On this page you can read about every type of process and get a broader understanding of how the procedures work.
Aluminium alloys are anodized to increase corrosion resistance, to increase surface hardness, and to allow dyeing (coloring), improved lubrication, or improved adhesion. The anodic layer is non-conductive.
When exposed to air at room temperature, or any other gas containing oxygen, pure aluminium self-passivates by forming a surface layer of amorphous aluminium oxide 2 to 3 nmthick, which provides very effective protection against corrosion. Aluminium alloys typically form a thicker oxide layer, 5-15 nm thick, but tend to be more susceptible to corrosion. Aluminium alloy parts are anodized to greatly increase the thickness of this layer for corrosion resistance. The corrosion resistance of aluminium alloys is significantly decreased by certain alloying elements or impurities: copper, iron, and silicon, so 2000, 4000, and 6000-series alloys tend to be most susceptible.
Some aluminium aircraft parts, architectural materials, and consumer products are anodized. Anodized aluminium can be found on mp3 players, flashlights, cookware, cameras, sporting goods, window frames,roofs, in electrolytic capacitors, and on many other products both for corrosion resistance and the ability to retain dye. Although anodizing only has moderate wear resistance, the deeper pores can better retain a lubricating film than a smooth surface would.
Anodized coatings have a much lower thermal conductivity and coefficient of linear expansion than aluminium. As a result, the coating will crack from thermal stress if exposed to temperatures above 80 °C. The coating can crack, but it will not peel. The melting point of aluminium oxide is 2050 °C, much higher than pure aluminium's 658 °C.
In typical commercial aluminium anodization processes, the aluminium oxide is grown down into the surface and out from the surface by equal amounts. So anodizing will increase the part dimensions on each surface by half of the oxide thickness. For example a coating that is (2 μm) thick, will increase the part dimensions by (1 μm) per surface. If the part is anodized on all sides, then all linear dimensions will increase by the oxide thickness. Anodized aluminium surfaces are harder than aluminium but have low to moderate wear resistance, although this can be improved with thickness and sealing.
Preceding the anodization process, wrought alloys are cleaned in either a hot soak cleaner or in a solvent bath and may be etched in sodium hydroxide (normally with addedsodium gluconate), ammonium bifluoride or brightened in a mix of acids. Cast alloys are normally best just cleaned due to the presence of intermetallic substances unless they are a high purity alloy such as LM0.
The anodized aluminium layer is grown by passing a direct current through an electrolytic solution, with the aluminium object serving as the anode (the positive electrode). The current releases hydrogen at the cathode (the negative electrode) and oxygen at the surface of the aluminium anode, creating a build-up of aluminium oxide. The voltage required by various solutions may range from 1 to 300 V DC, although most fall in the range of 15 to 21 V. Higher voltages are typically required for thicker coatings formed in sulfuric and organic acid. The anodizing current varies with the area of aluminium being anodized, and typically ranges from 0.3 to 3 amperes of current per square decimeter (20 to 200 mA/in²).
Aluminium anodizing is usually performed in an acid solution which slowly dissolves the aluminium oxide. The acid action is balanced with the oxidation rate to form a coating with nanopores, 10-150 nm in diameter. These pores are what allows the electrolyte solution and current to reach the aluminium substrate and continue growing the coating to greater thickness beyond what is produced by autopassivation. However, these same pores will later permit air or water to reach the substrate and initiate corrosion if not sealed. They are often filled with colored dyes and/or corrosion inhibitors before sealing. Because the dye is only superficial, the underlying oxide may continue to provide corrosion protection even if minor wear and scratches may break through the dyed layer.
Conditions such as electrolyte concentration, acidity, solution temperature, and current must be controlled to allow the formation of a consistent oxide layer. Harder, thicker films tend to be produced by more dilute solutions at lower temperatures with higher voltages and currents. The film thickness can range from under 0.5 micrometers for bright decorative work up to 150 micrometers for architectural applications.
The most widely used anodizing specification, MIL-A-8625, defines three types of aluminium anodization. Type I is Chromic Acid Anodization, Type II is Sulfuric Acid Anodization and Type III is sulfuric acid hardcoat anodization. Other anodizing specifications include MIL-A-63576, AMS 2469, AMS 2470, AMS 2471, AMS 2472, AMS 2482, ASTM B580, ASTM D3933, ISO 10074 and BS 5599. None of these specifications define a detailed process or chemistry, but rather a set of tests and quality assurance measures which the anodized product must meet. BS 1615 provides guidance in the selection of alloys for anodizing.
The oldest anodizing process uses chromic acid. It is widely known as the Bengough-Stuart process. In North America it is known as Type I because it is so designated by the MIL-A-8625 standard, but it is also covered by AMS 2470 and MIL-A-8625 Type IB. Chromic acid produces thinner, 0.5 μm to 18 μm (0.00002" to 0.0007") more opaque films that are softer, ductile, and to a degree self-healing. They are harder to dye and may be applied as a pretreatment before painting. The method of film formation is different from using sulfuric acid in that the voltage is ramped up through the process cycle.
Sulfuric acid is the most widely used solution to produce anodized coating. Coatings of moderate thickness 1.8 μm to 25 μm (0.00007" to 0.001") are known as Type II in North America, as named by MIL-A-8625, while coatings thicker than 25 μm (0.001") are known as Type III, hardcoat, hard anodizing, or engineered anodizing. Very thin coatings similar to those produced by chromic anodizing are known as Type IIB. Thick coatings require more process control, and are produced in a refrigerated tank near the freezing point of water with higher voltages than the thinner coatings. Hard anodizing can be made between 25 and 150 μm (0.001" to 0.006") thick. Anodizing thickness increases wear resistance, corrosion resistance, ability to retain lubricants and PTFE coatings, and electrical and thermal insulation. Standards for thin (Soft/Standard) sulfuric anodizing are given by MIL-A-8625 Types II and IIB, AMS 2471 (undyed), and AMS 2472 (dyed), BS EN ISO 12373/1 (decorative), BS EN 3987 (Architectural) . Standards for thick sulfuric anodizing are given by MIL-A-8625 Type III, AMS 2469, BS 5599, BS EN 2536 and DEF STAN 03-26/1.
Under normal conditions of pH and oxygen concentration, passivation is seen in such materials as aluminium, iron, zinc, magnesium,copper, stainless steel, titanium, and silicon. Ordinary steel can form a passivating layer in alkali environments, as rebar does inconcrete. The conditions necessary for passivation are recorded in Pourbaix diagrams.
Pourbaix diagram of iron.
Some corrosion inhibitors help the formation of a passivation layer on the surface of the metals to which they are applied.
Some compounds, dissolving in solutions (chromates, molybdates) form non-reactive and low solubility films on metal surfaces.
Aluminium may be protected from oxidation by anodizing and/or allodizing, or any of an assortment of similar processes. In addition, stacked passivation techniques are often used for protecting aluminium. For example, chromating is often used as a sealant to a previously-anodized surface, to increase resistance to salt-water exposure of aluminium parts by nearly a factor of 2 versus simply relying on anodizing.
Ferrous materials, including steel, may be somewhat protected by promoting oxidation ("rust") and then converting the oxidation to a metalophosphate by using phosphoric acidand further protected by surface coating. As the uncoated surface is water-soluble a preferred method is to form manganese or zinc compounds by a process commonly known as Parkerizing or phosphate conversion. Similar chemically-similar electrochemical conversion coatings includes bluing, also known as black oxide.
Stainless Steels can be passivated using a solution of nitric acid, to remove foreign particles form the surface and promote the growth of a protective oxide layer.
Nickel can be used for handling elemental fluorine, thanks to a passivation layer of nickel fluoride.
Chromate conversion coating is a type of conversion coating applied to passivate aluminium, zinc, cadmium, copper, silver, magnesium, tin and their alloys to slow corrosion. The process uses various toxic chromium compounds which may includehexavalent chromium.
Chromating is commonly used on zinc-plated parts to make them more durable. The chromate coating acts like a paint, protecting the zinc from white corrosion, this can make the part several times more durable depending on chromate layer thickness. It cannot be applied directly to steel or iron. It is also commonly used on aluminium alloy parts in the aircraft industry where it is often called chemical film. It has additional value as a primer for subsequent organic coatings, as untreated metal, especially aluminium, is difficult to paint or glue. Chromated parts retain their electrical conductivity to varying degrees, depending on coating thickness. The process may be used to add color for decorative or identification purposes.
Chromate coatings are soft and gelatinous when first applied but harden and become hydrophobic as they age. Curing can be accelerated by heating up to 70°C, but higher temperatures will gradually damage the coating over time. Some chromate conversion processes use brief degassing treatments at temperatures of up to 200°C, to prevent hygdrogen embrittlement of the substrate. Coating thickness vary from a few nanometers to a few micrometers thick.
The protective effect of chromate coatings on zinc is indicated by color, progressing from clear/blue to yellow, gold, olive drab and black. Darker coatings generally provide more corrosion resistance. Chromate conversion coatings are common on everyday items such as hardware and tools and usually have a distinctive yellow color.