title: Factors Affecting MoO4(2-) Inhibitor Release from Zn2Al Based Layered Double Hydroxide and Their Implication in Protecting Hot Dip Galvanized Steel by Means of Organic Coatings.
abstract: Zn2Al/-layered double hydroxide (LDH) with intercalated MoO4(2-) was investigated as a potential source of soluble molybdate inhibitor in anticorrosion coatings for hot dip galvanized steel (HDG). The effect of solution pH, soluble chlorides, and carbonates on the release kinetics of the interleaved MoO4(2-) ions from the LDH powder immersed in solutions containing different anions was studied by X-ray diffraction, in situ attenuated total reflectance infrared (ATR-IR) spectroscopy, and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The effect of the solution composition on the total release and the release kinetics was demonstrated. Less than 30% of the total amount of the intercalated MoO4(2-) was released after 24 h of the immersion in neutral 0.005-0.5 M NaCl and 0.1 M NaNO3 solutions whereas the complete release of MoO4(2-) was observed after 1 h in 0.1 M NaHCO3 or Na2SO4 and in alkaline solutions. The in situ ATR-IR experiments and quantification of the released soluble species by ICP-AES demonstrated the release by an anion exchange in neutral solutions and by the dissolution of Zn2Al/-LDH in alkaline solutions. The anion exchange kinetics with monovalent anions was described by the reaction order n = 0.35 ± 0.05 suggesting the diffusion control; for divalent anions, n = 0.70 ± 0.06 suggested the control by a surface reaction. Dissolution of Zn from coated HDG with and without Zn2Al/-MoO4(2-) fillers, leaching of MoO4(2-) from the coating, and the electrochemical impedance spectroscopy response of the coated systems were measured during the immersion in 0.5 M NaCl solutions with and without 0.1 M NaHCO3. Without carbonates, the release of soluble MoO4(2-) was delayed for 24 h with no inhibiting effect whereas with 0.1 M NaHCO3 the immediate release was accompanied by the immediate and strong inhibiting effect on Zn dissolution. The concept of controlling the inhibition performance of LDH hybrid coatings by means of the environment composition is discussed.
authors.affiliation: PSL Research University, Institut de Recherche Chimie Paris, CNRS - Chimie-ParisTech, 11 rue Pierre et Marie Curie, Paris 75005, France.
authors.forename: V
authors.initials: V
authors.lastname: Shkirskiy
authors.affiliation: BASF Coatings GmbH , Glasuritstrasse 1, 48165 Münster, Germany.
authors.forename: P
authors.initials: P
authors.lastname: Keil
authors.affiliation: BASF Coatings GmbH , Glasuritstrasse 1, 48165 Münster, Germany.
authors.forename: H
authors.initials: H
authors.lastname: Hintze-Bruening
authors.affiliation: Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand (ICCF, UMR-CNRS 6296), BP 80026, F-63171 Aubiere, France.
authors.forename: F
authors.initials: F
authors.lastname: Leroux
authors.affiliation: Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand (ICCF, UMR-CNRS 6296), BP 80026, F-63171 Aubiere, France.
authors.forename: P
authors.initials: P
authors.lastname: Vialat
authors.affiliation: PSL Research University, Institut de Recherche Chimie Paris, CNRS - Chimie-ParisTech, 11 rue Pierre et Marie Curie, Paris 75005, France.
authors.forename: G
authors.initials: G
authors.lastname: Lefèvre
authors.affiliation: PSL Research University, Institut de Recherche Chimie Paris, CNRS - Chimie-ParisTech, 11 rue Pierre et Marie Curie, Paris 75005, France.
authors.forename: K
authors.initials: K
authors.lastname: Ogle
authors.affiliation: PSL Research University, Institut de Recherche Chimie Paris, CNRS - Chimie-ParisTech, 11 rue Pierre et Marie Curie, Paris 75005, France.
authors.forename: P
authors.initials: P
authors.lastname: Volovitch
keywords: LDH; corrosion; galvanized steel; hybrid coating; inhibitor release