Optically black coating and process for forming it

• US 4,111,762 A
• Filed: 01/13/1977
• Issued: 09/05/1978
• Est. Priority Date: 01/31/1975
• Status: Expired due to Term

• Current Assignee: Martin Marietta Corporation
• Original Assignee: Martin Marietta Corporation
• Inventors: Wade, Jackie F., Klitzky, Bruce R., Groff, Roy E., Peyton, John E.
• Primary Examiner(s): Andrews, R. L.
• Application Number:
  US05/758,951
• Time in Patent Office: 600 Days
• Field of Search: 204/58, 204/35 N, 204/33, 204/29
• US Class Current: 205/208
• CPC Class Codes: C25D 11/08 containing inorganic acids
• CPC Class Codes: C25D 11/16 Pretreatment , e.g. desmutting
• CPC Class Codes: C25D 11/18 After-treatment, e.g. pore-sealing
• CPC Class Codes: C25D 11/24 Chemical after-treatment
• CPC Class Codes: F24S 70/225 for spectrally selective absorption
• CPC Class Codes: F24S 70/25 Coatings made of metallic material
• CPC Class Codes: Y02E 10/40 Solar thermal energy, e.g. solar towers

Abstract

A product capable of extremely high absorption of electromagnetic radiation, including visible light, useful in optical applications and as a decorative panel comprises a body made of anodizable metal, preferably aluminum having a roughened surface over which an oxide layer is deposited by anodization. The anodized surface is characterized by a roughened surface of pronounced peaks and valleys and a columnar, fault-ridden structure of the anodized oxide layer itself.

The product is made by honing the anodizable metal surface by impacting it with aluminum oxide particles, preferably of 100 to 200 mesh size, to form peaks and valleys thereon. After honing, the surface is anodized under controlled conditions to develop the oxide layer thereover. After anodizing, the surface may be dyed and sealed. A vacuum drying and hydrogen fluoride treatment step to dry and "water-proof" the surface may be utilized to eliminate reflectance peak values at certain wavelengths.

When dyed black, more than 98% of the impinging radiation of the vast majority of wavelengths of up to 120 microns is absorbed and dissipated by the surface. More than 98% of infrared radiation (above about 7.8 microns wavelength) is absorbed and dissipated by the undyed surface.

Claims

1. In a method of improving the absorbency of electro-magnetic radiation of an oxide layer produced on the surface of an anodizable metal selected from aluminum and aluminum alloys by sulfuric acid anodization at from about 80°

F. to 100°

F. and a voltage between about 12 to 25 volts for from 1.5 to 2.5 hours in a sulfuric acid solution having a specific gravity of from 1.10 to 1.13 measured at 70°

F. the improvement which comprises heating said layer under a pressure no greater than about 1 mm Hg. at a temperature of at least 105°

C. to remove moisture therefrom, and contacting said surface with hydrogen fluoride gas in an amount sufficient to raise the pressure to at least about 50 mm. Hg. for a period of time sufficient to render said layer resistant to re-absorption of moisture.

2. The method of claim 1 wherein said oxide layer is produced by anodization of an aluminum body in a sulfuric acid solution of specific gravity of between about 1.102 to 1.128 measured at 70°

F., at a temperature of between about 80°

to 100°

F. for a period of from about 13/4 to about 21/4 hours at a voltage between about 12 to 25 volts.

3. A method of making a product having a surface of extremely low reflectance of electromagnetic radiation for the majority of wavelengths including the near ultra-violet, visible and infra red ranges up to at least about 20 microns comprising the steps of honing an aluminum metal body by impacting therein a slurry of grit particles in water by means of air pressure, said grit particles being of a size not more than 100 mesh,

anodizing the honed surface in a sulfuric acid solution having a specific gravity of between about 1.10 to 1.13 measured at 70°

F., said anodization step being carried out at a sulfuric acid solution temperature of between about 80°

to 100°

F. with an applied voltage of between about 12 to 25 volts for a period of time from between about 13/4 to 21/4 hours to form an oxide layer on the surface,

dyeing the surface,

sealing the dyed surface with hot water at a temperature between about 180°

F. and 200°

F.,

heating the surface to an elevated temperature under vacuum to remove water from said oxide layer, and

maintaining the surface under vacuum while contacting it with hydrogen fluoride for a period of time sufficient to render said oxide layer resistant to re-absorption of moisture.

4. The method of claim 3 wherein said period of time is at least about 4 hours, said vacuum is a pressure of not less than about 1 mm Hg. and said elevated temperature is at least about 105°

C., and said hydrogen fluoride is maintained at a pressure of at least about 50 mm Hg. over said oxide layer.

5. A method of making a product having a surface of extremely low reflectance of electromagnetic radiation including the near ultra-violet, visible and infra red ranges comprising the steps of honing an anodizable aluminum metal body by impacting thereon a slurry of grit particles in water to form a plurality of peaks and valleys on the surface of said metal body,

the grit particles being of a size between 100 to 200 mesh and the slurry being impacted against the metal by compressed air at a pressure of between 80 to 150 pounds per square inch,

anodizing said surface in a sulfuric acid solution having a specific gravity of between about 1.10 to 1.13 measured at 70°

F., at a temperature of between about 80°

to 100°

F. with an applied voltage of between about 12 to 25 volts, and conducting said anodization for a period of from between about 11/2 to 21/4 hours,

dyeing the oxide layer and sealing it in hot water at a temperature not greater than 200°

F., and

heating said oxide layer to an elevated temperature under vacuum to remove water therefrom, and contacting said oxide layer with hydrogen fluoride while maintaining it under vacuum.

6. The method of claim 5 wherein said vacuum under which said oxide layer is heated is a pressure not less than about 1 mm Hg. and said elevated temperature is not less than about 105°

C.

7. The method of claim 6 wherein said contacting with hydrogen fluoride is carried out for at least about 41/2 hours.

8. The method of claim 7 wherein said elevated temperature is between about 105°

to 110°

C.

9. A method of making a product having a surface of extremely low reflectance of electromagnetic radiation in wavelengths ranging from 0.27 to about 30 microns which comprises the steps of providing a workpiece of aluminum, honing the surface of the aluminum workpiece with alumina grit particles having a particle size between 100 and 200 mesh dispersed in water and directed at the aluminum workpiece under pressure;

etching the surface with a caustic etch solution and rinsing the surface;

anodizing the etched rinsed surface in an aqueous sulfuric acid solution having a specific gravity of between about 1.10 and 1.13 measured at 70°

F., at a temperature of between about 80°

F. to 100°

F. and a voltage between about 12 to 25 volts and carrying out said anodization for a period of between about 13/4 to 21/4 hours, rinsing the surface, said anodized surface being characterized by a columnar structure defined by faults extending longitudinally therein, dyeing the surface in an organic black dye bath, rinsing the workpiece after dyeing to remove excess dye, and then sealing the surface with hot, distilled water, said product being further characterized in that it has a fractional reflectance of under 2 percent for the majority of wavelengths in the range of 0.27 to 30 microns.

10. A method of making a product having a surface of extremely low reflectance of electromagnetic radiation in wavelengths ranging from 0.27 to about 30 microns which comprises the steps of providing a work piece of aluminum, vapor honing the surface with alumina grit particles having a particle size between 100 and 200 mesh dispersed in water projected against the surface of the aluminum work piece with compressed air at a pressure between 80 and 150 pounds per square inch, etching the surface with a caustic etch solution and rinsing the surface, and anodizing the etched rinsed surface in an aqueous carbon dioxide saturated sulfuric acid solution having a specific gravity of between about 1.10 and 1.13 measured at 70°

F., at a temperature of between about 80°

F. and 100°

F. with an applied voltage of between about 12 to 25 volts and carrying out said anodization for a period of between about 13/4 to 21/4 hours and rinsing the surface, said anodized surface being characterized by a columnar structure defined by faults extending longitudinally therein, dyeing the surface in an organic black dye bath, rinsing the work piece after dyeing to remove excess dye, and then sealing the surface with not distilled water, said product being further characterized in that it has a fractional reflectance of under 2 percent for the majority of wavelengths in the range of 0.27 to 30 microns.

11. The process of claim 10 in which the anodized surface is dyed black with nigrosine black dye.

12. A product having a surface of enhanced nonreflectance of electromagnetic radiation at wavelengths up to 30 microns comprising a body made of an anodizable metal and having an anodized surface defined by a plurality of peaks and valleys having an oxide layer formed thereon by anodization, said oxide layer having been reacted with hydrogen fluoride.

13. The product of claim 12 wherein the oxide layer is a dyed and sealed layer.

14. The product of claim 13 wherein the oxide layer is dyed black.

15. A product having a surface of extremely low reflectance of electromagnetic radiation at wavelengths up to 30 microns comprising a body made of an anodizable metal selected from aluminum and aluminum alloys and having a black anodized surface defined by a plurality of peaks and valleys having an oxide layer formed thereon by sulfuric acid anodization at from about 80°

F. to 100°

F. and a voltage between about 12 to 25 volts for from 1.5 to 2.5 hours in a sulfuric acid solution having a specific gravity of from 1.10 to 1.13 measured at 70°

F. and dyed black, said anodized surface having a fractional reflectance of under 2% for majority of wavelengths up to 30 microns, and said oxide layer is a vacuum dryed, hydrogen fluoride-treated oxide layer of enhanced resistance to absorption of moisture.

16. The product of claim 15 wherein said fractional reflectance is less than 2% for all wavelength regions up to 30 microns except for a reflectance peak occuring in a region centered at about 4.8 microns.

17. The product of claim 15 wherein said anodizable metal is aluminum.

18. The product of claim 15 wherein said oxide layer has a columnar structure defined by faults extending therein.

19. The product of claim 18 wherein the metal is aluminum and the oxide layer is one which is formed by anodization in a sulfuric acid solution of a specific gravity of between about 1.10 to 1.13 measured at 70°

F., at a temperature of between about 80°

to 100°

F. for a period of 11/2 to 21/2 hours at a voltage of between about 12 to 25 volts, and wherein the oxide layer is dyed and sealed in hot water at a temperature from about 180°

F. to 200°

F.

20. The product of claim 18 wherein the oxide layer is dyed and sealed in hot water at a temperature from about 180°

F to 200°

F.

21. The product of claim 20 wherein said oxide layer has an enhanced resistance to moisture reabsorption due to being vacuum dried and treated under vacuum and hydrogen fluoride.

22. The product of claim 15 in which the anodized surface is dyed black with nigrosine black dye.