CN116507588A - Method for producing barium titanyl oxalate and method for producing barium titanate - Google Patents
Method for producing barium titanyl oxalate and method for producing barium titanate Download PDFInfo
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Abstract
A process for producing barium titanyl oxalate, characterized in that a solution (A) containing oxalic acid and a solution (B) containing a titanium source and a barium source are mixed and reacted to produce barium titanyl oxalate, wherein the A solution and the B solution are supplied to one end side of a reaction solution flow path, the A solution and the B solution are mixed in the reaction flow path, the reaction solution is discharged from the other end side of the reaction solution flow path, and then solid-liquid separation of the reaction solution is performed; the residence time of the reaction liquid in the reaction liquid flow path is within 30 seconds; or the liquid A and the liquid B are respectively supplied to one end side of the reaction liquid flow path, the liquid A and the liquid B are mixed at one end side of the reaction liquid flow path, the reaction liquid is moved to the other end side of the reaction liquid flow path while swirling the reaction liquid, the reaction liquid is discharged from the other end side of the reaction liquid flow path, and then the solid-liquid separation of the reaction liquid is performed.
Description
Technical Field
The present invention relates to a method for producing barium titanyl oxalate useful as a raw material for functional ceramics such as dielectrics, piezoelectrics, optoelectronic materials, semiconductors, sensors, and the like.
Background
Currently, barium titanate is generally produced by a solid phase method, a hydrothermal synthesis method, an alkoxide method, an oxalate method, or the like.
In the solid phase method, since the solid phase method is produced by a dry method in which constituent raw material powders and the like are mixed and the mixture is heated at a high temperature, the obtained powder forms aggregates exhibiting irregular shapes, and further, high-temperature firing is required to achieve desired characteristics. Although the hydrothermal synthesis method has the advantage of good powder properties, it is industrially disadvantageous because it is complicated in synthesis steps and uses an autoclave, and therefore, it is inferior in productivity, and the cost for producing the powder is high. In addition, the alkoxide method is difficult to handle the starting material, is expensive, and is industrially disadvantageous.
Barium titanate obtained by the oxalate method can be produced at a low cost as compared with the hydrothermal synthesis method and the alkoxide method, and has a characteristic of having a uniform composition as compared with barium titanate produced by the solid phase method. As a conventional oxalate method, there is a method in which a titanium source such as titanium tetrachloride, a barium source such as barium chloride, and oxalic acid are reacted in a solvent such as water to obtain barium titanyl oxalate, and then the barium titanyl oxalate is fired (for example, see patent documents 1 to 3).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2005-500239
Patent document 2: japanese patent application laid-open No. 2010-202610
Patent document 3: japanese patent laid-open publication No. 2013-63867
Disclosure of Invention
Technical problem to be solved by the invention
However, since barium titanyl oxalate obtained in the above patent document produces barium titanate at a firing temperature of 700 ℃ or higher, the crystallinity is low at the time of production of barium titanate, but some degree of grain growth occurs. When such barium titanyl oxalate is fired at a high temperature, the barium titanyl oxalate is large in size even if it is highly crystallized, and thus the barium titanyl oxalate cannot satisfy the characteristics as a functional ceramic raw material.
Accordingly, an object of the present invention is to provide a method for producing barium titanyl oxalate, which can produce barium titanate having a small particle size and high crystallinity.
Technical scheme for solving technical problems
The inventors of the present invention have made intensive studies in view of the above-described circumstances, and as a result, have found that by supplying a solution containing oxalic acid (solution a) and a solution containing a titanium compound and a barium compound (solution B) to one end side of a reaction solution flow path formed in an in-line mixer, a microreactor or the like, respectively, mixing the solution a and the solution B in the reaction flow path, and discharging the reaction solution from the other end side of the reaction solution flow path, the mixing time of the solution a and the solution B can be shortened, whereby fine barium titanyl oxalate can be obtained; when such fine barium titanyl oxalate is fired, carbon dioxide which is thermally decomposed easily escapes, and the temperature at which barium titanate is produced can be reduced; further, by producing barium titanate at a low temperature, barium titanate can be highly crystallized at a low temperature as compared with the prior art, and thus the grain growth of barium titanate can be suppressed, and thus, barium titanate having fine particles and high crystallinity can be obtained as compared with the prior art, and the present invention has been completed.
Further, the inventors of the present invention have made intensive studies in view of the above-described circumstances, and as a result, have found that by supplying a solution containing oxalic acid (solution a) and a solution containing a titanium compound and a barium compound (solution B) to one end side of a reaction solution channel, respectively, mixing the solution a and the solution B while generating a vortex in the reaction channel, and discharging the reaction solution from the other end side of the reaction solution channel, the reaction raw materials in the solution a and the solution B can be brought into rapid contact, whereby fine barium titanyl oxalate can be obtained; when such fine barium titanyl oxalate is fired, carbon dioxide which is thermally decomposed easily escapes, and the temperature at which barium titanate is produced can be reduced; further, by producing barium titanate at a low temperature, barium titanate can be highly crystallized at a low temperature as compared with the prior art, and thus the grain growth of barium titanate can be suppressed, and thus, barium titanate having fine particles and high crystallinity can be obtained as compared with the prior art, and the present invention has been completed.
Namely, the present invention (1) provides a method for producing barium titanyl oxalate, characterized by comprising; in a method for producing barium titanyl oxalate by mixing and reacting a solution (A solution) containing oxalic acid and a solution (B solution) containing a titanium source and a barium source, the A solution and the B solution are supplied to one end side of a reaction solution flow path, respectively, the A solution and the B solution are mixed in the reaction flow path, the reaction solution is discharged from the other end side of the reaction solution flow path, and then solid-liquid separation of the reaction solution is performed, wherein the residence time of the reaction solution in the reaction solution flow path is 30 seconds or less.
The present invention also provides (2) the method for producing barium titanyl oxalate according to (1), characterized by comprising:
the reaction liquid flow path is formed in the static mixer by supplying the liquid A and the liquid B to one end side of the static mixer, respectively.
The present invention also provides (3) the method for producing barium titanyl oxalate according to (1), characterized by comprising: the liquid A and the liquid B are supplied to one end of a reaction liquid flow path of a continuous flow type microreactor, respectively, whereby the reaction liquid flow path is formed in the microreactor.
The present invention also provides (4) a method for producing barium titanyl oxalate, comprising: in a method for producing barium titanyl oxalate by mixing and reacting a solution (A solution) containing oxalic acid and a solution (B solution) containing a titanium source and a barium source, the A solution and the B solution are supplied to one end side of a reaction solution flow path, respectively, the A solution and the B solution are mixed at one end side of the reaction solution flow path, the reaction solution is moved to the other end side of the reaction solution flow path while swirling the reaction solution, the reaction solution is discharged from the other end side of the reaction solution flow path, and then solid-liquid separation of the reaction solution is performed.
The present invention also provides (5) a method for producing barium titanyl oxalate according to (4), characterized by comprising: the residence time of the reaction solution in the reaction solution flow path is 60 seconds or less.
The present invention also provides (6) a method for producing barium titanyl oxalate according to (4), characterized by comprising: the vortex is a taylor vortex.
The present invention also provides (7) the method for producing barium titanyl oxalate according to (1) or (4), characterized by comprising: the solvent of the solution A is an organic solvent.
The present invention also provides (8) the method for producing barium titanyl oxalate according to (1) or (4), characterized by comprising: the solvent of the solution A is 1 or more than 2 selected from methanol, ethanol, propanol, butanol, diethyl ether, 1, 3-butanediol, ethylene glycol, propylene glycol, dipropylene glycol, glycerol, N-dimethylformamide and acetone.
The present invention also provides (9) the method for producing barium titanyl oxalate according to (1) or (4), characterized by comprising: the solvent of the solution B is water.
The present invention also provides (10) the method for producing barium titanyl oxalate according to (1) or (4), characterized by comprising: the titanium compound in the solution B is titanium tetrachloride, and the barium compound is barium chloride.
The present invention also provides (11) the method for producing barium titanyl oxalate according to (1) or (4), characterized by comprising: the mixing temperature of the solution A and the solution B is below 75 ℃.
The present invention also provides (12) the method for producing barium titanyl oxalate according to (1) or (4), characterized by comprising: the average particle diameter of the barium titanyl oxalate is 1.0 μm or less.
The present invention also provides a method for producing barium titanate, characterized by comprising: firing the barium titanyl oxalate obtained by the production method according to any one of (1) to (6).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a method for producing barium titanyl oxalate, which can obtain barium titanate having a small particle size and high crystallinity as compared with conventional barium titanyl oxalate when firing at the same temperature.
Drawings
FIG. 1 shows the results of thermogravimetric analysis of barium titanyl oxalate obtained in example 1 and comparative example 1.
FIG. 2 is an SEM photograph of barium titanyl oxalate obtained in example 1.
Fig. 3 is an SEM photograph of the barium titanate obtained in example 1.
FIG. 4 is an SEM photograph of barium titanyl oxalate obtained in comparative example 1.
FIG. 5 is an SEM photograph of the fired product obtained in comparative example 1.
FIG. 6 shows the results of thermogravimetric analysis of barium titanyl oxalate obtained in example 6 and comparative example 5.
FIG. 7 is an SEM photograph of barium titanyl oxalate obtained in example 6.
Fig. 8 is an SEM photograph of the barium titanate obtained in example 6.
FIG. 9 is an SEM photograph of barium titanyl oxalate obtained in comparative example 5.
FIG. 10 is an SEM photograph of the fired product obtained in comparative example 5.
Detailed Description
The first invention of the present invention will be described.
< first invention >)
The method for producing barium titanyl oxalate of the present invention is a method for producing barium titanyl oxalate, characterized by comprising:
the solution (solution A) containing oxalic acid and the solution (solution B) containing a titanium source and a barium source are mixed and reacted to produce barium titanyl oxalate,
in the method for producing barium titanyl oxalate, the A liquid and the B liquid are supplied to one end side of a reaction liquid flow path, the A liquid and the B liquid are mixed in the reaction flow path, the reaction liquid is discharged from the other end side of the reaction liquid flow path, then solid-liquid separation of the reaction liquid is performed,
the residence time of the reaction solution in the reaction solution flow path is within 30 seconds.
The solution A of the method for producing barium titanyl oxalate according to the present invention is a solution containing oxalic acid. The concentration of oxalic acid ions in the solution A is not particularly limited, but is preferably 0.1 to 7.0mol/L, particularly preferably 0.6 to 5.0mol/L.
The solvent of the liquid a may be an aqueous solvent, an organic solvent or a mixed solvent thereof, and is preferably an organic solvent from the viewpoint of obtaining fine particles of barium titanyl oxalate. The organic solvent is not particularly limited as long as it is hydrophilic and inactive to the raw material, and 1 or 2 or more selected from methanol, ethanol, propanol, butanol, diethyl ether, 1, 3-butanediol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, N-dimethylformamide and acetone may be used. In the case of a mixed solvent of water and an organic solvent or a mixed solvent of a plurality of organic solvents, the mixing ratio thereof can be appropriately selected.
The solution B of the method for producing barium titanyl oxalate of the present invention is a solution containing a titanium compound and a barium compound. The concentration of the titanium ion in the solution B is not particularly limited, but is preferably 0.04 to 4.0mol/L, and particularly preferably 0.2 to 3.0mol/L. The concentration of barium ions in the solution B is not particularly limited, but is preferably 0.08 to 6.5mol/L, and particularly preferably 0.4 to 3.0mol/L.
The titanium compound according to the method for producing barium titanyl oxalate 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 combination of 1 kind or 2 or more kinds. Titanium tetrachloride is preferred as the titanium source.
The barium compound according to the method for producing titanyl barium oxalate of the present invention is not particularly limited, and examples thereof include barium chloride, barium carbonate, barium hydroxide, barium acetate, barium nitrate, and the like. The barium compound may be used in combination of 1 or 2 or more. The barium compound is preferably 1 or 2 or more selected from barium chloride, barium acetate, barium nitrate and barium hydroxide, and particularly preferably barium chloride.
In the method for producing barium titanyl oxalate of the present invention, the solution a and the solution B are supplied to one end side of the reaction solution flow path, respectively, and the solution a and the solution B are mixed in the reaction solution flow path, whereby the reaction for producing barium titanyl oxalate proceeds in the reaction solution flow path.
As a method of mixing the liquid a and the liquid B in the reaction channel by supplying the liquid a and the liquid B to one end side of the reaction channel, for example, a method of supplying the liquid a and the liquid B to one end side of an in-line mixer such as a static mixer, a screw mixer, and a dynamic mixer, and mixing the liquid a and the liquid B in the in-line mixer may be mentioned. In the case of using an in-line mixer, a reaction liquid flow path is formed in the in-line mixer. As the in-line mixer, a static mixer is preferably used in order to easily obtain fine barium titanyl oxalate. The static mixer is not particularly limited, and examples thereof include MC08-32 manufactured by Tomita Engineering Co., ltd.
As a method of mixing the liquid a and the liquid B in the reaction channel by supplying the liquid a and the liquid B to one end side of the reaction channel, for example, a method of mixing the liquid a and the liquid B in the channel of a continuous flow type microreactor by supplying the liquid a and the liquid B to one end side of the microreactor may be mentioned. Wherein the microreactor means, for example, a reactor having: a flow path composed of a pipe having a flow path of 0.1 to 10mm and a length of 1 to 2000 mm; and a reaction device for simultaneously supplying the liquid A and the liquid B to one end side of the flow path. In the case of using a continuous flow type microreactor, a reaction liquid flow path is formed in the flow path of the continuous 0 flow type microreactor.
In the method for producing barium titanyl oxalate of the present invention, the solution a and the solution B are supplied to the reaction liquid flow path, and in the reaction liquid flow path, the solution a and the solution B are mixed, and the reaction raw materials in the solution a and the solution B react to produce the particulate barium titanyl oxalate. In the method for producing barium titanyl oxalate according to the present invention, the solution a and the solution B are supplied from one end side of the reaction channel, and the reaction liquid thus produced is discharged from the other end side of the reaction channel.
In the method for producing barium titanyl oxalate of the present invention, the residence time of the reaction solution in the reaction solution flow path is 30 seconds or less, preferably 10 seconds or less, and particularly preferably 0.1 to 5 seconds. The residence time of the reaction solution in the reaction solution passage is in the above range, whereby fine particles of barium titanyl oxalate can be obtained. The residence time of the reaction solution in the reaction solution channel is the time when the mixture of the solution A and the solution B supplied to one end of the reaction solution channel reaches the other end of the reaction solution channel.
The mixing temperature of the solution A and the solution B, that is, the temperature of the reaction solution in the reaction solution channel is preferably 75℃or lower, and particularly preferably 5 to 50 ℃.
The mixing ratio of the solution a and the solution B is such that the ratio of the number of moles of titanium and barium in the solution B in terms of atoms to the number of moles of oxalic acid in the solution a is preferably 0.01 to 20.0, particularly preferably 0.10 to 10.0.
Next, in the method for producing barium titanyl oxalate according to the present invention, solid-liquid separation of the reaction liquid discharged from the reaction liquid flow path is performed.
After the solid-liquid separation, the solid component is washed with water. The water washing method is not particularly limited, and a method of washing by repulping or the like is preferable in terms of high washing efficiency. After washing, the solid component is dried and pulverized as necessary to obtain barium titanyl oxalate.
Next, a second invention of the present invention will be described.
< second invention >)
The method for producing barium titanyl oxalate of the present invention is a method for producing barium titanyl oxalate, characterized by comprising: mixing the solution (solution A) containing oxalic acid with the solution (solution B) containing a titanium source and a barium source, reacting them, thereby producing barium titanyl oxalate,
in the method for producing barium titanyl oxalate, the liquid A and the liquid B are supplied to one end of a reaction liquid flow path, the liquid A and the liquid B are mixed at one end of the reaction liquid flow path, the reaction liquid is moved to the other end of the reaction liquid flow path while swirling the reaction liquid, the reaction liquid is discharged from the other end of the reaction liquid flow path, and then solid-liquid separation of the reaction liquid is performed.
The solution A of the method for producing barium titanyl oxalate according to the present invention is a solution containing oxalic acid. The concentration of oxalic acid ions in the solution A is not particularly limited, but is preferably 0.1 to 7.0mol/L, particularly preferably 0.6 to 5.0mol/L.
The solvent of the liquid a may be an aqueous solvent, an organic solvent or a mixed solvent thereof, and is preferably an organic solvent from the viewpoint of obtaining fine particles of barium titanyl oxalate. The organic solvent is not particularly limited as long as it is hydrophilic and inactive to the raw material, and 1 or 2 or more selected from methanol, ethanol, propanol, butanol, diethyl ether, 1, 3-butanediol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, N-dimethylformamide and acetone may be used. In the case of a mixed solvent of water and an organic solvent or a mixed solvent of a plurality of organic solvents, the mixing ratio thereof can be appropriately selected.
The solution B of the method for producing barium titanyl oxalate of the present invention is a solution containing a titanium compound and a barium compound. The concentration of the titanium ion in the solution B is not particularly limited, but is preferably 0.04 to 4.0mol/L, and particularly preferably 0.2 to 3.0mol/L. The concentration of barium ions in the solution B is not particularly limited, but is preferably 0.08 to 6.5mol/L, and particularly preferably 0.4 to 3.0mol/L.
The titanium compound according to the method for producing barium titanyl oxalate 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 combination of 1 kind or 2 or more kinds. Titanium tetrachloride is preferred as the titanium source.
The barium compound according to the method for producing titanyl barium oxalate of the present invention is not particularly limited, and examples thereof include barium chloride, barium carbonate, barium hydroxide, barium acetate, barium nitrate, and the like. The barium compound may be used in combination of 1 or 2 or more. The barium compound is preferably 1 or 2 or more selected from barium chloride, barium acetate, barium nitrate and barium hydroxide, and particularly preferably barium chloride.
In the method for producing barium titanyl oxalate according to the present invention, a solution a and a solution B are supplied to one end of a reaction solution channel, respectively, and then, a reaction solution (a mixed solution of the solution a and the solution B) obtained by mixing the solution a and the solution B is caused to swirl at one end of the reaction solution channel, and the reaction solution is moved to the other end of the reaction solution channel, whereby a reaction for producing barium titanyl oxalate is performed in the reaction solution channel, and then, the reaction solution is discharged from the other end of the reaction solution channel.
In the method for producing barium titanyl oxalate according to the present invention, the reaction raw material in the liquid a and the liquid B is reacted while the mixed liquid of the liquid a and the liquid B in the reaction liquid flow path is caused to swirl, whereby the reaction raw material in the liquid a and the liquid B can be brought into rapid contact. Therefore, in the method for producing barium titanyl oxalate of the present invention, after mixing the liquid a and the liquid B, a large amount of nuclei of barium titanyl oxalate can be produced in the obtained reaction liquid (mixed liquid), and therefore it is difficult to produce barium titanyl oxalate having a large particle size and barium titanyl oxalate having a small particle size. In the method for producing barium titanyl oxalate according to the present invention, the reaction raw materials in the obtained reaction solution (mixed solution) can be brought into rapid contact, so that the reaction time (residence time) can be shortened, and thus the reaction efficiency can be improved.
The vortex generated in the reaction liquid flow path may be, for example, taylor vortex. The taylor vortex is an annular vortex generated when the inner cylinder is rotated in a state where a gap of a double cylinder composed of the inner cylinder and the outer cylinder is filled with a fluid.
Examples of the device that discharges the discharged liquid from the other end side of the flow path while supplying the supply liquid from one end side of the flow path and generating the taylor vortex in the flow path include devices disclosed in japanese patent application laid-open publication nos. 2011-83768, 2016-10774, 2017-209760, and the like, and taylor vortex type stirring devices such as TVF manufactured by Tipton corporation and small reactor (reactor) crystal manufactured by german corporation.
In the method for producing barium titanyl oxalate of the present invention, the liquid A and the liquid B are supplied to one end of the reaction liquid flow path, and the resultant reaction liquid is discharged from the other end of the reaction liquid flow path. Between the supply and discharge reaction liquid flow paths, if the reaction liquid stays within a residence time described later, for example, as described in the above-mentioned japanese patent application laid-open publication No. 2011-83768, a plurality of reaction devices that generate a vortex such as taylor vortex may be used in combination.
In the method for producing barium titanyl oxalate of the present invention, the residence time of the reaction solution in the reaction solution flow path is preferably 60 seconds or less, more preferably 20 seconds or less, and particularly preferably 0.1 to 10 seconds. The residence time of the reaction solution in the reaction solution passage is in the above range, whereby fine particles of barium titanyl oxalate can be easily obtained. The residence time of the reaction solution in the reaction solution channel is the time taken for the mixture of the solution a and the solution B (the reaction solution produced by mixing the solution a and the solution B) supplied to one end of the reaction solution channel to reach the other end of the reaction solution channel from the one end of the reaction solution channel.
The mixing temperature of the solution A and the solution B, that is, the temperature of the reaction solution in the reaction solution channel is preferably 75℃or lower, and particularly preferably 5 to 50 ℃.
The mixing ratio of the solution a and the solution B is such that the ratio of the number of moles of titanium and barium in the solution B in terms of atoms to the number of moles of oxalic acid in the solution a is preferably 0.01 to 20.0, particularly preferably 0.10 to 10.0.
Next, in the method for producing barium titanyl oxalate according to the present invention, solid-liquid separation of the reaction liquid discharged from the reaction liquid flow path is performed.
After the solid-liquid separation, the solid component is washed with water. The water washing method is not particularly limited, and a method of washing by repulping or the like is preferable in terms of high washing efficiency. After washing, the solid component is dried and pulverized as necessary to obtain barium titanyl oxalate.
Next, a description will be given of barium titanyl oxalate obtained by carrying out the method for producing barium titanyl oxalate according to the first and second aspects of the present invention.
The barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is a barium titanyl oxalate characterized in that the temperature at which the weight reduction rate reaches 99% in thermogravimetric analysis is 600 to 700 ℃, preferably 610 to 690 ℃, particularly preferably 615 to 685 ℃ relative to the weight reduction rate at 1000 ℃. The weight reduction ratio at 1000℃in thermogravimetric analysis means a weight reduction ratio at an analysis temperature of 1000℃in thermogravimetric analysis. In the thermogravimetric analysis, the temperature at which the weight loss rate reaches 99% with respect to the weight loss rate at 1000 ℃ is the temperature at which the weight loss rate reaches 99% with respect to the weight loss rate at the start of the analysis at 1000 ℃.
In thermogravimetric analysis, the temperature at which the weight reduction rate reaches 99% with respect to the weight reduction rate of 1000 ℃ means a temperature at which the barium titanyl oxalate is thermally decomposed to terminate the change to barium titanate, that is, a temperature at which barium titanate is generated from the barium titanyl oxalate. When the weight of the sample to be measured was decreased by thermogravimetric analysis of barium titanyl oxalate, if the temperature of the sample to be measured was raised from room temperature at 10 ℃/min, a slight weight decrease was observed, and after that, the weight decrease was not observed in the vicinity of 700 ℃, and finally, it was confirmed that the sample was thermally decomposed into barium titanate. The weight of the conventional barium titanyl oxalate was not reduced at 700 to 720 ℃, and it was confirmed that barium titanate was obtained in this temperature range. However, since the weight of the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is not significantly reduced at 600 to 700 ℃, preferably 610 to 690 ℃, particularly preferably 615 to 685 ℃, barium titanate can be obtained from the barium titanyl oxalate at a lower temperature than in the prior art. The inventors of the present invention considered that the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is a fine particle having an average particle diameter of preferably 1.0 μm or less, particularly preferably 0.01 to 0.5 μm, and therefore carbon dioxide during thermal decomposition is likely to escape, and can be changed into barium titanate at a lower temperature than in the prior art.
In the titanyl barium oxalate obtained by the method for producing titanyl barium oxalate of the present invention, barium titanate can be produced at a temperature ranging from 600 to 700 ℃, preferably from 610 to 690 ℃, particularly preferably from 615 to 685 ℃, and preferably from 610 to 690 ℃, particularly preferably from 615 to 685 ℃, in which the weight reduction rate reaches 99% relative to the weight reduction rate at 1000 ℃ in thermogravimetric analysis. Accordingly, the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention can produce barium titanate at a low temperature, and thus barium titanate can be highly crystallized at a lower temperature than in the prior art. In addition, in the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate according to the present invention, since barium titanate can be highly crystallized at a lower temperature than in the prior art, the growth of crystal grains of barium titanate can be suppressed, and thus, barium titanate that is fine particles and highly crystallized can be obtained as compared with the prior art. Therefore, when the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate according to the present invention is fired at the same temperature, barium titanate having finer and higher crystallinity can be obtained than the conventional barium titanyl oxalate. On the other hand, if the weight reduction ratio exceeds 700 ℃ with respect to the weight reduction ratio of 1000 ℃, the temperature at which barium titanate is produced from barium titanyl oxalate increases, and therefore the heating temperature for subsequent high crystallization also increases, and as a result, the particle diameter of barium titanate increases.
The thermogravimetric analysis device used for the thermogravimetric analysis of barium titanyl oxalate is not particularly limited, and examples thereof include TGA/DSC 1 manufactured by METTER TOLEDO Co., ltd.
The barium titanyl oxalate obtained by the method of the present invention preferably has a specific surface area of 15 to 20m by a heating test at 700.+ -. 10 ℃ for 2 hours in the atmosphere 2 Barium titanyl oxalate of barium titanate with a ratio of/g and c/a of 1.0030 to 1.0055. The specific surface area of barium titanate obtained by subjecting barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention to a heating test at 700.+ -. 10 ℃ for 2 hours in the atmosphere is particularly preferably 16 to 19m 2 And/g. In addition, the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is particularly preferably 1.0035 to 1.0050 in terms of c/a of barium titanate obtained by a heating test at 700±10 ℃ for 2 hours in the atmosphere. The specific surface area of barium titanate produced by the heating test at 700.+ -. 10 ℃ for 2 hours in the atmosphere is in the above range and c/a is in the above range, and even if grain growth occurs during heating for high crystallization after barium titanate is produced during firing, finer and finer barium titanyl oxalate can be obtained than in the conventional case Highly crystalline barium titanate. In the heating test of barium titanyl oxalate, a sample to be measured was held for 2 hours in a heating apparatus having a temperature adjusted to 700±10 ℃ and subjected to the heating test, and after cooling, the sample to be measured after the heating test was subjected to a specific surface area analysis by the BET method and an X-ray diffraction analysis, and the specific surface area and c/a of the sample to be measured after the heating test were obtained.
The average particle diameter of the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is preferably 1.0 μm or less, more preferably 0.005 to 1.0 μm, particularly preferably 0.01 to 0.5 μm. By the average particle diameter of barium titanyl oxalate being in the above range, barium titanate can be produced at low temperature. In the present invention, the average particle size of barium titanyl oxalate is 200 particles arbitrarily measured by Scanning Electron Microscope (SEM) photograph, and the average value is taken as the average particle size.
The barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is barium titanyl oxalate capable of producing barium titanate when heated at a temperature in the range of 600 to 700 ℃, preferably 610 to 690 ℃, particularly preferably 615 to 685 ℃.
The barium titanyl oxalate obtained by the method of the present invention is suitable for use as a raw material for producing barium titanate-based ceramics as a dielectric ceramic material. The method for producing barium titanate of the present invention is as follows.
The method for producing barium titanate of the present invention is characterized in that: the barium titanyl oxalate obtained by the method for producing barium titanyl oxalate of the present invention is fired.
The organic matter derived from oxalic acid contained in the final product is not preferable because it impairs dielectric properties of the material and is a major factor causing unstable behavior in the thermal process of ceramization. Therefore, in the present invention, it is necessary to obtain the target barium titanate by thermally decomposing barium titanyl oxalate by firing and to sufficiently remove the organic matter derived from oxalic acid. Regarding the firing conditions, the firing temperature is preferably 600 to 1200 ℃, more preferably 620 to 1100 ℃. At firing temperatures less than 600 ℃, only a portion of the barium titanate is produced, or barium titanate of a single phase is not readily available. On the other hand, if the firing temperature exceeds 1200 ℃, the variation in particle size becomes large. The firing time is preferably 0.5 to 30 hours, more preferably 1 to 20 hours. The firing atmosphere is not particularly limited, and the firing may be performed in an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, or in the atmosphere while introducing water vapor.
Firing may be performed several times as needed. Alternatively, the product after the primary firing may be pulverized and then re-fired in order to make the powder characteristics uniform.
After firing, the mixture is cooled appropriately and pulverized as necessary to obtain barium titanate powder. The pulverization, if necessary, is suitably performed when the barium titanate obtained by firing is relatively brittle and lump, and the particles themselves of the barium titanate have the following specific average particle diameter and BET specific surface area. That is, the average particle diameter of the barium titanate powder obtained above as determined by Scanning Electron Microscope (SEM) is preferably 0.5 μm or less, more preferably 0.02 to 0.5. Mu.m. BET specific surface area is preferably 2 to 100m 2 Preferably 2.5 to 50m 2 And/g. In addition, regarding the composition of barium titanate obtained by the production method of the present invention, the molar ratio of Ba to Ti (Ba/Ti) is preferably 0.998 to 1.004, particularly preferably 0.999 to 1.003. In addition, the specific surface area of barium titanate is 15m 2 When the ratio of the c-axis to the a-axis, which is an index of crystallinity, is within a range of not less than/g, the c-axis to a-axis ratio is preferably within a range of 1.0030 to 1.0055, and particularly preferably within a range of 1.0035 to 1.0050. When the firing temperature becomes high, grain growth occurs, and thus the specific surface area becomes less than 15m 2 The c-axis/a-axis ratio is preferably larger than 1.0055, more preferably 1.0070 or more, particularly preferably 1.0075 or more.
In the barium titanate obtained by the method for producing barium titanate of the present invention, a compound containing a subcomponent element may be added to the barium titanate obtained by the method for producing barium titanate of the present invention to contain a subcomponent element, if necessary, in order to adjust dielectric characteristics and temperature characteristics. Examples of usable compounds containing subcomponent elements include compounds containing at least 1 element selected from the group consisting of Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu rare earth elements, ba, li, bi, zn, mn, al, si, ca, sr, co, ni, cr, fe, mg, ti, V, nb, mo, W and Sn.
The compound containing a subcomponent element may be any of an inorganic substance and an organic substance. Examples thereof include oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates, alkoxides, and the like containing the above elements. In the case where the compound containing a subcomponent element is a compound containing an Si element, not only an oxide or the like but also silica sol, sodium silicate or the like may be used. The compound containing subcomponent elements may be used in an amount of 1 or 2 or more kinds thereof may be suitably combined. The combination of the amount and the compound added may be carried out according to a usual method.
In order to contain the subcomponent element, for example, barium titanate and a compound containing the subcomponent element may be mixed uniformly and then fired. Alternatively, the barium titanyl oxalate may be mixed with a compound containing a subcomponent element uniformly and then fired.
In the case of manufacturing, for example, a monolithic ceramic capacitor using barium titanate obtained by the method for manufacturing barium titanate of the present invention, first, barium titanate powder is mixed and dispersed in an appropriate solvent together with a compounding agent such as a conventionally known additive containing subcomponent elements, an organic binder, a plasticizer, and a dispersing agent, and slurried to form a sheet. Thus, a ceramic sheet for manufacturing a multilayer ceramic capacitor was obtained. In manufacturing a multilayer ceramic capacitor from the ceramic sheet, first, a conductive paste for forming internal electrodes is printed on one surface of the ceramic sheet. After drying, a plurality of the ceramic sheets are laminated and pressure-bonded in the thickness direction, thereby forming a laminate. Then, the laminate is subjected to a heat treatment, a binder removal treatment, and firing to obtain a fired body. Then, the fired body is coated with Ni paste, ag paste, nickel alloy paste, copper alloy paste, or the like, and baked to obtain a multilayer ceramic capacitor.
The barium titanate powder obtained by the method for producing barium titanate of the present invention can be used as a material for a printed wiring board, a multilayer printed wiring board, or the like by mixing the barium titanate powder with a resin such as an epoxy resin, a polyester resin, or a polyimide resin to form a resin sheet, a resin film, an adhesive, or the like, or 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, or a dielectric material for an inorganic EL.
The barium titanate obtained by the method for producing barium titanate of the present invention is suitable for use as a catalyst for use in reactions such as removal of exhaust gas and chemical synthesis, and as a surface modifying material for a print cartridge to which antistatic and cleaning effects are imparted.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
(1) Thermogravimetric analysis of barium titanyl oxalate
30mg of the sample was measured in an air stream of 50mL/min at a temperature rising rate of 10 ℃/min from 30℃to 1200℃using a thermogravimetric measurement device TGA/DSC 1 manufactured by METTER TOLEDO Co.
(2) Average particle diameter of barium titanyl oxalate and barium titanate
200 particles were arbitrarily measured by Scanning Electron Microscope (SEM) photograph, and the average value thereof was taken as the average particle diameter.
(3) Specific surface area of barium titanate
Obtained by the BET method.
(4) C/a value of barium titanate
The ratio c/a of c-axis to a-axis was measured by an X-ray diffraction apparatus (D8 ADVANCE, manufactured by Bruker Co.) using Cu-K.alpha.line as a radiation source.
Example 1
25.0g of oxalic acid 2 hydrate was dissolved in 100g of ethylene glycol to prepare 120mL of an oxalic acid component-containing solution (solution A) having oxalic acid concentration of 2.21 mol/L. In addition, 64.4g of titanium tetrachloride and 32.0g of barium chloride were dissolved in 210g of pure water to prepare 270mL of a solution (solution B) containing a titanium component and a barium component, wherein titanium tetrachloride was 0.59mol/L and barium chloride was 0.63 mol/L.
Next, liquid a was supplied at a rate of 4.3L/hr and liquid B was supplied at a rate of 9.6L/hr in a static mixer (Tomita engineering co., ltd., MC 08-32), and the reaction solution was discharged from the static mixer. At this time, the residence time in the static mixer of the reaction solution was set to 2 seconds. The ratio of the supply speed of oxalic acid ions to the supply speed of Ba element and Ti element in the static mixer was 1.91 in terms of a molar ratio.
The reaction liquid discharged from the static mixer was subjected to solid-liquid separation to obtain a precipitate. The precipitate was washed and dried to obtain barium titanyl oxalate. Physical properties of the obtained barium titanyl oxalate are shown in Table 1. The results of measuring the weight reduction rate of the obtained barium titanyl oxalate by thermal analysis are shown in fig. 1. As a result, the weight loss at 680℃was 45.42%, and the weight loss at 1000℃was 45.74% and 99.30%.
The obtained barium titanyl oxalate was fired at 700℃for 2 hours to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 1.
Examples 2 to 4
Barium titanyl oxalate obtained in example 1 was fired at the temperature shown in table 1 to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 1.
Example 5
25.0g of oxalic acid 2 hydrate was dissolved in 100g of ethylene glycol to prepare 120mL of an oxalic acid component-containing solution (solution A) having an oxalic acid concentration of 2.21 mol/L. In addition, 64.4g of titanium tetrachloride and 32.0g of barium chloride were dissolved in 210g of pure water to prepare 270mL of a solution (solution B) containing a titanium component and a barium component, wherein titanium tetrachloride was 0.59mol/L and barium chloride was 0.63 mol/L.
Next, in the microreactor (flow path diameter: 1.0mm, flow path length: 1000 mm), the solution A was supplied at a rate of 72 mL/min, the solution B was supplied at a rate of 160 mL/min, and the reaction solution was discharged from the microreactor. At this time, the residence time in the microreactor of the reaction solution was set to 2.6 seconds. The ratio of the supply rate of oxalic acid ions to the supply rate of Ba element and Ti element in the microreactor was 1.91 in terms of a molar ratio.
The reaction liquid discharged from the microreactor was subjected to solid-liquid separation to obtain a precipitate. And cleaning the precipitate, and drying to obtain the barium titanyl oxalate. Physical properties of the obtained barium titanyl oxalate are shown in Table 1. Further, the results of measuring the weight reduction rate of the thermal analysis of the obtained barium titanyl oxalate are shown in fig. 1. As a result, the weight loss at 680℃was 48.53%, and the weight loss at 1000℃was 45.28%, 99.40%.
The obtained barium titanyl oxalate was fired at 700℃for 2 hours to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 1.
Comparative example 1
A solution (solution a) containing a barium component and an oxalic acid component, in which the barium concentration was 1.10mol/L and the oxalic acid concentration was 2.20mol/L, was prepared by dissolving 35.0g of barium chloride 2 water salt and 35.0g of oxalic acid 2 water salt in 120g of pure water, and 120mL of the solution was prepared. In addition, 54.0g of titanium tetrachloride was dissolved in pure water to prepare 260mL of a solution (solution b) containing a titanium component having a titanium concentration of 0.40 mol/L.
Next, the solution b was added for 90 seconds while stirring the solution a, and after holding for 1 hour, solid-liquid separation was performed to obtain a precipitate. The precipitate was washed and dried to obtain barium titanyl oxalate. Physical properties of the obtained barium titanyl oxalate are shown in Table 1. Further, the results of measuring the weight reduction rate of the thermal analysis of the obtained barium titanyl oxalate are shown in fig. 1. As a result, the weight loss at 680℃was 37.71%, and the weight loss at 44.81% relative to 1000℃was 84.15%.
The resulting barium titanyl oxalate was fired at 700℃for 2 hours. However, it is found from the measurement results of the weight reduction rate by the thermogravimetric analysis that barium titanate is not obtained.
Comparative examples 2 to 4
The barium titanyl oxalate obtained in comparative example 1 was fired at the temperature shown in table 1 to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 1.
TABLE 1
As shown in table 1, it can be judged from comparison of the average particle diameter, BET specific surface area, and c/a values at the time of firing at the same temperature that the barium titanate obtained in examples is fine particle and highly crystalline particle as compared with the barium titanate obtained in comparative examples. Further, as shown in fig. 1, it was judged that barium titanate was obtained at 700 ℃ by thermogravimetric analysis of barium titanyl oxalate obtained in example 1, but barium titanate was not obtained even at 700 ℃ of barium titanyl oxalate obtained in comparative example 1.
Example 6
25.0g of oxalic acid 2 hydrate was dissolved in 100g of ethylene glycol to prepare 120mL of an oxalic acid component-containing solution (solution A) having an oxalic acid concentration of 2.21 mol/L. In addition, 64.4g of titanium tetrachloride and 32.0g of barium chloride were dissolved in 210g of pure water to prepare 270mL of a solution (solution B) containing a titanium component and a barium component, wherein the titanium tetrachloride was 0.59mol/L and the barium chloride was 0.63 mol/L.
Next, the solution a was supplied to a taylor vortex type stirring device (TVF-01, manufactured by Tipton corporation) at a rate of 4.3L/hr, the solution B was supplied at a rate of 9.6L/hr, and the reaction solution was discharged from the taylor vortex type stirring device. At this time, the residence time in the taylor vortex type stirring device for the reaction liquid was set to 5 seconds. The ratio of the supply speed of oxalic acid ions to the supply speed of Ba element and Ti element in the taylor vortex type stirring device was 1.91 in terms of a molar ratio.
The reaction liquid discharged from the taylor vortex type stirring device is subjected to solid-liquid separation to obtain a precipitate. And cleaning the precipitate, and drying to obtain the barium titanyl oxalate. Physical properties of the obtained barium titanyl oxalate are shown in Table 2. The results of measuring the weight reduction rate of the obtained barium titanyl oxalate by thermal analysis are shown in fig. 6. As a result, the weight loss at 680℃was 48.53%, and the weight loss at 48.82% relative to 1000℃was 99.40%.
The obtained barium titanyl oxalate was fired at 700℃for 2 hours to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 2.
Examples 7 to 9
Barium titanyl oxalate obtained in example 7 was fired at the temperature shown in table 2 to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 2.
Comparative example 5
A solution (solution a) containing a barium component and an oxalic acid component, in which the barium concentration was 1.10mol/L and the oxalic acid concentration was 2.20mol/L, was prepared by dissolving 35.0g of barium chloride 2 water salt and 35.0g of oxalic acid 2 water salt in 120g of pure water, and 120mL of the solution was prepared. In addition, 54.0g of titanium tetrachloride was dissolved in pure water to prepare 260mL of a solution (solution b) containing a titanium component having a titanium concentration of 0.40 mol/L.
Next, the solution b was added for 90 seconds while stirring the solution a, and after holding for 1 hour, solid-liquid separation was performed to obtain a precipitate. The precipitate was washed and dried to obtain barium titanyl oxalate. Physical properties of the obtained barium titanyl oxalate are shown in Table 2. The results of measuring the weight reduction rate of the obtained barium titanyl oxalate by thermal analysis are shown in fig. 6. As a result, the weight loss at 680℃was 37.71%, and the weight loss at 44.81% at 1000℃was 84.15%.
The resulting barium titanyl oxalate was fired at 700℃for 2 hours. However, it was found from the measurement results of the weight reduction rate by thermogravimetric analysis that barium titanate was not obtained.
Comparative examples 6 to 8
Barium titanyl oxalate obtained in comparative example 5 was fired at the temperature shown in table 2 to obtain barium titanate. Physical properties of the obtained barium titanate are shown in table 2.
TABLE 2
As shown in table 2, it can be judged from comparison of the average particle diameter, BET specific surface area, and c/a values at the time of firing at the same temperature that the barium titanate obtained in examples is fine particle and highly crystalline particle, compared with the barium titanate obtained in comparative examples. Further, as shown in fig. 6, it was judged that barium titanate was obtained at 700 ℃ by thermogravimetric analysis of barium titanyl oxalate obtained in example 6, but barium titanate was not obtained even at 700 ℃ of barium titanyl oxalate obtained in comparative example 5.
Claims (13)
1. A method for manufacturing barium titanyl oxalate is characterized in that:
a method for producing barium titanyl oxalate by mixing and reacting a liquid A and a liquid B described below,
the solution A is a solution containing oxalic acid, the solution B is a solution containing a titanium source and a barium source,
in the production method, the A liquid and the B liquid are respectively supplied to one end side of a reaction liquid flow path, the A liquid and the B liquid are mixed in the reaction flow path, the reaction liquid is discharged from the other end side of the reaction liquid flow path, then solid-liquid separation of the reaction liquid is performed,
the residence time of the reaction solution in the reaction solution flow path is within 30 seconds.
2. The method for producing barium titanyl oxalate according to claim 1, wherein:
The reaction liquid flow path is formed in the static mixer by supplying the liquid a and the liquid B to one end side of the static mixer, respectively.
3. The method for producing barium titanyl oxalate according to claim 1, wherein:
the liquid A and the liquid B are supplied to one end side of a reaction liquid flow path of a continuous flow type microreactor, respectively, whereby the reaction liquid flow path is formed in the microreactor.
4. A method for manufacturing barium titanyl oxalate is characterized in that:
a method for producing barium titanyl oxalate by mixing and reacting a liquid A and a liquid B described below,
the solution A is a solution containing oxalic acid, the solution B is a solution containing a titanium source and a barium source,
in the above-described production method, the liquid A and the liquid B are supplied to one end of a reaction liquid channel, the liquid A and the liquid B are mixed at one end of the reaction liquid channel, the reaction liquid is moved to the other end of the reaction liquid channel while swirling the reaction liquid, the reaction liquid is discharged from the other end of the reaction liquid channel, and then solid-liquid separation of the reaction liquid is performed.
5. The method for producing barium titanyl oxalate according to claim 4, wherein:
The residence time of the reaction solution in the reaction solution flow path is 60 seconds or less.
6. The method for producing barium titanyl oxalate according to claim 4, wherein:
the vortex is a taylor vortex.
7. The method for producing barium titanyl oxalate according to claim 1 or 4, wherein:
the solvent of the solution A is an organic solvent.
8. The method for producing barium titanyl oxalate according to claim 1 or 4, wherein:
the solvent of the solution A is 1 or more than 2 selected from methanol, ethanol, propanol, butanol, diethyl ether, 1, 3-butanediol, ethylene glycol, propylene glycol, dipropylene glycol, glycerol, N-dimethylformamide and acetone.
9. The method for producing barium titanyl oxalate according to claim 1 or 4, wherein:
the solvent of the solution B is water.
10. The method for producing barium titanyl oxalate according to claim 1 or 4, wherein:
the titanium compound in the solution B is titanium tetrachloride, and the barium compound is barium chloride.
11. The method for producing barium titanyl oxalate according to claim 1 or 4, wherein:
the mixing temperature of the solution A and the solution B is below 75 ℃.
12. The method for producing barium titanyl oxalate according to claim 1 or 4, wherein:
The average particle diameter of the barium titanyl oxalate is 1.0 μm or less.
13. A method for producing barium titanate, characterized by:
firing the barium titanyl oxalate obtained by the production method according to any one of claims 1 to 6.
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