See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/287690751

MIC of storage tank aluminum floating roofs during hydrotest

Article  in  Materials Performance · April 2002

CITATIONS READS

8 1,363

4 authors, including:

Robert Armon Alec Shaya Groysman

Technion - Israel Institute of Technology Technion - Israel Institute of Technology
150 PUBLICATIONS   3,311 CITATIONS    52 PUBLICATIONS   671 CITATIONS   

SEE PROFILE SEE PROFILE

David Starosvetsky
Technion - Israel Institute of Technology
58 PUBLICATIONS   1,931 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Algae - CO2 capture and storage View project

General environmental microbiology View project

All content following this page was uploaded by Robert Armon on 06 June 2017.

The user has requested enhancement of the downloaded file.

 This article was originally published in a journal published by
Elsevier, and the attached copy is provided by Elsevier for the
author’s benefit and for the benefit of the author’s institution, for
non-commercial research and educational use including without
limitation use in instruction at your institution, sending it to specific
colleagues that you know, and providing a copy to your institution’s
administrator.
All other uses, reproduction and distribution, including without
limitation commercial reprints, selling or licensing copies or access,
or posting on open internet sites, your personal or institution’s
website or repository, are prohibited. For exceptions, permission
may be sought for such use through Elsevier’s permissions site at:

http://www.elsevier.com/locate/permissionusematerial
 Engineering Failure Analysis 14 (2007) 1500–1511
www.elsevier.com/locate/engfailanal

Identification of microbiologically influenced corrosion (MIC)

py
in industrial equipment failures
a,*
, D. Starosvetsky b, R. Armon a

co
J. Starosvetsky
a
Division of Environmental, Water and Agricultural Engineering, Faculty of Civil Engineering, Technion, Haifa 32000, Israel
b
Division of Corrosion and Electrochemical Processes, Faculty of Materials Engineering, Technion, Haifa 32000, Israel

Received 17 August 2006; accepted 6 January 2007

Available online 2 March 2007

Abstract
al
on
The present study demonstrates different approaches towards MIC identification in three real cases of technological
equipment failures.
In the first case the failure of carbon steel heat exchanger as a result of tubes, lids, tube sheets, and connection pipes
rs

clogging was investigated. Chemical analysis of cooling water and precipitates, as well laboratory screening of deposits
for bacteria, revealed that activity of iron-oxidizing bacteria present in cooling water led to heat exchanger blockage.
The second case is related to MIC detection on floating roofs made of magnesium–aluminum alloy following a 3-weeks
pe

hydro-test. Corrosion tests carried out on the original and sterilized water used in hydro-test confirmed MIC process.
In the third case the potential of MIC occurrence in engine cooling system made of cast aluminum alloy and filled with
20% ethylene glycol coolant solution was evaluated. The simulation tests allowed determining the real causes of the severe
corrosion attack of examined system, including MIC high probability.
 2007 Elsevier Ltd. All rights reserved.

Keywords: MIC identification; Failure analysis; Simulation

r's

1. Introduction
o

In the last two decades MIC was recognized as an important mechanism of metallic construction materials
th

degradation. The heavy cost of microbial corrosion in various branches of modern industry is now well doc-
umented [1,2]. However, ignoring this problem, taking as yet place in practice, gives rise new and new case
histories of metallic equipment failure due to participation of microbes in corrosion processes.
Au

Uncovering of biological factor in corrosion processes that occurs in modern industry is quite an intricate
task, since MIC does not produce any unique type of localized corrosion. Even isolation of corrosion induced
microorganisms from a specific environment is not a sufficient argument to exclusively state that these
microbes were responsible in initiating or accelerating the corrosion failure. Successful identification of

*
Corresponding author. Tel.: +972 4 9591160.
E-mail address: starjean@tx.technion.ac.il (J. Starosvetsky).

1350-6307/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2007.01.020
 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511 1501

MIC having a multi-disciplinary nature requires an integrated approach. Chemical and microbiological anal-
ysis of the milieu, examination of metal characteristics and its corrosion behavior, examination of corrosion
products, etc. are necessary to understand the corrosion problem, however only corrosion process simulation
may exclusively confirm microorganisms contribution in the corrosion failure and assess their true role. In this
work we present three typical investigations from our failure analysis practice devoted to assessing of micro-
organisms involving in corrosion destructions occurred in Israeli industry.

2. Experimental

py
Water or coolant samples were collected in 1 L sterile plastic or glass containers. As a rule corrosion prod-
ucts were sampled from the most damaged sites of the corroded surface by scrapping. For microbiological
analysis part of the collected corrosion products were resuspended in sterile phosphate buffer. Prior to inves-

co
tigation the taken probes were stored at 4 C. Chemical composition of water was determined by atomic
adsorption method. Chemical composition and morphology of corrosion deposits were detected by means
energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). To estimate the role of micro-
organisms in destructive processes several bacterial groups were selected as an index of biofouling and biocor-
rosion potential: heterotrophic aerobic bacteria (HAB), sulfate-reducing bacteria (SRB), iron-oxidizing
bacteria (IOB) and fungi. These bacterial groups are dominant and most important microorganisms associ-

al
ated with bio-deposits formation and acceleration of corrosion processes. The isolation and count of the
microbes was performed according to Standard Methods [3] as it was described in [4–6].
on
3. Results and discussion

3.1. Case 1. Fouling of carbon steel heat exchanger caused by iron bacteria
rs

A carbon steel (CS) heat exchanger was installed along a fresh water line at the reverse osmosis unit at the
Haifa Refinery Plant, Israel. After 11/2 years from start-up the heat exchanger failed as a result of rust-colored
pe

deposits formation that clogged tubes, leads, tube sheets and connecting pipes. The goals of the study were to
detect the causes of such fast clogging occurred under operation conditions, to estimate the bacterial effect on
the process, and to evaluate the countermeasures.

3.1.1. Field conditions

The heat exchanger was used to heat water from 15 to 25 C during the cold season of the year, feeding a
reverse osmosis unit. During warm seasons, the heat exchanger was not active. Consequently, for several
r's

months the internal water was subjected to very low flow conditions or stagnancy. Feed water to the reverse
osmosis unit flowed through the tubes with steam on the shell side. The source water was a mixture of surface
and potable well water stored in a large open air reservoir.
o

3.1.2. On-site observation

th

Visual observation revealed that practically all parts of tested heat exchanger were plugged with brown rust
deposits in the form of various dimension tubercles, which were strongly adhered to the steel surface (Fig. 1a
and b). These deposits were accumulated from both sides of the heat exchanger (water inlet and outlet). The
Au

sediments layer thickness ranged from 1 to 6 cm. Shallow and dip pits (up to 10 mm) were detected on tube
sheets and led surfaces following removal of the tubercles. Both ends of the tubes were severely damaged by
corrosion.

3.1.3. Results of the investigations

The analyses of incoming water (Table 1) showed that this chemical combination could not provide an
extreme milieu that would cause the observed fast accumulation of rust detected on the internal heat exchan-
ger surface and high corrosion rate of CS.
Microbiological analysis conducted in water (planktonic bacteria) and in corrosion products scrapped from
the corroded surface (sessile bacteria) revealed (Table 2) that most of the cultivable bacteria were HAB. The
1502 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511

py
co
al
on
rs

Fig. 1. (a) Tube sheet ends damaged by corrosion beneath deposits. (b) Corrosion slime sediments formed on inside surface of the pipe.
pe

Table 1
Chemical composition of cooling water
Parameters Unit Value
pH – 6.9–7.4
p-alkalinity CaCO3 (ppm) 0
Total alkalinity CaCO3 (ppm) 80–190
Cl NaCl (ppm) 210–350
r's

SO2
4 SO2
4 (ppm) 40–48
Fe+2/Fe+3 (soluble) ppm 0.04–0.11
Fe (total) ppm 0.1–06
SiO2 ppm 5–10
o

Total hardness CaCO3 (ppm) 210–230

Ca hardness CaCO3 (ppm) 110–185
Mg hardness CaCO3 (ppm) 100–125
th

NO 3 ppm 8–11

NHþ 4 ppm 0.1–0.4
COD MgO2/L 3800–4700
Au

Chlorine ppm 0.2–0.7

TOC mg/L 2.8
Conductivity lS/cm 900–1100
Suspended solids ppm 1–4

cooling water carried a high concentration of iron bacteria and SRB. As expected, in the rust slime sediments
the concentration of these bacteria was several orders of magnitude higher, especially for iron bacteria (IOB)
and HAB.
Physicochemical analysis (EDS) of rust deposits sampled from internal surface of tested heat exchanger
showed that the examined slime contained up to 18% of organic substances. Elevated concentration of organic
 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511 1503

Table 2
Bacterial count of tested bacteria in cooling water and slime sediments
Microbial group type Planktonic bacteria (CFUa/ml) Sessile bacteria (CFU/g)
b
HAB (TPC) 2.2 · 104 4.5 · 109
SRBc (total count) 52 5.4 · 103
IOBd (total count) 4.0 · 102 4.9 · 107
a
CFU-colony forming units (viable cells).
b
Heterotrophic aerobic bacteria (HAB), total plate count (TPC).

py
c
Sulfate-reducing bacteria (SRB).
d
Iron-oxidizing bacteria (IOB).

co
matter detected in slime rust indicated participation of isolated microorganisms in the process of slime forma-
tion. Despite of the fact that concentration of HAB in examined rust was the highest, this type of bacteria
cannot be assumed to be responsible for accumulation of the large amounts of iron oxides and hydroxides,
which led to the heat exchanger clogging. The isolated both in water and corrosion products SRB, presumably
played certain role in localization of corrosion process occurred on heat exchanger surface under sediments,
but also did not participated in slime deposits formation. Even sulfur compound traces were not found in

al
scrapped deposits analyzed by EDS, despite the fact that H2S produced by SRB may react with metal ions
present in water to form insoluble sulfides of metals.
The corrosion failure and rusty slime accumulation found on the inner surface of the heat exchanger may be
on
attributed to iron bacteria activity. The EDS analysis revealed that sediments were comprised mainly of iron
and oxygen (2:3 ratio). According to SEM examination, the rust deposit contained two different morpholog-
ical forms: compact, dense particles, and crumbly, highly porous deposits with organic inclusions. After stain-
rs

ing the deposit with crystal violet solution, numerous filamentous bacteria cells were found among the rust
particles. The filaments resembled the classical form of iron-oxidizing (iron-precipitating) bacteria of Lepto-
thrix or Sphaerotilus genera. Microbiological analysis of iron bacteria mixed culture isolated from examined
pe

rusty slime showed that the culture consisted only of Sphaerotilus genera.
It is well known that these bacteria may significantly participate in rusty slime formation, producing
large amounts of iron oxides and hydroxides precipitates in a very short period of time. It was shown
that a biotic oxidation of rate of Fe(II) is at least one order of magnitude higher than an abiotic one.
At a biotic oxidation of Fe(II) rusty deposits are usually very abundant in comparison with bacterial cells.
Starkey [7] and Stephenson [8] calculated ratio iron-to-cell materials: it was 448–500:1. Iron–oxidizing bac-
teria generate energy for growth by oxidation of ferrous ions to ferric ions. Some types of iron bacteria
r's

may catalyze precipitation of preoxidized soluble ferric ions [9]. Iron bacteria were identified at high con-
centration both in the cooling water and particularly in corrosion sediments (Table 2). According to Culli-
mor and McCann [10], in running water iron bacteria proliferation could be observed if the ferrous ion
o

concentrations were to exceed 0.2–0.5 mg/l. Iron bacteria also may acquire iron from equipment materials
made of iron or CS (pipes, heat exchangers, etc.) In the present case concentration of soluble ferrous ions
th

in tested cooling water (see Table 1) was insufficient (<0.2 mg/l) to assist proliferation of iron bacteria.
Nevertheless, a high corrosion rate of CS in fresh water can provide a high rate of ferrous ions transfer
into the water phase, which can be used as additional energy source to iron-oxidizing and iron precipitat-
Au

ing bacteria. Hence, it is fair to assume that the investigated water system had a high potential to carry
iron bacteria activity, particularly through period of continuous flow. Under these favorable growth con-
ditions, iron bacteria present in cooling water could stimulate deposition of Fe(III) on the heat exchanger
inner surface, accelerating the corrosion rate of steel beneath deposits to cause plugging of the water
system.
This assumption is supported by experimental results, such as:

– An high ratio 1:5.5 between organic matter and inorganic iron-containing compounds, indicating that
deposits were most likely a result of microbial activity.
– High numbers of iron-oxidizing bacteria found in source water and particularly in rust sediments.
1504 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511

– The tubercle-shaped morphology of deposits, which are typical for rust slime formed due to iron bacteria
activity.

Thus, on the base of conducted investigations it was concluded that failure of tested heat exchanger (clog-
ging and severe localized corrosion) was directly related to the activity of iron-oxidizing bacteria detected in
use cooling water. Heat exchanger made of carbon steel most likely served as a nutrient source for iron bac-
teria. Continuous leaching of ferrous ions into the running water coupled with good aeration of running
water, resulted in corrosion of mild steel in fresh water encouraging aerobic iron bacteria growth and fast pro-

py
duction of large amounts of biogenic rusts. Pitting corrosion observed under rust-slime layers (tubercles) on
the parts of heat exchanger (tubes, sheets etc.) was probably caused by action of concentration cells formed on
metallic surface due to creation of differential aeration zones under primary deposits and accumulation of
SRB, chlorides and other corrosive components in that zones.

co
3.2. Case 2. MIC of aluminum alloy floating roofs for storage tanks during hydro-test

At Gadiv Petrochemical Company (Haifa, Israel) four steel tanks with aluminum alloy 5052 (USN A95052)
floating roofs were erected to storage of aromatic solvents. Prior to use, these tanks were hydrostatically tested
at ambient temperature for 3 weeks. The test revealed severe localized corrosion (up to full penetration) on

al
the underside of the roofs. In order to determine why tested roofs were subjected to such severe corrosion so
quickly, this study was performed.
on
3.2.1. Field conditions
The tanks of 3000 m3 volume were made of mild steel. Test water came from the fire water piping without
any pre-treatment. The tanks were filled and exposed to ambient temperature ranging from 12 C (night) to
rs

25 C (day) for 3 weeks. The floating roofs dimensions were 16.8 m in diameter and 0.48 mm. thick. Chemical
composition of the roof’s alloy was: (weight%): Mg 2.2–2.8; Si + Fe < 0.45; Cu max 0.1; Mn max 0.1; Al –
remainder.
pe

3.2.2. On-site observation and sampling

The roofs were inspected following drainage of water. Visual observation revealed that remarkable amount
of white corrosion products had formed on the underside of the roofs (Fig. 2a). The entire roof surface in con-
tact with water suffered severe localized corrosion. Shallow and deep pits, and even holes of various shapes
and dimensions, were found under the white deposits (Fig. 2b). Corrosion products were scraped from various
locations for chemical and microbiological composition. Water samples for chemical and microbiological
r's

analysis were collected from the fire water piping at the same tap that supplied the hydro-test water.

3.2.3. Results of the investigations

o

Table 3 shows the chemical composition of water used for hydro-test. The susceptibility of aluminum and
its alloys to localized corrosion is well known [11]. Chloride ions and pH are the main factors that determine
th

the corrosion resistance of aluminum and its alloys in water.

In the present study the pH of the water had a slightly basic value, which is not harmful to an aluminum
alloy. The high chloride content could be considered a potential cause of pitting attack initiation of the roofs.
Au

However, the water parameters likely would not have caused the fast and severe corrosion attack observed
during the hydro-test.
The EDS analysis revealed that corrosion products taken from different parts of the corroded aluminum
alloy roofs primarily contained aluminum and oxygen. Chlorides were detected in only one of the tested
probes. Analytical determination of chlorides in the corrosion products showed: their chloride content: was
0.17%. The concentration of sulfur and sulfates was 0.24%. It was found only minute amounts of copper,
silicon (alloying elements), carbon and calcium – and no traces of magnesium (the main alloying element
of the alloy) – in the corrosion products.
Water and corrosion product deposits were also tested for the presence of corrosion inducing microorgan-
isms (Table 4).
 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511 1505

py
co
al
on
rs
pe

Fig. 2. (a) Corrosion products formed on the underside of the roofs. (b) Severe localized corrosion of the roof ’s inside surface.

Table 3
The chemical content of the fire-extinguishing water
Parameter Unit Value
r's

pH 7.6–8.2
p-Alkalinity ppm CaCO3 2–40
Total alkalinity ppm CaCO3 150–200
Cl ppm 400–630
o

SO24 ppm 60–180

Total hardness ppm CaCO3 250–300
th

Ca hardness ppm CaCO3 110–160

Mg hardness ppm CaCO3 130–140
Iron ppm 0.5–16
Au

Oil ppm 1
NO 3 ppm 10
TOC ppm 3.0
Conductivity S/cm 900–1300

Results of microbiological analysis showed, that water used in hydro-test was contaminated with various
types of microorganisms considered highly corrosive. The fire water contained high concentrations of fungi
(1.7 · 102 cells/ml) and HAB and HAnB (>103cells/ml). SRB and iron-oxidizing bacteria were also isolated
from water samples, but T. thiooxidans was not detected. The number of isolated microorganisms in corrosion
products was two to four orders of magnitude higher than detected in water.
1506 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511

Table 4
Bacterial count of microorganisms in fire-extinguishing pipelines water and corrosion products
Microbial group type Water (CFU/ml) Corrosion products (CFU/g)
HAB (TPC) 2.4 · 103 2.2 · 107
HAnBa (TPC) 5.1 · 103 4.5 · 107
SRB (total count) 2.2 6.7 · 102
IOB (total count) 3.2 1.4 · 104
T. thiooxidans Not detected Not detected
Fungi (TPC) 7 · 102 8.0 · 106

py
a
Heterotrophic anaerobic bacteria (HAnB).

Microorganisms accumulation in the corrosion products indicates that biofouling processes occurred on
roof surfaces during the hydro-test. As known, biofouling may initiate and accelerate corrosion attack [1,2].

co
The availability of corrosion inducing microorganisms in water and even their adsorption to a surface is
required, but it alone is not a sufficient condition for biocorrosion process development. This process heavily
depends on metal or alloy type, physico-chemical parameters of the medium and microbial composition. A
very important factor in biocorrosion initiation is bacteria metabolic activity; it depends on the suitability
of the chemical compounds that are present in the water, which may serve as carbon and energy sources
required for bacterial metabolism.

al
Consequently, the chemical and microbiological results did not yield a definite conclusion on the role of
microorganisms in the corrosion attack. At this stage, there was no way to separate the corrosion effect of
chloride concentration from that of microorganisms.
on
To clarify the role of microorganisms in this matter, laboratory corrosion tests were performed with
untreated and membrane-filtration sterilized waters. In these experiments coupons made of aluminum alloy
Al 5052 (rings with diameter 30 mm, thickness 1.7 mm, and width 10 mm) and pure aluminum Al 1100
rs

(UNS A91100) (rectangular plates of 20 · 20 · 3 mm) were used. Chemical composition of tested aluminum
was: (weight% ) Cu 0.06; Al-remainder Table 5 shows the results.
No evidence of corrosion was detected on pure aluminum (1100) coupons exposed for 90 days in both
pe

untreated and sterilized by filtration waters. In addition, no signs of corrosion on Al 5052 aluminum alloy spec-
imens exposed to sterilized water were observed during the entire experiment. The aluminum alloy coupons
tested in untreated water revealed visual corrosion on the 14th day of exposure. The corroded areas exhibited
a strongly localized character and were accompanied by the formation of flaky, white corrosion products (Fig. 3).
Corrosion tests showed conclusively that the microflora in the water used for the hydrates played a very
important role in producing corrosion on the roofs.
Data show that microorganisms may severely damage aluminum and its alloys in a fairly short time period
r's

– even in such relatively clean (from a microbiological point of view) but unsterile media. High susceptibility
of aluminum and its alloys to localized corrosion makes it particularly vulnerable to MIC [12]. Hence, it is
reasonable to expect a higher risk of MIC initiation when untreated water is contaminated with corrosion-
o

inducing microorganisms.
The experiments demonstrated that in bacterially polluted water the aluminum-magnesium alloy coupons
th

sustained strong corrosion attack, unlike pure aluminum. It should be emphasized that both waters had the
same chloride concentration; this comparison indicates that an alloying element such as magnesium reduces
the corrosion resistance of aluminum. Because the corrosion product probes detected no traces of magnesium,
Au

one can assume that magnesium forms soluble corrosion products. A likely scenario is that magnesium ions
emitted from the corroded surface interact with some organic metabolites excreted by biofilm bacteria, creat-
ing soluble complex compounds. Pitting initiation on aluminum alloys is usually attributed to the presence of
chloride ions. The investigation revealed that the activity of microorganisms present in the surrounding
Table 5
Results of corrosion tests carried out for 90 days in untreated and sterilized fire water pipelines
Metal Untreated water Sterilized water
Al 1100 No corrosion No corrosion
Al 5052 Pitting corrosion on the 14th day of exposure No corrosion
 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511 1507

py
co
Fig. 3. Picture of Al 5052 alloy coupons exposed to original (left flask) and sterilized (right flask) waters on 14th day of corrosion test.

medium may substantially accelerate the corrosion process. It was demonstrated that strong localized corro-
sion of the aluminum alloy Al 5052 floating roofs that occurred during the hydrotesting was directly related to

al
the activity of microflora introduced with untreated water to tested tanks.

3.3. Case 3. Investigation of severe corrosion of aluminum parts from inoperative diesel engine cooling systems
on
Diesel engines were placed in long-term storage in an operational status in a low-humidity controlled atmo-
sphere to prevent corrosion. The engines were serviced every two years, a process that included the replace-
ment of engine coolant. Severe corrosion occurred on some of the aluminum components of the cooling
rs

systems (Fig. 4). The analysis was done in order to determine the causes of the acute corrosion.

3.3.1. Field conditions and on-site observations

pe

The coolant was a non-commercial, tailor-made formulation used for long-term storage. It was composed
of 99.4% ethylene glycol (EG) (to prevent freezing) and several corrosion inhibitors that were intended to pro-
o r's
th
Au

Fig. 4. Corrosion damage in cooling system components made of A03560 cast aluminum alloy. (a) Radiator elbow. (b) Thermostat cover.
(c) Radiator housing.
1508 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511

tect the various metal components of the engine (aluminum, copper, steel, cast iron, etc.) against corrosion.
The inhibitors consist of borates, nitrates, phosphates, silicates, and some supplementary organic inhibitors.
The coolant is supplied by several vendors and each lot is tested according to ASTM D-1384 [13] require-
ments. Because the coldest winter temperature in Israel is only near freezing, and also to cut maintenance
costs, the engine cooling systems were supplied with 20% coolant (diluted with tap water) instead of the usual
50% concentration. Field experience suggested that the concentration of EG might be lowered to a range of
20–30%.
During the scheduled replacement of the engine coolant, mechanics observed some leaks that were caused

py
by corrosion attack on various aluminum A03560-T6 parts such as: elbows, pipes, covers, etc. (Fig. 4).
The causes of observed corrosion failures were investigated.

3.3.2. Supplementary experimental procedure

co
The coolant samples (duplicates) from ten systems were examined for presence of corrosion induced micro-
organisms. To evaluate the possible proliferation of micro-flora in the coolant, the activity and growth of
HAB, which are naturally found in tap water, were monitored in coolant of various concentrations diluted
with tap water. Experiments were carried out in 1%, 5%, 10%, 20% and 50% (v/v) aqueous EG solutions pre-
pared from a stock coolant. With the aim of accelerating the process, 500 mL experimental solutions were
maintained at 31 C. The monitoring interval was 100 days.

al
The electrochemical behavior of cast aluminum alloy (A03560) specimens in coolant solutions was studied
in a standard 1 L electrochemical glass cell controlled by a M263 potentiostat/galvanostat (EG&G, USA). The
potentials throughout the text refer to a saturated calomel electrode (SCE). A platinum wire was used as a
on
counter electrode. These experiments were carried out on 15 · 15 · 3 mm flag-type specimens that were cut
of the damaged parts. Prior to measurement, the specimens were degreased in acetone, washed in distilled
water, and air-dried. Potentiodynamic cathodic and anodic polarization curves were measured at a scan rate
rs

of 1 mV/s. The potentiodynamic measurements were initiated from an extra negative potential (250 mV)
compared to steady-state Ecorr value of a working electrode.
pe

3.3.3. Results and discussion

To evaluate the possible microbial contribution to corrosion damage, a microbiological analysis of corro-
sion-inducing microorganisms was performed with coolant probes sampled from several cooling systems
(Table 6). The coolant probes were originally contaminated with corrosive microorganisms capable of induc-
ing biofouling and corrosion processes under appropriate conditions. MIC associated with contaminated die-
sel engine coolants was previously reported [14].
The isolated microorganisms were presumably introduced into the system through non-sterile tap water
r's

used to dilute the coolant. Chemical composition of the water was very close to that given in Table 1. An addi-
tional aspect was revealed during bacterial counting of the experimental probes: the higher the dilution of
coolant, the higher the number of HAB detected. This phenomenon occurs when certain dilution of the cool-
o

ant diminishes the biocidic effect of present inhibitors. The original combination of parameters such as: (a)
th

Table 6
Composition of corrosion-inducing microorganisms in the coolant probes (CFU/100 ml)
Number pH HAB SRB Iron Bacteria Fungi and Yeast
Au

a
1 8.40 48 N.D. N.D. 8
2 8.20 1.2 · 105 N.D. N.D. 1.8 · 102
3 8.90 1.1 · 107 N.D. 57 3.0 · 103
4 8.50 26 1.8 · 102 N.D. 2
5 8.61 22 5.5 · 102 N.D. N.D.
6 8.44 2.5 · 105 N.D. 2.3 · 102 1.3 · 105
7 8.43 3.6 · 102 N.D. N.D. N.D.
8 8.46 1.1 · 103 N.D. N.D. N.D.
9 8.78 2.4 · 106 N.D. 9.5 · 102 1.0 · 103
10 8.46 2.0 · 102 90 N.D. N.D.
a
N.D. – not detected.
 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511 1509

basic pH (8.5) of coolant that is not optimal for microorganism’s activity, (b) the presence of borates (with
biocidic features), and (c) high concentrations of EG lead to the inhibition of bacterial proliferation. Further
experiments done were to assess the role of these microorganisms and whether they could proliferate at dif-
ferent EG solution concentrations. The growth potential of HAB that were originally seeded into 1%, 5%,
10%, 20% and 50% (v/v) EG-containing solutions through dilution with non-sterile tap water was monitored
for a 100 days interval.
As shown in Fig. 5, during the first two weeks of exposure in EG-containing solutions (concentrations 1%,
5%, and 10%) a sharp increase in HAB concentration was observed (two to four orders of magnitude) com-

py
pared with the control (tap water) that revealed ‘‘regrowth’’ of only two orders of magnitude. Following this
initial ‘‘regrowth’’ period, the number of HAB in control continuously decreased (due to luck of nutrients),
while in EG solutions (1%, 5%, and 10%) bacterial cells continued to grow.
Around the 20th exposure day, the increase in the number of bacteria in dilutions 1% and 5% EG solutions

co
came to an end and persisted at the same level during the remaining exposure period. At 10% EG solution the
HAB growth was slower, but it reached the same number as 1% and 5% solutions after 100 days. At EG con-
centrations of 20% and 50%, a decrease of one order of magnitude during the 14 days was observed, followed
by an increase in HAB numbers of 3 1/2 orders of magnitude for the remaining time interval (approx. 85
days).
The initial HAB number decrease may likely be attributed to the higher concentration of biocides in these

al
samples. In due course, however, bacterial adaptation to toxic media can explain the re-growth and levels
achieved. In this experiment, the kinetics of HAB growth revealed that bacteria could most probably utilize
components of EG solutions for their metabolism and cell production.
on
This conclusion is confirmed by the viable bacterial number reduction in the control sample (tap water with
very low organic carbon content and without coolant solution).Throughout the preparation process of EG
solutions with tap water, the formation of large white precipitates was observed. This result was not observed
rs

when experimental solutions were prepared with double distilled water.

To determine whether the sediment formation affects the coolant corrosiveness on aluminum specimens,
comparative electrochemical measurements were conducted in 20% EG solutions (field concentration, as men-
pe

tioned earlier) diluted with tap and distilled water (Fig. 6). The potentiodynamic polarization curves showed
that in EG solution diluted with distilled water, the aluminum was characterized by deep passivity in a wide
potential range (up to 1 V). No evidence of pitting corrosion was detected in this kind of solution. In contrast,
the aluminum demonstrated high susceptibility to pitting corrosion with a breakdown potential around –
0.05 V (SCE) in EG solution diluted with tap water. These results demonstrate that in tap water dilutions,
the efficiency of the coolant’s inhibitors sharply decreased compared to dilutions with distilled water. This
effect could be attributed to chemical reaction between inhibitory compounds and bivalent ions such as
r's

Ca+2, Mg2+, and some other ions present in tap water that caused insoluble salts formation. Furthermore,
Cl ions from tap water promote pitting corrosion.
o
th

7
10
Bacteria number (CFU/ml)

6
10
Au

5
10
4
10
Tap water
3 1% EG
10
5% EG
2 10% EG
10 20% EG
50% EG
1
10
0 20 40 60 80 100
Time (day)
Fig. 5. Growth kinetics of HAB in different concentrations of EG in tap water at 36 C.
1510 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511

A- 20% EG in dist. water

B- 20% EG in tap water
0.5 A

Potential (VSCE )
0.0
B

-0.5

py
-1.0

10-7 10-6 10-5 10-4

(A/cm2)

co
Current
Fig. 6. Aluminum potentiodynamic polarization curves measured in 20 v% EG solution diluted with double distilled water (A) and tap
water (B). Scanning rate: 1 mV/s.

Thus, through simulation of different parameters that might be responsible for the strong corrosion attack
on the experimental cooling systems, four major failure factors were determined:

al
(1) Depletion of applied inhibitor additives because of the chemical reaction between inhibitors and ions
present in tap water (i.e. Ca+2, Mg+2), leading to formation of insoluble salts.
on
(2) Initiation of pitting corrosion by Cal ions introduced into coolant through tap water as diluent.
(3) MIC by the proliferation of corrosion-inducing caused by three factors: (a) the dilution of the original
coolant with tap water containing local bacteria and contamination, (b) the reduction in inhibitory com-
pounds through dilution and (c) the successful utilization of EG or inhibitors (at lower concentrations)
rs

by introduced bacterial population.

(4) Higher coolant concentrations (>20%) is less favorable for the development of corrosion-inducing
microorganisms and, consequently, to MIC development, and they can be used as a threshold to prevent
pe

corrosion damages in such systems.

4. Conclusions

The present study demonstrates that uncovering of MIC in technological equipment failures requires an
r's

individual approach of each case. These investigations also revealed that in certain cases, assessment of micro-
organisms present in surrounding medium role in corrosion destruction is possible only by simulation of the
corrosion parameters found in the field, which have a real effect on the process.
o

Acknowledgements
th

This work was accomplished with financial support and facilities of the Oil Refineries, Ltd. (Israel). J.S. and
D.S were partially supported by the Ministry of Adsorption.
Au

References

[1] Videla HA. Manual of biocorrosion. Boca Raton, New York, London, Tokio: Lewis Publishers; 1996.
[2] Borenshtein SW. Microbiologically influenced corrosion handbook. Cambridge, England: Woodhead Publishing Limited; 1994.
[3] Standard Methods for the Examination of Water and Wastewater, APHA, 19th ed., Washington, D.C., 1996.
[4] Starosvetsky J, Armon R, Groysman A, Starosvetsky D. Mater Perform 1999;38:55.
[5] Starosvetsky J, Armon R, Groysman A, Starosvetsky D. Mater Perform 2002;41:50.
[6] Starosvetsky J, Armon R, Groysman A, Starosvetsky D. Mater Perform 2005;44:56.
[7] Starkey RL. Science 1945;102:523.
[8] Stephenson M. Bacterial metabolism. New-York: Longmann, Green & Co.; 1950.
[9] Ehrlich H.L. Geomicrobiology. M. Dekker, editor. New-York-Basel-Hong-Kong, 1996.
 J. Starosvetsky et al. / Engineering Failure Analysis 14 (2007) 1500–1511 1511

[10] Cullimor DR, McCann AE. Aquatic microbiology. In: Skinner FA, Shewan JM, editors. London, New York, San Francisco:
Academic Press; 1977.
[11] Szklarska-Smialovska Z. Pitting corrosion of metals. An official NACE Publication; 1986.
[12] Schmitt CR. Corrosion-case histories in biologically influenced corrosion. In: Dexter SC, editor. NACE, Houston, TX. 1986.
[13] ASTM D1384-04. Standard test method for corrosion test for engine coolants in Glasswarem. Annual book of ASTM Standards,
West Conshohocken, PA: ASTM International, 2004.
[14] Genner C, Hill EC. Br Corros J 1980;15:95.

py
co
al
on
rs
pe
o r's
th
Au

View publication stats