353

SUSCEPTIBILITY OF STAINLESS STEEL WELDMENTS TO

MICROBIOLOGICALLY INFLUENCED CORROSION

SUSAN WATKINS BORENSTEIN

Pacific Gas and Electric Co., PO Box 77000 F1634, San Francisco, CA 94106

ABSTRACT
Microbiologically influenced corrosion (MIC) is the term used for the phenomenon where
corrosion is initiated or accelerated by microorganisms. Biofilms of bacteria form on metal surfaces
when exposed to natural waters. The activity of these biofilms and how they attach themselves to
metal surfaces directly influence corrosion mechanisms.
This paper describes the mechanisms for MIC and the factors which influence the
susceptibility of austenitic stainless steel weidments to MIC. The metallurgical, microbiological and
electrochemical factors that influence MIC are discussed. Case histories of MIC-related failures and
field test results of austenitic stainless steel weldments in various welded conditions are presented.

INTRODUCTION
For the last several years there has been renewed interest in MIC, although corrosion initiated
or accelerated by microorganisms has been recognized since the 30's. 1 For example, power
generation facilities have had many problems with MIC failures requiring costly repair 2-6
Analyses of costly pitting failures at nuclear power plants, chemical process plants, and pulp and
paper mills have indicated that stainless steels are susceptible to MIC. 7 tn particular, attack in the
form of pitting at or adjacent to weldments in austenitic stainless steels often occurs. Although
pitting is very localized, pitting failures can be devastating and lead to expensive repairs.
Many MIC failures in industry result in pitting or general corrosion to metals. In many cases
the engineers who perform the failure analyses do not consider MIC until it is too late to obtain
scrapings, water samples and corrosion deposit samples for analysis.
The following paper summarizes how biofilms are formed, mechanisms for MIC, how
corrosion is associated with weldments, and case studies of MIC. In addition to discussing case
histories, this paper reviews how welding, heat treatment and other metallurgical and process
variables relate to corrosion resistance.

MECHANISMS FOR MIC

One common example of MIC failures results when untreated or poorly treated water remains
in stainless steel components or piping systems after hydrostatic testing. Hydrostatic testing, also
known as hydrotesting, consists of filling the system with water and checking for leaks and
structural integrity under pressure. Although stagnant water conditions, per se, are not likely to
produce direct corrosive attack because of the inherent corrosion resistance of the materials, they
are ideal for MIC.
It is very important to remember that natural water and even potable water contains bacteria.
The concept of "good water" is often treated very lightly. Costly failures have resulted from the
failure to keep the water properly treated. In general, water will pick up significant amounts of
contaminants and organisms if stored more than three days in equipment or storage vessels. This is

Mat. Res. Soc. Symp. Proc. Vol. 294. 1993 Materials Research Society

354

especially true during hydrostatic testing. Of course, the exception is when the water is being
monitored or treated regularly or if the water is kept under the close supervision of a water
treatment specialist.
The microorganisms' metabolic processes, 8which are sustained by chemical reactions, can
influence the corrosion behavior of materials by:
1. Destroying the protective surface films;
2. Producing a localized acidic or sulfide-rich environment;
3. Creating corrosive deposits;
4. Altering anodic and cathodic reactions depending on the environment and organisms involved,
or other, less understood, mechanisms.
Development of a Biofilm
Natural water and even potable water contain bacteria. When a metallic surface is immersed in
natural water, two processes occur simultaneously: corrosion starts immediately, and a biofilm
9
begins to form. A biofilm is a microbial mass composed of aquatic bacteria, algae and other
microorganisms. See Figure 1.

Flowing Water

BulkFluid

Aerobic Biofilm
Anaerobic Biofilm

Substrate

Figure 1. Sketch of Biofilm Formed on a Metal Surface

10
Microorganisms can adhere to almost any surface in contact with natural waters. 1 Organisms
reproduce and many produce exopolymers, secretions which form a matrix of fibers. 1,12
13
The development of a film can be divided into four stages. The four stages are as follows:

&

Comments

1. Conditioning

Instantaneous chemical adsorption of

organics; organisms not directly involved

2. Colonization by "pioneer"
bacterial species

Fast growing bacterial periphytes become

established in a matter of hours

3. Colonization by
microorganisms

Other bacteria and fungi may develop

extensively in a matter of days

4. Accumulation

Adhesion of particles, dead cells and

chelation of heavy metals from water (both as
corrosion products and ions in bulk solution)

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AUSTENITIC STAINLESS STEELS

Welding of Stainless Steels
Austenitic stainless steels are the most weldable of the four types of other stainless steels.
Strength requirements, as well as the factors of corrosion and oxidation resistance, make it
necessary for the weld metal composition of stainless steels to match fairly closely the base metal
composition. 14 The properties and characteristics of the metals must be accounted for in welding to
avoid subsequent corrosion susceptibility problems.
Austenitic steels have a higher coefficient of expansion, higher electrical resistivity, and
lower thermal conductivity than ferritic steels. The lower thermal conductivity of austenitic
stainless steel results in higher metal temperatures in the weld region. Therefore, these alloys often
require the use of a low heat input welding process. Figure 2 shows in a general sense how a weld
is commonly made. Generalities in the behavior of the materials being joined14during welding and
physical events that take place during welding may be summarized as follows:
1. The base metal is partially melted and the regions near the weld are heated to high temperatures.
2. The weld metal'forms a miniature casting which becomes an ingot upon solidification.
3. Stresses and strains result from the conditions encountered during welding (related to the
temperature changes and solidification).
4. Some chemical reactions can occur such as alloying or oxidation.
5. The temperature changes are extremely rapid and usually localized.

Prepared weld joint

Root pass of weld

HAZ

Completed weld
Figure 2. Schematic of How a Weld is Made

Welded joints consist of two basic areas: the heat-affected zone (HAZ), which includes the
volume of unmelted base metal immediately adjacent to the weld metal nugget, and the cast weld
metal. The properties of the HAZ are determined by the composition of the base metal and the
thermal cycles (heating and cooling) resulting from welding or heat treatment. The properties of the
cast weld metal are determined by chemical composition, dissolved gases, and thermal cycles,
assuming that the deposited metal is sound and free from cracks or porosity.

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Weld Microstructure of Stainless Steels

The overall arrangement of grains, boundaries, and phases present in a metal alloy is termed
microstructure and is largely responsible for the properties of the alloy. 14 Weld microstructure
depends on the chemical composition, the solidification mode, and the cooling rate. 15 Depending
on the way the austenitic stainless steel weld is made and the composition of filler metal, the
microstructure is either fully austenitic or duplex (austenite plus delta ferrite).
Austenitic stainless steels are basically iron-chromium-nickel alloys with varying amounts of
carbon and other elements to provide special properties. A small amount of delta ferrite (which
forms at elevated temperature) may remain in a metastable form after cooling to room temperature
of these nominally fully austenitic steels. The amount of delta ferrite which is present in the weld is
described by means of a ferrite number (FN), which roughly corresponds to the percentage of
ferrite in the weld. Austenitic stainless steel welds commonly have a structure that consists of
vermicular delta ferrite, which is the primary solidifying phase. 16
The composition (amount of alloying element added) is important. The tendency to form delta
ferrite at the solution treatment temperature will decrease if the element added is an austenite former
or increase if a ferrite former. 17 ,18 Using empirical constitution diagrams proposed by Schaeffler
and DeLong 1 9,20 the as-welded ferrite content can be predicted from the chemical composition of
the deposited weld metal. The balance between ferrite forming elements (expressed as chromium
equivalent [Creq]) and austenite formers (expressed as a nickel equivalent [Nieq]) controls the
structure of the weld metal. The influence of the residual elements is factored into the equations for
Creq and Nieq. Chemical compositions of welding electrodes generally aim at a balance giving 3 to
10 percent ferrite in the weld deposit.
The ferrite in a weld exhibits a relatively high solubility for sulfur, phosphorous, and other
constituents which are known to cause hot cracking. 21 ,2 2 Consequently, welds which contain too
little delta ferrite are susceptible to hot cracking. On the other hand, too much ferrite can produce a
cracking problem in service under certain conditions.
Sensitization
Sensitization, the susceptibility of stainless steels to intergranular corrosion (localized attack
occurring along the grain boundaries), can occur after thermal processing or as a result of
welding. 2 3 Sensitization in austenitic stainless steels can occur under the following conditions:
1. Ordinary stainless as-welded,
2. Ordinary stainless improperly heat treated
3. Stabilized stainless improperly heat treated.
Austenitic stainless steels are solid solutions of chromium and nickel in iron. When the
solubility for carbon is exceeded (within the matrix), a second phase forms. Upon heating, the
second phase chromium carbides tend to nucleate and grow at the grain boundaries. As the
carbides form, they deplete chromium in the adjacent region. A minimum chromium level (about
12 percent Cr) is required to maintain a protective passive film on stainless steels. The chromiumdepleted regions do not contain enough chromium to maintain this protective passive film and
consequently are susceptible to corrosion.
Carbon content is the most important factor in determining the susceptibility of austenitic
stainless steels to sensitization. The carbon content can be limited
by changing to L-grade (carbon
24
below 0.03 percent) material. This usually avoids sensitization.
Sensitization occurs when the austenitic stainless steels are heated or cooled slowly through the
sensitizing range of 800 to 1600 degrees F. Good welding practice limits the maximum interpass
temperature (temperature between passes) to 350 degrees F as a practical limit for minimizing
sensitization by reducing the amount of time spent in the sensitizing temperature range.
A method of testing for sensitization is described in ASTM A262 "Standard Practices for
Detecting Susceptibility to Intergranular Attack in Austenitic Stainless Steels."

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Corrosion of Weldments
In general, for austenitic stainless steels, the weld metal is less resistant to pitting than the base
metal. This is due to differences in composition and structure resulting from the rapid heating and
cooling rates produced by welding. Weld metal properties may differ from the base metal even
when the nominal compositions are matching since the filler metal composition is usually adjusted
to provide an optimum amount of ferrite as discussed above to prevent hot cracking. The weld
usually contains ferrite which is not present in the base metal.
Stalder and Duquette 25 found a higher pitting potential for welded 304L stainless steel with 710 FN than for unwelded fully austenitic stainless steel. They found that for the duplex (austenite
and ferrite) structure, pit initiation occurred both in the austenite phase and on the ferrite-austenite
boundary.
Garner 2 6 studied the pitting of austenitic stainless steels in both the welded and unwelded
conditions. He found that autogenous welding had a detrimental effect on pitting resistance. The
2 26
pitting potential and the critical pitting temperature were lower for welded than unwelded steel. 5,
27
Other studies ,28 showed that pits can develop as a result of the action of a macrocell between the
anodic weld metal and cathodic base metal. This is considered significant in terms of MIC. It is this
area of electrical activity that may influence the bacteria to select weldments for colonization,
leading to localized corrosion cells and subsequent pitting corrosion.
Heat Tint
Heat tint is an oxide film on the surface of a metal typically occurring after welding. For
austenitic stainless steels the film is composed primarily of iron and chromium which have been
selectively oxidized from the base metal. The heat tint area is less corrosion resistant than the
unaffected area. 29 Certain environments are more actively aggressive to the heat tint and some
30
alloys are more resistant than others when heat tinted.

CASE HISTORIES
The austenitic stainless steels have the best corrosion resistance of the four groups of stainless
steels and so are often chosen for corrosive service. The corrosion resistance of austenitic stainless
31
steels is a result of the passive oxide film. This film is not completely understood, but Uhlig
describes it as an adsorbed layer of oxygen and other ions. The passive
film can break down and result in corrosion in certain environments. For austenitic stainless steels
the resulting corrosion often takes the form of localized corrosion attack.
32
Most documented cases of MIC to austenitic stainless steels involve localized corrosion.
There are two general conditions in which MIC to austenitic stainless steels can occur. These are
33
(1) after hydrostatic testing or during outages and (2) in crevice or gasket conditions.
Kobrin 34 reported MIC to 304L and 316L used in storage tanks. The tanks failed due to MIC
after hydrostatic testing. The chloride content of the water was 20 ppm and the tanks were drained
after testing but refilled later. The corrosion was detected two to four months later when the welds
were found to be leaking. Inspection revealed many pits originating on the inside surfaces of the
tanks at the butt welds. The pits were under reddish-brown deposits and showed a large
subsurface cavity and a small surface pinhole. Water analyses showed high concentrations of the
iron bacteria, Gallionella,and the iron and manganese bacteria, Siderocapsa..
Tatnall 35 discussed MIC to gasketed flanges in a Type 304 stainless steel piping system. The
system had been in service for 3 years using river water. The corrosion sites were covered by
slimy brown deposits. The pitting was characterized by broad open pits. Adjacent to the corroded
area were black deposits that smelled like H2 S when treated with HCI. Analysis showed high
concentrations of iron bacteria and slime-forming bacteria and sulfate reducing bacteria.

358

Kearns and Borenstein 36 reported on field tests of several austenitic stainless steels in various
welded conditions. They found Types 304L and 316L base metals welded with ER308L and E312
filler metals are susceptible to MIC in the as-welded condition. Solution annealing and pickling
were found to significantly reduce the susceptibility of welded Types 304L and 316L pipe. It was
not possible to determine if pickling would have decreased susceptibility to MIC. The ferrite
numbers (FN) ranged from 0.3 to greater than 28, as measured with a magna gage. The FN of the
ER308L welds decreased with solution annealing, but the welds made using E312 filler maintained
a FN greater than 28 after solution annealing. No pits were found on any of the solution annealed
and pickled welds.

CONCLUSIONS
Resistance to corrosion for austenitic stainless steels is strongly affected by practices of design.
fabrication, surface conditioning, and maintenance 37 . Metallurgical features that could influence the
corrosion of welds in microbially active water include ferrite content, filler metal composition.
sensitization and heat tint. MIC to austenitic stainless steel welds is generally found as pitting, at oi
adjacent to weldments. These pits are usually found under tubercles at welds or in the heat affectec
zone regions.
Major factors in material selection include cost, material properties, fabrication characteristics,
and resistance to corrosion. Resistance to corrosion is important not only during service but alsc
during repair and refurbishment. Metallurgical aspects such as surface features, composition
welding details, etc. affect a metal's susceptibility to MIC.
The following generalizations can be made about MIC in austenitic stainless steels:

"*
"
"*
"*
"*

MIC often occurs near weldments in austenitic stainless steels. The pitting may be in the weld
in the HAZ, in the base metal near the weld, or along the fusion line. Either or both phases
delta ferrite and austenite, may be susceptible to MIC. In general, two-phase microstructure:
are less corrosion resistant to MIC than single phase structures.
Various combinations of weld metal and base metal have resulted in failures by MIC.
Welds made with various amounts of filler metal in both 304L and 316L stainless steel hav(
failed by MIC.
Sensitization is sometimes found in combination with MIC in failures of austenitic stainles;
steel welds.
Surface conditions that are associated with poor corrosion resistance may increase thi
susceptibility to MIC.

ACKNOWLEDGMENTS
The author would like to thank the following microbiologists and corrosion scientists for thei
numerous discussions on MIC; D. N.J.E. Dowling - UNIREC, Lyon, France, Dr. R.A
Buchanan-Univ. of Tennessee at Knoxville. In addition, I would like to thank Dr. R.A. White ani
Mr. Yun Chung - Bechtel Group, Inc. of San Francisco and Dr. D.C. White - Institute for Appliei
Microbiology, Univ. of Tennessee at Knoxville for their advice and support. And special thanks b
Mr. J.R. Kearns of Allegheny Ludlum Corp. and Mr. D.E. Sachs of Arizona Public Service o
Wintersburg, AZ for their encouragement.

359

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27
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17
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15 9 2
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Parkville, Australia,Extended Abstracts, (1975).
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(MS Thesis, University. of Tennessee, 1983).
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Engineers, Houston, TX, 1986), p. 12 1 .
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466
.
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Metals Park, OH, 1987), p. 115.
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Metals Park, OH, 1987), p. 117.
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1986), p. 33.

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35.
36.
37.

R.E. Tatnall, Materials Performance 20 (8), p. 41 (1981).

J.R. Kearns and S.W. Borenstein in Proceedings Corrosion/91 (NACE, Houston, TX.
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