Electrochemical and DFT Study of NaNO2/NaNO3 Corrosion Inhibitor Blends for Rebar in Simulated Concrete Pore Solution
Abstract
:1. Introduction
2. Materials and Methods
3. Results
4. Conclusions
- A mixture of NaNO2 and NaNO3 corrosion inhibitors can successfully protect carbon steel rebar in simulated concrete pore solution with 0.6 M NaCl. All mixtures tested, including 1:0.5, 1:1, and 0.5:1 NO2–:NO3– ratios, showed improvement in the corrosion properties compared to the control test with no inhibitors. The best performing inhibitor mixture was the 1:0.5 ratio, showing an icorr of 1.16 × 10−7 A/cm2 at 25 °C.
- Greater concentrations of NO2– were associated with higher corrosion inhibition; specifically, the 1:0.5 and 1:1 NO2–:NO3– solutions showed the lowest icorr and highest resistance values associated with passive film (Rf) values of 1.67 × 103 and 1.60 × 103 Ω cm2, respectively, and corrosion process (Rct) values of 1.31 × 105 and 2.39 × 105 Ω cm2, respectively. The activation energy (Ea) also followed this trend, the 1:0.5 inhibitor mixture showing the highest activation energy of 12.1 kJ/mol, indicating that a greater energy barrier needed to be overcome for the corrosion process to be initiated with higher amounts of nitrite compared to nitrate inhibitors. Therefore, the dominating inhibitor in the mixture was found to be NO2−. The inhibitor blends of 1:0.5 and 1:1 NaNO2:NaNO3 showed the best corrosion inhibition; thus, the optimal ratio is 1:1 to maximize inhibition efficiency while minimizing NO2−, as it is toxic and can be harmful to the environment.
- Finally, by comparison of two commercially available mixtures, the inhibitor mixture with the higher nitrite concentration (Sika) showed the most passive Ecorr of −292 mVSCE and a lower icorr of 4.27 × 10−7 A/cm2, corroborating the hypothesis that nitrite dominated the inhibition process of the NO2–:NO3– mixture.
- By DFT analysis of the inhibitors, the EHOMO, ELUMO, ΔE, and dipole moment values obtained were found to be consistent with the experimental results. The EHOMO values indicated that nitrite more readily donated its electrons to the metal atoms and that the ΔE was lower, −5.74 eV, for the higher nitrite mixture (1:0.5), which has been correlated with better corrosion inhibition in the literature.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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C | Mn | P | S | Si | Cu | Ni | Cr | Mo | V | Fe |
---|---|---|---|---|---|---|---|---|---|---|
0.28 | 1.08 | 0.019 | 0.043 | 0.20 | 0.37 | 0.16 | 0.16 | 0.050 | 0.0379 | Bal. |
Temp. °C | Molar Ratio NO2−:NO3− | Rs Ω cm2 | Rf Ω cm2 | Rct Ω cm2 | Yf S cm−2 snf | nf | Ydl S cm−2 sndl | ndl | χ2 | Ceff,f F cm−2 | Ceff,dl F cm−2 | deff nm |
---|---|---|---|---|---|---|---|---|---|---|---|---|
25 | 1:0.5 | 19 | 1.67 × 103 | 1.31 × 105 | 7.50 × 10−5 | 0.75 | 1.66 × 10−6 | 0.77 | 9.18 × 10−4 | 3.03 × 10−4 | 9.40 × 10−8 | 9 |
0.5:1 | 18 | 1.31 × 103 | 1.09 × 105 | 6.07 × 10−5 | 0.75 | 9.61 × 10−6 | 0.79 | 2.26 × 10−3 | 4.29 × 10−4 | 4.18 × 10−7 | 6 | |
1:1 | 18 | 1.60 × 103 | 2.39 × 105 | 7.69 × 10−5 | 0.72 | 8.87 × 10−6 | 0.72 | 9.40 × 10−4 | 3.74 × 10−4 | 1.40 × 10−7 | 7 | |
35 | 1:0.5 | 21 | 1.92 × 103 | 1.76 × 105 | 5.54 × 10−5 | 0.76 | 3.76 × 10−6 | 0.80 | 3.90 × 10−4 | 3.78 × 10−4 | 3.54 × 10−7 | 7 |
0.5:1 | 22 | 1.61 × 103 | 1.66 × 104 | 8.35 × 10−6 | 0.76 | 4.01 × 10−5 | 0.78 | 9.61 × 10−4 | 4.98 × 10−4 | 3.95 × 10−5 | 5 | |
1:1 | 21 | 1.80 × 103 | 1.04 × 105 | 2.28 × 10−5 | 0.71 | 4.44 × 10−6 | 0.70 | 1.70 × 10−3 | 4.60 × 10−4 | 4.58 × 10−7 | 6 | |
45 | 1:0.5 | 23 | 5.15 × 103 | 1.98 × 104 | 2.44 × 10−4 | 0.81 | 1.40 × 10−4 | 0.72 | 2.04 × 10−3 | 4.47 × 10−4 | 7.90 × 10−6 | 6 |
0.5:1 | 22 | 2.27 × 103 | 9.28 × 103 | 1.89 × 10−4 | 0.75 | 5.83 × 10−4 | 0.71 | 4.69 × 10−4 | 6.05 × 10−4 | 1.81 × 10−5 | 4 | |
1:1 | 24 | 3.59 × 103 | 1.34 × 104 | 2.08 × 10−4 | 0.75 | 1.44 × 10−4 | 0.88 | 6.94 × 10−4 | 5.07 × 10−4 | 6.16 × 10−5 | 5 |
Temperature °C | Molar Ratio NO2–:NO3– | Ecorr mVSCE | icorr A/cm2 | βa V/dec | –βc V/dec | IE % | Rp Ω cm2 |
---|---|---|---|---|---|---|---|
25 | Control | −487 | 1.49 × 10−6 | 0.082 | 0.126 | - | - |
0.5:1 | −345 | 4.32 × 10−7 | 0.229 | 0.185 | 71 | 1.33 × 105 | |
1:1 | −341 | 1.51 × 10−7 | 0.257 | 0.159 | 90 | 1.11 × 105 | |
1:0.5 | −303 | 1.16 × 10−7 | 0.503 | 0.187 | 93 | 2.41 × 105 | |
35 | Control | −440 | 2.01 × 10−6 | 0.110 | 0.191 | - | - |
0.5:1 | −325 | 6.38 × 10−7 | 0.115 | 0.096 | 68 | 1.78 × 105 | |
1:1 | −326 | 4.34 × 10−7 | 0.211 | 0.142 | 78 | 1.82 × 104 | |
1:0.5 | −299 | 2.07 × 10−7 | 0.412 | 0.354 | 90 | 1.05 × 105 | |
45 | Control | −449 | 3.81 × 10−6 | 0.098 | 0.208 | - | - |
0.5:1 | −343 | 1.27 × 10−6 | 0.183 | 0.229 | 67 | 2.50 × 104 | |
1:1 | −305 | 9.07 × 10−7 | 0.191 | 0.191 | 76 | 1.16 × 104 | |
1:0.5 | −257 | 7.75 × 10−7 | 0.204 | 0.201 | 80 | 1.72 × 104 |
Corrosion Inhibitor Blend | Rs Ω cm2 | Rf Ω cm2 | Rct Ω cm2 | Yf S cm–2 snf | nf | Ydl S cm–2 sndl | ndl | χ2 |
---|---|---|---|---|---|---|---|---|
Yara | 16 | 969 | 2.44 × 105 | 3.02 × 10−5 | 0.71 | 6.12 × 10−6 | 0.75 | 2.99 × 10−3 |
Sika | 16 | 1230 | 1.25 × 107 | 2.82 × 10−5 | 0.70 | 2.14 × 10−6 | 0.78 | 4.68 × 10−3 |
Control | 21 | 20 | 4.72 × 103 | 5.46 × 10−4 | 0.84 | 9.15 × 10−6 | 0.71 | 2.74 × 10−3 |
Corrosion Inhibitor Blend | Ecorr mVSCE | icorr A/cm2 | IE % |
---|---|---|---|
Sika | −292 | 4.27 × 10−7 | 71 |
Yara | −336 | 5.62 × 10−7 | 62 |
Control | −487 | 1.49 × 10−6 | - |
Inhibitor | EHOMO eV | ELUMO eV | ΔE eV | µD eV |
---|---|---|---|---|
NO2− | −5.55 | −0.55 | −5.74 | 121.91 |
NO3− | −6.49 | −0.78 | −5.45 | 199.55 |
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Ress, J.; Martin, U.; Breimaier, K.; Bastidas, D.M. Electrochemical and DFT Study of NaNO2/NaNO3 Corrosion Inhibitor Blends for Rebar in Simulated Concrete Pore Solution. Coatings 2022, 12, 861. https://doi.org/10.3390/coatings12060861
Ress J, Martin U, Breimaier K, Bastidas DM. Electrochemical and DFT Study of NaNO2/NaNO3 Corrosion Inhibitor Blends for Rebar in Simulated Concrete Pore Solution. Coatings. 2022; 12(6):861. https://doi.org/10.3390/coatings12060861
Chicago/Turabian StyleRess, Jacob, Ulises Martin, Karl Breimaier, and David M. Bastidas. 2022. "Electrochemical and DFT Study of NaNO2/NaNO3 Corrosion Inhibitor Blends for Rebar in Simulated Concrete Pore Solution" Coatings 12, no. 6: 861. https://doi.org/10.3390/coatings12060861