Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

Lecture 15
Prevention Strategies - Inhibitors and Surface Engineering
Keyword: Inhibitors, Passivators, Surface Engineering.

Inhibitors are chemicals which adsorb on metal surfaces. A corrosion inhibitor can
act in several ways:
Arrest or slow down anodic or cathodic reactions by blocking active sites on
metal surfaces.
Eg: Amines, thiourea, benzoate, antimony trichloride.
Promote surface passivation (active-passive metals and alloys).
Eg: Chromate, nitrite, red lead, calcium plumbate.
Formation of a surface layer blocking exposure of the bare metal to corrosive
medium. Eg: Phosphate, silicate, bicarbonate, hexametaphosphate.
Hexylamines or sodium benzoate radiator fluids in cooling circuits of engines.
Antimony trichloride De-scaling of steels in sulfuric acid.
Volatile (vapour phase) inhibitors (Amines) -Metal (steel) articles or equipment
during transport.
A classification of inhibitors based on their functionality is given below:
Passivating inhibitors
Cathodic inhibitors
Organic inhibitors
Precipitation inhibitors
Volatile corrosion inhibitors.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

Two types of passivating inhibitors.

Oxidizing anions Chromate, nitrite and nitrate that can passivate steel in
absence of oxygen.
Nonoxidizing ions phosphate, tungstate and molybdate that require oxygen
to passivate steel.
Inhibitors to be used in just the required concentration.
Higher concentration Over protection? or corrosion?
Lower concentration do not protect!
Inhibitors generally used in quantities less than 0.1% by weight.
Cathodic inhibitors:

Slow down cathodic reaction or selectively precipitate on cathodic areas.

Act as poisons, precipitates or as oxygen scavenger.
Compounds of As and Sb make combination of and discharge of hydrogen
difficult. Ions of Ca, Zn or Mg precipitate as oxides to form protective layers.
Oxygen scavengers prevent cathodic depolarization due to O2 (Na2 SO3).
Organic inhibitors Both anodic and cathodic effects.
Adsorption depending on charge of inhibitor.
Precipitation inhibitors: Film forming compounds block anodic and
cathodic sites. (E.g.: calcium, magnesium precipitation of silicates and
phosphates).

Vapour phase inhibitors used during transport in closed environment.

Morpholine, Hydrazine.
Vapor condenses and hydrolyzed by moisture to liberate protective ions.
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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

Corrosion inhibitors used in:

Chemicals processing
Petroleum refining
Cement and concrete
Pulp and paper
Oil and gas production
Metals
Utilities
Effect of addition of cathodic, anodic and mixed inhibitors on the corrosion rate of a
metal is illustrated in Fig. 15.1, 15.2 and 15.3. Influence of the inhibitors on the
anodic and cathode reactions, respectively could be seen. As can be seen, cathodic
inhibitors selectively influence the cathodic polarization, bringing down corrosion
rates. Similarly, anodic inhibitors specifically interfere with the anodic oxidation
reactions, decreasing icorr values. On the otherhand, mixed inhibitors influence both
anodic and cathodic reaction rates.

Fig 15.1 Role of cathodic inhibitor on corrosion rate of a metal.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

Fig 15.2 Role of anodic inhibitors on the corrosion rate of a metal

Mixed inhibitors (amines, selenides)

Fig 15.3 Role of mixed inhibitors on the corrosion rate of a metal

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

General inhibitors used in some industrial operations are listed in Table 15.1
Table 15.1 Industrial uses of inhibitors

Recirculation cooling water -

Silicates, chromate, nitrate, polyphosphates

Automotives coolants

Benzoate, borax, phosphate, nitrite

Mercaptobenzothiazole.

Steam condensates

Ammonia, amines (benzylcyclohexamine).

Octadecylamine (long chain aliphatic)

Sea Water and brines

Chromates, nitrite etc.

Pickling acids

Phenylthiourea, mercaptans, quinoline,

Pyridine, various long chain amines.

Oil refining and production -

Primary, amido-, quaternary amines

Imidazoline.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

Surface modification approaches for corrosion protection of steels.

Modification of surface region of engineering alloys through diffusion of different
elements and formation of a layer having desirable chemical composition,
microstructure and properties.
Thermo-chemical treatments Physical and chemical
Vapour deposition.
Coatings by plasma spraying
Electrospark deposition
Ion implantation
Sputter deposition of selected elements and compounds.
Surface layers developed by such materials, can be classified as:
Overlay coatings
Diffusion coatings
Recast layers
Thermo-chemical treatment for surface modification of steels nonmetals or metals
introduced into metal surfaces by thermo - diffusion after chemical reaction and
adsorption.
Caburizing, nitriding, carbonitriding, boronizing, chromising and aluminizing are
some popular methods. Other examples include surface modification by Electrical
Discharge Machining to remove surface material-Melted zones are transformed to
recast layers with specific structures.
Surface modification by electrical discharge treatment in electrolyte where a high
energy thermal process is involved at surfaces leading to melting, vaporization,
activation and alloying in an electrolyte.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 15: Prevention Strategies Inhibitors and Surface Engineering

NPTEL Web Course

Laser surface engineering for corrosion protection

a) Microstructure modification
Laser surface melting
Laser shock peening.
b) Chemical composition and microstructure modification.
Laser cladding
Laser surface alloying
Pulsed laser deposition
Laser based thermal spray
Types of surface engineering
Coatings sputtering, CVD, spin coat,
Passivation
Chemical treatment
Plasma treatment
Surface derivitization
Laser treatment
Plasma deposition
Polymerized coatings
Fluropolymers and siloxanes
Scratch - resistant coats
Paint adhesion
Electropolishing 316 stainless steel, Nitinol (oxide enrichment).
Conversion coatings
Oxidation, passivation
Chromate, phosphate, black oxide
Pore surface engineering.
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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore