Paper No
Paper No
10473
ABSTRACT
The main purpose of this study was to monitor the growth of the marine bio-film, of micro/macro-
organisms, on the surface of different metallic alloys in seawater by electrochemical impedance
spectroscopy (EIS). The alloys used in this study were; UNS 1020 carbon steel, stainless steel 304,
stainless steel 316L, Sanicro 28, Cu–Ni 70–30, Hastelloy G-30, and titanium. The EIS was used to measure
the A.C. Impedance (Z) and the double layer capacitance (Cdl) of the formed bio-film in seawater on a
frequent basis. The total exposure time of the tests was ranged between 90 days to 180 days. The visual
inspection of the tested samples showed a bio-film formation on the surface of these samples. The
microbiologically induced corrosion(MIC) was observed only on the carbon steel. Monitoring the growth
of the bio-film formation was accomplished by the EIS during the 90-180 days exposure of the tested
samples. A gradual monitoring of the growth of the bio-film formation was achieved by mathematically
correlating the obtained the A.C. Impedance (Z) and the double layer capacitance (Cdl) of the bio-film to
the thickness of the bio-film formation. The advantage of EIS is a non-invasive technique with a sensing
(spatial) resolution in a nanometer scale in a comparison to other techniques of monitoring the growth of
bio-films on metallic alloys in aqueous solutions.
Key Words: Marine bio-film; Electrochemical impedance spectroscopy; Seawater , A.C. Impedance (Z),
Double layer capacitance (Cdl).
THEORETICAL ANALYSIS
In literature, the relationship between the A.C. Impedance (Z) and the double layer capacitance (Cdl) of a
developed film on a metal sample to the thickness of the formed film is given as the
Following7-8
|Z |= 1/ Cdl = L/(e eo A) (1)
Where:
Z is the A.C. impedance of the formed film, Ohm.cm2.
Cdl is the Double layer capacitance of the formed bio-film, F.
eo is the permittivity of the free space, 8.85 X 10 -14 Farad/cm.
A is the area of the sample that exposed to the seawater, 1cm2.
L is the thickness of the formed biofilm, nm, which can be obtained here by EIS, via equ.(1).
e is the static dielectric constant of the material under the investigation, of the biofilm.
©2018 by NACE International.
Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to
NACE International, Publications Division, 15835 Park Ten Place, Houston, Texas 77084.
The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association.
2
In this investigation, the dielectric constant of the bio-film has been extended to account for the volume
fraction of the seawater in the film, as biological membrane9-10. So;
e= (e bf + vsw esw), where
ebf is the dielectric constant of the formed biofilm; ebf =5, when the pore fraction is equal to 0, an adhered
thin layer9-10.
esw is the dielectric constant of the seawater, esw =70.2 at 18 oC11 and esw =67.4, at 33oC11 .
vsw is the volume fraction of the seawater in the film. The value of vsw =50% and 75% will be considered
in the film as the film grows outward of the surface of the alloys. The value of esw =70.2 at 18oC11 will
be considered at an exposure time of 0,1,5,10,20,30,60.90 days, from the November to February season.
Furthermore, the value of esw =67.4 at 33oC11 will be considered at an exposure time of 130,150,180 days,
from the March to May season.
Equation (1) describes the relationship between the A.C. impedance and the double layer capacitance of
the thickness of the biofilm. In other words, one can measure the thickness of the biofilm by knowing the
A.C. impedance as well as the double layer capacitance of the biofilm from EIS measurements.
EXPERIMENTAL WORK
Metallic samples of UNS 1020 carbon steel (0.18-.23% C, 0.3-0.6% Mn, and balanced of Fe), stainless
steel 304, UNS S304, (18-20% Cr, 8-12% Ni, 2% Mn,1% Si, 0.08% C, and balance of Fe) stainless steel
316L, UNS S31603, (16-18% Cr, 10-14% Ni, 2-3% Mo, 2% Mn,1% Si,0.03% C, and balance of Fe),
Sanicro 28, UNS S 62800, (27% Cr, 31% Ni,3.5 % Mo, 0.002% C, and balance of Fe), Cu–Ni 70–30 (69%
Cu, 30% Ni, 0.5% Fe, and 0.6% Mn), Hastelloy G-30 (44% Ni,22% Cr, 7% Mo, 20% Fe, 2% Cu, and
0.015% C) and commercial pure titanium, UNS R50250, (0.2% Fe, 0.18% O, and balance of Ti) were
used in this investigation. Those seven alloys have been selected in this study because of their common
applications in seawater12. All samples were mounted on a Teflonsample holder. The sample holder was
especially designed to seal the samples from the surroundings, except the exposed area of 1 cm2. The
exposed surface of each material was first cleaned with 5% HCl, and then mechanically polished with
silicon carbide paper up to the finest grade, 1200 grit finish. The electrochemical test cell was designed to
support the continuous flow of fresh seawater of the Gulf seawater and to facilitate the EIS measurements.
The dimensions of the cell were 100 cm in length x 60 cm in height x 40 cm in width. The seawater was
pumped from a depth of several meters, of Doha Desalination plant, in Kuwait, to storage tanks. Then the
seawater was filtered prior to the electrochemical tests. This process was carried out on a frequent basis
during the 180 days of exposure to seawater. More details on the experimental set up is given elsewhere13.
Also, the cell is equipped with a reference electrode which was a saturated calomel electrode (SCE), 241
mV versus SHE, and a counter electrode which was a graphite rod. Electrochemical impedance
measurements14-16 were performed using an EG&G impedance analyzer system model 6310, and the
software used for analyzing the outputs was EG&G, 398 model(2). The frequency range used was between
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(2)
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©2018 by NACE International.
Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to
NACE International, Publications Division, 15835 Park Ten Place, Houston, Texas 77084.
The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association.
3
100 kHz to 10 mHz, and the voltage amplitude was ±5 mV root mean square (rms). Each EIS test was
obtained after monitoring the open-circuit potential for 1 h. The output data of EIS were the Nyquist and
Bode plots. From these plots, the A.C. Impedance (Z) and the double layer capacitance Cdl were obtained.
A simple Randles circuit was used for interpreting the EIS data. The Randles semi circle was used for data
fitting of the experimental results. The acquired electrochemical data (Z & Cdl) were obtained from 11
tests in 180 days of exposure to seawater (0,1,5,10,20, 30,60,90,120,150,and 180 days) for each alloy.
The temperature of the seawater during the tests was varied from 18 0C in winter days to 33 0C in the
summer days. Also, the resistance of the seawater has an average value of 8 Ohms cm2.
Table 3—The EIS data of Cdl & calculated L of the bio-film of all alloys in seawater, vsw =75% and
esw =70.2 at 18oC (0,1,5,10,20,30,60,90 days) & esw =67.4 at 33oC (120,150,180 days).
Materials Carbon Stainless Stainless Sanicro 28 Cu-Ni 7-- Hastelloy Titanium
Steel Steel 304 Steel 30 G-30
316L
Exposure Cdl L Cdl L Cdl L Cdl L Cdl L Cdl L Cdl L
Time (days) (F) (nm) (F) (nm) (F) (nm) (F) (nm) (F)) (nm) (F) (nm) (F) (nm)
0 0.25 204.1 1.78 28.7 1.1 46.4 0.74 68.9 1.14 44.7 0.58 88 0.65 78.5
1 4.4 11.6 1.23 41.5 1.14 44.7 0.58 88 2.7 18.9 0.67 76.1 0.268 190.4
5 8.5 6 1.26 40.5 1.1 46.4 0.91 56.1 8.85 5.8 0.722 70.7 0.28 182.2
10 0.158 323 - - - - - - - - - - - --
20 0.214 238.4 1.38 37 1.13 45.1 - - 0.48 106.9 0.77 66.2 1.1 46.4
30 0.195 261.6 1.33 38.4 9.6 5.3 0.7 72.9 0.68 75 0.654 78 0.31 164.6
60 0.216 236.3 3.97 12.8 3.78 13.5 0.36 141.7 0.69 73.9 0.632 80.7 - -
90 0.25 204.1 0.62 82.3 - - 0.6 85 0.42 121.4 1.06 48.1 0.296 172.4
120 - - 1.3 37.8 9.6 5.1 0.59 83.3 0.56 87.8 0.64 76.8 0.256 192
150 - - 0.89 43.7 6.26 7.9 0.58 84.8 0.54 90.8 0.54 91 0.325 1
180 - - 1.55 31.7 9 5.5 0.688 71.4 0.56 87.8 1.07 45.9 - -
Figures 1-7 illustrate the growth of the bio-film (L) as a function of exposure time for the UNS 1020
carbon steel, stainless steel 304, stainless steel 316L, Sanicro 28, Cu–Ni 70–30, Hastelloy G-30, and
titanium, respectively. In general, biofilms were visually observed on the seven alloys during the 0-180
days exposure. The L of the biofilm was visually estimated in a range of 20-50m13. On the contrary,
the L value of the biofilms, which corresponds to the obtained values of Cdl, was calculated in the range
of nanometer to fraction of micrometer, see Tables 1-3. In other words, the predicted L was much smaller
than the visually estimated one. Also, it is obvious from the Figs. 1-7 that as the volume fraction of the
seawater (vsw) was observed to increase in the bio-film, as a biological membrane, the L value of the
biofilm increased as well, in the outward direction from the surface of alloys. This implies that the closer
the bio-film layer to the surface of the alloys, the more adhered the bio-film to the surface in a comparison
(3)
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(4)
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©2018 by NACE International.
Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to
NACE International, Publications Division, 15835 Park Ten Place, Houston, Texas 77084.
The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association.
6
350
300
250
L,nm 200
150
100
50
0
0 20 40 60 80 100
-50
Exposure Time, days
Figure 1: The growth of the bio-film as a function of exposure time of the carbon steel to seawater.
The lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film. The
average temperature of the seawater was 18oC during the 90 days, November-February.
90
80
70
60
L,nm
50
40
30
20
10
0
0 50 100 150 200
Exposure Time, days
Figure 2: The growth of the bio-film as a function of exposure time of the stainless steel 304 to seawater.
The lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film. The average
temperature of the seawater was 18oC during the 1st 90 days, November-February and was 33 oC during
the 2nd 90 days March-May.
50
40
L,nm
30
20
10
0
0 50 100 150 200
Exposure Time, days
Figure 3: The growth of the bio-film as a function of exposure time of the stainless steel 316L in
seawater. The lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film.
The average temperature of the seawater was 18oC during the 1st 90 days, November-February and was
33 oC during the 2nd 90 days March-May.
160
140
120
100
80
L,nm
60
40
20
0
0 50 100 150 200
-20
Exposure Time, days
Figure 4: The growth of the bio-film as a function of exposure time of the Sanicro 28 in seawater. The
lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film. The average
temperature of the seawater was 18oC during the 1st 90 days, November-February and was 33 oC during
the 2nd 90 days March-May.
120
100
L,nm 80
60
40
20
0
0 50 100 150 200
-20
Exposure Time, days
Figure 5: The growth of the bio-film as a function of exposure time of the Cu-Ni 70-30 in seawater. The
lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film. The average
temperature of the seawater was 18oC during the 1st 90 days, November-February and was 33 oC during
the 2nd 90 days March-May.
100
90
80
70
60
L,nm
50
40
30
20
10
0 Exposure Time, days
0 50 100 150 200
Figure 6: The growth of the bio-film as a function of exposure time of the Hastelloy G-30 in seawater.
The lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film. The average
temperature of the seawater was 18oC during the 1st 90 days, November-February and was 33 oC during
the 2nd 90 days March-May.
200
L,nm 150
100
50
0
0 20 40 60 80 100 120 140 160
Figure 7: The growth of the bio-film as a function of exposure time of the Titanium in seawater.The
lines represent vsw =0% (blue), vsw =50% (orange), and vsw =75%(gray) in the bio-film. The average
temperature of the seawater was 18oC during the 1st 90 days, November-February and was 33 oC during
the 2nd 90 days March-May.
CONCLUSIONS
The following conclusions have been drawn from the present investigation:
1-The EIS has been successfully applied to real-time monitoring the growth (L) of the biofilm of several
metallic alloys in sweater, leading to the MIC in solely the carbon steel samples during 90 days of
exposure.
2-EIS was found a non-invasive technique of monitoring the MIC due to the growth of the bio-film of
metallic alloys in seawater in a comparison to other techniques.
3-The sensing (spatial) resolution of EIS was found in a nanometer scale as compared to the other techniques,
in a micrometer scale.
4- The L value of the biofilms, which corresponds to the obtained values of C dl, was calculated in the
range of nanometer to fraction of micrometer, as a function of the volume fraction of seawater in the
biofilm, vsw =0,50,75%, and the dielectric constant of the seawater at different temperature, esw =70.2 at
18oC (November to February) & esw =67.4 at 33oC (March to May).
5-The growth of the adhered bio-film layer was observed to maintain a constant thickness during the 180
days of exposure of the alloys to seawater, blue line in Figs.1-7.
6- The loosely biofilm layer was observed to grow in a random fashion during the 180 days of exposure
of the alloys to seawater, orange and gray lines in Figs.1-7, independent of the seasonal temperature.
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©2018 by NACE International.
Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to
NACE International, Publications Division, 15835 Park Ten Place, Houston, Texas 77084.
The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association.
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