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Corrosion of Carbon Steel in IL
Abstract:
The corrosion of carbon steel in the ionic liquid (IL)[P 14666][Br] was studied with
the IL in contact with an inert (Ar) or oxidizing (air) cover gas in the presence and absence of
γ-radiation. Significant corrosion was observed for the tests performed in the absence of γ-
radiation while a protective oxide layer is formed in the presence of γ-radiation. The
corrosion is attributed to the presence of impurity H 2 O and O 2 dissolved in the IL, and a
corrosion mechanism is proposed.
MCB Model Simulation of Stellite-6 Corrosion
Abstract
A mass and charge balance (MCB) model that can simulate oxide growth and dissolution kinetics simultaneously during corrosion of an alloy has been recently developed. In this study, the MCB model was applied to the corrosion of the Co-Cr alloy Stellite-6. The construction of the model and the assignment of values to the rate parameters for the model are presented. The model simulation results are then compared with experimental corrosion data collected as a function of pH, temperature and polarization potential. The data include the current during potentiostatic polarization, the corrosion potential under open-circuit conditions, and post-test analyses of the oxide formed and the amount of metal dissolved. Excellent agreement between the model results and experimental data are found. This is evidence that the MCB model is a useful tool for predicting time-dependent corrosion while an oxide film is evolving.
Chemical Stability of IL under Gamma Radiation
Abstract
The effects of γ-radiation on the physicochemical and ion transport properties of phosphonium-based ionic liquids (ILs) were investigated. Five ILs that have different physical properties of hydrophobicity, viscosity and conductivity were studied. Gaseous radiolysis products were analyzed using GC-MS, and the IL phase was analyzed using UV-vis, NMR, FTIR and Raman spectroscopy, and conductivity measurement. The results show that the ILs are relatively resistant to radiolytic degradation, but measurable quantities of small organic species are formed. These arise from the radiolytic dissociation of the P–C bond in the cation moiety. These small organic molecules induce agglomeration within the IL and this results in substantial changes to some of the IL properties.

The formation of Cr2O3 nanoparticles by γ-irradiation of dichromate solutions was investigated in the presence of radical scavengers, tert-butyl alcohol, nitrous oxide, and dissolved oxygen. The concentrations of CrVI and CrIII species and the chemical composition and sizes of particles that were formed were measured as a function of irradiation time. A mechanism is proposed that is consistent with the observed effects of scavengers on the kinetics of reduction of CrVI in solution to solid CrIII and the final size of Cr2O3 nanoparticles that are formed. The chromium reduction occurs in three stages: Stage I involves homogeneous aqueous reduction of CrVI(aq) to CrIII(aq) followed by spontaneous condensation of Cr(OH)3, providing nucleation sites onto which CrVI and CrIII coprecipitate and form mixed CrVI/CrIII oxide/hydroxide particles. In Stage II, the aqueous reduction of CrVI(aq) and CrIII(aq) reaches steady state but the adsorption of CrVI continues, growing the mixed CrVI/CrIII oxide/hydroxide particles. Stage 3 involves the solid-state conversion of CrVI and CrIII, and the particles slowly convert from a mixed CrVI/CrIII oxide/hydroxide to Cr(OH)3 and then to Cr2O3. Adding a radical scavenger in solution affects the kinetics of particle formation and growth at different stages differently. This information can be used to tailor the final sizes of particles.
Radiation-Induced Formation of Chromium Oxide Nanoparticles
Radiation-induced formation of Co3O4 nanoparticles
The effects of the Co2+ content and different radical scavengers on the kinetics of γ-radiation-induced Co3O4 nanoparticle formation and growth were investigated. There are four distinct stages of particle formation with different oxidation rates. Scavengers and [Co2+]0 affect the oxidation kinetics in the different stages and consequently the final size of the particles formed. Radiolysis model calculations were performed to obtain the time-evolution of the concentrations of key oxidants and reductants, and the effect of scavengers on those concentrations. Based on the model results and experimental data a reaction mechanism for Co3O4 particle formation by γ-irradiation of solutions containing Co2+(aq) is proposed. The main cobalt oxidation reaction changes with time. Oxidation of Co2+(aq) to Co3+(aq) by radiolytically produced ˙OH occurs first in the solution phase. This is followed by spontaneous co-precipitation of mixed CoII/CoIII hydroxide nucleate particles. Adsorption of CoII(ad) followed by surface oxidation of CoII(ad) to CoOOH(ad) by H2O2 grows particles with a solid CoOOH(s) phase. In parallel, the solid-state transformation of CoOOH(s) and CoII(ad) to form Co3O4(s) occurs.
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Recent Papers
2015
L.M. Alrehaily, J.M. Joseph, J.C. Wren, Radiation-Induced Formation of Co3O4 Nanoparticles from Co2+ (aq): probing the kinetics using radical scavengers, Phys. Chem. Chem. Phys. 17 (2015) 24138 - 24150.

L.M. Alrehaily, J.M. Joseph, J.C. Wren, Radiation-Induced Formation of Chromium Oxide Nanoparticles:  Role of  Radical Scavengers on the Redox Kinetics and Particle  Size, J. Phys. Chem. C, 119 (2015) 16321-16330.

M. Momeni and J.C. Wren. A Mechanistic Model for Oxide Growth and Dissolution during Corrosion of Cr-Containing Alloys. Faraday Discuss. 180 (2015) 113-135.

R.P. Morco, J.M. Joseph, and J.C. Wren. The Chemical Stability of Phosphonium-based Ionic Liquids under Gamma Irradiation. RSC Adv., 5 (2015) 28570-28581.

A.Y. Musa, M. Behazin, and J.C.Wren. Potentiostatic Oxide Growth Kinetics on Ni-Cr and Co-Cr Alloys: Potential and pH Dependences. Electrochim. Acta, 162 (2015) 185-197.

H. Subramanian, V. Subramanian, M. Momeni, J.J. Noël, J.M. Joseph, D.A. Guzonas, J.C. Wren, The Effect of Water Radiolysis on Corrosion in High-temperature Steam, 17th International Conference on Environmental Degradation of Materials in Nuclear Power Systems - Water Reactors, August 9-13, 2015, Ottawa, Ontario, Canada

B. Ibrahim, D. Zagidulin, J. M. Smith, S. Ramamurthy, J. C. Wren, and D. W. Shoesmith, Radiolytic Corrosion of Cu Nuclear Waste Containers, 17th International Conference on Environmental Degradation of Materials in Nuclear Power Systems - Water Reactors, August 9-13, 2015, Ottawa, Ontario, Canada.

L. Wu, D. Guo, A. Van Belois, J.J. Noël, P.G. Keech, J.C. Wren. Radiation-Assisted Corrosion of Carbon Steel Nuclear Waste Container. 17th International Conference on Environmental Degradation of Materials in Nuclear Power Systems - Water Reactors, August 9-13, 2015, Ottawa, Ontario, Canada.

V. Subramanian, J.M. Joseph, H. Subramanian, J.J. Noel, D.A. Guzonas, J.C. Wren*. Chemical Kinetic Model Calculations for Gamma-Radiolysis of Supercritical Water. Proc. The 7th International Symposium on Supercritical Water-Cooled Reactors ISSCWR-7, 15-18 March 2015, Helsinki, Finland, (2015).

J. Mauzeroll, G. Thornton, T. Rayment, V. Maurice, D. Williams, F. Heberling, P. Marcus, J.C. Wren, K. Yliniemi, R. Lindsay, S. Lyth, T. Majchrowski, H. Hussain, G. Hunt, F. Renner, G. Williams, R. Newman, G. Frankel, J. Lützenkirchen, H. Bluhm.  Solid/fluid interface: general discussion. Faraday Discuss. 180 (2015) 81-96.

A. Cook, G. Frankel, A. Davenport, T. Hughes, S. Gibbon, D. Williams, H. Bluhm, V. Maurice, S. Lyth, P. Marcus, D.W. Shoesmith, J.C. Wren, J. Wharton, G. Hunt, S. Lyon, T. Majchrowski, R. Lindsay, G. Williams, B.  Oller, Rico, M. Todorova, S. Nixon, S. Cheng, J. Scully, A. Wilson, F. Renner, Y.H. Chen, C. Taylor, H. Habazaki, A. Michaelides, S. Morsch, P. Visser, L. Kyhl, A. Kokalj.  Corrosion control: general discussion.  Faraday Discuss. 180 (2015) 543 – 576.

G. Frankel, J. Mauzeroll, G. Thornton, H. Bluhm, J. Morrison, V. Maurice, T. Rayment, D. Williams, A. Cook, G. Joshi, A. Davenport, S. Gibbon, D. Kramer, M. Acres, M. Tautschnig, H. Habazaki, P. Marcus, D.W. Shoesmith, J.C. Wren, T. Majchrowski, R. Lindsay, M. Wood, M. Todorova, J. Scully, F. Renner, A. Kokalj, C. Taylor, S. Virtanen, J. Wharton. Corrosion scales and passive films: general discussion. Faraday Discuss. 180 (2015) 205-232.

G. Frankel, G. Thornton, S, Street, T. Rayment, D. Williams, A. Cook, A. Davenport, S. Gibbon, D. Engelberg, C. Örnek, A. Mol, P. Marcus, D.W. Shoesmith, J.C. Wren, K. Yliniemi, G. Williams, S. Lyon, R. Lindsay, T. Hughes, J. Lützenkirchen. S.T. Cheng, J. Scully, S.F. Lee, R. Newman, C. Taylor, R. Springell, J. Mauzeroll, S. Virtanen, S. Heurtault, J. Sullivan. Localised corrosion: general discussion.  Faraday Discuss. 180 (2015) 381-414.
2014
Z. Qin, W.-J. Cheong, P.G. Keech, J.C. Wren, and D.W. Shoesmith. Modelling Development of Acidification within Corroding Sites on Spent Fuel Surfaces. Corros. Eng. Sci. Tech. 49 (2014) 583-587

M. Behazin, J.J. Noel, and J.C. Wren. Combined Effects of pH and γ-Irradiation on the Corrosion of Co-Cr Alloy Stellite-6, Electrochim. Acta, 134 (2014) 399-410.

R. P. Morco, A. Y. Musa and J. C. Wren, The molecular structures and the relationships between the calculated molecular and observed bulk phase properties of phosphonium-based ionic liquids, Solid State Ionics, 258 (2014) 74–81.

M. Behazin, J.J. Noel, J.C. Wren. Effect of Water Radiolysis on Corrosion of Co-Cr Alloy.  Proc. 19th Pacific Basin Nuclear Conference (PBNC 2014), Vancouver, Aug 24-27 (2014).

A.Y. Musa, J.C. Wren, Effect of Water Radiolysis on Corrosion of Alloy 600 at 150oC,  Proc. 19th Pacific Basin Nuclear Conference (PBNC 2014), Vancouver, Aug 24-27 (2014).


2013
S. D. Pretty, A. Y. Musa and J. C. Wren, Reactions of bromide and iodide ions with silver oxide films on Ag substrates, J. Electrochem. Soc., 160 (2013) H13–H21.

L. M Alrehaily ,  J. M Joseph,  M. C. Biesinger, D. Guzonas, J. C. Wren, Gamma-Radiolysis-Assisted Cobalt Oxide Nanoparticle Formation, Phys. Chem. Chem. Phys., 15 (2013) 1014-1024.

L. M. Alrehaily, J. M. Joseph, A. Y. Musa, D. A. Guzonas, J. C. Wren, Gamma-radiation induced formation of chromium oxide nanoparticles from dissolved dichromate, Phys. Chem. Chem. Phys. 15 (2013) 98-107.

2012
L. Wang, K. Daub, Q. Knapp, Z. Qin, J.J. Noel, J.C. Wren. Effect of Ferrous Ions on Oxide Film Formation and Conversion on Stainless Steel. J. Electrochem. Soc., 159 (2012) C503-C512.

Q.W. Knapp, and J.C. Wren, FilM formation on Type-316L stainless steel as a function of potential: Probing the role of gamma-radiation, Electrochim. Acta, 80 (2012) 90–99.

M. Behazin, M.C. Biesinger, J.J. Noël, J.C. Wren. Comparative study of film formation on high-purity Co and Stellite-6: Probing the roles of a chromium oxide layer and gamma-radiation, Corros. Sci., 63(2012) 40–50.

L. Wang, K. Daub, Z. Qin, J.C. Wren, Effect of dissolved ferrous iron on oxide film formation on carbon steel, Electrochim. Acta, 76 (2012) 208–217.

T.J. Stockmann, J. Zhang, and J.C. Wren, Z. Ding,Hydrophobic Alkylphosphonium Ionic Liquid for Electrochemistry at Ultramicroelectrodes and Micro Liquid|Liquid Interfaces, Electrochim. Acta, 62 (2012) 8–18.

Q.W. Knapp, K. Daub, A. Musa, J.C. Wren. Radiation-Induced Corrosion of 316L Stainless Steel and Carbon Steel. Proc. Nuclear Plant Chemistry Conference, Paris, Sept. 23-27, 2012.

L.M. Alrehaily, J.M. Joseph, D. Guzonas, J.C. Wren. Formation of Chromium Oxide Nano-particles by Gamma Irradiation of Chromate Solutions. Proc. Nuclear Plant Chemistry Conference, Paris, Sept. 23-27, 2012.

M. Behazin, J.C. Wren. Radiation-Induced Corrosion on Stellite-6. Proc. Nuclear Plant Chemistry Conference, Paris, Sept. 23-27, 2012.

K. Daub, J.J. Noël, J-W. Yeon, J.C. Wren, Gamma Radiation-Induced Carbon Steel Corrosion, Transactions of the Korean Nuclear Society Conference, May 16-18 2012, Jeju, Korea.
2011
D. Fu, P.G. Keech, X.A. Sun, and J.C. Wren. Iron Oxyhydroxide Nanoparticles by Forced Hydrolysis: Dependence of Phase Composition on Solution Concentration. Phys. Chem. Chem. Phys., 13 (2011) 18523-18529.

S. Howett, J.M. Joseph, J.J. Noel, and J.C. Wren. Effect of Gamma Irradiation on Gas-Ionic Liquid and Water-Ionic Liquid Interfacial Stability. J. Col. Inter. Sci., 361 (2011) 338-350.

K. Daub, X. Zhang, L. Wang, J.J. Noel, and J.C. Wren. Oxide Growth and Conversion on Carbon Steel as a Function of Temperature over 25 and 80°C. Electrochim. Acta, 56 (2011) 6661-6672.

X. Zhang, J.C. Wren, I. Betova, and M. Bojinov. Estimation of Kinetic Parameters of the Passive State of Carbon Steel in Mildly Alkaline Solutions from EIS and XPS Data. Electrochim. Acta, 56 (2011) 5910-5918.
P.A. Yakabuskie, J.M. Joseph, C. Stuart, and J.C. Wren. Long-Term Gamma-Radiolysis Kinetics of NO3- and NO2- Solutions, J. Phys. Chem. A, 115 (2011) 4270-4278.

P.A. Yakabuskie, J.M. Joseph, P.Keech, G. Botton, D. Guzonas, and J.C. Wren. Iron Oxyhydroxide Colloid Formation by Gamma-Radiolysis. Phys. Chem. Chem. Phys., 13 (2011) 7167-7175.
S.D. Pretty, P.G. Keech, X. Zhang, J.J. Noel, and J.C. Wren. Investigation of Interfacial Reaction Kinetics of I(aq) with Ag2O(s) on Ag Substrate: Determining Mass Transport and Surface Reaction Rates. Electrochim. Acta, 56 (2011) 2754-2761.
K. Daub, X. Zhang, J.J. Noël, and J.C. Wren. Gamma-Radiation-Induced Corrosion of Carbon Steel in Neutral and Mildly Basic Water at 150 C. Corros. Sci., 53 (2011) 11-16.

K. Daub, X. Zhang, J.J. Noël, J.C. Wren. Gamma-Radiation-Induced Carbon Steel Corrosion. Corrosion Issues in Nuclear Waste Storage: ECS transactions, 33 (2011) 15-24.

2016
M. Sterniczuk, P.A. Yakabuskie, J.C. Wren, J.A. Jacob, D.M. Bartels, Low LET radiolysis escape yields for reducing radicals and H2 in pressurized high temperature water, Rad. Phys. Chem. 121 (2016) 35-42

R.P. Morco, A.Y. Musa, M. Momeni, and J.C. Wren, Corrosion of Carbon Steel in the [P14666][Br] Ionic Liquid: The Effects of γ-Radiation and Cover Gas. Corros. Sci., 102 (2016) 1-15.

M. Momeni, M. Behazin, and J.C. Wren, Mass and Charge Balance (MCB) Model Simulations of Current, Oxide Growth and Dissolution during Corrosion of Co-Cr Alloy Stellite-6, J. Electrochem. Soc., 163 (2016) C64-C105.

A.Y. Musa and J.C. Wren, Combined effect of gamma-radiation and pH on corrosion of Ni–Cr–Fe alloy inconel 600Corros. Sci., in press.

V. Subramanian, J.M. Joseph, H. Subramanian, J.J. Noël, D.A. Guzonas, J.C. Wren, Steady-State Radiolysis of Supercritical Water: Model Predictions and Validation, J. Nuclear Eng. Rad. Sci., 2 (2016) 021021.