CHAPTER 1

Introduction to Corrosion and its Prevention

A brief introduction to corrosion, its manifestations, consequences and methods

generally used to control corrosion are discussed in this chapter. Both the direct and

indirect consequences of corrosion are discussed. The various methods to control

corrosion such as material selection, design, cathodic and anodic protection,

inhibitors, and coatings are described in this chapter. Corrosion of iron and low alloy

steels particularly in coastal and humid atmosphere is described with details of

mechanism of uniform and localized corrosion. The necessity to protect them by

surface treatment and coatings, and the role of inhibitors and coatings for this purpose

is addressed. The main focus in this chapter is to highlight the necessity to develop

surface treatments and coatings for corrosion protection of structural components.

1.1 Corrosion and its Manifestations

The very common meaning of corrosion to the great majority of the people is rust. The

word “Rust” is more specifically reserved for iron, whereas corrosion is commonly

defined as the deterioration of a substance (usually a metal) or its properties because of

a reaction with its environment. The terms corrosion and rust are almost synonymous

since iron and its alloys are the most commonly used material by mankind and

corrosion of iron must have been the one of the first serious corrosion problems

affected humans [1]. Corrosion is a naturally occurring phenomenon and just like all

natural processes, corrosion of materials is spontaneous and it drives the materials to its

lowest possible energy states. Most of the metals and alloys have a natural tendency to

combine with water and oxygen present in its environment and return to its most stable

state. Iron and steel quite often interact with their environment return to their native and

stable oxide states. Similar to any natural disasters such as earthquakes or severe

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weather changes, corrosion results in dangerous and expensive damage to everything

from automobiles, home appliances, drinking water systems, gas and petroleum

pipelines, bridges and buildings [2].

Corrosion takes place in several different ways and it can be classified based on one of

the three factors:

 Nature of the corrodent: This classification is based on “wet” or “dry” conditions in

which corrosion occurs. The presence of moisture is essential for wet corrosion and

dry corrosion usually involves reaction with gases at high temperatures.

 Mechanism of corrosion: Corrosion can occur either electrochemically or with

direct chemical reactions.

 Appearance of the corroded metal: Corrosion can be either uniform or localized.

The metal corrodes at the same rate over the entire surface for the former and only

small areas are affected in localized corrosion.

Classification by appearance is manifested by the morphology of the corrosion attack

and this can be visualized either by naked eye or magnification [2]. The schematic

given in Figure 1.1 illustrates some of the most common forms of corrosion.

Figure 1.1: Schematics of the common forms of corrosion [2]

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Based on the appearance of corroded metal, eight forms of wet corrosion can be

identified. These are:

 Uniform or general corrosion

 Pitting corrosion

 Crevice corrosion, including corrosion under tubercles or deposits, filiform

corrosion, and poultice corrosion

 Galvanic or two metal corrosion

 Erosion-corrosion, including capitation corrosion and fretting corrosion

 Intergranular corrosion, including sensitization and exfoliation

 Environmentally assisted cracking, including stress corrosion cracking, corrosion

fatigue and hydrogen damage

 Selective leaching or parting

Even though the eight forms of corrosion are unique, all of them are more or less

interrelated. Furthermore, the localized corrosion attack can be classified as

microscopic and macroscopic forms. Figure 1.2 depicts microscopic and macroscopic

forms of localized corrosion.

Figure 1.2: Macroscopic and microscopic forms of localized corrosion [2]

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Macroscopic corrosion affects most of the areas of the metal and which can be

observed with the help of naked eye or can be viewed by with the aid of low

magnifying power devices. However, microscopic form of corrosion can cause

considerable damage to materials before even noticed by naked eye.

1.2 Consequences of Corrosion

Corrosion is having both direct and indirect effects on our daily life. It can affect the

useful life of various materials we possess. We can easily recognize corrosion on

automobile parts, grills, metal furniture and other household tools made up of metals

and alloys. Corrosion can cause far more serious consequences to human lives when a

bridge is collapsed due to the corrosion of the steel reinforcing bar in concrete or the

collapse of electric towers and damage to buildings. The major cost and consequences

of corrosion can be represented in three ways [1-3]:

 It is extremely expensive financially

 It is extremely wasteful of natural recourses

 It causes considerable inconveniences and injuries to human beings and sometimes

even loss of life.

Corrosion results in tremendous economic loss and it slow down the economic growth

of all countries. The annual cost of corrosion worldwide is estimated to be $ 2.2 trillion

[4]. National Association of Corrosion Engineers, NACE estimated that the direct cause

of corrosion in the US was $ 276 billion in 1998, approximately 3.1% of Gross

Domestic Product (GDP) [5]. However, by including the indirect losses of corrosion it

was estimated to exceed $1trillion [5]. Our country India looses a staggering amount of

Rs 2 lakh crore per year due to corrosion and related issues [6, 7].

The major economic and social consequences of corrosion are described here [1, 2, 8].

 Replacements of corroded equipments and materials

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 Aesthetic appearance of materials is very important since corroded surfaces are

unlikable to the eye. Hence, equipments and structures are required to paint to

improve its appearance to the observer.

 Shutdown of plants and equipments due to corrosion failure. Because of unexpected

corrosion failures, electrical, chemical, nuclear power plants are shut down.

 Contamination of products

 Loss of valuable products

 Inability to use otherwise desirable objects

 Damage of equipments due to corrosion failures

 Serious damage to the liability of products

 Safety and health of public, for example, sudden failure of plants can cause fire,

explosion, release of toxic gases and acids and other hazardous and flammable

materials

 Depletion of natural recourses, including metals and the fuels used to manufacture

them.

Corrosion is causing a huge amount of financial damage to economies, wasting a vast

amount of natural recourses and giving rise to a great deal of human sufferings.

1.3 Atmospheric Corrosion Behaviour of Iron and Low Alloy Steels

Atmospheric corrosion is the most visible form of corrosion processes. It is difficult to

provide a clear definition for atmospheric corrosion, since it lies in a region between

immersed corrosion and dry oxidation. Broadly, atmospheric corrosion can be defined

as the corrosion of materials exposed to air and its impurities, rather than immersed in a

liquid. The most widely studied corrosion process is the atmospheric corrosion or

rusting of iron and steels. Atmospheric corrosion of iron and steels is electrochemical in

nature in opposition to dry oxidation [9-11]. Atmospheric corrosion of metals generally

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results from surface wetting and it occurs in thin films or adsorbed layers of electrolyte

on the metal surface. Due to the thin film nature of atmospheric corrosion, the process

is very sensitive and easily influenced by factors such as temperature, relative humidity,

precipitation, air currents, orientation of the metal samples and airborne pollutants and

particulars [12]. The atmospheric rusting of iron and steels can be considered as wet

corrosion in the thin water film formed on the surface of iron and steel and its physical

and electrochemical mechanisms are quite complex [12,13].

The following scheme summarizes electrochemical process, which requires aqueous

conditions for the atmospheric rusting of iron and alloy steels.

Figure 1.3: Electrochemical process of atmospheric rusting

The equation in Figure 1.3 shows that atmospheric oxidizer (O2) in the presence of a

water layer oxidizes iron substrate and this leads to the formation of rust. In fact, the

formed rust layer is quite complex and contains several oxides and hydroxides of iron

as presented in Table 1.1[14]. The major parameter influencing the atmospheric

corrosion is the interaction between rust layer and electrolyte. An electrolyte layer is

formed on the surface of the metal due to the condensation of water. The time of

wetness depends on the relative humidity at a given temperature [9, 14]. There is a

direct relationship between the amount of relative humidity and thickness of the

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electrolyte formed on the metal surface. The variations in relative humidity and

temperature form wet-dry cycles on the surface of the metal [14].

Composition Name Crystal system

Fe3O4 Magnetite Cubic (spinel)

γ-Fe2O3 Maghemite Cubic (spinel)

α-FeOOH Goethite Orthorhombic

γ-FeOOH Lepidocrocite Orthorhombic

β-FeOOH Akaganeite Tetragonal

γ-Fe.OH.OH Reduced lepidocrocite Orthorhombic

Fe(OH)2 Ferrous hydroxide Hexagonal

Table 1.1: Oxides and hydroxides found in rust layers

The alternative wet-dry cycle results from the temperature fluctuations between day

and night is the most typical feature of atmospheric corrosion which makes drastic

changes in the mechanism of rusting in opposition to bulk aqueous corrosion [9,14-16].

According to earlier studies reported by Evans and Taylor and Stratmann, atmospheric

corrosion occurs in three stages [9-11, 17]. During the wetting stage, electrolyte is

building up on the surface of iron or iron based alloys and this leads to the anodic

dissolution of iron. In this first stage (wetting) of atmospheric corrosion, anodic

dissolution of iron occurs and it is balanced mainly by the reduction of ferric species

within the rust layer and the reduction of oxygen is very little. Even though oxygen is

readily available for reduction to balance the anodic dissolution of Fe, the rate of

oxygen reduction is very small due to the slow diffusion of oxygen through the thick

electrolyte layer on the top of iron surface. However, another oxidizer is available in

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the rust layer itself is γ-FeOOH. One of the proposed reduction reactions for γ-FeOOH

is as follows.

γ γ

Hence, during the wetting stage, rust layer itself is responsible for corrosion, i.e. the

anodic dissolution of Fe is balanced by the reduction of γ-FeOOH available within the

rust layer.

During the second stage (wet stage) of atmospheric corrosion, oxidation of Fe occurs

on the small metal area in contact with the electrolyte at the bottom of the pores and

oxygen reduction reaction takes place on the large cathodic area of γ-Fe.OH.OH. The

oxygen reduction reaction occurring at the cathodic area is as follows

After the wetting stage, adequate amount of γ-FeOOH is reduced and the reduction of

oxygen becomes the main cathodic reaction [18]. It is proposed that first atmospheric

oxygen is dissolved at the metal/electrolyte interface and then the dissolved oxygen

diffuses through the electrolyte and the pores of the rust layer [14].

During the drying stage, the thickness of the electrolyte layer decreases. Due to the

decrease in the thickness of the electrolyte layer, the reduction current is also

decreased. According to Nishikata et al., at the stage of drying, no more diffusion of

oxygen occurs and only oxygen salvation determines the reduction current [19]. Zhang

et al. explained that drying results in the decrease of anodic and cathodic area, which

would eventually stop the electrochemical reactions due to the scarcity of electrolyte

[20]. Another possible mechanism for the decrease of reduction current is related to the

phenomenon of passivation. Both the decrease in the electrolyte layer thickness and

increase of the concentration of species during the first stage of wet-dry cycle result in

the covering of the surface of the metal. This in due course decreases both the cathodic

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and anodic areas and hence the covering of small anodic area prevents further iron

dissolution. Thus, the blocking of the anodic sites and the diffusion of the dissolved

species limit the oxidation current. The anodic sites blocking process is occurring

according to the following equation.

At the end of the drying stage, the rust layer is polarized to more positive potential due

to the increasing cathodic current and this would in turn results in the regeneration of γ-

FeOOH from γ-Fe.OH.OH. This will allow another cycle to occur when the rust is

wetted again [21].

In brief, a wet-dry cycle of atmospheric corrosion can be explained as follows [14]:

Wetting: The thickness of the electrolyte layer increases from the surface of the rust

layer. Fe dissolution occurs. The cathodic reaction is the reduction of γ-FeOOH and the

system is under cathodic control.

Wet Stage: The thickness of the electrolyte layers remains almost constant. The

cathodic reaction is oxygen reduction and the system is under the cathodic control.

Beginning of the Drying: The cathodic reaction is oxygen reduction. Anodic sites are

being blocked and the system is under anodic control.

End of the Drying: There is no more electrochemical corrosion and the rust layer is re-

oxidized to start another cycle.

Marine environment contains significant amounts of chloride ions that have a big role

in the corrosion process of iron and steels. The deposition of chloride ions has a

significant impact on the composition of the rust layer and its thickness. According to

Stratmann et al. and Asami et al., the rust layer formed during atmospheric corrosion

mainly constitute goethite (α-FeOOH), akaganeite (β-FeOOH) and lepidocrocite (γ-

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FeOOH) [9, 23]. However, β-FeOOH existed in high chloride containing environments

[24, 25]. The phase β-FeOOH accelerates the corrosion process, since its reduction

reactivity is higher than that of γ-FeOOH. Antony et al. reported that when both γ-

FeOOH and β-FeOOH exists together, β-FeOOH plays the major role in determining

the rate of corrosion of Fe [26]. On the other hand, when the concentration of chloride

ions is very low, goethite (α-FeOOH) and lepidocrocite (γ-FeOOH) are the major

corrosion products in the rust layer [25]. Generally, β-FeOOH present on the outer

surface of the rust layer and it is formed probably due to the reaction between iron ions

and atmospherically deposited chloride ions [23]. Sometimes, β-FeOOH appears in the

inner layer of the rust also and this may be due to the diffusion of the chloride ions

dissolved in the water layer [23, 25].

The detailed mechanism of the accelerated effect of chloride ion deposition is given

below. The high amount of chloride ions helps in the formation of β-FeOOH and this in

turn decreases the corrosion resistance of steel accelerates the corrosion process [25].

In Wet Cycle

Anodic Reactions:

Cathodic Reactions:

Total Reactions:

In Dry Cycle

At low concentration of chloride ions or when the concentration of chloride ion is

below the critical concentration, chloride ions help in the transformation of γ-FeOOH

to α-FeOOH. The overall transformation process is given in the following scheme.

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Figure 1.4: The process of atmospheric rusting in low concentration of chloride

content in atmosphere [25]

1.4 Influence of Cr and Mo on the Atmospheric Corrosion of Steel

The addition of alloying element chromium to steels has a major influence on

atmospheric corrosion and electrochemical properties of steel. Chromium containing

steels generally have a surface rust layer with duplex structure, consisting of an outer

layer of γ-FeOOH and inner layer of ultra fine chromium enriched α-FeOOH. It was

reported that the Cr enriched α-FeOOH helped to form a stable protective rust layer

[27]. Lai et al. reported that chromium enriched inner most oxide scale resisted the

migration of ions and electrons better than FeO [28]. According to Wang et al.

chromium could easily enrich in the rust layers compared to that of other alloying

elements irrespective of environments [29]. Stratmann et al. pointed out that

atmospheric corrosion resistance of chromium containing steel depends on the ratio of

crystalline α-FeOOH (goethite) to all other forms of ferrous oxides such as γ-FeOOH,

δ-FeOOH. It was found that the atmospheric corrosion resistance enhanced when the

mass ratio is higher than 1. The addition of Cr influences the atmospheric corrosion

only during the drying stage. According to Stratmann, the reason for higher

atmospheric corrosion resistance of chromium containing steel during drying stage

might be due to the inhibition of rust reduction and the formation of Fe2+ states within

the rust layer in the presence of Cr enriched oxide layer. This would in turn decrease

oxygen reduction rate during drying stage since the electron transfer reaction is the

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rate-determining step for the overall reaction [30]. Moreover, in a recent study, Y.

Qian reported that higher content of chromium in steel promoted the formation of

crystalline α-FeOOH (goethite) and increases the mass ratio of α-FeOOH (goethite) to

all other forms of ferrous oxides and hence, showed better atmospheric corrosion

resistance [31]. According to their study, Cr plays two roles in improving the

atmospheric corrosion resistance

1) Promotion of formation of rust layers mainly containing α-FeOOH

2) Improving the passivation capability of steels

M. Yashimata and his coworkeers conducted investigations on the composition of rust

layers containing Cr. Mossbauer spectroscopy studies revealed that the rust layers of

Fe-Cr alloy film consisting of supermagnetic ultra fine Cr-goethite with crystal size in

the range of 15 nm. The rust layers were mainly composed of γ-FeOOH and ultra fine

Cr-goethite with the latter in abundance. Moreover, they proposed a mechanism for the

formation of Cr enriched goethite. Due to the solubility difference of Cr3+ to that Fe2+

ions, dissolved Cr3+ ions precipitates as hydroxides at the substrate interface during the

initial stages of corrosion. Cr3+ ions act as nucleus for the growth of Cr-goethite

crystals. Moreover, the oxidation of Cr ion is very fast since the diffusion of oxygen

through a very thin film is not kinetically limited. This in turn helps in the nucleation of

Cr-goethite at various sites on the Fe-Cr alloy surface. The Cr3+ in the rust layer is

coordinated with O2- and positioned in the double chains of vacant sites in the network

of FeO3(OH)3 octahedra in the goethite crystals [32, 33]. X-ray Absorption Fine

Structure (XAFS) spectroscopy studies revealed that Cr3+ in the rust layer is

coordinated with O2- and might form CrOx3-2x complex anion and it is located in the

double chains of vacant sites in the network of FeO3(OH)3 octahedra as a surface

adsorbed or intergranular ion in the ultrafine goethite crystal [34].

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The major purpose of adding Mo to steel is to increase the strength and hardness. The

influence of Mo addition on corrosion resistance of steels is evident only when Mo is

used in combination with other alloying elements and Mo content exceeds 3%

simultaneously [35].

1.5 Corrosion Prevention Methods

Although corrosion is a natural process, it can be controlled by using effective methods

and strategies. There are mainly five primary ways to control corrosion. These are:

 Materials selection

 Design

 Cathodic and anodic protection

 Inhibitors

 Coating

1.5.1 Materials Selection: The most common and important method of controlling

corrosion is the selection of the right and proper materials for particular corrosive

environments. Corrosion behavior of each metal and alloy is unique and inherent and

corrosion of metal and alloy has a strong relation with the environment to which it is

exposed. A general relation between the rate of corrosion, corrosivity of the

environment and corrosion resistance of materials can be elucidated as follows [2]:

corrosivity of environment
rate of corrosive attack (1.1 )
corrosion resistance of metal

The rate of corrosion directly depends upon the corrosivity of the environment and

inversely proportional to the corrosion resistance of the metal. Hence, the knowledge of

the nature of the environment to which the material is exposed is very important.

Moreover, the corrosion resistance of each metal can be different in different exposure

conditions. Therefore, the right choice of the materials in the given environment (metal-

corrosive environment combination) is very essential for the service life of equipments

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and structures made of these materials. It is possible to reduce the corrosion rate by

altering the corrosive medium. The alteration of the corrosive environment can be

brought about by lowering temperature, decreasing velocity, removing oxygen or

oxidizers and changing concentration. Consideration of corrosion resistance based on

the corrosion behaviour of the material and the environment in which it is exposed is an

essential step in all industry [1, 2, 8].

1.5.2 Design: The design of a structure is as equally important as the choice of

materials of construction since it can greatly reduce the time and cost associated with

corrosion maintenance and repair [2]. The proper design of equipment or tools made up

of metals and alloys must consider mechanical and strength requirements along with

corrosion resistance. Prior knowledge about the corrosion resistance of the candidate

material and the environment in which it functions is very essential for proper design of

any equipment. The most common rule for design is avoiding heterogeneity. It is very

important to make all conditions as uniform as possible throughout the entire system

[8]. Corrosion frequently happens in dead spaces or crevices and it is highly

recommended to eliminate or minimize these areas while designing. All the

components and structures should be designed by keeping its expected service life,

otherwise premature collapse of the component or structure is the inevitable and large

sum of money should be spent for its repair or replacement. The ever-changing

environment during the different stages of manufacture, transit and storage as well as

the daily and seasonal variations in the environment in which the components are

exposed should be considered for its maximum service life. It is highly essential to

avoid all unnecessary bimetallic corrosion cells in components by coupling dissimilar

metals. The metals involved in coupling should be widely separated in the galvanic

series to have a maximum service life of components. Galvanic corrosion can be

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controlled effectively by either preventing access of electrolyte to dissimilar metal

joints by applying barrier coatings or insulating both the anodes and cathodes to

prevent the flow of electrons across the joint. Dissimilar corrosion rate can also be

minimized by keeping the anodes as large as possible in the particular component or

location to reduce the current density [1, 2, 8].

1.5.3 Cathodic and Anodic Protection: Cathodic protection is an electrochemical way

of controlling corrosion in which the object to be protected is the cathode. Cathodic

protection is achieved by suppressing the corrosion current in a corrosion cell and by

supplying electrons to the metal to be protected. The principle of cathodic protection

can be explained with the help of a typical corrosion reaction of a metal M in an acid

medium [35]. Consider an electrochemical reaction in which metal dissolution and

hydrogen evolution are involved; for example

Equations (1.2) and (1.3) show that the addition of electrons to the structure would

reduce the metal dissolution and increase the rate of evolution of hydrogen. Cathodic

protection of a structure can be achieved by two ways: (1) by an external power supply

(2) by appropriate galvanic coupling. Most of the pipelines and marine structures are

protected by using an external power supply. Both the buried anodes and the objects to

be protected are connected to a direct current (dc) power supply. Generally, the buried

anode materials are inert materials and natural cathodes to steel pipelines or tanks to be

protected. However, with the aid of the dc power supplies the natural polarities of the

materials are reversed and steel pipelines are cathodically protected. Instead of the

corrosion reaction of the anodes, some other oxidation reactions such as oxygen or

chlorine evolution occur at the anode and thus the anodes are not consumed. Cathodic

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coupling by galvanic coupling is realized by using active metal anodes, for example,

zinc or magnesium, which is connected to the structure to provide the cathodic

protection current. In this case, the anode is called a sacrificial anode, since it is

consumed during the protection of the steel structure [2, 8, 36].

In contrast to cathodic protection, anodic protection is one of the more recently

developed electrochemical methods for controlling corrosion. Anodic protection is

based on the principles of passivity and it is generally used to protect structures used

for the storage of sulphuric acid [37, 38]. The difference of anodic protection from

cathodic protection is how the metal to be protected is polarized. The component that is

to be protected is made as anode in anodic protection. Since the anodic protection is

based on the phenomenon of passivity, metals and alloy systems, which exhibit active

passive behaviour when subjected to anodic polarization, can be protected by anodic

polarization. The corrosion rate of an active-passive metal can be significantly reduced

by shifting the potential to the passive range. Anodic protection is used to make a

protective passive film on the metal or alloy surface and thereby controlling the

corrosion [37].

1.5.4 Inhibitors: According to the definition given by NACE International, “inhibitor is

a substance that retards corrosion when added to an environment in small

concentrations” [39]. An inhibitor can be considered as a retarding catalyst that reduces

the rate of corrosion. The mechanism of inhibition is quite complex and it is not well

understood. It is established that inhibitors function in more than one way: (a) by

adsorption of a thin film on the corroding surface of a metal; (b) by forming a thick

corrosion product, or (c) by changing the properties of the environment and thereby

slows down the corrosion rate [40]. According to Uhlig et al, inhibitors can be broadly

classified as passivators, organic inhibitors and vapor phase inhibitors [35]. The

16
inhibitors can also be classified based on their mechanism of inhibition and

composition [8]. A large number of inhibitors fall under the category of adsorption type

inhibitors. These are generally organic compounds and function by adsorbing on anodic

and cathodic sites and reduces the corrosion current. Another class of inhibitors is

hydrogen evolution poisons. Arsenic and antimony are generally used as hydrogen

evolution poisons and they specifically retard the hydrogen evolution reactions. This

type of inhibition is very effective only in those environments where hydrogen

evolution is the main cathodic reactions and hence these inhibitors are very effective in

acid solutions.

The inhibitive substances, which act by removing the corrosive reagents from solution,

are known as scavengers. Sodium sulfite and hydrazine are these types of inhibitors,

which remove dissolved oxygen from aqueous solutions. These inhibitors function very

effectively in those solutions where oxygen reduction is the main cathodic reaction.

Oxidizers are also a kind of inhibitors. Substances such as chromate, nitrate, and ferric

salts act as corrosion inhibitors in certain systems. Generally, they inhibit the corrosion

of metals and alloys that exhibits active-passive transitions. Inorganic oxidizing

materials such as chromates, nitrites and molybdates are generally used to passivate the

metal surface and shift the corrosion potential to the noble direction. Paint primers

containing chromate pigments are widely used to protect aluminum alloys and steel.

Inhibitors that are very similar to organic adsorption type with very high vapor pressure

are known as vapor phase inhibitors. They are also known as volatile corrosion

inhibitors (VCI). According to Miksic and Miller “Volatile corrosion inhibitors are

secondary-electrolyte layer inhibitors that possess appreciable saturated vapor

pressure under atmospheric conditions, thus allowing vapor-phase transport of the

inhibitive substance” [41]. These inhibitors are generally placed very near to the metal

17
surface to be protected and they are transferred by sublimation and condensation to the

metal surface. Hence, these inhibitors can be used to protect metals from atmospheric

corrosion without being placed in direct contact with the metal surface. Vapor phase

inhibitors are very successful, if they are used in closed packages or the interior of

equipments [42].

1.5.5 Coatings: Protective coatings are the most generally used method for preventing

corrosion. The function of a protective coating is to provide a satisfactory barrier

between the metal and its environment. Coatings can be broadly classified into three

types. These are:

 Metallic coatings

 Inorganic coatings

 Organic coatings

Usually, an anticorrosive coating system is multifunctional with multiple layers with

different properties. A typical multifunctional coating can provide an aesthetic

appearance, corrosion control, good adhesion, and abrasion resistance. The functioning

of any protective coatings is based upon three basic mechanisms:

 Barrier Protection

 Chemical inhibition

 Galvanic (sacrificial) protection

Completely isolate metals and alloys from its environment achieve barrier protection.

Protection of metals through chemical inhibition is achieved by adding inhibitor

molecules into the coating system. An active metal is coated on the surface of the metal

to achieve sacrificial or galvanic protection [2, 8, 43].

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1.5.5.1 Metallic Coatings: Metals and sometimes their alloys are applied to other

metals and alloys to prevent corrosion. Metallic coatings are applied to a metal surface

by using following methods:

 Electroplating

 Electroless plating

 Hot dipping

 Thermal spraying

 Cladding

 Vapor deposition

 Ion implantation

 Laser processing

A metallic coating can function either as noble coatings or as sacrificial coatings.

Electroplated coatings are produced by the electrodeposition of an adherent metallic

coating upon a metal or alloy which is to be protected [44]. This is carried out by

immersing a metal or part of the metal to be coated in a solution of the metal to be

coated and passing direct current between the metal and another electrode. It is also

known as electroplating and it is generally used for decoration, protection, corrosion

resistance, electrical and magnetic properties. The nature of the deposit depends mainly

on factors such as temperature, current density, time and composition of the bath. A

coating of desired thickness and property can be achieved by changing these variables.

Generally zinc and cadmium deposits on steel act as active coatings and protect steel by

cathodic protection. Several metals commonly coated on steel are noble to iron. These

noble coatings act as an effective barrier to deny access for any corrosive species and to

ensure this the noble coating should be pore free and flawless.

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Electroless metal coatings are prepared without the help of electric current. Electroless

nickel coatings are achieved by the autocatalytic chemical reduction of nickel ions from

aqueous solution. Generally nickel-phosphorous and nickel-boron coatings are

produced. These coatings are amorphous in nature and provide excellent corrosion

resistance in a wide range of environments [2].

Hot-dip coating is a process in which a low melting point metal is applied as a

protective coating on steel wherein the material to be coated is immersed in a molten

bath of the coating metal. Although hot dipping method can be applied over a wide

variety of materials, it is commonly used to protect steels. Hot-dip coating can be

applied by continuous or batch process. Aluminum and zinc are most commonly used

metals to be coated to steel. Hot-dip zinc coated steels are generally known as

galvanized steels [2, 8].

Thermal spraying consists of a group of processes including flame spraying, plasma

spraying, arc metallization, detonation gun, high velocity oxyfuel, and cold spray and

that can be used to apply a variety of coating materials for corrosion prevention. The

coating materials can be powder, rod, wire or liquid. The coating materials are heated

to a plastic or molten state and propelled by a stream of compressed gas onto the

substrate. When these particles strike the metal surface, they flatten and form thin

platelets and adhered to the prepared surface. Generally, a spray gun is used to generate

the required heat for melting through combustion of gases, electric arc or plasma [8,

45].

Cladding is the bonding together of dissimilar metals. It is achieved by rolling of two

sheets of metal together. The principle of cladding includes hot-roll bonding, cold roll

bonding, explosive bonding, and weld cladding. For example, a nickel and steel sheets

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are hot rolled to get a composite nickel-steel sheet. Similarly, high strength aluminum

alloys are clad with commercially pure aluminum to have a good barrier to corrosion.

Vapor deposited coatings are accomplished in a high vacuum chamber. There are

mainly two types of vapor deposition: physical vapor deposition (PVD) and chemical

vapor deposition (CVD). Usually, the coating material is vaporized by heating

electrically and the vapors are allowed to deposit on the part to be protected. The major

vapor deposition method are sputtering, evaporation, ion plating (all of which are PVD

processes) and CVD. The species to be deposited is transferred and deposited in the

form of individual atoms or molecules. The most important advantage of vapor

deposited thin coating is that it is pore free and highly dense. However, its application

in corrosion protection is limited since this method is more expensive compared to

other methods [2].

Ion implantation and laser processing are two surface modification methods

accomplished by the use of high-energy or particle beam. High-energy ion beams are

used to modify surfaces to combat issues related to corrosion and wear. By ion

implantation, it is possible to enhance the passivation characteristics or create a novel

material. Ion implantation commonly finds its application in semiconductor industry.

Lasers with output power 0.5 to 10 kW can be employed to engineer the metallurgical

structure of a surface and tailor its surface property by leaving its bulk properties intact.

Laser processing helps to produce corrosion resistant surface layers. Transformation

hardening, surface melting, and surface alloying achieve laser processing [2, 8].

1.5.5.2 Inorganic Coatings: Nonmetallic inorganic coatings include ceramic coatings,

conversion coatings, and anodized coatings. One of the most widely used ceramic

coatings is zinc silicates [46, 47]. Sol-gel based silica and titania coatings are another

type of inorganic coatings. The sol-gel process to produce ZrO2, TiO2, SiO2, ZnO

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coatings is very well studied and established [48-52]. The inorganic particles in the sol-

gel coatings generally act as a good barrier against corrosive species. These coatings

give excellent abrasion resistance, low UV-absorption rate, high abrasion resistance and

aesthetic appearance to the metal. However, sol-gel based inorganic coatings cannot be

prepared in the thickness required for very high corrosion resistance since it is prone to

have cracks in the coating.

Phosphate coating and chromate conversion coatings are two largely used inorganic

conversion coatings. Phosphate coating is produced on the metal surface by immersion

the metal in a bath mainly contains phosphoric acid and other chemicals. During the

immersion, the metal reacts with phosphoric acid and other chemical contained in the

bath and produce a crystalline insoluble protective phosphate layer. Phosphate

conversion coatings are generally used to improve the corrosion resistance and the

adhesion of paints. Commonly used phosphate conversion coatings are zinc phosphate,

iron phosphates, and manganese phosphates. The basic principle involves in any

phosphate coating is the precipitation of a divalent metal and phosphate ions (PO43-) on

a metal surface. The phosphate conversion coatings can be applied either by spraying or

by immersion [2].

Chromate conversion coatings are produced on the metal surface by a chemical or

electrochemical treatment of the metals or metallic coatings in solutions containing

hexavalent chromium (Cr6+) and other components. Chromate conversion coatings are

primarily applied to improve the corrosion resistance of the metal and to improve the

adhesion of paints on the metal surface. Chromate conversion coatings are applied by

both spraying and immersion methods. However, various governments and regulatory

bodies recommend the replacement of chromate conversion coating with some other

green alternative since hexavalent chromium is carcinogenic and toxic [2].

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Anodizing is one of the most important surface modifications carried out for aluminum

alloys for improving the corrosion resistance and other purposes. Aluminum oxide

(Al2O3) films are formed on the surface when aluminum and aluminum alloys are

polarized anodically in electrolyte solutions. Since all of the anodic process form

porous Al2O3 films, it is required to seal the pores by immersion the coated materials in

hot water. The hot water treatment would hydrate the coating and seal the pores by

forming Al2O3. 3H2O [2].

1.5.5.3 Organic Coatings: Organic coatings act as relatively thin layer between the

substrate materials and the environment. The terms organic protective coatings and

paints are generally used interchangeably for both having an organic base. According to

the definition of coating mentioned in the Manuals for Coatings of Light Water Nuclear

Plants, “Coatings (paints) are polymeric materials that applied in fluid stage, cure to

form a continuous film”[53, 54]. This is a general definition given very broadly and

simply for both coatings and paints. However, as far as corrosion protection is

concerned, it is very necessary to define both these terms very specifically. “Paint can

be defined as any liquid material containing drying oils alone or in combination with

natural resins and pigments which , when applied to a suitable substrate, will combine

with oxygen from air to form a solid, continuous film over the substrate, thus providing

a weather resistive decorative surface”[53]. During its entire lifetime, a paint film

continues to oxidize and slowly become porous to oxygen, water and other corrosive

species, thus giving a less permanent protection against corrosion than the more

sophisticated protective coating.

A protective coating is chemically a considerably different material from paint. It

surpasses paint in adhesion, toughness, and resistance to chemical, weather, humidity,

and water. “A protective coating can be defined as any materials composed essentially

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of synthetic resins or inorganic silicate polymers which, when applied to a suitable

substrate, will provide a continuous coating that will resist industrial or marine

environments and prevents serious breakdown of the basic structure in spite of

abrasion, holidays, or imperfections in the coating”[53]. In order to provide maximum

protection, a protective coating should: (a) resist the penetration of ions from salts that

are in contact with the coatings; (b) minimize the action of osmosis; (c) expand and

contract with the underlying metal surface; and (d) retain the aesthetic appearance over

a long period.

1.6 The Organic Coating System

A typical anticorrosive coating system consists of a primer, one or several intermediate

coats and a top coat [46, 53, 55]. Figure 1.5 illustrates a typical coating system used for

highly corrosive industrial and marine environments.

Figure 1.5: A typical coating system for marine and industrial applications

Prior to the application of a primer, the substrates to be coated should be cleaned neatly

and pretreated to improve the adhesion of the subsequent coatings. Generally, sand

blasting, polishing with emery sheets and pickling are employed for surface finishing.

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A primer is considered the most important components of the coating system [8, 46,

53]. The major purposes of a primer are listed as follows:

 Good adhesion to the substrate

 High bond to intermediate coats

 Appropriate flexibility with subsequent coatings

 Strong resistance to corrosion and other chemicals

The primer is the base coat on which the rest of the coating system is applied and hence

it should have strong adhesion to the surface of the substrate. The primer generally

contains some inhibitive pigments and these pigments used to passivate the metal

surface and improve its corrosion resistance. A primer should protect the surface for

many days or months prior to the application of top coats and thus the primer coat

should be highly adherent and inert.

The specific purpose of the application of intermediate coating is to increase the

thickness of the coating system and resist the infiltration of corrosive species to the

metal surface [46, 53]. The major use of intermediate coats is to provide:

 Building up the thickness of the coating

 Improve the chemical resistance of the coating

 Retard the moisture vapor transfer

 Increase the electrical resistance of the coating

 Strong cohesion

 Improve the adhesion between the primer and topcoat.

The topcoat is the final finish coat it is always exposed to the external environment.

The topcoat should have required colour and gloss to please the eyes of an observer. It

is the first line of defense against corrosion in a coating system and hence it should

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have enough barrier property to impede the transport of aggressive species through the

coating system. The important function of a topcoat is to provide [46, 53, 56, 57]:

 A resistant seal for the coating system

 Initial barrier to the external environment

 Good resistance to water, chemicals, and weather

 Strong and wear resistant surface

 Aesthetic look to the coating system

 High resistance to ultraviolet radiation

The above-mentioned coating system is not necessary for all applications. Different

combinations of coating system can be obtained depending upon the corrosive

situations. Even a single coat can function satisfactorily for some particular corrosive

environment. Sometimes a single coating formulation applied in more than two coats

can provide required protection for metals and alloys.

1.7 Recent Advances in Protective Coatings

Application of organic/polymeric coating system is one of the widely used strategies to

combat corrosion of metals and alloys under service conditions [46]. Such polymer

coating system includes a pre-treatment layer or conversion layer, a primer and a

topcoat. These pre-treatment or conversion layers are generally applied to improve the

corrosion protection efficiency and to impart good adhesion of organic coatings applied

subsequently [58]. Chromate and phosphate conversion coatings are widely used

strategies to obtain a pre-treatment layer to improve the adhesion of subsequent organic

coatings for both ferrous and non-ferrous alloys [59]. However, the superior oxidation

property of Cr (VI) causes several health problems to humans and it is carcinogenic

[60]. The main disadvantage of inorganic corrosion inhibitors such as chromates,

phosphate is its toxicity. The common usage of chromate is banned in several countries

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considering health and safety reasons and the protection of the environment. Similarly,

the corrosion protection performance of zinc phosphate treatment is not good enough

for outdoor exposure [59]. Hence, the necessity of developing an environmentally

friendly surface pre-treatment is vital.

One of the most promising alternatives to aforementioned toxic surface treatment for

corrosion protection is sol-gel coatings. A sol-gel based dip coating is a very simple

method consists of the withdrawal of a substrate from a fluid sol and this results in the

deposition of a thin solid film due to gravitational draining, solvent evaporation and

further condensation reactions [61, 62]. Compared to other conventional thin solid film

deposition techniques such as chemical vapor deposition (CVD), physical vapor

deposition (PVD), electrochemical deposition, and sputtering, sol-gel dip coating

method requires considerably less equipments and it is potentially less expensive [63].

The sol-gel process is a chemical synthesis method based on the hydrolysis and

condensation reactions of metal alkoxides (M (OR)n). Sol-gel derived coatings have

many advantages such as high corrosion resistance, nontoxic and environmentally

compatible, and good adhesion to both metallic substrate and organic topcoat. One of

the fascinating features of sol-gel based coating is its functionalization and tailoring the

properties of the deposited sol-gel film.

The sol-gel process can be used to prepare either organic or inorganic based protective

coatings. Moreover, the low reaction temperature required for sol-gel process makes

easy the introduction of organic groups in the inorganic material leading to the

fabrication of a new class of hybrid coatings consisted of both organic and inorganic

components [62]. The functionalities imparted by both organic and inorganic moieties

in hybrid coatings are different. The inorganic parts confer enhanced mechanical

properties, scratch resistance, durability and adhesion to metallic substrate. On the other

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hand, the organic part contributes to the increase of density, flexibility and functional

compatibility with polymeric paint systems applied as topcoats. Moreover, organically

modified coatings are generally thick and pore free dense coatings [64, 65].

The corrosion resistance of sol-gel derived film is mainly due to its physical barrier

property, which obstructs the entry of corrosive species and water through the coatings

and protects the underlying metal surface. Corrosion protection provided by a barrier

film which avoid any contact between metallic substrate and external environment is

known as passive protection. However, sol-gel coatings are not free from cracks and

other defects (such as scratches and pores) and this leads to the penetration of

electrolyte and water towards metal surface and instigates corrosion. Even though the

physical barrier coatings provide resistance against corrosion, any occurrence of failure

in this barrier layer leads corrosive ions to permeate to the metal surface leading to the

onset of corrosion. Hence, it is required to introduce active agents or corrosion

inhibitors into the barrier coatings to improve its anticorrosion property. Corrosion

protection provided by active agents or corrosion inhibitors is known as active

corrosion protection. In active corrosion protection methods, corrosion inhibitors are

incorporated into the protective barrier layers to decrease the corrosion rate when the

passive barrier layer starts deteriorating [58, 66]. The corrosion inhibitor can be

introduced into the coatings in two ways: (i) adding the inhibitors directly into the

coating (ii) loading or encapsulating the inhibitors in some containers or reservoirs and

then adding into the coating [58].

It was proved that the direct addition of inhibitors had a negative effect on the stability

of the sol-gel coating and thereby deteriorates the physical barrier functionality of the

coating [66]. Hence, the second approach, loading or encapsulating the inhibitors in

containers prior to mixing with coating, is the favored one. Recent developments in

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nanotechnology and surface engineering pave avenues for fabricating novel class of

coatings, which can impart both barrier protection and active functionalities. Nano or

microcontainers with sustained release properties can be used in a new class of self-

healing coatings. When the environment around the coatings changes, the inhibitor

from the nanocontainers would be released quickly and delays corrosion activity. There

are many advantages in adopting this novel strategy for corrosion protection compared

to conventional barrier coatings. This strategy avoids the direct contact between the

inhibitor molecules and barrier coatings and hence reduces the negative effect of the

inhibitors on the integrity of the coating. It helps in releasing the inhibitors at the right

time in the right quantity and thereby no uncontrolled leaching of the inhibitors into the

coatings [58, 66, 67].

1.8 Summary

Corrosion of materials and structures is a big hindrance to the development of the

economy and cause a lot of damage to our life and hence its prevention is a great

challenge for humanity. Corrosion prevention by protective coatings has a greater role

to play in curbing this menace. Sol-gel based protective layers equipped with active

functionalities is the ideal replacements for both chromate and phosphate coatings as

pre-treatment or conversion layers, since sol-gel derived coatings are eco-friendly.

However, it is required to utilize the recent developments in nanotechnology to

improve the properties of coatings to have multifunctional capabilities.

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