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THE ANNALS OF “DUNĂREA DE JOS“ UNIVERSITY OF GALAŢI

FASCICLE VIII, TRIBOLOGY, 2011 (XVII), Issue 1
ISSN 1221-4590

MODELLING OF SOME DEGRADATION PROCESSES BY

CORROSION FATIGUE OF METALLIC SURFACES

Svetlana BĂICEAN, Mihaela BUCIUMEANU, Liviu PALAGHIAN

Faculty of Mechanical Engineering, “Dunarea de Jos” University, Galati, ROMANIA

mihaela.buciumeanu@ugal.ro

ABSTRACT
Based on the well known fatigue corrosion effects, the mechanical stress and the
corrosive environment have a significant effect on the prediction of the lifespan of
the equipments that work in corrosive environment, two models are proposed. The
first model is dedicated to the evolution of the pits volume that occurs on the
specimen surface, while the second one is dedicated to the electrode potential
evolution of the material. It was observed a good correlation between the
experimental and the predicted results.

Keywords: naval steel, fatigue, corrosion, pitting corrosion

1. INTRODUCTION the variable stress amplitude and the tensile strength,

 a  r has been considered.
The results obtained by experimental research
regarding the degradation by fatigue in corrosive 2. EXPERIMENTAL PROCEDURE
environment can be the necessary base to model this
process. Based on these models, the degradation state
can be evaluated and it can be predicted the lifespan
2.1. Materials
of the equipments that work in corrosive environment.
The low alloy steel, compared to the carbon steel,
Such models, as in the case of mechanical degradation
has been widely used in naval construction due to its
models, follow the development of some kinetic
higher mechanical properties taking into account the
equation of degradation [1].
both effects: the mechanical stress and the marine
In varied studies [2, 3, 4] it has been
environment. The carbon steel can be used in marine
demonstrated that the degradation process by fatigue
structures only in immersion conditions, where these
corrosion is an evolutionary process with physical,
materials present a good corrosive resistance.
chemical and mechanical modifications. The synergy
The present studies are focused on the naval steel
between the electrochemical and mechanical
(grade E36). The specimens used to carry out the tests
processes leads to changes on the shape and the
are flat specimens.
structure of the superficial layer. As a consequence,
The naval steel E36 is used in naval structures,
the corrosion pits are considered as stress
mainly to manufacture the resistance elements that are
concentration factors that will modify the geometry
located in the central zone of the heavy shipbuildings.
and the stress concentration level [5].
The chemical and mechanical properties of this
These pits are characterized by their volumes,
material are presented in Tables 1 and 2.
and, as a consequence, it leads to a surface where
electrochemical phenomena occur [6].
Table 1. Chemical composition of the E36 naval steel
In the present paper are presented two features of
Steel Chemical composition, [%]
the degradation process by fatigue corrosion, which
grade
are interconnected: voids volume (occurred to the C Si Mn P S
fatigue corrosion) and the localized electrochemical 0.18 0.28 1.5 0.018 0.008
parameter (determined by electrode potential). As a E36 Al As Ti V Cu
common feature for both models, the ratio between 0.03 0.005 0.004 0.06 0.01
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THE ANNALS OF “DUNĂREA DE JOS“ UNIVERSITY OF GALAŢI
FASCICLE VIII, TRIBOLOGY, 2011 (XVII), Issue 1
ISSN 1221-4590
Table 2. Mechanical properties of the E36 naval steel
Material Mechanical properties
u [N/mm2] y [N/mm2]
E36 steel 559 460
2.2. Experimental Setup
The schematic test configuration is presented
in Figure 1. Tests were performed in a cycle of
alternate plane symmetric bending (R=-1) with
cantilever specimen. In order to carry out
electrochemical studies, a potentiostatic assembly was
employed consisting of a potentiostat type VoltaLab
PGZ 100 ALL-IN-ONE. The potentiostatic assembly
is presented in Figure 2.
Fig. 1. Plate specimens testing rig for fatigue in a
corrosive environment: 1. PGZ100 All-in-one
Potentiostat; 2. work electrode (WE); 3. container;
4. solution 3.5%NaCl; 5. auxiliary electrode (CE);
6. reference electrode (RE); 7. electrochemical cell;
8. salt bridge
Fig. 2. The potentiostatic assembly: 1. PGZ100 All-
in-one Potentiostat; 2. specimen; 3. container; 4.
solution 3.5%NaCl; 5. auxiliary electrode (CE); 6.
reference electrode (RE); 7. electrochemical cell; 8.
salt bridge
The potentiostatic assembly uses a dedicated
software (VoltaMaster 4), which allows recording in
situ the evolution of the electrode potential.
The evolution of the surface layer degradation by
fatigue and pitting corrosion processes has been analysed
based on the evolutionary studies of the surface micro-
geometry by means of a 3D profilometer type CETR
PRO500. This profilometer allows (SPIP-Scanning
Probe Imagine Processor) assessing the size of the
corrosion pit and the corresponding state of the
degradation of the areas on the examined specimens [7].
3. RESULTS AND DISCUSSION
3.1. Modelling of the Pits Volume Evolution
The analysis of the surface layer degradation with
a 3D profilometer allows obtaining the evolution of
the pits volume that occurs on the specimen surface
(Figs. 1 and 2) [2, 8].
In order to obtain the evolution of the pits’ volume
during the fatigue corrosion process, the assessment of
the condition of degradation was achieved at three
increasing levels of variable tensions and at different
levels of time during the stress application.
The mass transfer by diffusion and ion migration
leads to an anodic dissolution of the alloyed substrate.
In this way, in the first degradation stages localized
corrosion processes (pitting) occur, which are
increased by the mechanical factor [9, 10].
The proposed model is based on the Harlow and
Wei’s model [1] (based on Faraday’s law). The
Harlow and Wei’s model allows to determine the
evolution in time of the mature pits under fatigue
corrosion (tension conditions). This model was
modified by factors that take into consideration the
influence of the variable loading and the mechanical
properties of the studied material. Up to now, to the
authors’ knowledge, these factors have not been taken
into account in the existing models.
Therefore, the relationship combines the
influence of the mass loss described by the
electrochemical factors with the mechanical factor
characterized by the tensile strength of the material,
 r and the variable stress amplitude  a :
At  I   
Vgol  V0   k   1  a
 (1)
nF   r 
where: Vgol – the void volume; V0 - the void volume
at baseline; A - the molecular weight; t – time; I -
the corrosion current intensity ; n - the material
valence; F - Faraday constant;  - the material
density; k - the material factor;  a - the variable
stress amplitude;  r - the rupture strength.
Corrosion current intensity can be determined
as follows:
I  icorr  a (2)
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THE ANNALS OF “DUNĂREA DE JOS“ UNIVERSITY OF GALAŢI
FASCICLE VIII, TRIBOLOGY, 2011 (XVII), Issue 1
ISSN 1221-4590

where: icorr - corrosion current density; a – the area The comparative analyses of predictions based
of the measured zone. on the proposed equation and on the experimental
Table 3 presents the parameters proposed to be data are presented in Tables 7-9 and Figures 3-5.
used in the model and Tables 4-6 present the variable
parameters at three increasing levels of variable Table 7. The results obtained by modelling the pits
loadings. volume evolution,   236 .25 MPa
Time, tmin Void volume, [μm3]
Table 3. Fix parameters of the analysed model 0 146
Parameters Value 60 177.565
Void volume at baseline, V m 3
0   146 120 215.14
180 249.779
Material factor, k 0.3
 
300 327.268
Area of the measured zone, a m 2 .5  10 5
2
420 390.242
540 460.698
Table 4. Variable parameters of the analysed model 670 535.432
Flat specimens from naval steel grade E36,
 a  236.25MPa Table 8. The results obtained by modelling the pits
volume evolution,   267 .76 MPa
Time, tmin
Time, Density of Corrosion current
tmin corrosion current, intensity, Void volume, [μm3]
I  A  0 146
icorr  A / m 2  100 202.096
 
190 248.413
0 0.5856 0.00146400
310 323.275
60 0.5493 0.00137325.
360 348.694
120 0.6016 0.00150400
180 0.6020 0.00150500 Table 9. The results obtained by modelling the pits
300 0.6309 0.00157725 volume evolution,   325 .5 MPa
420 0.6072 0.00151800 Time, tmin Void volume, [μm3]
540 0.6085 0.00152125
0 146
670 0.6069 0.00151725
90 182.48
Table 5. Variable parameters of the analysed model 120 198.224
Flat specimens from naval steel grade E36, 150 206.364
 a  267.76 MPa 200 233.65
250 253.813
Time, Density of Corrosion current
tmin corrosion intensity,
current, I  A 

icorr A / m2 
0 0.6588 0.00164700
100 0.6491 0.00162275
190 0.6237 0.00155925
310 0.6617 0.00165425
360 0.6515 0.00162875

Table 6. Variable parameters of the analysed model

Fig. 3 The void volume evolution with time,
Flat specimens from naval steel grade E36,   236 .25 MPa
 a  325.5 MPa
Time, Density of Corrosion
tmin corrosion current, current,

i A / m
corr
2
 I  A 
0 0.5538 0.00138450
90 0.5850 0.00146250
120 0.6281 0.00157025
150 0.5808 0.00145200
200 0.6325 0.00158125 Fig. 4. The void volume evolution with time,
250 0.6224 0.00155600   267 .76 MPa
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ISSN 1221-4590

m  0.03...0.5 ;  a - the variable stress amplitude,

MPa;  r - the rupture strength, MPa, t - time.
The comparative analysis of the prediction
based on the proposed model and the experimental
results is within a relative mean error of 0.7…1%
(Figures 6 – 8).

Fig. 5. The void volume evolution with time,

  325 .5 MPa

It can be observed a good correlation between

the experimental and predicted results. The relative
mean error is between 3…10%. It was observed a
decrease of the relative error with the increase of the
mechanical loading. Fig. 6. The electrode potential evolution vs. the
potential of the work electrode with time
3.2. Modelling of the Electrode Potential  a  236.25 MPa
Evolution
The electrode potential evolution of the material
versus the potential of the work electrode with time
can give information over the degradation level under
the variable loading in a corrosive environment. The
research regarding the electrochemical characteristics
of the system metal – corrosive environment showed
that these modify during the cyclic loading of the
specimen [7, 11, 12]. There is a significant
dependence between the electrochemical factors
evolution and the accumulation of the degradation by Fig. 7. The electrode potential evolution vs. the
fatigue corrosive processes [9, 13]. During the cyclic potential of the work electrode with time
loading processes of the steel in a corrosive  a  267.76 MPa
environment, as a function of the applied stress, it was
observed a movement towards more negative values
of the electrode potential. It was demonstrated that the
size and the rate of the electrode potential are
dependent on the mechanical applied stress. Thus, in
this paper it is proposed a model to predict the
evolution of the electrode potential with time for
specimens manufactured from E36 steel as a function
of the level of the variable applied stress [14, 15].
The presented model includes, besides the time
Fig. 8. The electrode potential evolution vs. the
evolution of electrode potential, the mechanical
potential of the work electrode with time,
characteristic of the tested material (  r ) and the  a  325.5 MPa
characteristic of the external load (  a ).
The proposed model is summarized by the 4. CONCLUSIONS
following relation:
   The conclusions drawn from this work are as
E  E0  1  m  a  lnt  (2) follows:
 r  - the evolutionary degradation process of the
where: E – the potential of the work electrode superficial layer under the variable stresses and a
(specimen) versus the potential of the reference corrosive environment can be physically modelled;
electrode, mV; E0 - the initial potential of the the model is based on the applied stress and on the
specimen, E0  610 mV ; m – a material constant, physico-chemical and mechanical parameters of the
material;
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THE ANNALS OF “DUNĂREA DE JOS“ UNIVERSITY OF GALAŢI
FASCICLE VIII, TRIBOLOGY, 2011 (XVII), Issue 1
ISSN 1221-4590

- the proposed model to predict the volume pits
evolution achieves the synergy between the
electrochemical processes (that lead to the mass loss),
mechanical processes (determined by the mechanical
properties of the material) and the characteristics of
the cyclic stress;
- the electrochemical parameters are connected to
the local topography of the surface that can give
information about the degradation level of the
superficial layers;
- the modelling of these parameters under the
influence of the mechanical and chemical properties
of the material and the parameters of the cyclic stress
can be a step in assessing interventions on product
maintenance and appreciation of its reliability.
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