CN111465580A - Method for producing perovskite barium titanate powder - Google Patents
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Abstract
A method for producing a perovskite barium titanate powder, comprising: a firing step of firing a composite organic acid salt containing Ba atoms and Ti atoms in a firing furnace while introducing humidified air having a dew point of 45 ℃ or higher and lower than 100 ℃ into the firing furnace to obtain a fired product; and a pulverization step of pulverizing the fired product to obtain perovskite barium titanate powder. According to the present invention, a method for producing a fine perovskite barium titanate powder having high tetragonal crystallinity by an industrially advantageous method using a complex organic acid salt can be provided.
Description
Technical Field
The present invention relates to a method for producing a perovskite barium titanate powder, and more particularly to a method for producing a perovskite barium titanate powder useful as a raw material for functional ceramics such as piezoelectric materials, photoelectric materials, dielectric materials, semiconductors, and sensors.
Background
Conventionally, perovskite barium titanate powder has been used as a raw material for functional ceramics such as piezoelectric bodies and multilayer ceramic capacitors. However, in recent years, in order to increase the capacity of multilayer ceramic capacitors, it has been required to increase the number of layers to be stacked and to increase the dielectric constant, and thus, fine and highly tetragonal perovskite barium titanate powder is desired as a raw material.
As 1 method for producing perovskite barium titanate powder, there is a method of pre-firing a complex organic acid salt containing Ba atoms and Ti atoms. For example, a typical oxalate method is a method in which a solution containing barium chloride and titanium chloride is brought into contact with an oxalic acid aqueous solution to react and obtain barium titanyl oxalate, and then the barium titanyl oxalate is pre-fired to perform a de-oxalic acid treatment. Although the perovskite barium titanate powder obtained by the oxalate method has a uniform composition, attempts have been made to obtain a finer powder having high tetragonal crystallinity as a measure for improving other characteristics.
For example, patent document 1 below proposes a method of crushing a fine barium titanyl oxalate (BaTiO (C) obtained by mixing a water-soluble barium salt, a water-soluble titanium salt and an aqueous solution of oxalic acid at the same time and strongly stirring the obtained gel in a short time2O4)·4H2O) is pre-fired at 700 to 900 ℃.
Further, patent documents 2 and 3 below propose a method in which barium titanyl oxalate is subjected to wet pulverization treatment to obtain fine barium titanyl oxalate, and the obtained barium titanyl oxalate is then subjected to pre-firing.
In addition, patent document 4 below proposes a method including the steps of: a step of adding a mixed aqueous solution of a barium chloride aqueous solution and a titanium chloride aqueous solution to an oxalic acid aqueous solution to precipitate barium titanyl oxalate, followed by aging, washing, filtering, and drying to produce barium titanyl oxalate; pre-firing the produced barium titanyl oxalate for 1 time, and then crushing for 1 time to produce fine barium titanate powder; and a step of calcining the barium titanate powder of the fine particles 2 times, and then grinding the calcined barium titanate powder 2 times.
However, although the above method can obtain a perovskite type barium titanate powder which is fine to some extent and has high tetragonal crystallinity to some extent, a method which can produce a perovskite type barium titanate powder which is fine and has high tetragonal crystallinity by an industrially advantageous method is desired.
In contrast, patent document 5 discloses a method for producing a perovskite type barium titanate powder by pre-firing a complex organic acid salt containing Ba atoms and Ti atoms in a firing furnace, wherein the pre-firing is performed while introducing humidified air into the firing furnace, the humidified air being humidified by passing air through water whose temperature has been adjusted. Patent document 5 discloses a perovskite barium titanate powder having a small average particle size and high tetragonal crystallinity.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 61-146710
Patent document 2: japanese patent laid-open publication No. 2004-123431
Patent document 3: japanese laid-open patent publication No. 2002-53320
Patent document 4: japanese patent laid-open publication No. 2003-212543
Patent document 5: japanese patent No. 5119008
Disclosure of Invention
Technical problem to be solved by the invention
In the method of patent document 5, a perovskite barium titanate powder having characteristics of a small average particle diameter and high tetragonal crystallinity is obtained. However, when the multilayer ceramic capacitor is further increased in capacity and dielectric constant, there is room for further investigation of the characteristics of the perovskite barium titanate powder as a raw material. Specifically, it is necessary to obtain a perovskite barium titanate powder having a small average particle size and a narrow particle size distribution range and having a uniform particle size.
Accordingly, an object of the present invention is to provide a method for producing a perovskite barium titanate powder which is not only fine and highly tetragonal but also has a uniform particle size, by an industrially advantageous method using a complex organic acid salt.
Technical solution for solving technical problem
The above-described problems are solved by the present invention described below.
That is, the present invention (1) provides a method for producing a perovskite barium titanate powder, comprising:
a firing step of firing a composite organic acid salt containing Ba atoms and Ti atoms in a firing furnace while introducing humidified air having a dew point of 45 ℃ or higher and lower than 100 ℃ into the firing furnace to obtain a fired product; and
and a grinding step of grinding the fired product to obtain perovskite barium titanate powder.
The present invention also provides (2) the process for producing a perovskite barium titanate powder according to (1), wherein the dew point of the humidified air is 50 to 90 ℃.
The present invention (3) provides the method for producing a perovskite barium titanate powder according to (1) or (2), wherein the humidified air is prepared by humidifying air by passing the air through temperature-adjusted water.
The present invention also provides (4) the process for producing a perovskite barium titanate powder according to any one of (1) to (3), wherein the complex organic acid salt is fired at 500 to 1200 ℃.
Further, the present invention (5) provides the method for producing a perovskite barium titanate powder according to any one of (1) to (4), wherein the complex organic acid salt is a carboxylate.
Further, the present invention (6) provides the process for producing a perovskite barium titanate powder according to any one of (1) to (5), wherein the complex organic acid salt is an oxalate or a citrate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a method for producing a perovskite barium titanate powder which is not only fine and highly tetragonal but also has a uniform particle size, by an industrially advantageous method using a complex organic acid salt.
Drawings
FIG. 1 is a schematic view showing an example of the form of a firing furnace.
Detailed Description
The method for producing a perovskite barium titanate powder according to the present invention is characterized by comprising:
a firing step of firing a composite organic acid salt containing Ba atoms and Ti atoms in a firing furnace while introducing humidified air having a dew point of 45 ℃ or higher and lower than 100 ℃ into the firing furnace to obtain a fired product; and
and a grinding step of grinding the fired product to obtain perovskite barium titanate powder.
The method for producing a perovskite barium titanate powder according to the present invention comprises: a firing step of firing the composite organic acid salt containing Ba atoms and Ti atoms in a firing furnace to obtain a fired product; and a pulverization step of pulverizing the fired product obtained by the firing step to obtain perovskite barium titanate powder.
In the firing step of the method for producing a perovskite barium titanate powder of the present invention, the compound organic acid salt containing Ba atoms and Ti atoms (hereinafter, also simply referred to as "compound organic acid salt") as a firing raw material is not particularly limited as long as a complex salt of Ba and Ti is formed, and examples thereof include carboxylate salts such as formate, oxalate, acetate, propionate, succinate, malate, tartrate, citrate and lactate, and complex salts containing 2 or more of these carboxylic acids, and examples thereof include a complex salt of a carboxylic acid containing both oxalic acid and lactic acid (see, for example, japanese patent application No. 2007 40018). Examples of the complex organic acid salt include barium titanyl oxalate, barium titanyl citrate, and barium titanyl succinate. Among these, oxalate and citrate are preferable as the complex organic acid salt because the complex organic acid salt having an atomic ratio of Ba/Ti close to 1 can be easily produced and the production cost is reduced.
The content ratio of Ba atoms to Ti atoms in the composite organic acid salt is 0.99 to 1.01, preferably 0.995 to 1.005, in terms of the molar ratio of Ba atoms to Ti atoms (Ba/Ti). When the molar ratio of Ba atoms to Ti atoms (Ba/Ti) is in the above range, fine perovskite barium titanate having high tetragonal crystallinity can be obtained.
In addition, the composite organic acid salt may contain Ca atoms and/or Sr atoms instead of a part of Ba atoms of the a-site element of the produced perovskite barium titanate powder, and may contain Zr atoms instead of a part of Ti atoms of the B-site element. In this case, the substitution amount of Ca atoms or/and Sr atoms as a part of the Ba atoms is not particularly limited, but is preferably less than 50 mol% with respect to the Ba atoms. The substitution amount of Zr atoms for substituting a part of Ti atoms is not particularly limited, but is preferably less than 50 mol% based on Ti atoms. The mixing ratio of Ti and Zr (B site element) to Ba and Ca and/or Sr (A site element) is 0.99 to 1.01, preferably 0.995 to 1.005 in terms of molar ratio (A site element/B site element).
The average particle size of the complex organic acid salt is not particularly limited, and the average particle size determined by a laser diffraction scattering method is preferably 200 μm or less, and particularly preferably 100 μm or less, in view of obtaining a fine perovskite barium titanate having high tetragonal crystallinity.
The complex organic acid salt can be produced by a known method. The oxalate salt is produced, for example, by bringing an aqueous solution containing titanium chloride and barium chloride into contact with an aqueous oxalic acid solution to precipitate the oxalic acid salt, performing a ripening reaction if necessary, then performing solid-liquid separation by a conventional method to recover the oxalate salt, and washing, drying, pulverizing, and the like if necessary. Examples of the oxalate include a complex organic acid salt produced by the method described in, for example, Japanese patent application laid-open Nos. 2006-321722, 2006-321723, 2006-348026, and 2004-123431.
The citrate is produced, for example, by adding a barium chloride solution to a citric acid solution of titanium to precipitate the citrate, performing a ripening reaction if necessary, then performing solid-liquid separation by a conventional method to recover the citrate, and washing, drying, pulverizing, and the like if necessary. Examples of the citrate include a complex organic acid salt produced by a method described in U.S. Pat. No. 3,231,328 and the like.
Further, a complex salt of carboxylic acid containing both oxalic acid and lactic acid is produced by, for example, bringing a solution containing a titanium component, a barium component, and a lactic acid component into contact with a solution containing an oxalic acid component in a solvent containing an alcohol to react with each other (see pamphlet of international publication No. WO 2008/102785).
The compound organic acid salt is not particularly limited, and can be pulverized by a wet method or a dry method. For example, when the slurry is subjected to a wet method, a slurry containing the complex organic acid salt is charged into a wet grinding apparatus and ground. Examples of the wet grinding apparatus include a ball mill and a bead mill. As the solvent used for preparing the slurry, a solvent inactive to the complex organic acid salt is used, and examples thereof include water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide, diethyl ether, and the like. Among these, as a solvent used for preparing the slurry, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide, and diethyl ether are preferable. The solvent used for preparing the slurry may be 1 kind alone or a combination of 2 or more kinds. After the wet treatment, the entire slurry may be dried by using a spray dryer. In the case of the dry method, the composite organic acid salt may be pulverized by a dry pulverizing apparatus such as a jet mill, a pin mill, a roll mill, a hammer mill, or a pulverizer (pulverizer).
In order to obtain high-purity perovskite barium titanate powder, it is preferable to use a high-purity complex organic acid salt.
Then, in the firing step of the method for producing a perovskite barium titanate powder of the present invention, the complex organic acid salt is fired in the firing furnace while introducing humidified air having a dew point of 45 ℃ or higher and lower than 100 ℃ into the firing furnace.
In the firing step, the dew point of the humidified air introduced into the firing furnace is 45 ℃ or higher and less than 100 ℃, preferably 50 to 90 ℃. When the dew point of the humidified air is in the above range, perovskite barium titanate having high tetragonal crystallinity, fine particle size and uniform particle size can be obtained.
The method for producing the humidified air is not particularly limited as long as the dew point of the humidified air is within the above range, and for example, the humidified air may be produced by passing air through water whose temperature has been adjusted, or the humidified air may be produced by mixing water vapor with air.
Dew point (. degree. C.) is shown in Table 1 together with dry air 1m2The amount of saturated water vapor (humidity 100%) (g) contained.
[ Table 1]
| Dry air 1m2Amount of vapor (g) contained | Dew point (. degree. C.) |
| 65.3 | 45 |
| 82.8 | 50 |
| 104 | 55 |
| 130 | 60 |
| 160 | 65 |
| 197 | 70 |
| 240 | 75 |
| 291 | 80 |
| 350 | 85 |
| 418 | 90 |
| 498 | 95 |
The amount of the humidified air introduced into the firing furnace varies depending on the capacity of the firing furnace, and is appropriately selected depending on the firing furnace, and the amount of the humidified air introduced into the firing furnace per unit capacity of the firing furnace is preferably 0.3L/(min L (capacity of firing furnace)) or more, and particularly preferably 0.5 to 3L 0/(min L (capacity of firing furnace)). furthermore, the amount of the humidified air introduced into the firing furnace per unit capacity of the firing furnace is calculated by dividing the amount of the humidified air introduced into the firing furnace per unit time (L/min) by the capacity of the firing furnace (L), and for example, when a firing furnace having a capacity of 10L is used, the amount of the humidified air introduced into the firing furnace per unit capacity of the firing furnace is preferably 0.3L/(min L (capacity of firing furnace)) or more, and particularly preferably 0.5 to 3L/(min L (capacity of firing furnace)), and the amount of humidified air introduced into the firing furnace per unit time is preferably in a range of 0.3 to 3 min L min, and the amount of humidified air introduced into the firing furnace is preferably in a range capable of preventing the barium dioxide from being introduced into the firing furnace due to a low reaction temperature per unit volume of the firing furnace.
The firing temperature of the composite organic acid salt in the firing process is 500-1200 ℃, and preferably 600-1000 ℃. When the firing temperature of the complex organic acid salt in the firing step is lower than the above range, the perovskite type barium titanate generation reaction cannot proceed and the complex organic acid salt is likely to be in an unreacted state.
The firing time of the composite organic acid salt in the firing step is preferably 4 hours or more, and particularly preferably 6 to 30 hours. The firing atmosphere of the composite organic acid salt in the firing step is an oxidizing gas atmosphere containing humidified air, such as an atmosphere containing humidified air, an oxygen atmosphere containing humidified air, or the like. The firing pressure of the composite organic acid salt in the firing step is atmospheric pressure.
In the firing step, the firing furnace for firing the composite organic acid salt may be a batch-type or continuous-type electric furnace or a gas furnace, and examples thereof include a roller kiln, a rotary kiln, and a pusher furnace.
In the firing step, the material once fired may be pulverized and then fired again in order to make the powder characteristics uniform.
By performing the firing step in this manner, a fired product of the composite organic carbonate is obtained. In the fired product obtained by the firing step, primary particles of perovskite barium titanate aggregate to form secondary particles. That is, the fired product obtained by the firing step is secondary particles in which primary particles of perovskite barium titanate are aggregated.
In the pulverization step of the method for producing a perovskite barium titanate powder, a fired product obtained by firing is pulverized to obtain a perovskite barium titanate powder.
In the grinding step, a method for grinding the fired product obtained by firing is not particularly limited, and wet grinding or dry grinding may be used. Examples of the wet grinding device include a ball mill and a bead mill, and examples of the dry grinding device include a jet mill, a pin mill and a roll mill.
After the pulverization step, the perovskite barium titanate powder may be washed with an acid solution, washed with water, dried, classified, or the like, as necessary. The drying method may be a conventional method, but when wet pulverization treatment is performed, for example, a method using a spray dryer can be used.
The perovskite-type barium titanate powder obtained by performing the method for producing a perovskite-type barium titanate powder of the present invention preferably has an average particle diameter (D50) of 0.330 μm or less, and particularly preferably 0.010 to 0.328 μm. The D90 of the perovskite-type barium titanate powder obtained by the method for producing a perovskite-type barium titanate powder of the present invention is preferably 0.930 μm or less, and particularly preferably 0.650 to 0.900 μm. Thus, the perovskite-type barium titanate powder obtained by performing the method for producing a perovskite-type barium titanate powder of the present invention is fine and suppresses the generation of large particles, and therefore, the perovskite-type barium titanate powder has a narrow particle size distribution width and a uniform particle size. In the present invention, the particle size of the perovskite barium titanate powder is determined by a laser diffraction scattering method. In the present invention, the average particle diameter (D50) means a particle diameter at which the cumulative distribution on a volume basis reaches 50%, and means a median diameter, and D90 means a particle diameter at which the cumulative distribution on a volume basis reaches 90%.
The particle size distribution index ((D90-D10)/D50) of the perovskite barium titanate powder obtained by performing the method for producing a perovskite barium titanate powder of the present invention is preferably 2.410 or less, and particularly preferably 2.405 or less. That is, the particle size distribution of the perovskite type barium titanate powder obtained by performing the method for producing a perovskite type barium titanate powder of the present invention is narrow.
The method for producing the perovskite barium titanate powder according to the present inventionThe perovskite barium titanate powder obtained by the method has a specific surface area of 2m2A total of 3 to 50m, preferably2/g。
In the X-ray diffraction analysis of the perovskite barium titanate powder obtained by the method for producing a perovskite barium titanate powder of the present invention, the ratio (c/a) of the c-axis to the a-axis, which is an index of tetragonal crystal, is preferably 1.004 or more, and preferably 1.005 to 1.010. Thus, the perovskite-type barium titanate powder obtained by performing the method for producing a perovskite-type barium titanate powder of the present invention has high tetragonal crystallinity.
The perovskite barium titanate powder obtained by the method for producing a perovskite barium titanate powder of the present invention is extremely high in purity, and is a perovskite barium titanate powder useful as a raw material for functional ceramics for electronic components such as piezoelectric bodies, optoelectronic materials, dielectrics, semiconductors, and sensors.
In the method for producing a perovskite-type barium titanate powder of the present invention, by firing the complex organic acid salt while introducing humidified air into the reaction furnace in the firing step, carbon dioxide generated in the firing furnace in the production reaction for producing perovskite-type barium titanate can be efficiently absorbed by the humidified air, and thus perovskite-type barium titanate having high tetragonal crystallinity can be obtained, and by setting the dew point of the humidified air within a specific range, a fired product which is easily pulverized in the pulverizing step, that is, secondary particles of perovskite-type barium titanate which are easily pulverized in the pulverizing step can be obtained. Therefore, in the method for producing a perovskite barium titanate powder of the present invention, secondary particles of perovskite barium titanate having high tetragonal crystallinity, being fine and having a uniform particle diameter can be obtained through the pulverization step after the firing step.
In the method for producing a perovskite-type barium titanate powder of the present invention, a perovskite-type barium titanate powder containing an oxide of a subcomponent element can be obtained by adding a compound containing a subcomponent element to a complex organic acid salt as a firing raw material in a firing step as necessary, and the perovskite-type barium titanate powder of the present invention containing a subcomponent element can also be obtained by adding a compound containing a subcomponent element to a fired product obtained by performing a firing step and firing the mixture, and examples of such subcomponent element include at least 1 element selected from Sc, Y, L a, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, L u and other rare earth elements, L i, Bi, Zn, Mn, Al, Si, Sr, Co, V, Nb, Ni, Cr, B, Fe and Mg.
The combination and addition amount of these subcomponent elements are arbitrarily set in accordance with the dielectric characteristics required for the ceramic in which the produced perovskite barium titanate powder is used. For example, the additive amount of the subcomponent element is 0.1 to 5 parts by mass in terms of atom per 100 parts by mass of the perovskite barium titanate powder.
The perovskite-type barium titanate powder obtained by performing the method for producing a perovskite-type barium titanate powder of the present invention is used as a raw material for producing a multilayer capacitor. For example, first, a perovskite type barium titanate powder obtained by performing the method for producing a perovskite type barium titanate powder of the present invention is mixed and dispersed with conventionally known compounding agents such as an additive, an organic binder, a plasticizer, and a dispersant to form a slurry, and the solid content in the slurry is molded to obtain a ceramic sheet. Next, a conductive paste for forming internal electrodes is printed on one surface of the ceramic sheets, dried, and then a plurality of the ceramic sheets are laminated and then pressure-bonded in the thickness direction, thereby forming a laminated body. Then, the laminate is subjected to a heat treatment to remove the binder, and is subjected to a preliminary firing to obtain a preliminary fired body. Then, an In — Ga paste, a Ni paste, an Ag paste, a nickel alloy paste, a copper alloy paste, or the like is applied to the fired body and fired, thereby obtaining a multilayer capacitor.
The perovskite type barium titanate powder obtained by performing the method for producing a perovskite type barium titanate powder of the present invention can be suitably used as a material for a printed wiring board, a multilayer printed wiring board, or the like, for example, by blending the perovskite type barium titanate powder obtained by performing the method for producing a perovskite type barium titanate powder of the present invention into a resin such as an epoxy resin, a polyester resin, a polyimide resin, or the like, and can be suitably used as a material for a printed wiring board, a multilayer printed wiring board, or the like, and the perovskite type barium titanate powder obtained by performing the method for producing a perovskite type barium titanate powder of the present invention can also be suitably used for a dielectric material for an E L element, a common material for suppressing a difference in shrinkage between an internal electrode and a dielectric layer, a catalyst used in reactions such as removal of exhaust gas or chemical synthesis, a surface-modifying material for a printing toner for imparting an antistatic effect or a cleaning effect, or.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
< preparation of barium titanyl oxalate >
A mixed solution of 600g (2.456 mol) of barium chloride dihydrate and 444g (2.342 mol) of titanium tetrachloride dissolved in 4100ml of water was prepared as solution A, then 620g of oxalic acid was dissolved in 1500ml of warm water at 70 ℃ to prepare an oxalic acid aqueous solution as solution B, the solution B was added to the solution A while maintaining 70 ℃ for 120 minutes under stirring, further aged while stirring at 70 ℃ for 1 hour, cooled, filtered to recover barium titanyl oxalate, then the recovered barium titanyl oxalate was repulped 3 times with distilled water 4.5L to wash it, then dried at 105 ℃ and pulverized to obtain barium titanyl oxalate (BaTiO (C. sub.) (BaTiO (C. sub.2O4)·4H2O)1000 g. The Ba/Ti molar ratio of the obtained barium titanyl oxalate was 1.00.
Further, regarding the Ba/Ti molar ratio, the Ba/Ti molar ratio was calculated based on a value analyzed by fluorescent X-ray.
(examples 1 and 2, comparative examples 1 and 2)
In a firing furnace (capacity: 10L) comprising a batch-type electric furnace shown in FIG. 1, 1kg of the barium titanyl oxalate sample obtained as described above was fired under atmospheric air by introducing humidified air having a dew point shown in Table 2 at a rate of 20L/min into the firing furnace and raising the temperature at a rate of 2.5 ℃/min to the temperature shown in Table 2 and holding the temperature for 6 hours, and after the firing, the barium titanate powder was obtained by cooling and pulverizing the barium titanate powder.
The average particle diameter (D50), D90, particle size distribution index ((D90-D10)/D50), specific surface area, and ratio of c-axis to a-axis (c/a) of the obtained barium titanate powder were determined. The results are shown in Table 2.
The firing furnace shown in fig. 1 has four surfaces inside a furnace 1 covered with alumina fiber boards, and a sample 3 is stored in a sample container 2 made of alumina inside the furnace, and humidified air 6 is introduced into the furnace from an inlet 5 of an inlet pipe 4 and discharged to the outside of the furnace from an outlet 8 of a discharge pipe 7.
< method for measuring particle diameters D50, D90 and D10 >
The measurement was performed by a laser diffraction/scattering method using MT3000 manufactured by microtrac be L.
< c/a value >
The ratio c/a of the c-axis to the a-axis was measured using an X-ray diffraction device (model X' PartMPD, manufactured by Philips, Japan) using Cu-K α radiation as a radiation source.
[ Table 2]
In examples 1 and 2, powders having high tetragonal crystallinity, a D90 particle size of 0.9 μm or less, and a narrow particle size distribution were obtained.
On the other hand, in comparative examples 1 and 2, powders having D90 exceeding 0.9 μm and a broad particle size distribution were obtained, although having high tetragonal crystallinity.
Industrial applicability
The present invention can produce a perovskite type barium titanate powder which is fine, has a narrow particle size distribution, and has high tetragonal crystallinity, and therefore, the produced perovskite type barium titanate powder can be suitably used as a raw material for functional ceramics for electronic parts such as piezoelectric bodies, optoelectronic materials, dielectrics, semiconductors, and sensors.
Description of the symbols
1: a furnace; 2: a sample container; 3: a sample; 4: an introducing pipe; 5: an inlet port; 6: humidifying the air; 7: a discharge pipe; 8: an outlet port; 9: and (7) a cover.
Claims (6)
1. A method for producing a perovskite barium titanate powder, comprising:
a firing step of firing a composite organic acid salt containing Ba atoms and Ti atoms in a firing furnace while introducing humidified air having a dew point of 45 ℃ or higher and lower than 100 ℃ into the firing furnace to obtain a fired product; and
and a grinding step of grinding the fired product to obtain perovskite barium titanate powder.
2. The method for producing a perovskite barium titanate powder according to claim 1, wherein:
the dew point of the humidified air is 50-90 ℃.
3. The method for producing a perovskite barium titanate powder according to claim 1 or 2, characterized by:
humidifying air by passing the air through the temperature-adjusted water, thereby preparing the humidified air.
4. The method for producing a perovskite barium titanate powder according to any one of claims 1 to 3, characterized by:
and firing the composite organic acid salt at 500-1200 ℃.
5. The method for producing a perovskite barium titanate powder according to any one of claims 1 to 4, characterized by:
the compound organic acid salt is carboxylate.
6. The method for producing a perovskite barium titanate powder according to any one of claims 1 to 5, wherein:
the compound organic acid salt is oxalate or citrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-235032 | 2017-12-07 | ||
| JP2017235032A JP6573653B2 (en) | 2017-12-07 | 2017-12-07 | Method for producing perovskite-type barium titanate powder |
| PCT/JP2018/040087 WO2019111586A1 (en) | 2017-12-07 | 2018-10-29 | Method for producing perovskite barium titanate powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111465580A true CN111465580A (en) | 2020-07-28 |
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| CN201880078761.5A Pending CN111465580A (en) | 2017-12-07 | 2018-10-29 | Method for producing perovskite barium titanate powder |
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| JP (1) | JP6573653B2 (en) |
| KR (1) | KR102536054B1 (en) |
| CN (1) | CN111465580A (en) |
| TW (1) | TW201925095A (en) |
| WO (1) | WO2019111586A1 (en) |
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| KR20220035115A (en) * | 2019-07-16 | 2022-03-21 | 니폰 가가쿠 고교 가부시키가이샤 | Me element substituted organic acid barium titanyl, method for producing same, and method for producing titanium-based perovskite-type ceramic raw material powder |
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| US6066581A (en) * | 1995-07-27 | 2000-05-23 | Nortel Networks Corporation | Sol-gel precursor and method for formation of ferroelectric materials for integrated circuits |
| JP2005314153A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Chemical Co Ltd | Method of manufacturing barium titanate powder |
| JP2009209002A (en) * | 2008-03-04 | 2009-09-17 | Nippon Chem Ind Co Ltd | Method for producing perovskite-type barium titanate powder |
| JP2009209001A (en) * | 2008-03-04 | 2009-09-17 | Nippon Chem Ind Co Ltd | Method for producing perovskite-type barium titanate powder |
| JP2012116728A (en) * | 2010-12-03 | 2012-06-21 | Tdk Corp | Method for producing barium titanate, dielectric ceramic composition, and ceramic electronic component |
| JP2017071537A (en) * | 2015-10-09 | 2017-04-13 | 日本化学工業株式会社 | Method for producing barium titanate powder |
| TW201718434A (en) * | 2015-10-09 | 2017-06-01 | 日本化學工業股份有限公司 | Method for producing barium titanate powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5119008B2 (en) | 1973-04-02 | 1976-06-14 | ||
| JPS61146710A (en) | 1984-12-19 | 1986-07-04 | Central Glass Co Ltd | Production of fine barium titanate particle of high purity |
| TW527321B (en) | 2000-08-09 | 2003-04-11 | Samsung Electro Mech | A method for producing barium titanate based powders by oxalate process |
| JP2003212543A (en) | 2002-01-17 | 2003-07-30 | Samsung Electro Mech Co Ltd | Method for manufacturing barium titanate powder through oxalate |
| JP4759211B2 (en) | 2002-10-01 | 2011-08-31 | 日本化学工業株式会社 | Method for producing perovskite-type barium titanate powder |
| KR20080062631A (en) * | 2006-12-29 | 2008-07-03 | 건국대학교 산학협력단 | Process for preparing nano-sized titanate particles by flame spray pyrolysis |
| TW200838805A (en) | 2007-02-20 | 2008-10-01 | Nippon Chemical Ind | Amorphous fine-particle powder, process for production thereof and perovskite-type barium titanate powder made by using the same |
-
2017
- 2017-12-07 JP JP2017235032A patent/JP6573653B2/en active Active
-
2018
- 2018-10-29 KR KR1020207016425A patent/KR102536054B1/en active IP Right Grant
- 2018-10-29 CN CN201880078761.5A patent/CN111465580A/en active Pending
- 2018-10-29 WO PCT/JP2018/040087 patent/WO2019111586A1/en active Application Filing
- 2018-11-09 TW TW107139858A patent/TW201925095A/en unknown
Patent Citations (7)
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| US6066581A (en) * | 1995-07-27 | 2000-05-23 | Nortel Networks Corporation | Sol-gel precursor and method for formation of ferroelectric materials for integrated circuits |
| JP2005314153A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Chemical Co Ltd | Method of manufacturing barium titanate powder |
| JP2009209002A (en) * | 2008-03-04 | 2009-09-17 | Nippon Chem Ind Co Ltd | Method for producing perovskite-type barium titanate powder |
| JP2009209001A (en) * | 2008-03-04 | 2009-09-17 | Nippon Chem Ind Co Ltd | Method for producing perovskite-type barium titanate powder |
| JP2012116728A (en) * | 2010-12-03 | 2012-06-21 | Tdk Corp | Method for producing barium titanate, dielectric ceramic composition, and ceramic electronic component |
| JP2017071537A (en) * | 2015-10-09 | 2017-04-13 | 日本化学工業株式会社 | Method for producing barium titanate powder |
| TW201718434A (en) * | 2015-10-09 | 2017-06-01 | 日本化學工業股份有限公司 | Method for producing barium titanate powder |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019111586A1 (en) | 2019-06-13 |
| JP2019099440A (en) | 2019-06-24 |
| JP6573653B2 (en) | 2019-09-11 |
| KR20200096530A (en) | 2020-08-12 |
| KR102536054B1 (en) | 2023-05-24 |
| TW201925095A (en) | 2019-07-01 |
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