Copper oxide infrared pigment

Patent metadata

Field	Value
Publication number	US-9683107-B2
Application number	US-201515300821-A
Country	US
Kind code	B2
Filing date	Mar 19, 2015
Priority date	Apr 2, 2014
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

Copper oxide particles having particular starting size and surface area characteristics can be processed by heat and milling to achieve sizes and particle size distributions that give the copper oxide properties as an infrared reflective pigment without addition of other metals or oxides.

First claim

The invention claimed is:

1. A method of preparing an infrared reflective copper oxide pigment, comprising:
a. providing starting copper oxide particles that are at least 99% pure CuO and have the following characteristics:
i. D 10 particle size of 0.25-2 microns,
ii. D 50 particle size of 0.5-6 microns,
iii. D 90 particle size of 1-30 microns,
iv. span ΔD of 1-12,
v. specific surface area of 5-50 m 2 /g,
vi. a crystallite size of 1-19.5 nanometers,
vii. when present in an alkyd melamine paint, exhibit a total solar reflectance over black of less than 17,

b. heating the copper oxide particles at a temperature of 900° F. to 1600° F., for a time of 1-1000 minutes,
c. milling the copper oxide particles sufficiently to produce finished copper oxide particles having the following characteristics:
i. D 10 particle size of 0.3-2 microns,
ii. D 50 particle size of 0.6-3 microns,
iii. D 90 particle size of 0.9-5 microns,
iv. span ΔD of 0.7-3.0,
v. specific surface area of 2-10 m 2 /g,
vi. a crystallite size of 19.6-42 nanometers,
vii. when present in an alkyd melamine paint, exhibit a total solar reflectance over black of 17 or greater, and
viii. has a tint-strength of 60% to 150% relative to V-774 pigment when used in polyvinyl chloride.

2. The method of claim 1 , wherein the starting copper oxide particles have a specific surface area of 22-39 m 2 /g.

3. The method of claim 1 , wherein the starting copper oxide particles exhibit at least one characteristic selected from the group consisting of:
a. D 10 particle size of 0.3-1.5 microns,
b. D 50 particle size of 0.7-5.5 microns,
c. D 90 particle size of 1.5-25 microns,
d. specific surface area of 22-39 m 2 /g,
e. span ΔD of 1.3-10, and
f. crystallite size of 5 to 19 nanometers.

4. The method of claim 1 , wherein the starting copper oxide particles exhibit at least one characteristic selected from the group consisting of:
a. D 10 particle size of 0.4-1.2 microns,
b. D 50 particle size of 0.9-5.1 microns,
c. D 90 particle size of 2-22.2 microns,
d. span ΔD of 1.6-8.8, and
e. crystallite size of 10-18 nanometers.

5. The method of claim 1 , wherein the starting copper oxide particles are milled sufficiently to achieve at least one characteristic selected from the group consisting of:
a. D 10 particle size of 0.4-1.4 microns,
b. D 50 particle size of 0.7-2.2 microns,
c. D 90 particle size of 1-4 microns,
d. specific surface area of 2-10 m 2 /g,
e. span ΔD of 0.8-2.5, and
f. crystallite size of 22-40 nanometers.

6. The method of claim 1 , wherein the starting copper oxide particles are milled sufficiently to achieve at least one characteristic selected from the group consisting of:
a. D 10 particle size of 0.5-0.9 microns,
b. D 50 particle size of 0.8-1.5 microns, and
c. D 90 particle size of 1.3-2.8 microns,
d. specific surface area of 3-4.5 m 2 /g,
e. span ΔD of 0.9-1.4, and
f. crystallite size of 25-38.5 nanometers.

7. The method of claim 6 , wherein at least two said characteristics are achieved.

8. The method of claim 6 , wherein at least three said characteristics are achieved.

9. The method of claim 6 , wherein at least four said characteristics are achieved.

10. The method of claim 1 , wherein the starting copper oxide particles do not contain any intentional additions of any element selected from the group consisting of alkali metals, alkaline-earth metals, early transition metals, late transition metals, post-transition metals, poor metals, rare earths and metalloids.

11. The method of claim 1 , wherein there are no intentional additions of metal or metal oxides that would be sufficient to cause a transformation of copper(II) oxide away from a monoclinic crystal system.

12. The method of claim 1 , wherein the starting copper oxide particles do not contain any intentional additions of any metal selected from the group consisting of Bi, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Tc, Ru, Rh, Pd, Ag, and Cd.

13. The method of claim 1 , wherein the starting copper oxide particles further comprise up to a total of 1% of at least one element selected from the group consisting of Mg, Al, Si, In, Sn, Ce, Ta, and F or wherein said elements are intentionally added to the starting copper oxide particles.

14. The method of claim 1 , further comprising step (a1): combining with the starting copper oxide particles 0.001 to 0.4 wt % of a source of at least one selected from the group consisting of Mg, Al, Si, In, Sn, Ce, Ta, and F.

15. The method of claim 1 , further comprising step (a1): combining with the starting copper oxide particles 0.01-1 wt % of a source of at least one oxide selected from the group consisting of TiO 2 , ZnO, Bi 2 O 3 , and Nb 2 O 5 .

16. The method of claim 1 , wherein the starting copper oxide particles are provided by heat treatment of at least one copper compound wherein copper is in the +1 or +2 oxidation state and decomposes or oxidizes upon heating to copper (II) oxide.

17. A composition comprising particles made by the method of claim 1 , wherein the composition exhibits a total solar reflectance over black in accordance with ASTM E903, which is calculated based on standard reference spectral irradiance ASTM G173, of at least 17%.

18. The composition of claim 17 , wherein the composition exhibits at least one of the following: (a) CIELAB “L” masstone of 27 to 29, (b) “a” masstone of 0 to +1, and (c) “b” masstone of −1 to +0.5.

19. The composition of claim 18 , wherein the composition exhibits at least two of (a), (b) and (c).

20. A method of preparing an infrared reflective copper oxide pigment, comprising:
a. providing starting copper oxide particles that are at least 99% pure CuO and have the following characteristics:
i. D 10 particle size of 0.4-1.2 microns,
ii. D 50 particle size of 0.9-5.1 microns,
iii. D 90 particle size of 2.0-22.2 microns,
iv. span ΔD of 1.6-8.8,
v. specific surface area of 22-39 m 2 /g, and
vi. crystallite size of 10-18 nanometers,

b. heating the copper oxide particles at a temperature of 1100° F. to 1500° F., for a time of 20-120 minutes,
c. milling the copper oxide particles sufficiently to achieve at least one characteristic selected from the group consisting of:
i. D 10 particle size of 0.5-0.9 microns,
ii. D 50 particle size of 0.8-1.5 microns,
iii. D 90 particle size of 1.3-2.8 microns,
iv. span ΔD of 0.9-1.4 and
v. specific surface area of 3.0-4.5 m 2 /g, and
vi. crystallite size of 25-38.5 nanometers.

21. A copper oxide pigment having the following characteristics
a. D 10 particle size of 0.3-2 microns,
b. D 50 particle size of 0.6-3 microns,
c. D 90 particle size of 0.9-5 microns,
d. span ΔD of 0.7-3.0, and
e. specific surface area of 2-10 m 2 /g and
f. crystallite size of 19.6-42 nanometers.

22. A composition comprising the copper oxide pigment of claim 21 .

Assignees

• Ferro Corp

Inventors

• Milliken Elena D
• Detrie Terry J
• Sakoske George E

Classifications

• C08K2201/005

  Additives being defined by their particle size in general · CPC title

• C08K2201/006

  Additives being defined by their surface area · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title

• C01P2006/62

  L* (lightness axis) · CPC title

• C09C3/043

  Drying, calcination · CPC title