European Journal of Scientific Research

ISSN 1450-216X Vol.22 No.4 (2008), pp.508-516

© EuroJournals Publishing, Inc. 2008
http://www.eurojournals.com/ejsr.htm

Corrosion Analysis of Stainless Steel

Seifedine Kadry
Lebanese International University, Lebanon
E-mail: skadry@gmail.com

Abstract

The article analyses stainless steel resistance to burning products released by heat
burners. The research methodology as well as result findings are presented in the article as
well.

Keywords: Stainless steel, corrosion.

Introduction
Ten years ago with the increase of fuel prices, upper combustion burners of solid fuel were being
replaced by lower combustion burners due to a longer burning cycle of loading and higher coefficient
of efficiency. The temperature of smoke, released from these types of burners is lower than 200 0C.
When the products of combustion cool down on the top of a chimney, water steam condenses [1, 2].
The condensate is made of various compounds, including sulfur as well. The saturated condensate
erodes the chimney and the soot that sticks in the place, where the condensate forms, blocks the
chimney. The saturated place of the chimney becomes more transcalent and the fume is cooled more
intensively; thus, the process speeds up and lower parts of the chimney saturate with the condensate as
well. These types of troubles could be avoided by fitting in a steel insert that weighs several kilograms.
The insert heats up very fast and the due point is passed over the period of 10-20 minutes as the air-gap
between the chimney and the insert contains quite a high resistance. However, the majority of stainless
steel is acid nonresistant; and the products of corrosion can include poisonous compounds of chromium
and nickel. In this article, we analyze the corrosion of chimney parts made of stainless steel under the
conditions of acid environment. Several types of stainless steel were examined.

Why stainless steels?

Corrosion is deterioration of essential properties in a material due to reactions with its surroundings.
Millions of dollars are lost each year because of corrosion [3]. Much of this loss is due to the corrosion
of iron and steel, although many other metals may corrode as well. The problem with iron as well as
many other metals is that the oxide formed by oxidation does not firmly adhere to the surface of the
metal and flakes off easily causing "pitting". Extensive pitting eventually causes structural weakness
and disintegration of the metal.
Although one of the main reasons why stainless steels are used is corrosion resistance, they do
in fact suffer from certain types of corrosion in some environments and care must be taken to select a
grade which will be suitable for the application. Corrosion can cause a variety of problems, depending
on the applications:
• Perforation such as of tanks and pipes, which allows leakage of fluids or gases,
Corrosion Analysis of Stainless Steel 509

• Loss of strength where the cross section of structural members is reduced by corrosion,
leading to a loss of strength of the structure and subsequent failure,
• Degradation of appearance, where corrosion products or pitting can detract from a
decorative surface finish,
• Finally, corrosion can produce scale or rust which can contaminate the material being
handled; this particularly applies in the case of food processing equipment.
Corrosion of stainless steels can be categorized as one of [4]:
• General Corrosion
• Pitting Corrosion
• Crevice Corrosion
• Stress Corrosion Cracking
• Sulfide Stress Corrosion Cracking
• Intergranular Corrosion
• Galvanic Corrosion
• Contact Corrosion

General Corrosion
Corrosion whereby there is a general uniform removal of material, by dissolution, e.g. when stainless
steel is used in chemical plant for containing strong acids. Design in this instance is based on published
data to predict the life of the component. Published data list the removal of metal over a year. Tables of
resistance to various chemicals are published by various organizations and a very large collection of
charts, lists, recommendations and technical papers are available though stainless steel manufacturers
and suppliers.

Pitting Corrosion
Under certain conditions, particularly involving high concentrations of chlorides (such as sodium
chloride in sea water), moderately high temperatures and exacerbated by low pH (i.e. acidic
conditions), very localized corrosion can occur leading to perforation of pipes and fittings etc. This is
not related to publish corrosion data as it is an extremely localized and severe corrosion which can
penetrate right through the cross section of the component. Grades high in chromium, and particularly
molybdenum and nitrogen, are more resistant to pitting corrosion.

Pitting Resistance Equivalent number (PRE)

The Pitting Resistance Equivalent number (PRE) has been found to give a good indication of the
pitting resistance of stainless steels. The PRE can be calculated as:
PRE = %Cr + 3.3 x %Mo + 16 x %N
One reason why pitting corrosion is so serious is that once a pit is initiated there is a strong
tendency for it to continue to grow, even although the majority of the surrounding steel is still
untouched. The tendency for a particular steel to be attacked by pitting corrosion can be evaluated in
the laboratory. A number of standard tests have been devised, the most common of which is that given
in ASTM G48. A graph can be drawn giving the temperature at which pitting corrosion is likely to
occur, as shown in Figure 1.
510 Seifedine Kadry
Figure 1: Temperature at which pitting corrosion is likely to occur

This is based on a standard ferric chloride laboratory test, but does predict outcomes in many
service conditions.

Crevice Corrosion
The corrosion resistance of a stainless steel is dependent on the presence of a protective oxide layer on
its surface, but it is possible under certain conditions for this oxide layer to break down, for example in
reducing acids, or in some types of combustion where the atmosphere is reducing. Areas where the
oxide layer can break down can also sometimes be the result of the way components are designed, for
example under gaskets, in sharp re-entrant corners or associated with incomplete weld penetration or
overlapping surfaces. These can all form crevices which can promote corrosion. To function as a
corrosion site, a crevice has to be of sufficient width to permit entry of the corrodent, but sufficiently
narrow to ensure that the corrodent remains stagnant. Accordingly crevice corrosion usually occurs in
gaps a few micrometers wide, and is not found in grooves or slots in which circulation of the corrodent
is possible. This problem can often be overcome by paying attention to the design of the component, in
particular to avoiding formation of crevices or at least keeping them as open as possible. Crevice
corrosion is a very similar mechanism to pitting corrosion; alloys resistant to one are generally resistant
to both. Crevice corrosion can be viewed as a more severe form of pitting corrosion as it will occur at
significantly lower temperatures than does pitting.

Stress Corrosion Cracking (SCC)

Under the combined effects of stress and certain corrosive environments stainless steels can be subject
to this very rapid and severe form of corrosion. The stresses must be tensile and can result from loads
applied in service, or stresses set up by the type of assembly e.g. interference fits of pins in holes, or
from residual stresses resulting from the method of fabrication such as cold working. The most
damaging environment is a solution of chlorides in water such as sea water, particularly at elevated
temperatures. As a consequence stainless steels are limited in their application for holding hot waters
(above about 50°C) containing even trace amounts of chlorides (more than a few parts per million).
This form of corrosion is only applicable to the austenitic group of steels and is related to the nickel
content. Grade 316 is not significantly more resistant to SCC than is 304. The duplex stainless steels
are much more resistant to SCC than are the austenitic grades, with grade 2205 being virtually immune
at temperatures up to about 150°C, and the super duplex grades are more resistant again. The ferritic
grades do not generally suffer from this problem at all. In some instances it has been found possible to
improve resistance to SCC by applying a compressive stress to the component at risk; this can be done
by shot penning the surface for instance. Another alternative is to ensure the product is free of tensile
stresses by annealing as a final operation. These solutions to the problem have been successful in some
cases, but need to be very carefully evaluated, as it may be very difficult to guarantee the absence of
residual or applied tensile stresses. From a practical standpoint, Grade 304 may be adequate under
Corrosion Analysis of Stainless Steel 511

certain conditions. For instance, Grade 304 is being used in water containing 100 - 300 parts per
million (ppm) chlorides at moderate temperatures. Trying to establish limits can be risky because
wet/dry conditions can concentrate chlorides and increase the probability of stress corrosion cracking.
The chloride content of seawater is about 2% (20,000 ppm). Seawater above 50°C is encountered in
applications such as heat exchangers for coastal power stations. Recently there have been a small
number of instances of chloride stress corrosion failures at lower temperatures than previously thought
possible. These have occurred in the warm, moist atmosphere above indoor chlorinated swimming
pools where stainless steel (generally Grade 316) fixtures are often used to suspend items such as
ventilation ducting. Temperatures as low as 30 to 40°C have been involved. There have also been
failures due to stress corrosion at higher temperatures with chloride levels as low as 10 ppm. This very
serious problem is not yet fully understood.

Sulfide Stress Corrosion Cracking (SSC)

Of greatest importance to many users in the oil and gas industry is the material's resistance to Sulfide
stress corrosion cracking. The mechanism of SSC has not been defined unambiguously but involves
the conjoint action of chloride and hydrogen Sulfide, requires the presence of a tensile stress and has a
non-linear relationship with temperature. The three main factors are Stress Level, Environment and
Temperature.

Stress Level
A threshold stress can sometimes can be identified for each material - environment combination. Some
published data show a continuous fall of threshold stress with increasing H2S levels. To guard against
SSC NACE specification MR0175 for Sulfide environments limits the common austenitic grades to
22HRC maximum hardness [5].

Environment
The principal agents being chloride, hydrogen Sulfide and pH. There is synergism between these
effects, with an apparently inhibiting effect of Sulfide at high H2S levels.

Temperature
With increasing temperature, the contribution of chloride increases but the effect of hydrogen
decreases due to its increased mobility in the ferrite matrix. The net result is a maximum susceptibility
in the region 60-100°C. A number of secondary factors have also been identified, including amount of
ferrite, surface condition, presence of cold work and heat tint at welds.

Intergranular Corrosion
Intergranular corrosion is a form of relatively rapid and localized corrosion associated with a defective
microstructure known as carbide precipitation. When austenitic steels have been exposed for a period
of time in the range of approximately 425 to 850°C, or when the steel has been heated to higher
temperatures and allowed to cool through that temperature range at a relatively slow rate (such as
occurs after welding or air cooling after annealing), the chromium and carbon in the steel combine to
form chromium carbide particles along the grain boundaries throughout the steel. Formation of these
carbide particles in the grain boundaries depletes the surrounding metal of chromium and reduces its
corrosion resistance, allowing the steel to corrode preferentially along the grain boundaries. Steel in
this condition is said to be "sensitized". It should be noted that carbide precipitation depends upon
carbon content, temperature and time at temperature. The most critical temperature range is around
700°C, at which 0.06% carbon steels will precipitate carbides in about 2 minutes, whereas 0.02%
carbon steels are effectively immune from this problem. It is possible to reclaim steel which suffers
from carbide precipitation by heating it above 1000°C, followed by water quenching to retain the
carbon and chromium in solution and so prevent the formation of carbides. Most structures which are
welded or heated cannot be given this heat treatment and therefore special grades of steel have been
512 Seifedine Kadry

designed to avoid this problem. These are the stabilized grades 321 (stabilized with titanium) and 347
(stabilized with niobium). Titanium and niobium each have much higher affinities for carbon than
chromium and therefore titanium carbides, niobium carbides and tantalum carbides form instead of
chromium carbides, leaving the chromium in solution and ensuring full corrosion resistance [6].
Another method used to overcome intergranular corrosion is to use the extra low carbon grades
such as Grades 316L and 304L; these have extremely low carbon levels (generally less than 0.03%)
and are therefore considerably more resistant to the precipitation of carbide.
Many environments do not cause intergranular corrosion in sensitized austenitic stainless steels,
for example, glacial acetic acid at room temperature, alkaline salt solution such as sodium carbonate,
potable water and most inland bodies of fresh water. For such environments, it would not be necessary
to be concerned about sensitization. There is also generally no problem in light gauge steel since it
usually cools very quickly following welding or other exposure to high temperatures.
It is also the case that the presence of grain boundary carbides is not harmful to the high
temperature strength of stainless steels. Grades which are specifically intended for these applications
often intentionally have high carbon contents as these increases their high temperature strength and
creep resistance. These are the "H" variants such as grades 304H, 316H, 321H and 347H, and also 310.
All of these have carbon contents deliberately in the range in which precipitation will occur [7].

Galvanic Corrosion
Because corrosion is an electrochemical process involving the flow of electric current, corrosion can be
generated by a galvanic effect which arises from the contact of dissimilar metals in an electrolyte (an
electrolyte is an electrically conductive liquid). In fact three conditions are required for galvanic
corrosion to proceed; the two metals must be widely separated on the galvanic series (see Figure 2),
they must be in electrical contact and their surfaces must be bridged by an electrically conducting fluid.
Removal of any of these three conditions will prevent galvanic corrosion [8, 9].

Figure 2: Galvanic series for metals in flowing sea water.

The obvious means of prevention is therefore to avoid mixed metal fabrications. Frequently this
is not practical, but prevention can also be by removing the electrical contact - this can be achieved by
the use of plastic or rubber washers or sleeves or by ensuring the absence of the electrolyte such as by
improvement to draining or by the use of protective hoods. This effect is also dependent upon the
relative areas of the dissimilar metals. If the area of the less noble material (the anodic material, further
towards the right in Figure 2) is large compared to that of the more noble (cathodic) the corrosive
Corrosion Analysis of Stainless Steel 513

effect is greatly reduced, and may in fact become negligible. Conversely a large area of noble metal in
contact with a small area of less noble will accelerate the galvanic corrosion rate. For example it is
common practice to fasten aluminum sheets with stainless steel screws, but aluminum screws in a large
area of stainless steel are likely to rapidly corrode.

Contact Corrosion
This combines elements of pitting, crevice and galvanic corrosion, and occurs where small particles of
foreign matter, in particular carbon steel, are left on a stainless steel surface. The attack starts as a
galvanic cell - the particle of foreign matter is anodic and hence likely to be quickly corroded away, but
in severe cases a pit may also form in the stainless steel, and pitting corrosion can continue from this
point. The most prevalent cause is debris from nearby grinding of carbon steel, or use of tools
contaminated with carbon steel. For this reason some fabricators have dedicated stainless steel
workshops where contact with carbon steel is totally avoided. All workshops and warehouses handling
or storing stainless steels must also be aware of this potential problem, and take precautions to prevent
it. Protective plastic, wood or carpet strips can be used to prevent contact between stainless steel
products and carbon steel storage racks. Other handling equipment to be protected includes fork lift
tines and crane lifting fixtures. Clean fabric slings have often been found to be a useful alternative [10].
Passivation and Pickling
If stainless steel does become contaminated by carbon steel debris this can be removed by
passivation with dilute nitric acid or pickling with a mix of hydrofluoric and nitric acids [11].

Experiment Results
The article analyses the corrosion of chimney parts made of stainless steel under the conditions of acid
environment. Several types of stainless steel were examined. The chemical composition of the types of
steel researched is presented in Table 1.

Table 1: Chemical composition of stainless steel

Chemical composition %
Sample number
C Si Mn Cu Al Cr Mo Ni V Ti Nb
a 0.08 0.48 1.45 0.20 0.065 18.48 2.05 10.89 0.07 0.52 0.01
b 0.06 0.54 1.92 0.26 0.41 17.85 2.19 10.95 0.07 0.25 0.01
c 0.06 0.38 1.59 0.19 0.007 18.95 0.32 9.05 0.07 0.01 0.00

The resistance of steels for corrosion was examined using 10 % sulfuric acid with impurities of
sodium chloride. The samples were preserved in the solution for a particular period and the loss of the
weight of a sample was indicated. The software “Statistics” was used for carrying out statistic
calculations.
The results of the analysis are indicated in Fig. 1. The findings clearly indicate that stainless
steel resistance to corrosion in 10% sulfuric acid depends on its chemical composition. The most
resistant steels are the ones, containing titanium and molybdenum. The total loss of the weight of the
sample, including 0, 52 % titanium and 2, 05 % molybdenum, kept in the sulfuric acid for 30 days and
night was 1, 97 mg/dm2. The total loss of weight of stainless steel sample containing 0, 01% of
titanium and 0, 32% of molybdenum, examined under the same conditions was135 mg/dm2. The
impurity of chlorides of the solution decreases the resistance of stainless steel to corrosion.
514 Seifedine Kadry
Figure 1: The loss of chromium, nickel and iron within the samples of stainless steel, affected by 10 %
sulfuric acid with impurities of sodium chloride. a, b, c indicate a steel sample number.

The existence of titanium and molybdenum in the composition of stainless steel increases its
resistance to corrosion noticeably if the amount of chloride impurities does not exceed 2 %. The most
resistant steels have mono-phase structure; however, under the conditions of higher concentration of
chloride impurities, the weight loss of all the composition samples is similar. The addition of
molybdenum decreases the resistance to corrosion of the steels of 316, when they are affected by nitric
acid of higher concentration, but the amount of nitrogen compounds is small.
The structure of the type of stainless steel, containing a bigger amount of molybdenum and
titanium in its composition (sample 1) is smaller in comparison to sample 3 (Fig. 2) that contains a
smaller concentration of titanium and molybdenum. Usually the types of steel that have bigger iron
granules are less corrosion resistant [12].
The chemical composition of sample 1 corresponds to the type of steel 1.4301. The pictures of
parts of the insert for a chimney made of this type of steel, used for 6 years are displayed in Fig. 3.

Figure 2: The structure of stainless steel samples

Corrosion Analysis of Stainless Steel 515
Figure 3: The pictures of the chimney insert after 6 years of usage

The picture reveals that the lowest part of the chimney near the cleaning opening was most
corrosion affected. Here the flowing condensate does not dry up for a long time as hot products of
combustion do not pass. The Fig. 3 presents affected spot-welding places. Steels containing 17 % of
chromium are assigned to a poli-ferrite or ferrite class. If the amount of carbon is close to 0, 1 %, steel
can be assigned to a class of semi-ferrites. This type of steel is marked by a reduced resistance to
corrosion in the places of welding seams. This is partially determined by metal granules, increased due
to high temperature during the process of welding [3]. The intercrystalline corrosion is more easily
observed in these types of steel. The addition of titanium increases corrosion resistance, but the
minimum margin of titanium should be five times bigger in comparison to carbon. Fig. 3 presents a
part made of this composition of steel, containing 0,08 % of carbon, 0,39 % of titanium, 18,63 % of
chromium, 9,12 % of nickel, 0,30 % of molybdenum, 1,05 % of manganese, 0,35 % of silicon, 0,25 %
of copper, 0,116 % of aluminum, 0,09 % of vanadium, 0,03 % of niobium, 0.07 % of cobalt and 0,50
% of wolfram. The article presents the composition of steels indicates applying the method of a
spectral analysis with a spectrum analyzer Belec 2000.

Conclusions
Following the conclusions of the experimental tests:
• The most stable steels in the aggressive environment of condensate are those with a bigger
amount of titanium and molybdenum.
• Chloride ions, existing in combustion, decrease corrosion resistance of chromic-nickel steels.
• It is necessary to find out for solutions how to increase corrosion resistance of welded parts.
516 Seifedine Kadry

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Atmospheric Environment, 1983, V. 17, N 9, p. 1837.
[2] Baltenenneck S. Flue Pipes in Stain-steel. - Revue de metallurgie-caniers d informations
techniques, 1994, 91(10), p.1469.
[3] http://www.azom.com/details.asp?ArticleID=1257#_Sensitivity_Analysis
[4] Steel Glossary. American Iron and Steel Institute (AISI). Retrieved on July 30, 2006.
[5] Ashby, Michael F.; & David R. H. Jones [1986] (1992). "Chapter 12", Engineering Materials 2,
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[6] What is Stainless Steel?. Nickel Institute. Retrieved on 2007-08-13.
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[11] ThyssenKrupp Nirosta: History. Retrieved on 2007-08-13.
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