The effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined cast iron, lined cast iron, and polyvinyl chloride was measured using pipe coupons exposed for three months. Roughness of each pipe coupon was measured with an optical surface profiler before and after exposure to inhibitors. For most materials, inhibitor did not have a significant effect on surface roughness; instead, the most significant factor determining the final surface roughness was the initial surface roughness. Coupons with low initial surface roughness tended to have an increase in surface roughness during exposure, and vice versa, implying that surface roughness tended to regress towards an average or equilibrium value. For unlined cast iron, increased alkalinity and increased temperature tended to correspond with increases in surface roughness. Unlined cast iron coupons receiving phosphate inhibitors were more likely to have a significant change in surface roughness, suggesting that phosphate inhibitors affect stability of iron pipe scales. Similar roughness data collected with new copper coupons showed that elevated orthophosphate, alkalinity, and temperature were all factors associated with increased copper surface roughness. The greatest increases in surface roughness were observed with copper coupons receiving phosphate inhibitors. Smaller increases were observed with copper coupons receiving silicate inhibitor or no inhibitor. With phosphate inhibitors, elevated temperature and alkalinity were associated with larger increases in surface roughness and blue-green copper (II) scales.. Otherwise a compact, dull red copper (I) scale was observed. These data suggest that phosphate inhibitor addition corresponds with changes in surface morphology, and surface composition, including the oxidation state of copper solids. The effects of corrosion inhibitors on copper surface chemistry and cuprosolvency were investigated. Most copper scales had X-ray photoelectron spectroscopy binding energies consistent with a mixture of Cu2O, CuO, Cu(OH)2, and other copper (II) salts. Orthophosphate and silica were detected on copper surfaces exposed to each inhibitor. All phosphate and silicate inhibitors reduced copper release relative to the no inhibitor treatments, keeping total copper below the 1.3 mg/L MCLG for all water quality blends. All three kinds of phosphate inhibitors, when added at 1 mg/L as P, corresponded with a 60% reduction in copper release relative to the no inhibitor control. On average, this percent reduction was consistent across varying water quality conditions in all four phases. Similarly when silicate inhibitor was added at 6 mg/L as SiO2, this corresponded with a 25-40% reduction in copper release relative to the no inhibitor control. Hence, on average, for the given inhibitors and doses, phosphate inhibitors provided more predictable control of copper release across changing water quality conditions. A plot of cupric ion concentration versus orthophosphate concentration showed a decrease in copper release consistent with mechanistic control by either cupric phosphate solubility or a diffusion limiting phosphate film. Thermodynamic models were developed to identify feasible controlling solids. For the no inhibitor treatment, Cu(OH)2 provided the closest prediction of copper release. With phosphate inhibitors both Cu(OH)2 and Cu(PO4)·2H2O models provided plausible predictions. Similarly, with silicate inhibitor, the Cu(OH)2 and CuSiO3·H2O models provided plausible predictions.

L’alliage d’aluminium 2024 est très répandu dans l’industrie aéronautique et automobile. Le processus de corrosion peut entrainer des dommages irréversibles pouvant engendrer des issues fatales dans le domaine aéronautique. Ainsi plusieurs couches de revêtements sont déposées à la surface du métal à protéger pour prévenir le processus de corrosion. Depuis le début du 20ième siècle, le chrome hexavalent (CrVI) a été largement utilisé comme inhibiteur de corrosion dans les différentes couches du revêtement (prétraitement, primer et top-coat). La toxicité de ce composé envers l’homme et l’environnement a entrainé son interdiction et donc son remplacement comme agent de protection. Le confinement d’agent anticorrosif dans des nano-conteneurs a ainsi été reporté puisqu’un effet auto-réparant, en relargant sur demande, peut-être apporté : l’inhibiteur de corrosion agit quand le dommage apparait. Cette étude est focalisée sur l’utilisation de matériaux de type Hydroxydes Doubles Lamellaires (HDL) comme réservoir d’inhibiteurs de corrosion en raison leur propriété d’échange. Dans ce travail, plusieurs molécules ont été étudiées comme potentiel inhibiteur de corrosion. Celles-ci ont été tout d’abord caractérisées par DC-polarisation afin de déterminer la nature de leur comportement inhibiteur (anodique, cathodique ou les deux). Ensuite, ces agents anticorrosifs ont été intercalés dans des matrices HDL et leur capacité de relargage ainsi que leur comportement face au processus de corrosion ont été étudiés. Les particules HDL ainsi obtenues ont été dispersées dans la formulation d’un revêtement primaire et déposé directement sur l’alliage aluminium 2024. La résistance à la corrosion a été suivie par spectroscopie d’impédance complexe. Les propriétés d’auto-protection de notre revêtement (relargage d’agent anticorrosive encas de dommage) et leur propriété barrière, apportée par la morphologie lamellaire des nano-conteneurs, entrainant une diminution de la perméabilité aux espèces agressives (ex. eau, O2, électrolyte) responsable de l’apparition de cloques sur les revêtements, ont ainsi été caractérisées. / Aluminum alloy 2024 is widely used in aircraft and automotive industry. Corrosion processes can provide irreversible damage on the metal substrate which could have a tragic issue in the aircraft domain. Thus, several coating layers have been applied on the metal substrate to prevent corrosion process. Since the beginning of the 20th century, hexavalent chromate compounds have been extensively used as corrosion inhibitor agents for paint, primer and conversion coating. The toxicity for human health and environment has led to replace such compounds. The literature has reported different possibilities to replace such unfriendly compounds. Moreover, the entrapment of corrosion inhibitors in nanocontainer provides a self-healing effect by releasing, on demand, the active species when damage occurs. This study focuses on Layered Double Hydroxide (LDH) material as reservoir due to its exchange properties. This study has characterized several potential corrosion inhibitor molecules by DC-Polarization to determine the nature of the inhibitor compound (i.e. anodic, cathodic or both of them). Further, active anticorrosive species have been intercalated into LDH framework. Then, the release of inhibitor agents and their subsequent behaviour toward corrosion inhibition have been evaluated. Modified LDH materials have been further dispersed in the primer coating formulation and applied on aluminum alloys 2024 substrate. Corrosion inhibition has been followed by electrochemical impedance spectroscopy experiments on scratched and unscratched panel which have permitted to evaluate the self-healing property of these modified LDH materials when damage occurs and the barrier property provided by the lamellar morphology of the inorganic reservoir that is found to decrease the permeation by enhancing the tortuosity of the coating layer towards aggressive species (i.e. water, O2, electrolyte) responsible of the blistering phenomenon.

Rebar corrosion in reinforced concrete structures is a big issue to technical studies, because it has, besides the maintenance costs, indirect costs which affect bridges and building users. Corrosion inhibitors are chemical substances that added to concrete reduce or retard rebar corrosion. In this thesis we described the behavior of sodium molybdate and thiourea used as corrosion inhibitors (CI) for concrete mixes submitted to chloride medium. Calcium hydroxide solution, cement paste, mortar and concrete were used to understand corrosion inhibitors effects on their properties. Dosage study was performed using solutions, with and without the CI, applying cyclic voltammetry and steady-state polarization. Effects on cement paste and concrete were studied using four different dosages of the proposed CI and two commercial products, two different cements and silica fume as supplementary cementitious material. Concretes mixes were tested by workability, compression strength and resistance to chloride penetration, using ASTM C 1202 and ASTM C 1543. ASTM G 109 was used as standard to determine CI efficiency on corrosion inhibition and two techniques were used to determine concrete electrical resistivity: electrochemical impedance spectroscopy and conductivimetry. The proposed inhibitors showed, in 2% sodium molybdate and 0,67% thiourea, slight effects on concrete properties and good effects on improving the resistance to chloride penetration and to corrosion due chloride ions. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A corrosão de armaduras de concreto armado em pontes, viadutos e edifícios tem preocupado o meio técnico, pois além do custo de manutenção, há o custo indireto devido à quedas de estruturas, interdições e incômodos causados aos usuários. Entre os métodos para minimizar a corrosão, podem ser citados os inibidores de corrosão, os quais são adicionados ao concreto e atuam na interface concreto/aço, diminuindo a taxa de corrosão. Neste trabalho, são relatados os estudos do comportamento de inibidores de corrosão à base de molibdato de sódio e tiouréia, aplicados em concretos submetidos à ação de íons cloreto e comparados a dois inibidores comerciais. Foram realizados estudos em solução e em pastas, argamassas e concretos, com dois cimentos diferentes, sem e com adição de 5 e 10% de sílica ativa. A determinação das dosagens de inibidores foi feita em solução saturada de hidróxido de cálcio, utilizando técnicas eletroquímicas como polarização em estado quase-estacionário e voltametria cíclica. Foram estudados os efeitos dos inibidores propostos, em várias dosagens, e de dois inibidores comerciais, nas propriedades de pastas e concretos sem e com sílica ativa. Além da trabalhabilidade e da resistência à compressão, foi testada a resistência à penetração de cloretos pelos métodos ASTM C 1202 e ASTM C 1543. A avaliação da eficiência frente à corrosão provocada por íons cloreto seguiu a norma ASTM G 109. A resistividade elétrica foi determinada utilizando espectroscopia de impedância eletroquímica e condutivimetria. Os inibidores propostos, nas concentrações de 2% de molibdato de sódio e 0,67% de tiouréia, mostraram resultados bastante promissores, tanto na avaliação quanto à influência sobre as propriedades físicas e mecânicas do concreto, quanto à diminuição da penetração de cloretos e eficiência na inibição da corrosão.

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