Method for continuous preparation of indium-tin coprecipitates and indium-tin-oxide nanopowders with substantially homogeneous indium/tin composition, controllable shape and particle size

• US 9,296,622 B2
• Filed: 11/07/2012
• Issued: 03/29/2016
• Est. Priority Date: 08/22/2012
• Status: Active Grant

• Current Assignee: CarbonMasters Coatings Ltd.
• Original Assignee: Hy-Power Coatings Limited
• Inventors: Mahabadi, Hadi K, Bravo-Vasquez, Juan-Pablo, Abraham, Sinoj, Gerein, Nathan, Ma, Guibun
• Primary Examiner(s): Ahvazi, Bijan
• Application Number:
  US13/671,150
• Publication Number:
  US 20140054521A1
• Time in Patent Office: 1,238 Days
• Field of Search: 106/286.4, 252/518.1, 252/520.1, 252/587, 423/594.9, 423/618, 427/62, 427/163.1, 427/165, 427/168, 427/162
• US Class Current: 1/1
• CPC Class Codes: B82Y 20/00 Nanooptics, e.g. quantum optics or photonic crystals
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 19/00 Compounds of tin
• CPC Class Codes: C01G 19/02 Oxides
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/76 by a space-group or by other symmetry indications
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/20 extending in two dimensions, e.g. plate-like
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/80 Compositional purity
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 2217/231 In2O3/SnO2
• CPC Class Codes: C03C 2218/114 by brushing, pouring or doctorblading
• CPC Class Codes: G02B 1/002 made of materials engineered to provide properties not available in nature, e.g. metamaterials
• CPC Class Codes: G02B 2207/101 Nanooptics
• CPC Class Codes: G02B 5/206 comprising particles embedded in a solid matrix
• CPC Class Codes: G02B 5/208 for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
• CPC Class Codes: H01B 1/08 : oxides

Abstract

Disclosed herein are indium-tin-oxide nanoparticles and a method for continuously producing precipitated indium-tin nanoparticles having a particle size range of substantially from about 10 nm to about 200 nm and a substantially consistent ratio of indium to tin in the resultant nanoparticles across the duration of the continuous process, based on the ratio of indium to tin in a seeding solution. The method comprises preparing intermediate indium and tin compounds of the general formula [M(OH)_xC_y], where M represents the indium or tin ionic component of indium or tin salts, C represents the cationic component of indium or tin salt(s), x is a number greater than 0 and y=[M*valance−x]/C* valance in the seeding solution. The intermediate compounds are continuously precipitated with a base solution in a reaction vessel initially having a solvent contained therein. The method also provides a means for controlling the shape of the resultant nanoparticles. The resultant indium-tin nanoparticles may be further processed into dispersions.

Claims

1. A process for preparing an indium-tin-oxide nanopowder having a substantially consistent indium-to-tin ratio, a desired particle size range and desired particle shape comprising:

a) preparing a seeding solution including at least one indium salt, at least one tin salt, at least one solubility modifier, and at least one base in a solvent so as to form a substantially clear solution of intermediate indium compounds and tin compounds having a general formula expressed as [M(OH)_xC_y], where M is an indium or tin ion, and C is the cationic part of the at least one indium salt or the least one tin salt, x is a number greater than 0 and y=[M valence−

x]/C valence;

b) adjusting the pH of the seeding solution and the concentration of the solubility modifier so as to solubilize the indium and tin intermediate compounds to near the onset of precipitation wherein the pH of the seeding solution is about 0 to about 3;

c) continuously introducing into a reaction vessel the seeding solution having the indium and tin intermediate compounds therein;

d) continuously introducing into the reaction vessel a base solution comprising one or more bases;

e) continuously mixing in the reaction vessel the seeding solution and the base solution such that the indium and tin intermediate compounds react with the base solution to form a mixture including crystalline and amorphous precipitated indium-tin nanoparticles, the rate of the introduction of the seeding solution and the base solution to the reaction vessel each being independently adjustable so as to maintain the pH of the mixture in the reaction vessel at a substantially constant pH of greater than about 3 and a substantially constant ratio of indium intermediate compounds to tin intermediate compounds in the mixture;

f) continuously collecting and removing from the reaction vessel a portion of the mixture having therein indium-tin precipitated nanoparticles;

g) washing and drying the removed indium-tin precipitated nanoparticles; and

h) heating the washed and dried indium-tin precipitated nanoparticles so as to obtain the indium-tin-oxide nanopowder.

2. The process according to claim 1, wherein the indium-tin-oxide is formed into a shape by molding or formed into a dispersion.

3. The process according to claim 2, wherein the dispersion is carried out in a dispersion solvent, the dispersion solvent being one of more of water;

methanol;

ethanol;

n- and isopropanol;

butanol;

glycols and glycol esters;

ethylene glycol;

propylene glycol;

butylene glycol and the corresponding di-, tri-, tetra-, penta-, or hexamers and the corresponding mono- or diethers, where one or both hydroxyl groups are replaced a methoxy, ethoxy, a propoxy, a butoxy group;

a ketone;

acetone;

butanone;

an ester;

ethyl acetate;

an ether;

diethyl ether;

tetrahydrofuran;

tetrahydropyran;

an amide;

dimethylacetamide;

dimethylformamide;

a sulphoxide;

a sulphone;

a sulpholane;

dimethyl sulphoxide;

an aliphatic hydrocarbon;

pentane;

hexane;

cyclohexanone;

a polyols;

2-methyl-2,4-pentanediol;

polyethylene glycols and ethers thereof;

diethylene glycol;

diethylene glycol;

tetraethylene glycol;

diethylene glycol diethyl ether;

tetraethylene glycol dimethyl ether;

diethylene glycol mono butyl ether;

ethylene glycol;

diethylene glycol;

diethylene glycol mono butyl ether;

3,6,9-trioxadecanoic acid;

beta-alanine;

polyoxyethylene(20);

sorbitan monooleate;

caprolactam;

citric acid;

glycolic acid or malic acid.

4. The process according to claim 2, wherein the dispersion is provided as a paste having, on a weight/weight basis, an indium-tin-oxide nanoparticle concentration of about 10% to about 80%.

5. The process according to claim 2, wherein the dispersion includes one more surfactants.

6. The process according to claim 5, wherein the one or more surfactant is selected from the group consisting of:

a cationic surfactant;

an anionic surfactant;

a non-ionic surfactant;

an amphoteric surfactant;

a saturated or unsaturated polyethylene oxide derivatives;

a (mono)carboxylic acid with the carboxylic acid having more than 7 carbon atoms, a (mono)carboxylic acid with the carboxylic acid having more than 11 carbon atoms;

stearic acid;

palmitic acid;

oleic acid;

sorbitan esters;

polyethylene oxide (mono)alkyl ethers with alcohols having more than 7 carbon atoms;

or polyethylene oxide (mono)alkyl ethers with alcohols having more than 11 carbon atoms, and mixtures thereof;

the one or more surfactant being present in the dispersion, on a weight/weight basis, in a concentration range of about 2% to about 40% of the total mass of the dispersion.

7. The process according to claim 1, wherein the pH and temperature of the mixture in the reaction vessel are maintained at predetermined levels during the continuous precipitation of the crystalline and amorphous indium-tin nanoparticles.

8. The process according to claim 7, wherein the pH of the mixture in the reaction vessel is maintained about 9 to about 13, the temperature of the reactant mixture is maintained at about 20°

C. to about 50°

C. and the crystalline and amorphous precipitated indium-tin nanoparticles are collected at a pH of about 9 to about 13.

9. The process according to claim 8, wherein the pH of the mixture is maintained at about 12 and the temperature of the mixture is about 20°

C. to about 24°

C.

10. The process according to claim 8, wherein the indium-tin-oxide nanoparticles are substantially spherically-shaped and have particle size range about 8 nm to about 200 nm.

11. The process according to claim 8, wherein the indium-tin-oxide nanoparticles are substantially spherically-shaped and have particle size range of about 8 nm to about 70 nm.

12. The process according to claim 7, wherein the pH of the mixture is maintained at about 3 to about 6, the temperature of the mixture is maintained at about 40°

C. to about 60°

C. and the crystalline and amorphous precipitated indium-tin nanoparticles are collected at a pH of about 9 to about 10;

the crystalline and amorphous precipitated indium-tin nanoparticles comprised of substantially plate-like-shaped nanoparticles having an average plate dimension of about 60 nm×

200 nm.

13. The process according to claim 1, wherein the at least one solubility modifier is provided in a ratio of about 0.75 moles to about 2.0 moles per mole of tin.

14. The process according to claim 1, wherein the at least one base to tin is provided in a molar ratio of about 0.5 to about 3.0.

15. The process according to claim 1, wherein the seeding solution of a);

the crystalline and amorphous precipitated indium-tin nanoparticles of e); and

the indium-tin-oxide nanopowder of h) have substantially the same ratio of indium to tin at any given time point in the continuous reaction.

16. The process according to claim 15, wherein the ratio of the at least one indium salt to the at least one tin salt in the seeding solution is about 5% to about 15%.

17. The process according to claim 15, wherein the seeding solution has a ratio of indium to tin of about 90:

10, the crystalline and amorphous precipitated indium-tin nanoparticles have a ratio of indium to tin of about 90;

10 which remains substantially consistent from one nanoparticle to another nanoparticle throughout the process and the indium-tin-oxide nanopowder has a ratio of indium to tin of about 90;

10.

18. The process according to claim 1, wherein:

the at least one indium salt is selected from the group consisting of;

indium (III) chloride, indium (I) chloride, indium (I) iodide, indium (III) iodide, indium (III) acetate, indium bromide, indium (III) nitrate, indium (III) sulfate, indium (III) alkoxides and mixtures thereof; and

wherein the at least one tin salt is selected from the group consisting of;

tin (II) chloride, tin (IV) chloride, tin (IV) sulfate, tin (II) sulfate, tin (IV) alkoxides, tin (II) alkoxides and mixtures thereof.

19. The process according to 1, wherein:

the at least one solubility modifier is selected from the group consisting of;

a carboxylic acid, hydroxy acid, amine, amide, do-decyl amine, decylamine, tartaric acid, citric acid, β

-alanine, methyl amine, ethyl amine, n- and i-propyl amine, butyl amine, poly-ethylene amine, caprolactam, nonanolactam and mixtures thereof; and

the at least one solubility modifier is present in a concentration of about 0.75 moles to about 2.0 moles per mole of tin.

20. The process according to claim 1, wherein:

the at least one base and the base solution is selected from the group consisting of;

sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, ammonia, a primary aliphatic amine, a secondary aliphatic amine, a tertiary aliphatic amine, a primary aromatic amine, secondary aromatic amine, a tertiary aromatic amine and mixtures thereof.

21. The process according to claim 1, wherein the mixture including crystalline and amorphous precipitated indium-tin nanoparticles has a residence time in the reaction vessel of about 15 minutes to about 300 minutes.

22. An indium-tin-oxide nanopowder produced according to the process of claim 1, wherein at least 90% of the indium-tin precipitated nanoparticles and the indium-tin-oxide nanoparticle powder particles have the same ratio of indium to tin as in the seeding solution within a measurement error of +/−

10 percent.

23. An indium-tin-oxide nanoparticle preparation according to the process of claim 1, which when entrained at a concentration of about 6%, on a weight/weight basis, in a given polymer coating material and applied to a glass substrate at a thickness of about 6 microns, blocks at least 90% of near infrared light at wavelengths of 1100 nm.