n iron rusts, the oxides take up more volume than the original metal; this expansion can generate enormous forces, damaging structures made with iron. See economic effect for more details.
The rusting of iron is an electrochemical process that begins with the transfer of electrons from iron to oxygen. The iron is the reducing agent (gives up electrons) while the oxygen is the oxidising agent (gains electrons). The rate of corrosion is affected by water and accelerated by electrolytes, as illustrated by the effects of road salt on the corrosion of automobiles. The key reaction is the reduction of oxygen:
Because it forms hydroxide ions, this process is strongly affected by the presence of acid. Likewise, the corrosion of most metals by oxygen is accelerated at low pH. Providing the electrons for the above reaction is the oxidation of iron that may be described as follows:
- Fe → Fe2+ + 2 e−
The following redox reaction also occurs in the presence of water and is crucial to the formation of rust:
- 4 Fe2+ + O2 → 4 Fe3+ + 2 O2−
In addition, the following multistep acid–base reactions affect the course of rust formation:
as do the following dehydration equilibria:
From the above equations, it is also seen that the corrosion products are dictated by the availability of water and oxygen. With limited dissolved oxygen, iron(II)-containing materials are favoured, including FeO and black lodestone or magnetite (Fe3O4). High oxygen concentrations favour ferric materials with the nominal formulae Fe(OH)3−xOx⁄2. The nature of rust changes with time, reflecting the slow rates of the reactions of solids.
Furthermore, these complex processes are affected by the presence of other ions, such as Ca2+, which serve as electrolytes which accelerate rust formation, or combine with the hydroxides and oxides of iron to precipitate a variety of Ca, Fe, O, OH species.
The onset of rusting can also be detected in the laboratory with the use of ferroxyl indicator solution. The solution detects both Fe2+ ions and hydroxyl ions. Formation of Fe2+ ions and hydroxyl ions are indicated by blue and pink patches respectively.
Because of the widespread use and importance of iron and steel products, the prevention or slowing of rust is the basis of major economic activities in a number of specialized technologies. A brief overview of methods is presented here; for detailed coverage, see the cross-referenced articles.
Rust is permeable to air and water, therefore the interior metallic iron beneath a rust layer continues to corrode. Rust prevention thus requires coatings that preclude rust formation.
Stainless steel forms a passivation layer of chromium(III) oxide. Similar passivation behavior occurs with magnesium, titanium, zinc, zinc oxides, aluminium, polyaniline, and other electroactive conductive polymers.
Special "weathering steel" alloys such as Cor-Ten rust at a much slower rate than normal, because the rust adheres to the surface of the metal in a protective layer. Designs using this material must include measures that avoid worst-case exposures, since the material still continues to rust slowly even under near-ideal conditions.
Galvanization consists of an application on the object to be protected of a layer of metallic zinc by either hot-dip galvanizing or electroplating. Zinc is traditionally used because it is cheap, adheres well to steel, and provides cathodic protection to the steel surface in case of damage of the zinc layer. In more corrosive environments (such as salt water), cadmium plating is preferred. Galvanization often fails at seams, holes, and joints where there are gaps in the coating. In these cases, the coating still provides some partial cathodic protection to iron, by acting as a galvanic anode and corroding itself instead of the underlying protected metal. The protective zinc layer is consumed by this action, and thus galvanization provides protection only for a limited period of time.
More modern coatings add aluminium to the coating as zinc-alume; aluminium will migrate to cover scratches and thus provide protection for a lo