Process for preparing perovskite-type crystalline compound powders

• US 20060045840A1
• Filed: 08/29/2005
• Published: 03/02/2006
• Est. Priority Date: 02/28/2003
• Status: Abandoned Application

• Current Assignee: Beijing University of Chemical Technology, NanoMaterials Technology Pte Ltd
• Original Assignee: Beijing University of Chemical Technology, NanoMaterials Technology Pte Ltd
• Inventors: Chen, Jianfeng, Shen, Zhigang, Jimmy, Yun
• Application Number:
  US11/214,145
• Publication Number:
  US 20060045840A1
• Time in Patent Office: Days
• US Class Current: 423/598
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 1/02 Oxides
• CPC Class Codes: C01G 23/006 Alkaline earth titanates
• CPC Class Codes: C01G 25/006 Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01P 2002/34 perovskite-type (ABO3)
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C04B 2235/3213 Strontium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3215 Barium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3293 Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
• CPC Class Codes: C04B 2235/444 Halide containing anions, e.g. bromide, iodate, chlorite
• CPC Class Codes: C04B 2235/528 Spheres
• CPC Class Codes: C04B 2235/5454 nanometer sized, i.e. below 100 nm
• CPC Class Codes: C04B 2235/768 Perovskite structure ABO3
• CPC Class Codes: C04B 35/4682 based on BaTiO3 perovskite phase
• CPC Class Codes: C04B 35/49 containing also titanium oxides or titanates

Abstract

A process for preparing perovskite-type compound A_x(BO₃)_y powders involving reacting a solution containing A and a solution containing B, or a combined solution comprising A and B, with an alkaline solution in a high-gravity reactor at a temperature ranging from about 60° C. to about 100° C. A is one or more metal elements selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Pb, Sm, La, Nd, Bi, and other rare-earth metal elements. B is one or more metal elements selected from the group consisting of Ti, Zr, Sn, Hf, Nb, Ce, Al, Zn, Mn, Co, Ni, Fe, Cr, Y, Sc, W, Ta, and the like. The resulting mixture is then filtered, rinsed and dried to obtain the desired powders. The obtained perovskite-type compound A_x(BO₃)y powders have a small average particle size with a narrow particle size distribution, a perfect crystal form and a uniform particle shape, and is suitable for use as raw material for making dielectric, piezoelectric, anti-ferroelectric, pyroelectric, pressure-resisting, sensing, microwave media, and other ceramics.

Claims

1. A process for preparing perovskite-type compound A_x(BO₃)_y powders, comprising the steps of:

a) providing a solution containing cation A, a solution containing cation B, and an alkaline solution; and

b) reacting the solution containing cation A and the solution containing cation B with an alkaline solution, under a high-gravity field at a temperature of from about 60°

C. to about 100°

C.;

wherein A is a metal element selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Pb, Sm, La, Nd, Bi, and other rare-earth metal elements, and mixtures thereof;

wherein B is a metal element selected from the group consisting of Ti, Zr, Sn, Hf, Nb, Ce, Al, Zn, Mn, Co, Ni, Fe, Cr, Y, Sc, W, Ta, and mixtures thereof;

wherein x and y are numbers which balance the valence; and

provided that compound A_x(BO₃)_y is not BaTiO₃ and SrTiO₃.

2. The process according to claim 1, wherein the step of reacting is selected from:

1) reacting separately the solutions comprising cation A and cation B, with the alkaline solution;

2) reacting a combined solution comprising cation A and B, with the alkaline solution;

3) reacting a combined solution comprising cation A and the alkaline solution, with the solution containing cation B; and

4) reacting a combined solution comprising cation B and the alkaline solution, with the solution containing cation A.

3. The process according to claim 1, wherein said alkali is selected from the group consisting of hydroxides of alkali metals or alkali earth metals, ammonium hydroxide and tetramethylammonium hydroxide.

4. The process according to claim 2, wherein said alkali is selected from the group consisting of sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide.

5. The process according to claim 4, wherein A is a metal element selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Pb, Sm, La, Nd, and Bi, and mixtures thereof;

and B is a metal elements selected from the group consisting of Ti, Zr, Sn, Hf, Nb, Ce, Al, Zn, Mn, Co, Ni, Fe, Cr, Y, Sc, W, and Ta, and mixtures thereof.

6. The process according to claim 4, wherein A is selected from the group consisting of Mg, Ca, Sr, and Ba, and mixtures thereof;

and B is selected from the group consisting of Ti, Zr, and Sn, and mixtures thereof.

7. The process according to claim 1, wherein the compound supplying A is selected from the group consisting of chloride of A, nitrate of A, hydroxide of A, oxalate of A, perchloride of A, acetate of A, organic salt of strontium including alkoxide of strontium, and mixtures thereof;

and the compound supplying B is selected from the group consisting of chloride of B, nitrate of B, hydroxide of B, organic salt of B, and mixtures thereof.

8. The process according to claim 4, wherein the compound supplying A is selected from the group consisting of chloride of A, nitrate of A, hydroxide of A, oxalate of A, perchloride of A, acetate of A, organic salt of strontium including alkoxide of strontium, and mixtures thereof;

and the compound supplying B is selected from the group consisting of chloride of B, nitrate of B, hydroxide of B, organic salt of B, and mixtures thereof.

9. The process according to claim 5, wherein the compound supplying A is selected from the group consisting of chloride of A, nitrate of A, hydroxide of A, oxalate of A, perchloride of A, acetate of A, organic salt of strontium including alkoxide of strontium, and mixtures thereof;

and the compound supplying B is selected from the group consisting of chloride of B, nitrate of B, hydroxide of B, organic salt of B, and mixtures thereof.

10. The process according to claim 1, wherein the ratio of volume flow rate of the alkaline solution to the solution containing A, the ratio of volume flow rate of the alkaline solution to the solution containing B, and the ratio of volume flow rate of the alkaline solution to the mixture of solutions containing A and B, are each independently within the range from 0.5 to 1.0.

11. The process according to claim 5, wherein the ratio of volume flow rate of the alkaline solution to the solution containing A, the ratio of volume flow rate of the alkaline solution to the solution containing B, and the ratio of volume flow rate of the alkaline solution to the mixture of solutions containing A and B, are each independently within the range from 0.5 to 1.0.

12. The process according to claim 1, wherein the molar ratio of cation A to cation B ranges from 0.70 to 1.30.

13. The process according to claim 5, wherein the molar ratio of cation A to cation B ranges from 0.70 to 1.30.

14. The process according to claim 7, wherein the molar ratio of cation A to cation B ranges from 0.70 to 1.30.

15. The process according to claim 7, wherein the concentration of the solution containing Ti⁴⁺ ranges from 0.1 to 3.0 mol/L.

16. The process according to claim 10, wherein the concentration of the alkaline solution ranges from 0.5 to 15.0 mol/L.

17. The process according to claim 15, wherein the concentration of the alkaline solution ranges from 0.5 to 15.0 mol/L.

18. The process according to claim 4, wherein A is Sr, and the substance supplying Sr²⁺ is selected from the group consisting of strontium chloride, strontium nitrate, strontium hydroxide, strontium oxalate, strontium perchloride, strontium acetate, and organic salts of strontium including alkoxylates of strontium, and mixtures thereof;

and B is Ti, and the substance supplying Ti⁴⁺ is selected from the group consisting of titanium chloride, titanium nitrate, titanium hydroxide, titanium oxychloride, organic salts of titanium including alkoxylates of titanium, and mixtures thereof.

19. The process according to claim 1, wherein the high-gravity field comprises a centrifugal acceleration of about 20 to about 40,000 m/s².

20. A perovskite-type compound A_x(BO₃)_y powder, made according to the process of claim 1 wherein the powders consist essentially of spherical primary particles having an average size from 70 to 200 mm.