Anodizing

Anodising (also spelled anodizing in American English) is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts. Anodising (also spelled anodizing in American English) is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts. The process is called anodising because the part to be treated forms the anode electrode of an electrolytic cell. Anodising increases resistance to corrosion and wear, and provides better adhesion for paint primers and glues than bare metal does. Anodic films can also be used for a number of cosmetic effects, either with thick porous coatings that can absorb dyes or with thin transparent coatings that add interference effects to reflected light. Anodising is also used to prevent galling of threaded components and to make dielectric films for electrolytic capacitors. Anodic films are most commonly applied to protect aluminium alloys, although processes also exist for titanium, zinc, magnesium, niobium, zirconium, hafnium, and tantalum. Iron or carbon steel metal exfoliates when oxidized under neutral or alkaline microelectrolytic conditions; i.e., the iron oxide (actually ferric hydroxide or hydrated iron oxide, also known as rust) forms by anoxic anodic pits and large cathodic surface, these pits concentrate anions such as sulfate and chloride accelerating the underlying metal to corrosion. Carbon flakes or nodules in iron or steel with high carbon content (high-carbon steel, cast iron) may cause an electrolytic potential and interfere with coating or plating. Ferrous metals are commonly anodized electrolytically in nitric acid or by treatment with red fuming nitric acid to form hard black Iron(II,III) oxide. This oxide remains conformal even when plated on wire and the wire is bent. Anodizing changes the microscopic texture of the surface and the crystal structure of the metal near the surface. Thick coatings are normally porous, so a sealing process is often needed to achieve corrosion resistance. Anodized aluminium surfaces, for example, are harder than aluminium but have low to moderate wear resistance that can be improved with increasing thickness or by applying suitable sealing substances. Anodic films are generally much stronger and more adherent than most types of paint and metal plating, but also more brittle. This makes them less likely to crack and peel from aging and wear, but more susceptible to cracking from thermal stress. Anodizing was first used on an industrial scale in 1923 to protect Duralumin seaplane parts from corrosion. This early chromic acid–based process was called the Bengough–Stuart process and was documented in British defence specification DEF STAN 03-24/3. It is still used today despite its legacy requirements for a complicated voltage cycle now known to be unnecessary. Variations of this process soon evolved, and the first sulfuric acid anodizing process was patented by Gower and O'Brien in 1927. Sulfuric acid soon became and remains the most common anodizing electrolyte. Oxalic acid anodizing was first patented in Japan in 1923 and later widely used in Germany, particularly for architectural applications. Anodized aluminium extrusion was a popular architectural material in the 1960s and 1970s, but has since been displaced by cheaper plastics and powder coating. The phosphoric acid processes are the most recent major development, so far only used as pretreatments for adhesives or organic paints. A wide variety of proprietary and increasingly complex variations of all these anodizing processes continue to be developed by industry, so the growing trend in military and industrial standards is to classify by coating properties rather than by process chemistry. Aluminium alloys are anodized to increase corrosion resistance and to allow dyeing (coloring), improved lubrication, or improved adhesion. However, anodizing does not increase the strength of the aluminium object. The anodic layer is non-conductive. When exposed to air at room temperature, or any other gas containing oxygen, pure aluminum self-passivates by forming a surface layer of amorphous aluminum oxide 2 to 3 nm thick, which provides very effective protection against corrosion. Aluminum 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 Al alloys tend to be most susceptible. Although anodizing produces a very regular and uniform coating, microscopic fissures in the coating can lead to corrosion. Further, the coating is susceptible to chemical dissolution in the presence of high- and low-pH chemistry, which results in stripping the coating and corrosion of the substrate. To combat this, various techniques have been developed either to reduce the number of fissures, to insert more chemically stable compounds into the oxide, or both. For instance, sulfuric-anodized articles are normally sealed, either through hydro-thermal sealing or precipitating sealing, to reduce porosity and interstitial pathways that allow corrosive ion exchange between the surface and the substrate. Precipitating seals enhance chemical stability but are less effective in eliminating ion exchange pathways. Most recently, new techniques to partially convert the amorphous oxide coating into more stable micro-crystalline compounds have been developed that have shown significant improvement based on shorter bond lengths.