Asprec, Renz Marvin S.

2011-29274

Journal Reviewed:
Wei Liu, Songle Lu, Peng Zhang, Juanjuan Dou, Qinghe Zhao. Effect of silty sand with different
sizes on corrosion behavior of 3Crsteel in CO2aqueous environment. Applied Surface Science.
As stated in the introduction of the journal, CO 2 corrosion is of the most common and
import corrosion encountered in the production and transportation of oil and gas. Sand particles
entering the system in a CO 2 aqueous environment may lead to serious damage. The usual effect
of this is in terms of localized corrosion, specifically erosion corrosion. In erosion corrosion, the
corrosion is due to the mechanical effect of a moving liquid or solids suspended in a liquid
against a metal surface.
According to the journal, there were previous studies concerning sand damage with sand
size ranging from 100 to 500 m. However, silty sand, sand of size below 50 m, could still
enter the system. Presently, there were studies about silty sand showing that it could reduce the
corrosion rate of carbon steel in a CO2 aqueous environment.
The corrosion of behavior of 3Cr steel in CO 2 aqueous environment is to be studied. It is
highly researched because of its high corrosion resistance and low cost. Amorphous metals,
compared to their crystalline counterparts, such as 3Cr steel generally have reduced corrosion
rates. They exhibit anodic current density which is several orders of magnitude lower than
crystalline. They are more protective than crystalline because of the lack of grain boundaries and
defects with are possible sites for localized corrosion.
The dissolution of Cr3+ ions from the surface of the steel results to the rapid deposition of
Cr(OH)3 and eventually a Cr-rich layer with the corrosion product FeCO 3.This Cr-rich layer is
compact and increases the resistance to corrosion. 3Cr steel is widely employed in a silty sand-
containing environment, and this study aims to give an insight regarding this system.
The chemical composition of the 3Cr steel studied is shown in Table 1. The chemical
composition of the test solution is shown in Table 2. There are two sizes of silty sand that was
used for the corrosion test which are, 5000 mesh (2 m), and 1000 mesh (13 m).
The schematic diagram of the corrosion equipment is shown in Fig 1a. The solution in the
equipment was first deaerated with CO2 for 12h before the start of the test. The test solution is in
a temperature of 80C. The specimens were vertically placed in the test solution. Then, 1 wt% of
silty sand was put into the equipment and mixed with test solution using a magnetic stirrer
rotating at a speed of 600 rpm. CO2 was continuously introduced into the system at a pressure of
1 atm and flow rate of 100 mL/min during the corrosion tests. The corrosion test was run for 120
h. However, the authors did not show any reference as to why a basis of 120 h for the corrosion
time was used. The corrosion time used will have an effect to the measurements and data
obtained. The same test was done for a test solution without silty sand. There were, in total, 6
specimens used for different analyses including corrosion mass loss measurement, surface and
cross-sectional morphology observation, and composition of corrosion scale.
The morphology of the corrosion scale was observed using a scanning electron
microscopy (SEM, JSM-6510). Meanwhile, the element distributions and compositions of
corrosion scale were analyzed using energy dispersive X-ray spectrometry (EDS, JSM-6510) and
X-ray photoelectron spectroscopy (XPS, PHI5300X).
Shown in Fig 1b is the schematic diagram of the equipment for electrochemical
measurements. A three-electrode cell system was used for all the measurements. This is
composed of a working electrode, which was 3Cr steel with a tested surface area of 1 cm2, a
reference electrode, which was saturated calomel electrode, and the counter electrode, which was
a platinum plate. The measurements were made for the test solutions with and without silty sand
at the same rotating speed. The electrochemical measurements are potentiodynamic polarization
curves and electrochemical impedance spectroscopy (EIS). The range of the potential for the
potentiodynamic polarization curves is 250 mV vs OCP. Meanwhile, the frequency range for
the EIS measurement is from 100 kHz to 10 mHz with a 5 mV amplitude (peak to zero) at OCP.
Fig 2 shows the corrosion rates for the 3Cr steel samples in different conditions after a
corrosion time of 120 h. The results show that the corrosion rate for the 5000 mesh was lower
compared to the one without silty sand. This confirms that addition of silty sand of 5000 mesh
could reduce the corrosion rate. However, the corrosion rate for the 1000 mesh was higher
compared to the one without silty sand, meaning that it promotes the corrosion process.
Fig 3 shows the different macroscopic morphologies of 3Cr steel in different conditions
of silty sand. Fig 3a shows that the surface of 3Cr steel in the condition without silty sand was
covered with uniform black corrosion products. Fig 3b shows a rough matrix surface. Fig 3c
shows that the corrosion scale of 3Cr steel in 5000 mesh silty sand was covered with silty sand
particles. Fig 3d shows a smoother matrix surface compared to the one without silty sand. Fig 3e
shows that the corrosion scale of 3Cr steel in 1000 mesh silty sand was covered with silty sand
particles. Fig 3f shows a rough matrix surface with pits. The increased corrosion rate of the 1000
mesh silty condition is associated with the low protection effect of corrosion scale and the
formation of these pits.
Fig 4 shows the microscopic morphologies of 3Cr steel in different conditions of silty
sand. Fig 4a shows that the surface of the 3Cr steel without silty sand is covered with corrosion
product and little granular products. The EDS results in Table 3 show the main elements of the
corrosion scale. Based on the results there is Cr enrichment in the corrosion scale. Fig 4b shows
the corrosion scale on the surface of 3Cr steel in 5000 mesh silty sand condition. There were
irregular silty sand particles deposited on the corrosion scale. Table 3 shows that the corrosion
scale are Cr-containing products and silty sand (SiO2). Meanwhile, the irregular solid particles
are small sized silty sand. Fig 4c shows the corrosion scale on the surface of 3Cr steel in 1000
mesh silty sand condition. The corrosion scale was porous and, from the EDS results, it is a
mixture of corrosion products and silty sand. Fig 4d shows the corrosion product inside the
corrosion pit. There was a large number of cubic crystals was found inside the pit. There was no
Cr found inside the pit and it was inferred that the cubic crystals were FeCO3.
 Fig 5 shows the measured and fitted XPS spectra of the elements Fe, O, Cr, and Si in the
corrosion scale for both 5000 mesh and 1000 mesh of silty sand. Fig 5a and 5b show that in the
Fe fitted spectra, there are 2 pairs of fitted peaks which correspond to FeCO3. Fig 5c and 5d
show that in the O fitted spectra, there are four fitted peaks. These correspond to SiO 2, FeCO3,
Cr(OH)3, and Cr2O3. Fig 5e and 5f show that in the Cr fitted spectra, there are 2 pairs of fitted
peaks. These correspond to Cr(OH)3 and Cr2O3. Fig 5g and 5h show that the Si fitted spectra only
had one peak. This corresponds to SiO2. In general, the XPS results showed that the corrosion
scales of both 5000 mesh and 1000 mesh silty sand are composed of FeCO 3, Cr(OH)3, Cr2O3, and
silty sand (SiO2).
The cross section of corrosion scale of 3Cr steel in different silty sand conditions was
shown in Fig 6 and the EDS results are shown in Table 4. Fig 6a and b show that there is only
one layer of corrosion scale formed which was a Cr-rich layer. For 5000 mesh silty sand, Fig 6c
and d show that there is a duplex structure formed, an inner and an outer layer. The outer layer is
a Si/Cr-rich layer with high Si content while the inner layer is a Cr-rich layer with low Si
content. For the 1000 mesh silty sand, Fig 6e and f show that there is only one layer of corrosion
scale formed. This layer is a porous silty sand layer without Cr enrichment, consisting mainly of
silty sand and FeCO3.
The potentiodynamic polarization curves of 3Cr steel are shown in Fig 7 with the
corresponding electrochemical parameters shown in Table 5. The impingement of silty sand
could prohibit the diffusion of the corrosive anion and adsorption on the surface. This leads to
the low cathodic polarization current for both 5000 mesh and 1000 mesh silty sand. But for the
anodic current, the 5000 mesh becomes lower than that of the silty sand-free condition, while the
1000 mesh becomes higher than that of the silty sand-free condition. The corrosion potential,
Ecorr, and corrosion current density, icorr, for the different conditions are presented in Table 5.
For all the conditions, Ecorr is roughly the same ranging between -765 mV to -736 mV.
Meanwhile, the icorr for 5000 mesh is significantly lower than the silty sand-free condition. This
means that it corrodes at a much lower rate. On the other hand, the icorr for 1000 mesh is higher
than the silty sand-free condition.
The EIS electrochemical parameters are quantified using two circuits shown in Fig 9.
Table 6 gives the electrochemical impedance parameters fitted from EIS data.
There were differences in the corrosion behavior for the 5000 mesh and the 1000 mesh
silty sand conditions. The corrosion morphology for the for the 5000 mesh silty sand was
uniform corrosion whereas the corrosion morphology for the 1000 mesh silty sand was localized
corrosion involving corrosion pits.
The corrosion scale for the 5000 mesh silty sand was composed of two Cr-rich layers.
Silty sand mainly existed in the outer layer. Also, the Cr content was higher in the inner layer
than in the outer layer. For the 1000 mesh silty sand, the corrosion scale was composed of a
single porous layer without enrichment of Cr. This difference in corrosion behavior can be
attributed to the separation effect of the two sizes of silty sand on the corrosion products. The
5000 mesh silty sand could not separate the corrosion products due to its small size. This leads to
the formation of a Cr-rich corrosion scale. However, the 1000 mesh silty sand, because of its
large size, could separate the corrosion products. This leads to the formation of a porous scale.
The Cr compound dropped off resulting to a corrosion scale without Cr enrichment. Moreover,
pitting corrosion occurred at the surface, where corrosion products dropped off.
The formation of the compact Cr-rich corrosion scale of 3Cr steel inhibited the anodic
reaction due to the reduction of area of the active region of the electrode surface and the
improvement of CO2 corrosion resistance. The anodic current of 3Cr steel was increased for the
1000 mesh silty sand because the porous corrosion scale formed increased the area of active
region of electrode surface. This leads to the lowering of resistance to anodic reaction.
The solutions containing silty sand inhibited corrosion process by the prohibition of
anions from its barrier to anion transport and adsorption on the surface of the 3Cr steel electrode.
Cathodic current was reduced for both sizes of silty sand but the cathodic process was not
affected by the size. The result of the EIS showed that the charge transfer resistance was much
lower for the porous corrosion scale without Cr enrichment compared to the compact Cr-rich
scale. The inductance characteristic from the EIS results also showed that there is non-uniformity
of electrochemical activity for the surface of the porous corrosion scale.