Indi an Journal of Chemical Technology

Vol. 6. Jul y 1999. pp. 207 -2 18

A review of electrochemical techniques applied to microbiologically

influenced corrosion in recent studies
R Sagar Dubey, R S Dubey* & S N Upadhyay
De partment o f Chemical Engineering and Technology, Institute of Technology,
Banaras Hindu University, Varanasi 221 005, India

Received 14 October 1997; accepted 10 Jun e 1999

Mic robiologicall y influ enced corrosion (MIC) has been receiving attention from different areas in the last years, as an
answer to the demand of variou s industries. Remedy for most of the MIC problems can be achieved by establishing a close
link between mi crobi ology, electrochemistry, medical science and metallurgy. The present paper critically reviews the ·e lec·
trochemi cal techniques employed in se veral recent publications on the subject, with the aim of clarifying basic and applied
aspects o f mi crobi o logically influenced corrosion (MIC) and biofouling. During MIC corrosion products migrate from the
metal to th e so luti on ro llowed by the settelment of biofilm from the bulk solution to the metal surface. These processes can
be studi ed by e lectrochemi cal tec hniques, such as the measurement of open circuit potential, potentiodynamic polarization ,
electrochemical impedance techniques, pol arization resistance measurements, electrochemical sensors, and electrochemical
noi se analys is.

Corrosion is an irreversible interfacial reaction of a
material (metal, ceramic, polymer) with its environ-
ment which results in consumption of the material or
in dissolution into the material of a component of the
environment J. Around 70% of the earth sruface is
marine and seawater contains about 3.4% salt and is
slightly alkaline (PH 8) in nature. Sulphate reducing
bacteria (SRB) thrive frequently in sea water2.3 and
even in deep ocean sediments4 .5 . Their survival in the
well oxygenated (225 11 mollL) seawater is due to the
presence of the oxygen-protectiv.e enzyme catalase
and superoxide dismutase 6 . When suitable growth
s'lbstrates are available, the high sulphate content of
sea water (29 11 moUL) allows rapid SRB ,prolifera-
tion .
Microbiologically Influenced Corrosion (MIC)
Microbiologically influenced corrosion is the dete-
rioration of metals by corrosion processes that occur
directly or indirectly, as a result of metabolic activity
of microorganisms? Alternatively microbial corrosion
may be defined as the degradation or deterioration of
metallic structures due to the activity of various or-
ganisms which either produce aggressive metabolites
to render the environment corrosive or are able to
participate directly in the electrochemical reactions
*Present address: Department of Chemistry. R. J. College, Ghat·
kopar. Mumbai.
occurring on the metal surface. The presence of mi-
crobial growths or deposits on a metal surface en-
courages the formation of different aeration cells
between the deposit and the surrounding environment
which stimulate the corrosion processes B•
The biodeterioration of off-shore structures, stor-
age facilities, transmission lines associated with oil
and gas production, propellers, shafts, heat exchang-
ers, ship hulls and ropes etc. causes substantial in-
vestment loss and danger to the human life. MIC is
not only limited to metals, but concrete, ceramics,
polymers and a variety of materials are involved in
this process. There are some empirical environmental
conditions which can be used to predict the environ-
ment of microorganisms in the corrosion process.
These are:
(i) Proper environment - suitable pH values ranging
between 4 and 9 (some sulphur oxidisers toler-
ate even a lower level), temperatures generally
below 50-60°C, approximately redox conditions,
and an appropriate nutrient for the activity of the
. .
mIcroorganIsms.
(ii) Typical morphology and chemistry of the corro-
sion products.
(iii) Typical changes in the environment due to mi-
crobial activity, for example marked changes in
pH in either acid or alkaline medium.
 208 INDIAN 1. CHEM. TECHNOL., JULY 1999
Bacteri al corrosion is electrochemical in nature like
other corrosion reactions, except for the fact that one
never knows the exact chemicals involved in the cor-
rosion process. Corrosion may be enhanced biologi-
cally, through direct enzymatic action of bacteria, or
abioticall y, as a result of reaction with metabolic by-
products or changes in local conditions (for example
9 2o
pH) by the bacterial activity. Many workers - have
reported the process of biofouling, mechanisms,
method of detection, case hi stories, treatment and
prevention of mi crobio logically influenced corrosion
in biological processes. Sugars, carbohydrates, succi-
nate, fumarate, pyruvate, NH" N0 2-, H 2S, S20/-,
2 pled electrodes in inoculated and sterile media, po-
Fe + , H2 are substrates which may be oxidized in
biological proeesses and O 2, NO,-, SO/-, Fe'+, H 20,
CO 2 etc are reducible species. Therefore, it can be
concluded that most of the reactions involved in bio-
logical corrosion processes are electrochemical in
nature and e lectrochemical measurement techniques
are the most widely applicable techniques In ex-
plaining the corrosion phenomenon.
Mechanisms of Microbial Corrosion
When a metal is immersed in water, damp soil or
other aqueous environment, the initial reaction is the
di sso luti on of the metal as metallic cations which
leave be hind an excess of electrons. For example in
case of iron:
... (I)
These e lec trons are consumed at near by cathodic
sites by the bal ancin g reaction, which in near neutral
so luti on is usu all y the reduction of oxygen to hy-
droxyl ions,
. . . (2)
In the absence of oxygen the usual cathodic reaction
for corrosion processes is the reduction of hydrogen
... (3)
a reac ti on is rapidly limited to neutral solutions thu s
stifling the co rros ion process.
Many workers reported that for microorganisms to
participate in co rrosion, the production of oxidising
agents throu gh th eir metabolism is an essential proc-
ess. Th e ro le of mi croorganisms is to participate di-
rect ly in one or both of the e lectrochemical reactions
on th e metal thereby initiating or exacerbating the
reaction. Previous rev iews 23 .24 classify microbial cor-
rosion on the basis of metabolism of organisms as
follows:
(a) Absorption of nutrients (oxygen) by microbial
growths adhering to the metal surface,
(b) Liberation of corrosive metabolites or end-
products of fermentative growth,
(c) Production of sulphuric acid, and
(d) Interference in the cathodic process under oxy-
gen free condition by obligate anaerobes.
Electrochemical techniques include. measurement
of redox potentials and potential s of corrosion elec-
trodes, measurement of current density between cou-
tentiodynamic polarization, polarization resistance,
potentiokinetic curves, electrochemical impedance
spectroscopy, electrochemical noise and electro-
chemical sensors.
Open Circuit Potential Measurements
When a metal specimen is immersed in a corrosive
medium, both oxidation and reduction processes oc-
cur on its surface. Typically the specimen oxidizes
(corrodes) and the medium (solution) is reduced. The
specimen must function as both anode and cathode,
and both anodic and cathodic currents occur on the
specimen surface at anodic and cathodic areas . .
When a specimen is in contact with an aqueous
medium and is not connected to any instrumentation,
it assumes a potential , which is termed as the open
circuit potential or corrosion potential. The Eoc can be
defined as the potential at which the rate of oxidation
is exactly equal to the rate of reduction . It is usually
measured relative to a reference electrode. A speci-
men at Eoc has both anodic and cathodic currents pre-
sent on its surface. However, these currents are ex-
actly equal in magnitude so there is no net current to
be measured. The specimen is at quasi-equilibrium
with the environment.
Open circuit potential measurements have been
. d out b y severa I wor kers 2526·
carrIe j'ff erent mICro-
. In (I .
bial corrosion systems. Gundersen et al .25 reported
the variation of open c ircuit potential with time for
254 SMO, SAF 2507 and SIS 2343 stainless steel
immersed in natural seawater with and without
chlorination . When OCP shifts in negative direction,
it· indicates the increase of corrosion rate whereas a
shift of OCP in noble direction is generally responsi-
ble for decrease of corrosion of the metal or alloy un-
der study. Fig. la-c show Eoc during continuous
chlorination with 0. 1, 0.2 and 100 ppm res idual chlo-
 DU BEY et at.: A REVIEW OF MICROBIOLOGICALLY INFLUENCED CORROSION 209

2·4
(0 )
Pt
2·0

Hi

1.2

0.8

0
..
~ 0·4
u >
'"
<t w'
0·0
( D)
Pt
'"
<t 800 -0·4
.;.
> lAF 2507
> '254 SMO
E 400
-1 .2
--
0
\
SIS 2343
-6 ·0 - 5·0 -"·0 -3·0 -2 ·0
.. 0
log ~ A/cm 2
0
a.
(c)
PI Fig. 2-Polarization curves 22 at 25°C of 99.99% AI in :
800
(a) sterile electro lyte (0.25 ~m diamond po li shi ng paste sur-
"-SIS 2343 "-254 SMO face fini sh)
(b) sterile ele(; trol yte (600 grid surface finish)
400 (c) anodic in in ocu lated electrolyte
(d) cathodic in inocul ated electrolyte
(e) cath odic in steril e electro lyte
o

o 20 40
Exposure time, doys
Fig. I-Open ci rcuit potenti al for 254 SMO, SAF 2507 ,SIS 2343,
and Pt vs time of immersion in natural seawater during intermit-
tent chlorin ation wi th 0. 1. 0 .2 and 100 ppm resid ual chlorine
res pec ti ve ly. 30 min/day.
rine, respec tive ly. The time dependence of Eoc con-
tinues to ri se s low ly even a fte r 40 days of exposure at
0.1 ppm. The response in potenti al for various mate-
ria ls are di ffe re nt at low chlorine concentration. The
least nobl e of the sta inless steel SIS 2343 has a con-
sistently lower ElK than the more nobe l alloys. The
ope n c ircuit pote nti a l for SAF 2507 is generally
hi ghe r th a n that fo r 254 SMO in the c hl orinated sea-
water.
Potentiodynamic Polarization Measurements
The deve lopment of potenti ostat a ll o wed the use of
pote nti ostati c and po te ntiod yna mic po larization tech-
niques, with Oliver's pape r on the pass ivation be-
haviour of Fe-Cr a ll oys27 The potentiodynamic tech-
niqu e is ll sed to exa min e the overa ll corrosion be-
ha viour of a syste m . In a typical potenti od yna mi c
scan, th e pote nti a l is s low ly swept over a ve ry wide
potenti a l ra nge (typica ll y -2 to +2 vo lt s rel ative to a
re fe re nce e lectrode). During the s weep , the me ta l
sampl e may unde rgo diffe re nt electrochemical reac-
ti o ns, res ultin g in anodi c and cathodic ce ll currents
which may va ry ove r man y orders of magnitude. Fig.
2 shows the polarization curves of 99.99 % Al in dif-
fere nt e lec tro lytes with and without the fungu s lIor-
moconis resinae 2H . Curves (a), (b) and (c) show the
anodic nat ure , whereas curve (d ) and (e) are cathodic.
28
The proliferation of Hormoconis resinae on th e
tes ted sa mpl es dec reases the pitting potenti al (Epit ) by
2.6V fo r 99.99 % pure a luminum.
Pol arizati o n tec hnique s have also been applied for
the eva lu ati on of loca li zed corrosion phenomena. The
pittin g potential Epit and the protection potenti a l Ep rot
have bee n used to c harac terize the susceptibility of
me ta ls a nd a ll oys to pitting corrosion. The difference
in El'il a nd the co rrosion po te nti a l ELorr has been used
to asses the susceptibility of a me tal to pittin g in a
g ive n e nviro nme nt. EI'II is th e pote ntial value at w hi ch
th e curre nt density begins to increase drasti cally in
the pass ive range in so luti o ns containin g aggressive
ani o ns (Cl , Br- , e tc.). Ep,ol is the protecti on potential ,
i.e., th e pote nti a l be low w hic h no pittin g occurs and
above whic h pits a lready nucl eated can growN
Fig.J shows th e anodi c po la rizati o n curves of mi ld
stee l in ste ril e Pos tagate C med ium and a SRB culture
in th e same medium 'O .
marked decrease of the pi t-
tin g pote ntial as we ll as a diminuti o n of the pass ive
210 INDIAN 1. CHEM . TECHNOL..1ULY 1999

zone can be noticed due to the synergic action of 0 ·0

chloride anion s contained in the med ium and sulphide
anion s produced by the metabolic activity of the bac-
w
teria. u a
<.f)

.,;
> -0·4
Tafel Plots
The Tafel technique is used to obtain an accurate >
estimate of the corrosion rate of a metal in solution. ...c
0

Cell current is measured during a slow sweep of the ...

ClJ
0
potential. The sweep typically is from -250 to +250 a. - 0·8
mV relative to Eoc. An electrochemical half-reaction
31
uhder kinetic control obeys the Tafel equation : .
o (231l3(£-C°)th ) . 2
I = Ie .. . (4) - - Current Density, mA/cm

Fi g. 3--An odic polari zati on curves of mild steel in steri le Posta-

In this equation I is the current resulting from the gate C Medium.
reaction, 10 is a reaction dependent constant called
the exchange current, E is the electrode potential, EO
-0·3 , - - -- - - -- - - -
is the equilibrium potential ( constant for a given re-
action), and b is the reaction 's ~ coefficient (constant - 0·4
/
for a given reaction), ~ has a unit of Volts/decade. ANODIC
The Tafel equation describes the behaviour of one -0·5
isolated reaction . In a corrosion system, there are two
opposing reactions . The Tafel equation for both the > -0·6

anodic and cathodic reactions in a corrosion system o

'" '"
- - - - - - - - /l'\ '" Ecorr
can be· combined to generate the Stern-Geary equa- ..
C -0·7
o
1\
I
tion 32. 34 . Q.

-0·8
I = I Carr \e
(. 2303(E- Ec",, )lba )
-e
- (2 .303(E - E Carr )/ bC ') CATHODIC
- 0· 9
... (5)
- 1· 0
: teorr
where I is the measured cell current in ampere, l eorr is 1
-1· 1 ..........~-----'---'--'--_--'- _ _...l-_--'
tbe corrosion current in ampere, E corr is the corrosion 2 3
potential in volts, b a is the anodic ~ coefficient in log Current Density, JlA Icm 2

volts/decade, and be is the cathodic ~ coefficient in

volts/decade. Fig. 4--Tafel plot co nstru cted form data obtained during polari-
zation of mild steel coupo n in B Ii) medi um26
Log I versu s E plot is generally called a Tafel plot.
A Tafel plot is performed to experimentally deter-
mine l eorr ' from which the corrosion rate is calculated. E Corr is we ll applicable in the case of charge-transfer
26
l eorr as obtained by extrapolating tbe linear portion controlled corrosion reactions which give well de-
of Tafel plot to E eorr . as shown in Fig. 4 . The corro- fin ed Tafel plots. In the case of processes which are
sion rate can be calculated from ICorr by using the fol- diffu sion controll ed, the extrapol ated values depend
lowing equation , stron gly on the properties of the reacting interface
and on the hydrodynami c conditi ons. Lorenz and
Corrosion rate R(mpy ) = 15
Mansfeld reported th at ex trapolati on procedure can
0. 1288/~A/cm 2 ) eq.wt(g ) ... (6) not be used for sys tems havin g non-lin ear behaviour.
D{g / em 3
) However, their non linearity can be overcome by
means of pul se polari zation conditions, because under
where I is the current density and D is the specimen these conditi ons the surface properti es of the corrod-
density. The extrapol ation of polarization curves to . e Iec tro de remam
mg . co nstant"14 .
 DUBEY el al.: A REVIEW OF MICROBIOLOGICALLY INFLUENCED CORROSION 211

Polarization Resistance Method 105

Polarization res istance is defined as the slope (0 )
(dE/dJ) at the corrosion potential of a poten- PH=2 ·0
E 70
tial/current den sity curve. This slope has units of re- r;
0
sistance area and is known as the polarization resis- ......
III

tance. In I'nathematical form polarization resistance, ~'

35
:z
Rp , is expressed as :
W
0
Rp =( dE) ,E = ECorr ... (7) 0 60 120 180 240 300
dI ai DAYS
150
5 J6
Stern and Gear/ . simplified the fundamental equa-
tion for s imple charge tran sfer controlled reaction, in
E 100
which the relation ship between ICorr and Rp has the r;
0
form: ......
III

~, 50
~
... (8) W

where ~ a and ~ c are the anodic and cathodic Tafel DAYS

slopes. For a quantitative determination of ICorr ; ~a ,
~ c and Rp have to be determined. Computer programs
H J8 w embedded in concrete 3S .
such as CORFIT , POLCURR and POLEFIT have
been developed by Mansfeld and co-workers for the
determination of prec ise va lue of Icorr . Kasahara and
Kajiyama 40 used po larizati on res istance technique for
active and in acti ve SRB condition s.
Mansfe ld et al.~J have used the linear polarization
technique to determin e Rp for mild steel sensors em-
bedded in co ncrete . The concrete samples were ex-
posed to sewer e nvironmen t for about nine months.
One sample was peri odi ca lly flu shed with sewage in
an attempt to remo ve the acidic environment pro-
du ced by the bi ofilm, the other sa mple was used as
control. A spec ial data logg ing system was used to
co ll ec t Rp dat a at 10 min interval s simultaneously for
the two co rros ion senso rs and two pH electrodes
which were placed on the concrete surface. Fig. 5
shows the cumulati ve co rros ion loss LINT, where
INT was obta ined by integration of the IlRp-time
curves as
t,
INT= J-=-dtlR p
t J
) A quantitative measure of corrosion rate can be
obtained from slope of the curves in Fig. 5. The cor-
rosion loss remained very low during the first two
month and then showed a large increase for both
samples . The total corrosion loss as determined from
the integrated Rp data was less for the control than for
the flushed sample.
Fig. 5--lntegrated corro sion loss LINT for mild steel sensors
Some of the most common errors that are poss ible
in this method is the invalidation of results through
oxidation of so me other electroactive species besides
the corroding metal concerned, a change in corrosion
potential , Ecorr during the time taken to perform the
measurement and the application of a large applied
potential resulting in inadvertent departure from lin-
ear current density versus potential behaviour.
Electrochemical Impedance Spectroscopy (EIS)
The term electrochemical impedance spectroscopy
was first introduced by Mansfeld 42.43 by replacing the
previou sly used term AC impedance. Since its intro-
duction by Epelboin et al.~, EIS has become very
popular and has been applied to all types of corrosio n
phenomenon . Some of the ad vantage of EIS tech-
niques are the use of only very sma ll signals which do
not di sturb the electrode properties to be measured,
... (9) the poss ibility of studying corrosion reaction and
measuring corrosion rates in low conductivity media
where traditiona l DC methods fail, and the fact th at
polarization resi stance as well as double layer ca-
pacitance data can be obtained in the sa me measure-
ment.
Application of EIS in MIC studies ha ve included
monitoring corrosion over time on carbon steel ex-
posed to bacteria~ 5, carbon steel exposed to bacteria
212 INDIAN 1. CHEM. TECHNOL., JULY 1999
and treated with 'biocides46 , stainless steel weldments
47
exposed to bacteria and stainless steel samples ex-
48
posed to natural seawater . The advantages of using
EIS in MIC studies have been reviewed 49 • One of the
advantages of using EIS is that small amplitude sig-
nals, within the linear response range and generally 5
mY rms or less, are applied. Repeated EIS analysis on
stainless steel samples with biofilm caused no change
in the open-circuit potential after the analysis, pro-
viding indirect evidence that EIS do not damage the
metal samples or biofilms 50 . Effect of EIS on micro-
bial biofi.lm cell numbers, viability and activities of
sessile bacteri a on stainless steel have been reported
51
by Franklin et ai. • They concluded that EIS can be
used to study mec hani sms of MIC with little or no
damage to the numbers of viable bacteria in a biofilm
or to th e activity of the bacteria.
It is ass umed that elec trochemical reactions that
determine th e corrosion behaviour can be defined in
terms of c harge transfer across an interface between a
sol id elec trode and an electrolyte. The driving force
for th e charge tran sfer reaction is the ' potential drop
across the interface, E, usually measured against a
reference e lec trode. Thi s requires that the electric
current betwee n the e lectrode and the electrolyte will
be a uni que function of the voltage drop across the
interface . All th e mechani stic information about the
rate limiting steps in sllch a system is contained in
thi s functi onal relation , i.e., I(£) . If we introduce a
small time depende nt perturbation in the voltage, M,
the resulti ng c hange in the cllnent can be extended in
Taylor series to yield :
I (E+M)= I ~E) + (oJ /OEh,M
+ ~0 2 1 /~ E )E,I M 2 ... (10)
If the' mplitude ofJhe perturbation is small enough
slIch....t+rat the second and higher derivatives can be
neglected then the resulting change in the current can
be expressed as :
M = (011 OE)E.I M ... ( II)
Yew) = Z-I(w) == (Ol / oE)E! is defined as the ad-
mittance of the system and Z(w) as its impedance; w
is the angu lar freq uency of the perturbation.
The measuremen t is relative ly simple. In the most
co mmon app licati on, a small AC component which
vari es with time in a sinusoidal way: M(t) = fiE Sin
WI , is superimposed on the DC voltage and the change
in the current is measured . The change in the cunent
can be exp ressed as 6/(t) = M SIn (wt+ 8) , where 8 is
c
RS
RS =Sotution resistance
Ret= Charge transfer imped-once
C = Double layer capacitance
W =War burg impedance
Fig. &---Equivalent ci rcui t fo r a corroding electrode.
the phase difference between the perturbation and the
response.
When the result is ex pressed in thi s way, imped-
ance measure ment do not provide direct information
about the system. In order to gain useful information
one has to solve the full/(£) equation, or to represent
the sys tem in electri cal engineering terms, or to
model the system as a parallel plate capac itor.
One approac h that is applied in many practical
cases is the network an alysis. Th is implies utilizing
electri cal circuit elements such as capacitors and re-
sistors, correlatin g these elements with some physical
process and c harge accumu lation modes in the elec-
troc hemical corrosion system, building the electrical
network and composing the respon se of the network
with the measured response. One usuall y finds (hat
the mathematics is relatively easy and much of the
work is already done and results can be found in any
good book on circuit analysis.
To illustrate the application of these principles let
us assume that the electrochemical reactions that de-
termine the corrosion behaviour are of very simple
nature and can be represented by the familiar Ran-
dle's equivalent circuit shown in Fig. 6.
Rs represents the seri es resistance of the electrolyte,
ReI is the charge transfer resistance, W is the Warburg
impedance, and C is the double layer capacitance,
From Fig. 6, it follows that the system impedance is
gi ven by-
Z(w) = Rs + [Ill we + ( IIReT + aw- 1n - icrw- 1I2)]
(J 2)
where (J is the Warburg impedance. From this com-
plicated ex pression two limiting cases can be consid-
ered. First, when charge transfer is important, and
when electroactive species are always at their Nem-
 DUBEY et aL.: A REVIEW OF MICROBIOLOGICALLY INFLUENCED CORROSION
stian concentration at the electrode surface, Eq. (9)
simplifies to -
Z(w) - R +
R
cl
iroeRb ... (13)
- S 1+ ro 2
e Rb 1 + ro 2 e 2 Rb
2 Rct
If the imaginary component of this impedance, Z ',
is plotted versus the real component of the imped-
ance, Z, for each excitation frequency, a single semi
circle is obtained (Fig. 7), having a diameter of nu-
merical value ReI (=l/w*c, where w* is the fre-
quency/HZ at the maximum of the semicircle). This
representation for evaluating AC impedance data is
known as Nyquist plot, or Cole-Cole plot, or complex
impedance plane diagram. When charge transfer is
small compared with diffusion , the impedance is
given by, .
Z(w ) =Rs + Rel + crw- 11 2- .l(crw-1/2 + 2a-.1.c ) .. . (14)
In this case the impedance spectrum in the complex
plane is a straight line of slope 45°. For cases where
neither charge transfer nor diffusion is solely impor-
tant, there is interaction between the interfacial im-
pedance and the Warburg impedance. In general, the
shapes obtained in the complex impedance plane de-
pend on the relative values of RCt , cr, and e, and typi-
cal diagram is shown in Fig. 8. Fig. 9 is the Bode plot
for the same data as in Fig. 8. This format permits
examination of the absolute impedance, (Z), as cal-
culated by
(Z) =(i 2 + i '2) 112 .. .
as a fun cti on of frequency. The Bode plot is useful
alternati ve to the Nyqui st plot to avoid the longer
measurement times associated with low frequency ReI
determinations. Thi s is because the log (Z) versus log
f plot so metimes a llows a more effective extrapola-
ti on of data from higher frequencies. The Bode for-
mat is also desi rable when data scatter precludes ade-
quate fitting of the Nyqui st semicircle. In general, the
Bode plot prov ides a c lear description of the electro-
chemical system 's frequency-dependent behaviour
that does the Nyqui st plot where the frequency values
are implicit.
Other types of plots (e.g. Randell plots, i versus
)
WZ' etc.) optimize data interpretation for special ex-
perimental systems, providing better information than
the Nyqui st or Bode Plots. Since today most of the
more sophi sticated ex perimental setup attached to
some form of computing facility for data handling,
the transfer of data from one form to the next is not
213
Decreasing frequency -
=2Mtan ex.
Fig. 7--Estimation of charge transfer impedance by tangential
method.
W=2nf c= __1 _
2nf*R ct
Z" f Decreasing
\
,
\
I
Z'
Fig. 8--Typical Nyquist plot.
very difficult. The importance of a particular data
presentation lies in its ability to suggest to the inves-
ti gator the general feature of a model that might be
applicable for anal ys is of the system.
(\5) Analy sis of carbon steel affected by Vibrio natri-
gens in batch and continuous flow culture using EIS
and direct current techniques has been made by
Dowling et ai. 52 Most of the impedance diagrams ex-
hibited single depressed capacitive loops with centres
below the real axis [Fig. \0 a & b) . A comparison of
the corrosive effects of V. natrigens in batch culture
with that of a sterile chamber over a three day period
showed that the presence of the bacteria considerably
increased the corrosion rate. If the assumption that a
is good approximation of Rp proves true and the ano-
dic Tafel slopes (Pa) is assumed to be constant, then ,
I
C OlT
=~
2 .3A
... (\6)
Thus the presence of V. natrigens in batch culture
accelerated the corrosion rate compared with the
sterile side over the same period and also the intitial
rate before passivation.
Hernandez et at. 53 have reported the EIS study of
the corrosion inhibition of steel by Psuedomonas sp.
214 INDIAN 1. CHEM . TECHNOL., JULY 1999

1·6 6 90

' ·4 (0 )
• (0 )
-
- - - With bactcr io
Without bact.rio

' ·2 •
5
-- -'I ,/
..--
'\~
\\
75

4
, 60
'·0 • 3 I
I .......
\
\ 45
0 ·8 I

06
• NE 2 I
I
\
\
N
E • ..
u
I I
I 30
.'"
u 0.4
• ~
..
0.
'"
E
c.
a
0·2 ••· .
a ~a
I Dp
• ",'

::?
:> 0
15

0
"
",-

0-
.><
I c
"a ( t»
- - - 20 da ys 0

,N "' (~ )
:[
0- 5 - - 30doys
75 :l:0
-, , ·0 ~ c
a.
1

0·8 60

06
• • • e •• 45

••
04
30
02
0 · 0~-nD-~~-L~~~-L~~~ 15
0.0 0·2 0 4 0·6 0 ·8 , ·0 ' ·2 ' ·4 ' .6
0 0
Z'I k ohms . cm
2 -1 a 2 3 4
tog Fre que ncy, Hz

Fig. 9--Typi cal Bode plo t.

Fi g. I I- a- EIS spec tra obta in ed afte r 20 d ays o f the exposu re
with and without Pseudo mon as sp. S ~ . Curves are g iven fo r indi-
2·0 , - - - - - - - - - - -- ---. vidu alrun s. Stand ard devi:lli o n between rep li cates was ±IO%. b-

~
(a )
E IS s pectra obtai ned afte r differen t ti mes of exposu re in NSS with
•• 8"':; ... . . DOY4 Pseudomon as sp . S ~. Curves are given for ind ivi du al run s. Stan-
dard deviatio n between rep li eales was ± I 0 % .
1·0 0" 000 :-' "

E rr-.;f8 0 ~o • • ,
u 80
reaction kinetics at th e metal electro lyte inte rface was
E 0·0 L @
C.
very hi gh and could not be ca lcu lated at low fre-
:, 2'0t; b ) Day 9 quency limit used .
54
~I !I Mans fe ld states that EIS can also be used for the
1· 0r- 0
o'to o
" 0 0
detec ti on and monitoring of locali zed corros ion of
0 0. . . • • • ' 0 .~. " '\,
aluminium a lloys and alumi num based metal matrix

0.0- 1
00
lt ,
"

' ·0
..

' . ' 0'b: ~

2 ·0
I
0

3· 0
I
40
composi tes. Thus it can be co nclu ded th at EIS can be
best appl ied in mon it orin g and study of MIC.

Z') k oh ms .c m 2 Electrochemical Sensors

Various types of e lec trodes, avail a ble for the
Fig. IO---Impedance data monocu1tute of V I1Glrigells (closed measure ment of d issolved O 2 , CO 2 , pH, redox poten-
circle) was compared with a cul ture of the vi brio and two SRB (0)
in continuo us flow (Days 4) and bath culture :Day 9)
tial (E H ) and H concentration (CH ) in steel, are of gal-
vanic (potent iometric) or poiarographic (am-
S9 in synthetic scaw;.:ter. Fig. II a & b shows imped- perome tric) types. Hydrogen embri ttle ment (HE) oc-
ance spectra ohtai ned after 20 days of immersion in cu rs du to the penetration of atomic hydrogen (H
: !uile an d inoculated ni ne salt solution (NSS). T he atoms) into a metal, which res ult s in de arburization, 1
!Jhase angle vers us frequency curve showed a maxi - loss of duc tility and te nsile strength cf the metal. Hy-
lum at 45" fo r the steri le so luti on ind icati ng a Wai- drogen can be absorbed by steel in several way and
burg type impedance, the cu rves of modules versus one of th most important of these is th e corrosion
frequency il1d icated little corrosion occurred du ing influenced by sulphate reducing bacteria (SRB). b
the first 20 day s in 11e case of bacterial suspension, the presence of SRB , the common cathodic reaction is
since the charge transfe r resistance characterizing the the educ tion of H 20 to hydrogen ato 1S . By using
 D UBEY er af. : A REVIEW OF MICROBIOLOGICALLY INFLUENCED CORROSION 215

Shitld.d Cu wi~
ShietcMd compen!I<JllId •
thermocoUple •• tcnsion
wire
TMnnoc"",* juoclion
c:ompcnsat i on moduW:

Chort rvc",d~r
(mullirongz)

Fig. 13--Typical response chart for tests using Hay sensors (test
solution= NACE TM 0177) .'7
ru~r QOSkel

l~
mask
woll JII t2 I2 ( I I
Corrosi..- _dium

I~ I I:; '~( J I/2 [

EQlJIVALEHT : CORROSIVE (H I No + OICoq
CIRCUIT MEDIUM
I t¢J
Fig. 12--Secti onal view and eq uival ent ci rcuit of Hay sensors.
some of thi s hydrogen in the con version of sulphate
to sulphide, as given in Eq . (14), the bacteria are
tbought to depolarize the cathodic reaction at the steel
surface and the corrosion rate is increased 55 ,56.
SO ~- + 4 H 2 ---7 S 2- + 4 H 2 0
The presence of su lph ide promotes the absorption
of hydrogen due to the following cathodic reaction .
The measurement of hydrogen concentration at the
inner surface of steel (CHi) is pe rformed by am-
perometric sensors . Potentiome tric sen sors enable
calculation of the equivalent pressure of H2 gas
(PH2et:l' by application of the Nemst equation. In
Devanathan-S tachurski cell,57.59 the concentration of
hydrogen in the metal is est imated as 60 ,
CHi =1JIDapp
where, 1 is hydrogen atom fl ux , J is the thickness of
the diaphram and Dapp is the diffusion coeffic ient.
Hydrogen atom flu x (1) is determined by measuring
the current density which IS rela ed to each other by
tbe equati on .
exp - 4Dapp ~- 12
... (21 )
I Ni NiO
I
Th e amperometric senso r desc ribed by Hay is
show n in F ig. 1261.62. The meta l diapharm, Fe(H) in
the equi va le nt c ircuit , was the steel pipe line int o
which hydrogen was introduced by the corrosive me-
dium. React io ns at the interface I and II cou ld be
writte n as :
Reacti on I : Hl'e ---7 H ~q + e l- ... (22)
Reaction Il :
.. . ( 17)
e~ + H IIlI + II2NiO ---71/ 2H 20 + II2Ni (23)
The nicke l-ni cke l ox ide e lectrode (cathode) co m-
prised an e lectron si nk, and the current is measured
... (18) by the pote nti al d rop (E) across a standard resisto r
(R). CHi is calculated by Eq ( 16). Dapp for H in steel
cou ld be de termined by Eq. ( 18) .
In pract ica l app li cati o n, th e surface of th e mild
stee l is c lean ed with emery pape r and degreased wi th
appropriate so lvent. The sensor is mounted on the
steel . urface a nd sea led wi th sui tabl e epoxy res in .
Now the sa mple is e xposed to the corrosive e nvi ro n-
ment and measure ment is pe rformed. Fig. 13 shows
... (19) the res ponse c hart from H ay senso r6J. There is maxi-
mum po te ntial d ro p across the standard resistor whic h
is fo ll owed by a 'Iow decline. CHi determined from
the Hay se nsor was reported in the above experi-
me nt}' arou nd 4 .62 x 10'c to 7.17 x 10. 2 mL (STP) g
tee I.

J = ifF .. . (20) Elec tr ochemical Noise A nalysis

where i is the current den sity and F is the Faraday
constant. The diffusio n coeffc ie ni: Dapp may be de-
temuned from the current iransient at two shor t times
tl and l 2 as
More recent ly , s ign ificant deve;opments describing
the use of e lect rochemical no ise techn iques have been
repo rted fr:om whi c h insigh ts into electrode processes
a nd hence corrosi o n phe nome na can be obta ined by
mo nitori ng the "po ntaneou, fluctuations of poten tial
 216 INDIAN J. CHEM . TECHNOL., JULY 1999

TIME RECORD : NP26

+ 0 .053Or-( 0-)--,.--------=-='.:-:-\-,--~-~-.t..-~-.- - , due to localized breakdown of film fo llowed by rapid
repassivation.
+0·0576 .r';
'. : I. Finally it can be concluded that electrochemical
.; noise techniques are very useful in evaluating the
~
o :~ nature of the corrosion process and in monitoring mi-
~ -0 ·0530 I- :;
-..J crobial corrosion but presently this technique is under
-..J
~ the initial stage of its development.
-0 · 1737
Conclusion
~ Since MIC is a complex process in the corrosion
-0·2943 I I
38·96 39·03 39·10 39·17 39·24 phenomenon, it may be concluded that electrochemi-
TIME ,h
cal techniques are very useful in the study of micro-
POTENTIAL DISTRIBUTION (+ve & '"'IIt!)
1000 1000 bial corrosion. Electrochemical tenchiques coupled
(b)
with chemical and biochemical techniques can solve
- - Magnitude
> - - - - Population most of the problems in the diagnosis, surveillance
E 100 t- 100z and monitoring of bacterial corrosion processes . Most
0
w' i=
0 ct of the microbial corrosion and microbial metabolisms
::l I
~
v
I
-..J
l-
.t' ::l which are associated with MIC may be studied with
z 10 b- 10
el.
\!)
I !I' 0
electrochemical techniques . Mechanistic investiga-
ct I~ el.
.1 1
~
tions and microstructure of biofilm as well as the cor-
,, il/\U
I

I
1 1
0·001 0·01 0·1
MILLIVOLTS
Fig. 14--Tirne record after 216 days for covered reinforcements
in media containing active cultures of SRB . ~3
or current that occur at electrode/electrolyte inter-
faces . The minute variations in potential can be
measured using a sensitive voltmeter, coupled to a
microprocessor, and analyzed usi ng Fast Fourier
Transforms (FFT) or Minimum Entropy Model
(MEM ) analysi s routines. For example, the current
noise measurements have been made under poten-
'tiostatic control in pitting and passivity studies64 .65 .
Voltage and current noise measurements have also
been analyzed from corroding electrode under open
circuit conditions 66. 68 .
69
Moosavi, et al. reported electrochemical noise
analysis on the corrosion of reinforced concrete ex-
posed to sulphate reducing bacteria in marine envi-
ronment. Fig. 14 shows a time-potential record and a
potential distribution chart showing the population
and the magnitude of potential fluctuation. The po-
tential fluctuation f the specimens were measured at
Ec orr . The time record after 218 days for the covered
rebar reveals that the magnitude of noise fluctuations
depends on the total impedance of the system. A cor-
roding metal undergoing uniform corrosion with
fairly high corrosion rate might be less noisy than a
passive metal which shows occasional bursts of noise
rosion behavious of various specific-systems in the
1 10 100 course of MIC can be best elucidated by applying a
combination of electrochemical techniques and sur-
face analytical techniques such as electron spectros-
copy for chemical analysis (ESCA), Auger electron
spectroscopy, strain electrometry, ellipsometery,
transmission and scanning electron microscopy (TEM
and SEM), energy di spersive X-ray analysis (EDAX),
low energy electron diffraction (LEED), reflection
electron diffraction (RED) and ion microprobe mass
spectrometry . Thus electrochemical techniques are
equally applicable in basic research and fie ld appli-
cations and also in es tab lishing a link between elec-
troc hemistry and microbiology.
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