Titre : Electrochemical formation and transformation of corrosion products on carbon steel under cathodic protection in seawater
Année : 2013
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Carbon steel coupons were permanently exposed to seawater in the low water zone of two French harbors
for 5 years before to be subjected to cathodic protection (potential about 0.95 V vs. Ag/AgCl/seawater)
for 1 year. The application of cathodic polarization to the previously unprotected coupons
induced the transformation of GR(SO2 4 ) into GR(CO2 3 ). Other coupons were permanently protected by
cathodic protection during the 6 years immersion. A thin film of green rust and mackinawite was
observed on the steel surface. This film was covered by a thicker layer of calcareous deposits.
2013 Elsevier Ltd. All rights reserved.
Elsevier - Corrosion Science 71 (2013) 32-36
Titre : Electrochemical formation and transformation of corrosion products on carbon steel under cathodic protection in seawater
Année : 2013
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Carbon steel coupons were permanently exposed to seawater in the low water zone of two French harbors
for 5 years before to be subjected to cathodic protection (potential about 0.95 V vs. Ag/AgCl/seawater)
for 1 year. The application of cathodic polarization to the previously unprotected coupons
induced the transformation of GR(SO2 4 ) into GR(CO2 3 ). Other coupons were permanently protected by
cathodic protection during the 6 years immersion. A thin film of green rust and mackinawite was
observed on the steel surface. This film was covered by a thicker layer of calcareous deposits.
2013 Elsevier Ltd. All rights reserved.
Elsevier - Corrosion Science 71 (2013) 32-36
Titre : Electrochemical formation and transformation of corrosion products on carbon steel under cathodic protection in seawater
Année : 2013
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Carbon steel coupons were permanently exposed to seawater in the low water zone of two French harbors
for 5 years before to be subjected to cathodic protection (potential about 0.95 V vs. Ag/AgCl/seawater)
for 1 year. The application of cathodic polarization to the previously unprotected coupons
induced the transformation of GR(SO2 4 ) into GR(CO2 3 ). Other coupons were permanently protected by
cathodic protection during the 6 years immersion. A thin film of green rust and mackinawite was
observed on the steel surface. This film was covered by a thicker layer of calcareous deposits.
2013 Elsevier Ltd. All rights reserved.
Elsevier - Corrosion Science 71 (2013) 32-36
Titre : Efficacy and environmental acceptability of two ballast water treatment chemicals and an alkylamine based-biocide
Année : 2010
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Ship's ballast waters transport large numbers of organisms which may become invasive in coastal regions.
One option to address this problem is the use of biocides as ballast water treatment (BWT). Ef?cacy and
environmental acceptability of three commercial active substances (the BWT biocides Peraclean® Ocean and
Seakleen®, and alkylamine-based biocide Mexel® 432/336) were tested against three bacteria species, two
vegetative microalgae and one zooplanktonic larva, in 10 and 30 Practical Salinity Unit (PSU) waters. In both
salinities, PeraClean® Ocean was the most effective biocide against bacteria causing N 90% mortality at 20 mg/l,
compared with 50 mg/l for Mexel® 432/336 and N 500 mg/l for Seakleen®. Regarding zooplankton, Seakleen®
was the most effective chemical causing 90% mortality in 24 h at concentrations b 6 mg/l (LC9024 h) in both
salinities, compared with 23 and 26 mg/l for Mexel® 432/336 and 370 and 480 mg/l for PeraClean® Ocean in
10 and 30 PSU, respectively. Similar pattern of ef?cacy was obtained for microalgae in 30 PSU: effective
concentrations inducing 50% growth inhibition in 4 days were ? 1.6 mg/l for Seakleen®, ? 10.1 mg/l for
Mexel® 432/336 and ?30.9 mg/l for PeraClean® Ocean. Our work highlighted that treated waters displayed
residual toxicity after 24 h still inducing mortality depending on the organism and biocide. However Mexel®
432/336 is the only biocide which had no impact on oyster larvae development at effective concentration.
Altogether our data showed that Mexel® 432/336 was the only biocide displaying a broad spectrum ef?cacy in
concentrations b 50 mg/l and not toxic for oyster larvae development at this concentration. However residual
toxicity of treated waters for any organism should be taken into account in BWT systems utilising biocides.
STOTEN-12286; No of Pages 9
Titre : Formation of the Fe(II-III) hydroxysulphate green rust during marine corrosion of steel associated to molecular detection of dissimilatory sulfite-reductase
Année : 2008
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Titre : Process and Efficiency of In Situ Experimentation for Accelerated Corrosion Studies, in French Marine Ports
Année : 2008
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Non disponible
Material Performance, October 2008, p. 2-6
Titre : Carbonate and sulphate green rusts – Mechanisms of oxidation and reduction
Année : 2008
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : The oxidation and reduction of carbonate, GR(CO3), and sulphate, GR(SO4), green rusts (GR) have been
studied through electrochemical techniques, electrochemical quartz crystal microbalance (EQCM), FTIR,
XRD and SEM. The used samples were made of thin films electrodeposited on gold substrate. The results
from the present work, from our previous studies and from literature were compiled in order to establish
a general scheme for the formation and transformation pathways involving carbonate or sulphate
green rusts. Depending on experimental conditions, two routes of redox transformations occur. The first
one corresponds to reaction via solution and leads to the formation of ferric products such as goethite
or lepidocrocite (oxidation) or to the release of FeII ions into the solution (reduction) with soluble
FeII–FeIII complexes acting as intermediate species. The second way is solid-state reaction that involve
conversion of lattice Fe2+ into Fe3+ and deprotonation of OH groups in octahedra sheets (solid-state oxidation)
or conversion of lattice Fe3+ into Fe2+ and protonation of OH groups (solid-state reduction). The
solid-state oxidation implies the complete transformation of GR(CO3) or GR(SO4) to ferric oxyhydroxycarbonate
exGRc-Fe(III) or ferric oxyhydroxysulphate exGRs-Fe(III), for which the following formulas
can be proposed, FeIII
6(OH)(12-2y)(O)(2+y)(H2O)(y)(CO3) or FeIII
6(OH)(12-2z)(O)(2+z)(H2O)(6+z)(SO4) with 0 <=y
or z<=2. The solid-state reduction gives ferrous hydroxycarbonate exGRc-Fe(II) or ferrous hydroxysulphate
exGRs-Fe(II), which may have the following chemical formulas, [FeII
6(OH)10(H2O)2]·[CO3, 2H2O] or
[FeII
6(OH)10(H2O)2]·[SO4, 8H2O].
Titre : Study of FeII/FeIII ratio in thin films of carbonate or sulphate green rusts obtained by potentiostatic electrosynthesis
Année : 2008
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Thin films of carbonate or sulphate green rusts were synthesised from potentiostatic oxidation of solutions
containing ferrous species and bicarbonate or sulphate ions at slightly alkaline pHs and ambient
temperature. The thin films were characterised by means of electrochemical quartz crystal microbalance,
scanning electron microscopy, X-ray diffraction and infrared reflection–absorption spectroscopy.
The composition of carbonate or sulphate green rusts was studied through chemical titration, inductively
coupled plasma-optical emission spectroscopy (ICP-OES) and gravimetry and is as follows:
[FeII
(2R)FeIII
2(OH)(4R'2R'+6)(H2O)(2R'-2)]2R'+·[R'CO3, (2R-{3 or 4}R' + 2)·H2O]2R'-
and [FeII
(2R)FeIII
2(OH)(4R?2R''+6)(H2O)(2R''-2)]2R''+·[R''SO4, (4R-4R' + 4)·H2O]2R''-
FeII/FeIII ratio R depends on the concentration of soluble ferrous species that are located at electrode
surface during the potentiostatic synthesis and increases as the potential is made more negative. R-values
are in the ?2–2.5 range for carbonate green rust, and in the ~2–2.2 range for sulphate green rust. The
obtained R'- and R''-values are 1–1.3 and 1.1–1.4 for carbonate and sulphate green rusts, respectively.
The present study excludes the existence of green rusts with FeII/FeIII ratio, R, lower than 2. The R-values
lower than 2 that are found in some studies might relate to mixtures of the green rust and its solid-state
oxidation product exGR-Fe(III) (ferric oxyhydroxycarbonate or ferric oxyhydroxysulphate) rather than to
pure green rust.
Titre : Marine corrosion: a widespread, underestimated and poorly understood phenomenon
Année : 2007
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Seawater is a universal fluid – it is the medium where oceanographic moorings, ships, harbour
installations and offshore platforms spend their life. Seawater is also widely used in industrial
applications: for cooling and for use against fire in ships and platforms, and in coastal installations
such as refineries, chemical/petrochemical plants, desalination plants and power stations. By
nature, seawater is very corrosive to metallic materials; it contains, for example, dissolved oxygen,
micro-organisms, and high concentrations of chloride ions and other chemical species deleterious
to the integrity of metallic materials, such as hydrogen sulphide and ammonia compounds.
Therefore, when designing any equipment or industrial plant that will be in contact with seawater,
it is important to know about, and to take into account, the behaviour of metallic materials in
seawater. It is also absolutely essential to evaluate the effects not only of corrosion, but also the
environmental effects of measures taken to counteract it.
Ocean Challenge, Vol. 15; No. 1, p. 38-43
Titre : Electrochemical study of indoor atmospheric corrosion layers formed on ancient iron artefacts
Année : 2007
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Several indoor atmospheric corrosion layers (0–800 years old) were selected from different localisations in France. Each sample was scrapped from its iron substrate. The resulting powder was mixed with graphite in appropriate proportions and the mixture was pressed onto a stainless steel grid to constitute a composite electrode. The electrochemical responses of the different samples were recorded under galvanostatic regulation, in a near-neutral pH-buffered NaCl solution at 25 °C. The E–t reduction curves allowed the determination of two characteristic parameters, E?/2, the potential value obtained at half the transition time, and Q?, the coulombic charge obtained at the end of the reduction. The diminution of E?/2 and Q? with the age of the corrosion layer showed that the “reduction reactivity” decreases with time, suggesting a progressive stabilisation of the corrosion layer.
In a second part of the work, we synthesised several common ferric or ferrous/ferric products (goethite, lepidocrocite, magnetite, maghemite, ferrihydrite) and compared their reduction responses (product alone or mixture of 2 or 3 products) to those of corrosion samples.
Electrochimica Acta
Titre : Electrochemical reduction of ferric corrosion products and evaluation of galvanic coupling with iron
Année : 2006
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Corrosion Sciences, Volume 48, Issue 8, Août 2006, Pages 2050-2063
Titre : Study of lepidocrocite electrochemical reduction in neutral and slightly alkaline solutions at 25°C
Année : 2005
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : The electrochemical reduction of lepidocrocite ?-FeOOH was investigated at 25 °C in neutral or slightly alkaline solutions containing chloride, sulphate or bicarbonate anions by means of thin lepidocrocite film electrodeposited on inert gold substrate or graphite/lepidocrocite powder composite electrode. Electrochemical measurements were coupled to in situ electrochemical quartz crystal microbalance (EQCM) and ex situ SEM and FTIR analysis. The reduction of lepidocrocite occurs in all the electrolytes considered here. The initial reduction product is adsorbed ferrous ion, Feads2+. The desorption of Feads2+ is promoted as pH increases, leading to an increase of reduction depth. This promotion is related to the formation of secondary FeII-containing species, as revealed by SEM and FTIR. The comparison of ?-FeOOH reduction potentials and iron corrosion potentials let us state that the galvanic coupling is possible.
Titre : Impact de la protection cathodique sur l’activité corrosive de la flore sulfurogène
Année : 2004
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Non disponible
Matériaux et Techniques, spécial biodétérioration. N° 7-8-9 2004 p.38-43
Titre : Thin layers of iron corrosion products electrochemically deposited on inert substrates: synthesis and behaviour
Année : 2004
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : The deterioration of iron-based materials due to corrosion is a well-known problem. A variety of corrosion products can be formed depending on the species present in the medium (soil, water, etc.). Understanding the transformation pathways during the evolution of a corrosion layer is a hard challenge since it is difficult to clearly identify the contributions of each corrosion product. That is why the development of electrodes with only one iron corrosion product deposited as thin layers on inert substrates (gold, silver) presents many advantages to carry out electrochemical studies. In this way, the present paper reports successful electrochemical synthesis of thin layers deposited on inert substrates (gold, silver) of commonly occurring iron corrosion products as siderite, green rusts incorporating carbonate or sulphate anions, magnetite and goethite. The films are characterised by usual ex-situ techniques: FTIR, SEM, and XRD. The study of the electrochemical behaviour of thin films of green rust deposited on silver illustrates the potential application of such electrodes.
Titre : Electrochemical synthesis of lepidocrocite thin films on gold substrate—EQCM, IRRAS, SEM and XRD study
Année : 2004
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Lepidocrocite thin films have been electrochemically synthesised on polycrystalline Au substrates following two ways, direct synthesis and synthesis via green rust (GR). The direct synthesis consists in oxidising Fe(II) species in a 0.4 M NaCl/0.02 M Met-Imidazole/0.01 M FeCl2 solution at pH 7.5. The synthesis via GR consists in converting a green rust thin film into lepidocrocite thin film by galvanostatic oxidation. The thin films have been characterised by means of electrochemical quartz crystal microbalance, scanning electron microscopy, X-ray diffraction and infrared reflection–absorption spectroscopy.
Titre : Electrochemical study of lepidocrocite reduction and redox cycling for the mechanistic modelling of atmospheric corrosion
Année : 2004
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Non disponible
Science and Technology series, Ed ANDRA, Proceedings of the 2nd International Workshop, Eurocorr, Nice, September 2004
Titre : Généralités sur la biocorrosion
Année : 2003
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Non disponible
Techniques de l’Ingénieur
Titre : Interrelationship between cathodic protection and microbiologically influenced corrosion in marine environment: brief-review and prospects
Année : 2003
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Cathodic protection is widely used to prevent corrosion of steel constructions exposed to seawater. This protection causes a calcareous deposit as well as a biofilm formation. The Sulphate-Reducing Bacteria (SRB) and Thiosulphate-Reducing Bacteria (TRB) are involved in the steel biodegradation phenomena in marine environment. The surface colonization by these species under cathodic protection are described particularly for the TRB and with immersion periods of over 30 days. After a brief-review, preliminary studies explain the first results of our investigation in natural seawater and carbon steel during 4 to 8 weeks experiment. We have made experiments with natural strains of SRB/TRB, with monoculture of Desulfovibrio halophilus (SRB) and Dethiosulfovibrio peptidovorans (TRB), with potential a Cathodic Protection (CP) of –900 mV/SCE and –1000 mV/SCE and without CP. These results seem indicate that the effects of CP on the sulphide-producing bacteria metabolism is the reduction of their corrosive activity.
Harbour Congress Proceeding, Antwerpen-Belgium, March-April 2003. Proceedings p.169-178
Titre : Electrochemical deposition of thin films of green rusts 1 and 2 on inert gold substrate
Année : 2003
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
Abstract : Green rusts are layered Fe(II)–Fe(III) hydroxy-salts that play an important role in iron corrosion, soil chemistry, and environmental engineering. Successful electrochemical depositions of thin layers of green rusts incorporating anions such as carbonate or chloride (GRs1) or sulphate (GR2) on gold substrate are presented. As far as we know, it is the first time that such synthesis has been reported. The thin layers of green rusts were characterized by ex situ methods such as XRD, SEM, EDS and FTIR. This new way of synthesis allowed us to get green rust particles with sizes significantly larger than those obtained from the ways reported until now.
Electrochemistry Communications, Volume 5, Issue 3, March 2003, Pages 208-213
Titre : Influence de la protection cathodique, d’acier immergé en milieu marin, sur la vitesse de colonisation de la flore sulfurogène
Année : 2002
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph.
