WO2013039108A1 - Procédé de production d'oxalate de baryum titanyle et procédé de production de titanate de baryum - Google Patents

Procédé de production d'oxalate de baryum titanyle et procédé de production de titanate de baryum Download PDF

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WO2013039108A1
WO2013039108A1 PCT/JP2012/073341 JP2012073341W WO2013039108A1 WO 2013039108 A1 WO2013039108 A1 WO 2013039108A1 JP 2012073341 W JP2012073341 W JP 2012073341W WO 2013039108 A1 WO2013039108 A1 WO 2013039108A1
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barium
titanyl oxalate
liquid
solution
oxalic acid
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PCT/JP2012/073341
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Japanese (ja)
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井上　秀樹
加藤　達也
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日本化学工業株式会社
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Priority to CN201280044902.4A priority Critical patent/CN103796956B/zh
Priority to KR1020147006674A priority patent/KR101904579B1/ko
Publication of WO2013039108A1 publication Critical patent/WO2013039108A1/fr

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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1

Definitions

  • the present invention particularly relates to a method for producing barium titanyl oxalate useful as a raw material for functional ceramics such as piezoelectric materials, optoelectronic materials, dielectric materials, semiconductors, and sensors, and a method for producing barium titanate using the same. is there.
  • barium titanate is produced by a solid phase method, a hydrothermal synthesis method, an alkoxide method, an oxalate method, or the like.
  • the solid phase method constituent raw material powders and the like are mixed, and the mixture is manufactured by a dry method in which the mixture is heated at a high temperature. Therefore, the obtained powder forms an agglomerate having an irregular shape and has desired characteristics. High temperature firing is necessary to achieve.
  • the hydrothermal synthesis method has a complicated synthesis process in spite of the advantages of good powder characteristics, and is inferior in productivity because of the use of an autoclave, and the production powder is expensive and not industrially advantageous.
  • the alkoxide method is difficult to handle starting materials, is expensive, and is not industrially advantageous.
  • Barium titanate obtained by the oxalate method can be manufactured at a low cost compared with hydrothermal synthesis method or alkoxide method, and compared with barium titanate manufactured by solid phase method, It has the feature that the composition is uniform.
  • a conventional oxalate method an aqueous solution of TiCl 4 and BaCl 2 is dropped into an H 2 C 2 O 4 aqueous solution while stirring to obtain barium titanyl oxalate, and the barium titanyl oxalate is baked. Is common (see, for example, Non-Patent Document 1 and Patent Document 1).
  • barium titanate obtained by the oxalate method exhibits excellent performance as a dielectric ceramic material, further improvement in performance is required due to the recent increase in required performance. It is known that the characteristic of barium titanate as a dielectric ceramic is generally high in crystallinity and has good dielectric characteristics (see, for example, JP-A-2006-117446).
  • the present inventors examined barium titanyl oxalate obtained by a conventional method, and these barium titanyl oxalates have a bulk Ba / Ti molar ratio of about 0.998 to 1.002.
  • the Ba / Ti molar ratio for each particle size varies, and the smaller the Ba / Ti molar ratio (in other words, the larger the specific surface area), while the smaller the Ba / Ti molar ratio (in other words, the larger the particle size). And “the smaller the specific surface area”), the Ba / Ti molar ratio was found to be large. For this reason, the oxalate method has found that it is difficult to obtain barium titanate having a small particle size and a Ba / Ti molar ratio of about 0.998 to 1.002 and high crystallinity.
  • an object of the present invention is to provide a method for producing barium titanyl oxalate capable of obtaining barium titanate having excellent crystallinity despite the small particle size by the oxalate method. Furthermore, it is providing the method which can manufacture the barium titanate which was excellent in crystallinity with the fine particle.
  • the present inventors have added an aqueous solution (liquid B) containing titanium tetrachloride to a reaction containing at least oxalic acid and barium chloride (liquid A).
  • liquid B aqueous solution
  • barium titanyl oxalate having a Ba / Ti molar ratio of 0.998 to 1.002
  • the barium titanyl oxalate should be used.
  • barium titanate having high crystallinity can be obtained even though the particle size is small, it has been found that a dielectric ceramic material having excellent performance can be provided, and the present invention has been completed.
  • the first invention to be provided by the present invention is characterized in that an aqueous solution (liquid B) containing titanium tetrachloride is added to a solution (liquid A) containing at least oxalic acid and barium chloride to carry out the reaction. And a method for producing barium titanyl oxalate.
  • the second invention to be provided by the present invention is a method for producing barium titanate characterized by firing the barium titanyl oxalate obtained by the first invention.
  • the production method of the present invention is characterized in that an aqueous solution (liquid B) containing titanium tetrachloride is added to a solution (liquid A) containing at least oxalic acid and barium chloride to carry out the reaction.
  • the barium titanyl oxalate produced according to the production method of the present invention preferably has a Ba to Ti molar ratio (hereinafter referred to as “Ba / Ti molar ratio”) of 0.998 to 1.002, preferably about 1.
  • Ba / Ti molar ratio Ba to Ti molar ratio
  • the solution A used in the present invention is a solution containing at least oxalic acid and barium chloride.
  • the liquid A according to the present invention can contain barium oxalate as a component other than water, oxalic acid and barium chloride, and further a chlorine ion source such as hydrochloric acid.
  • the mixing ratio of oxalic acid and barium chloride of liquid A, or oxalic acid, barium chloride and barium oxalate, and the chlorine ion source to liquid A is determined by the concentration of oxalic acid and barium in liquid A and the concentration of oxalic acid and barium. If the molar ratio and further the chlorine ion concentration is within the range described later, the blending ratio of each raw material is not particularly limited.
  • the composition in the liquid A is 0.7 to 2.5 mol / L, preferably 1.0 to 2.2 mol / L in terms of oxalic acid (H 2 C 2 O 4 ), and 0.4 to 0.4 in terms of Ba.
  • the chlorine ion concentration in the liquid A is 0.7 to 2.5 mol / L, preferably 1.0 to 2.2 mol / L in terms of Cl, and the Ba / Ti molar ratio is high with a high yield. From the viewpoint that approximately 1 and fine barium titanyl oxalate can be obtained.
  • a solution obtained by contacting oxalic acid and barium chloride in an aqueous solvent can be used as it is.
  • oxalic acid and barium chloride are brought into contact with each other in an aqueous solvent, oxalic acid and barium chloride partially react to precipitate fine barium oxalate.
  • the composition of the liquid A at this time is water, oxalic acid, barium chloride, and further contains barium oxalate and hydrochloric acid as other components.
  • the liquid is particularly preferably used from the viewpoint that the reactivity with titanium tetrachloride is high and the target barium titanyl oxalate can be obtained in a high yield.
  • the mixing ratio of oxalic acid and barium chloride may be in a range such that the concentration of oxalic acid and barium in the liquid A, the molar ratio of oxalic acid and barium, and the chlorine ion concentration are within the above ranges.
  • the contact of the oxalic acid and barium chloride relating to the preparation of the liquid A can be performed with stirring to obtain a suspension in which the precipitated fine barium oxalate is uniformly dispersed.
  • the contact temperature is not particularly limited, and in many cases, it is 100 ° C. or less, preferably about room temperature (15 to 30 ° C.).
  • the contact time between oxalic acid and barium chloride in the preparation of solution A is not particularly limited, but in many cases, a solution A having satisfactory physical properties can be obtained in 0.25 hours or more, preferably 0.5 to 2 hours. It is done.
  • Examples of contact methods of oxalic acid and barium chloride include 1) a method of adding barium chloride as an aqueous solution or powder to an oxalic acid aqueous solution, and 2) a method of adding oxalic acid as an aqueous solution or powder to an aqueous barium chloride solution. 3) A method of adding oxalic acid and barium chloride to a container charged with water, 4) A method of adding water to a container charged with oxalic acid and barium chloride, etc. Thus, an advantageous method can be selected as appropriate.
  • the B solution used in the present invention is an aqueous solution containing titanium tetrachloride.
  • concentration of titanium tetrachloride in the liquid B is 0.1 to 1.2 mol / L, particularly 0.3 to 1.0 mol / L as Ti
  • the Ba / Ti molar ratio is about 1 with high yield.
  • the chlorine ion concentration in the B liquid is 0.7 to 2.5 mol / L, preferably 1.0 to 2.2 mol / L in terms of Cl, with a high yield, fine particles, and Ba From the viewpoint of obtaining barium titanyl oxalate having a / Ti molar ratio of about 1.
  • the ratio of the chlorine ion concentration in the liquid B to the chlorine ion concentration in the liquid A (B / A) is 0.
  • the Ba / Ti molar ratio is 0.998 to 1 It is easy to obtain 0.002 and preferably about 1 barium titanyl oxalate.
  • a chlorine ion source can be added to A liquid and B liquid for adjustment of chlorine ion concentration. Examples of the chlorine ion source include hydrochloric acid, sodium chloride, potassium chloride, lithium chloride, organic compounds containing chlorine ions, and the like.
  • the liquid B is added to the liquid A to react. Addition of B liquid to A liquid is carried out so that the molar ratio of barium atoms to titanium atoms in the reaction liquid after addition is 1.0 to 1.5, particularly 1.1 to 1.3. Since barium titanyl oxalate having a Ti molar ratio of about 1 is obtained in a high yield, it is preferable.
  • the addition rate is appropriately selected depending on the size of the reaction vessel, the amount of the reaction solution, and the like. For example, at the laboratory level of 0.5 L scale, the addition rate of solution B is 5 L / hour or more, preferably 8 to 11 L. / Hour is preferable.
  • the addition temperature of the B liquid to the A liquid is 40 ° C. or less, preferably 25 to 40 ° C. In the oxalate method, this addition temperature is often performed at a temperature of 50 ° C. or higher, but in this production method, the elution of Ba from the barium titanyl oxalate produced by lowering the addition temperature to 40 ° C. Since it can suppress and the change of the molar ratio of fine barium titanyl oxalate can be suppressed, it becomes easy to obtain a Ba / Ti molar ratio closer to 1.
  • the temperature of the B liquid is not particularly limited, but it is preferable that the temperature is within the same range as the temperature of the A liquid because the reaction operation becomes easy.
  • the B liquid is added to the A liquid with stirring.
  • the agitation is strengthened to cause a rapid reaction, thereby suppressing the nucleus growth and obtaining a finer powder.
  • the stirring speed is appropriately selected depending on the size of the reaction vessel, the diameter of the stirring blade, the amount of the reaction solution, and the like. For example, on the basis of a laboratory level of 0.5 L scale, the peripheral speed of the stirring blade is 0.5.
  • the peripheral speed of the stirring blade is particularly preferably 1.6 to 1.8 m / sec.
  • the aging temperature is not particularly limited, but is preferably the same as the reaction temperature for easy operation.
  • the aging time is not particularly limited, but in many cases it is 0.5 hours or longer, preferably 0.5 to 2 hours.
  • the solid and liquid are separated by a conventional method and then washed with water.
  • the cleaning method is not particularly limited. Washing with repulp or the like is preferable because the washing efficiency is good. Next, it is dried and, if necessary, ground or crushed to obtain barium titanyl oxalate.
  • an average particle size determined by a laser diffraction / scattering method is 4 ⁇ m or less, preferably 0.1 to 4 ⁇ m.
  • the composition of the barium titanyl oxalate has a Ba / Ti molar ratio of 0.998 to 1.002, preferably about 1.
  • the barium titanyl oxalate obtained by the production method of the present invention can be suitably used as a production raw material for a barium titanate ceramic as a dielectric ceramic material.
  • the manufacturing method of the barium titanate of this invention is as follows.
  • the method for producing barium titanate according to the present invention is characterized in that barium titanyl oxalate obtained by the above-mentioned method is fired.
  • ⁇ Organic material derived from oxalic acid contained in the final product is not preferable because it impairs the dielectric properties of the material and causes unstable behavior in the thermal process for ceramicization. Therefore, in the present invention, it is necessary to thermally decompose barium titanyl oxalate by firing to obtain the target barium titanate and to sufficiently remove organic substances derived from oxalic acid.
  • the firing conditions are such that the firing temperature is preferably 600 to 1200 ° C., more preferably 700 to 1100 ° C. When the firing temperature is less than 600 ° C., it is difficult to obtain single-phase barium titanate. On the other hand, when the firing temperature exceeds 1200 ° C., the variation in particle diameter increases.
  • the firing time is preferably 2 to 30 hours, more preferably 5 to 20 hours.
  • the firing atmosphere is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the air, or firing is performed in the atmosphere while introducing water vapor. May be.
  • Calcination may be performed as many times as desired.
  • the fired material may be pulverized and then refired.
  • the barium titanate powder obtained by firing is fragile and in a block shape, and the barium titanate particles themselves have the following specific average particle diameter and BET specific surface area. It is what you have. That is, the barium titanate powder obtained above has an average particle size determined from a scanning electron micrograph (SEM) of preferably 0.5 ⁇ m or less, more preferably 0.05 to 0.5 ⁇ m.
  • SEM scanning electron micrograph
  • the BET specific surface area is preferably 2 to 20 m 2 / g, more preferably 2.0 to 10 m 2 / g.
  • the composition of barium titanate obtained by the production method of the present invention is preferably such that the molar ratio of Ba to Ti (Ba / Ti) is 0.998 to 1.002, particularly about 1. Further, it is more preferable that the c-axis / a-axis ratio serving as an index of crystallinity is 1.007 or higher, preferably 1.0085 or higher.
  • the barium titanate obtained by carrying out the method for producing barium titanate of the present invention is prepared by adding the subcomponent element-containing compound to the method for producing barium titanate of the present invention for the purpose of adjusting dielectric properties and temperature characteristics as necessary.
  • subcomponent elements can be contained.
  • the subcomponent element-containing compound that can be used include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu rare earth elements. At least one selected from the group consisting of Ba, Li, Bi, Zn, Mn, Al, Si, Ca, Sr, Co, Ni, Cr, Fe, Mg, Ti, V, Nb, Mo, W and Sn Examples include compounds containing elements.
  • the subcomponent element-containing compound may be either inorganic or organic. Examples thereof include oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates and alkoxides containing the above elements.
  • the sub-component element-containing compound is a compound containing Si element, silica sol, sodium silicate, or the like can be used in addition to the oxide or the like.
  • the subcomponent element-containing compounds can be used alone or in combination of two or more. What is necessary is just to perform the combination of the addition amount and an addition compound according to a conventional method.
  • barium titanate and the subcomponent element-containing compound may be uniformly mixed and then fired.
  • baking may be performed after uniformly mixing barium titanyl oxalate and the subcomponent element-containing compound.
  • a multilayer ceramic capacitor using the barium titanate obtained by the method for producing barium titanate according to the present invention, first, a known addition of barium titanate powder including subcomponent elements is added. A sheet is formed by mixing and dispersing in a suitable solvent together with a compounding agent such as an agent, an organic binder, a plasticizer, and a dispersant. Thereby, the ceramic sheet used for manufacture of a multilayer ceramic capacitor is obtained.
  • an internal electrode forming conductive paste is printed on one surface of the ceramic sheet. After drying, a plurality of the ceramic sheets are laminated and pressed in the thickness direction to obtain a laminated body. Next, this laminate is heat treated to remove the binder, and fired to obtain a fired body. Furthermore, Ni paste, Ag paste, nickel alloy paste, copper paste, copper alloy paste, and the like are applied to the fired body and baked to obtain a multilayer ceramic capacitor.
  • the barium titanate powder obtained by carrying out the method for producing barium titanate of the present invention is blended with a resin such as an epoxy resin, a polyester resin, a polyimide resin, etc., and a resin sheet, a resin film, an adhesive, etc. Then, it can be used as a material for printed wiring boards and multilayer printed wiring boards, as well as co-materials for suppressing shrinkage differences between internal electrodes and dielectric layers, electrode ceramic circuit boards, glass ceramic circuit boards, circuit peripherals It can also be used as a dielectric material for materials and inorganic EL.
  • a resin such as an epoxy resin, a polyester resin, a polyimide resin, etc.
  • the barium titanate obtained by the method for producing barium titanate of the present invention is a catalyst used in reactions such as exhaust gas removal and chemical synthesis, and surface modification of printing toner that imparts antistatic and cleaning effects. It is suitably used as a material.
  • the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder.
  • Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
  • the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder.
  • Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
  • the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder.
  • Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
  • the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder.
  • Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
  • the oxalic acid concentration in the table indicates the concentration of oxalic acid dihydrate.
  • Oxalic acid in the table indicates dihydrate.
  • BTO indicates barium titanyl oxalate.
  • the barium titanyl oxalate obtained in the examples has an average particle size of 4 ⁇ m or less determined by the laser diffraction / scattering method, and the composition of the barium titanyl oxalate has a Ba / Ti molar ratio of 1. It was approximately 1 between 0.000 and 1.002. From Table 3, the barium titanyl oxalate obtained in the comparative example has an average particle size larger than 4 ⁇ m determined by the laser diffraction / scattering method, and the composition of the barium titanyl oxalate has a Ba / Ti molar ratio of 0. .997 to 1.001.
  • BTO indicates barium titanyl oxalate.
  • BT represents barium titanate.
  • the one using barium titanyl oxalate (Example 15) obtained in the present invention has a c-axis / a-axis ratio as compared with the comparative example. It can be seen that high barium titanate is obtained. It can also be seen that the barium titanate obtained even when the firing temperature is lowered to 875 ° C. (Example 16) has a high c-axis / a-axis ratio of 1.0085 or more.
  • the present invention it is possible to provide approximately 1 barium titanyl oxalate having a Ba / Ti molar ratio of 0.998 to 1.002 even when the average particle size is as small as 4 ⁇ m or less.
  • barium titanyl oxalate By using such barium titanyl oxalate, a dielectric ceramic material having high crystallinity and excellent performance can be provided by the oxalate method even though the particle size is small.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production d'oxalate de baryum titanyle, dans lequel il est possible d'obtenir un titanate de baryum présentant une excellente cristallinité indépendamment du petit diamètre de particules au moyen d'une technique à l'oxalate. L'invention concerne également un procédé de production de titanate de baryum fin présentant une excellente cristallinité. Le procédé de production d'oxalate de baryum titanyle est caractérisé en ce qu'une solution aqueuse (solution B) comprenant un tétrachlorure de titane est ajoutée et mise à réagir avec une solution (solution A) contenant au moins un acide oxalique et un chlorure de baryum ; et, la solution A est obtenue de préférence en amenant l'acide oxalique et le chlorure de baryum en contact l'un avec l'autre dans un solvant aqueux.
PCT/JP2012/073341 2011-09-15 2012-09-12 Procédé de production d'oxalate de baryum titanyle et procédé de production de titanate de baryum WO2013039108A1 (fr)

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CN201280044902.4A CN103796956B (zh) 2011-09-15 2012-09-12 草酸氧钛钡的制造方法和钛酸钡的制造方法
KR1020147006674A KR101904579B1 (ko) 2011-09-15 2012-09-12 옥살산바륨티타닐의 제조 방법 및 티탄산바륨의 제조 방법

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CN107311224A (zh) * 2017-07-14 2017-11-03 安徽拓吉泰新型陶瓷科技有限公司 一种钛酸钡粉体的制备方法

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JP6217599B2 (ja) * 2014-11-17 2017-10-25 株式会社村田製作所 チタン酸バリウム系粉末の製造方法
JP7102462B2 (ja) * 2020-06-12 2022-07-19 日本化学工業株式会社 シュウ酸バリウムチタニル、その製造方法及びチタン酸バリウムの製造方法
WO2022107695A1 (fr) * 2020-11-19 2022-05-27 日本化学工業株式会社 Procédé de production d'oxalate de baryum titanyle et procédé de production de titanate de baryum
JP7110306B2 (ja) * 2020-11-19 2022-08-01 日本化学工業株式会社 シュウ酸バリウムチタニルの製造方法及びチタン酸バリウムの製造方法
JP7110305B2 (ja) * 2020-11-19 2022-08-01 日本化学工業株式会社 シュウ酸バリウムチタニルの製造方法及びチタン酸バリウムの製造方法

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JPH03103323A (ja) * 1989-09-14 1991-04-30 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JPH03103322A (ja) * 1989-09-14 1991-04-30 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JP2012077068A (ja) * 2010-09-07 2012-04-19 Nippon Chem Ind Co Ltd シュウ酸バリウムチタニル粒子、その製造方法及びチタン酸バリウムの製造方法

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KR100434883B1 (ko) 2001-08-14 2004-06-07 삼성전기주식회사 티탄산바륨계 파우더의 제조방법
CN1712356A (zh) * 2004-06-21 2005-12-28 肇庆羚华有限责任公司 制备钛酸钡粉末的反应装置、所用方法及所得产品

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JPH0388720A (ja) * 1989-08-30 1991-04-15 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JPH03103323A (ja) * 1989-09-14 1991-04-30 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JPH03103322A (ja) * 1989-09-14 1991-04-30 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JP2012077068A (ja) * 2010-09-07 2012-04-19 Nippon Chem Ind Co Ltd シュウ酸バリウムチタニル粒子、その製造方法及びチタン酸バリウムの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107311224A (zh) * 2017-07-14 2017-11-03 安徽拓吉泰新型陶瓷科技有限公司 一种钛酸钡粉体的制备方法

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CN103796956A (zh) 2014-05-14
JP2013063867A (ja) 2013-04-11

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