Method for preparing barium titanate powder by oxalate synthesis

• US 6,692,721 B2
• Filed: 01/15/2002
• Issued: 02/17/2004
• Est. Priority Date: 01/15/2002
• Status: Expired due to Fees

• Current Assignee: Samsung Electro-Mechanics Co., Ltd. (Samsung Group)
• Original Assignee: Samsung Electro-Mechanics Co., Ltd. (Samsung Group)
• Inventors: Lee, Jai Joon, Hur, Kang Heon
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US10/045,103
• Publication Number:
  US 20030133869A1
• Time in Patent Office: 763 Days
• Field of Search: 423/598, 423/71, 501/137
• US Class Current: 423/598
• CPC Class Codes: C01G 23/006 Alkaline earth titanates
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2006/10 Solid density
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/82 water content
• CPC Class Codes: C04B 2235/3215 Barium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3236 Alkaline earth titanates
• CPC Class Codes: C04B 2235/3262 Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
• CPC Class Codes: C04B 2235/449 Organic acids, e.g. EDTA, citrate, acetate, oxalate
• CPC Class Codes: C04B 2235/5445 submicron sized, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 2235/5481 Monomodal
• CPC Class Codes: C04B 2235/761 Unit-cell parameters, e.g. lattice constants
• CPC Class Codes: C04B 2235/79 Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1
• CPC Class Codes: C04B 2235/96 Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 35/4682 : based on BaTiO3 perovskite phase
• CPC Class Codes: C04B 35/62605 : Treating the starting powders individually or as mixtures
• CPC Class Codes: C04B 35/6262 : of calcined, sintered clinker or ceramics
• CPC Class Codes: C04B 35/62645 : Thermal treatment of powders or mixtures thereof other than sintering

Abstract

Disclosed is a method for preparing barium titanate powder by oxalate synthesis, whereby barium titanate powder or doped barium titanate powder with excellent powder properties can be produced at high efficiency and with economic benefit. An aqueous solution containing barium chloride and titanium chloride or further containing at least one dopant serving as a donor or acceptor is mixed with an aqueous oxalic acid solution to afford barium titanyl oxalate (BTO) or doped-BTO as a precipitate which is then aged, washed, and dried, followed by primary calcination and pulverization and secondary calcination and pulverization.

Claims

1. A method for preparing barium titanate by oxalate synthesis, comprising the steps of:

adding an aqueous barium chloride solution and an aqueous titanium chloride solution to an aqueous oxalic acid solution to give barium titanyl oxalate as a precipitate, aging, washing, filtering and drying the precipitate;

primary calcination of the barium titanyl oxalate, followed by primary pulverization to form fine barium titanyl powder; and

secondary calcination of the fine barium titanyl powder, followed by secondary pulverization.

2. The method as set forth in claim 1, wherein the aqueous barium chloride solution, the aqueous titanium chloride solution, and the aqueous oxalic acid solution range, in concentration, from 0.2 to 2.0 mol/l, from 0.2 to 2.0 mol/l, and from 0.2 to 5.0 mol/l, respectively.

3. The method as set forth in claim 1, wherein the adding step is carried out in such a way that the molar ratios of barium chloride to titanium chloride are in the range of 0.90-1.50 and the molar ratios of oxalic acid to titanium chloride are in the range of 1.0-5.0.

4. The method as set forth in claim 1, wherein the adding step is carried out by dropping a mixture of the aqueous barium chloride solution and the aqueous titanium chloride solution at a rate of 5-5,000 mL/min to the aqueous oxalic acid solution.

5. The method as set forth in claim 1, wherein the aqueous oxalic acid solution is maintained at 30-100°

C.

6. The method as set forth in claim 1, wherein the primary calcining step and the secondary calcining step are carried out at 500-1,100°

C. and at 900-1,300°

C., respectively.

7. The method as set forth in claim 1, wherein the barium titanyl oxalate is broken down into a mean particle size of 0.1-1.0 μ

m upon the primary pulverizing step and into a mean particle size of 0.1-5.0 μ

m upon the secondary pulverizing step.

8. A method for preparing barium titanate by oxalate synthesis, comprising the steps of:

dissolving at least one donor or acceptor in a mixture of an aqueous barium chloride solution and an aqueous titanium chloride solution to give a dopant element-containing solution, said donor or acceptor being in a form of oxides, hydroxides, carbonates, nitrides, sulfates or salts, and being selected from the group consisting of Y, La, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Rh, Ni, Cu, Zn, Ga and rare-earth elements;

adding the dopant element-containing solution to an aqueous oxalic acid solution to give doped-barium titanyl oxalate as a precipitate, aging, washing, filtering and drying the precipitate;

primary calcination of the doped-barium titanyl oxalate, followed by primary pulverization to form fine doped-barium titanyl powder; and

secondary calcination of the doped-fine barium titanyl powder, followed by secondary pulverization.

9. The method as set forth in claim 8, wherein the aqueous barium chloride solution, the aqueous titanium chloride solution, and the aqueous oxalic acid solution range, in concentration, from 0.2 to 2.0 mol/l, from 0.2 to 2.0 mol/l, and from 0.2 to 5.0 mol/l, respectively.

10. The method as set forth in claim 8, wherein the adding step is carried out in such a way that the molar ratios of barium chloride to titanium chloride are in the range of 0.90-1.50 and the molar ratios of oxalic acid to titanium chloride are in the range of 1.0-5.0.

11. The method as set forth in claim 8, wherein the adding step is carried out by dropping the dopant element-containing solution at a rate of 5-5,000 mL/min to the aqueous oxalic acid solution.

12. The method as set forth in claim 8, wherein the donor or acceptor is added in an amount of 10 mol % or less based on the moles of titanium.

13. The method as set forth in claim 8, wherein the primary calcining step and the secondary calcining step are carried out at 500-1,100°

C. and at 900-1,300°

C., respectively.

14. The method as set forth in claim 8, wherein the barium titanyl oxalate is broken down into a mean particle size of 0.1-1.0 μ

m upon the primary pulverizing step and into a mean particle size of 0.1-5.0 μ

m upon the secondary pulverizing step.