Inhibitors

Sources:
1. McCafferty, Introduction to Corrosion Science
2. R.W. Revie, H.H. Uhlig, Corrosion & Corrosion Control
 Protection discussed so far
Different methods of corrosion protection
Changing the electrode potential
CP, AP
Changing the nature of metal surface-
coatings
Sacrificial
Noble
Materials selection
More corrosion resistant alloy
Limited by
Need for a desirable property, e.g. mechanical strength
Cost
 Introduction
Corrosion inhibitor
a chemical substance added to the environment (solution),
usually in small amounts to increase the corrosion resistance
Modify electrochemical rxns on the solution side of the
metal/solution interface
In uniform corrosion i0 i
%I 100
%I = percent inhibition i0
i0 = corrosion rate without inhibitor
i = inhibited value
In pitting
it raises Epit, pit growth rate , pit density
In crevice corrosion
Rate of propagation of crevice corrosion
In SCC
Time to (crack initiation, crack growth) failure
 Characteristics
An inhibitor forms a protective coating in situ
by reaction of the solution with the corroding
surface
Compound in small quantities reduces the
corrosivity of environ
Inhibition is reversible
A minimum concentration must be present to
maintain the inhibiting film
Good circulation & absence of stagnant areas-
necessary
 Characteristics
Effectiveness decreases with increase in
solution corrosivity, concentration, & T
Many inhibiting compounds are toxic
Many are effective for more than one type of
alloy
An inhibitor for one metal may be a corrosive
for others
Often mixtures of inhibitors are used-
synergism
 Applications
Recirculating systems greatest use
Once-through systems- uneconomical
3 types of environ- greatest use
Natural, supply water, industrial cooling waters in
nearly neutral range (pH 5 to 9)
Acid solutions for pickling to remove mill-scale/
rust
Primary & secondary production of crude oil &
subsequent refining processes
 Common industrial inhibitors
Environment Inhibitors
Water
Potable water Silicates, polyphosphates, zinc salts, CaCO3 deposition
Recirculating Chromate, nitrate at 300-500 ppm, calcium polyphospahte at 15-
cooling water 37 ppm, silicates at 20-40 ppm
Automotive Nitrite, benzoate, borax, phosphate, benzotriozole
coolants
Acid pickling
solutions:
Sulphuric acid Phenylthiourea, di-ortho-tolyl-thiourea, sulphides, mercaptans,
0.003-0.01 %
HCl Pyridine, quinoline, amines, phenylthiourea, dibenzylsulphoxides
Oil Production
Primary & Fatty imidazolines, various amines, alkyl pyridines
secondary
Refining Imidazoline & derivatives
 Types of Inhibitors
Adsorption inhibitors
Film-forming inhibitors

Another classification based on which partial rxn

is inhibited
Anodic inhibitors- chromates
Cathodic inhibitors- phosphates
Mixed inhibitors- organic compounds
 Adsorption Inhibitors
Form a chemisorptive bond with metal surface & impede electrochem.
dissolution rxn
e.g. Most organic inhibitors
Aliphatic
organic
amine

Metal

Array of hydrophobic hydrocarbon

tails provide additional protection!
-Keep aggressive ions (eg. Cl) and
water molecule away
 Chemisorption type inhibitors usually contain
N, S, O atoms
Chemisorption from donation of e from these
atoms to the metal surface
Order of inhibition is
Se > S > N > O
Increasing electronegativity S is a better e donor than N

Increasing inhibition

N compounds have more solubility

 Effect of adsorption inhibitor concentration
Inhibition efficiency increases
with [dissolved inhibitor]

Fe in 6M HCl with diamine inhibitor

concentration
 Organic inhibitor
Effectiveness depends on 3 factors
Electron donor ability of the molecule
Size of the molecule (larger the better)
Its solubility
Less soluble tends
to adsorb more
 Water molecules play a role in corrosion rxn
They need to be adsorbed on the surface for
charge transfer to occur & aid in release of metal
atom
replacement of water molecule by an organic
molecule alters the kinetics of anodic
dissolution rxn.
Electrical double layer (edl)
Plays a role in adsorption
Organic molecules must enter the
edl to get adsorbed
This intrusion changes its
composition & structure
Long chain molecules increase the
thickness of edl & decreases the
effective dielectric constant

Cdl
l
Capacitance decreases
Decrease in Cdl (from EIS) confirms
that the inhibitor is adsorbed
 Film Forming Inhibitors
2 types
Passivating inhibitors
Promote formation of a passive film
Oxidizing inhibitors
Chromates adsorb on iron/steel
Chromate ion is reduced to Cr2O3 or Cr(OH)3 on surface to
give mixed oxides of Fe/Cr
Non-oxidizing passivators
Benzoates, phosphates, azelates
Precipitation inhibitors
Precipitation rxn between corroding metal cations & the
inhibitor anions
Solubility product for the salt formed- exceeded
barrier film forms on surface
Eg. Phosphates, silicates
 Passivating inhibitors
Passivators in contact
effect of passivator concentration on
with a metal surface
corrosion of Fe
initiate high current
densities that exceed ic
for passivation at anodic
areas
An oxidizing
substance that Passivating ions should
reduces -have oxidizing capacity in the
sluggishly does
thermodynamic sense (noble
not induce
passivity redox potential)
-be readily reduced (flatter
cathodic polarization curve)
 extent of chemical reduction on initial contact of
a passivator with metal must be at least
chemically equivalent to the amount of passive
film formed
For the passive film on iron, this is ~ 0.01 C/cm2
of apparent surface area
Chromates (& nitrites) satisfy this requirement

Cr3+ remains on the surface in adsorbed form or as

hydrated Cr2O3
Reduction of passivator continues at a low rate
after passivity is achieved
 For optimum inhibition, [passivator] > certain critical
value (for CrO4 2, NO2, MoO4 2, or WO4 2 is ~ 10 3 to
10 4 M)
Low [passivator] correspond to more active values of its
redox potential, and the cathodic polarization curve
intersects the anodic curve in the active region instead of
in the passive region alone
[Cl- ] and elevated T increase ic as well as ipassive
critical [passivator] is increased.
Influence of stagnancy:
if the passivator concentration falls below the critical value
in stagnant areas (e.g., at threads of a pipe or in crevices)
Stagnant areas active pot
Other inhibited areas- noble pot
localized corrosion (eg. Pitting) at the active areas.
Stirring/rapid flow, avoiding crevices helps
 Classification depending on mechanism of inhibiting
action- Anodic inhibitors

Ecorr Anodic inhibitor eg.

Ecorr chromate, phosphate,
molybdate, vanadate,
E benzoate

i icorr icorr

Reduce anode area by acting on anodic sites, thus polarize

the anodic rxn
Ecorr is displaced to nobler values
icorr is decreased
These are mainly oxidizing inorganic inhibitors
Often form protective film on anode
 Anodic inhibitors
Anodic inhibitors are anions which that migrate to
anode surfaces
Oxidizing type (chromates, nitrites) - may passivate
anode in presence of O (passivators)
Usually produce oxide films
Compact, thick, pore-free film protection
Filming type (non-oxidizing anions) produce isolating
films
e.g. Alkalies, molybdates, phosphates, benzoates
Rxn between dissolving metal and the inhibitor
precipitates insoluble products on anode
Anodic inhibitors: dangerous inhibitors
Low concentration- incomplete coverage of film
=> small anode:cathode disastrous e.g. Pitting in Cl
 Cathodic Inhibitors
E
e.g. salts of Zn, Mg, Ca

Ecorr

Ecorr

i icorr icorr

Polarize the cathodic rxn by reducing the cathode area

Ecorr is displaced to active values
icorr is reduced
Unlike anodic inhibitors, cathodic inhibitors are safe when the amount is
insufficient
No risk of pitting attack
Less efficient than anodic inhibitors
Not much used in neutral & alkaline media
 Cathodic inhibitors
3 catagories
1. Those that absorb oxygen (deaerators/
scavengers)
2. Those that reduce the area of cathode
3. Those that increase the hydrogen overvoltage of
the cathodic process ( H2 evolution poison)
//Hydrogen overvoltage is the potential difference that can be
found between an electrode and a reversible hydrogen
electrode within a single solution//
1. Those that absorb oxygen (deaerators/ scavengers)
Na sulphite 2 Na2 SO3 O2 2 Na2 SO4
Hydrazine N 2 H 4 O2 N 2 2 H 2O
Effective in closed systems where oxygen
reduction is the controlling cathodic rxn
Not effective in acidic solutions 2H 2e H 2
These inhibitors can be stimulators if the metal is
in a passive state before adding inhibitor
Loss of oxygen can activate the stainless steel by
addition of sulphite
In boiler water corrosion control, hydrazine is
preferred
water hardness is not increased
Scale formation in presence of free Ca+ is minimized
2. Those that reduce the area of cathode (filming type)
Ca(HCO3)2, ZnSO4, etc
Cations migrate towards cathode surface & react
with cathodically formed alkali to produce
insoluble films/layers slowing the cathodic rxn

Ca 2 2 HCO3 OH CaCO3 HCO3 H 2O
from hard water alkali cathodic film
Zn 2 OH Zn (OH ) 2
cathodic inhibitor alkali cathodic film
Experience- hard waters are less corrosive to Fe!
3. Those that increase the hydrogen overvoltage of the
cathodic process ( H2 evolution poison)
Arsenic, bismuth, antimony ions
Poison (retard) the H2 evolution rxn
Electrically non-conducting coatings of As, Bi, Sb
on cathode by cathodic rxn
Overpotential for H+ reduction is considerably
increased
Ineffective in media where other reduction rxns
are dominating eg. O2 reduction
 Mixed Inhibitors

Mixed inhibitors (e.g. agar agar, gelatin,

Ecorr organic inhibitors containing N and/or S)
Ecorr
E

icorr i icorr

Influence both anodic & cathodic rxns

Ecorr change is smaller and direction is decided by relative
size of anodic & cathodic effects
Generally, adsorption type
If influence of inhibitor on anodic rxn is dominant =>
dangerous type
 Combination of inhibitors
Economical
Individual inhibitors are effective only on certain
metals
Protection of multi-metal systems require more than
one
Separate advantages for each type
e.g. some good in aerated others in acidic etc
Synergism
Patented information
Combinations of polyphosphates, chromates, zinc
salts, organic materials
 Slushing Compounds
Non-drying organic coatings readily removable
with available solvents
Temporary corrosion-preventive coatings
Oils, greases, waxes with small amounts of organic
additives (a long chain molecule having a polar group
at one end- aryl amines, quinones, Zn naphthanates,
etc)
Mechanism
Adsorption on surface in neutral pH range
Few molecular layers thick film
Coating through which water is difficult to penetrate
 Properties desired of slushing compounds
Prevent corrosion for the desired period
Should not affect the metal surface much
Relatively inert & not get affected by oxidation
Ease of application and removal without damaging
the metal surface
 Vapour Phase Inhibitors
High vapour pressure substances
Sublimation & condensation
spread and get adsorbed on metallic surfaces
protection from atmospheric corrosion
Can not be used in open atmosphere
Place in the vicinity of the metal
inside the packages, as a coating on inside of wrapping material,
interior of machinery as powder during shipping or storage
Useful when slushing compounds are unsuitable
Immediate use of protected article without need for cleaning
eg. oil, grease need removal
Reach every nook & corner
Complicated assemblies
Labor & time is saved
No application on surface, no removal before use of protected
article
 Some disadvantages
Accelerate corrosion of some non-ferrous metals
Discolor some plastics
Effective sealing of a package is required
Protective action:
adsorbed film formation on the metal surface that
provides protection against water or oxygen, or
both retarding anodic or cathodic rxn
 dicyclohexylammonium nitrite-
most effective
white, crystalline, almost odorless, and relatively nontoxic
vapor pressure of 0.0001 mm Hg at 21C
1 g saturates about 550 m3 of air
inhibits corrosion of steel over a period of years
Corrosion of Zn, Mg, and Cd is accelerated
Cyclohexylamine carbonate
reduce corrosion of steel, Al, solder, and Zn, but it has no
inhibiting effect on Cd. It increases corrosion of copper, brass,
and magnesium.
Use:
Protecting critical machine parts (e.g., ball bearings or other
manufactured steel articles) temporarily during shipping or
storage