RANDHIR KUMAR SINGH ASST PROFESSOR OPJIT

Anodizing is an electrochemical process of growing conversion oxide coating as a result of oxidation of an anodically connected metal in an acidic electrolyte solution.
Conversion coating is a film of a chemical compound formed in the reaction of the substrate substance with another substance. This reaction distinguishes conversion coating from a conventional coating applied on the substrate surface without changing its chemical state. Examples of conversion coating are black oxide, which is formed on the metal surface as a result of a chemical reaction of the metal atoms with an oxidizing agent (air, aqueous solution, molten salts) and Phosphating (coating consisting of an insoluble crystalline metal-phosphate salt formed in a chemical reaction between the substrate metal and a phosphoric acid solution). Anodizing is mostly used for aluminum. Other commercially anodized metals are tantalum and niobium.

Electrochemistry of anodizing Oxide layer structure Clear anodizing Hard anodizing Dying Electrolytic coloring Sealing Stages of anodizing process Applications

Anodizing process occurs in an electrochemical cell, in which the anode is the anodized part and the cathode is a plate/rod made of a material chemically inert in the acidic electrolyte (carbon, Stainless steels, nickel).

Electrochemical reaction at the anode 2Al + 3H2O = Al2O3 + 6H+ + 6e-

Electrochemical reaction at the cathode

6H+ + 6e- = 3H2 Resulting anodizing reaction

2Al + 3H2O = Al2O3 + 3H2 In aqueous solutions aluminum oxide may form various hydrates
Al2O3*(H2O)n n=1 to 3

Fig. Sketch illustrating ion transport through the oxide film.

Oxide coating formed as a result of anodizing may be in two forms: thin barriertype layer or thick porous cellular layer. The barrier-type oxide film forms in neutral electrolyte solutions (eg. ammonium borate), in which aluminum oxide does not dissolve. Thickness of barrier-type film is determined by the voltage applied between the anode and cathode. Maximum film thickness built at 700V is below 0.04 mil (1 m). The porous oxide film forms in acidic electrolyte solution (eg. diluted sulfuric acid), in which aluminum oxide not only grows but also dissolves. Cellular (porous) structure of the oxide layer is a result of fluctuations on the metal surface causing local concentrations of the electric current and enhanced oxide film growing.
Thickness of the porous oxide layer may reach 4 mil (100 m). Oxide coating is always thicker than the metal layer converted to oxide: 40% of the total oxide film penetrates below the original metal surface; 60% of the thickness is above the original metal surface. The pore structure is very fine: their surface density is typically varies in the range 30-60*1010 cells/in (50-100 cells/m).

Idealized structure of anodic porous aluminum oxide

Clear anodizing is the anodizing process resulting in formation of translucent clear film.

Clear anodize coating is usually up to 0.001 (25 m) thickness. It is produced in sulfuric acid solutions and then sealed in hot water.
Clear anodizing provides good corrosion resistance and moderate wear resistance.

Hard anodizing is the anodizing process resulting in formation of high density coating with large cells and small pores. It is produced in sulfuric acid at low temperature. Hard anodize coating is extremely durable and abrasion/wear resistant.

Dying is a process of absorption of organic or inorganic molecules in the pores of an anodize coating.
The dye fills the microscopic pores and imparts the coating a color.

The dyed coating is usually sealed in hot water. Dying provides excellent decorative appearance to the anodized part.

Electrolytic (2-step) coloring is a process of Clear anodizing followed by AC deposition of a metal (commonly tin or nickel) onto the bottom of the oxide pores.
Electrolytic coating produces bronze color due to optical interference caused by the metal deposition. Electrolytic (2-step) coating possess stable and durable color.

Sealing of an anodize oxide coating is performed in order to trap the dye locating in the pores and prevent absorption of undesired molecules in the pores. Sealing is conducted in hot water at a temperature about 200F (93C). Crystals of hydrated aluminum oxide form in hot water. The crystals seal the pores opening. Sealing may also be provided by deposition of metal salts (nickel acetate) dissolved in hot water at 180F (86C). Anodize coatings used for application of paints and adhesives are not sealed.

Racking - connection of the part to a system providing electrical connection of the part and its transportation through the baths of the anodizing line. Surface preparation - a series of cleaning treatments (alkaline cleaning, etching by sodium hydroxide, desmutting in acid) of the substrate surface prior to the anodizing operation, intended for ensuring strong and uniform adhesion of the coating to the substrate. Anodizing in 10% sulfuric acid solution by DC current of density 10-20 A/ft (1-2 A/dm) for 10-60 min. Dying or Electrolytic coloring. Sealing. Unracking. Inspection.

A few of the more important applications are described below, as well as new nanotechnology applications that may grow in importance.
Clear anodize Clear anodize usually means sulfuric acid anodize followed by hot water seal. This is the most widely used anodize coating. It is used on some aluminum alloys as the surface finish for automotive trim. It is also the surface for commercial photolithography plates. The photo emulsion adheres to the anodize coating, and the printing pattern is made by selective dissolution of emulsion. Printing ink adheres to the emulsion and water adheres to exposed oxide. The oxide surface is wear resistant and stands the rigors of high speed printing presses. Immersing the anodize coating in a dye solution before sealing creates an attractive colored surface for consumer products.

Hard anodize is generally made by anodizing in sulfuric acid at low temperature. This produces a coating with large cells and small diameter pores. The coating is extremely hard and durable and is used for engineering applications such as bearing surfaces. A thin phosphoric acid anodize coating is used as an adhesive bonding primer coat on aircraft and aerospace alloy sheets. This is an excellent surface for the epoxy adhesive and also improves corrosion resistance. Chromic acid anodize is used for optimum corrosion resistance for severe applications, such as aerospace and military use, but because chrome, in some form, is a carcinogen this process is being phased out.

Architectural applications for anodized aluminum include door and window trim and exterior structural panels. These surfaces must be stable for many years under harsh atmospheric conditions. Neither clear nor dyed coatings are satisfactory. Coatings ranging in color from gold to dark bronze are made by "integral coloring" that is achieved by using certain organic acids in the anodizing bath. The organic anions become incorporated in the oxide and cause it to darken.

Similar hues are produced by a two-step anodizing process in which an ac anodizing follows the dc sulfuric acid step. In the ac step a metal, usually tin or nickel, is deposited at the bottom of the pores. The metal deposit changes the optical properties of the coating and the thickness of the metal deposit is controlled to produce the desired color by optical interference. These coatings have superior long term stability compared with integral colored coatings.

Nanotechnology applications
The importance of surface texture in the development of pores has recently been dramatically demonstrated, and the results open new applications for anodized structures.

A hexagonal array of nanoscale (on the order of billionth of a meter) depressions was impressed on an aluminum surface using a silicon carbide die fabricated using electron beam lithography.
Feature interval was 70-500 nm, feature depth was 200 nm, and feature width was of similar magnitude. This sequence is illustrated in the sketch in Figure 1.

In this particular experiment, anodization in oxalic acid solution produced perfectly ordered arrays of pores corresponding to the patterned texture. This is shown in Figure 9, where the oxide on the left grew on the patterned surface, in contrast to the oxide on the right that grew on a surface that was not patterned. Adjustment of process conditions produces precisely ordered pore arrays with dimensions suitable for use as 2-D (two-dimensional) photonic crystals in the visible wavelength.

Fig. 2. Scanning Electron Microscopy micrograph of surface showing ideally ordered pores (left) and usual random distribution

Fig. 1. Process for fabrication of ideally ordered porous oxide. Black structure is SiC (silicon carbide) mold used to make ordered array of convex dimples in aluminum surface prior to anodization

Pores can be used as templates to make structures such as nanowires and nanotubes. To make nanowires the pores are filled with a metal, or other material, by cathodic deposition or electroless deposition. Tubes are made by coating the pore walls; addition of functional groups to the tube interior wall creates tubular nanoreactors. The wires and tubes are recovered by dissolving the alumina (aluminum oxide) template in a reagent that does not attack the nanostructures. Figure 3 shows pyrolytic carbon tubes created by flowing propylene at a temperature of 800oC (1472oF) through a porous alumina membrane that had been separated from its metal substrate. The alumina was then dissolved in hydrofluoric acid solution.

Fig. 3. Carbon tubes prepared by pyrolytic deposition of carbon in porous aluminum oxide (From T. Kyotani, L. Tsai, and A. Tomita, Chemistry of Materials, Vol. 8, p 2109, 1996).

Electrolytic capacitors
The main commercial application of the anodic barrier oxide is as the dielectric film in electrolytic capacitors.

These capacitors have high energy density, wide voltage range (3 volt to 600 volt) and are relatively low cost.
These capacitors are of two types: wet and solid. Wet type uses an organic electrolyte as electrical contact between oxide dielectric and a current collector. Most aluminum electrolytic capacitors are of this type and contain a roll of two aluminum foils one foil with the oxide dielectric separated by a paper spacer impregnated with the organic electrolyte.

Solid capacitors use a conducting oxide, usually manganese dioxide, or a conducting organic polymer (for example, polythiophene) as the contact between oxide dielectric and current collector. These are mostly tantalum capacitors, although there are some aluminum and more recently niobium capacitors with this design.
To enhance the capacitance per unit volume, the surface area of metal substrate is increased before deposition of the anodic oxide dielectric.

Aluminum foil is etched and tantalum or niobium powder is sintered to make a high surface area pellet. The high specific area, thin dielectric layer, and relatively high dielectric constant (about 8 for aluminum oxide and 25 for tantalum oxide) combine to make capacitors with higher energy density than with any other type of dielectric, such as polymer film or ceramic.