Doped zinc oxide-based pigment

• US 5,094,693 A
• Filed: 02/20/1990
• Issued: 03/10/1992
• Est. Priority Date: 02/20/1990
• Status: Expired due to Fees

• Current Assignee: International Lead Zinc Research Organisation Inc.
• Original Assignee: International Lead Zinc Research Organisation Inc.
• Inventors: Cordaro, James F., Rafla-Yuan, Howard C.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): Jones, Deborah
• Application Number:
  US07/482,161
• Time in Patent Office: 749 Days
• Field of Search: 106/425, 106/426, 423/622, 252/62.3 ZT
• US Class Current: 106/425
• CPC Class Codes: C01P 2002/50 Solid solutions
• CPC Class Codes: C01P 2002/70 defined by measured X-ray, neutron or electron diffraction data
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 9/02 Ingredients treated with inorganic substances
• CPC Class Codes: C09C 1/04 Compounds of zinc C09C1/0003, C09C1/0009, C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/043 Zinc oxide
• CPC Class Codes: C09D 7/48 Stabilisers against degradation by oxygen, light or heat

Abstract

There is disclosed a doped zinc oxide pigment composition and method of preparing said composition, wherein the dopant is uniformly dispersed in the zinc oxide matrix in the form of a solid solution such that the mechanism by which undoped zinc oxide absorbs blue or near ultraviolet light is suppressed, thereby yielding a whiter composition. Preferred dopants are Al and Li.

Claims

1. A substantially pure white doped zinc oxide pigment composition, said composition comprising a matrix of substantially pure zinc oxide and a dopant, said dopant containing at least one of the elements selected from the gorup B, Al, Ga, In, Sc, Y, La, H, Li, Na and K, and being distributed throughout the zinc oxide so as to form a substantially homogeneous alloy, said dopant being present in an amount sufficient to render said composition substantially resistant to radiation-induced discoloration.

2. A doped zinc oxide pigment composition according to claim 1 wherein the concentration of said dopant is from about 0.001 mol % to about 10 mol %.

3. A doped zinc oxide pigment composition according to claim 2 wherein the dopant is present in the zinc oxide in the form of a solid solution.

4. A doped zinc oxide pigment composition according to claim 1 wherein the dopant functions to supprses the formation of oxygen vacancies or zinc interstitials in the zinc oxide, thereby rendering the zinc oxide more stoichiometric and less yellow than substantially pure zinc oxide without said dopant.

5. A doped zinc oxide pigment composition according to claim 1 wherein the dopant functions as a free electron donor.

6. A doped zinc oxide pigment composition according to claim 1 wherein the dopant is aluminum.

7. A doped zinc oxide pigment composition according to claim 1 wherein the dopant is Li.

8. A doped zinc oxide pigment composition according to claim 1 wherein the dopant is In.

11. In a ceramic glaze composition containing a pigment, the improvement wherein the pigment is the doped zinc oxide pigment composition according to claim 1.

12. In a liquid paint composition comprising a liquid pain vehicle and a pigment, the improvement wherein the pigment is the doped zinc oxide pigment composition according to claim 1.

13. The liquid paint composition according to claim 12 wherein said liquid paint vehicle includes an interior or exterior latex-based vehicle.

14. The liquid paint composition according to claim 12 wherein said liquid paint vehicle includes an silicate-based vehicle.

9. A substantially pure white doped zinc oxide pigment composition, said composition comprising a matrix of substantially pure zinc oxide and from about 0.001 mol % to about 10 mol % of dopant, said dopant containing at least one of the elements selected from the group B, Al, Ga, In, Sc, Y, La, H, Li, Na and K, and being present in an amount sufficient to suppress the formation of oxygen vacancies or zinc interstitials in the zinc oxide, thereby rendering the zinc oxide more stoichiometric and resistant to radiation induced yellowing.

15. In a paint composition comprising a liquid paint vehicle and a pigment, the improvement wherein the pigment is the doped zinc oxide pigment composition according to claim 9.

16. The paint composition according to claim 15 wherein said liquid paint vehicle includes an interior or exterior latex-based vehicle.

17. The paint composition according to claim 15 wherein said liquid paint vehicle includes a silicate-based vehicle.

10. A substantially pure white doped zinc oxide pigment composition, said composition comprising a matrix of substantially pure zinc oxide and from about 0.001 mol % to about 10 mol % of dopant, said dopant containing at least one of the elements selected from the group B, Al, Ga, In, Sc, Y, La, H, Li, Na and K, and being present in an amount sufficient to raise the Fermi level of the composition beyond that of undoped zinc oxide, thereby suppressing electron ransitions which cause the zinc oxide to absorb blue or near ultraviolet light and thereby appear yellow.

18. In a paint composition comprising a liquid paint vehicle and a pigment, the improvement wherein the pigment is the doped zinc oxide pigment composition according to claim 10.

19. The paint composition according to claim 18 wherien said liquid paint vehicle includes an interior or exterior latex-based vehicle.

20. The paint composition according to claim 18 wherein said liquid paint vehicle includes a silicate-based vehicle.

21. A method of preparing a substantially pure white doped zinc oxide pigment composition comprising the steps of dissolving from about 0.001 mol % to about 10 mol %, relative to the mole % of zinc oxide to be added, of a dopant in a solvent, said dopant containing at least one of the elements selected from the group B, Al, Ga, In, Sc, Y, La, H, Li, Na and K, and;

dispersing from about 99.999 mol % to about 90 mol % zinc oxide in said solvent so as to form a slurry;

drying said slurry so as to drive off substantially all of said solvent; and

calcining said dried composition to (a) drive off substantially all carbon and hydrogen which may be present in said dopant and (b) to diffuse the dopant into the zinc oxide thereby obtaining a substantially pure white doped zinc oxide with said dopant present therein in solid solution, said doped zinc oxide being substantially resistant to radiation induced discoloration.

22. A method of preparing a doped zinc oxide pigment composition according to claim 21 wherein the dopant is capable of functioning as a free electron donor such that said composition is less yellow than substantially pure zinc oxide without said dopant.

24. A method of preparing a substantially pure white doped zinc oxide pigment composition according to claim 21 including the steps of dissolving aluminum acetylacetonate in an alcohol solvent so as to form a solution;

uniformly dispersing zinc oxide in said solution to form a slurry;

drying the slurry so as to form a powder;

calcining the powder at at least 650°

C. for a period of at least 8 hours;

thereby forming doped zinc oxide pigment composition having from about 0.001 mol % to about 10 mol % aluminum in solid solution as a dopant, said doped zinc oxide being substantially resistant to radiation induced discoloration.

25. A method of preparing a doped zinc oxide pigment composition according to claim 21 including the step of adjusting the pH of the slurry to at least pH 8 prior to drying and calcining.

26. A method of preparing a doped zinc oxide pigment composition according to claim 21 wherein the pH is adjusted by the addition of NH₄ OH.

23. A method of preparing a doped zinc oxide pigment composition according to cliam 21 wherein the dopant is aluminum.

27. A method of preparing a substantially pure white doped zinc oxide pigment compositino including the steps of heating metallic zinc and a dopant to a temperature sufficient to cause zinc and dopant vapor to be formed, said dopant containing at least one of the elements selected from the group B, Al, Ga, In, Sc, Y, La, Li, Na and K,

contacting the zinc and dopant vapor with oxygen so as to burn said vapor and form a mixture of zinc oxide and an oxide of the dopant,

and collecting said mixture as solid particles, said solid particles being substantially resistant to radiation induced discoloration.