Powder of coagulated spherical zirconia particles and process for producing them

Claim 2

Powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed or primary particles of less than 500 Å in the crystallite size, and obtained by calcining ultrafine, zirconia particles with or without other metal compounds, said ultrafine zirconia particles being coagulated spherical zirconia particles having a coagulated particle size within a range from 0.2 μm to 3 μm and composed of monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other.

Claim 3

The powder of coagulated spherical particles according to claim 1, which contains another metal compound selected from the group consisting of salts, hydroxides and oxides of rare earth elements, alkaline earth metals and aluminum.

Claim 4

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm and composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing an aqueous solution of a zirconia salt under heating at a temperature from 90° to 250° C. and separating coagulated zirconia particles of greater than about 1000 Å in coagulated particle size from coagulated zirconia particles composed of ultrafine monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other prepared by the hydrolysis; (b) adding a zirconium salt and water to the thus separated coagulated particles to prepare an aqueous suspension having a pH lower than 1; (c) hydrolyzing the aqueous suspension under heating at a temperature from 90° to 250° C. to grow the particles and increase the particle size and thereafter, repeating once or more the procedures of adding the zirconium salt and applying hydrolysis under heating at a temperature from 90° to 250° C., thereby growing the particles into spherical particles of essentially uniform particle size within a range from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (d) drying the particles separated from the aqueous suspension to obtain a powder of ultrafine zirconia particles; and (e) calcining said ultrafine zirconia particles with or without other metal compounds at a temperature of less than 1000° C., and pulverizing the obtained calcined product.

Claim 5

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm and composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing an aqueous solution of a zirconia salt under heating at a temperature from 90° to 250° C. and separating coagulated zirconia particles of greater than about 1000 Å in coagulated particle size from coagulated zirconia particles composed of ultrafine monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other prepared by the hydrolysis; (b) adding a zirconium salt and water to the thus separated coagulated particles to prepare an aqueous suspension having a pH lower than 1; (c) hydrolyzing the aqueous suspension under heating at a temperature from 90° to 250° C. to grow the particles and increase the particle size and thereafter, repeating once or more the procedures of adding the zirconium salt and applying hydrolysis under heating at a temperature from 90° to 250° C., thereby growing the particles into spherical particles of essentially uniform particle size within a range from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (d) drying the particles separated from the aqueous suspension to obtain a powder of ultrafine zirconia particles; and (e) calcining said ultrafine zirconia particles with or without other metal compounds at a temperature of less than 1000° C., and pulverizing the obtained calcined product.

Claim 6

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed of primary particles of less than 500 Å in the crystallite size comprising: (a) adding an acid to a sol of coagulated zirconia particles of greater than about 1000 Å in the coagulated particle size composed of ultrafine monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other so that the acid concentration of the sol reaches higher than 1.5 N to precipitate temporarily coagulated particles containing those of from 0.2 μm to 3 μm in the coagulated particle size; (b) applying heat treatment at a temperature from 90° to 250° C. with or without adding a zirconium salt to the thus formed precipitated coagulated particles thereby separating spherical particles of from 0.2 μm to 3 μm in the particle size from the aqueous suspension; (c) drying the particles thus separated in the above step to obtain a powder of ultrafine zirconia particles; and (d) calcining ultrafine zirconia particles with or without other metal compounds at a temperature of less than 1000° C., and pulverizing the obtained calcined product.

Claim 7

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed of primary particles of less than 500 Å in the crystallite size comprising: (a) adding an acid to a sol of coagulated zirconia particles of greater than about 1000 Å in the coagulated particle size composed of ultrafine monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other so that the acid concentration of the sol reaches higher than 1.5 N to precipitate temporarily coagulated particles containing those of from 0.2 μm to 3 μm in the coagulated particle size; (b) applying heat treatment at a temperature from 90° to 250° C. with or without adding a zirconium salt to the thus formed precipitated coagulated particles thereby separating spherical particles of from 0.2 μm to 3 μm in the particle size from the aqueous suspension; (c) drying the particles thus separated in the above step to obtain a powder of ultrafine zirconia particles; and (d) calcining ultrafine zirconia particles with or without other metal compounds at a temperature of less than 1000° C., and pulverizing the obtained calcined product.

Claim 8

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing an acidic aqueous solution of a water soluble zirconium salt containing chlorides of one or more metals selected from the group consisting of aluminum, alkaline earth metals, alkali metals and rare earth elements at a high concentration of greater than 4 N in total under heating at a temperature from 90° C. to 250° C., thereby growing spherical particles from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (b) drying the grown particles separated in said step to obtain a powder containing ultrafine zirconia particles; and (c) calcining said ultrafine zirconia particles with or without other metal compounds at a temperature of less than 1000° C., and pulverizing the obtained calcined product.

Claim 9

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing an acidic aqueous solution of a water soluble zirconium salt containing chlorides of one or more metals selected from the group consisting of aluminum, alkaline earth metals, alkali metals and rare earth elements at a high concentration of greater than 4 N in total under heating at a temperature from 90° C. to 250° C., thereby growing spherical particles from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (b) drying the grown particles separated in said step to obtain a powder containing ultrafine zirconia particles; and (c) calcining said ultrafine zirconia particles with or without other metal compounds at a temperature of less than 1000° C., and pulverizing the obtained calcined product.

Claim 10

The process of claim 3, 4 or 5, wherein said zirconium salt is zirconium oxychloride, zirconium carbonate, zirconium nitrate or zirconium acetate.

Claim 11

The process of claim 3, 4 or 5, wherein the concentration of said zirconium salt in said aqueous solution is 0.05 to 2 mole/liter.

Claim 12

The process of claim 3 wherein the concentration of said zirconium salt in step (b) is 0.2 to 2 mole/liter.

Claim 13

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm and composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing a aqueous solution of a zirconium salt under heating at a temperature from 90° to 250° C. and separating coagulated zirconia particles of greater than about 1000 Å in coagulated particle size from coagulated zirconia particles composed of ultrafine monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other prepared by the hydrolysis; (b) adding a zirconium salt and water to the thus separated coagulated particles to prepare an aqueous suspension having a pH lower than 1; (c) hydrolyzing the aqueous suspension under heating at a temperature from 90° to 250° C. to grow the particles and increase the particle size, thereby growing the particles into spherical particles of essentially uniform particle size within a range from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (d) drying the particles separated from the aqueous suspension to obtain a powder of ultrafine zirconia particles; and (e) calcining said ultrafine zirconia particles with or without other metal compounds and pulverizing the obtained calcined product.

Claim 14

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm and composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing a aqueous solution of a zirconium salt under heating at a temperature from 90° to 250° C. and separating coagulated zirconia particles of greater than about 1000 Å in coagulated particle size from coagulated zirconia particles composed of ultrafine monoclinic primary particles of less than 100 Å in the crystallite size coagulated with each other prepared by the hydrolysis; (b) adding a zirconium salt and water to the thus separated coagulated particles to prepare an aqueous suspension having a pH lower than 1; (c) hydrolyzing the aqueous suspension under heating at a temperature from 90° to 250° C. to grow the particles and increase the particle size, thereby growing the particles into spherical particles of essentially uniform particle size within a range from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (d) drying the particles separated from the aqueous suspension to obtain a powder of ultrafine zirconia particles; and (e) calcining said ultrafine zirconia particles with or without other metal compounds and pulverizing the obtained calcined product.

Claim 15

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing and heating an acidic aqueous solution of a water soluble zirconium salt containing chlorides of one or more metals selected from the group consisting of aluminum, alkaline earth metals, alkali metals and rare earth elements at a high concentration of greater than 4 N under conditions which hinder the formation of new nuclei in the aqueous solution, thereby growing spherical particles having a uniform secondary coagulated particle size from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (b) drying the grown particles separated in said step to obtain a powder containing ultrafine zirconia particles; and (c) calcining said ultrafine zirconia particles with or without other metal compounds and pulverizing the obtained calcined product.

Claim 16

A process for producing calcined powder of coagulated spherical particles having a uniform secondary coagulated particle size of 0.2 μm to 3 μm composed of primary particles of less than 500 Å in the crystallite size comprising: (a) hydrolyzing and heating an acidic aqueous solution of a water soluble zirconium salt containing chlorides of one or more metals selected from the group consisting of aluminum, alkaline earth metals, alkali metals and rare earth elements at a high concentration of greater than 4 N under conditions which hinder the formation of new nuclei in the aqueous solution, thereby growing spherical particles having a uniform secondary coagulated particle size from 0.2 μm to 3 μm and separating the thus grown particles from the aqueous suspension; (b) drying the grown particles separated in said step to obtain a powder containing ultrafine zirconia particles; and (c) calcining said ultrafine zirconia particles with or without other metal compounds and pulverizing the obtained calcined product.

Claim 17

The process of claim 10, wherein said temperature is from 120° to 200° C.

Claim 18

The process of claim 10, wherein said coagulated spherical particles are composed of ultrafine crystalline primary particles of less than 100 Å.

Claim 19

A powder of spherical particles having a uniform secondary coagulated particle size produced by the process of claim 3, 4, 5, 8, 9, 10, 11 or 12.

Claim 20

The process of claim 5, which further comprises the steps of repeating the procedures of adding the grown particles thus obtained to the acidic aqueous solution of the zirconium salt in the step (a) and hydrolyzing the crystals under heating at a temperature from 90° C. to 250° C. thereby separating grown particles.