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Chp 10

Chp 10

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309
10
Corrosion Inhibitors
Corrosion o metallic suraces can be controlled or reduced by the addi-tion o chemical compounds to the corrodent. This orm o corrosion con-trol is called
inhibition
and the compounds added are known as
corrosioninhibitors.
These inhibitors will reduce the rate o either anodic oxidation,cathodic reduction, or both. The inhibitors themselves orm a protective lmon the surace o the metal. It has been postulated that the inhibitors areadsorbed onto the metal surace either by physical (electrostatic) adsorptionor chemisorption.Physical adsorption is the result o electrostatic orces between the organicions and the electrically charged metal surace. Chemisorption is the trans-er, or sharing, o the inhibitor molecule’s charge to the metal surace, orm-ing a coordinate-type bond. The adsorbed inhibitor reduces the corrosionrate o the metal surace either by retarding the anodic dissolution reactiono the metal, by the cathodic evolution o hydrogen, or both.Inhibitors can be classied in many dierent ways according to:1. Their chemical nature (organic or inorganic substances)2. Their characteristics (oxidizing or nonoxidizing compounds)3. Their technical eld o application (pickling, acid cleaning, descal-ing, cooling water systems, etc.)The most common and widely known use o inhibitors is their applicationin automobile cooling systems and boiler eed waters.By considering the electrochemical nature o corrosion processes, consti-tuted by at least two electrochemical partial reactions, inhibition may bedened on an electrochemical basis. Inhibitors will reduce the rates o eitheror both o these partial reactions (anodic oxidation and/or cathodic reduc-tion). As a consequence, there can be anodic, cathodic, and mixed inhibitors.Inhibitors can be used in electrolytes at dierent pH values, rom acid tonear-neutral or alkaline solutions. Because o the very dierent situationscreated by changing various actors such as medium and inhibitor in thesystem, metal/aggressive medium/inhibitor, various inhibition mechanismsmust be considered.
1–6
An accurate analysis o the dierent modes o inhibiting electrode reac-tions, including corrosion, was carried out by Fisher.
7
He distinguishedamong various mechanisms o action such as:
© 2010 by Taylor and Francis Group, LLC
 
310
Fundamentals of Corrosion
Interace inhibition
•
Electrolyte layer inhibition
•
Membrane inhibition
•
Passivation
•
Subsequently, Lorenz and Manseld
8
proposed a clear distinction betweeninterace and interphase inhibition, representing two dierent types o retar-dation mechanisms o electrode reactions, including corrosion. Interaceinhibition presumes a strong interaction between the inhibitor and thecorroding surace o the metal.
1, 7, 9
In this case, the inhibitor adsorbs as apotential-dependent, two-dimensional layer. This layer can aect the basicreactions in dierent ways:By a geometric blocking eect o the electrode surace because o the
•
adsorption o a stable inhibitor at a relatively high degree o cover-age o the metal surace.By blocking the eect o the surace sites because o the adsorption
•
o a stable inhibitor at a relatively low degree o coverage.By reactive coverage o the metal surace. In this case, the adsorption
•
process is ollowed by electrochemical or chemical reactions o theinhibitor at the interace.According to Lorenz and Manseld,
8
interace inhibition occurs in cor-roding systems exhibiting a bare metal surace in contact with the corro-sive medium. This condition is oten realized or active metal dissolutionin acid solutions.Interphase inhibition presumes a three-dimensional layer between thecorroding surace and the electrolyte.
7, 10, 11
Such layers generally consist oweakly soluble corrosion products and/or inhibitors. Interphase inhibitionis mainly observed in neutral media with the ormation o porous or nonpo-rous layers. Clearly, the inhibition eciency strongly depends on the proper-ties o the ormed three-dimensional layer.
10.1 Inhibitor Evaluation
Because there may be more than one inhibitor suitable or a specic applica-tion, it is necessary to have a means o comparing the perormance o each.This can be done by determining the inhibitor eciency according to theollowing correlation:
© 2010 by Taylor and Francis Group, LLC
 
Corrosion Inhibitors
311
 
I =R RR100
eff O iO
×
where I
e
is the eciency o the inhibitor (%), R
0
is the corrosion rate o themetal without inhibitor present, and R
i
is the corrosion rate o the metalwith inhibitor present. R
0
and R
i
can be determined by any o the standardcorrosion testing techniques. The corrosion rate can be measured in anyunit, such as weight loss (mpy), as long as the units are consistent across both tests.
10.2 Classiication o Inhibitors
Inhibitors can be classied in several ways, as previously indicated. Inhibitorswill be classied and discussed under the ollowing headings:1. Passivation inhibitors2. Organic inhibitors3. Precipitation inhibitors4. Vapor phase inhibitors
10.2.1 Pssvton inhtos
10.2.1.1 Mechanism of Passivation
Passivators in contact with a metal surace act as depolarizers initiatinghigh current densities at residual anodic areas that exceed i
(critical)
or pas-sivation. The only ions that can serve as passivators are those that have bothan oxidizing capacity in the thermodynamic sense (noble oxidation-reduc-tion potential) and that are readily reduced (shallow cathodic polarizationcurve (Figure 10.1). Hence, SO
4
or ClO
4
ions are not passivators or iron because they are not readily reduced, nor are NO
3 
ions compared to NO
2
, because nitrates are reduced less rapidly than are nitrites, the ormer reduc-ing too sluggishly to achieve the required high value o i
(critical)
.
 
The extent ochemical reduction on initial contact o a passivator with metal, accordingto this viewpoint, must be at least chemically equivalent to the amount opassive lm ormed as a result o such reduction. For the passive lm oniron, this is on the order o 0.01 coulomb/cm
2
o apparent surace. The totalequivalents corresponding to chemical reduction o chromates is ound to be o this order and is probably also the same or other passivators actingon iron. The amount o chromate reduced in the passivation process derives
© 2010 by Taylor and Francis Group, LLC

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