 2.0 ml/min or more.
The method for producing the Me element-substituted barium titanyl organic acid powder of the present invention is a method for producing the following Me element-substituted barium titanyl organic acid: first, the whole of the solution B used for the reaction was charged into the reaction vessel, and then the solution a was supplied into the reaction vessel, and the solution a was added to the solution B to carry out the formation reaction of barium titanyl organic acid substituted with Me element.
The solution a relating to the method for producing barium titanyl oxalate by Me element substitution according to the present invention is an aqueous solution obtained by mixing a barium compound, a Me element compound and a titanium compound in water.
The barium compound related to the method for producing barium titanyl oxalate by Me element substitution according to the present invention is not particularly limited, and barium chloride, barium carbonate, barium hydroxide, barium acetate, barium nitrate, and the like can be mentioned. The barium compound may be used in 1 kind, or 2 or more kinds may be used in combination. The barium compound is preferably 1 or 2 or more selected from barium chloride, barium carbonate and barium hydroxide.
The Me element compound according to the method for producing barium titanyl oxalate by Me element substitution of the present invention is not particularly limited, and examples thereof include chlorides, hydroxides, carbonates, acetates, nitrates and the like containing 1 or 2 or more elements selected from Ca, Sr and Mg. The Me element compound may be used in 1 kind, or 2 or more kinds may be used in combination. The Me element compound is preferably 1 or 2 or more selected from the group consisting of a chloride of Me element, a carbonate of Me element, and a hydroxide of Me element.
The titanium compound in the method for producing barium titanyl Me-substituted organic acid of the present invention is not particularly limited, and titanium tetrachloride, titanium lactate and the like can be mentioned. The titanium compound may be used in 1 kind, or 2 or more kinds may be used in combination. Titanium tetrachloride is preferred as the titanium compound.
Examples of the organic acid related to the method for producing barium titanyl oxalate by Me element substitution according to the present invention include oxalic acid, citric acid, malonic acid, succinic acid, and the like. The organic acid may be 1 type, or 2 or more types may be used in combination. As the organic acid, oxalic acid is preferable.
In the present invention, it is preferable to use barium chloride as the barium compound, Me element chloride as the Me element compound, titanium tetrachloride as the titanium compound, and oxalic acid as the organic acid, because the reactivity is high and a stable quality product is obtained in a high yield.
In the solution a, the molar ratio of Me element to Ba (Me/Ba) in terms of atoms is 0.020 or more and 5.000 or less, preferably 0.050 or more and 4.000 or less. When the molar ratio of the Me element to Ba in terms of atoms (Me/Ba) in the solution a is in the above range, the Me element-substituted organic acid oxotitanyl barium powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained, and the Me element-substituted barium titanate powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained by firing. On the other hand, when the molar ratio of Ba to Ti in terms of atoms (Ba/Ti) in the solution a is less than the above range, substitution with Me element is difficult, and when it exceeds the above range, segregation of Me element is likely to occur.
In the solution a, the molar ratio of Ba to Ti (Ba/Ti) in terms of atoms is 0.300 to 1.200, preferably 0.350 to 1.150. When the molar ratio of Ba to Ti in terms of atoms (Ba/Ti) in the solution a is in the above range, the Me element-substituted barium oxotitanate organic acid having Me elements uniformly distributed in the entire particle and less segregation of the Me element can be obtained, and the Me element-substituted barium titanate having Me elements uniformly distributed in the entire particle and less segregation of the Me element can be obtained by firing. On the other hand, when the molar ratio of Ba to Ti in terms of atoms (Ba/Ti) in the solution a is less than the above range, substitution with Me element is difficult, and when it exceeds the above range, segregation of Me element is likely to occur.
The concentration of Ba in the solution A is not particularly limited, but is preferably 0.05 to 1.00mol/L, and particularly preferably 0.10 to 0.90mol/L in terms of atomic conversion.
The concentration of Me element in solution A is not particularly limited, but is preferably 0.002 to 6.50mol/L, particularly preferably 0.10 to 6.00mol/L in terms of atomic conversion.
The Ti concentration in the solution A is not particularly limited, but is preferably 0.05 to 1.35mol/L, particularly preferably 0.10 to 1.30mol/L in terms of atomic conversion.
The solution B relating to the method for producing barium titanyl oxalate with Me element substitution according to the present invention is an organic acid aqueous solution obtained by dissolving an organic acid in water.
The ratio of the total mole number of Ba, Me elements and Ti in terms of atoms in the solution a to the mole number of the organic acid ions in the solution B is 0.800 to 1.400, preferably 0.850 to 1.300, and particularly preferably 0.900 to 1.250. When the ratio of the total mole number of Ba, Me and Ti in terms of atoms in the solution a to the mole number of the organic acid ion in the solution B is in the above range, the Me element uniformly distributed in the entire particles and the Me element having less segregation can be obtained by substituting the organic acid barium titanyl oxide with the Me element.
The concentration of the organic acid ion in the solution B is not particularly limited, but is preferably 0.10 to 5.00mol/L, and particularly preferably 0.50 to 3.00 mol/L.
In the method for producing barium titanyl oxalate substituted with Me element according to the present invention, first, the entire amount of the solution B is charged into the reaction vessel, then the solution a is supplied into the reaction vessel, and the solution a is added to the solution B, thereby carrying out the production reaction of barium titanyl oxalate substituted with Me element in the reaction vessel.
When the solution a is added to the solution B, the rate of addition of the solution a is also determined by the scale of the implementation, and is preferably 2.0 ml/min or more, and particularly preferably 3.0 ml/min or more, for example, at a laboratory level of 0.5L scale. By adding the solution a to the solution B at the above-described addition rate, the Me element-substituted barium titanyl organic acid in which the Me element is uniformly distributed in the entire particle and segregation of the Me element is small can be obtained. The upper limit is not particularly limited as long as the addition rate is satisfied.
The mixing temperature when the solution A is added to the solution B, i.e., the temperature of the solution A and the reaction solution (or the solution B) in the reaction vessel when the solution A is added to the reaction vessel, is usually 10 to 50 ℃, preferably 15 to 45 ℃. By adding the solution a to the solution B at the above-mentioned mixing temperature, the Me element-substituted barium titanyl organic acid in which the Me element is uniformly distributed in the entire particle and segregation of the Me element is small can be obtained.
After all of the solution a is added to the solution B, the reaction solution may be cooled immediately, or the reaction solution may be removed by filtration or the like, whereby the reaction may be terminated, or after all of the solution a is added to the solution B, the reaction solution may be aged while being maintained at a predetermined temperature for a predetermined time. In the case of aging, the aging temperature is preferably 10 ℃ or higher, particularly preferably 20 to 80 ℃, and the aging time is preferably 0.1 hour or longer, particularly preferably 0.2 hour or longer.
When the solution a is added to the solution B, it is preferable to add the solution a to the solution B while stirring the reaction solution (or the solution B). In addition, in the case where the aging is performed after all of the solution a is added to the solution B, the aging is preferably performed while stirring the reaction solution. The stirring speed is not particularly limited, and in the case where the aging is performed from the start of the addition of the solution A to the solution B to the end of the addition of the solution A, the stirring speed may be such that the produced reaction solution containing Me element-substituted barium oxotitanate is kept in a fluid state until the end of the aging.
When the aging is performed after adding all of the solution A to the solution B, after the completion of the aging, the reaction solution is subjected to solid-liquid separation by a usual method, and then the solid portion is washed with water. The washing method is not particularly limited, and washing by repulping or the like is preferable in view of high washing efficiency. After washing, the solid portion was dried and pulverized as necessary to obtain barium titanyl organic acid in which Me element replaces barium titanyl organic acid, that is, barium titanyl organic acid in which a part of Ba site is replaced by Me element.
In this way, the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the Me element-substituted barium titanyl organic acid powder according to the present invention is barium titanyl organic acid in which a part of Ba sites is substituted with Me element, the molar ratio ((Ba + Me)/Ti) of the total of Ba and Me elements to Ti is 0.980 or more and less than 0.999, and the molar ratio (Me/Ba) of Me element to Ba is 0.001 or more and 0.250 or less.
In the Me element-substituted barium oxotitanate powder obtained by the method for producing the Me element-substituted barium oxotitanate powder according to the present invention, the Me element represents at least 1 element selected from Ca, Sr and Mg, preferably Ca and Sr, and particularly preferably the molar ratio ((Ba + Me)/Ti) of the total of Ca, Ba and Me elements to Ti is 0.980 or more and less than 0.999, preferably 0.983 or more and 0.998 or less, and particularly preferably 0.985 or more and 0.997 or less, and the molar ratio (Me/Ba) of the Me element to Ba is 0.001 or more and 0.250 or less, and preferably 0.005 or more and 0.150 or less.
The average particle size of the Me-substituted barium titanyl organic acid powder obtained by the method for producing a Me-substituted barium titanyl organic acid powder of the present invention is not particularly limited, but is preferably 0.1 to 300. mu.m, and particularly preferably 0.5 to 200. mu.m.
By using the method for producing the Me element-substituted organic acid titanyl barium powder of the present invention, the Me element-substituted organic acid titanyl barium powder in which the Me element is uniformly distributed in the entire powder and segregation of the Me element is small can be obtained. It is confirmed that the Me element is uniformly distributed in the entire Me element-substituted barium titanyl organic acid powder and segregation of the Me element is small as follows: the Me element-substituted organic acid barium oxotitanate powder obtained by the method for producing the Me element-substituted organic acid barium oxotitanate powder of the present invention is fired at 600 to 1200 ℃ to obtain Me element-substituted barium titanate, and the Me element-substituted barium titanate is subjected to mapping analysis by EPMA.
In addition, in the Me element-substituted barium titanate obtained by firing the Me element-substituted barium titanyl organic acid powder obtained by the method for producing a Me element-substituted barium titanyl organic acid powder of the present invention at 600 to 1200 ℃, preferably 650 to 1100 ℃, the Me element is uniformly distributed on the particle surface. In addition, in the Me element-substituted barium titanyl organic acid powder obtained by performing the method for producing a barium titanyl organic acid powder substituted with Me element according to the present invention, the Me element is uniformly distributed in the depth direction of the particles.
The Me element-substituted organic acid titanyl barium powder of the present invention and the Me element-substituted organic acid titanyl barium powder obtained by firing the Me element-substituted organic acid titanyl barium powder obtained by the method for producing the Me element-substituted organic acid titanyl barium powder of the present invention are suitable as a titanium-based perovskite-type ceramic raw material powder for a dielectric ceramic material. That is, the Me element-substituted organic acid titanyl barium powder of the present invention or the Me element-substituted organic acid titanyl barium powder obtained by the method for producing Me element-substituted organic acid titanyl barium powder of the present invention is fired at 600 to 1200 ℃, preferably 650 to 1100 ℃, whereby titanium-based perovskite-type ceramic raw material powder can be obtained.
The Me element-substituted barium titanate powder obtained by firing the Me element-substituted barium titanyl organic acid powder of the present invention and the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the Me element-substituted barium titanyl organic acid powder of the present invention is a Me element-substituted barium titanate powder represented by the following general formula (2).
(Ba1－xMex)yTiO3 (2)
In the general formula (2), Me is at least 1 selected from the group consisting of Ca, Sr and Mg. x is 0.001. ltoreq. x.ltoreq.0.200, preferably 0.005. ltoreq. x.ltoreq.0.150. Y is 0.980. ltoreq. y < 0.999, preferably 0.983. ltoreq. y.ltoreq.0.998, and particularly preferably 0.985. ltoreq. y.ltoreq.0.997.
Before the firing, if necessary, in order to obtain a fine titanium perovskite type ceramic raw material powder having high crystallinity even when fired in a low temperature range and in order that the average particle diameter of the Me element-substituted barium oxotitanate is preferably 4 μm or less, particularly preferably 0.02 to 0.5 μm, the Me element-substituted barium oxotitanate powder may be subjected to wet pulverization treatment by a ball mill, a bead mill or the like. In this case, as the solvent used for the wet pulverization treatment, a solvent inactive to the Me element-substituted barium titanyl organic acid can be used, and examples thereof include water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide, diethyl ether and the like. Among them, as the solvent for wet pulverization treatment, from the viewpoint of obtaining a titanium perovskite ceramic raw material powder having high crystallinity, a solvent in which an organic solvent such as methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide, or diethyl ether is less eluted with Ba element, Ti element, and Me element is preferable.
The method for producing a titanium perovskite ceramic raw material powder of the present invention is characterized by: the Me element-substituted barium titanyl organic acid powder of the present invention or the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the Me element-substituted barium titanyl organic acid powder of the present invention is fired to obtain the Me element-substituted barium titanate.
Substitution of the organic substance derived from the organic acid contained in the barium titanyl organic acid powder by Me element is not preferable because it impairs the dielectric characteristics of the material and is a factor causing unstable behavior in the thermal process for ceramization. Therefore, in the method for producing a titanium perovskite ceramic raw material powder of the present invention, the Me element-substituted organic acid titanyl barium powder is fired to thermally decompose the Me element-containing organic acid titanyl barium to obtain the Me element-substituted barium titanate as the target titanium perovskite ceramic raw material powder, and organic substances derived from the organic acid are removed.
In the method for producing a titanium perovskite ceramic raw material powder of the present invention, the firing temperature at the time of firing is 600 to 1200 ℃, preferably 650 to 1100 ℃. When the firing temperature is less than the above range, it is difficult to obtain a single-phase titanium-based perovskite ceramic powder, and when the firing temperature exceeds the above range, variation in particle size becomes large. In the method for producing a titanium perovskite ceramic raw material powder of the present invention, the firing time at the time of firing is preferably 0.2 to 30 hours, and particularly preferably 0.5 to 20 hours. In the method for producing a titanium perovskite ceramic raw material powder of the present invention, the firing atmosphere at the time of firing is not particularly limited, and may be in an atmospheric atmosphere or an inert gas atmosphere.
In the method for producing a titanium perovskite ceramic raw material powder of the present invention, firing may be performed only 1 time, or may be repeated 2 times or more as necessary. When the firing is repeated, the powder after 1 firing may be pulverized and then fired again in order to make the powder characteristics uniform.
In the method for producing a titanium perovskite ceramic raw material powder of the present invention, after firing, Me element-substituted barium titanate powder suitable as a titanium perovskite composite oxide and a titanium perovskite ceramic raw material powder is obtained by appropriately cooling and, if necessary, pulverizing. The pulverization according to need is suitably performed when the Me element-substituted barium titanate powder obtained by firing is in the form of a weakly bonded mass or the like, and the particles of the Me element-substituted barium titanate powder themselves have a specific average particle diameter and BET specific surface area. That is, the Me element-substituted barium titanate powder obtained by the method for producing a titanium perovskite-type ceramic raw material powder of the present invention has an average particle diameter of 0.01 to 4 μm, preferably 0.02 to 0.5 μm, as determined by a Scanning Electron Microscope (SEM), and a BET specific surface area of 0.25 to 100m2Preferably 2 to 50 m/g2(g), the composition deviation is small. In the present invention, the average particle size of the Me element-substituted barium titanate powder was arbitrarily measured at 200 particles in a Scanning Electron Microscope (SEM) photograph, and the average value thereof was defined as the average particle size.
In the titanium perovskite type ceramic raw material powder obtained by performing the method for producing a titanium perovskite type ceramic raw material powder of the present invention, a compound containing a subcomponent element may be added to the titanium perovskite type ceramic raw material powder and contained, as necessary, for the purpose of adjusting dielectric characteristics and temperature characteristics. Examples of the subcomponent element-containing compound that can be used include compounds containing at least 1 element selected from the group consisting of rare earth elements of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, Li, Bi, Zn, Mn, Al, Si, Co, Ni, Cr, Fe, Ti, V, Nb, Mo, W, and Sn.
The compound containing the subcomponent element may be any of inorganic substances and organic substances, and examples thereof include oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates, and alkoxides containing the above elements. When the compound containing the subcomponent element is a compound containing an Si element, silica sol, sodium silicate, or the like can be used in addition to the above oxide or the like. The above-mentioned subcomponent element-containing compounds may be used in 1 kind, or 2 or more kinds may be used in an appropriate combination, and the amount of addition and combination of the additional compounds are appropriately selected according to the purpose.
Examples of the method for adding the subcomponent elements to the titanium-based perovskite-type ceramic raw material powder include: a method of uniformly mixing the titanium perovskite ceramic raw material powder obtained by the method for producing a titanium perovskite ceramic raw material powder of the present invention with a compound containing a subcomponent element and then firing the mixture; alternatively, the organic acid titanyl barium powder of the present invention or the organic acid titanyl barium powder of the present invention obtained by the method for producing an organic acid titanyl barium powder of the present invention is uniformly mixed with a compound containing a subcomponent element and then fired.
The titanium perovskite type ceramic raw material powder obtained by performing the method for producing a titanium perovskite type ceramic raw material powder of the present invention is mixed and dispersed in an appropriate solvent together with compounding agents containing, for example, subcomponent elements, conventionally known additives, organic binders, plasticizers, dispersants, etc. to form a slurry, and then sheet-formed, thereby obtaining a ceramic sheet for producing a multilayer ceramic capacitor.
When a multilayer ceramic capacitor is produced from ceramic sheets, first, a conductive paste for forming internal electrodes is printed on one surface of the ceramic sheets, and after drying, a plurality of the ceramic sheets are laminated and pressure-bonded in the thickness direction to form a multilayer body. Subsequently, the laminate was subjected to heat treatment, binder removal treatment and firing to obtain a fired body. Then, a Ni paste, an Ag paste, a nickel alloy paste, a copper alloy paste, or the like is applied to the sintered body, followed by baking, thereby obtaining a multilayer ceramic capacitor.
In addition, for example, when the titanium perovskite type ceramic raw material powder obtained by performing the method for producing a titanium perovskite type ceramic raw material powder of the present invention is blended with a resin such as an epoxy resin, a polyester resin, a polyimide resin, or the like to prepare a resin sheet, a resin film, an adhesive, or the like, it can be suitably used as a material for a printed wiring board, a multilayer printed wiring board, or the like, and can also be used as a common material for suppressing a difference in shrinkage between an internal electrode and a dielectric layer, an electrode ceramic circuit board, a glass ceramic circuit board, a circuit peripheral material, a dielectric material for inorganic EL, or the like.
The titanium perovskite ceramic raw material powder obtained by performing the method for producing a titanium perovskite ceramic raw material powder of the present invention is also suitable as a catalyst used in reactions such as exhaust gas removal and chemical synthesis, and as a surface modification material for a printing toner for imparting antistatic and cleaning effects.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Examples
In the examples, the characteristics were measured by the following methods.
(1) Molar ratio of Ba atom, Ca atom and Ti atom
The molar ratio of each atom was calculated based on the measurement value of a fluorescent X-ray analyzer (ZSX 100e, manufactured by shinko corporation).
(2) Average particle diameter of Me element-substituted barium titanyl oxalate powder
The particle size distribution was measured by a laser diffraction-scattering method using MT3000 manufactured by microtrac bel, and the particle size at 50% of the particle size distribution by volume (D50) was defined as the average particle size.
(3) Average particle diameter of Me-substituted barium titanate
200 particles were arbitrarily measured using a Scanning Electron Microscope (SEM) photograph using S4800 manufactured by hitachi High Technologies, and the average value thereof was defined as the average particle diameter.
(4) Ca atom mapping analysis using EPMA
Mapping analysis was performed on Ca atoms using an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by Nippon electronics Co., Ltd.).
(5) X-ray diffraction analysis of Me element-substituted barium titanyl oxalate powder
X-ray diffraction analysis was performed using UltimaIV manufactured by ltd.
(example 1)
50.0g of barium chloride dihydrate, 10.0g of calcium chloride dihydrate and 120.0g of titanium tetrachloride were dissolved in 500ml of pure water to prepare a mixed aqueous solution, which was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30 ℃ to prepare an oxalic acid aqueous solution as solution B.
Then, while maintaining the solution B (the reaction solution after the start of the dropwise addition) at 30 ℃ and using it under stirring, the solution A was added at a rate of 4.2 ml/min for 120 minutes, and the mixture was further aged at 30 ℃ for 60 minutes under stirring. After cooling, filtering and recovering the titanyl barium calcium oxalate powder.
Next, the recovered barium calcium titanyl oxalate powder was repulped in distilled water to perform washing. Then, the resultant was dried at 80 ℃ to obtain barium calcium titanyl oxalate powder. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired at 800 ℃ and mapping analysis was performed on Ca atoms using an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by japan electronics corporation). The results are shown in FIG. 1. From the results of fig. 1, it is understood that the obtained barium calcium titanate powder does not show segregation of Ca atoms, and Ca is uniformly dispersed. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.020 and (Ba + Ca)/Ti was 0.994.
It can be confirmed that the barium calcium titanyl oxalate obtained in example 1 was (Ba) based on the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding solution a to solution B0.080Ca0.020)0.994TiO(C2O4)2·4H2And O. The results of the X-ray diffraction analysis are shown in fig. 2.
(example 2)
A mixed aqueous solution was prepared by dissolving 40.0g of barium chloride dihydrate, 20.0g of calcium chloride dihydrate and 120.0g of titanium tetrachloride in 500ml of pure water, and the mixed aqueous solution was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30 ℃ to prepare an oxalic acid aqueous solution as solution B.
Then, while maintaining the solution B (the reaction solution after the start of the dropwise addition) at 30 ℃ and using it under stirring, the solution A was added at a rate of 4.2 ml/min for 120 minutes, and the mixture was further aged at 30 ℃ for 60 minutes under stirring.
The subsequent operations were carried out in the same manner as in example 1. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired, and mapping analysis of Ca atoms was performed on the obtained barium calcium titanate powder using EPMA. The results are shown in FIG. 3. From the results of fig. 3, it is understood that the obtained barium calcium titanate powder does not show segregation of Ca atoms, and Ca is uniformly dispersed. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.05 and (Ba + Ca)/Ti was 0.998.
The elemental analysis results of the obtained barium calcium titanate powder and the grass obtained by adding solution A to solution BX-ray diffraction analysis of barium calcium titanyl oxalate confirmed that the barium calcium titanyl oxalate obtained in example 2 was (Ba)0.08Ca0.05)0.998TiO(C2O4)2·4H2And O. The results of the X-ray diffraction analysis are shown in fig. 2.
(example 3)
A mixed aqueous solution was prepared by dissolving 40.0g of barium chloride dihydrate, 7.5g of calcium chloride dihydrate and 120.0g of titanium tetrachloride in 500ml of pure water, and the mixed aqueous solution was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30 ℃ to prepare an oxalic acid aqueous solution as solution B.
Then, while maintaining the solution B (the reaction solution after the start of the dropwise addition) at 30 ℃ and using it under stirring, the solution A was added at a rate of 4.2 ml/min for 120 minutes, and the mixture was further aged at 30 ℃ for 60 minutes under stirring.
The subsequent operations were carried out in the same manner as in example 1. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired, and mapping analysis of Ca atoms was performed on the obtained barium calcium titanate powder using EPMA. The results are shown in FIG. 4. From the results of fig. 4, it is understood that the obtained barium calcium titanate powder does not show segregation of Ca atoms, and Ca is uniformly dispersed. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.02 and (Ba + Ca)/Ti was 0.991.
It can be confirmed that the barium calcium titanyl oxalate obtained in example 3 was (Ba) based on the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding solution a to solution B0.08Ca0.02)0.991TiO(C2O4)2·4H2And O. The results of the X-ray diffraction analysis are shown in fig. 2.
(example 4)
A mixed aqueous solution was prepared by dissolving 52.0g of barium carbonate, 4.7g of calcium carbonate and 120.0g of titanium tetrachloride in 420ml of pure water, and the mixed aqueous solution was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Subsequently, 70.0g of oxalic acid was dissolved in 420ml of 30 ℃ warm water to prepare an oxalic acid aqueous solution as solution B.
Then, while maintaining the solution B (the reaction solution after the start of the dropwise addition) at 30 ℃ and using it under stirring, the solution A was added at a rate of 3.5 ml/min for 120 minutes, and the mixture was further aged at 30 ℃ for 60 minutes under stirring. After cooling, filtering and recovering the titanyl barium calcium oxalate powder.
Subsequently, the recovered barium calcium titanyl oxalate powder was repulped with distilled water and washed. Then, the resultant was dried at 80 ℃ to obtain barium calcium titanyl oxalate powder. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired at 800 ℃ and mapping analysis was performed on Ca atoms using an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by japan electronics corporation). The results are shown in FIG. 5. From the results of fig. 5, it is understood that the obtained barium calcium titanate powder did not show segregation of Ca atoms, and Ca was uniformly dispersed. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.026 and (Ba + Ca)/Ti was 0.998.
It can be confirmed that the barium calcium titanyl oxalate obtained in example 4 was (Ba) based on the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding solution a to solution B0.08Ca0.03)0.998TiO(C2O4)2·4H2And O. The results of the X-ray diffraction analysis are shown in fig. 2.
(example 5)
A mixed aqueous solution was prepared by dissolving 360.0g of barium chloride dihydrate, 72.0g of calcium chloride dihydrate and 864.0g of titanium tetrachloride in 3600ml of pure water, and the mixed aqueous solution was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Next, 504.0g of oxalic acid was dissolved in 3600ml of warm water at 30 ℃ to prepare an oxalic acid aqueous solution, which was used as solution B.
Then, while maintaining the solution B (reaction solution after the start of the dropwise addition) at 30 ℃ and using it under stirring, the solution A was added at a rate of 30 ml/min for 120 minutes, and the mixture was further aged at 30 ℃ for 60 minutes under stirring. After cooling, filtering and recovering the titanyl barium calcium oxalate powder.
Subsequently, the recovered barium calcium titanyl oxalate powder was repulped with distilled water and washed. Then, the resultant was dried at 80 ℃ to obtain barium calcium titanyl oxalate powder. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired at 800 ℃ and mapping analysis was performed on Ca atoms using an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by japan electronics corporation). The results are shown in FIG. 6. From the results of fig. 6, it is understood that the obtained barium calcium titanate powder does not show segregation of Ca atoms, and Ca is uniformly dispersed. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.025 and (Ba + Ca)/Ti was 0.994.
It can be confirmed that the barium calcium titanyl oxalate obtained in example 5 was (Ba) based on the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding solution a to solution B0.08Ca0.02)0.994TiO(C2O4)2·4H2And O. The results of the X-ray diffraction analysis are shown in fig. 2.
Comparative example 1
A mixed aqueous solution was prepared by dissolving 150.0g of barium chloride dihydrate, 10.0g of calcium chloride dihydrate and 120.0g of titanium tetrachloride in 500ml of pure water, and the mixed aqueous solution was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30 ℃ to prepare an oxalic acid aqueous solution as solution B.
Then, while maintaining the solution B at 30 ℃, the solution A was added at a rate of 4.2 ml/min for 120 minutes under stirring, and the mixture was further aged at 30 ℃ for 60 minutes under stirring. After cooling, filtering and recovering the titanyl barium calcium oxalate powder.
The subsequent operations were carried out in the same manner as in example 1. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired, and mapping analysis of Ca atoms was performed on the obtained barium calcium titanate powder using EPMA. The results are shown in FIG. 7. From the results of fig. 7, it is understood that Ca atoms are segregated in the obtained barium calcium titanate powder. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.020 and (Ba + Ca)/Ti was 1.000.
It can be confirmed that the barium calcium titanyl oxalate obtained in comparative example 1 was (Ba) from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding the solution a to the solution B0.080Ca0.020)1.000TiO(C2O4)2·4H2O。
Comparative example 2
A mixed aqueous solution was prepared by dissolving 27.0g of barium chloride dihydrate, 5.4g of calcium chloride dihydrate and 64.1g of titanium tetrachloride in 180ml of pure water, and the mixed aqueous solution was used as solution A. Table 1 shows the molar ratio of each element in solution a.
Then, 32.5g of oxalic acid was dissolved in 140ml of warm water at 55 ℃ to prepare an oxalic acid aqueous solution as solution B.
Then, while maintaining the temperature of the solution B at 55 ℃, the solution A was added at a rate of 1.5 ml/min for 120 minutes under stirring, and the mixture was aged at 55 ℃ for 60 minutes under stirring. After cooling, filtering and recovering the titanyl barium calcium oxalate powder.
The subsequent operations were carried out in the same manner as in example 1. The physical properties of the obtained barium calcium titanyl oxalate powder are shown in table 1. The obtained barium calcium titanyl oxalate powder was fired, and mapping analysis of Ca atoms was performed on the obtained barium calcium titanate powder using EPMA. The results are shown in FIG. 8. From the results of fig. 8, it is understood that Ca atoms are segregated in the obtained barium calcium titanate powder. Further, elemental analysis of the obtained barium calcium titanate powder revealed that Ca/Ba was 0.020 and (Ba + Ca)/Ti was 0.999.
It can be confirmed that the barium calcium titanyl oxalate obtained in comparative example 2 was (Ba) based on the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding the solution a to the solution B0.080Ca0.020)0.999TiO(C2O4)2·4H2O。
[ Table 1]
Figure BDA0003470373090000211
The results in Table 1 and FIGS. 1 to 8 show that: the barium calcium titanate obtained from the barium calcium titanyl oxalate of the examples was uniformly distributed without segregation of calcium atoms, as compared with the barium calcium titanate obtained from the barium calcium titanyl oxalate of the comparative examples.

Claims (10)

1. A Me element replaced organic acid titanyl barium powder is characterized in that:
wherein Me is a substitution of Me element in which a part of Ba site is substituted by Me element for barium oxotitanate of organic acid, wherein Me represents at least 1 selected from Ca, Sr and Mg,
the molar ratio of the total of Ba and Me elements to Ti ((Ba + Me)/Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is 0.001 or more and 0.250 or less.
2. The barium titanyl Me element-substituted organic acid powder of claim 1, wherein:
in Electron Probe Microanalyzer (EPMA) analysis, the Me element was uniformly distributed in particles of Me element-substituted barium titanate powder obtained by firing the Me element-substituted organic acid barium titanyl powder.
3. The barium titanyl Me element-substituted organic acid powder of claim 1, wherein:
on the surface of the green compact of Me element-substituted barium titanate obtained by firing the Me element-substituted organic acid barium titanyl powder, mapping analysis of 256 points in vertical and horizontal directions was performed at 0.8 μm intervals within a square having a side length of 205 μm by analysis with an Electron Probe Microanalyzer (EPMA), and the CV value (standard deviation/average value) of Ca in the obtained image analysis was 0.4 or less.
4. A manufacturing method of Me element replaced organic acid barium titanyl oxide powder is characterized in that:
mixing a barium compound, a Me element compound and a titanium compound in water to obtain an aqueous solution (solution A), adding the aqueous solution (solution A) to an aqueous organic acid solution (solution B) to obtain Me element-substituted barium titanyl organic acid, wherein Me represents at least 1 selected from the group consisting of Ca, Sr and Mg,
in the solution A, the molar ratio of Me element to Ba (Me/Ba) is 0.020 to 5.000 in terms of atomic conversion, the molar ratio of Ba to Ti (Ba/Ti) is 0.300 to 1.200, and the mixing temperature of the solution A and the solution B is 10 to 50 ℃.
5. The method for producing Me element-substituted barium titanyl organic acid powder according to claim 4, wherein:
the barium compound is at least 1 selected from the group consisting of barium chloride, barium carbonate, and barium hydroxide.
6. The method for producing Me element-substituted barium titanyl organic acid powder according to claim 4 or 5, wherein:
the Me element compound is at least 1 selected from the group consisting of a chloride of Me element, a carbonate of Me element and a hydroxide of Me element.
7. The method for producing Me element-substituted barium titanyl organic acid powder according to any one of claims 4 to 6, wherein:
the titanium compound is at least 1 selected from titanium tetrachloride and titanium lactate.
8. The method for producing Me element-substituted barium titanyl organic acid powder according to any one of claims 4 to 7, wherein:
the organic acid is at least 1 selected from oxalic acid, citric acid, malonic acid and succinic acid.
9. A method for producing a titanium perovskite ceramic raw material powder, characterized by comprising:
the Me element-substituted barium titanyl titanate powder according to any one of claims 1 to 3 is fired to obtain Me element-substituted barium titanate.
10. A method for producing a titanium perovskite ceramic raw material powder, characterized by comprising:
a Me-substituted barium titanyl titanate powder obtained by the method for producing a Me-substituted barium titanyl titanate powder according to any one of claims 4 to 8 is fired.
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