Corrosion of Stainless Steel

OBJECTIVE/SCOPE

To discuss the mechanisms of corrosion in stainless steel and give guidance on selecting
the appropriate grade for the application. Guidance on good detailing practice to avoid
corrosion is also given.

PREREQUISITES

Lecture 18.1: Introduction to Stainless Steel

RELATED LECTURES

Lecture 18.2: Structural Behaviour and Design

Lecture 18.4: Fabrication

SUMMARY

This lecture describes why stainless steel may corrode, the mechanisms of corrosion in
stainless steel and grade selection to avoid corrosion. Guidance is also given on good
detailing practice, storage and handling to obtain the best properties of stainless steel, i.e.
good aesthetics and stability of its appearance throughout.

1. INTRODUCTION
All common structural metals form surface oxide films when exposed to dry air. The
oxide formed on mild steel is readily broken down, and in the presence of moisture, it is
not repaired. Thus, a reaction can take place between the steel (Fe), the moisture (H2O)
and oxygen (O2) to form rust. The reaction is complex but can be represented by a
chemical equation of the form:

4 Fe + 2 H2O + 3 O2 = 2 Fe2O3.H2O

Fe2O3.H2O is what is commonly known as rust and, as it is not usually protective, the
corrosion process is not impeded.

An oxide is also formed on stainless steel. It consists of a chromium-rich oxide which is

stable, non-porous and tightly adherent to the metal. However, unlike that formed on mild
steel, if it is broken down (e.g. by scratching or cutting), it is capable of self repair in the
presence of air or an oxidising environment. It is also highly resistant to chemical attack.
For these reasons it is known as a "passive film". Although the film is very thin
(approximately 10-6mm), it gives stainless steel its high corrosion resistance properties by
preventing the steel from reacting with the atmosphere.
The behaviour of the passive film depends on the composition of the steel, its surface
treatment and the corrosive nature of its environment. The stability of the layer increases
as the chromium content increases, that is, nickel that is added for making steel working
easier also decreases the corrosion rate. To enhance their corrosion resistance, some
stainless steels are "low carbon content" or are stabilised by additions of titanium and
niobium, others contain extra molybdenum.

The concept of passive film formation is important because any conditions which prevent
the formation of the film or cause it to break down will also lead to loss of corrosion
resistance. Corrosion in stainless steel therefore occurs if the passive film is damaged and
is not allowed to re-form.

This lecture describes why stainless steel may corrode, the mechanisms of corrosion in
stainless steel and grade selection to avoid corrosion. Guidance is also given on good
detailing practice, storage and handling to improve corrosion resistance. Further guidance
can be found in [1].

2. BEHAVIOUR OF STAINLESS STEELS IN

CORROSIVE ENVIRONMENTS
Stainless steels are generally very corrosion resistant and will perform satisfactorily in
most environments. The limit of corrosion resistance of a given stainless steel depends on
its alloying elements which means that each grade has a slightly different response when
exposed to a corrosive environment. Care is therefore needed to select the most
appropriate grade of stainless steel for a given application. Generally, the higher the level
of corrosion resistance required, the higher the level of alloying elements and the greater
the cost of the material.

The most common reasons for a metal to fail to live up to expectations regarding
corrosion resistance are:

a) incorrect assessment of the environment or exposure to unexpected conditions, e.g.

unsuspected contamination by chloride ions.

b) the way in which the stainless steel has been worked or treated may introduce a state
not envisaged in the initial assessment.

Although stainless steels may be subject to discolouration and staining (often due to
carbon steel contamination), they are extremely durable in buildings. In aggressive
industrial and marine environments, tests have shown no indication of reduction in
component resistance even where a small amount of weight loss occurred. However,
unsightly rust staining on external surfaces may still be regarded as a failure by the user.
Experience indicates that any serious corrosion problem is most likely to show up in the
first two or three years of service; problems can usually be explained by defects in
bringing stainless steels into operation. Except in the case of bad choice of grade,
stainless steel can be "cleaned" and gives good results on a very large lifetime. For
instance, CHRYSLER BUILDING ROOF in New York made in 1929 and cleaned in the
80's is still in perfect condition.

In certain aggressive environments some grades of stainless steel are susceptible to

localised attack. Six mechanisms are described below, although the last three are very
rarely encountered in buildings onshore.

2.1 Pitting

Pitting is a localised form of corrosion which can occur in wet conditions as a result of
exposure to specific environments, most notably those containing chlorides. Pitting
occurs because chloride ions penetrate the passive film in weak spots. A local element is
formed with the penetrated area as the anode and the surrounding passive film as the
cathode. Since the anode area is small and the cathode area large, the current density, and
thereby the corrosion rate on the anode surface becomes very high. Pitting needs wet
conditions; it stops when surface is dried by sun and cannot appear if surface is kept dry.

In most structural applications, the extent of pitting is likely to be superficial and the
reduction in section of a component is negligible. However, corrosion products can stain
architectural features. A less tolerant view of pitting should be adopted for services such
as ducts, piping and containment structures. If there is a known pitting hazard, then a
molybdenum bearing stainless steel will be required.

2.2 Crevice Corrosion

Crevice corrosion is a localised form of attack which is initiated by the extremely low
availability of oxygen in a crevice. It is only likely to be a problem in stagnant solutions
where a build-up of chlorides can occur. The severity of crevice corrosion is very
dependent on the geometry of the crevice; the narrower and deeper the crevice, the more
severe the corrosion. Crevices typically occur between nuts and washers or around the
thread of a screw or the shank of a bolt. Crevices can also occur in welds which fail to
penetrate and under deposits on the steel surface. To avoid crevice corrosion under
deposits, periodic cleaning is recommended; washing by rain helps considerably;
however, periodic cleaning should be part of the building maintenance. To avoid crevice
corrosion under bolts etc., it is recommended to avoid water penetration by use of plastics
or rubber gaskets, or by filling crevices with adherent sealant or mastic.

2.3 Bimetallic Corrosion

Bimetallic (galvanic) corrosion may occur when dissimilar metals are in electrical contact
in a common electrolyte (e.g. rain, condensation etc.). If current flows between the two,
the less noble metal (the anode) corrodes at a faster rate than would have occurred if the
metals were not in contact.
The rate of corrosion also depends on the relative areas of the metals in contact, the
temperature and the composition of the electrolyte. In particular, the larger the area of the
cathode in relation to that of the anode, the greater the rate of attack. Adverse area ratios
are likely to occur with fasteners and at joints. Carbon steel bolts in stainless steel
members should be avoided because the ratio of the area of the stainless steel to the
carbon steel is large and the bolts will be subject to aggressive attack.

Stainless steels usually form the cathode in a bimetallic couple and therefore do not suffer
corrosion. An exception is the couple with copper which should generally be avoided
except under benign conditions. Contact between austenitic stainless steels and zinc or
aluminium may result in some additional corrosion of the latter two metals. The corrosion
is unlikely to be significant structurally, but the resulting white/grey powder may be
deemed unsightly.

Bimetallic corrosion may be prevented by excluding water from the detail (e.g. by
painting or taping over the assembled joint) or isolating the metals from each other (e.g.
by painting the contact surfaces of the dissimilar metals). Isolation around bolted
connections can be achieved by non-conductive plastic or rubber gaskets and nylon or
teflon washers and bushes. This system is a time consuming detail to make on site and it
is not usually possible to provide the necessary level of site inspection to check that all
the washers and sleeves have been installed properly.

2.4 Stress Corrosion Cracking

The development of stress corrosion cracking (SCC) requires the simultaneous presence
of tensile stresses and specific environmental factors unlikely to be encountered in
normal building atmospheres. The stresses do not need to be very high in relation to the
proof stress of the material and may be due to loading and residual effects from
manufacturing processes such as welding or bending. Caution should be exercised when
austenitic stainless steel members containing high residual stresses, e.g. due to cold
working, are used in chloride rich environments, e.g. swimming pools, marine, offshore
and mainly if the temperature of the steel can reach 50°C or more, e.g. roofing.

The likelihood of SCC increases with increasing tensile stress and with increasing
temperature. Ferritic and austeno ferritic stainless steels are in general completely proof
against SCC. In austenitic stainless steels, an extra nickel content, a molydnenum
addition reduces the sensitivity to SCC.

2.5 General (Uniform) Corrosion

General corrosion is much less severe in stainless steel than in other metals. It only
occurs when the stainless steel is at a pH value which is either very low (acid
environments) or very high (alkaline environments) at high temperature. In normal
building applications, general acid corrosion cannot occur. Sometimes it can occur in
industrial or chemical atmospheres or most commonly by contact with products that are
incompatible with stainless steels, e.g. hydrochloric acid used to "clean concrete or
ceramics". Insurance of compatibility should be obtained from product information;
reference should be made to tables in manufacturers' literature or the advice of a
corrosion engineer should be sought.

2.6 Intergranular Attack and Weld Decay

When austenitic stainless steels are subject to prolonged heating between 450-850°C, the
carbon in the steel diffuses to the grain boundaries and precipitates chromium carbide.
This process removes chromium from the solid solution and leaves a lower chromium
content adjacent to the grain boundaries. Steels in this condition are termed 'sensitised'.
With a chromium level lower than 12% the grain boundaries become prone to general
corrosion in pickling solution or to preferential attack on subsequent exposure to a
corrosive environment. This phenomenon is known as weld decay when it occurs in the
heat affected zone of a weldment.

There are three ways to avoid intergranular corrosion:

• To use steel having a low carbon content.

• To use steel stabilised with titanium or niobium. These elements have a better
ability to bind carbon than chromium has, thereby reducing the risk of formation
of chromium carbide.
• To use heat treatment. This method is rarely used in practice.

Experience has shown that a low carbon content (~0,05%) in most cases is sufficiently
low to guard against intergranular corrosion after welding. This is particularly so when
welding is done by arc processes (giving rapid heating and cooling), even for plate
thicknesses up to 20mm.

3. GRADE SELECTION
The selection of the correct grade of stainless steel must take into account the
environment of the application, the fabrication route, surface finish and the maintenance
of the structure. Although the material has low maintenance requirements, where it is
selected for use in a corrosive environment corrosion engineering needs to take a higher
profile.

The first step is to characterise the service environment. The corrosiveness of an

environment is governed by a number of variables such as humidity, air temperature,
presence of chemicals and their concentration, oxygen content, etc. Moisture must be
present for corrosion to occur. For example, heated and ventilated buildings can be
classified as dry and corrosion is unlikely to occur in such environments. The risk of
condensation is higher in areas such as kitchens and laundries. Coastal areas are very
corrosive due to the presence of high concentrations of chloride ions in the air and
structures exposed to sea spray are particularly prone to corrosive attack.
Having characterised the general environment, it is then necessary to consider the effect
of the direct surroundings on the stainless steel (e.g. elements and substances which the
material is likely to come into contact with). The surface condition, the temperature of the
steel and the anticipated stress could also be important parameters.

Consideration should then be given to mechanical properties. The different types of

loading should be defined, e.g. service loads, cyclic loads, vibrations, seismic loads. The
effect of heating/cooling cycles may also need to be quantified. Ease of fabrication,
availability of product forms, surface finish and cost also need to be considered.

Assessing the suitability of grades is best approached by referring to experience of

stainless steels in similar applications and environments. Table 1, which is extracted from
[2], gives guidance for selecting suitable grades for atmospheric environments. It is based
on long term exposure of stainless steel sheet samples at a variety of locations. Expert
advice should always be sought for more specialist applications, e.g. stainless steel
immersed or in contact with chemicals.

Caution should be exercised when considering the use of "free-machining" stainless

steels for fasteners. The addition of sulphur in the composition of these steels (commonly
designated 303 in the austenitic class) renders them more liable to corrosion, especially in
industrial and marine environments.

Table 1: Suggested grades for atmospheric applications

Steel grade Location

Rural Urban Industrial Marine

L M H L M H L M H L M H

/
430 (/) (/) X X X X X X X X X

/ / / / / /
304, 302 (inc 304L, (/) (/) (/) X (/) X
321, 347)

/ / / / / /
316 (inc 316L, 316Ti) O O O O (/) (/)

L - Least corrosive conditions within that category, e.g. tempered by low humidity, low
temperatures.

M - Fairly typical of that category.

H - Corrosion likely to be higher than typical for that category, e.g. increased by
persistent high humidity, high ambient temperatures, particularly aggressive air
pollutants.

O - Potentially over-specified from a corrosion point of view.

/ - Probably the best choice for corrosion resistance and cost.

X - Likely to suffer excessive corrosion.

(/) - Worthy of consideration if precautions are taken (i.e. specifying a relatively smooth
surface and if regular washing is carried out).

Note: Special ferritic or austenoferritic stainless steels and high alloys grade could be
used in very corrosive environments. Consult manufacturers' literature.

4. DETAILING CONSIDERATIONS
The main step in preventing corrosion problems is in selecting an appropriate grade of
stainless steel with suitable fabrication procedures. As well as careful material grade
selection, good detailing and workmanship can significantly reduce the likelihood of
staining and corrosion whilst poor detailing and workmanship can be detrimental to
corrosion performance. The following practical guidance of good practice will help
ensure satisfactory performance of the material; not all points would necessarily be
always applicable.

• Avoid arrangements which allow dirt entrapment or chemical concentration

• Provide clear drainage paths.
• Avoid crevices gaps, ledges and slits.
• Specify smooth contours and radii for corners.
• Avoid sharp changes in section and other stress raisers.
• Minimize fabrication stresses by careful choice of welding procedures.
• Avoid contamination from carbon steel.
• Insulate at connections to other metals.
• Avoid details which create access problems for welding and may lead to
undercutting or lack of penetration.

Figure 1 illustrates some good and poor design features to prevent corrosion.
5. STORAGE AND HANDLING
All stainless steel should be carefully stored so that the surfaces are protected from
mechanical damage and chemical pollution, e.g. ferrous contamination. Storage areas
should be dry and clean. The use of protective films may be beneficial for architectural
applications. Further advice can be obtained from the steelmaker.

It is necessary to avoid contamination of the surface of stainless steel components by

carbon steel at all stages of fabrication, handling, storage, transportation and erection. In
particular, the fabricator should take care to prevent contamination e.g. by quarantined
work areas or specific maintenance procedures. This is to prevent carbon steel pick-up
during rolling or from grinding debris or swarf which may rust when exposed to moisture
and stain the surface. When carbon steel lifting or handling equipment such as strapping,
crane hooks, chains or rollers are being used, suitable protective material should be
placed between the stainless and carbon steel to prevent damage. Clean, heavy cardboard
or light plywood are suitable materials for this purpose. Erection tools such as spanners
and drifts should be stainless steel to ensure surface contamination does not take place.
Grinders should also be reserved exclusively for use on stainless steel.

Contact with organic contaminants such as oils, greases, dyes, glues, adhesive tape and
other similar deposits should be avoided. When they are used, their suitability should be
checked with their manufacturer. Stainless steel can be disfigured by certain chemicals
and checks should be made to ensure that any erection marks penned on the surface can
be easily removed.

The designer must specify any visual requirements so that the fabricator can take due care
to protect the particular surface.

Should components require cleaning for aesthetic reasons, soap, detergent or a solution of
ammonia may be used with scrubbing brushes. The stainless steel should be rinsed down
afterwards with clean water and then wiped dry. Inspections to detect signs of mechanical
damage, surface contamination or incipient corrosion attack are recommended for
exposed architectural features.

Strong acid solutions are sometimes used to clean the masonry and tiling of buildings but
they should never be permitted to come into contact with any metal, including stainless
steel., If this should happen, the acid solution must be washed off immediately with
generous amounts of water.

6. CONCLUDING SUMMARY
• Stainless steel possesses superior corrosion resistance to carbon steel. This
resistance is provided by a passive film which forms on the surface of the metal
and prevents it from reacting with the environment.
 • Corrosion of stainless steel can occur where a grade is used in an environment for
which it is not suited or where the stainless steel has been treated in such a way
which reduces its corrosion resistance.
• There are a number of different corrosion mechanisms which can affect stainless
steel. These can be "designed out" by appropriate grade selection.
• Good detailing practice has an important role to play in improving corrosion
resistance; bad detailing can be detrimental to corrosion resistance.
• Where stainless steel is used for architectural purposes, it is important to avoid
contamination of the stainless steel surface by carbon steel which may
subsequently rust and stain the surface.

7. REFERENCES
[1] Burgan, B. A., Concise guide to the structural design of stainless steel, The Steel
Construction Institute, SCI-P-123, Second Edition, 1993.

[2] Nickel Development Institute, An architect's guide on corrosion resistance, NiDI,

1990.