CN114127013B - Me element-substituted organic acid barium titanyl oxide, process for producing the same, and process for producing titanium perovskite ceramic raw material powder - Google Patents
Me element-substituted organic acid barium titanyl oxide, process for producing the same, and process for producing titanium perovskite ceramic raw material powder Download PDFInfo
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- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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Abstract
The invention provides a Me element substituted organic acid oxygen titanium barium powder, which is characterized in that: the organic acid titanyl barium powder is a powder in which a part of Ba is replaced with Me element (Me represents at least 1 selected from Ca, sr and Mg), wherein the molar ratio ((Ba+Me)/Ti) of the sum 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.
Description
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 functional ceramics such as dielectrics, piezoelectrics, optoelectronics, semiconductors, sensors, and the like with another element, and a method for producing the same.
Background
The dielectric layer of a laminated ceramic chip capacitor (MLCC) is generally in the form of a multicomponent system composed of barium titanate as a main raw material and a trace amount of additives. For example, although calcium is a component commonly used as an additive, it is known that substitution solid solution is performed to barium in barium titanate, and this has an effect as an inhibitor for smoothing the temperature characteristic of the dielectric constant, or can be used as a glass component of 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 method for producing 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 according to the composition ratio (Ba/Ti) of barium to titanium in the precursor crystal.
Regarding the oxalate method, several processes have been reported, and a method of adding a mixed solution of titanium chloride and barium chloride to an aqueous oxalic acid solution to perform a reaction has been generally used in industry. A method for producing barium titanyl oxalate is proposed, which uses the oxalate method to replace a part of barium element with another metal element.
For example, patent document 1 describes a method in which a mixed solution of titanium chloride and barium chloride contains a substituted other alkaline earth metal compound and is added to an aqueous oxalic acid solution. However, it is difficult to quantitatively conduct the reaction, and thus there is a disadvantage in that it is industrially disadvantageous.
Accordingly, in order to quantitatively perform the reaction, patent document 2 describes that: when a solution containing titanium tetrachloride and oxalic acid is added to a solution containing a barium compound and a compound containing another element to be substituted for each other for reaction, 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 that: the first aqueous solution containing oxalic acid and titanium is added dropwise to the second aqueous solution containing ammonia and at least 1 selected from calcium, barium and strontium, and mixed, whereby a ceramic raw material fine powder having good dispersibility of alkaline earth metals such as barium and calcium and titanium and excellent uniformity can be obtained.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2003-212543
Patent document 2: japanese patent laid-open No. 2006-188469
Patent document 3: japanese patent laid-open No. 4-292455
Disclosure of Invention
Technical problem to be solved by the invention
However, in the method described in the cited document 2, although other elements such as calcium can be substituted with a high probability at the barium site, there is a problem that it is difficult to uniformly distribute the substitution element throughout the barium titanyl oxalate because of the excessively high reactivity.
Further, according to the example of the cited document 3, it is described that a product having a composition corresponding to the additive composition can be obtained, but uniformity is not evaluated, and pH adjustment may be performed using ammonia, which is not an industrially advantageous method.
Accordingly, the present invention aims to: provided are an organic acid titanyl barium powder and a barium titanate powder substituted with a Me element, which are organic acid titanyl barium and barium titanate in which a part of Ba site is substituted with another element (Me element), wherein the substitution element is uniformly distributed in the whole of the organic acid titanyl barium powder or the whole of the barium titanate powder without segregation, and a method for industrially advantageously producing the organic acid titanyl barium or the barium titanate powder.
Technical scheme for solving technical problems
In view of the above, the inventors of the present invention have made intensive studies and as a result, have found that an organic titanyl barium powder having little segregation can be obtained by setting the molar ratio of the total of Ba and Me elements of the organic titanyl barium to Ti to 0.980 to 0.999 in a range of slightly less than 1 and setting the molar ratio of Me element to Ba to 0.001 to 0.200, and have completed the present invention.
That is, the present invention (1) provides a barium titanyl powder containing an organic acid substituted with a Me element, characterized in that: which is an organic acid titanyl barium in which a part of Ba is replaced with Me element (Me represents at least 1 selected from Ca, sr and Mg),
the total molar ratio of Ba and Me elements ((Ba+Me)/Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me elements (Me/Ba) to Ba is 0.001 or more and 0.250 or less.
In addition, the present invention (2) provides a barium titanyl organic acid powder substituted with Me element of (1), characterized in that: in an Electron Probe Microanalyzer (EPMA) analysis, the Me element was uniformly distributed in particles of a Me element-substituted barium titanate powder obtained by firing the Me element-substituted barium titanyl oxide powder.
In addition, the present invention (3) provides a barium titanyl organic acid powder substituted with Me element of (1), characterized in that: on the surface of the powder compact of the Me element-substituted barium titanate obtained by firing the above-mentioned Me element-substituted barium titanyl organic acid powder, mapping analysis of 256 points in the longitudinal and transverse directions was performed at intervals of 0.8 μm in the range of a square having a side length of 205 μm by means of Electron Probe Microanalyzer (EPMA) analysis, and in the obtained image analysis, the CV value (standard deviation/average value) of Ca was 0.4 or less.
The present invention also provides (4) a method for producing a barium titanyl powder containing a Me element replaced with an organic acid, characterized by 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 aqueous organic acid solution (solution B) to obtain a Me element substituted organic acid titanyl barium,
in the liquid A, the molar ratio (Me/Ba) of Me element to Ba is 0.020-5.000, the molar ratio (Ba/Ti) of Ba to Ti is 0.300-1.200, and the mixing temperature of liquid A and liquid B is 10-50 ℃.
The present invention also provides (5) a method for producing a barium titanyl organic acid powder by replacing the Me element of (4), characterized by comprising: the barium compound is at least 1 selected from the group consisting of barium chloride, barium carbonate and barium hydroxide.
The present invention also provides (6) a method for producing a barium titanyl organic acid powder by substituting the Me element of (4) or (5), characterized by comprising: 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.
The present invention also provides (7) a method for producing a barium titanyl organic acid powder substituted with the Me element according to any one of (4) to (6), characterized by comprising: the titanium compound is at least 1 selected from titanium tetrachloride and titanium lactate.
The present invention also provides (8) a method for producing a barium titanyl organic acid powder substituted with the Me element according to any one of (4) to (7), characterized by comprising: the organic acid is at least 1 selected from oxalic acid, citric acid, malonic acid and succinic acid.
The present invention also provides (9) a method for producing a titanium perovskite ceramic raw material powder, characterized by comprising: firing the barium titanyl oxide powder of the Me element-substituted organic acid according to any one of (1) to (3), thereby obtaining Me element-substituted barium titanate.
The present invention also provides a method for producing a titanium-based perovskite ceramic raw material powder, characterized by comprising: the method for producing a barium titanyl oxide powder containing a Me element substitution organic acid according to any one of (4) to (8) is performed by firing the barium titanyl oxide powder containing a Me element substitution organic acid, thereby producing a barium titanate powder containing a Me element substitution organic acid.
Effects of the invention
With the present invention, it is possible to provide an organic acid titanyl barium powder and a barium titanate powder substituted with a Me element which is an organic acid titanyl barium powder and barium titanate in which a part of Ba site is substituted with another element (Me element) and the substitution element is uniformly distributed in the whole of the organic acid titanyl barium powder or the whole of the barium titanate powder without segregation, and a method for industrially advantageously producing the organic acid titanyl barium or the barium titanate powder.
Drawings
FIG. 1 shows the result of a 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 result of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 2.
Fig. 4 shows the result of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 3.
Fig. 5 shows the result of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 4.
Fig. 6 shows the result of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in example 5.
Fig. 7 shows the result of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in comparative example 1.
Fig. 8 shows the result of mapping analysis of Ca atoms by EPMA of the barium calcium titanate powder obtained in comparative example 2.
Detailed Description
The Me element replacement organic acid oxygen titanium barium powder is characterized in that: which is an organic acid titanyl barium in which a part of Ba is replaced with Me element (Me represents at least 1 selected from Ca, sr and Mg),
the total molar ratio of Ba and Me elements ((Ba+Me)/Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me elements (Me/Ba) to Ba is 0.001 or more and 0.250 or less.
The powder of the organic acid barium titanyl oxide in which the Me element is substituted is in the form of powder, and is an aggregate of particles of the organic acid barium titanyl oxide in which a part of the Ba site is substituted with the Me element.
In the Me element substituted titanyl barium organic acid powder of the present invention, the Me element substituted for a part of Ba site of titanyl barium organic acid is at least 1 element selected from Ca, sr and Mg, preferably Ca, sr, and particularly preferably Ca. The number of Me may be 1 or 2 or more.
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, preferably oxalic acid, citric acid, and particularly preferably oxalic acid.
The molar ratio ((Ba+Me)/Ti) of the total of Ba and Me elements in the organic acid titanyl barium powder of the present invention is 0.980 or more and less than 0.999. Preferably from 0.983 to 0.998, particularly preferably from 0.985 to 0.997. When (ba+me)/Ti falls within the above range, a Me element-substituted barium titanyl organic acid powder in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small can be obtained, and by firing, a Me element-substituted barium titanate powder in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small can be obtained. On the other hand, when (ba+me)/Ti is smaller than the above range, it is difficult to obtain a substituted barium titanate with Me element having desired characteristics, and when it exceeds the above range, segregation of Me element is likely to occur.
The molar ratio (Me/Ba) of Me element in the organic acid titanyl barium powder of the present invention is 0.001 to 0.250, preferably 0.005 to 0.150. By the Me/Ba being in the above range, it is possible to obtain Me element substituted barium titanyl organic acid in which the Me element is uniformly distributed in the whole powder and the segregation of the Me element is small, and by firing, it is possible to obtain Me element substituted barium titanate in which the Me element is uniformly distributed in the whole particle and the segregation of the Me element is small. On the other hand, when the Me/Ba is smaller than the above range, it is difficult to obtain a substituted barium titanate with a Me element having desired properties, and when it exceeds the above range, segregation of the Me element is likely to occur.
Among the Me-substituted titanyl-barium-organic-acid powder of the present invention, as an example of the organic acid being oxalic acid, there may be mentioned, for example, a Me-substituted titanyl-barium-oxalate powder represented by the following general formula (1).
(Ba 1－p Me p ) q TiO(C 2 O 4 ) 2 ·nH 2 O (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 < 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. The number of Me may be 1 or 2 or more. That is, a part of the Ba site of the barium titanyl oxalate powder is substituted with 1 or 2 or more kinds selected from Ca, sr and Mg by the Me element represented by the general formula (1).
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 in the above range, a Me element-substituted barium titanyl oxalate powder in which Me element is uniformly distributed throughout the powder and the segregation of Me element is small can be obtained, and a Me element-substituted barium titanate powder in which Me element is uniformly distributed throughout the powder and the segregation of Me element is small can be obtained by firing. On the other hand, when q is smaller than the above range, it is difficult to obtain a substituted barium titanate with a Me element having desired properties, and when q exceeds the above range, segregation of the Me element is likely to occur.
In the general formula (1), p corresponds to the molar ratio (Me/Ba) of Me element to 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, it is possible to obtain Me-element-substituted barium titanyl oxalate in which Me element is uniformly distributed throughout the powder and the segregation of Me element is small, and by firing, it is possible to obtain Me-element-substituted barium titanate in which Me element is uniformly distributed throughout the particle and the segregation of Me element is small. On the other hand, when p is smaller than the above range, it is difficult to obtain a substituted barium titanate with a Me element having desired properties, and when p exceeds the above range, segregation of the Me element is likely 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 represented by the general formula (1) to each atom of Ti, ba, and Me in barium titanyl oxalate can be calculated based on the measured value of a fluorescent X-ray analyzer (manufactured by the company corporation, ZSX100 e). The molar ratio of each atom of Ti, ba, and Me in the Me element substituted titanyl barium oxalate shown in the general formula (1) may be calculated based on the obtained value by firing the Me element substituted titanyl barium oxalate, and measuring the obtained Me element substituted barium titanate by a fluorescent X-ray analyzer (ZSX 100e, manufactured by the company corporation).
The average particle diameter of the Me element-substituted organic acid barium titanyl powder of the present invention is not particularly limited, but is preferably 0.1 to 300. Mu.m, particularly preferably 0.5 to 200. Mu.m. In the present invention, the average particle diameter of the barium titanyl organic acid substituted with the Me element means a particle diameter (D50) obtained by adding up 50% by volume in a particle size distribution obtained by a laser diffraction/scattering method.
The barium titanyl powder of the present invention is fired at 600 to 1200 ℃, preferably 650 to 1100 ℃, to obtain a fired product of titanium perovskite composite oxide, and barium titanate in which a part of the Ba site is substituted 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).
(Ba 1－x Me x ) y TiO 3 (2)
In the general formula (2), me is at least 1 selected from Ca, sr, and Mg. x is 0.001-0.200, preferably 0.010-0.150. Y is 0.980.ltoreq.y < 0.999, preferably 0.983.ltoreq.y.ltoreq.0.998, 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: by Electron Probe Microanalyzer (EPMA) analysis, a mapping analysis of 256 points in the longitudinal and transverse directions was performed at 0.8 μm intervals over the surface of a powder compact of barium titanate substituted with Me element in the range of a square having a side length of 205 μm, 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 producing the Me element substituted organic acid titanyl barium powder of the present invention is characterized by comprising the steps of: mixing a barium compound, a Me element compound (Me represents at least 1 selected from Ca, sr, and Mg) and a titanium compound in water to obtain an aqueous solution (solution a), and adding the aqueous solution (solution a) to an aqueous organic acid solution (solution B) to obtain a Me element substituted organic acid titanyl barium, wherein in the solution a, a molar ratio (Me/Ba) of the Me element to Ba is 0.020 or more and 5.000 or less in terms of atom conversion, a molar ratio (Ba/Ti) of Ba to Ti is 0.300 or more and 1.200 or less in terms of atom conversion, and an addition rate of the solution a to the solution B is 2.0 ml/min or more.
The method for producing the Me element substituted organic acid titanyl barium powder of the present invention is a method for producing Me element substituted organic acid titanyl barium as follows: first, the entire amount of the liquid B for the reaction is added to the reaction vessel, then the liquid a is supplied to the reaction vessel, and the liquid a is added to the liquid B to perform the reaction of forming barium titanyl organic acid substituted with Me element.
The solution A of the method for producing an organic acid barium titanyl substituted with Me element 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 according to the method for producing titanyl barium organic acid of the present invention is not particularly limited, and examples thereof include barium chloride, barium carbonate, barium hydroxide, barium acetate, and barium nitrate. The number of barium compounds may be 1, or 2 or more 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 the barium titanyl organic acid 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 number of Me element compounds may be 1, or 2 or more may be used in combination. The Me element compound is preferably 1 or 2 or more kinds 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 used in the method for producing the barium titanyl organic acid of the present invention is not particularly limited, and examples thereof include titanium tetrachloride and titanium lactate. The titanium compound may be used in an amount of 1 or 2 or more. Titanium tetrachloride is preferred as the titanium compound.
Examples of the organic acid involved in the method for producing barium titanyl organic acid with Me element substitution of the present invention include oxalic acid, citric acid, malonic acid, succinic acid, and the like. The number of organic acids may be 1, or 2 or more organic acids may be used in combination. Oxalic acid is preferred as the organic acid.
In the present invention, barium chloride is preferably used as the barium compound, a chloride of Me element is preferably used as the Me element compound, titanium tetrachloride is preferably used as the titanium compound, and oxalic acid is preferably used as the organic acid, in view of high reactivity and stable quality of the product obtained in high yield.
In the liquid A, the molar ratio (Me/Ba) of Me element to Ba in terms of atom is 0.020 to 5.000, preferably 0.050 to 4.000. When the molar ratio (Me/Ba) of the Me element in atomic terms to Ba in the a solution falls within the above range, a Me element-substituted barium titanyl organic acid powder in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small can be obtained, and by firing, a Me element-substituted barium titanate powder in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small can be obtained. On the other hand, when the molar ratio of Ba to Ti (Ba/Ti) in the a liquid in terms of atoms is smaller than the above range, substitution of Me element is difficult, and when it exceeds the above range, segregation of Me element is likely to occur.
In the liquid 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 (Ba/Ti) of Ba in terms of atoms in the liquid a to Ti falls within the above range, it is possible to obtain Me-substituted barium titanyl organic acid in which the Me element is uniformly distributed throughout the particles and the segregation of the Me element is small, and by firing, it is possible to obtain Me-substituted barium titanate in which the Me element is uniformly distributed throughout the particles and the segregation of the Me element is small. On the other hand, when the molar ratio of Ba to Ti (Ba/Ti) in the a liquid in terms of atoms is smaller than the above range, substitution of Me element is difficult, and when it exceeds the above range, segregation of Me element is likely to occur.
The Ba concentration in the solution A is not particularly limited, but is preferably 0.05 to 1.00mol/L, particularly preferably 0.10 to 0.90mol/L, in terms of atomic conversion.
The concentration of Me element in the A solution 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 liquid B of the method for producing barium titanyl organic acid by replacing the Me element of the present invention is an aqueous solution of an organic acid obtained by dissolving an organic acid in water.
The ratio of the total mole number of the Ba, me elements and Ti in terms of atoms in the liquid a to the mole number of the organic acid ions in the liquid 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 element and Ti in terms of atoms in the liquid a to the mole number of organic acid ions in the liquid B falls within the above range, it is possible to obtain a Me element substituted organic acid titanyl barium in which Me element is uniformly distributed throughout the particles and the segregation of Me element is small.
The concentration of the organic acid ion in the liquid B is not particularly limited, but is preferably 0.10 to 5.00mol/L, particularly preferably 0.50 to 3.00mol/L.
In the method for producing a Me-element-substituted organic acid titanyl barium of the present invention, all of the liquid B is first added to the reaction vessel, then the liquid A is supplied to the reaction vessel, and the liquid A is added to the liquid B to thereby carry out the reaction of producing a Me-element-substituted organic acid titanyl barium in the reaction vessel.
When adding the liquid A to the liquid B, the rate of addition of the liquid A is also determined by the scale of implementation, and is preferably 2.0 ml/min or more, particularly preferably 3.0 ml/min or more, for example, in terms of laboratory level on a 0.5L scale. By adding the liquid a to the liquid B at the above-described addition rate, it is possible to obtain a barium titanyl organic acid substituted with the Me element in which the Me element is uniformly distributed throughout the particle and the segregation of the Me element is small. The upper limit is not particularly limited as long as the above-described addition speed is satisfied.
The mixing temperature at the time of adding the liquid A to the liquid B, that is, the temperature of the liquid A and the reaction liquid (or the liquid B) in the reaction vessel at the time of adding the liquid A to the reaction vessel is usually 10 to 50℃and preferably 15 to 45 ℃. By adding the liquid a to the liquid B at the above mixing temperature, it is possible to obtain a barium titanyl organic acid substituted with the Me element in which the Me element is uniformly distributed throughout the particle and the segregation of the Me element is less.
The reaction may be terminated by cooling the reaction solution immediately after the entire amount of the liquid A is added to the liquid B, or by removing the reaction solution by filtration or the like, or the reaction solution may be cured at a predetermined temperature for a predetermined time after the entire amount of the liquid A is added to the liquid B. In the case of curing, the curing temperature is preferably 10℃or higher, particularly preferably 20 to 80℃and the curing time is preferably 0.1 hours or longer, particularly preferably 0.2 hours or longer.
When adding the solution A 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 the case of adding all of the liquid a to the liquid B and then curing, it is preferable to cure the liquid B while stirring the reaction liquid. The stirring speed is not particularly limited, and in the case of aging from the start of the addition of the liquid a to the liquid B to the completion of the addition of the liquid a, the reaction liquid containing the barium titanyl organic acid substituted with the Me element may be produced at such a stirring speed that the reaction liquid is kept in a flowing state until the completion of the aging.
When the liquid a is added to the liquid B in its entirety and then the mixture is aged, the solid-liquid separation of the reaction liquid is performed by a usual method after the completion of the aging, and then the solid portion is washed with water. The washing method is not particularly limited, but washing by repulping or the like is preferable in view of high washing efficiency. After washing, the solid portion is dried and pulverized as necessary to obtain barium titanyl organate in which Me element is substituted, that is, barium titanyl organate in which part of Ba site is substituted with Me element.
In this way, the Me-element-substituted titanyl-organic acid barium powder obtained by the method for producing a Me-element-substituted titanyl-organic acid barium powder of the present invention is an titanyl-organic acid barium in which a part of the Ba site is substituted with a 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 titanyl-barium organic acid obtained by the method for producing a Me-element-substituted titanyl-barium organic acid powder of the present invention, me represents at least 1 element selected from Ca, sr and Mg, preferably Ca, sr, particularly preferably Ca, and 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, preferably 0.983 or more and 0.998 or less, particularly preferably 0.985 or more and 0.997 or less, and the molar ratio (Me/Ba) of Me element to Ba is 0.001 or more and 0.250 or less, preferably 0.005 or more and 0.150 or less.
The average particle diameter of the Me-element-substituted organic acid barium titanyl powder obtained by the method for producing the Me-element-substituted organic acid barium titanyl powder of the present invention is not particularly limited, but is preferably 0.1 to 300. Mu.m, particularly preferably 0.5 to 200. Mu.m.
The method for producing the organic acid titanyl barium powder with Me element substitution according to the present invention can obtain the organic acid titanyl barium powder with Me element substitution in which Me element is uniformly distributed in the whole powder and the segregation of Me element is less. The fact that the Me element is uniformly distributed throughout the whole of the Me element-substituted titanyl-barium organic acid powder and that the segregation of the Me element is small can be confirmed as follows: 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 is fired at 600 to 1200 ℃ to obtain Me element-substituted barium titanate, and mapping analysis is performed on the Me element-substituted barium titanate by EPMA.
In addition, in the Me-element-substituted barium titanate obtained by firing the Me-element-substituted organic acid titanyl-barium powder obtained by the method for producing a Me-element-substituted organic acid titanyl-barium powder of the present invention at 600 to 1200 ℃, preferably 650 to 1100 ℃, the Me element is uniformly distributed on the particle surface. In the Me-substituted titanyl-organic acid barium powder obtained by the method for producing the Me-substituted titanyl-organic acid barium powder of the present invention, the Me element is uniformly distributed in the depth direction of the particles.
The Me-element-substituted barium titanate powder obtained by firing the Me-element-substituted barium titanyl powder of the present invention and the Me-element-substituted barium titanyl powder obtained by the method for producing the Me-element-substituted barium titanyl powder of the present invention is suitable for use as a titanium-based perovskite ceramic raw material powder for dielectric ceramic materials. That is, the titanium perovskite ceramic raw material powder can be obtained by firing 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 the Me element-substituted organic acid titanyl-barium powder of the present invention at 600 to 1200 ℃, preferably 650 to 1100 ℃.
The Me-element-substituted barium titanate powder obtained by firing the Me-element-substituted barium titanyl powder of the present invention and the Me-element-substituted barium titanyl powder obtained by the method for producing the Me-element-substituted barium titanyl powder of the present invention is a Me-element-substituted barium titanate powder represented by the following general formula (2).
(Ba 1－x Me x ) y TiO 3 (2)
In the general formula (2), me is at least 1 selected from Ca, sr, and Mg. x is 0.001-0.200, preferably 0.005-0.150. Y is 0.980.ltoreq.y < 0.999, preferably 0.983.ltoreq.y.ltoreq.0.998, particularly preferably 0.985.ltoreq.y.ltoreq.0.997.
Before the firing, if necessary, the titanyl barium organic acid powder may be subjected to wet grinding treatment by a ball mill, a bead mill or the like in order to obtain a fine titanium perovskite ceramic raw material powder having high crystallinity even when firing in a low temperature range, and in order to obtain an average particle size of the titanyl barium organic acid substituted with a Me element of preferably 4 μm or less, particularly preferably 0.02 to 0.5 μm. In this case, as the solvent used for the wet pulverization treatment, a solvent in which barium titanyl organic acid is replaced with Me element is inactive, and examples thereof include water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, methylene chloride, ethyl acetate, dimethylformamide, diethyl ether, and the like. Among them, from the viewpoint of obtaining a titanium perovskite ceramic raw material powder having high crystallinity, a solvent for wet grinding is preferably an organic solvent such as methanol, ethanol, propanol, butanol, toluene, xylene, acetone, methylene chloride, ethyl acetate, dimethylformamide, diethyl ether, or the like, and a solvent in which the elution of Ba element, ti element, or Me element is small.
The method for producing a titanium perovskite ceramic raw material powder of the present invention is characterized by comprising: the Me element-substituted barium titanyl titanate powder of the present invention or the Me element-substituted barium titanyl titanate powder obtained by the method for producing the Me element-substituted barium titanyl titanate powder of the present invention is fired to obtain Me element-substituted barium titanate.
The Me element replaces organic matters derived from organic acids contained in the organic acid titanyl barium powder, and is not preferable because it deteriorates dielectric properties of the material and is a major factor of unstable behavior in a thermal process for ceramization. In the method for producing a titanium-based perovskite ceramic raw material powder of the present invention, the organic acid-containing titanyl barium is thermally decomposed by firing a Me-element-substituted organic acid-titanyl barium powder to obtain a target titanium-based perovskite ceramic raw material powder, that is, a Me-element-substituted barium titanate, and at the same time, an organic substance derived from an organic acid is removed.
In the method for producing a titanium-based 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 perovskite ceramic powder, and when the firing temperature exceeds the above range, the variation in particle size becomes large. In the method for producing a titanium-based 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-based perovskite ceramic raw material powder of the present invention, the firing atmosphere at the time of firing is not particularly limited, and may be either an atmospheric atmosphere or an inert gas atmosphere.
In the method for producing a titanium-based perovskite ceramic raw material powder of the present invention, firing may be performed only 1 time, or may be repeated 2 or more times as necessary. In the case of repeating firing, in order to make the powder characteristics uniform, the next firing may be performed after pulverizing the powder after 1 firing.
In the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, after firing, the powder is cooled appropriately and pulverized as necessary, whereby a barium titanate powder is obtained which is a titanium-based perovskite-type composite oxide and in which an appropriate Me element is substituted as the titanium-based perovskite-type ceramic raw material powder. The pulverization, if necessary, is suitably performed when the Me-substituted barium titanate powder obtained by firing is in the form of a weakly bonded lump or the like, and the particles of the Me-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-based perovskite ceramic raw material powder of the present invention has an average particle diameter of 0.01 to 4. Mu.m, preferably 0.02 to 0.5. Mu.m, and a BET specific surface area of 0.25 to 100m as measured by a Scanning Electron Microscope (SEM) 2 Preferably 2 to 50m 2 And/g, the composition deviation is small. In the present invention, the average particle diameter of the Me element-substituted barium titanate powder was arbitrarily measured by Scanning Electron Microscope (SEM) photographs, and the average value of 200 particles was used as the average particle diameter.
In the titanium-based perovskite ceramic raw material powder obtained by carrying out the method for producing a titanium-based perovskite ceramic raw material powder of the present invention, a subcomponent-element-containing compound may be added to the titanium-based perovskite ceramic raw material powder for the purpose of adjusting dielectric characteristics and temperature characteristics, if necessary. Examples of the subcomponent-containing element compound that can be used include compounds containing at least 1 element selected from the group consisting of a rare earth element Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, li, bi, zn, mn, al, si, co, ni, cr, fe, ti, V, nb, mo, W and Sn.
The subcomponent-containing element compound may be any of an inorganic substance and an organic substance, and examples thereof include oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates, alkoxides, and the like containing the above elements. In the case where the subcomponent element-containing compound is a compound containing an Si element, silica sol, sodium silicate, or the like can be used in addition to the above-described oxide or the like. The above-mentioned subcomponent-containing element compounds may be used in 1 kind, or in 2 kinds or more in combination, and the addition amount and the combination of the added compounds are appropriately selected according to the purpose.
Examples of the method for adding subcomponent elements to the titanium perovskite ceramic raw material powder include: a method in which the titanium-based perovskite ceramic raw material powder obtained by the method for producing a titanium-based perovskite ceramic raw material powder of the present invention and a subcomponent element-containing compound are uniformly mixed and then fired; alternatively, the method of firing the organic acid titanyl barium powder of the present invention obtained by uniformly mixing the organic acid titanyl barium powder of the present invention or the organic acid titanyl barium powder production method of the present invention with a subcomponent element-containing compound.
The titanium-based perovskite ceramic raw material powder obtained by the method for producing a titanium-based perovskite ceramic raw material powder of the present invention is mixed and dispersed in a suitable solvent together with a compounding agent containing, for example, subcomponent elements, a conventionally known additive, an organic binder, a plasticizer, a dispersant, and the like, and slurried, and then subjected to sheet molding, whereby a ceramic sheet for producing a multilayer ceramic capacitor can be obtained.
In producing a multilayer ceramic capacitor from ceramic sheets, first, an internal electrode forming conductive paste is printed on one surface of the ceramic sheets, and after drying, a plurality of ceramic sheets are stacked and pressure-bonded in the thickness direction, thereby forming a laminate. Subsequently, the laminate is subjected to a heat treatment, a 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, and then baked, thereby obtaining a multilayer ceramic capacitor.
The titanium-based perovskite ceramic raw material powder obtained by the method for producing a titanium-based perovskite ceramic raw material powder of the present invention is blended with a resin such as an epoxy resin, a polyester resin, or a polyimide resin, and is suitably used as a material for a printed wiring board, a multilayer printed wiring board, or the like, and is also useful 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 an inorganic EL, or the like, for example, when the titanium-based perovskite ceramic raw material powder is produced into a resin sheet, a resin film, an adhesive, or the like.
The titanium-based perovskite ceramic raw material powder obtained by the method for producing titanium-based perovskite ceramic raw material powder of the present invention is also suitable for use as a catalyst for reactions such as exhaust gas removal and chemical synthesis, and a surface-modifying material for a printing toner that imparts antistatic and cleaning effects.
The present invention will be described in detail 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 measured value of the fluorescent X-ray analyzer (ZSX 100e, manufactured by co.
(2) Me element substituted titanyl barium oxalate powder average particle diameter
The particle size distribution was measured by a laser diffraction/scattering method using MT3000 manufactured by microtricEL corporation, and the particle size (D50) of 50% of the volume of the particle size distribution was used as the average particle size.
(3) Average particle diameter of Me element substituted barium titanate
200 particles were arbitrarily measured using a Scanning Electron Microscope (SEM) photograph, S4800 manufactured by Hitachi High Technologies, and the average value was used as the average particle diameter.
(4) Ca atom mapping analysis using EPMA
Ca atoms were mapped and analyzed by an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by Japanese electric Co., ltd.).
(5) X-ray diffraction analysis of Me element substituted titanyl-barium oxalate powder
The X-ray diffraction analysis was performed using UltimaIV manufactured by the company of Kyowa Co.
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. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30℃to prepare an aqueous oxalic acid solution as solution B.
Then, while maintaining the solution B (reaction solution after the start of the dropwise addition) at 30℃for 120 minutes under stirring, the solution A was added at a rate of 4.2 ml/min, and further cured under stirring at 30℃for 60 minutes. And (3) after cooling, filtering and recovering the barium calcium titanyl oxalate powder.
The recovered barium titanyl oxalate powder was then repulped in distilled water to perform washing. Then, the mixture was dried at 80℃to obtain barium calcium titanyl oxalate powder. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired at 800℃and Ca atoms were mapped and analyzed by an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by Japanese electric Co., ltd.) to obtain barium calcium titanate powder. The results are shown in FIG. 1. As is clear from the results of fig. 1, the calcium titanate powder obtained was free from segregation of Ca atoms and Ca was uniformly dispersed. The elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.020 and (Ba+Ca)/Ti was 0.994.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding solution a to solution B, it was confirmed that the barium calcium titanyl oxalate obtained in this example 1 was (Ba 0.080 Ca 0.020 ) 0.994 TiO(C 2 O 4 ) 2 ·4H 2 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 was used as solution A. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30℃to prepare an aqueous oxalic acid solution as solution B.
Then, while maintaining the solution B (reaction solution after the start of the dropwise addition) at 30℃for 120 minutes under stirring, the solution A was added at a rate of 4.2 ml/min, and further cured under stirring at 30℃for 60 minutes.
The subsequent operations were performed in the same manner as in example 1. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired, and the obtained barium calcium titanate powder was subjected to mapping analysis of Ca atoms using EPMA. The results are shown in FIG. 3. As is clear from the results of fig. 3, the segregation of Ca atoms was not seen in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. The elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.05 and (Ba+Ca)/Ti was 0.998.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding solution a to solution B, it was confirmed that the barium calcium titanyl oxalate obtained in example 2 was (Ba 0.08 Ca 0.05 ) 0.998 TiO(C 2 O 4 ) 2 ·4H 2 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 was used as solution A. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30℃to prepare an aqueous oxalic acid solution as solution B.
Then, while maintaining the solution B (reaction solution after the start of the dropwise addition) at 30℃for 120 minutes under stirring, the solution A was added at a rate of 4.2 ml/min, and further cured under stirring at 30℃for 60 minutes.
The subsequent operations were performed in the same manner as in example 1. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired, and the obtained barium calcium titanate powder was subjected to mapping analysis of Ca atoms using EPMA. The results are shown in FIG. 4. As is clear from the results of fig. 4, the segregation of Ca atoms was not seen in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. The elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.02 and (Ba+Ca)/Ti was 0.991.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding solution a to solution B, it was confirmed that the barium calcium titanyl oxalate obtained in this example 3 was (Ba 0.08 Ca 0.02 ) 0.991 TiO(C 2 O 4 ) 2 ·4H 2 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 was used as solution A. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 70.0g of oxalic acid was dissolved in 420ml of warm water at 30℃to prepare an aqueous oxalic acid solution as solution B.
Then, while maintaining the solution B (reaction solution after the start of the dropwise addition) at 30℃for 120 minutes under stirring, the solution A was added at a rate of 3.5 ml/min, and further cured under stirring at 30℃for 60 minutes. And (3) after cooling, filtering and recovering the barium calcium titanyl oxalate powder.
Then, the recovered barium titanyl oxalate powder was repulped with distilled water and washed. Then, the mixture was dried at 80℃to obtain barium calcium titanyl oxalate powder. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired at 800℃and Ca atoms were mapped and analyzed by an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by Japanese electric Co., ltd.) to obtain barium calcium titanate powder. The results are shown in FIG. 5. As is clear from the results of fig. 5, the segregation of Ca atoms was not seen in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. Further, elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.026 and (Ba+Ca)/Ti was 0.998.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding solution a to solution B, it was confirmed that the barium calcium titanyl oxalate obtained in this example 4 was (Ba 0.08 Ca 0.03 ) 0.998 TiO(C 2 O 4 ) 2 ·4H 2 O. The results of the X-ray diffraction analysis are shown in fig. 2.
Example 5
360.0g of barium chloride dihydrate, 72.0g of calcium chloride dihydrate and 864.0g of titanium tetrachloride were dissolved in 3600ml of pure water to prepare a mixed aqueous solution, which was used as solution A. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 504.0g of oxalic acid was dissolved in 3600ml of warm water at 30℃to prepare an aqueous oxalic acid solution, which was used as solution B.
Then, while maintaining the solution B (reaction solution after the start of the dropwise addition) at 30℃for 120 minutes under stirring, the solution A was added at a rate of 30 ml/min, and then cured under stirring at 30℃for 60 minutes. And (3) after cooling, filtering and recovering the barium calcium titanyl oxalate powder.
Then, the recovered barium titanyl oxalate powder was repulped with distilled water and washed. Then, the mixture was dried at 80℃to obtain barium calcium titanyl oxalate powder. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired at 800℃and Ca atoms were mapped and analyzed by an Electron Probe Microanalyzer (EPMA) (JXA 8500F, manufactured by Japanese electric Co., ltd.) to obtain barium calcium titanate powder. The results are shown in FIG. 6. As is clear from the results of fig. 6, the segregation of Ca atoms was not seen in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. The elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.025 and (Ba+Ca)/Ti was 0.994.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding solution a to solution B, it was confirmed that the barium calcium titanyl oxalate obtained in this example 5 was (Ba 0.08 Ca 0.02 ) 0.994 TiO(C 2 O 4 ) 2 ·4H 2 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 was used as solution A. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 70.0g of oxalic acid was dissolved in 500ml of warm water at 30℃to prepare an aqueous oxalic acid solution as solution B.
Then, while maintaining the temperature of the solution B at 30℃for 120 minutes under stirring, the solution A was added at a rate of 4.2 ml/min, and the mixture was cured under stirring at 30℃for 60 minutes. And (3) after cooling, filtering and recovering the barium calcium titanyl oxalate powder.
The subsequent operations were performed in the same manner as in example 1. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired, and the obtained barium calcium titanate powder was subjected to mapping analysis of Ca atoms using EPMA. The results are shown in FIG. 7. As is clear from the results of fig. 7, ca atoms segregate in the obtained barium calcium titanate powder. The elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.020 and (Ba+Ca)/Ti was 1.000.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium oxalate obtained by adding solution a to solution B, the oxalic acid obtained in comparative example 1 was confirmedThe oxygen titanium barium calcium is (Ba) 0.080 Ca 0.020 ) 1.000 TiO(C 2 O 4 ) 2 ·4H 2 O。
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 was used as solution A. The molar ratios of the respective elements in the liquid a are shown in table 1.
Subsequently, 32.5g of oxalic acid was dissolved in 140ml of warm water at 55℃to prepare an aqueous oxalic acid solution as solution B.
Then, while maintaining the temperature of the solution B at 55℃for 120 minutes under stirring, the solution A was added at a rate of 1.5 ml/min, and the mixture was cured under stirring at 55℃for 60 minutes. And (3) after cooling, filtering and recovering the barium calcium titanyl oxalate powder.
The subsequent operations were performed in the same manner as in example 1. Physical properties of the obtained barium titanyl oxalate powder are shown in Table 1. The obtained barium calcium titanyl oxalate powder was fired, and the obtained barium calcium titanate powder was subjected to mapping analysis of Ca atoms using EPMA. The results are shown in fig. 8. As is clear from the results of fig. 8, ca atoms segregate in the obtained barium calcium titanate powder. The elemental analysis was performed on the obtained barium calcium titanate powder, and as a result, ca/Ba was 0.020 and (Ba+Ca)/Ti was 0.999.
From the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding solution a to solution B, it was confirmed that the barium calcium titanyl oxalate obtained in comparative example 2 was (Ba 0.080 Ca 0.020 ) 0.999 TiO(C 2 O 4 ) 2 ·4H 2 O。
TABLE 1
From the results of table 1 and fig. 1 to 8, it can be seen that: the barium calcium titanate obtained from the barium titanyl calcium oxalate of the example was uniformly distributed without segregation of calcium atoms, compared with the barium calcium titanate obtained from the barium titanyl calcium oxalate of the comparative example.
Claims (8)
1. The Me element substituted organic acid oxygen titanium barium powder is characterized in that:
which is a barium titanyl organic acid substituted with a Me element in which a part of the Ba site is substituted with a Me element, wherein Me represents at least 1 selected from Ca, sr and Mg,
the total molar ratio of Ba and Me elements ((Ba+Me)/Ti) is 0.980 or more and less than 0.999, the molar ratio of Me elements (Me/Ba) to Ba is 0.001 or more and 0.250 or less,
in an Electron Probe Microanalyzer (EPMA) analysis, the Me element is uniformly distributed in particles of Me element substituted barium titanate powder obtained by firing the Me element substituted organic acid barium titanyl powder,
performing mapping analysis of 256 points in the longitudinal and transverse directions at intervals of 0.8 μm on the surface of a pressed powder of Me element-substituted barium titanate obtained by firing the Me element-substituted barium titanyl organic acid powder by an Electron Probe Microanalyzer (EPMA) analysis, wherein the CV value (standard deviation/average value) of Ca is 0.4 or less in the obtained image analysis,
The Me element substituted organic acid oxygen titanium barium powder is obtained by the following manufacturing method:
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 solution of an organic acid (solution B) to obtain a Me element-substituted organic acid titanyl barium, wherein Me represents at least 1 selected from Ca, sr and Mg,
in the liquid A, the molar ratio (Me/Ba) of Me element to Ba is 0.020-5.000, the molar ratio (Ba/Ti) of Ba to Ti is 0.300-1.200, and the mixing temperature of liquid A and liquid B is 10-50 ℃.
2. A method for producing the Me-element-substituted organic acid titanyl-barium powder according to claim 1, characterized by 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 aqueous organic acid solution (solution B) to obtain a Me element substituted organic acid titanyl barium, wherein Me represents at least 1 selected from Ca, sr and Mg,
in the liquid A, the molar ratio (Me/Ba) of Me element to Ba is 0.020-5.000, the molar ratio (Ba/Ti) of Ba to Ti is 0.300-1.200, and the mixing temperature of liquid A and liquid B is 10-50 ℃.
3. The method for producing the barium titanyl organic acid powder substituted with the Me element according to claim 2, wherein:
the barium compound is at least 1 selected from the group consisting of barium chloride, barium carbonate, and barium hydroxide.
4. A method for producing the barium titanyl organic acid powder substituted with Me element according to claim 2 or 3, 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.
5. The method for producing the barium titanyl organic acid powder containing the Me element substitution according to any one of claims 2 to 4, wherein:
the titanium compound is at least 1 selected from titanium tetrachloride and titanium lactate.
6. The method for producing the barium titanyl organic acid powder containing the Me element substitution according to any one of claims 2 to 5, wherein:
the organic acid is at least 1 selected from oxalic acid, citric acid, malonic acid and succinic acid.
7. A method for producing a titanium perovskite ceramic raw material powder, characterized by comprising:
firing the Me-element-substituted barium titanyl organic acid powder of claim 1 at 600 to 1200 ℃ to obtain Me-element-substituted barium titanate.
8. A method for producing a titanium perovskite ceramic raw material powder, characterized by comprising:
The method for producing a Me-element-substituted barium titanyl powder according to any one of claims 2 to 6, wherein the Me-element-substituted barium titanyl powder is obtained by firing the Me-element-substituted barium titanyl powder at 600 to 1200 ℃.
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| JP2019130950 | 2019-07-16 | ||
| JP2019-130950 | 2019-07-16 | ||
| JP2020115142A JP7438867B2 (en) | 2019-07-16 | 2020-07-02 | Me element-substituted organic acid barium titanyl, method for producing the same, and method for producing titanium-based perovskite ceramic raw material powder |
| JP2020-115142 | 2020-07-02 | ||
| PCT/JP2020/027199 WO2021010368A1 (en) | 2019-07-16 | 2020-07-13 | Me ELEMENT-SUBSTITUTED ORGANIC ACID TITANYL BARIUM, METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING TITANIUM-BASED PEROVSKITE-TYPE CERAMIC RAW MATERIAL POWDER |
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- 2020-07-13 WO PCT/JP2020/027199 patent/WO2021010368A1/en active Application Filing
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| WO2021010368A1 (en) | 2021-01-21 |
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