CORROSION

ENGINEERING

WHAT IS CORROSION?

Corrosion is defined as the gradual destruction or deterioration of metals or alloys by the chemical or electrochemical reaction with its environment.

CONSEQUENCES OF CORROSION
Due to formation of corrosion product over the machinery, the efficiency of the machine gets lost. The products gets contaminated due to corrosion.

The corroded equipment must be replaced frequently.

Plant gets failure due to corrosion. Corrosion releases toxic products, health hazard, etc.

CORROSION METALLURGY IN REVERSE Corrosion: Metallurgy in Reverse2

2Fontana,

M.G., Corrosion Engineering. 3rd ed. 1986, New York: McGraw-Hill.

CORROSION ON WRECKAGE OF TITANIC

BHOPAL ACCIDENT RESULT OF CORROSION

Bhopal Accident

 In the early morning of December 3, 1984, water inadvertently entered the methylisocyanate (MIC) storage tank, where more than 40 metric tons of MIC was stored. The addition of water to the tank caused a runaway chemical reaction, resulting in a rapid rise in pressure and temperature. The heat generated by the reaction, the presence of higher than normal concentrations of chloroform, and the presence of an iron catalyst, produced by the corrosion of the stainless steel tank wall, resulted in a reaction of such momentum that gases formed could not be contained by safety systems.

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 Consequently, MIC and other reaction products, in liquid and vapor form, escaped from the plant into the surrounding areas. There was no warning for people surrounding the plant since the emergency sirens had been switched off. The effect on the people living in the shanty settlements just over the fence was immediate and devastating. Many died in their beds, others staggered from their homes, blinded and choking to die in the street. It has been estimated that at least 3000 people died as a result of this accident, while figures for the number of people injured currently range from 200,000 to 600,000, with an estimated 500,000 typically quoted.
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WHY DO METALS CORRODE?

A significant amount of energy is put into a metal when it is extracted from its ores, placing it in a high-energy state. These ores are typically oxides of the metal such as hematite (Fe2O3) for steel or bauxite (Al2O3H2O) for aluminum. One principle of thermodynamics is that a material always seeks the lowest energy state. In other words, most metals are thermodynamically unstable and will tend to seek a lower energy state, which is an oxide or some other compound. The process by which metals convert to the lower-energy oxides is called corrosion. 12

PROCESS OF CORROSION
Corrosion of most common engineering materials occurs in aqueous environment (electrolyte) at near-ambient temperature and is electrochemical in nature. The moist soil acts as aqueous environment (electrolyte) for underground corrosion. The corrosion process involves the removal of electrons (oxidation) of the metal and the consumption of those electrons by some other reduction reaction, such as oxygen or water reduction.

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CORROSION REACTIONS
Removal of electrons (Oxidation / Anodic reaction) Fe Fe++ + 2e(equation 1) Consumption of electrons (Reduction / Cathodic reaction) Oxygen reduction O2 + 2H2O + 4e- 4OH(equation 2) Water reduction 2H2O + 2e- H2 + 2OH-

(equation 3)
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 Both these electrochemical reactions are necessary for corrosion to occur.

The oxidation reaction causes the actual metal loss in corrosion process. The reduction reaction is required to consume the electrons liberated by the oxidation, to maintain charge neutrality. In absence of reduction reaction, a large negative charge would rapidly develop between the metal and the electrolyte and the corrosion process would cease.
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 The oxidation and reduction reactions are sometimes referred to as half-cell reactions and can occur at the same site on the metal or can be physically separated. When the electrochemical reactions are physically separated, the process is referred to as a differential corrosion cell. Four necessary components of a differential corrosion cell are: anode, cathode, a metallic path required to connect the anode and cathode electrically (normally the metal itself), and an electrically conductive electrolyte to immerse the anode and cathode (normally moist soil).

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DIFFERENTIAL CORROSION CELL

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 The site where the metal is being oxidized is referred to as the anode. At anode, direct electric current flows from the metal surface into the electrolyte as the metal ions leave the surface. This current flows in the electrolyte to the site where oxygen, water, or some other species is being reduced. This site is referred to as the cathode.
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CLASSIFICATION OF CORROSION
Based on the environment, corrosion is classified in to 1. Dry or Chemical corrosion 2. Wet or Electrochemical corrosion. Dry or Chemical corrosion: Dry corrosion is due to the attack of metal surfaces by the atmospheric gases such as oxygen, hydrogen sulphide, sulphur dioxide, nitrogen, inorganic liquids etc. There are three main types of dry corrosion; 1. Oxidation corrosion (or) corrosion by oxygen 2. Corrosion by hydrogen. 3. Liquid metal corrosion.

OXIDATION CORROSION

Oxidation corrosion is brought about by the direct attack of oxygen at low or high temperatures on metal surface in the absence of moisture. Alkali metals like (Li, Na, K, etc) and alkaline-earth metals (Mg, Ca, Sr, etc) are rapidly oxidised at low tempt. At high temperature, almost all metals (expect Ag, Au and Pt) are oxidized.

MECHANISM OF DRY CORROSION

Oxidation occurs first at the surface of the metal resulting in the formation of metal ions (M2+), which occurs at the metal/oxide interface. M M2+ +2e-

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Oxygen changes to ionic form (O2-) due to the transfer of electron from metal, which occurs at the oxide film / environment interface. O2 + 2e- O2Oxide ions reacts with the metal ion to form the metal- oxide film.

M + O2 M2+ +O2- MO (Metal-oxide film)

NATURE OF OXIDE FILM

The nature of oxide film formed on the metal surface plays in important role in oxidation corrosion.

(i) STABLE OXIDE LAYER

A stable oxide layer behaves as a protective coating and no further corrosion can develop. Example: oxides of Al, Sn, Pb, Cu, etc., are stable oxide layers. (ii) UNSTABLE OXIDE LAYER Unstable oxide layer is mainly produced on the surface of noble metals, which decomposes back in to the metal and oxygen. Metal oxide Metal +Oxygen Example: Oxides of Pt, Ag, etc., are unstable oxide layers.

(iii) VOLATILE OXIDE LAYER

The oxide layer volatilizes as soon as it is formed, leaving the metal surface for further corrosion. Example: Molybdenum oxide is volatile. (iv) POROUS OXIDE LAYER Metal oxides having pores and cracks allow penetration of oxygen to the underlying metal, resulting in the complete conversion of metal into its oxide.

PILLING BEDWORTH RATIO

The ratio of the volume of the oxide formed to the volume of the metal consumed is called pilling-bedworth ratio. R = Md/nmD Where M - mass of metal oxide m - atomic weight d - density of the metal D - density of the scale n- number of metal atoms in a formula of the scale

(PILLING-BEDWORTH RULE) According to PillingBedworth rule, 1. If the volume of the oxide layer formed is less than the volume of the metal, the oxide layer is porous and nonprotective. Example: Oxides of alkali and alkaline earth metals. 2. If the volume of the oxide layer formed is greater than the volume of the metal, the oxide layer is subjected to cracking and spalling resulting in poor oxidation resistance and protection. Example: Oxides of heavy metals such as Sb,V, W, etc.

3. If the volume of oxide layer is equal to the volume of the metal then there will be protective oxide film formation. Example: Oxides of Al, Pb, Ni, etc.
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CORROSION BY OTHER GASES Gases like SO2, CO2, Cl2, H2S etc induce corrosion action on metals Corrosion effect depends on between the metal and the gas. the chemical affinity

The degree of attack by gases depends on the formation of protective or non-protective films on the metal surface. If the film is non-porous or protective, the intensity of attack decreases. Eg. AgCl film attack of Cl2 on Ag

(1)

(2)

If the film is porous or non-portective, the surface of the whole metal is gradually destroyed.
Eg. Dry Cl2 gas attack on Sn formation of volatile SnCl4 27 fresh surface is exposed for further attack

CORROSION BY HYDROGEN
(a) HYDROGEN EMBRITTLEMENT: Contact of metal with H2S results in the generation of atomic hydrogen E.g. Fe + H2S FeS + 2H H + H H2

Corrosion caused by the exposure of metal to hydrogen environment. Hydrogen in atomic state diffuses into the metal matrix and collects in the voids present in the metal. The hydrogen atoms combine to form H2 gas. A very high pressure is developed, which results in cracks and blisters on metal. This process is called hydrogen embrittlement.

(b) DECARBURISATION
At higher temperature atomic hydrogen is formed by the thermal dissociation of molecular hydrogen. H2 2H When steel is exposed to this environment, the atomic hydrogen readily combines with carbon of steel and produces methane gas. C + 4H CH4 Collection of these gases in the voids develop very high pressure, which causes cracking. Thus the process of decreases in carbon content in steel is termed as Decarburisation of steel.

LIQUID - METAL CORROSION

This is due to the chemical action of flowing liquid metal at high temperature. The corrosion reaction involves either,
(i) Dissolution of a solid metal by a liquid metal (or) (ii) Liquid metal may penetrate in to the solid metal.

WET (or) ELECTRO-CHEMICAL

CORROSION
Wet corrosion occurs under the following conditions,
When two dissimilar metals are in contact with each

other in the presence of an aqueous solution or moisture. contact with an aqueous solution of an electrolyte.

When two dissimilar parts of the same metal are in

MECHANISM OF WET CORROSION

According to electrochemical theory of corrosion, the wet corrosion involves two steps. a) Oxidation or metal dissolution b) Reduction Metal dissolution occurs always at anode leading to the formation of metal ions and electrons

M Mn+ + neAt cathode, electron consumption resulting in either evolution of hydrogen or absorption of oxygen depending on the nature of corrosion environment.
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(a) Acidic environment

If the corrosive environment is acidic, hydrogen evolution occurs at cathodic part.

2H+ + 2e- H2

(b) Alkaline or Neutral environment

If the corrosive environment is slightly alkaline (or) neutral, hydroxide ion forms at cathodic part. O2 + 2e- +H2O 2OHThus the metal ions (from anodic part) and non-metallic ions (from cathodic part ) diffuse towards each other through conduction medium and form a corrosion product between anode and cathode.

a) Hydrogen evolution type corrosion

Metals have negative reduction potential

i.e., below hydrogen reduction potential value in the electrochemical series get dissolved in acidic solution with simultaneous liberation of hydrogen gas. Example: Iron metal in contact with nonoxidizing acid like HCl results in H2 evolution At anode: Iron (Fe) undergoes dissolution to Fe2+ with the liberation of electrons. At cathode: The liberated electrons follow from anode to cathode, where H+ ions get reduced to H2.
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b) Absorption of oxygen or formation of hydroxide ion type corrosion

Fe surface usually contains a coating of Iron oxide and if

this oxide layer develops, cracking happens. As a result anodic areas are created on the surface and remaining area acts as cathode. Example: Iron metal in contact with a neutral solution of electrolyte in the presence of O2, OH- ions are formed. At anode: Iron (Fe) undergoes dissolution to Fe2+ with the liberation of electrons. At cathode: The liberated electrons follow from anode to cathode, where dissolved O2 is consumed to form OHions.

1/2O2 + H2O + 2eFe2+ + 2OHFe(OH)2 + 2H2O + O2

2OHFe(OH)2 4Fe(OH)3 (rust)

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Chemical Corrosion

Electrochemical Corrosion

It occurs only in dry condition

It occurs in the presence of moisture or electrolyte

It is due to the direct chemical It is due to the set up of a attack of the metal by the large number of cathodic and environment anodic areas Even a homogeneous metal surface gets corroded Corrosion products accumulate in the same place, where corrosion occurs. Chemical corrosion is selfcontrolled Hetergeneous surface or bimetallic contact is required for corrosion Corrosion occurs at the anode, while products formed elsewhere It is continuous process

It follows adsorption It follows electrochemical mechanism reaction Eg. Formation of mild scale on Eg. Rusting of iron in moist 36 iron surface atmosphere

TYPES OF ELECTROCHEMICAL CORROSION

GALVANIC CORROSION
When two different metals are in contact with each other in the presence of an aqueous solution or moisture, galvanic corrosion occurs. Here, the more active metal (with more negative electrode potential) acts as anode and the less active metal (with less negative potential) acts as cathode. Example for galvanic corrosion Steel screw in a brass marine hardware corrodes. This is due to galvanic corrosion. Iron (higher position in electrochemical series) because anodic and is attacked and corroded, while brass (lower in electrochemical series) acts as cathodic and is not attacked.

Bolt and nut made of the same metal is preferred. Why? It is preferred in practice, because galvanic corrosion is avoided due to homogeneous metals (no anodic and cathodic part). Prevention: Avoid unfavorable area effect Selection of metals & alloys Insulating dissimilar metals Using inhibitors Applying cathodic protection

DIFFERENTIAL AERATION CORROSION

This type of corrosion occurs when a metal is exposed to varying concentration of oxygen or any electrolyte on the surface of the base metal. Example Metals partially immersed in water (or) conducting solution (called water line corrosion). If a metal is partially immersed in a conducting solution the metal part above the solution is more aerated and hence become cathodic.

On the other hand, the metal part inside the solution is less aerated and thus, become anodic and suffers corrosion.

At anode (less aerated) corrosion occurs M M2+ +2eAt cathode (more aerated part) OH- ions are produced O2 +H2O + 2e- 2 OH40

Examples for differential aeration corrosion Pitting or localized corrosion Crevice corrosion Soil corrosion. Corrosion on wire fence.

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(a) Pitting Corrosion

This is a localised attack, resulting in the formation of a hole around which the metal is relatively unattacked. Example Metal area covered by a drop of water, sand, dust, scale etc., Consider a drop of water or aqueous NaCl resting on a metal surface.

The area covered by the drop of H2O acts as an anode due to less O2 conc., and suffers corrosion.
The uncovered area (freely exposed to air) acts as a cathode due to high oxygen concentration

The rate of corrosion will be more, when the area of cathode is larger and the area of anode is smaller. A small hole or pit is formed on the surface of the metal. At anode Iron is oxidized to Fe2+ ions (Fe Fe2+ +2e-)

At cathode Oxygen is converted to OH- ions. (1/2O2 +H2O +2e- 2OH-) Net reaction is Fe2+ +2OH- Fe(OH)2 Fe(OH)3 This type of corrosion is called pitting.

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(b) Crevice corrosion

If a crevice between different metallic objects or between metal and non-metallic material is in contact with liquids, the crevice becomes the anodic region and suffers corrosion. This is due to less oxygen with crevice area. The exposed areas act as the cathode.

(c) PIPELINE CORROSION

Differential aeration corrosion may also occur in different parts of pipeline. Buried pipelines or cables passing from one type of soil to another, example from clay (less aerated) to sand (more aerated) may get corroded due to differential aeration.

(d) CORROSION ON WIRE-FENCE

A wire fence in which the areas where the wires cross are less aerated than the rest of the fence and hence corrosion occurs at the wire crossings, which are anodic. Other examples for differential aeration corrosion (i) Corrosion occurring under metal washers, where oxygen cannot diffuse easily. (ii) Lead pipeline passing through clay to cinders undergo corrosion. Since the pipeline under cinders is more aerated, it gets corroded easily.

FACTORS INFLUENCING CORROSION

The rate and extent of corrosion depends mainly on i. Nature of the metal ii. Nature of the environment

Nature of the metal A) Position in EMF series

The extent of corrosion depends upon the

position of the metal in the EMF series. Greater the oxidation potential, greater is the rate of corrosion.

When two metals are in electrical contact, the metal higher (-) ve electrode potential in the EMF series becomes anodic and suffers corrosion.
Further, the rate and severity of corrosion depends upon the difference in their positions in the EMF series. Greater the difference, faster is the corrosion of anodic metal.

(b) Relative areas of the anode & cathode

The rate of corrosion is more when area of the cathode is larger. When cathodic area is larger, the demand for electrons will be more and this results in an increased rate of dissolution of metals at anodic regions.

(c) Purity of the metal

The 100% pure metal will not undergo any type

of corrosion. But, the presence of impurities in a metal create heterogeneity and thus galvanic cells are sets up with distinct anodic and cathodic area in the metal. Higher the percentage of impurity, faster is the rate of corrosion of the anodic metal.

(d) Physical state of the metal

Metal components subjected to unevenly

distributed stresses are easily corroded.

Even in a pure metal, the areas under stress

tend to be anodic and suffer corrosion.

(f) Nature of the Corrosion Product

If the corrosion product is soluble in the corroding medium, the corrosion of the metal will proceed faster.
On the other hand, if the corrosion

product is insoluble, then the protective film formed will tend to suppress corrosion.

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(G) Nature of the oxide film

Metals such as Mg, Ca, Ba, etc., form oxides

whose volume is less than the volume of the metal. the oxide film formed will be porous, through which oxygen can diffuse and bring about further corrosion. etc. form oxides whose volume is greater and the non-porous oxide film so formed will protect the metal from further corrosion.
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Hence,

On the other hand metals like Al, Cr, Ni

NATURE OF THE ENVIRONMENT (A) Temperature The rate of chemical reaction and the rate of diffusion of ions increases with rise in temperature Hence, corrosion increases with temperature. A passive metal may become active

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(B) Humidity The rate of corrosion will be more, when the humidity in the environment is high. The moisture acts as a solvent for the oxygen in the air to produce the electrolyte, which is essential for setting up a corrosion cell. Rusting of iron increases when the relative humidity of air reaches from 60 to 80 percent.
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(C) Effect of pH The rate of corrosion is maximum when the corrosive environment is acidic. In general, acidic environment is more corrosive than alkaline or neutral medium. Corrosion rate can be reduced by increasing the pH of the medium. But metals such as Al, Zn dissolves in alkaline medium.

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(D) NATURE OF THE ELECTROLYTE

If the electrolyte consists of silicate ions,

they form insoluble silicates and prevent further corrosion.

On the other hand if chloride ions present,

they destroy the protective film and the surface is exposed for further corrosion.

If the conductance of electrolyte is more,

the corrosion current is easily conducted and hence the rate of corrosion is increased.
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(E) Conductance of the corroding medium The corrosion current depends upon the internal resistance of the short circuited cells, which in turn depends on the conductance of the electrolytic medium. If the conductance of the soil is more, the corrosion of underground structure will also be more. Conductance in clayey, soils and mineralized soils is more.
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CORROSION CONTROL
The rate of corrosion can be controlled by either modifying the metal or the environment. 1. Proper Designing A major factor in the corrosion failure of a component is a faulty geometrical design. Some important design principles are: 1) Avoid crevices 2) Avoid residual moisture 3) Avoid galvanic corrosion Galvanic corrosion can be prevented by the following methods, a) Use an electrical insulators b) Introduce an easily exchangeable corroding places 4) Avoid protruding parts.

2. Cathodic Protection
The principle involved in cathodic protection is to force the metal to be protected to behave like a cathode. Since, there will not be any anodic area on the metal, corrosion does not occur. There are two types of cathodic protection. Sacrificial anodic protection method Impressed current cathodic protection method.

SACRIFICIAL ANODIC PROTECTION METHOD In this method, the metallic structure to be protected is made cathode by connecting it with more active metal (anodic metal). So that all the corrosion will concentrate only on the active metal. The artificially made anode thus gradually gets corroded protecting the original metallic structure. Hence this process is otherwise known as sacrificial anodic protection.

Examples of sacrificial anode This method is used for the protection of ships and boats. Sheets of zinc and magnesium are hung around the hull of the ship. Zinc and magnesium being anodic to iron get corroded. Since they are sacrificed in the process of saving iron (anode), they are called sacrificial anodes.

Applications of Sacrificial Anode

Protection of underground pipelines and cables from soil corrosion. Magnesium rods are inserted in to domestic water boilers or tanks to prevent the formation of rusty water. Calcium metal slag's are employed to minimize engine corrosion.

IMPRESSED CURRENT CATHODIC PROTECTION

In this method, an impressed current is applied in the opposite direction to nullify the corrosion current and convert the corroding metal from anode to cathode. This can be done by connecting negative terminal of the battery to the metallic structure to be protected. Positive terminal of battery is connected to an inert anode. inert anode used for this purpose is graphite or platinised titanium.

The anode is surrounded by backfill (containing mixture of gypsum, coke, breeze, sodium sulphate) to improve the electrical contact between the anode and the surrounding soil. APPLICATION OF IMPRESSED CURRENT PROTECTION This type of cathodic protection is applied to open water-box coolers, water tanks, buried oil and water pipes, condensers, marine piers, transmission line towers, etc.,

Comparison of sacrificial anode and impressed current cathodic method

Sacrificial anodic method No external power supply is necessary. This method requires periodical replacement of sacrificial anode. Investment is low.

Impressed current method External power supply must be present. Here anodes are stable and do not disintegrate. Investment is more.

Soil corrosion effects are not taken in to account. This is most economical method especially when short-term protection is required.

Soil corrosion effects are taken in to account. This method is well suited for large structures and long term operations.

Control of corrosion by modifying the environment DEAREATION The presence of increased amount of oxygen is harmful and increase the corrosion rate. Deareation involves removal of dissolved oxygen by increase of temperature with mechanical agitation. It also removes dissolved CO2 of water.

DEHUMIDIFICATION
In this method, moisture from the air is removed by lowering the relative humidity of the surrounding air. This is done by adding silica gel (or) alumina, which adsorbs moisture preferentially on its surface.
ALKALINE NEUTRALISATION

The acidic character of the corrosive environment (due to presence of H2S, HCl, CO2, SO2, etc) can be neutralized by spraying alkaline neutralisers (like NH3, NaOH, lime etc).

CORROSION INHIBITORS DEFINITION

A corrosion inhibitors is a substance which when added to in small quantities to the aqueous corrosive environment effectively decreases the rate of corrosion of the metal.

Inhibitors are classified in to three types, ANODIC CATHODIC VAPOUR PHASE

ANODIC INHIBITORS
Chromates, phosphates, tungstates of transition elements, inhibit the anodic corrosion reaction by forming sparingly soluble compound with a newly produced metal ion. They are absorbed on the metal surface forming a protective film or barrier thereby reducing corrosion rate. This kind of corrosion rate is not fully reliable since certain areas left uncovered by the film can produce severe corrosion.

CATHODIC INHIBITORS
In acidic solution, the main cathodic reaction is evolution of hydrogen. 2H+(aq) +2e- H2 (g) In an acidic solution, the corrosion can be controlled by slowing down the diffusion of H+ ions through the cathode. This can be done by adding organic inhibitors like amines, pyridine, azoles, etc. They absorb over the cathodic metal surface and act as a protective layer.

In a neutral solution, the cathodic reaction is, H2O + O2 + 2e- 2OH-(aq) The formation of OH- ions is only due to the presence of oxygen. By eliminating the oxygen from the medium, the corrosion rate can be reduced. O2 can be removed by adding some reducing agents like Na2SO3 or by deaeration. Salts of Zn, Mg, Ni are employed as they form insoluble metallic hydroxide which forms impermeable self barriers.

VAPOUR PHASE INHIBITORS Vapour phase inhibitors are organic inhibitors which readily sublime and form a protective layer on the metal surface. Example : Dicyclohexyl ammonium nitrite, Benzotriazole. Vapour phase inhibitors are used in the protection of machineries, sophisticated equipments, etc. which are sent by ships. The condensed inhibitor can be easily wiped off from the metal surface.

PROTECTIVE COATING INTRODUCTION Protective coatings are used to protect the metals from corrosion.
It acts as a physical barrier between the

coated metal surface and the environment.

They impart some special properties such

as hardness, electrical properties and thermal insulating properties to the protected surface.

Protective coatings

Inorganic coating Metallic coating Chemical Conversion

Organic coating 1. Paints 2. Varnishes 3. Enamels 4. Ceramic

Sample Preparation
Mechanical cleaning To remove loose scale and rust, using hammer, wire-brushing, grinding and polishing. Sandblasting To clean large surface areas in order to produce enough roughness for good adherence of protective coating, using sand with air stream at 25-100 atm. Solvent Cleaning To remove oil, grease, rust using organic solvents like alcohol, xylene, toluene, hydrocarbons followed by cleaning hot water or steam.
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Sample Preparation (contd..)

Alkali Cleaning To remove old paints that are soluble in alkaline medium using chemicals like NaOH, Na3PO4 etc. After cleaning, the metal is washed with 1% chromic acid solution.

Acid pickling and etching Base metal is dipped inside acid solution at a higher tempt for a long duration. Acids used are HCl, H2SO4, H3PO4, HNO3, under dilute conditions.

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Metallic coatings
Anodic coating Galvanization:
It is produced by anodic coating metals (Zn, Al, Cd) on the surface of base metal (Fe) based on the relative negative electrode potential.

Cathodic coating:
It is produced by cathodic coating metals (Sn, Cr, Ni) on Fe surface based on the relative positive electrode potential of coat metal.
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Methods of application of metallic coating

Hot dipping Metal cladding Electroplating Cu, Cr, Ni, Au, Ag Cementation Vacuum metalizing Metal spraying
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Hot Dipping
It is one of the common method of applying metallic coating on the surface of base metals. Hot dipping is a process of coating the base metal by immersing it in the molten coat metal. Examples: Galvanizing and Tinning

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Galvanizing: Fe or steel is coated with a thin coat of Zn by immersing in molten Zn to prevent rusting. Fe or steel base metal is cleaned by acid pickling using dil. H2SO4 (60-90 0C) for 15-20 min. Base metal dipped in molten Zn (430 0C) and then passed through rollers to correct the thickness of the film. NH4Cl flux used to protect the surface of molten Zn from oxide formation. Annealed at 250 0C and cooled slowly Coating of Iron pipes, screws, bolts, wires, etc. Poisonous for utensils that store food stuffs
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Tinning: In this process tin is coated over mild steel sheets immersed in molten tin (Sn). The sheet is subject to acid pickling and passed through a bath of molten tin covered with a flux of ZnCl2. After coating, the sheet is passed through palm oil to protect from oxidation Finally the sheet is passed to roller to get uniform thickness. It is used for the coating of steel, Cu and brass sheets that store food stuffs.
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Metal Cladding
It is the process of sandwitching the base metal between two thin layers of coating metal by hot-rolling the composite to produce a firm bonding. The coat metals are usually metals of least reactivity (Cu, Ni, Ag, Pt, Ti) The cladding layer should be very thin and its thickness is only 5% of the total composite metal. Duraluminium sandwiched between Al sheets and hot rolled to produce Alkad composite which is free from stress corrosion
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ELECTROPLATING
PRINCIPLE Electroplating is the process in which the coating metal is deposited on the base metal by passing a direct current through an electrolytic solution containing the soluble salt of the coating metal. Electroplating is probably the most important and most frequently applied industrial method of producing metallic coatings. The metal film produced is quite uniform with little or no pinholes per unit area. When the thickness of the deposit increases, the number of pinholes decreases.
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 The base metal to be plated is made cathode of an electrolyte cell, whereas the anode is either made of the coating metal itself or an inert material of good electrical conductivity.
THEORY If the anode is made of coating metal itself in the electrolytic cell, during electrolysis, the concentration of electrolytic bath remains unaltered, since the metal ions deposited from the bath on cathode are replenished continuously by the reaction of free anions with the anode.
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Objectives of electroplating:
(i) To increase the resistance to corrosion and chemical attack of the plated metal. (ii) To obtain a polished surface (iii) To improve hardness and wear resistance Example: Electroplating of Cu, Au, Ag, Cr, Ni, Sn etc. Uses of electroplating: (i) It is often used in electronic industries for making printed circuit boards, edge connectors, semiconductor lead-out connection (ii) It is also used in the manufacture of jewelery, 85 refrigerator, electric iron etc.

Electroplating of Cu
For electroplating of Cu on metal surface, Electrolyte: (3-5%)H2SO4 / (15-30%) CuSO4 Anode: Pure Cu metal or Graphite (inert) Cathode: Metal to be coated Additive: Boric acid or gelatin Ionization reaction of electrolyte is observed, H2SO4 2H+ + SO42CuSO4 Cu2+ + SO42On passing current, Cu2+ + 2eSO42SO4 + 2e- (at anode) Cu (at cathode)

Due to common ion effect, the ionization rate of Cu2+ is controlled and the deposition process can also be controlled, with a current 86 density of 0.5 to 1.5 ampere/dm2.

Factors affecting electroplating

Surface cleaning for strong adherent Concentration of electrolyte. Conductivity and stability of electrolyte Thickness of the deposit for decorative purpose thin coating and for corrosion protection multiple coating. Current density (current per unit of the base metal) should be low for uniform controlled deposition Additives: Ensure strong adherence and mirror smooth coating. pH of the electrolytic bath
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Thin-Film Coatings
PVD Coating (Physical Vapor Deposition) CVD Coating (Chemical Vapor Deposition)

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PAINTS
DEFINITION Paint is a mechanical dispersion of one or more finely divided pigments in a medium (thinner + vehicle). When a paint is applied to a metal surface, the thinner evaporates, while the vehicle undergoes slow oxidation forming a pigmented film.

CHARACTERISTICS OF A GOOD PAINT It should spread easily on the metal surface. It should have high hiding power. It should not crake on drying. It should adhere well to the surface. The colour of the paint should be stable. It should be a corrosion and water resistant. It should give a glossy film.

CONSITITUENTS OF PAINTS

Paint essentially consists of the following Ingredients, 1. Pigments 2. Vehicle or drying oil 3. Thinners 4. Drier 5. Fillers or extenders 6. Plasticisers 7. Antiskinning
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PIGMENTS
Pigment is a solid and colour producing substance which is an essential constituent paint,

The functions of a pigment are To provide capacity, strength, desired colour and give aesthetical appeal to the paint film. To give resistance against UV-light, abrasion, wear, etc To improve the impermeability of paint film from moisture and increase weather resistance.

THE MOST COMMONLY USED PIGMENTS ARE,

White pigments: white lead, Zn, lithophone. Black pigments: Lamp black, Carbon black Red pigments: Venetian red, Indian red, Chrome red and Red lead. Blue pigments: Prussion blue. Green pigments: Chromium oxide. Yellow pigments: Chrome yellow and Zinc yellow.

VEHICLE OR DRYING OILS

1. It is film forming constituents of he paint . These are glyceryl esters of high molecular weight fatty acids present in animal and vegetable oils. FUNCTIONS: They form a protective film by the oxidation and polymerisation of the oil. They hold the pigment particles together on the metal surface. They impart water repellency, toughness and durability to the film. Examples : Linseed oil, Soyabeen oil, Dehydrated castor oil, Tung oil, etc.

THINNERS (or) SOLVENTS

Thinners are added to the paint to reduce the consistency or viscosity of the paints, so that they can be easily applied to the metal surface. Thinners are highly volatile solvent. FUNCTIONS They reduce the viscosity of the paint. They dissolve the oil, pigments, etc. and produce a homogeneous mixture. They increase the elasticity of the film. They evaporate readily and help the drying of the film. They increase the penetrating power of the vehicle. Ex: Turpentine, petroleum sprit, kerosene, xylol, etc.

DRIERS
Driers are used to accelerate or catalysing of the oil film by oxidation, polymerization and condensation. The main functions of drier is to improve the drying quality of the oil-film. Examples: Resonates, Linoleates, Tungstates and Napthenates of Cobalt, Lead, Manganese and Zinc.

FILLERS (or) EXTENDERS

Fillers are added to the paint to reduce the cost and increase the durability of the paint.
1. 2. 3.

FUNCTIONS They reduce the cost and increase the durability of the paint. They serve to fill the voids of the paint film. They help to reduce the cracking of paint.
Examples: Calcium carbonate, China clay, gypsum etc.

PLASTICISERS
Plasticisers are chemical added to the paint to give elasticity to the film and to prevent cracking of the film. Ex: Triphenyl phosphate, Tributyl phthalate, etc.

ANTISKINNING AGENTS
They are chemicals added to the paint to prevent gelling and skinning of the paint film. Important antiskinning agents are Polyhydroxy phenols.

Special Paints
Fire retardant paints Water repellant paints Temperature-indicating paints Heat resistant paints Surface Preparation for Metallic Coatings

Solvent cleaning Alkali cleaning Acid cleaning Mechanical cleaning Flame cleaning Sand-blasting

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Electroless Plating
Electroless plating is defined as the controlled auto catalytic deposition of a continuous film by the interaction of a solution of a metal salt and a chemical reducing agent. The reducing agent reduces the metallic salt to metal, which gets deposited over the catalytically activated surface giving a uniform thin coating.
Metal salt + Reducing agent Metal + Oxidized products
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Various Steps of Electroless Plating

Step 1: Pretreatment and activation of the surface: (i) Treatment with an organic solvent followed by conditioning or etching by dipping, in a bath of acid. (ii) Activation by immersion in a colloidal solution of tin or palladium. This yields a thin layer of Pd or Sn on the treated surface. (iii) A thin layer of the metal to be plated or anyother suitable metal is electroplated on the surface of the object.
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Step 2: Preparation of plating bath: The ingredients in the plating bath are, (i) Coating metal: Soluble salt of the metal to be deposited. (E.g., chlorides and sulphates) (ii) Reducing agent: It reduces the metal salt to metal (E.g., Formaldehyde, hyppphosphite etc.) (iii) Exaltant: It enhances the plating rate. (E.g., Succinate, fluoride etc.) (iv) Complexing agent: It improves the quality of the deposit. (E.g., Tartrate, citrate, succinate etc.) (v) Stabilizers: Stabilizers prevent the decomposition of the plating bath solution. (vi) Buffer solution: It is added to control the pH of the 102 bath. (E.g., CH3COONa, NaOH + rochelle salt)

Step 3: Procedure: The object to be placed is cleaned and activated and then immersed in the bath containing the salt of the metal, reducing agent, exaltant, complexing agent, stabilizer and buffer solution. The metal salt is reduced to the corresponding metal. Example: Electroless Nickel Plating

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HOT CORROSION
During Viet Nam War, hot gas turbine engine components suffered extreme corrosion attack. Sulfides were found in Ni-based alloys, and the protective oxide layers could not protect the alloys. The problem was called Sulfidation (a reaction with sulfur to form sulfides).
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 Sulfur is one of the most common corrosive contaminants in high-temperature industrial environments.
Sulfur is generally present as an impurity in fuels or feedstocks. Typically, fuel oils are contaminated with sulfur varying from fractions of 1% (No. 1 or No. 2 fuel oil) to about 3% (No. 6 fuel oil). Coal may contain from 0.5 to 5% S, depending on where it is mined. Sulfur is one of the corrosive species in petroleum refining operations.
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 Feedstocks for calcining operations in mineral and chemical processing are frequently contaminated with various amounts of sulfur.
Calcining is a thermal treatment process applied to ores and other solid materials to bring about a thermal decomposition, phase transition, or removal of a volatile fraction. The calcining process normally takes place at temperatures below the melting point of the product materials.
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 Several important engineering systems operating at high temperatures (650-11000C) involve contact of metallic surfaces with combustion product gases or other oxidizing gases containing inorganic impurities.
Hot corrosion is observed in boilers, incinerators, diesel engines, internal combustion engines, gas turbines engines (industrial, marine, and aircraft). Hot corrosion is an accelerated form of corrosion in which molten salts form a film on a metal surface that destroys the normal protective oxide layer.
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 The so-called dirty fuels contain impurities of sodium, sulfur, phosphorus, and vanadium. During combustion, these impurities melt or vaporize to get deposited on metal at temperatures below the condensation temperature of the specific species.
Molten salt mixtures of sulfates and vanadates, and hot combustion products such as oxides of sulfur and vanadium are corrosive in nature, and dissolve the protective oxide on the metal surface.
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 Molten salts, especially sodium sulfate (Na2SO4), react with the protective oxide layer or the underlying metallic material through coating defects causing severe hot corrosion damage.
In combustion products of fuel oil, sulfur is typically present as Na2SO4, that dissociates according to the following reaction at high temperatures: Na2SO4 Na2O + SO3 The corrosion rate increases with the salt deposition rate, but the relationship is nonlinear and depends on the composition of the salt and the substrate alloy or coating.
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 Vanadium as an impurity in fuel oil causes serious corrosion problems because of the formation of V2O5 which has a melting point of 6700C.
The problem is often compounded if sodium is present because some V-Na mixed oxides have still lower melting point. For example, sodium vanadyl vanadate 5Na2O.V2O5. 11V2O5 melts at 5450C. Liquid deposits formed in this way flux the protective oxide layers on structural alloys, making them vulnerable to rapid corrosion.
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 The specific chemical processes of corrosion vary according to temperature: Low Temperature Hot Corrosion (600-750C) High Temperature Hot Corrosion (850-950C).
Low temperature hot corrosion is very sensitive to SO3 partial pressures in the gas phase. High temperature hot corrosion is not quite as sensitive to SO3 levels.

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Low Temperature Hot Corrosion (600-750C)

LTHC involves metal-oxides such as NiO and CoO reacting with SO2 and SO3 in the air to form stable, low-melting point sulfates that deposit on to the coating (corrosion rates increase drastically when salt mixtures such as Na2SO4, NiSO4, CoSO4, and Na2S2O7 are in the liquid state). The sulfates can then cause pitting attack by reacting with the protective oxide layer through acidic fluxing. LTHC may also be attributed to the local formation of molten pyrosulfate.
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 Sulfate Formation NiO + SO3 NiSO4 CoO + SO3 CoSO4

Liquid Pyrosulfate Formation Na2SO4 (s) + SO3 (g) Na2S2O7 (l) Acidic Fluxing by Liquid Pyrosulfate Fe2O3 + 3Na2S2O7 2FeSO4 + 2Na2SO4 + 1/2O2 Resistant Materials: High chromium containing metallic coatings provide excellent resistance to low temperature hot corrosion.
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High Temperature Hot Corrosion (850-950C)

HTHC begins with molten sulfate deposition onto the protective oxide layer of the coating (usually Cr2O3 or Al2O3). Oxide reactions with molten Na2SO4 create oxygen anions leading to layer dissolution and formation of non-protective compounds through basic fluxing.

Nickel and cobalt sulfide formation can be especially catastrophic by both dissolving and preventing the reformation of the oxide layer, leaving the underlying superalloy exposed.
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 Formation of NiS and generation of O24Ni + Na2SO4 3NiO + NiS + Na2O Formations of non-protective oxides from O2NiO + O2- NiO22Al2O3 + O2- 2AlO2Cr2O3 + O2- 2CrO2 Resistant Materials: Platinum modified nickelaluminides and MCrAlX materials provide the best protection against high temperature hot corrosion.
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 Degradation mechanism of hot corrosion changes with time. There are two distinct stages of attack, an initial stage during which the attack is not too severe and a later stage for which the attack is substantially increased. These two stages are known as initiation stage and propagation stage.

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Initiation stage of hot corrosion

During the initiation stage elements in the alloy are selectively oxidized and the reaction products form a protective layer/barrier on the alloy surface. As the hot corrosion process continues, a salt layer is deposited above the reaction product barrier that affects the corrosion process.

Eventually the protective barrier formed is rendered ineffective, and the hot corrosion process enters into the propagation stage.
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PARABOLIC TIME DEPENDENCE

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Factors affecting initiation stage of hot corrosion

Alloy composition Alloy composition is a critical factor in the initiation of corrosion attack. No alloy is immune to hot corrosion attack indefinitely, although there are some alloy compositions that require extremely long initiation times before the propagation stage is evident. e.g. when the aluminum content of nickelchromium or cobalt-chromium alloy is increased from 6 to 11%, the length of initiation stage induced by Na2SO4 in air increases.
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 Temperature The time to initiate attack can be decreased as the temperature is increased. Gas composition The composition of the gas phase can produce very substantial effects on the initiation of attack, the rate of attack, and the particular propagation mode that is followed. Hot corrosion attack is more easily induced when a liquid phase is present.
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 Salt composition and deposition rate The composition of the deposit and the rate at which it accumulates on the surfaces of alloys affects not only the time required to initiate hot corrosion attack but also the type of propagation mode that is followed. The degradation becomes more severe as the NaCl concentration in the deposit is increased. Hot corrosion attack occurs because the deposit modifies the type of reaction that takes place between the alloys and the gas environments. Normally, a liquid deposit is most effective in causing hot corrosion attack, but it is not required to produce such attack.
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Propagation modes of hot corrosion

The propagation modes for hot corrosion are closely related to the reactions between the molten deposits and the alloys. The molten deposits result in formation of nonprotective reaction products. The propagation modes are divided into two groups: (a). Non-protective reaction product is formed because of some fluxing action of the molten deposit. (b). Non-protective reaction product is formed because a component of the deposit (S or Cl) plays a dominant role in the process.
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SALT FLUXING/DISSOLUTION
The protection efficiency of the surface oxide layer is lost as a result of dissolution of this layer with the molten salt. Types of fluxing
Basic fluxing Acidic fluxing

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BASIC FLUXING
Basic fluxing is combination of metal oxides with oxide ions (O2-) to form anions. Oxide ions are produced in the Na2SO4 deposit due to removal of oxygen and sulfur from the deposit via reaction with the alloy or metal. The oxide scales (MO) that normally would form as protective barriers on the surfaces of alloys can react with these oxide ions via reactions such as MO + O2- MO22and their protective properties are destroyed.
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ACIDIC FLUXING
Acidic fluxing is decomposition of metal oxides into the corresponding cations and oxide ions (O2-). MO M2+ + O2- . When a component present in the gas causes the deposit to be acidic, it is called Gas Phase Acidic Fluxing. When an oxide of an element present in the alloy causes the melt to become acidic, it is called Alloy Induced Acidic Fluxing.
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Gas Phase Acidic Fluxing

Gas phase acidic fluxing is observed at temperatures between 650 and 8000C, and hence is often called low temperature corrosion. SO3 + O2- SO42SO3 + SO42- S2O72-. With increase in temperature, the partial pressure of SO3 decreases and the corrosion attack also decreases. At the same SO3 pressure, the corrosion process is more severe at intermediate temperature, about 700C, than at 1000C.
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Alloy-Induced Acidic Fluxing

Alloy-induced acidic fluxing results from the accumulation of oxides, such as MoO3, WO3, V2O5 in the salt deposit. The solutions of oxides of these elements with Na2SO4 decrease the oxygen ion activity of the molten salts, producing melts that are acidic fluxes for the oxide scale. This form of hot corrosion attack may be reduced by decreasing the Mo, W, V concentration in the alloy.
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 Mo + 1.5O2 MoO3 MoO3 + Na2SO4 Na2MoO4 + SO3 Al2O3 + 3MoO3 (in Na2SO4) 2Al3+ + 3MoO42-

The Al2O3 dissolves into melt at regions where MoO3 activity is high and could precipitate out wherever the activity of MoO3 is low, as could occur at the surface of the melt where MoO3 is being lost to the gas phase.
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DEPOSIT-COMPONENT-INDUCED HOT CORROSION

An important characteristic of hot corrosion is the reduction of the oxygen activity over the alloys by the deposit. There are certain elements present in the alloys that have high affinities for oxygen, e.g. Sulfur and Chlorine. However, access of oxygen to the alloy is restricted due to the fact that it must diffuse through the deposit. Thus, conditions become more favorable for other elements in the deposit to react with the elements in the alloys.
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Sulfur Effects
In an alloy exposed to SO2-O2, sulphides result from the sulphur in the gas rather than from Na2SO4. The sulphides accumulation in the alloy negatively affects the protective oxide formation: when sulphur diffuses into the surface of the alloy, it usually reacts with the same elements that are diffusing to the surface that should react with oxygen to form a protective scale.

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 The sulphide production results in the flux to the surface of these elements, being selectively oxidized, to decrease and thus the formation of a less protective oxide scale, which brings about a substantial degradation during subsequent oxidation. The corrosion rate increases rapidly in the oxidation / sulphidation regime with increasingly sulphidation conditions and increases more slowly on entering the sulphidation regime.
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Chlorine Effects
Chlorine in deposits affects the hot corrosion of alloys in two ways. First, chlorine concentrations in the ppm range have been found to increase the tendency of oxide scales (Al2O3 and Cr2O3) on alloys to crack and spall (to break up into chips, fragments, or flakes). Second, larger concentrations of chloride in the deposits result in the development of pores or channels in alloys whereby the chromium and aluminum is preferentially removed, and totally non-protective oxide scales of these elements are formed on the surfaces of alloys.
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Losses due to Corrosion4

LOSSES DUE TO CORROSION

4Uhlig,

H.H. and R.W. Revie, Corrosion and Corrosion Control. 3rd ed. 1985, New York: John Wiley & Sons. 12

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 Loss of metal by corrosion is a waste not only of the metal, but also of the energy, the water, and the human effort that was used to produce and fabricate the metal structures in the first place. In addition, rebuilding corroded equipment requires further investment of all these resources metal, energy, water, and human.

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 Economic losses are divided into (1) direct losses and (2) indirect losses.
Direct losses include the costs of replacing corroded structures and machinery or their components, such as condenser tubes, mufflers, pipelines, and metal roofing, including necessary labor. Other examples are (a) repainting structures where prevention of rusting is the prime objective and (b) the capital costs plus maintenance of cathodic protection systems for underground pipelines. Direct losses include the extra cost of using corrosion - resistant metals and alloys instead of carbon steel where the latter has adequate mechanical properties but not sufficient corrosion resistance; there are also the costs of galvanizing or nickel plating of steel, of adding corrosion inhibitors to water, and of dehumidifying storage rooms for metal equipment. Indirect losses are more difficult to assess.
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SOCIAL CONSEQUENCES
Safety, e.g., sudden failure can cause fire, explosion, release of toxic product, and construction collapse. Health, e.g., pollution due to escaping product from corroded equipment or due to a corrosion product itself. Depletion of natural resources, including metals and the fuels used to manufacture them. Appearance as corroded material is unpleasing to the eye.
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COST OF CORROSION
Which cost more?
Corrosion Fire Flooding Earthquake

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Cost of Corrosion(2004)
Country
USA Japan Former USSR Germany UK Australia

Direct Cost (Billion $)

303.76 59.02 55.01 49.26 8.51 7.32

Indirect Cost (Billion $)

200 (approximately)

Belgium
India Poland Canada

6.75
3.78 3.53 3.38

.....
.. ..... Global 510.14 940 (approximately)
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EXAMPLE OF OVERDESIGN
An 8" internal diameter oil pipeline 225 miles long with 1 wall thickness is installed with no corrosion protection system With appropriate protection namely cathodic protection, it would require a thin wall thickness which would
save 3,700 tons of steel (worth more than one million dollar) increase internal capacity of the pipeline by about 5%.
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Any engineering project undertaken by an organization has the underlying aim of enhancing the wealth of its owners. Management in industry ultimately takes its decisions on this above principle, including those related to corrosion control. Key motives for making capital investments: 1. Expansion for increasing the scope and output of operations 2. Replacement for obsolete or rundown assets 3. Renewal for life extension of assets, as an alternative to replacement 4. Investment in nontangible assets such as advertising, research, information, management consulting, etc.

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CASH FLOW
Every corrosion engineering project will have a certain cash flow pattern over time. Usually, there is an initial outflow of cash, when a new asset fitted with a certain corrosion control system is acquired. Subsequently there are inflows of cash, resulting from operations and further cash outflows required for maintenance, corrosion control upgrades, running costs, and so forth.
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CAPITAL BUDGETING TECHNIQUES

In capital budgeting techniques the different cash flows involved in the project are identified, estimated, and analyzed, with a view to maximizing owners wealth. Types of capital budgeting techniques 1. Internal Rate of Return (IRR) 2. Present Worth of Future Revenue (PWRR) 3. Discounted Payback (DBP) 4. Benefit-Costs Ratios (BCR) 5. Net Present Value (NPV)

Requirements

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TIME VALUE OF MONEY

When the cash inflows and outflows over time are considered, the time value of money has to be taken in to consideration. The concept of time value of money implies that money has a value that varies depending on when it is received or disbursed.

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Important Capital Budgeting Techniques

Internal Rate of Return (IRR) The IRR is defined as the discount rate that equates the present value of all cash flows with the initial investment made in a project. The IRR consists essentially of the interest cost or borrowed capital plus any existing profit or loss margin. If the IRR is greater than the cost of capital, accept the project. If the IRR is less than the cost of capital, reject the project.

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Net present value The net present value (NPV) or net present worth (NPW) is defined as the present value of all inflows less the present value of all outflows.
Factors that need to be considered in calculating net present worth include: -Initial cost -Best estimate of expected life -Length of shutdown for emergency repair -Cost of maintenance during planned shutdowns -Effect of failure on total plant operation
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If...... NPV > 0

NPV < 0

NPV = 0

It means the investment would add value to the firm the investment would subtract value from the firm the investment would neither gain nor lose value for the firm

Then... the project may be accepted

the project should be rejected Decision should be based on other criteria, e.g. strategic positioning or other factors not explicitly included in the calculation.

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S P 1 i

RELATION BETWEEN FUTURE VALUE AND PRESENT VALUE S = P (1 + i)n

or S =P.FPS Future value = (present value) x (compound-interest factor) i = the rate of return n = time in years FPS = factor for converting P to S
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PR

(1 i) n 1 i(1 i) n

UNIFORM ANNUAL AMOUNT (UNACOST)

A uniform end-of-year annual amount R for a period of n years is called as unacost. P = R (1+i)n 1 i(1+i)n
or P = R.FRP

Present value = (unacost) x (unacost present-value factor)

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ANNUITY
A series of equal payments at equal intervals is called an annuity. An ordinary annuity has the payments at the end of the period. An annuity due has payments at the beginning of the period. A deferred annuity has the first payment delayed in date. A forborne annuity continues to earn interest after its termination when payments end. A perpetuity is an annuity that continues forever.
149