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The effects of the alloying elements in Stainless Steels

The alloying elements each have a specific effect on the properties of the steel. It is the combined effect of all the alloying elements and, to some extent, the impurities that determine the property profile of a certain steel grade. In order to understand why different grades have different compositions a brief overview of the alloying elements and their effects on the structure and properties may be helpful. The effects of the alloying elements on some of the important materials properties will be discussed in more detail in the subsequent sections. It should also be noted that the effect of the alloying elements differs in some aspects between the hardenable and the non-hardenable stainless steels.

Chromium (Cr) This is the most important alloying element in stainless steels. It is this element that gives the stainless steels their basic corrosion resistance. The corrosion resistance increases with increasing chromium content. It also increases the resistance to oxidation at high temperatures. Chromium promotes a ferrite structure.

Nickel (Ni) The main reason for the nickel addition is to promote an austenitic structure. Nickel generally increases ductility and toughness. It also reduces the corrosion rate and is thus advantageous in acid environments. In precipitation hardening steels nickel is also used to form the intermetallic compounds that are used to increase the strength.

Molybdenum (Mo) Molybdenum substantially increases the resistance to both general and localized corrosion. It increases the mechanical strength somewhat and strongly promotes a ferrite structure. Molybdenum also promotes the formation secondary phases in ferritic, ferritic-austenitic and austenitic steels. In martensitic steels it will increase the hardness at higher tempering temperatures due to its effect on the carbide precipitation.

Copper (Cu) Copper enhances the corrosion resistance in certain acids and promotes an austenitic structure. In precipitation hardening steels copper is used to form the intermetallic compounds that are used to increase the strength.

Manganese (Mn) Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at high temperatures it will stabilise ferrite. Manganese increases the solubility of nitrogen and is used to obtain high nitrogen contents in austenitic steels.

Silicon (Si) Silicon increases the resistance to oxidation, both at high temperatures and in strongly oxidising solutions at lower temperatures. It promotes a ferritic structure.

Carbon (C) Carbon is a strong austenite former and strongly promotes an austenitic structure. It also substantially increases the mechanical strength. Carbon reduces the resistance to intergranular corrosion. In ferritic stainless steels carbon will strongly reduce both toughness and corrosion resistance. In the martensitic and martensitic-austenitic steels carbon increases hardness and strength. In the martensitic steels an increase in hardness and strength is generally accompanied by a decrease in toughness and in this way carbon reduces the toughness of these steels.

Nitrogen (N) Nitrogen is a very strong austenite former and strongly promotes an austenitic structure. It also substantially increases the mechanical strength. Nitrogen increases the resistance to localised corrosion, especially in combination with molybdenum. In ferritic stainless steels nitrogen will strongly reduce toughness and corrosion resistance. In the martensitic and martensitic-austenitic steels nitrogen increases both hardness and strength but reduces the toughness.

Titanium (Ti) Titanium is a strong ferrite former and a strong carbide former, thus lowering the effective carbon content and promoting a ferritic structure in two ways. In austenitic steels it is added to increase the resistance to intergranular corrosion but it also increases the mechanical properties at high temperatures. In ferritic stainless steels titanium is added to improve toughness and corrosion resistance by lowering the amount of interstitials in solid solution. In martensitic steels

titanium lowers the martensite hardness and increases the tempering resistance. In precipitation hardening steels titanium is used to form the intermetallic compounds that are used to increase the strength.

Niobium (Nb) Niobium is both a strong ferrite and carbide former. As titanium it promotes a ferritic structure. In austenitic steels it is added to improve the resistance to intergranular corrosion but it also enhances mechanical properties at high temperatures. In martensitic steels niobium lowers the hardness and increases the tempering resistance. In U.S. it is also referred to as Columbium (Cb).

Aluminium (Al) Aluminium improves oxidation resistance, if added in substantial amounts. It is used in certain heat resistant alloys for this purpose. In precipitation hardening steels aluminium is used to form the intermetallic compounds that increase the strength in the aged condition.

Cobalt (Co) Cobalt only used as an alloying element in martensitic steels where it increases the hardness and tempering resistance, especially at higher temperatures.

Vanadium (V) Vanadium increases the hardness of martensitic steels due to its effect on the type of carbide present. It also increases tempering resistance. Vanadium stabilises ferrite and will, at high contents, promote ferrite in the structure. It is only used in hardenable stainless steels.

Sulphur (S) Sulphur is added to certain stainless steels, the free-machining grades, in order to increase the machinability. At the levels present in these grades sulphur will substantially reduce corrosion resistance, ductility and fabrication properties, such as weldability and formability.

Cerium (Ce) Cerium is one of the rare earth metals (REM) and is added in small amounts to certain heat resistant temperature steels and alloys in order to increase the resistance to oxidation and high temperature corrosion.

The effect of the alloying elements on the structure of stainless steels is summarised in the Schaeffler-Delong diagram (Figure below). The diagram is based on the fact that the alloying elements can be divided into ferritestabilisers and austenite-stabilisers. This means that they favour the formation of either ferrite or austenite in the structure. If the austenite-stabilisers ability to promote the formation of austenite is related to that for nickel, and the ferrite-stabilisers likewise compared to chromium, it becomes possible to calculate the total ferrite and austenite stabilising effect of the alloying elements in the steel. This gives the so-called chromium and nickel equivalents in the Schaeffler-Delong diagram:

Chromium equivalent = %Cr + 1.5 x %Si + %Mo Nickel equivalent = %Ni + 30 x (%C + %N) + 0.5 x (%Mn + %Cu + %Co)

In this way it is possible to take the combined effect of alloying elements into consideration. The Schaeffler- Delong diagram was originally developed for weld metal, i.e. it describes the structure after melting and rapid cooling but the diagram has been found to give a useful picture of the effect of the alloying elements also for wrought and heat treated material. However, in practice, wrought or heat treated steels with ferrite contents in the range 0-5% according to the diagram contain smaller amounts of ferrite than that predicted by the diagram. It should also be mentioned here that the Schaeffler-Delong diagram is not the only diagram for assessment of ferrite contents and structure of stainless steels. Several different diagrams have been published, all with slightly different equivalents, phase limits or general layout. The effect of some alloying elements has also been the subject of considerable discussion. For example, the austenitestabilising effect of manganese has later been considered smaller than that predicted in the Schaeffler-Delong diagram. Its effect is also dependent on temperature.

The Metallurgy Of Carbon Steel

The best way to understand the metallurgy of carbon steel is to study the Iron Carbon Diagram. The diagram shown below is based on the transformation that occurs as a result of slow heating. Slow cooling will reduce the transformation temperatures; for example: the A1 point would be reduced from 723C to 690 C. However the fast heating and cooling rates encountered in welding will have a significant influence on these temperatures, making the accurate prediction of weld metallurgy using this diagram difficult.

Austenite This phase is only possible in carbon steel at high temperature. It has a Face Centre Cubic (F.C.C) atomic structure which can contain up to 2% carbon in solution. Ferrite This phase has a Body Centre Cubic structure (B.C.C) which can hold very little carbon; typically 0.0001% at room temperature. It can exist as either: alpha or delta ferrite. Carbon A very small interstitial atom that tends to fit into clusters of

iron atoms. It strengthens steel and gives it the ability to harden by heat treatment. It also causes major problems for welding , particularly if it exceeds 0.25% as it creates a hard microstructure that is susceptible to hydrogen cracking. Carbon forms compounds with other elements called carbides. Iron Carbide, Chrome Carbide etc.

Cementite Unlike ferrite and austenite, cementite is a very hard intermetallic compound consisting of 6.7% carbon and the remainder iron, its chemical symbol is Fe3C. Cementite is very hard, but when mixed with soft ferrite layers its average hardness is reduced considerably. Slow cooling gives course perlite; soft easy to machine but poor toughness. Faster cooling gives very fine layers of ferrite and cementite; harder and tougher Pearlite A mixture of alternate strips of ferrite and cementite in a single grain. The distance between the plates and their thickness is dependant on the cooling rate of the material; fast cooling creates thin plates that are close together and slow cooling creates a much coarser structure possessing less toughness. The name for this structure is derived from its mother of pearl appearance under a microscope. A fully pearlitic structure occurs at 0.8% Carbon. Further increases in carbon will create cementite at the grain boundaries, which will start to weaken the steel.

Cooling of a steel below 0.8% carbon When a steel solidifies it forms austenite. When the temperature falls below the A3 point, grains of ferrite start to form. As more grains of ferrite start to form the remaining austenite becomes richer in carbon. At about 723C the remaining austenite, which now contains 0.8% carbon, changes to pearlite. The resulting structure is a mixture consisting of white grains of ferrite mixed with darker grains of pearlite. Heating is basically the same thing in reverse.

Martensite If steel is cooled rapidly from austenite, the F.C.C structure rapidly changes to B.C.C leaving insufficient time for the carbon to form pearlite. This results in a distorted structure that has the appearance of fine needles. There is no partial transformation associated with martensite, it either forms or it doesnt. However, only the parts of a section that cool fast enough will form martensite; in a thick section it will only form to a certain depth, and if the shape is complex it may only form in small pockets. The hardness of martensite is solely dependant on carbon content, it is normally very high, unless the carbon content is exceptionally low.

Tempering The carbon trapped in the martensite transformation can

be released by heating the steel below the A1 transformation temperature. This release of carbon from nucleated areas allows the structure to deform plastically and relive some of its internal stresses. This reduces hardness and increases toughness, but it also tends to reduce tensile strength. The degree of tempering is dependant on temperature and time; temperature having the greatest influence.

Annealing This term is often used to define a heat treatment process that produces some softening of the structure. True annealing involves heating the steel to austenite and holding for some time to create a stable structure. The steel is then cooled very slowly to room temperature. This produces a very soft structure, but also creates very large grains, which are seldom desirable because of poor toughness. Normalising Returns the structure back to normal. The steel is heated until it just starts to form austenite; it is then cooled in air. This moderately rapid transformation creates relatively fine grains with uniform pearlite. Welding If the temperature profile for a typical weld is plotted against the carbon equilibrium diagram, a wide variety of transformation and heat treatments will be observed.

Note, the carbon equilibrium diagram shown above is only for illustration, in reality it will be heavily distorted because of the rapid heating and cooling rates involved in the welding process.

a) Mixture of ferrite and pearlite grains; temperature below A1, therefore microstructure not significantly affected. b) Pearlite transformed to Austenite, but not sufficient temperature c) available to exceed the A3 line, therefore not all ferrite grains transform to Austenite. On cooling, only the transformed grains will d) be normalised. Temperature just exceeds A3 line, full Austenite transformation. On cooling all grains will be normalised Temperature significantly exceeds A3 line permitting grains to grow. On cooling, ferrite will form at the grain boundaries, and a course pearlite will form inside the grains. A course grain structure is more readily hardened than a finer one, therefore if the cooling rate between 800C to 500C is rapid, a hard microstructure will be formed. This is why a brittle fracture is most likely to propagate in this region.

Welds The metallurgy of a weld is very different from the parent material. Welding filler metals are designed to create strong and tough welds, they contain fine oxide particles that permit the nucleation of fine grains. When a weld solidifies, its grains grow from the course HAZ grain structure, further refinement takes place within these course grains creating the typical acicular ferrite formation shown opposite.

Recommended Reading

Metals and How To Weld Them :- Lincoln Arc Foundation

A very cheap hard backed book covering all the basic essentials of welding metallurgy. Welding Metallurgy Training Modules:- (Devised by The Welding Institute of Canada) Published in the UK by Abington Publishing. Not cheap but the information is clearly represented in a very readable format. Source: Posted by BR at 12:54 PM 0 comments


The above picture is of a new pressure vessel that failed during its hydraulic test. The vessel had been stress relieved, but some parts of it did not reach the required temperature and consequently did not experience adequate tempering. This coupled with a small hydrogen crack, was sufficient to cause catastrophic failure under test conditions. It is therefore important when considering PWHT or its avoidance, to ensure that all possible failure modes and their consequences are carefully considered before any action is taken. The post weld heat treatment of welded steel fabrications is normally carried out to reduce the risk of brittle fracture by:

Reducing residual Stresses. These stresses are created when a weld cools and its contraction is restricted by the bulk of the material surrounding it. Weld distortion occurs when these stresses exceed the yield point.

Finite element modelling of residual stresses is now possible, so that the complete welding sequence of a joint or repair can be modelled to predict and minimise these stresses.

Tempering the weld and HAZ microstructure. The microstructure, particularly in the HAZ, can be hardened by rapid cooling of the weld. This is a major problem for low and medium alloy steels containing chrome and any other constituent that slow the austenite/ferrite transformation down, as this will result in hardening of the micro structure, even at slow cooling rates.

The risk of brittle fracture can be assessed by fracture mechanics. Assuming worst-case scenarios for all the relevant variables. It is then possible to predict if PWHT is required to make the fabrication safe. However, the analysis requires accurate measurement of HAZ toughness, which is not easy because of the HAZs small size and varying properties. Some approximation is possible from impact tests, providing the notch is taken from the point of lowest toughness. If PWHT is to be avoided, stress concentration effects such as: - backing bars, partial penetration welds, and internal defects in the weld and poor surface profile, should be avoided. Good surface and volumetric NDT is essential. Preheat may still be required to avoid hydrogen cracking and a post weld hydrogen release may also be beneficial in this respect (holding the fabrication at a temperature of around 250C for at least 2 hours, immediately after welding). Nickel based consumables can often reduce or remove the need for preheat, but their effect on the parent metal HAZ will be no different from that created by any other consumable, except that the HAZ may be slightly narrower. However, nickel based welds, like most austenitic steels, can make ultrasonic inspection very difficult. Further reduction in the risk of brittle fracture can be achieved by refining the HAZ microstructure using special temper bead welding techniques.