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Corrosion USTH1

Corrosion USTH1

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Sections

  • I.1. Definition of Corrosion
  • I.2. Mechanisms of Corrosion
  • I.3. Thermodynamic of corrosion I.3.1. Electrode potential
  • I.4. Forms of Corrosion
  • I.5. Atmospheric corrosion
  • II.2.1. Classification of Inhibitors
  • II.2.2. Corrosion Inhibition Mechanism

CORROSION AND PROTECTION OF METALS

Assoc.Prof. To Thi Xuan Hang Institute for Tropical Techmology Vietnam Academy of Science and Technology 18 Hoang Quoc Viet, Cau Giay, Hanoi, Vietnam Email: ttxhang@itt.vast.vn; ttxhang60@gmail.com Tel : 0912178768

CORROSION AND PROTECTION OF METALS
I. Corrosion of metals I.1. Definitions of Corrosion I.2. Mechanism of corrosion

I.3. Thermodynamic of Corrosion I.4. Forms of Corrosion
I.5. Atmospheric Corrosion II. Corrosion protection II.1.Corrosion protection methods II.2. Corrosion Inhibitors: mechanisms and classifications II.3. Organic coatings: composition, protective mechanism II.4. Green technology in organic coatings II.5. Nanotechnology in organic coatings II.6. Corrosion testing of organic coatings: accelerated testing, electrochemical methods

I. CORROSION OF METALS
1. Definitions of Corrosion 2. Mechanism of corrosion 3. Thermodynamic of Corrosion 4. Forms of Corrosion 5. Atmospheric Corrosion

I.1. Definition of Corrosion Metals are high energy materials ie rg e en (Thermodynamically unstable) En erg y g d Ad lo ss in Natural ores (Thermodynamically stable) Corrosion products (Thermodynamically stable) .

iron + Aluminium Hydrated iron oxide (rust) Hydrated aluminium oxide + Degradation of polymer by UV radiation .Example of corrosion + Steel.

concrete and wood. .Definition of Corrosion + An attack on a metallic material by reaction with its environment + The chemical or electrochemical reaction between a material and its environments that produces a deterioration of the material and its properties + Corrosion is the deterioration of materials by chemical interaction with their environment + The term corrosion is sometimes also applied to the degradation of plastics.

cars. bridges.Consequences of corrosion 1. 2. Reduced value of goods due to deterioration of appearance. Hazards or injuries to people arising from structural failure or breakdown (e. Added complexity and expense of equipment which needs to be designed to withstand a certain amount of corrosion. Contamination of fluids in vessels and pipes 3. and to allow corroded components to be conveniently replaced. Reduction of metal thickness leading to loss of mechanical strength and structural failure or breakdown. 4. . aircraft).g.

790 .1% of GDP 1998 U. B$276 / year = 3.S.Corrosion cost Total Direct Cost of Corrosion in the U. GDP B$8.S.

Examples The cost of corrosion in industrialized countries has been estimated to be about 3– 4% of GNP > $200 million restoration project (1986). largely necessitated due to corrosion damage. Statue of Liberty (USA) . with significant internal galvanic corrosion damage.

2.Oxidation corrosion . Mechanisms of Corrosion Corrosion of metals: 2 groups + Dry or chemical corrosion: corrosive environment is a dry gas . .I.Liquid metal corrosion + Wet or electrochemical corrosion: corrosive environment is water with dissolved species.Corrosion by other gases .

Chemical corrosion Oxidation corrosion M ½ O2 + 2 e2M + ½ O2 Mn+ + ne- OM2O For alkali metals Oxidation of a metal layer of metal oxide inhibit further corrosion process of corrosion continues Stable. tightly adhering oxide film Porous oxide film .

Sn are stable. accelerates corrosion .Examples .MnO3is volatile.Alkali metals react with oxygen at room temperature . inhibit corrosion .Oxides of Pb. Pt are not oxidized. Au. Al. noble metals .Ag.

Liquid metal mercury dissolves most metals by forming amalgams.Chemical corrosion Corrosion by other gases: Cl2. H2S.Cl2 reacts with Ag and forms AgCl . NOx . SO2. thereby corroding them .H2S attacks steel forming FeS Liquid metal corrosion: molten metal .

Corrosion of metals in aqueous environments .Chemicals and humidity: electrolyte .Absorption of oxygen .Cathode: reduction .Electrochemical corrosion .Formation of galvanic cell on metals surface .Evolution of hydrogen .Anode: oxidation .

evolution of hydrogen 2H+ + 2 e.Overall reaction: M + nH+ H2 Mn+ + (n/2)H2 . loss of electrons Mn+ + neM .At anode: oxidation.At cathode: reduction.Electrochemical corrosion (deaerated acids) .

evolution of hydrogen 2H+ + 2 e.Example .At cathode: reduction.At anode: oxidation.Overall reaction: Fe + 2H+ H2 Fe2+ + H2 . loss of electrons Fe2+ + 2eFe .

loss of electrons Zn2+ + 2eZn • At cathode: reduction.Example • At anode: oxidation. evolution of hydrogen a 2H+ + 2 e• Overall reaction: Zn + 2H+ H2 Zn2+ + H2 .

Mechanism of wet corrosion in acids and absence of oxygen .

Electrochemical corrosion (alkaline and neutral aerated solution) .At anode: oxidation.At cathode: reduction. loss of electrons Fe2+ + 2eFe . absorption of oxygen O2 + 2 H2O + 2 e-Overall reaction: Fe + O2 + 2 H2O 4OHFe2+ + 2OH- .

Mechanism of wet corrosion in alkaline and neutral aerated solution .

in the presence of CO2 Cu: Cu(OH)2 CuO carbonate .nH2O Zn: Zn(OH)2 .Mechanism of wet corrosion in alkaline and neutral aerated solution Fe: formation of Fe(OH)2 Fe(OH)3or Fe2O3.

• It depends on the size of the anodic part of metal. • It is a rapid process. • It involves formation of electrochemical cells. • It involves direct attack of chemicals on the metal surface. • The process of corrosion is uniform.Differences between dry and wet corrosion Dry corrosion • Corrosion occurs in the absence of moisture. • Corrosion products are produced at the site of corrosion. . Wet corrosion • Corrosion occurs in presence of conducting medium. • The process is slow. • Corrosion occurs at anode but rust is deposited at or near cathode.

1.3.3.I. Electrode potential M Atom in metal surface Mn+ Ion in solution + neElectron(s) in metal Electrolyte Potential difference between the metal and the solution Electrode potential . Thermodynamic of corrosion I.

Electrode potential Mn+ + ne= E0 Mn+/M M RT + nF ln aMn+ Er. T : absolute temperature. aMn+: activity of of dissolved metal ions R : gas constant. F : Faraday n : number of electrons transferred per ion .Mn+/M E0 : standard reversible potential Eo for unit activity of dissolved metal ions.

5 M NaCl solution of some common metals .Standard electrode potential in 0.

Standard hydrogen electrode (SHE)

Potential of electrode reaction

Pourbaix diagram of iron in water at 25 oC, aFe2+ = 10-6 M
a/ Fe2+ + 2e- = Fe
e d
Corrosion Passivition

b/ Fe3O4 + 8H+ + 8e- = Fe + 4H2O c/ Fe3O4 + 8H+ + 2e- = 3Fe2+ + 4H2O
c b

f
a
immunity Corrosion

d/ Fe2O3 + 6H+ + 2e- = 2Fe2+ + 3H2O e/ O2 + 4H+ + 4e- = 2 H2O f/ 2H+ + 2e- = H2

Polarisation curve measurement Reference electrodes: Saturated calomel electrode (SCE) KCI (satd). chloride solution Copper/copper sulphate electrode Copper rod. Hg2CI2 (solid)/Hg Silver/silver chloride electrode. saturated solution of copper sulphate . silver wire coated with silver chloride.

Polarisation curve of iron Passive film on surface Fe Cathodic process: Fe2+ + 2e- 2H+ + 2eThe potential-current relationship H2 (g) .

• Corrosion current density.Expressions of Corrosion Rates • Thickness reduction of the material per unit time (mm/year). . • Weight loss per unit area and unit time.

4. Forms of Corrosion • • • • • • Uniform corrosion Galvanic corrosion Crevice corrosion Pitting corrosion Intergranular corrosion Stress corrosion cracking .I.

The corrosion rate is nearly constant at all locations.Anodic dissolution is uniformly distributed over the entire metallic surface.Uniform (general) corrosion Definition: . .

Uniform (general) corrosion + Uniform corrosion is the most common form of corrosion. cathodic protection or change of environment or material . is responsible for the most of material loss + It is not the dangerous form of corrosion + Prediction of thickness reduction rate can be done by means of simple tests + Prevention methods: coatings.

they will form a galvanic cell + a les noble metal will be oxidized and it will undergo corrosion .Galvanic corrosion Galvanic corrosion: bimetallic corrosion + Two metals (a more noble and a less one) are connected and exposed to an electrolyte.

Example of galvanic corrosion Zn Zn2+ + 2e- At anode: At cathode: Zn Cu2+ + 2e- Zn2+ + 2e. . zinc coating on mild steel. steel pipe connected to copper plumbing.(Oxidation) corrosion Cu (reduction) unaffected Examples of galvanic corrosion: Steel screws in brass marine hardware.

Galvanic series in sea water Anodic (active) Magnesium Zinc Aluminum Mild steel Cast iron Stainless steel 18/8 (active) Copper Stainless steel 18/8 (passive) Graphite Gold Platinum Cathodic (noble) .

50 -0.50to-0.50 -0.Brass.20 -0.10 -1.75 -1.60 -1.80 -0.20to-0.Bronze HighSiliconCastIron Carbon.20 +0.30 .Typical galvanic series METAL CommerciallyPureMagnesium MagnesiumAlloy Zinc AluminumAlloy VOLTS(SCE) -1.50 -0.80 -0.05 CommerciallyPureAluminum MildSteel(clean&shiny) MildSteel(rusted) CastIron(notgraphitized) Lead MildSteelinConcrete Copper.20 -0.Coke -0.Graphite.

Prevention of Galvanic corrosion + Galvanic corrosion can be avoided by coupling metals close to the electrochemical series. . + Fixing insulating material between two metals. + By using larger anodic metal and smaller cathodic metal.

Crevice corrosion .The scratched portion acts as small anode and the rest part will act as cathode forming a local cell. rivets and bolts.Crevice corrosion is formed near joints. . Changes in the concentration of oxygen/acidic medium causes crevice corrosion. .Surface of painted metal is scratched. it will undergo corrosion. .

Crevice corrosion -Crevice corrosion is a very similar mechanism to pitting corrosion .Crevice corrosion is less severe form of localized corrosion then pitting corrosion. . -The depth of penetration and the rate of propagation in pitting corrosion are significantly greater than in crevice corrosion.

. . there is formation of a local galvanic cell. It is the anodic area which will be corroded and the formation of a pit is observed.Pitting corrosion .Due to crack on the surface of a metal.The crack portion acts as anode and rest of the metal surface acts as cathode. chemical attack. sliding under load. local straining of metal.

Different shapes of corrosion pits .

Anodic overvoltage curve for an active–passive metal in an environment causing pitting corrosion .Pitting corrosion Ep: pitting potential Epass :passivation potential icr: critical current density ip: passive current density.

Pitting corrosion - - Fe Fe2+ + 2e- .

if there is a portion under stress.In a metallic structure.The tensile stresses may originate from external load. . it will act as anode and rest part of the structure will act as cathode . centrifugal forces or temperature changes.Stress corrosion cracking . or they may be internal stresses induced by cold working.Stress corrosion cracking can be defined as crack formation due to simultaneous effects of static tensile stresses and corrosion. welding or heat treatment .

.This corrosion is observed in case of alloys.Intergranular corrosion .Intergranular corrosion is localized attack on or at grain boundaries with insignificant corrosion on other parts of the surface.Welding. The corrosion product is observed at the boundaries of grains. . or overheating in service generally establish the microscopic. stress relief annealing. compositional inhomogeneities that make a material susceptible to intergranular corrosion. improper heat treating. .

Intergranular corrosion .

Corrosion in different environments Atmospheric corrosion Corrosion in fresh water and other water Corrosion in seawater Corrosion in soils Corrosion in concrete .

Atmospheric corrosion is electrochemical corrosion in a system that consists of a metallic material. corrosion products and possibly other deposits. a surface layer of water (often more or less polluted). and the atmosphere.Definition: Corrosion of materials exposed to air and its pollutants. . rather than immersed in a liquid. Atmospheric corrosion . .5.I.

• Urban: similar to the rural type. high humidity and chlorides. and nitrates. Corrosivity depends on wind direction. and distance from the coast . sulfur dioxide.phosphates. wind speed. The principal corrodents are moisture. • Marine: highly corrosive. • Industrial: highly polluted by industry smoke and precipitate.Types of atmospheres and environments • Rural (inland): the least corrosive. oxygen. chlorides. and carbon dioxide. additional contaminants are of the SOx and NOx. dry environment with little or no pollution.fine windswept chloride particles deposited on surfaces.

Typical corrosion rates for carbon steel in different types of atmospheres .

Atmospheric corrosion of iron .

Nature of corrosion products formed on four metals .

Important factors in atmospheric corrosion • Time of wetness (presence of electrolyte on the corroding surface) is a key parameter. acidification of electrolyte led to accelerated corrosion rate – Cl: increases distingcly atmospheric corrosion rate . form sulfuric acid • Formation of FeSO4. directly determining the duration of the electrochemical corrosion processes. • Composition of electrolyte: – SO2: industrial atmosphere.

At temperatures below freezing. .Raising the temperature leads to a decrease in relative humidity. where the electrolyte film solidifies. . and wetness time decrease of corrosion rate.Important factors in atmospheric corrosion • Temperature: . electrochemical corrosion activity will drop to negligible levels.An increase in temperature will tend to stimulate corrosive attack by increasing the rate of electrochemical reactions and diffusion processes. .

ISO 9223 Classification of Time of Wetness .

Rural environmentsfarfromindustrial areas Urbanorindustrialareas Industrialareaswithhighrelative humidity Coastalandoffshoreareas C4 C5-I C5-M Heavy Veryheavyindustry Veryheavymarine .Corrosivity categories and corresponding environmental impact factors Corrosivity category C1 C2 C3 Environmental impact Verylow Low Medium Environmentalexamples Indoorindryrooms(relativehumidity <60%) Indoorinnon-heatedandventilated rooms Indoorwithhighhumidityandpollution (productionareas).

Corrosion rate categories Corrosion rate for different metals for different corrosion categories .

1. Corrosion protection II. Corrosion protection methods Appropriate materials selection Suitable design Change of environment Cathodic protection Applications of coatings on the metal surface ( metallic coatings. organic coatings) .II.

• As far as possible. metal used in a structure should be extremely pure.Material selection and suitable design • Contact of two dissimilar metals must be avoided. • Putting an insulator between two metals resists corrosion. • The alloy used should be completely homogeneous. • Two different metals used in the structure should be such that they are occupying near positions in galvanic series. Anodic area should be very large compared to cathodic area. • Sharp edges and corners must be minimized .

Change of environment • Deaeration removes oxygen by adjusting temperature and mechanical ageing. • Deactivation involves addition of chemicals which absorb oxygen. • Dehumidification of environment is done by adding alumina or silica gel. These chemicals absorb humidity from metallic surface. . • Using Corrosion inhibitors.

thereby preventing corrosion. • Two methods: – Sacrificial anodic protection – Impressed current cathodic protection .Cathodic protection • Metal is forced to behave like cathode.

Sacrificial anodic protection • Sacrificial-anode-type cathodic protection systems provide cathodic current by galvanic corrosion. • The current is generated by metallically connecting the structure to be protected to a metal/alloy that is electrochemically more active than the material to be protected. • Both the structure and the anode must be in contact with the electrolyte. .

. only zinc (99.Sacrificial anodic protection Mg In practice.9 %) and alloys of magnesium are used for the protection of steel in soils.

Example of sacrificial anodic protection .

lead or nickel. • The positive terminal of the source is connected to the other electrode made of graphite or platinum.Impressed current cathodic protection • The object to be protected is made cathode and it is connected to the negative terminal of a DC (direct current) source. • The impressed current opposes the galvanic current (corrosion current) .

Impressed current cathodic protection

Protective coatings
Metallic coatings Anodic coating
- Coating is done by a metal which is situated prior to the base metal in electrochemical series. - Metal is immersed in molten coating metal. - The base metal should by very clear. - Anodic coating of iron is done by Zn, Al, Cd. - Steel with zinc coating: galvanised steel.

Protective coatings
Metallic coatings Cathodic coating
• Coating is done by another metal which occupies a position below it in electrochemical series but it will be higher corrosion resistant. • Cathodic protection of iron is successful only when there is no pit or crack formation on the surface of metal. • Coating of Sn over iron (tinning) is an example of cathodic protection. Tin-plated steel.

steel is covered with a thin coat of tin to prevent corrosion + Due to noble nature tin protects base metal + If the coating is puncture intense corrosion of steel occurs. + Since tin is non-toxic tinned containers can be used even for storing food.Differences between galvanizing and tinning + Galvanizing is the process of covering iron or steel with thin layer of Zn + Zinc protects iron sacrificially + Zinc protecte iron even when coating of zinc is punctured + Since zinc is toxic galvanized tensils are not used for storing food + In tinning. .

II.Good inhibitor: 95% inhibition at a concentration of 0.008% .2. Corrosion inhibitors • Definition: corrosion inhibitor is a chemical substance which decreases the corrosion rate when present in the corrosion system at suitable concentration without significantly changing the concentration of any other corrosive agent .

phosphate. Organic cationic. Only the negative anions of these compounds are involved in reducing metal corrosion. or molybdate.1. • .2. the zinc cation can add some beneficial effect. Their active portions are generally large aliphatic or aromatic compounds with positively charged amine groups. Classification of Inhibitors Classication by chemical functionality • Inorganic inhibitors. When zinc is used instead of sodium. • Organic anionic. These zinc-added compounds are called mixed-charge inhibitors. or mercaptobenzotriazole(MBT) are used commonly in cooling waters and antifreeze solutions. Sodium sulfonates.II. phosphonates. sodium chromate.

Examples of corrosion inhibitors .

Classication by inhibition mechanism • • • • Passivating (anodic) inhibitors Cathodic inhibitors Organic inhibitors Volatile corrosion inhibitors .

Passivating (anodic) inhibitors • Anodic inhibitors slow or stop the oxidation reaction of metal M Mn+ + ne- • Anodic inhibitors reduce the anodic current density and cause a large anodic shift of the corrosion potential towards the positive. forcing the metallic surface into the passivation range .

Passivating (anodic) inhibitors • Oxidizing anions: chromate. nitrite. and molybdate. tungstate. and nitrate that can passivate steel in the absence of oxygen Fe + Na2CrO4 + H2O   Fe2O3. that require the presence of oxygen .Cr2O3 + NaOH 2 Fe + NaNO2 + H2O   Fe2O3 + NaOH + NH3 • Nonoxidizing ions: phosphate.

zinc.Oxygen scavengers: sodium sulfite .Cathodic poisons: Arsenic and antimony .Cathodic precipitates: ions calcium. . or magnesium .Cathodic inhibitors • Cathodic inhibitors either slow the cathodic reaction itself or selectively precipitate on cathodic areas to increase the surface impedance and limit the diffusion of reducible species to these areas.

Organic inhibitors • Film-forming: Their effectiveness depends on the chemical composition. and their affinities for the metal surface. their molecular structure. • Film formation is an adsorption process. .

Organic inhibitors Blocking effects chemisorption properties donor-acceptor Dielectric effects interactions polar / water molecules Adsorption Hydrophobic effects structure of the compounds influence of the carbon chain .

Mercaptans. .mercaptobenzothiazole. Amines aromatiques : benzotriazole.Organic inhibitors • • • • Amines et polyamines. Thio-azotes : thioure. tolytriazole. Imidazolines.

Organic inhibitors .

dicyclohexylamine.Volatile corrosion inhibitors • Vapor phase inhibitors • Used in a closed environment (boilers. and hexamethylene-amine . cyclohexylamine. shipping containers) • Examples: morpholine or hydrazine.

and industrial cooling waters in the near neutral pH range (5 to 9). • Primary and secondary production of oil and subsequent refining and transport processes. or any other confined operation . • Atmospheric or gaseous corrosion in confined environments.2. during transport. storage. Corrosion Inhibition Mechanism 4 main environments: • Aqueous solutions of acids as used in metal cleaning processes such as pickling for the removal of rust or mill scale during the production and fabrication of metals or in the post service cleaning of metal surfaces.II. • Natural waters. supply waters.2.

and selenium. the presence of other species in the solution . sulfur.a/ Inhibitors for acid solutions • Inhibitors: organic compounds containing elements nitrogen. the pH of the acid. • Mechanism of action of an inhibitor may vary with factors such as its concentration. arsenic. oxygen. • The primary step is adsorption onto the metal surface • Adsorbed inhibitor then acts to retard the cathodic and/or anodic electrochemical corrosion processes. the nature of the anion of the acid. phosphorus.

– Interaction of the inhibitor with water molecules. • Adsorption of corrosion inhibitors depends on: – Surface charge on the metal. – Interaction of adsorbed inhibitor species. .Adsorption of corrosion inhibitors onto metals • The inhibitive efficiency is usually proportional to the fraction of the surface  covered with adsorbed inhibitor. – The functional group and structure of the inhibitor.

Factors influencing the adsorption of corrosion inhibitors • Surface charge on the metal • The functional group and structure of the inhibitor • Interaction of the inhibitor with water molecules • Interaction of adsorbed inhibitor species • Reaction of adsorbed inhibitors .

the adsorption of cations is favored. and as the potential becomes more negative. .Surface charge on the metal – Electrostatic attractive forces between ionic charges or dipoles on the adsorbed species and the electric charge on the metal at the metal-solution interface – Potential of a metallic surface becomes more positive. the adsorption of anions is favored.

The functional group and structure of the inhibitor • Inhibitors can also bond to metal surfaces by electron transfer to the metal to form a coordinate type of bond. • The presence of vacant electron orbitals of low energy. • Anions. • The electron density at the functional group increases. . and neutral organic molecules containing lone pair electrons or electron systems associated with multiple. the inhibitive efficiency increases due to increasing strength of coordinate bonding due to easier electron transfer and hence greater adsorption. in the metal. especially triple. bonds or aromatic rings.

• • . Change in interaction energy with water molecules in passing from the dissolved to the adsorbed state.Interaction of the inhibitor with water molecules • Adsorption of inhibitor molecules is a displacement reaction involving removal of adsorbed water molecules from the surface. Increasing inhibitive efficiency observed at constant concentrations with increasing molecular size.

Synergistic inhibitive effects occur in such mixtures of anionic and cationic inhibitors. Attractive interactions occur between molecules containing large hydrocarbon components.Interaction of adsorbed inhibitor species • • • • These lateral interactions may be either attractive or repulsive. • . Repulsive interactions occur between ions or molecules containing dipoles and lead to weaker adsorption at high coverage. Adsorption of both cations and anions in solutions may be enhanced and the inhibitive efficiency greatly increased compared to solutions of the individual ions.

to form a secondary product that may also be inhibitive inhibition .Reaction of adsorbed inhibitors • The adsorbed corrosion inhibitor may react. usually by electrochemical reduction.

Effects of inhibitors on corrosion processes • • • • Formation of a diffusion barrier Blocking of reaction sites Participation in the electrode reactions Alteration of the electrical double layer .

• Surface films of these types of inhibitors (compounds containing long hydrocarbonchains) give rise to resistance polarization .Formation of a diffusion barrier • Absorbed inhibitor may form a surface film that acts as a physical barrier to restrict the diffusion of ions or molecules to or from the metal surface and so retard the rate of corrosion reactions.

and both reactions are inhibited. • At higher surface coverage. causing retardation of the anodic reaction. adsorption occurs on both anodic and cathodic sites.Blocking of reaction sites • The simple blocking decreases the number of surface metal atoms at which corrosion reactions can occur. . • Adsorption of inhibitors at low surface coverage tends to occur preferentially at anodic sites.

• Inhibitors: such as phenyl thiourea. adsorbed (FeOH)). aniline derivatives. • Electrode processes may then proceed by alternative paths through adsorbed intermediates containing the inhibitor. benzaldehyde derivatives and pyrilium salts. acetylenic hydrocarbons. .Participation in the electrode reactions • The presence of adsorbed inhibitors will interfere with the formation of adsorbed intermediates of corrosion reactions (adsorbed hydrogen atoms.

and will affect the rates of the electrochemical reactions. This positive potential displacement retards the discharge of the positively charged hydrogen ion. • The adsorption of cations makes the potential more positive. .Alteration of the electrical double layer • The adsorption of ions on metal surfaces will change the electrical double layer at the metalsolution interface.

hydroxides.b/ Inhibitors in near-neutral solutions • Cathodic reaction in neutral solutions is the reduction of dissolved oxygen. or salts. • Substances that inhibit corrosion in acid solution by adsorption on oxide-free surfaces do not generally inhibit corrosion in neutral solution. • Corroding metal surfaces in acid solution are oxide-free. whereas in neutral solutions metal surfaces are covered with films of oxides. . whereas in acid solution it is hydrogen evolution.

Inhibitors in near-neutral solutions • Inhibitors for near-neutral solutions are the anions of weak acids: chromate. nitrite. and borate • Passivating oxide films on metals offer high resistance to the diffusion of metal ions. benzoate. phosphate. and the anodic reaction of metal dissolution is inhibited. and they are more generally used than cathodic inhibitors . • These inhibitive anions are often act as anodic inhibitors. silicate.

Important functions of inhibitors • Reduction of the dissolution rate of the passivating oxide film (form a surface complex with the metal ion of the oxide). • Repair of the oxide film by plugging pores with insoluble compounds. • Prevention of the adsorption of aggressive anions. . • Repair of the oxide film by promotion of the reformation of oxide.

which are more alkaline due to the hydroxyl ions produced by reduction of oxygen. and nickel.Inhibitors forming protective films • Salts of metals such as zinc. which produce a thin amorphous salt film. . again at cathodic areas where the high pH permits a sufficiently high concentration of carbonate ions. especially at cathodic areas. magnesium. • Polyphosphates in the presence of zinc or calcium. which can precipitate as calcium carbonate in waters containing carbon dioxide. manganese. which form insoluble hydroxides. • Soluble calcium salts.

/ Electrochimica Acta 47 (2002)4339/4346 .Examples Benzotriazole Structure of the films developed in the solution containing 10-2 M BTAH CuO: 17 % CuBTA: 53 % BTAH BTA- W.Qafsaoui et al.

Examples SEM photographs of steel surface after 3h of immersion in 3% NaCl solution containing HQ+ ATMP (a) in 3% NaCl solution containing HQ+ATMP + polyacrylic (b) Aminotrimetylphosphate (ATMP): 8-hydroxyquinolin (HQ) N OH .

Electrode surface after 2 h of immersion in NaCl 0.1 M solution with and without N5 1 g/l 0 g/l 0 g/l 1 g/l 3 g/l 3 g/l 5 g/l 5 g/l Only few corrosion products formed with the presence of Nanofil5 .

SEM photographs Clay N5 1 m 1 m Steel surface after 2h of immersion in NaCl 0.1 M solution Clay N5 Steel surface after 2h of immersion in NaCl 0.1 M solution + 3g/l N5 1 m Presence of Nanofil5 structure in the oxide layer on carbon steel .

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