Corrosion Control Measures

Barrier Protection
Provided by a protective coating
that act as a barrier between metal
substrate and corrosive environment

Cathodic Protection
Employs protecting one metal by
connecting it to another metal

Use of Corrosion Resistant Materials

Materials inherently resistant to
corrosion in certain environments
Use of Corrosion Inhibitors
Using organic compounds to inhibit
the corrosion.

2
 Corrosion Inhibitors
The practice of corrosion prevention by adding substances which can significantly retard corrosion when added in small
amounts is called corrosion inhibition.
Corrosion inhibitors are selected on the basis of solubility or dispersibility in the fluids which are to be inhibited.
The total consumption of inhibitors in USA alone costs over one billion dollars annually.

Application of Corrosion Inhibitors

Cooling Water Systems: The cooling water may be salt water (35 000
ppm TDS), brackish water (3000-5000 ppm) or fresh water (<300ppm
TDS). Inhibitor treatment is required for heat exchanger and
distribution lines.
Boilers Systems: Scales and deposits may also be formed by dissolved
and suspended solids. Excessive alkalinity in boilers can lead to caustic
cracking.
Petroleum Industry: corrosion occurs in petroleum industries due to
two phase medium of hydrocarbon/oil and water. Elimination of water
needed to reduce the corrosion rate. oil soluble-water insoluble types
or oil soluble-water dispersible compounds.
Portable water systems: Ca(HCCO3)2 and polyphosphate
Packaging Industry: VPI
Engine Coolants: NaCr04, NaN02, mercapta benzothiazole.,
 Selection and Classification of Inhibitors
1.The magnitude of suppression of uniform and localized corrosion.
2.Long range effectiveness.
3.Effect of temperature and concentration on the performance of inhibitors.
4.Effect of inhibitor on heat transfer characteristics.
5. Toxicity and pollution problems.
6. Economically and technically competitive with other considered inhibitors
 Inorganic-Anodic Inhibitors
Anodic/Passivation Inhibitors:
- act by a reducing anodic reaction, that is, blocks the anode reaction and supports the natural
reaction of passivation metal surface, also, due to the forming a film adsorbed on the metal.
- In general, the inhibitors react with the corrosion product, initially formed, resulting in a
cohesive and insoluble film on the metal surface.
- The anodic inhibitors reacts with metallic ions Men+ produced on the anode, forming generally, insoluble hydroxides which are
deposited on the metal surface as insoluble film and impermeable to metallic ion. From the hydrolysis of inhibitors results in OH-
- For the anodic inhibitors effect, it is very important that the inhibitor concentrations should be high enough in the solution. The
inappropriate amount of the inhibitors affects the formation of film protection, because it will not cover the metal completely,
leaving sites of the metal exposed, thus causing a localized corrosion.
- Some examples of anodic inorganic inhibitors are nitrates, molybdates,
sodium chromates, phosphates, hydroxides and silicates.
 Inorganic-Cathodic Inhibitors
- Cathodic corrosion inhibitors prevent the occurrence of the cathodic reaction of the metal.
- These inhibitors have metal ions able to produce a cathodic reaction due to alkalinity,
thus producing insoluble compounds that precipitate selectively on cathodic sites.
- Deposit over the metal a compact and adherent film, restricting the diffusion of
reducible species in these areas.
- When the cathodic reaction is affected the corrosion potential is shifted to more negative values.
- The cathodic inhibitors form a barrier of insoluble precipitates over the metal, covering it. Thus,
restricts the metal contact with the environment, even if it is completely immersed, preventing
the occurrence of the corrosion reaction. Due to this, the cathodic inhibitor is independent of
concentration, thus, they are considerably more secure than anodic inhibitor.
- the ions of the magnesium, zinc, and nickel that react with the hydroxyl (OH-)
of the water forming the insoluble hydroxides as (Mg(OH)2, Zn(OH)2, Ni(OH)2)
- polyphosphates, phosphates, tannins, lignins
 Organic Inhibitors
Organic compounds used as inhibitors,, they act as cathodic, anodic or together,
as cathodic and anodic inhibitors, act through a process of surface adsorption, designated as a film- forming.
These inhibitors build up a protective hydrophobic film adsorbed molecules on the metal surface, which provides
a barrier to the dissolution of the metal in the electrolyte.
The efficiency of an organic inhibitor depends of the:
• chemical structure, like the size of the organic molecule;
• aromaticity and/or conjugated bonding, as the carbon chain length;
type and number of bonding atoms or groups in the molecule (either π or σ);
• nature and the charges of the metal surface of adsorption mode like bonding
strength to metal substrate;
• ability for a layer to become compact or cross-linked,
• capability to form a complex with the atom as a solid within the metal lattice;
• type of the electrolyte solution like adequate solubility in the environment.
 Vapor Phase Inhibitors
Vapor phase inhibitors are organic inhibitors which readily forms protective layers on the surface of the metal.
Vapor phase inhibitors are used in the protection of machineries, sophicated equipments etc.., e.g. dicyclohexyl ammonium nitrate,
cyclohexylamine, and hexamethylene-amine.

Synergetic Inhibitors:

- The blends which are produced by mixing of multi-inhibitors are called

synergistic inhibitors.
- Examples include chromate-phosphates, polyphosphate-silicate,
zinc-tannins, zinc-phosphates.
.
 Scavengers
- Chemicals which eliminate oxygen from the closed systems are called scavenger.
- Examples: . Ammonium sulfite (NH4)2S03, and hydrazine (N2H4)
- Oxygen scavengers remove oxygen as shown below:
The following are new oxygen scavengers which are being
promoted in the market:
• Carbohydrazide
• Diethyel hydroxlamine (DEHA)
• Ammonium isocascorbate
• Hydroquinone

Neutralizers:
reduce corrosion by reducing the concentration of H+ ions in
solution.
The most commonly used neutralizing inhibitors are morpholine,
cyclohexylamine and diethylamine-ethanol.
 Important Inhibitors
Scale Inhibitors:
 Scale – Precipitates/deposits formed on metallic surface due to the accumulation of salt from sea water.
 Calcium carbonate and calcium sulfate are the major types of scales
 A large number of compounds are known to inhibit scale formation by removing the scale forming ions and
suspended solids from the water.
 sodium hexa meta phosphate and sodium tripoly phosphate, amino trimethylene phosphoric acid (ATMP) .

Rebar inhibitors:
 In steel reinforced concrete structure, corrosion attack is prevented by high alkaline environment in concentrate
(pH > 12.0) because of the development of a passive layer on steel surface under alkaline environment.
 This passive layer may, however, be destroyed due to ingress of chloride and carbon dioxide in certain environments
and serious corrosion is caused.
 Inhibitors, such as sodium tetraborate (Na2B2O7) and zinc borate (2ZnO3B203) have proved effective inhibitors.

Biocides:
 MIC – microbial influenced corrosion- corrosion attack due to the attachment of micro organics from sea water.
 Two types of chemicals are employed to control bacterial growth: bacteriostats or bacteriocides.
 Bacteriostats put the bacteria in a dormantstate without killing bacteria, whereas bactericides kill bacteria. Both
types are jointly called biocides.
 Examples - Cocoamine acetate, Dialkyl-benzyl ammonium chloride, Acrolein Chlorine dioxide
 Inhibitors Application Techniques

Continuous Inhibitor Injection:

 In the continuous injection method, a constant supply of chemicals is maintained at a controlled rate.
 Used in municipal water supplies, cooling towers and oil wells, to minimize scaling and corrosion problems.
 Normally the inhibitor is injected into the system using driven chemical pump at the point of turbulence to achieve
uniform mixing.
Batch Treatment:
 This is a periodic treatment in which a large quantity of chemicals is used for an extended period of time. Batch
treatment is also called slug treatment.
 It is commonly used to treat flowing oil wells. The inhibitor is displaced to the bottom of the tubing with the fluids in
the oil well. The well is closed for a specific period before operation.
 The batch is used mainly to treat water with biocides and not to supply inhibitors or scavengers.
Squeeze Treatment:
 Continuous treatment of oil wells by inhibitors is achieved by this method.
 The inhibitor is absorbed by the formation. It slowly escapes from the formation over a period of time to
inhibit the corrosive fluids.
 A continuous slow release of the inhibitor from this producing formation into the corrosive fluids is the key to the
success of this method.
 Protective Coatings
 An important method of protecting a metal from corrosion is to apply
a protecting coatings function as a physical barrier between the
atmosphere and the coated surface.
 The total amount of paint sold annually amounts to billions of gallons.
 U.S. demand for paint and coatings is forecast to grow 3.8 percent annually to
1.4 billion gallons in 2019, valued at $31.5 billion.

Coatings must have the following characteristics for good corrosion resistance:
 High degree of adhesion to the substrate.
 Minimum discontinuity in coating (porosity).
 High resistance to the flow of electrons.
 Sufficient thickness (the greater the thickness, the more the resistance).
 Low diffusion rate for ions such as Cl- and for H20.
 Corrosion Protection Mechanism

Corrosion protection by coatings can be achieved by one of the following mechanisms:

 A barrier coating that prevents the corrosive environment from reaching the
base metal (thick lining).
 A sacrificial metal coating that corrodes while giving cathodic protection to the
base metal (galvanizing).
 A noble metal coating that ensures that the base metal is in the passive state.
 An inhibitor coating that slows electrode reactions.
 An electrically resistive coating that slows down electrochemical corrosion
reactions (organic coating).
 Classification of Coatings

Hot-dip galvanizing
Electroplating
Electroless plating
Anodizing
Thermal spraying
Cladding
Diffusion coating Metallic

Paints
Protective Varnishes
coatings lacquers
Ceramics Epoxy
Enamels Silane coatings
Conversion coatings Inorganic Organic
 Requirements for Good Coatings
 Chemical resistance
 Low moisture permeability
 Good adhesion
 Flexibility (expand and contract with the metal substrate)
 Good impact and abrasion resistance
 Ease of applications
 Durability
 Low cost, Hence, no single coat can provide all needed properties
 For example:
 Coats for underground structures: resistance to abrasion
 Coats for atmospheric corrosion: resistance to UV
 Coats for marine environments: resistance to high humidity and Cl-
 Coats to industrial environments: resistance to high temp, high acidity
 We must use multiple coats to satisfy these requirements.
 Paint Coating Systems
One of the most common ways of preventing corrosion of metallic structures is to apply organic
coatings. A typical coating system consists of a primer, an intermediate coat, and one, or more,
topcoats.
Primer Coat:
Strong adhesion to substrate
• Resistant to Ion penetration Good adhesion to intermediate coat
Top Coat • Alkali Resistant 50 m
Resist chemical attack
• Insulator Resist water permeability
•p Low moisture and Carries corrosion inhibitor
Intermediate 100 m
Intermediate Coat:
Coat vapor transfer rate To reduce rate of moisture permeability
To increase chemical resistance
• Adheres to substrate 20-50 m To Increase resistance to electricity and
Primer • Resists corrosion impact, abrasion
Top Coat:
To provide durability
Metal Surface To provide color, gloss, and texture
Usually more dense but less thick than the
intermediate.
 Components of Paint Coatings

An organic paint consists of a liquid part known as a vehicle and

a solid part.
The vehicle part consists of:
 A binder or a resin (non-volatiles, it does not evaporate after
drying)
 A Solvent (volatiles)
 Liquid additives
The solid part consists of
 Powdery particles or pigments
 Solid additives
 Components of Paint Coatings
1. Pigment:
Pigment is a coloring substance, which is the main constituent of paint.
The pigment should have the following characteristics
a. It should be opaque
b. It should be non-toxic and chemically inert.
c. It should easily mix with film
d. It should be cheap.
Commonly used pigments:
a. – Titanium oxide, zinc oxide
b. Black pigment - Carbon black
c. Red pigment - Red lead, Ferric oxide
d. Blue pigment – Prussian blue, ultra marine blue
e. Green pigment – Chromium oxide, chrome green
f. Yellow pigment – Chrome yellow, zinc chromate.
Functions:
a. It gives desired color
b. It protects the paint film from ultra violet rays of sun.
c. It provides strength to the film
d. Provide capacity to paint
e. Provide resistance to paint film against abrasion, moisture etc..,
 Components of Paint Coatings

2. Drying oil or vehicle:

The drying oil is the film forming material of a paint. These are high molecular
weight fatty acids present in vegetable and animals oils e.g. Linseed oil, castor oil, fish oil.
Functions:
a) It gives better adhesion to the surface.
b) It is the main film forming constituents.
c) It imparts high durability, water repellency and toughness to the film.
d) It forms the protective film by oxidation.

3. Thinners:
Thinners dissolve the oil and pigments and produce a homogeneous mixture. They reduce the
viscosity of the paint.
e.g. Turpentine, spirit, kerosene.
Functions:
a. It dissolves the constituents of paint
b. It reduce the viscosity and helps in drying
c. It increases the penetration power of the vehicle.
 Components of Paint Coatings

4.Driers
Driers accelerate the process of drying of vehicles through oxidation,
polymerization and condensation. These are oxygen carrier catalyst.
e.g. Compounds of metals like Co, Mn, Pb dissolved in linseed oil
Cobalt substances - Surface driers
Lead substances - bottom driers
Manganese substance - thorough driers

Functions:
It improves the drying quantity of the oil film.
5. Fillers:
Fillers are used to increase the covering capacity of paint. The most commonly used fillers are gypsum, china clay,
silica, calcium carbonate, magnesium silicate etc..,
Function
a.It reduces the cost of the paint
b.It increases the durability of the paint
c. It helps to reduce the cracking of dry paint film
d.It serves to fill the voids in the film.
 Components of Paint Coatings

6.Plasticisers:
Plasticizers are used to provide elasticity to the paint film.
e.g. Tricresyl phosphate, triphenyl phosphate, tributyl phthalate.
Functions:
a. It gives elasticity to the paint film
b. It prevents cracking of the paint film

7.Antiskining agents:
Antiskining agents are chemicals added to paint to prevent skinning of the paint.
e.g.., poly hydroxyl phenols, guiacol
Function:
It prevents skinning of the paint
 Metallic Coatings - Electroplating
Electroplating is the process of producing thin metallic coating over base metal by passing a direct current through an solution
containing the soluble salt of the coating metal.
Theory of electroplating:
The base metal to be plated is made as the cathode whereas the anode is either made of the coating metal or an inert
material of good electrical conductivity like graphite. The solvable salt solution of coating metal is used as electrolyte.
For copper plating, copper sulphate is used as electrolyte. The metal to be coated is made as cathode and
copper electrode is made as anode.
The ionization reaction of the electrolyte is

CuSO4 === Cu2+ + SO42- ( oxidation)

On passing current, Cu2+ ions of the electrolyte get deposited at the cathode.
Reaction at anode:
Cu ---- Cu2+ + 2e-
Reaction at cathode:
Cu2+ + 2e- ----- Cu.
The concentration of Cu2+ in the electrolyte is kept minimum by adding sulphuric acid to
get uniform coating.
CuSO4 === Cu2+ + SO42-
H2SO4 == 2H+ + SO42-
 Metallic Coatings - Electroplating
The Concentration of Cu2+ ions in solution is depressed due to SO42- from sulphuric acid and controlled
deposition of Cu2+ ions on the surface of cathode takes place. The nature of the deposit depends on the following
factors.
(i) Metal surface
(ii) Concentration of the electrolyte
(iii) Current density
(iv) Temperature
(v) Presence of other additives.
And (vi) time.
Applications:
1.This is applied to improve physical appearance, hardness, surface properties and engineering effects.
2. Iron and steel are protected from corrosion using copper nickel chromium etc.,
3. Gold, silver, copper, nickel, chromium etc, are mostly used for decorative purposes. The base metal
used are steel, zinc, copper, aluminum etc..,
 Metallic Coatings – Electroless coating
 The process involves basically the reduction of metal ions to produce metal
atoms which are deposited on the cathode (work piece).
 Pure metals, such as copper, nickel, cobalt, gold, silver, etc. can be deposited
from their salts by the reduction process.
 The process is conducted in PTFE-lined stainless steel tank at 90°C. Uniform
deposits are obtained.
 The metal is formed by the reduction of nickel ions in solution by a reducing
agent.
 Sodium hypophosphite is used as a reducing agent.
 Conversion Coatings
Conversion coatings refer to the types of coating which on application convert the substrate into a compound with desirable
properties. The surface so prepared provides a high degree of adhesion and corrosion resistance.
Some important conversion coatings are described below.
Phosphate Coatings:
Phosphate conversion coatings are well-known and widely used for applications on steel, zinc and aluminum.
Phosphate coatings are of three types: (a) zinc phosphate, (b) iron phosphates and (c) manganese chromium phosphates.
Phosphate coatings are generally applied by immersion or spraying. The bath contains generally zinc phosphate in phosphoric
acid and an oxidizing agent, such as nitrate. The metallic work piece passes through the following stages.
A spray zinc phosphate process for steel and zinc is shown in Figure. The following is the process cycle:

(1) Alkaline cleaning with an alkali (3-8 g/l) at 82°C.

(2) Hot rinsing with water at ITC.
(3) Cold rinsing with water at 25°C.
(4) Acid pickling by H2S04 (15 wt%) at 60°C.
(5) Zinc phosphate bath at 25°C.
(6) Neutralization by NaNO2.
(7) Lubrication with soap at 66°C.

Phosphate coatings find application in

military equipment, cars, refrigerators,
washing machines, toys and steel strips for
painting
 Chromate Conversion Coatings
 used on Al,Zn and certain other metals.
 As a consequence of chemical attack on a metal when it is brought in contact with an aqueous solution of chromic acid,
chromium salts, hydrofluoric acid, salts, phosphoric acid or mineral acids.
 Chromate ions are known for their inhibition properties. If a chromate coating is to be deposited, the passivity on the
metal surface in solution must be broken down so that the coating is deposited on the metal surface.
 This is done by adding ions like chlorides and sulfates which break down the passivity.
 When the passive film is broken down by chloride ions, hydrogen is released which reduces the chromate ion to Cr2O3.CrO3.xH2O
 It is deposited on the metal surface. However, chromium is a health hazard.
 Chromate coatings are mostly applied on aluminum components,
particularly on aircraft components and on aluminum objects
 which are to be coated with paints.
They are beneficial in marine environments.
Chromium coatings provide an non-porous bond
for all paints.
 Anodized Coatings
Anodizing is the formation of a relatively thick coating and a coherent oxide film on the surface of a metal by making the metal
the anode in an electrolytic cell. The most common electrolytes used are chromic acid, sulfuric acid, phosphoric acid and
mixtures of theirs.
- Food packaging and processing industry as well as packaging of pharmaceutical products because of the high resistance of
these coatings to the food and pharmaceutical products.
- The corrosion resistance of anodized coatings can be further enhanced by sealing the pores of the coating and
incorporating inhibitors, such as dichromate in the sealing solution.
- An optimum resistance to corrosion is obtained if the coating is in the thickness range of 18-30 µm.

- Bright anodizing is a process in which aluminum is polished followed by the protection of

the shining aluminum surface with the deposition of a thin film of oxide. For bright anodizing a mixture of
phosphoric acid and nitric acid containing some acetic acid is used.
 Coatings Inspection and Testing

• Holiday: bare area in the coated

surface where there is a direct
contact between the environment
and the coated metal
• It is important to locate small
holidays and recoat
 Holiday Detection System

• Low voltage wet-sponge holiday detector Can detect holidays in non-

conductive coatings less than 20 mil thick (500 m)
• The holiday detector is connected to the metal substrate of the test piece using
a wetted sponge that conducts electricity. A low voltage is applied b/w the
detector and the metal.
• At holidays, a current will flow between the holiday and the detector. A beep
is sounds.
 Failures of Coatings

• Coating failure can be the result of many factors:

• Poor surface preparation
• Poor selection
• Poor application technique
• Unexpected changes in service environment
• Aging (weathering effects)

• Types of discontinuities in coating failure

• Holidays
• Pinholes: a hole in the coating penetrating all the way to the substrate
• Coating discontinuities usually appear at:
• Fabrication defects
• joints (welds, nuts, bolts, rivets)
• Hard to reach area during applications (corners)
• Sharp edges of the structure to be protected
 Common types of coating failure

• Blistering:
• appear as surface bubbles which are
filled by water vapor, air, or solvent
vapor.
• blisters may be
• at coating-substrate interface
• between adjacent coating layers
• Caused by the penetration of moisture
through the coating into areas of poor
adhesion.
• Incorrect selection of primer
 Common types of coating failure
• Cracking:
• appear as cracks
• caused by different degree in thermal expansion and
contraction between the coat and the metal.
• reduce corrosion protection
• Wrinkling:
• appear as ridges at the surface of the coat
• usually appear in thick coatings
• result from swelling of the surface
• Caused by difference in drying between the surface
and the body of the coat
• little effect on corrosion protection
• Flaking and Peeling
• Loss of paint due to loss of adhesion
• Caused by incorrect surface preparation or incorrect
primer primer/topcoat