3.1. Electrochemical Research on Steel Rebar Corrosion
The OCP is a type of mixed potential at which the anodic reaction rate equals the cathodic reaction rate, and the total net current is zero [
55]. For the anodic reaction, iron is oxidized to iron ions; for the cathodic reaction, oxygen is reduced to generate hydroxide ions [
56]. The OCP generally determined the corrosion state of the tested steel rebar. According to the test results, all samples had OCP values between −0.4 V and −0.7 V.
Figure 5 shows the tracking results of the open-circuit potentials of ordinary steel bar HRB400 and duplex stainless steel S2205 with 5% Cl
− concentration in the simulated seawater environment. The same concentration had a noticeable influence on the open-circuit potentials of two different steel bars, and the open-circuit potentials of both steel bars shifted negatively.
Figure 6 and
Figure 7 show the polarization curves of the HRB400 ordinary steel rebar and S32205 duplex stainless steel rebar in simulated seawater solutions, respectively. The polarization curves are based on the current density as the horizontal coordinate and the electrode potential as the vertical coordinate. The experimental method was designed to gradually increase the polarization of the working electrode from the self-corrosion potential at a certain potential scanning rate to a specific anodic current density value. Afterward, the working electrode is reverse-polarized at a certain scanning rate, continuously lowering its potential until reaching a self-corrosion potential, thus obtaining a curve describing the potential–current density relationship. The polarization curve can be measured by experimental methods. The analytical study of polarization curves is a basic method for explaining metal corrosion, revealing mechanisms, and exploring control pathways.
It can be seen from
Figure 7a,b that the anodic curves at different chloride ions were passivated when the potential was between −0.35 V and −0.7 V and between −0.45 V and 0.9 V, respectively. These results indicate that as the concentration of chloride ions increased, the self-corrosion potential of S32205 duplex stainless steel decreased. The density of the corrosion current increased slowly, and the polarization curve tended to move to the lower right corner. This process was accompanied by a decrease in the slope of the anodic polarization curve, indicating the generation of passivation films in simulated seawater for HRB400 ordinary steel rebars and S32205 duplex stainless steel. As the activity increased, corrosive pitting increased with chloride ion concentration, and the formed passivation film was susceptible to damage by chloride ions. As a result, the corrosion rate of the steel rebar increased, and the corrosion resistance decreased. The decrease in the slope of the anodic polarization curve was gradual, indicating that the damage by chloride ions to the passivation film of the steel rebar was corrosion damage accumulation instead of instantaneous breakdown. The passivation film was punctured when the corrosion damage accumulated to a certain level.
Based on the test results of day 7 and day 14 in
Figure 6 and
Figure 7, the variation of the polarization curve of the S32205 duplex stainless steel rebar differed from that of the HRB400 ordinary steel rebar. At the beginning of the test, the corrosion potential slightly increased, indicating that the ability of duplex stainless steel rebar to maintain the passivation state was significantly stronger than that of ordinary steel rebar. With the erosion of chloride ions, the polarization curve of the duplex stainless steel rebar gradually shifted to the right, and the corrosion level slightly increased. Furthermore, the slope of the anodic polarization curve gradually decreased, and the reaction resistance decreased, with higher corrosion rates indicating weaker corrosion resistance. Compared to the anodic polarization curve of ordinary steel rebar, that of duplex stainless steel rebar was steeper, indicating that even if the duplex stainless steel specimens were in a more severe corrosion environment, the stability of their passivation film was better than that of carbon steel passivation film. Based on these analyses, the chloride corrosion resistance of the S32205 duplex stainless steel rebar is significantly higher than that of the HRB400 ordinary steel rebar.
Table 2 presents the fitting data of the polarization curve for the test steel rebar in simulated seawater. The corrosion current can be obtained by fitting the polarization curve. The data from simulated seawater solutions showed that the self-corrosion current increased with extended corrosion time, and the increasing trend of self-corrosion current gradually accelerated. Changes in the self-corrosion current indicated that the formed corrosion products prevented corrosion and then slowly intensified it. At the beginning of the process, the anodic slope (βa) of HRB400 ordinary steel rebar and S32205 duplex stainless steel decreased and then increased, indicating a high resistance of the anodic dissolution process. The seawater environment in concrete formed a dense passivation film on the surface of the steel rebar, hindering the occurrence of anodic reactions.
According to the S32205 duplex stainless steel data, the self-corrosion current gradually increased with the extension of corrosion time, indicating that the corrosion of the steel rebar intensified with the extension of immersion time. Compared to HRB400 ordinary steel rebar, the self-corrosion current of S32205 was very small, indicating that S32205 duplex stainless steel had good corrosion resistance in a simulated seawater environment. Due to the short reaction time, a small amount of corrosion product film formed on the surface of the sample, resulting in a small corrosion current density during the corrosion process. The corrosion product film formed in a short period was relatively loose, increasing the contact area between the medium and the substrate, thus accelerating the corrosion of the steel rebar to a certain extent. In addition, the test data showed that with the extension of corrosion time, the self-corrosion current gradually increased. The generated corrosion product film was loose and unprotective, further exacerbating corrosion, with self-corrosion currents increasing faster.
The changes in corrosion current density (J0) and corrosion potential (E0) of HRB400 and S32205 are summarized based on
Table 2 and presented in
Figure 8 and
Figure 9. The corrosion potential of the S32205 duplex stainless steel showed an inflection point on day 14 and began to decrease, indicating signs of corrosion. In contrast, corrosion was observed on the HRB400 steel when transferred from the water bath on day 7. As shown in
Figure 8a, the self-corrosion current density of S32205 increased from 0.0000011 μA/cm
2 to 0.0000030 μA/cm
2 with increased corrosion time, indicating that the passivation film on the surface of the duplex stainless steel could effectively block the migration of Cl
− to the surface of the reinforcing steel at the initial stage of corrosion. (The corrosion current in
Figure 7a ranges from 0 to 0.00001 and measures as 0.0000011).
In addition to polarization curves, EIS has also been applied to reinforced concrete to simultaneously assess the protective effect of concrete on reinforcing steel and the corrosion resistance of reinforcing steel [
57,
58]. The basic idea for studying electrochemical systems via EIS is as follows. An electrochemical system can be viewed as an equivalent circuit with basic components, such as resistors, capacitors, and inductors, connected in series or in parallel. The process of the equivalent circuit and the values of each component can be determined through EIS, and the electrochemical meanings of these components can be used to analyze the electrochemical system and its properties.
Figure 10 and
Figure 11 show the AC impedance spectra of HRB400 ordinary steel rebar and S32205 duplex stainless steel rebar in simulated seawater solution, where the horizontal axis is the real part Z′ of the impedance, indicating the resistance value, while the longitudinal axis is the imaginary part Z″ of the impedance, indicating the capacitance or diffusion value.
Each point in the AC impedance spectra represents a frequency. The dense points on the left have high frequencies (hence the high-frequency region), and the dispersed points on the right have low frequencies (hence the low-frequency region).
Figure 10 and
Figure 11 show that the AC impedance spectra in different chloride ion solutions are composed of high and low-frequency capacitive reactance arcs, which are not semicircular. The radius of the capacitive reactance arc reflects the resistance of the passivation film and the charge transfer resistance during the electrode reaction. Generally, a greater radius of the capacitive reactance arc indicates better corrosion resistance of the metal matrix in the solution [
11].
The effect of Cl
− on the passivation film can also be observed from the EIS of OCP. Taking the EIS of the duplex stainless steel in
Figure 10 as an example, a linear curve obtained at high frequencies indicates capacitive resistance. The diameter of the capacitive reactance arc in the figure gradually decreases, indicating the formation of a passivation film on the surface of the specimen. Meanwhile, the corrosion of duplex stainless steel is aggravated, and the passivation film is damaged.
Figure 11a is an equivalent circuit diagram, where the line takes a semicircular shape, indicating that the battery is a simple equivalent circuit model comprising a resistor and capacitor in parallel. In the equivalent circuit, R1 is the solution resistance, R2 represents the charge transfer resistance, and CPE is the capacitance of the double electric layer. As the Cl
− concentration increases, the total impedance decreases, indicating an increasing corrosion rate.
As the temperature increased, R1 decreased while CPE increased. The decrease in R2 may be attributed to the activation of the double helix surface, indicating reduced corrosion resistance of the passivation film. Meanwhile, the continuously increasing CPE indicates that the steel–concrete interface increased due to pore exposure. The prolonged immersion promotes mass transfer, which increases the concrete porosity and rebar capacitance.
As the emersion time in the simulated seawater increased, the impedance arc radius gradually decreased, indicating a decreasing polarization resistance and increasing corrosion current. As shown in
Figure 10 and
Figure 11, a greater numerical value of the real part of the impedance indicated a lower electrochemical reaction rate and a lower charge transfer efficiency, meaning that the corrosion resistance of S32205 duplex stainless steel was gradually enhanced. Therefore, although the corrosion resistance of S32205 duplex stainless steel was good in the early stage of corrosion, its passivation film on the surface became damaged with prolonged reaction time, decreasing its corrosion resistance. The two different reinforcing bars exhibited poor corrosion resistance in the simulated seawater solution with 5% Cl
−. In practical applications, the corrosion resistance of S32205 duplex stainless steel in seawater is superior to that of ordinary HRB400 steel.