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Alexandria University
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Departamento de Quı´mica, Campus Andre´s Bello, Facultad de Ciencias, Universidad de La Serena, Colina el Pino S/N, La
Serena, Chile
KEYWORDS Abstract This paper describes the modeling of polarization curves not exhibiting a Tafel region
Lineal voltammetry; using Excel spreadsheets. Carbon steel in aerated NaCl unbuffered solutions was studied applying
Steel corrosion rate; a linear potential sweep technique. Current–potential curves were obtained from linear potential
Sodium chloride solution; sweep at a rate of 10 mV s1 in un-buffered 0.1, 0.4 and 0.9 M NaCl solutions, at a constant
Excel spreadsheet temperature of 25 C and potential sweeps that were conducted in a potential range 1.0 to
0.4 V vs. Ag/AgCl.
ª 2014 Production and hosting by Elsevier B.V. on behalf of Faculty of Engineering, Alexandria
University.
a platinum wire as a counter electrode and Ag/AgCl in 1 M the corrosion potential, obtained directly from the experimen-
KCl cell as a reference electrode. The composition of carbon tal polarization curve and electrochemical parameters of the
steel was SAE 1008 with chemical content wt% 98.5 Fe, 0.02 cathodic reaction for the reduction of oxygen under zero total
C, 0.15 Mn and traces of P, S, Si and Cr. The cell was current (it = 0) condition. The corrosion rate, it can be
immersed in a thermostatic Haake D1 bath operating at calculated using the expression given by Khaled and Amin
25 C. Measurements were conducted in water before air was [8] Eq. (4).
bubbled for about 15 min; air was bubbled into the water by CR ¼ 3; 28 icorr ðM=ndÞ ð4Þ
using a small fish-tank pump, this water was used to prepare
the test solutions. A PG 580 (Princeton Instrument) potentio- where CR is the corrosion rate (mm y1), M is the atomic
stat was employed with the software of the same company. weight of iron (55.85), n is the number of electrons transferred
Polarization curves were obtained from linear potential sweep in the corrosion reaction (2 in this case) and d is the density of
at a rate of 10 mV s1. Potential sweeps were conducted in the iron (7,88 g cm3).
potential range 700 to 100 mV/SHE in 0.1, 0.4 and 0.9 M
NaCl un-buffered solution. Unbuffered solutions were used 2.3. Adjustment of the kinetic model to the experimental data
to prevent adsorption of the buffer compounds and their com-
plexes on the surface of metal [12], because the Caceres model In this case in order to adjust Caceres model [13] to the exper-
does not evaluate compound adsorption effect. imental polarization curve a nonlinear least squares method
was used. This is an iterative method that estimates the mini-
2.2. Kinetic model mum of the function (SS), Eq. (5), via Excel solver function
[15].
The kinetic model chosen for this study was developed by and X N !2
i i
Caceres et al. [13], which uses the superposition model SS ¼ wi ð5Þ
proposed by Wagner and Traud in 1938 [14], method that con- i¼1
A exp A pred
siders that the total current density (it) is the algebraic sum of
where (i/A)exp is the experimental current density, (i/A)fit is
the anodic (ia) and cathodic (ic) current, which is:
the current density predicted by the model and wi is a weight
h i
io;O2 exp 2:3
EEeq;O2 function, designed to improve the fit, which in this case is
tc
ic ¼ h i ð1Þ defined by Eq. (6), as [16].
i 2 EEeq;O2
1 þ io;Ol;O2
exp 2:3 tc 1
wi ¼ ð6Þ
E Eeq;Fe s2
ia ¼ io;Fe exp 2:3 ð2Þ
ta where s is the standard deviation of the data predicted, defined
h i
EE
io;O2 exp 2:3ð tceq;O2 Þ by the Eq. (7) as:
E Eeq;Fe
it ¼ h i þ io;Fe exp 2:3 ð3Þ vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
i 2 EEeq;O2 ta uX
1 þ io;O exp 2:3 tc u N i
i
2
l;O
2
u
t A Average;fit A i;fit
where iL,O2 (A cm2) is the limiting current density for oxygen s¼ i¼1
ð7Þ
reduction, io,O2 (A cm2) is the exchanged current density for N1
oxygen, Eeq,O2 (V) is the potential balance for oxygen reduc- where (i/A)Average, fit is the average of the predicted current
tion, tc, is the pseudo Tafel slope for oxygen reduction,. io,Fe, density, (i/A)I, fit is the current density of each point and N is
is the exchange current density for iron, Eeq,Fe is the potential the total number of points. The goodness of fit of the data to
balance for iron and ta is the pseudo anodic Tafel slope. Cor- the model will be evaluated by using the regression coefficient
rosion intensity (icorr) can be calculated from Eq. (3) by using (R2) [15]. The sum of squared errors (SSE), the root mean
A exp
A ave; exp
i¼1 2.4. Construction of the Excel spreadsheet
!2
1X N
i i To construct the Excel spreadsheet, the indications given in
SSE ¼ ð9Þ Table 1 and Figs. 1–3 must be followed. Once the spreadsheet
N i¼1 A exp A fit
is built, the solver function of Excel has to be installed by
following the procedure described by Brow [15]. Once 2.5. Sensitivity analysis of corrosion rate prediction Caceres
installed, its mode of execution is as follows: model
1. The option Data has to be clicked and then a dialog Parameters considered in the sensibility analysis for the corro-
box of the solver function of Excel should appear as sion rate prediction Caceres model are listed in Table 3. The
follows. sensibility parameter, S is given by:
2. The set target cell has to be marked, in this case the cell ½ðO2 O1 Þ=O12
S¼ ð12Þ
marked is $M$7. ½ðI2 I1 Þ=I12
3. Then Min has to be marked.
where I1 and I2 are the least and greatest values of input used,
4. After marking Min the cells that are marked are
respectively. I12 is the average of I1 and I2. O1 and O2 are the
$M$1:$M$5, these are the cells of the kinetic constants of
output for the two input values, and O12 is the average of the
Caceres model (Eq. (3)) and the ones that solver will change
two outputs [18,19].
to minimize the function SS (Eq. (5)).
5. Finally with this data, the spreadsheet shown in Fig. 4 is
3. Results and discussions
created, and replacing the experimental corrosion potential
value therein, icorr is obtained for the condition where the
total current is approximately zero, i.e. ifit = 0.001 and with Figs. 5–7 show the correlation of polarization curves of carbon
this the corrosion rate. steel in un-buffered 0.1, 0.4 and 0.9 M NaCl solutions, at a
Modeling of polarization curves not exhibiting a Tafel region 981
Figure 4 Excel spreadsheet showing the calculation of the corrosion rate from experimental corrosion potential, the electrochemical
parameters and the condition that the total current density is approximately zero (it = 0.001).
-0,1
-0,1
Experimental
-0,2 Caceres Model Experimental
-0,2
Caceres Model
-0,3
-0,3
E (V vs. SHE)
-0,4
E (V vs. SHE)
-0,4
-0,5 -0,5
-0,6 -0,6
-0,7 -0,7
-0,8 -0,8
-5,0 -4,5 -4,0 -3,5 -3,0 -2,5 -5,0 -4,5 -4,0 -3,5 -3,0 -2,5
-2 -2
Log (i/A) A cm Log (i/A) A cm
Figure 5 Experimental polarization curve (X) for carbon steel in Figure 6 Experimental polarization curve (X) for carbon steel in
aerated 0.1 M NaCl solution un-buffered and fitted curve (con- aerated 0.4 M NaCl solution un-buffered and fitted curve (con-
tinuous line) calculated from the Caceres model using Excel tinuous line) calculated from the Caceres model using Excel
spreadsheet. spreadsheet.
-0,1
Table 3 Caceres model parameter values used for sensibility
Experimental analysis and parameter S.
-0,2
Caceres Model Parameter Base value Range of test S
-0,3 0.1 M NaCl
io,O2 8.84 * 104 1.0 * 104–1.77 * 103 1.03
E (V vs. SHE)
Acknowledgments
Table 2 Electrochemical parameters, corrosion rate and
statistical parameters of fit of polarization curves. The generous support of the FAU (Universidad Friedrich-
Electrochemical parameters 0.1 M NaCl 0.4 M NaCl 0.9 M NaCl Alexander of Erlangen-Nuremberg, in Germany, Friedrich-
io,O2 (A cm2) 8.84 * 104 1.48 * 103 9.53 * 104 Alexander-Universität Erlangen-Nürnberg, shortened FAU)
tc,O2 (V dec1) 2.04 4.32 2.00 Germany. Project of Cooperation Universidad de Erlanger
iL,O2 (A cm2) 0.02 0.6 0.3 Universidad de La Serena, Chile is gratefully appreciated.
io,Fe (A cm2) 1.10 * 103 1.48 * 103 2.09 * 103 Thanks to Prof. Dr. Ulrich Nickel for all those encouraging
ta,Fe (V dec1) 0.96 1.23 1.14 discussions.
Ecorr (V) 0.283 0.403 0.359
icorr (A cm2) 2.41 * 103 2.74 * 103 3.41 * 103
CR (mm y1) 2.80 * 102 3.19 * 102 3.97 * 102
References
[9] H. Flitt, D. Schweinsberg, Evaluation of corrosion rate from [15] M. Brown, A step-by-step guide to non-linear regression
polarisation curves not exhibiting a Tafel region, Corros. Sci. 47 analysis of experimental data using a Microsoft Excel
(2005) 3034–3052. spreadsheet, Comput. Meth. Prog. Biol. 65 (2001) 191–200.
[10] L. Cáceres, T. Vargas, L. Herrera, Determination of [16] D. Harris, Nonlinear least-squares curve fitting with Microsoft
electrochemical parameters and corrosion rate for carbon steel Excel solver, J. Chem. Educ. 75 (1998) 119–121.
in un-buffered sodium chloride solutions using a superposition [17] A. Vega-Galvez, E. Notte-Cuello, R. Lemus-Mondaca, L. Sura,
model, Corros. Sci. 49 (2007) 3168–3184. M. Miranda, Mathematical modelling of mass transfer during
[11] E. Howard, J. Cassidy, Analysis with microelectrodes using rehydration process of Aloe vera (Aloe barbadensis Miller),
Microsoft Excel solver, J. Chem. Educ. 77 (2000) 409–413. Food Bioprod. Process. 87 (2009) 254–260.
[12] M.A. Veloz, I. González, Electrochemical study of carbon steel [18] M.A. Nearing, L. Deer-Ascough, J.M. Laflen, Sensitivity
corrosion in buffered acetic acid solutions with chlorides and analysis of the WEPP hillslope profile erosion model, J. T.
H2S, Electrochim. Acta 48 (2002) 135–144. ASAE 33 (3) (1990) 839–849.
[13] L. Cáceres, T. Vargas, L. Herrera, Influence of pitting and iron [19] K. Siamphukdee, F. Collins, R. Zou, Sensitivity analysis of
oxide formation during corrosion of carbon steel in unbuffered corrosion rate prediction models utilized for reinforced concrete
NaCl solutions, Corros. Sci. 51 (2009) 971–978. affected by chloride, J. Mater. Eng. Perform. 22 (2013) 1530–
[14] C. Wagner, W. Traud, On the interpretation of corrosion 1540.
processes through the superposition of electrochemical partial
processes and on the potential of mixed electrodes, Corrosion 62
(2006) 844–855.