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In metallurgy, stainless steel is defined1 as a ferrous alloy with a minimum of 10.5% chromium content. The name originates from the fact that stainless steel stains, or rusts, less easily than ordinary steel. Stainless steel has higher resistance to oxidation (rust) and corrosion in several environments.
High oxidation resistance in air at ambient temperature is normally achieved with additions of more than 12% (by weight) chromium. The chromium forms a layer of chromium (III) oxide (Cr2O3) when exposed to oxygen. The layer is too thin to be visible, meaning the metal stays shiny. It is, however, impervious to water and air, protecting the metal beneath. Also, when the surface is scratched this layer quickly reforms. This phenomenon is called passivation by materials scientists, and is seen in other metals, such as aluminium. When stainless steel parts such as nuts and bolts are forced together, the oxide layer can be scraped off causing the parts to weld together. This effect is known as galling.
Types of stainless steel
There are different types of stainless steels: when nickel, for instance is added the austenite structure of iron is stabilized. This crystal structure makes such steels non-magnetic and less brittle at low temperatures. For higher hardness and strength, carbon is added. When subjected to adequate heat treatment these steels are used as razor blades, cutlery, tools etc.
Stainless steels are also classified by their crystalline structure:
- Austenitic stainless steels comprise over 70% of total stainless steel production. They contain a maximum of 0.15% carbon, a minimum of 16% chromium and sufficient nickel and/or manganese to retain an austenitic structure at all temperatures from the cryogenic region to the melting point of the alloy. A typical composition is 18% chromium and 8% nickel, commonly known as 18/8 stainless. "Superaustenitic" stainless steels, such as alloy AL-6XN, exhibit great resistance to chloride pitting, crevice corrosion and stress-corrosion cracking over the 300 series.
- Ferritic stainless steels are highly corrosion resistant, but far less durable than austenitic grades and cannot be hardened by heat treatment. They contain between 10.5% and 27% chromium and very little nickel, if any. Most recipes include molybdenum; some, aluminium or titanium. Common ferritic grades include 18Cr-2Mo, 26Cr-1Mo, 29Cr-4Mo, and 29Cr-4Mo-2Ni.
- Martensitic stainless steels are not as corrosion resistant as the other two classes, but are extremely strong and tough as well as highly machineable, and can be hardened by heat treatment. They contain 11.5 to 18% chromium and significant amounts of carbon. Some grades include additional alloying elements in small quantities.
The AISI defines the following grades among others:
- 200 Series—austenitic iron-chromium-nickel-manganese alloys
- 300 Series—austenitic iron-chromium-nickel alloys
- Type 301—highly ductile, for formed products. Also hardens rapidly during mechanical working.
- Type 303—equivalent to ISO2 A1. Free machining version of 304 via addition of sulfur
- Type 304—the most common; the classic 18/8 stainless steel; equivalent to ISO A2.
- Type 316—for food and surgical stainless steel uses; Alloy addition of molybdenum to prevent specific forms of corrosion; equivalent to ISO A4.
- 400 Series—ferritic and martensitic alloys
- Type 408—heat-resistant; poor corrosion resistance; 11% chromium, 8% nickel.
- Type 409—cheapest type; used for automobile exhausts; ferritic (iron/chromium only).
- Type 410—martensitic (high-strength iron/chromium); equivalent to ISO C1.
- Type 420 —"Cutlery Grade" martensitic; similar to the Brearley's original "rustless steel".
- Type 430—decorative, e.g. for automotive trim; ferritic.
Corrosion in stainless steel
Even a high-quality alloy can corrode under certain conditions. Because these modes of corrosion are more exotic and their immediate results are less visible than rust, they often escape notice and cause problems among those who are not familiar with them.
Passivation relies upon the tough layer of oxide described above. When deprived of oxygen (or when another species such as chloride competes as an anion), stainless steel lacks the ability to re-form a passivating film. In the worst case, almost all of the surface will be protected, but tiny local fluctuations will degrade the oxide film in a few critical points. Corrosion at these points will be greatly amplified, and can cause corrosion pits of several types, depending upon conditions. While the corrosion pits only nucleate under fairly extreme circumstances, they can continue to grow even when conditions return to normal, since the interior of a pit is naturally deprived of oxygen. In extreme cases, the sharp tips of extremely long and narrow pits can cause stress concentration to the point that otherwise tough alloys can shatter, or a thin film pierced by an invisibly small hole can hide a thumb sized pit from view. These problems are especially dangerous because they are difficult to detect before a part or structure fails. Pitting remains among the most common and damaging forms of corrosion in stainless alloys, but it can be prevented by ensuring that the material is exposed to oxygen (i.e., eliminating crevices) and protected from chloride wherever possible.
Weld decay and knifeline attack
Due to the elevated temperatures of welding or during improper heat treatment, chromium carbides can form in the grain boundaries of stainless steel. This chemical reaction robs the alloy of chromium in the zone near the grain boundary, making those areas much less resistant to corrosion. This creates a galvanic couple with the well-protected alloy nearby, which leads to weld decay (corrosion of the grain boundaries near welds) in highly corrosive environments. Special alloys, either with low carbon content or with added carbon "getters" such as titanium and niobium (in types 321 and 347, respectively), can prevent this effect, but the latter require special heat treatment after welding to prevent the similar phenomenon of knifeline attack. As its name applies, this is limited to a small zone, often only a few micrometres across, which causes it to proceed more rapidly. This zone is very near the weld, making it even less noticeable3.
A few corrosion-resistant iron artifacts survive from antiquity. A famous (and very large) example is the Iron Pillar of Delhi , erected by order of Kumara Gupta I around the year AD 400. However, unlike stainless steel, these artifacts owe their durability not to chromium, but to their high phosphorus content, which promotes the formation of a solid protective layer of iron oxides, rather than the non-protective, cracked oxide layer that develops on most ironwork.
The corrosion resistance of iron-chromium alloys was first recognized in 1821 by the French metallurgist Pierre Berthier, who noted their resistance against attack by some acids and suggested their use in cutlery. However, the metallurgists of the 19th century were unable to produce the combination of low carbon and high chromium found in most modern stainless steels, and the high-chromium alloys they could produce were too brittle to be of practical interest.
This situation changed in the late 1890s, when Hans Goldschmidt of Germany developed an aluminothermic (thermite) process for producing carbon-free chromium. In the years 1904-1911, several researchers, particularly Leon Guillet of France, prepared alloys that would today be considered stainless steel. In 1911, Philip Monnartz of Germany reported on the relationship between the chromium content and corrosion resistance of these alloys.
Harry Brearley of the Brown-Firth research laboratory in Sheffield, England is most commonly credited as the "inventor" of stainless steel. In 1913, while seeking an erosion-resistant alloy for gun barrels, he discovered and subsequently industrialized a martensitic stainless steel alloy. However, similar industrial developments were taking place contemporaneously at the Krupp Iron Works in Germany, where Eduard Maurer and Benno Strauss were developing an austenitic alloy (21% chromium, 7% nickel), and in the United States, where Christian Dantsizen and Frederick Becket were industrializing ferritic stainless.
-  American Iron and Steel Institute (AISI)
-  ISO 3506 : ISO standards for stainless steel
-  Denny A. Jones, Principles and Prevention of Corrosion, 2nd edition, 1996, Prentice Hall, Upper Saddle River, NJ. ISBN 0-13-359993-0
-  Stainless Steel products by the Allegheny Ludlum Corporation
-  Stainless Steels by the International Molybdenum Association
-  Caring for Stainless Steel by Suburban Surgical Company
-  History of Stainless Steels by Stainless Steel World
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