TUGAS

PENGENDALIAN KOROSI
“Pemodelan Proses Korosi Microbiologically Influenced Corrosion by
Iron Oxidizing Bacteria”

Disusun oleh :

Nabila Widadudari (205061101111023)

 BAB 1
PENDAHULUAN

1.1 Latar Belakang

Gas alam digunakan biasanya digunakan sebagai sumber pembangkit tenaga listrik.
Terdapat banyak masalah dalam pengolahan gas alam, diantaranya dari segi peralatan dan
perawatan dari peralatan tersebut. Masalah yang sering timbul dalam pengolahan gas alam
adalah terjadinya korosi. Umumnya proses korosi tidak dapat dihentikan sama sekali karena
merupakan suatu proses alami yang akan terjadi saat suatu logam kontak dengan lingkungannya.
Hal ini akan mengakibatkan berkurangnya nilai material secara teknis, penurunan kualitas
material dan akan berkurangnya umur pakai (lifetime) dari material tersebut. Salah satu
contohnya adalah pada material baja karbon yang banyak digunakan pada industri minyak dan
gas alam, yaitu sebagai pipa penyalur proses eksplorasi dan produksi.
MIC (microbiologically influenced corrosion) atau korosi yang dipengaruhi proses
mikrobiologis pada logam merupakan masalah utama bagi industri minyak dan gas. Diperkirakan
sekitar 20 - 40 % korosi internal pada pipa di industri minyak dan gas terjadi akibat MIC. MIC
atau biokorosi sering membentuk lubang (pitting corrosion) pada pipa baja karbon yang
menyebabkan kegagalan pipa dan tumpahan minyak. Biofilm yang menempel pada permukaan
material pipa merupakan faktor penting yang dapat menginduksi MIC. Biofilm merupakan
koloni dari sel mikroorganisme yang menempel pada substrat logam dan tidak bergerak, tumbuh
dan berkembang biak serta menghasilkan zat polimer ekstraseluler. Penempelan mikroorganisme
adalah proses yang sangat spontan, yang hampir dapat menyebabkan korosi pada semua material
logam. Hasil studi pengaruh bakteri terhadap sepuluh logam berbeda menunjukkan adanya
percepatan korosi baja karbon dan paduan tembaga-nikel dalam kondisi uji biotik. Biokorosi
telah membuat kerugian yang tinggi di industri minyak dan gas serta industri lainnya setiap
tahunnya. Sehingga pencegahan dan perlindungan permukaan material dari MIC menjadi
masalah penting yang perlu dipecahkan.
Meskipun sifat elektrokimia korosi tetap berlaku untuk proses korosi yang dipengaruhi
oleh proses mikrobiologis (MIC), peran mikroorganisme dalam proses korosi tetap menginduksi
beberapa parameter korosi, yang paling signifikan adalah modifikasi antarmuka logam dengan
larutan oleh pembentukan biofilm. Dalam kondisi anoksik (tanpa oksigen), satu- satunya reaktan
yang tersedia untuk mengoksidasi besi adalah proton yang diturunkan dari air. Pada keadaan ini,
kinetika reaksi berlangsung sangat lambat, sehingga terjadinya korosi secara teoritis dan teknis
dalam kondisi anoksik tanpa adanya oksigen tidak signifikan. Namun, hal lain terjadi jika dalam
kondisi anoksik terdapat bakteri atau mikroorganisme yang bersifat anerobik. Pada kondisi
ekstrim yang diamati di lingkungan anoksik, menunjukkan bahwa proses biologi memainkan
peran penting dalam korosi besi dan baja. Dilaporkan bahwa mikroorganisme sangat
mempengaruhi reaksi korosi dalam kondisi anoksik, seperti korosi internal pada pipa terkubur
[8] atau pipa bawah laut yang mengandung air dan/atau minyak.
 Biokorosi adalah fenomena yang menyebabkan kerusakan material logam atau non logam
yang dirangsang oleh mikroorganisme yang berbeda. Gambar 1 dan 2 merupakan kerusakan
berupa korosi eksternal akibat adanya MIC pada industri minyak bumi [22] dan gas serta industri
petrokimia. .MIC dianggap sebagai salah satu tantangan utama dalam industri minyak dan gas
sebagai hasil dari proses yang kompleks. MIC menjadi salah satu topik terpenting bagi para
insinyur dan ilmuwan di berbagai bidang industri karena masalah ini menyebabkan kerugian
ekonomi yang sangat besar pada perusahaan yang seringkali mencapai beberapa miliar dolar AS
setiap tahunnya. Bakteri pengoksidasi besi adalah bakteri kemotrofik yang memperoleh energi
dengan mengoksidasi besi terlarut. Mereka diketahui tumbuh dan berkembang biak di perairan
yang mengandung konsentrasi besi serendah 0,1 mg/L. Namun, setidaknya 0,3 ppm oksigen
terlarut diperlukan untuk melakukan oksidasi. Mikroorganisme ini mampu mengendapkan
besi/mangan hidroksida (karat) secara ekstraseluler dengan kecepatan ratusan kali lebih tinggi
daripada proses abiotik. Akibatnya, bakteri pengoksidasi besi/mangan dan bakteri pengendap
besi/ mangan termasuk mikroorganisme yang paling berbahaya dari sudut pandang biofouling
dan korosi. Organisme penyimpan logam menciptakan kondisi yang menguntungkan bagi korosi
lokal, terutama dalam kasus kepasifan logam (yaitu dalam kasus baja tahan karat).

BAB 2
PEMBAHASAN
Eksperimen dilakukan dengan spesimen berbentuk cakram dan elektroda tipe pensil yang
terbuat dari baja tahan karat 304L (UNS S30403) dan 316L (UNS S31603). Komposisi kimia
dari baja eksperimental ditunjukkan pada Tabel 1. Spesimen bentuk cakram dengan diameter 15
mm dan ketebalan 2 mm, digunakan untuk analisis pemindaian mikroskop elektron (SEM).
Elektroda tipe pensil untuk pengukuran elektrokimia dibuat dari baja yang sama dengan
memasang batang baja berdiameter 5 mm dalam resin epoksi. Spesimen eksperimental dikikis
melalui kertas metalurgi ikon sil karbida 600 grit, dihilangkan lemaknya dalam aseton, dicuci
dengan air suling tiga steril dan dikeringkan dalam desikator.
Bakteri besi eksperimental diisolasi dari endapan karat penukar panas baja karbon
tersumbat dari kilang minyak. Strain yang teridentifikasi primer adalah Sphaerotilus sp. Kultur
bakteri pengoksidasi besi ditumbuhkan pada media nutrisi Winogradsky (g l1 ): 0,5 K2HPO4,
0,5 NaNO3, 0,2 CaCl2, 0,5 MgSO4 · 7H2O, 0,5 NH4NO3, 6,0 amonium besi sitrat (pH 4,8).
Reaktan analitik dan air suling digunakan untuk persiapan larutan berair. Kultur
percobaan ditanam dengan pengocokan kuat selama 3 hari pada suhu kamar (22 ± 2 C).
Pertumbuhan bakteri dideteksi dengan perubahan warna medium dari hijau menjadi merah.
Pencacahan bakteri besi dilakukan dengan metode filtrasi membran seperti yang telah dijelaskan
[17], dilanjutkan dengan inkubasi selama 5 hari pada suhu 25 C pada media nutrisi Winogradsky
yang ditambah dengan 1,6 % bacto-agar. Konsentrasi bakteri besi (kultur campuran) setelah tiga
hari inkubasi mencapai 1,3 1010 CFU ml1 . Media nutrisi Winogradsky cair memiliki warna
kuning awal. Kultur Sphaerotilus sp. berumur 3 hari. bakteri memiliki warna oranye terang
karena pembentukan ion besi terlarut yang dihasilkan oleh bakteri tersebut.
Sebagai hasil dari aktivitas bakteri, warna medium kultur berangsur- angsur berubah dari kuning
menjadi merah-coklat intens (5-6 hari), dimana sedimentasi visual hidroksida besi berkembang
selama 4-7 hari berikutnya. Akhirnya, media kultur bakteri besi membentuk
dua fraksi: bagian bawah - lapisan tebal (2-3 cm) endapan merah- coklat, dan bagian atas - cairan
keruh yang tidak berwarna. Durasi tes keseluruhan adalah 30 hari. Untuk mempertahankan
konsentrasi awal klorida selama periode waktu percobaan, sebelum penambahan kultur,
konsentrasi larutan NaCl dinaikkan sehingga setelah penambahan media bakteri, tetap pada 3%.
Karena media kultur eksperimental mengikuti pembusukan pertumbuhan bakteri dengan
sedimentasi menjadi dua fase (presipitat besi hidroksida dan cairan bagian
atas), kupon yang diuji dan elektroda tipe pensil dipaparkan di bagian atas dan bawah labu yang
diuji, untuk menentukan variasi dalam perilaku elektrokimia. spesimen "atas" dan "bawah".
Karakteristik kimia dan mikrobiologi media yang diuji (pH, rasio Fe2+/Fe3+ , konsentrasi
bakteri). Menurut karakteristik elektrokimia yang diperoleh dengan elektroda "atas" dan
"bawah" kita dapat menyimpulkan bahwa ketahanan korosi elektroda "bawah", yang terpapar di
dalam lapisan deposit tebal hidroksida besi yang terbentuk secara biologis, berkurang jauh lebih
cepat dibandingkan dengan elektroda "atas". ” elektroda. Elektroda "bawah" yang terpapar dalam
bio presipitat mengalami aktivasi selama paparan OCP pada hari pengujian ke-21.
Perlu dicatat bahwa struktur endapan yang terdeteksi pada permukaan spesimen baja
tahan karat berbeda secara signifikan dengan yang terdeteksi pada permukaan spesimen baja
karbon setelah diekspos dalam larutan yang sama [18]. Endapan yang menutupi permukaan baja
karbon dalam larutan bakteri besi memiliki struktur berlapis. Lapisan atas endapan mengandung
agregat seperti spons dan berbentuk jarum. Analisis EDS kuantitatif menunjukkan bahwa agregat
ini ternyata adalah kristal Fe2sOte3ril. Di antara struktur kristaloid lapisan atas, akumulasi
bakteri berfilamen diidentifikasi sebagai Sphaerotilus sp. diamati. Tidak seperti baja karbon,
tidak ada bakteri berfilamen yang terdeteksi di antara endapan yang tertutup spesimen baja tahan
karat. Gambar 6 mengilustrasikan mikrograf permukaan baja 304L yang diekspos selama 30 hari
dalam kultur bakteri besi pada bagian labu atas (a) dan bawah (b). Sebelum pemeriksaan SEM
endapan yang diendapkan pada permukaan elektroda selama pemaparan ke media biakan
benar-benar dihilangkan. Tidak ada bukti korosi pitting terdeteksi di permukaan Perlu dicatat
bahwa struktur endapan yang terdeteksi pada permukaan spesimen baja tahan karat berbeda
secara signifikan dengan yang terdeteksi pada permukaan spesimen baja karbon
setelah diekspos dalam larutan yang sama. Endapan yang menutupi permukaan baja karbon
dalam larutan bakteri besi memiliki struktur berlapis. Lapisan atas endapan mengandung
agregat seperti spons dan berbentuk jarum. Analisis EDS kuantitatif menunjukkan bahwa agregat
ini ternyata adalah kristal Fe2sOte3ril.
Di antara struktur kristaloid lapisan atas, akumulasi bakteri berfilamen diidentifikasi
sebagai Sphaerotilus sp. diamati. Tidak seperti baja karbon, tidak ada bakteri berfilamen yang
terdeteksi di antara endapan yang tertutup spesimen baja tahan karat. Mikrograf permukaan baja
304L yang diekspos selama 30 hari dalam kultur bakteri besi pada bagian labu atas (a) dan
bawah (b). Sebelum pemeriksaan SEM endapan yang diendapkan pada permukaan elektroda
selama pemaparan ke media biakan benar-benar dihilangkan. Tidak ada bukti korosi pitting
terdeteksi di permukaan.

Gambar a. SEM stainless steel yang diberi larutan NaCl 3% steril dan diberi nutrisi
Gambar b. besi dengan tambahan Iron Oxidizing Bacteria

Hasil yang disajikan menunjukkan perilaku korosi dari dua SS di hadapan bakteri besi
pembentuk lendir pada berbagai tahap perkembangannya. Inisiasi serangan korosi lokal oleh
mikroorganisme yang diendapkan logam umumnya terjadi di perairan tawar dengan konsentrasi
chlo rides rendah (0,1–0,4 ppm). Untuk mempercepat inisiasi dan pengembangan korosi lokal
percobaan kami dilakukan dalam larutan dengan kandungan klorida yang jauh lebih tinggi (NaCl
3%). Pada dasarnya, baja tahan karat 304L dan 316L dicirikan oleh kepasifan yang relatif kuat
dan dapat tetap pasif dalam larutan klorida selama jangka waktu yang lama. Korosi lubang pada
baja ini dalam larutan yang mengandung klorida (tanpa oksidan) biasanya berhubungan dengan
ketidakteraturan struktur atau dengan terjadinya efek celah selama operasi. Eksperimen yang
dilakukan di media kontrol (larutan NaCl 3% steril dan larutan ini ditambah dengan media nutrisi
Winogradsky steril) menunjukkan bahwa kedua baja yang diuji tetap pasif selama seluruh waktu
pemaparan meskipun konsentrasi klorida meningkat. ECORR baja yang diuji sedikit meningkat
(dimuliakan) dengan waktu pemaparan dalam media kontrol yang diperiksa .
Namun, augmentasi larutan NaCl 3% dengan kultur bakteri besi, secara signifikan
mempengaruhi perilaku elektrokimia dan korosi baja yang diuji. Penurunan kuat ECORR yang
terdeteksi selama pemaparan baja dalam kultur bakteri besi benar-benar berlawanan dengan hasil
yang diperoleh dengan pengendapan mangan/besi hidroksida abiotik atau biotik pada permukaan
SS , yang menyebabkan pemuliaan substansial. dari potensi korosi.
 Available online at www.sciencedirect.com

Corrosion Science 50 (2008) 540–547

www.elsevier.com/locate/corsci

Electrochemical behaviour of stainless steels in media containing

iron-oxidizing bacteria (IOB) by corrosion process modeling
J. Starosvetsky a,*, D. Starosvetsky b, B. Pokroy b, T. Hilel b, R. Armon a
a
Division of Environmental, Water and Agricultural Engineering, Faculty of Civil and Environmental Engineering,
Technion – Israel Institute of Technology, Haifa 32000, Israel
b
Laboratory of Electrochemistry and Corrosion, Faculty of Materials Engineering, Technion – Israel Institute of Technology, Haifa 32000, Israel

Received 26 June 2007; accepted 27 July 2007

Available online 23 August 2007

Abstract

Localized corrosion mechanism of stainless steel (SS) types UNS S30403 and UNS 31603 in the presence of iron-oxidizing bacteria
Sphaerotilus spp. isolated from rust deposits was studied electrochemically. OCP transient, cyclic anodic and cathodic potentiodynamic
polarization curves were measured on steel electrodes through their exposure to 3% NaCl solution supplemented with Sphaerotilus cul-
ture. The exposure period was composed of three parts: (a) 5 days incubation of steel electrodes in sterile 3% NaCl solution; (b) addition
of 3 days-old Sphaerotilus culture to 3% NaCl at 3:2 v/v ratio with subsequent electrodes exposure for 11 days up to complete sedimen-
tation of ferric oxides and (c) subsequent exposure of electrodes for 14 days in upper and bottom (sediments layer) fractions of the exper-
imental medium. The results revealed an instantaneous gradual shift of the transient potential of both steels towards negative potentials
from steady-state value of 0.15 V to 0.35 to 0.42 V (SCE) during the whole exposure interval since IOB culture addition into sterile
3% NaCl solution.
No evidence of pitting corrosion was found on SS samples subsequent to their exposure to sterile 3% NaCl solution, though in the
presence of IOB culture, numerous pits were revealed on 304 L steels specimens exposed to iron hydroxides sediments layer. Electro-
chemical characteristics (OCP or corrosion potential – ECORR, breakdown potential – EBD, repassivation potential – ERP, passivation
current – iPASS) periodically measured by cyclic polarization method, allowed monitoring the electrochemical behavior changes of exper-
imental SS and to establish the initiation of pitting corrosion in the presence of IOB, resulting in crevice effect caused by biogenic ferric
oxides deposits precipitated on steel surface. Overall, steel 316L demonstrated higher resistance to pitting corrosion compared to 304L.
Ó 2007 Published by Elsevier Ltd.

Keywords: Pitting corrosion; Stainless steels; Iron-oxidizing bacteria; Rust deposits; Electrochemical characteristics

1. Introduction attack. Various scenarios of localized corrosion initiation

Numerous evidences obtained during the last two dec-
ades show that biofouling plays a key role in microbiolog-
ically influenced corrosion (MIC). The non-uniform
character of biofilms colonizing metal surface results in
irregular physico-chemical conditions on different surface
sites, and consequently, in a non-equal distribution of cor-
rosion rate over metal surface and localized corrosion
*
Corresponding author. Tel./fax: + 972 4 8293309.
E-mail address: starjean@tx.technion.ac.il (J. Starosvetsky).
and development under biofilms were described [1–4].
Important role in the mechanisms proposed by these stud-
ies was attributed to slime-forming microorganisms, which
in a short period of time produce large amounts of bio-
mass. Metal-depositing microorganisms (iron/manganese-
oxidizing or iron/manganese-precipitating bacteria) are
the best representative of this bacterial group. These
microorganisms are capable to deposit iron/manganese
hydroxides (rust) extracellularly at a rate of hundreds time
higher than the abiotic process [5,6]. Consequently, iron/
manganese-oxidizing and iron/manganese-precipitating
bacteria are among the most dangerous microorganisms

0010-938X/$ - see front matter Ó 2007 Published by Elsevier Ltd.

doi:10.1016/j.corsci.2007.07.008
 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547
from biofouling and corrosion point of view. Metal-depos-
iting organisms create conditions favorable to localized
corrosion, especially in the case of metals passivity (i.e. in
stainless steels case). Pitting corrosion of SS initiated by
metal-oxidizing bacteria in natural fresh waters had an
extremely high rate, as already published [7–9]. Various
explanations of this phenomenon were suggested
[3,4,8,10–13]. One of them is based on the principle of cre-
vice corrosion. According to this approach, [4,11] dense
deposits of biomass layer produced by metal-oxidizing
bacteria on metal surface provide conditions for the devel-
opment of crevice effect on metal/biomass interface initiat-
ing pitting phenomenon. This hypothesis is based on the
theory of localized corrosion proposed by Sato [14]. It
was suggested that pitting is favored by a deposit with
anion-selective membrane properties, while passivity is sta-
bilized by cation selectivity. Ferric hydroxides membranes
are anion-selective at neutral pH values, and therefore
should be aggressive towards stainless steel. Such mem-
brane may stabilize pitting by acting as a super crevice,
combining anion-selectivity with a relatively low ionic
resistance. Unfortunately little direct experimental evi-
dences are available to prove this elegant theory [11,15].
In the present study different aspects of stainless steels
corrosion initiated by IOB in chlorine-containing water
was electrochemically examined simulating different corro-
sion stages and conditions.
2. Methods and materials
The experiments were conducted with disc shape
specimens and pencil-type electrodes made of 304L (UNS
S30403) and 316L (UNS S31603) stainless steels. Chemical
compositions of the experimental steels are shown in
Table 1. Disc shape specimens with a diameter of 15 mm
and 2 mm thickness, were used for scanning electron
microscopy (SEM) analysis. Pencil-type electrodes for elec-
trochemical measurements were made of the same steels by
mounting 5 mm-diameter steel rode in an epoxy resin. The
experimental specimens were abraded through 600-grit sil-
icon carbide metallurgical paper, degreased in acetone,
washed with sterile three-distilled water and dried in a
desiccator.
Experimental iron bacteria were isolated from rust
deposits of clogged carbon steel heat exchanger from oil-
refinery plant (Haifa, Israel) [16]. The primary identified
strain was Sphaerotilus sp. The culture of iron-oxidizing
bacteria was grown on Winogradsky nutrient medium
(g l 1): 0.5 K2HPO4, 0.5 NaNO3, 0.2 CaCl2, 0.5 MgSO4 
7H2O, 0.5 NH4NO3, 6.0 ammonium iron citrate (pH 4.8).
Table 1
Chemical composition (w/w %) of tested SS detected by atomic adsorption
spectroscopy
Steel Fe Cr Ni Mn Si Mo P C
304L Bal 17.48 8.18 0.798 0.787 0.55 0.039 0.046
316L Bal 17.42 8.65 1.687 0.59 2.36 0.037 0.035
541
Analytical-grade reactant and distilled water were used
for aqueous solutions preparation. The experimental cul-
tures were grown by vigorous shaking for 3 days at room
temperature (22 ± 2 °C). Bacterial growth was detected
by medium color shift from green to red. Iron bacteria enu-
meration was performed by membrane filtration method as
already described [17], followed by 5 days incubation at
25 °C on Winogradsky nutrient medium supplemented
with 1.6 % bacto-agar. Iron bacteria (mixed culture) con-
centration after three days of incubation reached
1.3  1010 CFU ml 1. Liquid Winogradsky nutrient med-
ium had an initial yellow color. The 3 days-old culture of
Sphaerotilus sp. bacteria had light orange color due to for-
mation of soluble ferric-ions produced by these bacteria.
As an outcome of bacterial activity, culture medium color
gradually shifts with time from yellow to intense red–
brown (5–6 days), whereupon visual sedimentation of ferric
hydroxides developed during next 4–7 days. Finally, the
iron bacteria culture medium formed two fractions: the
bottom part - a thick layer (2–3 cm) of red–brown
precipitates, and the upper part - colorless, turbid liquid.
According to chemical and microbiological analysis it
was found that major fraction of iron bacteria cells and fer-
ric-ion compounds precipitated on the 11 to 13th day of
growth [18]. The pH of tested media was measured with
pH-meter PHM210-Meterlab (Radiometer Copenhagen).
The electrochemical measurements were performed with
potentiostat M273 (EG&G, USA). Corrosion test and elec-
trochemical measurements were conducted in 2 liters-flask
equipped with a saturated calomel reference electrode
(SCE), which was connected to flask through a Luggin–
Habber capillary tip assembly, and Pt-wire counter elec-
trode. Test commenced by immersion of coupons and
pencil-type electrodes in flask containing 800 ml of sterile
3% NaCl solution. After 5 days-exposure in the 3 days-
old Sphaerotilus sp. culture (1.2 L) was added to 3% NaCl
(3:2 v/v ratio). Further exposure of experimental specimens
was conducted in bacterial solution up to complete sedi-
mentation of ferric oxides and hydroxides. The overall test
duration was 30 days. In order to maintain the initial con-
centration of chlorides along the experimental time period,
prior to culture addition the concentration of NaCl solu-
tion was increased so that after bacterial medium augmen-
tation, it remained at 3%. Since the experimental culture
medium following bacterial growth decay by sedimentation
onto two phases (ferric hydroxides precipitates and upper
liquid) tested coupons and pencil-type electrodes were
exposed in upper and bottom parts of tested flask, in order
to determine the variations in electrochemical behavior of
‘‘top” and ‘‘bottom” specimens. Chemical and microbio-
logical characteristics of tested medium (pH, Fe2+/Fe3+
ratio, bacterial concentration) were reported elsewhere
[18]. During specimens exposure the ECORR transient and
polarization characteristics of tested steel were measured
S with pencil-type electrodes. Some coupons of tested stain-
0.016 less steel were periodically removed from solution for
0.029 following surface examination by optical and scanning
542 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547
electron microscopy (SEM). For comparison, similar
experiments with the same stainless steel coupons and pen-
cil-type electrodes were conducted for 30 days in sterile 3%
NaCl solution only and in 3% NaCl solution supplemented
with sterile Winogradsky nutrient medium (2:3 v/v accord-
ingly) without bacteria. After nutrient culture augmenta-
tion, final concentration of chloride was also adjusted to
3%. Prior to supplementation, the pH of Winogradsky
nutrient medium was adjusted to 7.2 with NaOH solution.
3. Results and discussion
ECORR transient of 304L steel measured by open circuit
potential, OCP, during exposure in 3% NaCl solution,
prior to and after addition of iron-oxidizing bacteria cul-
ture is shown in Fig. 1. As can be seen, ECORR of steel in
sterile NaCl solution (without culture medium augmenta-
tion) was relatively stable and slightly increased in the
range between 0.1 and 0.2 V throughout the 5 days of
exposure. Upon culture medium addition the ECORR
decreased in the range between 0.1 and 0.4 V. The
decrease in ECORR can be attributed either to weakening
of steel passivity or surface activation, or to decrease of
the cathodic process rate, for example due to decrease in
the oxygen concentration of dissolved in tested medium.
Marked decrease of ECORR was detected on the 2nd day
following culture augmentation (approx. five days before
visual sedimentation). During further exposure up to iron
hydroxides sedimentation this tendency persisted. After full
iron hydroxide sedimentation the ECORR becomes stable. It
should be noted that ECORR transients measured with spec-
imens exposed in upper and bottom parts of solution were
almost similar. In contrast to culture medium, no marked
changes in ECORR of 304L SS specimens were observed
during their exposure for 30 days in control media: NaCl
solution with addition of sterile Winogradsky nutrient
medium (3:2 v/v ratio).
SS 304L
-0 .1 Sedimentation
BOTTOM
TOP
Potential (VSCE)
-0 .2
-0 .3
Culture medium
-0 .4
-5 0 5 10 15 20 25
Time (day)
Fig. 1. Corrosion potential transients of 304L stainless steel in 3% NaCl
solution before and after augmentation with culture medium. Zero point
on the time scale corresponds to augmentation of NaCl solution in which
all specimens were previously exposed for 5 days.
Fig. 2 presents cyclic anodic potentiodynamic curves of
304L stainless steel measured after 9 days-exposure, includ-
ing 5 days-pre-exposure in NaCl and 4 days-exposure after
either nutrient or culture medium augmentation. It may be
seen that there are no marked differences in anodic curves
measured in these media on the 9th day of exposure. The
onset of anodic current was slightly above 0.2 V in both
tested solutions, i.e. it was slightly above ECORR values
measured by OCP at 9th exposure day. The wide region
of steel passivity approx. up to 0.4 V can be clearly seen
in potentiodynamic curve measured at positive potential
scan. Breakdown at potentials above 0.4 V was detected
in both curves. During further positive shift in applied
potential an anodic current sharply increased. Marked hys-
teresis, which was detected between anodic curves mea-
sured at positive scan and back scan both in bacterial
and model solutions, can be attributed to pitting phenom-
enon. It should be also noted that no marked differences in
anodic behavior of tested electrodes exposed at ‘‘top” and
‘‘bottom” parts of electrochemical cell were detected at this
test stage. This may be considered as the fact that sedimen-
tation process did not start so far after 9 days-exposure and
chemical composition of solutions at top and bottom parts
of cell was the same.
Significant changes in electrochemical behavior of tested
electrodes exposed at ‘‘top” and ‘‘bottom” parts of electro-
chemical cell was found after initiation of sedimentation
process. Cyclic polarization curves of 304L stainless steel
measured with ‘‘top” electrodes at 4th day after bacteria
augmentation and at 4th day of sedimentation (total expo-
sure time after bacterial medium augmentation was 11
days) are shown in Fig. 3. As can be seen, the onset of ano-
dic current in the curve following sedimentation occurred
at more negative potential value ( 0.34 V) compared to
that detected by measurement before sedimentation
( 0.2 V). Significant (approx. two times) increase of anodic
0.6 NaCl+Nutrient medium
NaCl+Culture m edium
0.4
Potential (VSCE)
0.2
0.0
-0.2
-5 -4 -3 -2
30 10-6 10 10 10 10
Current (A/c m 2)
Fig. 2. Cyclic anodic potentiodinamic curves of 304L stainless steel
measured after OCP exposure: (M) 5days in 3% NaCl solution and
additional 4 days-exposure after nutrient medium addition; (s) 5 days in
NaCl solution and further 4 days after bacterial culture addition.
 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547 543

0.6
0.4
0.4
Potential (VSCE)

0.2

Potential (VSCE)
0.2
0.0
0.0

-0.2 Time, days:

-0.2
1
4
-0.4 4 days of augmentation -0.4 9
4 days of sedimentation 21
-6 -5 -4 -3 -2
10 10 10 10 10 -6 -5 -4 -3 -2
2 10 10 10 10 10
Current (A/cm ) 2
Current (A/cm )
Fig. 3. Cyclic anodic polarization curves of 304L stainless steel measured
on 4th day after iron bacteria culture augmentation and 4th day after the 0.6
culture sedimentation (total 11 days); ‘‘top” electrodes.

0.4

Potential (VSCE)
current values was detected in the region of passivity when
an anodic curve was measured at 4th day of sedimentation 0.2
compared to the values obtained by measurements prior to
sedimentation. Subsequent to sedimentation, breakdown
0.0
(EBD) and repassivation (ERP) potentials measured in cyclic
polarization curves were much more negative (EBD was Time, days:
0.32 V and ERP was 0.05 V) than those detected before sed- -0.2 1
4
imentation (0.45 V and 0.15 V respectively). In accordance
9
with these results it can be suggested that initiated sedimen-
-0.4 21
tation causes markedly weaker passivation characteristics -6 -5 -4 -3 -2
of tested steel, even though the tested specimens were not 10 10 10 10 10
2
exposed within the precipitated mass. Current (A/cm )
It was also established that the longer exposure of tested
Fig. 4. Cyclic anodic polarization curves of 304L stainless steel measured
specimens under sedimentation process in culture medium, on 1, 4, 9, 15 and 21st day after sedimentation beginning; (a) ‘‘top”
a stronger reduction in protective characteristics of steel electrodes, (b) ‘‘bottom” electrodes.
passivity. This was true for tested electrodes exposed both
in upper and bottom parts of the cell. This phenomenon is in the upper part during the same time interval, did not
illustrated by cyclic polarization curves obtained with bring specimen surface to activation (Fig. 4a).
‘‘top” (Fig. 4a) and ‘‘bottom” (Fig. 4b) specimens of tested The different stages of steel exposure subsequent to
304L stainless steel after different time intervals of exposure NaCl augmentation with culture medium were also ana-
under sedimentation process. Fig. 4 shows significant lyzed by examination of surface morphology of tested cou-
decrease in protective characteristics of steel passivity pons following different exposure periods. Fig. 5 presents
(EBD decrease, increase of anodic current in the region of SEM micrographs obtained from surface of ‘‘bottom” cou-
passivity, iPASS) along exposure time under sedimentation pons after 4 days followed by culture augmentation and 7
process in iron bacteria containing medium. It should be days of sedimentation. A small amount of iron bacteria
noted that the electrochemical behaviour of 304 L speci- cells adsorbed to steel surface together with organics and
mens in control media practically did not changed during inorganic metabolites (dark spot) are seen on this SEM
whole test period of time. micrograph obtained at 4th day followed augmentation
According to electrochemical characteristics obtained (Fig. 5a). Practically whole electrode surface was covered
with ‘‘top’ and ‘‘bottom” electrodes we can conclude that with a dense deposit layer at 7th day of sedimentation pro-
corrosion resistance of ‘‘bottom” electrodes, exposed within cess (Fig. 5b). It was established by energy dispersive spec-
the thick deposit layer of biologically formed iron troscopy (EDS) that these deposits are evidently Fe2O3.
hydroxides, reduces much more rapidly compared with The SEM micrographs obtained with surface of coupons
‘‘top” electrodes. ‘‘Bottom” electrodes exposed within bio- exposed in the ‘‘top” part of flask both 4 days after aug-
precipitates undergone activation during OCP exposure at mentation and 7 days after sedimentation were similar to
the 21st test day (Fig. 4b), while exposure of steel specimens that presented in Fig. 5a.
544 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547
Fig. 5. SEM micrographs of 304 L stainless steel surface pre-exposed to 3% NaCl solution for 5 days and additionally exposed for 4 days in augmented
culture (a); and 7 days after sedimentation initiation (b).
It should be noted that the structure of deposits detected
on specimen surface of stainless steel significantly differs
from that detected on the surface of carbon steel specimens
after expose in the same solution [18]. Deposit covered the
carbon steel surface in iron bacteria solution had a layered
structure. The upper layer of deposit contained spongy and
needle-shaped aggregates. Quantitative EDS analysis
showed that these aggregates are evidently Fe2O3 crystals.
Among the crystalloid structures of the upper layer, accu-
mulation of filamentous bacteria identified as Sphaerotilus
sp. was observed [18]. Unlike carbon steel no filamentous
bacteria were detected among deposits covered stainless
steel specimens.
Fig. 6 illustrates micrographs of 304L steel surface
exposed for 30 days in iron bacteria culture at the upper
(a) and bottom (b) flask parts. Prior to SEM examination
the deposits precipitated on electrode surface during expo-
sure to culture medium were completely removed. No evi-
dence of pitting corrosion was detected on the surface
specimens, which were exposed at the upper part of flask
for 30 days (Fig. 6a). In contrast to ‘‘upper” specimens,
numerous dip pits were found on the surface of specimens
after 30 days-exposure at the bottom part of iron bacteria
culture medium (Fig. 6b). It should be also mentioned that
no pitting phenomenon was detected with specimens
exposed to control media: NaCl solution and NaCl solu-
tion augmented with sterile nutrient medium.
A similar corrosion and electrochemical tests were con-
ducted with 316L SS. Fig. 7 presents ECORR transient of
‘‘upper” and ‘‘bottom” specimens made of 316L steel dur-
ing their exposure to 3% NaCl solution before and after
culture medium addition. Concomitantly to iron bacterial
culture addition the ECORR of 316L SS of ‘‘upper” and
‘‘bottom” specimens gradually decreased during the whole
test period, except a short period between 5th and 7th days,
when small ennoblement of corrosion potential was
observed. It should be noted that similar corrosion poten-
tial ennoblement at the same exposure period was also
 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547
Fig. 6. SEM micrographs of 304 L stainless steel surface exposed for 30 days to sterile 3% NaCl solution with addition of nutrient medium (a) and iron
bacteria-containing medium (b).
detected in the case of 304L SS. The difference in ECORR
between ‘‘top” and ‘‘bottom” 316L SS specimens was very
small, except last period exposure (>20 days) when sedi-
mentation was finalized. At the end of corrosion test the
difference in ECORR values of ‘‘bottom” and ‘‘upper” elec-
trodes was approximately 0.17 V. The decrease of ECORR
during 316L SS exposure in iron bacteria solution can be
also attributed either to reduction in protective characteris-
tics of steel passivity or to decrease of oxygen concentra-
tion at steel/solution interface, as in the case of 304L SS.
Electrochemical measurements with ‘‘top” and ‘‘bot-
tom” 316L SS specimens were conducted after different
time expose both in 3% NaCl solution before and after
nutrient and cultural media supplementation. No marked
difference in anodic behaviour of 316L SS steel was
revealed in these solutions during long term exposure.
Small alterations in anodic behaviour were detected only
on later stages of sedimentation process. Fig. 8 represents
cyclic polarization curves obtained with ‘‘top” (8a) and
545
‘‘bottom” (8b) electrodes of 316L SS at 1st and 21st
sedimentation days. As can be seen (Fig. 8a), a small
decrease in protective characteristics of passivity was
determined with ‘‘top” specimens by cyclic polarization
experiments after 21 days exposure under sedimentation:
the onset of anodic current at 21st precipitation day
occurred at 0.52 V ( 0.38 at 1st day), EBD was 0.596 V
(0.66 V at 1st day) and iPASS slightly increased at potentials
above 0.5 V. Similar results were obtained with ‘‘bottom”
specimens (Fig. 8b). Small decrease in specimen passivity
was detected by increase of exposure time under sedimenta-
tion: the onset of anodic current decreased from 0.362 V
at 1st day of sedimentation to 0.505 V at 21st day and
EBD decreased from 0.608 V to 0.52 V. The values of iPASS
at 1st and 21st day of sedimentation were very close to
each other. Pits appearance was not detected on 316L SS
by SEM examination of both ‘‘top” and ‘‘bottom” speci-
men surface after 21 days of exposure to experimental
media.
546 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547

According to polarization characteristics obtained with

Calture addition
0.0 304L and 316L SS specimens during exposure in bacterial
Sedimintation medium before and after sedimentation one can conclude
that 316L SS is characterized by stronger passivity and,
-0.1 Oneset consequently, by enhanced resistance to pitting attack in
Potential (VSCE)

the presence of iron bacteria compared with 304L SS (see

End Figs. 6 and 8). All the breakdown parameters detected in
-0.2 cyclic polarization curves of 316L SS, such as: EBD, ERP
and iPASS were markedly superior to that obtained with
304L SS.
-0.3 The presented results demonstrate corrosion behaviour
BOTTOM of two SS in the presence of slime-forming iron bacteria
TOP at different stages of their development. The initiation of
-0.4
localized corrosion attack by metal-precipitated microor-
ganisms commonly occurs in fresh waters with low chlo-
-5 0 5 10 15 20 25 30
rides concentration (0.1–0.4 ppm). In order to accelerate
Time (h)
initiation and development of localized corrosion our
Fig. 7. Corrosion potential transients of 316L stainless steel in 3% NaCl experiments were conducted in solutions with much higher
solution before and after augmentation with culture medium. Zero point chloride content (3% NaCl). Essentially, 304L and 316L
on the time scale corresponds to augmentation of NaCl solution in which
stainless steels are characterized by relatively strong passiv-
all specimens were previously exposed for 5 days.
ity and could remained passive in chloride solution during
long periods of time. Pitting corrosion of these steels in
1.0 chloride containing solutions (without oxidants) is usually
Top
associated either with structure irregularities or with cre-
vice effect occurrence during operation. The experiments
conducted in control media (sterile 3% NaCl solution and
0.5
Potential (VSCE)

this solution augmented with sterile Winogradsky nutrient

medium) showed that both tested steels remained passive
during the whole exposure time despite of elevated chloride
concentration. The ECORR of tested steels slightly increased
0.0
(ennobled) with exposure time in examined control media.
Time, day: However, the augmentation of 3% NaCl solution with
iron bacterial culture, significantly affected electrochemical
1
-0.5 and corrosion behaviour of tested steels. The strong
21 decrease of ECORR detected during steels exposure in iron
10
-6
10
-5
10
-4
10
-3 -2
10 bacteria culture (Figs. 2 and 8) was completely opposite
2
Current (A/cm ) to the results obtained by deposition of abiotic or biotic
manganese/iron hydroxides on SS surface [19,20], which
caused substantial ennoblement of corrosion potential.
1.0 Bottom The decrease of ECORR measured during 304L and 316L
stainless steels exposure in iron bacteria culture medium
can be attributed to two different phenomena: (a) decrease
in protective characteristics of its passive film and/or steel
Potential (VSCE)

0.5
activation following culture medium addition and (b)
decrease of soluble oxygen concentration in solution due
to the respiratory activity of iron bacteria during their pro-
liferation (iron-oxidizing bacteria are obligate aerobes).
0.0
The occurrence of first scenario, namely, weakness of steel
Time, day: passivity and its activation presumably can be expected
1 only at final stages of exposure especially for the ‘‘bottom”
21 specimens situated into a thick, dense layer of ferric
-0.5
-6 -5 -4 -3 -2
hydroxides precipitates. At early stages of exposure the
10 10 10 10 10 decrease of ECORR is rather associated with oxygen defi-
2
Current (A/cm ) ciency. The activity of strictly aerobic iron bacteria, which
Fig. 8. Cyclic anodic polarization curves of 316L stainless steel measured accumulate on metal surface with biofilm formation, may
at 1st and 12th day after sedimentation beginning: (a) ‘‘top” electrodes, lead to significant decrease of oxygen concentration at
(b)‘‘bottom” electrodes. steel/solution interface. Since SS corrosion in neutral solu-
 J. Starosvetsky et al. / Corrosion Science 50 (2008) 540–547
tions occurs with oxygen depolarization it is reasonable to
suggest that decrease of oxygen concentration results in a
rate reduction of cathodic process and a shift of ECORR
to negative values during specimen OCP exposure. Sedi-
mentation of ferric oxides/hydroxides that took place after
a certain time of specimen exposure may substantially
aggravate the protective characteristics of passive film.
Deposition over SS specimen surface results in initiation
of crevice effect on the steel/deposit interface affecting the
steel passivity and even activating it during long term expo-
sure under sedimentation. The sedimentation effect was
very important for 304L SS specimens exposed to the flask
bottom part. The negative role of this phenomenon
was clearly seen by comparison of electrochemical charac-
teristic measured with ‘‘top” and ‘‘bottom” specimens at
different exposure periods under sedimentation. It was con-
firmed that electrodes located into biological slime,
undergo stronger decrease in protective characteristics of
passive film than those located in the upper zone of the
experimental flask. This phenomenon is highly reflected
in marked changes of EBD and iPASS measured with ‘‘bot-
tom” electrodes of 304L SS. After extended exposure into
the sediments, numerous pits were detected on 304 SS. It
should be noticed, that similar tendencies were observed
in electrochemical behaviour of ‘‘top” specimens, although
in this case the sedimentation effect was less pronounced.
The obtained results are in good agreement with earlier
investigations conducted in [11,15], which substantiated
the hypothesis of crevice corrosion mechanism for micro-
bial corrosion phenomenon in potable water.
316L SS revealed stronger corrosion resistance in iron-
oxidizing bacteria media compared to 304L SS. Only small
differences in anodic characteristics of 316L SS were
detected during its exposure in bacterial medium before
and after sedimentation and between ‘‘upper” and ‘‘bot-
tom” specimens.
4. Conclusions
1. Electrochemical behaviour of 304L and 316L SS pre-
exposed to 3% NaCl solution for 5 days and then
additionally exposed for 30 days in this solution supple-
mented with 3 days-old culture of Sphaerotilus sp. gen-
era was investigated.
2. Low corrosion resistance of 304L SS to localized corro-
sion attack was detected in 3% NaCl solution containing
iron bacteria culture. Strong decrease in corrosion resis-
tance of 304L SS as a function of exposure time, was
detected when steel specimens were located at the flask
547
bottom and remained prolonged period of time into a
layer of biogenic hydroxide sediments. Pitting corrosion
attack occurred on the surface of ‘‘bottom” specimens.
No pitting corrosion attack was detected on the surface
of ‘‘top” specimens.
3. 316L SS showed higher resistance to pitting corrosion in
iron bacteria-containing medium with 3% NaCl com-
pared with 304L SS.
4. According to the present experimental results it can be
suggested that MIC of stainless steels media of iron-oxi-
dizing bacteria can be explained by the mechanism of
crevice corrosion.
Acknowledgements
We would like to thank KAMEA Foundation, Ministry
of Immigration and Adsorption, Israel for the financial
support to two of the authors, D. Starosvetsky and J.
Starosvetsky.
References
[1] H-C. Fleming, G.G. Geesey, Biofouling and Biocorrosion in Indus-
trial Waters, Springer–Verlag, New York, 1991.
[2] H.A. Videla, W.G. Characklis, Inter. Biodeter. & Biodegrad. 29
(1992) 195.
[3] S.W. Borenstein, Microbiologically Influenced Corrosion Handbook,
Woodhead, Cambridge, London, 1994.
[4] B. Little, P. Wagner, Mater. Perform. 36 (6) (1997) 40.
[5] H.I. Ehrlich, Geomicrobiology, in: M. Dekker (Ed.), New York,
1996.
[6] D.R. Cullimor, Microbiology of well biofouling, Lewis Publishers,
Boca Raton-London-New York-Washington-DC, 1999.
[7] J.F.D. Stott, in: L.L. Shreir, R.A. Jarman, G.T. Burstein (Eds.),
Corrosion, third ed., Butterworth– Heinemann, UK, 1994.
[8] G. Kobrin, Mater. Perform. 33 (4) (1994) 62.
[9] J.T. Titz, Stainless Steel World 2 (1999).
[10] R.E. Tatnall, Mater. Perform. 20 (9) (1981) 32.
[11] M.I. Suleiman, I. Ragault, R.C. Newman, Corros. sci. 36 (1994) 479.
[12] X. Shi, R. Avci, M. Geiser, Z. Lewandowski, Corros. Sci. 45 (2003)
2577.
[13] P. Linhardt, Mater. Corros. 55 (2004) 158.
[14] N. Sato, Corros. Sci. 27 (1987) 421.
[15] I.G. Chamritski, G.R. Burns, B.J. Webster, N.J. Laycock, Corrosion
60 (2004) 658.
[16] J.O. Starosvetsky, R. Armon, J. Yahalom, D. Starosvetsky, Inter.
Biodeter. & Biodegrad. 47 (2) (2001) 79.
[17] D.R. Cullimor, A.E. McCann, Aquatic Microbiology, in: F.A.
Skinner, J.M. Shewan (Eds.), Symposium Series – Society for Applied
Bacteriology, vol. 6, Academic Press, 1977.
[18] J.O. Starosvetsky, R. Armon, A. Groysman, D. Starosvetsky, Mater.
Perform. 38 (1) (1999) 55.
[19] W.H. Dickinson, F. Caccavo, B. Olesen, Z. Lewandowski, Appl. and
Environ. Microbiol. 7 (1997) 2502.
[20] X. Shi, R. Avci, Z. Lewandowski, Corros. Sci. 44 (2002) 1027.