CORROSION OF METALS

Introduction Definition Economic impact Types of Corrosion Combating corrosion Anti corrosive coatings and Paints

The diffuse dispersion of metals in the society has many sources.

Any material which serves the humans needs such as housing, food, clothing, communication, transportation, energy, socioeconomic development has the inherent tendency to decay. Virtually no engineering material is stable. The rate of decay varies depending upon the material and its environment. The basic cause of corrosion is the instability of metals in their refined forms. The metals tend to revert to their natural states through the process of corrosion..

Corrosion - Introduction

No material is inert! All metals/alloys interact with the environment.

SO2

Metal runoff/release
Me, Men+

Corrosion process

Contd

Corrosion - Introduction

How to stop this reversion? In order to stop reversion to the natural state, engineering materials require
protective coatings, inhibitors, alloy additions, design procedures, maintenance and refurnishing. It is good to extend the life of materials, keep them corrosion free as possible. Extending the life of a 1000 megawatt nuclear power plant for one day would mean a saving of 0.5 mill dollars.

What is Corrosion ?
Corrosion is the gradual physico chemical destruction of materials by the attacking action of the environments.

The word corrosion originated from

the Latin word corrodereto gnaw

away.

Definition of Corrosion
Corrosion may be defined as the destruction of material by chemical, electrochemical, or metallurgical interaction between the environment and the material.
The term corrosion is sometimes also applied to the degradation of plastics, concrete and wood, but generally refers to metals.

Impacts of corrosion
Losses are economic and safety: Reduced Strength Downtime of equipment Escape of fluids Lost surface properties Reduced value of goods

Impacts of corrosion
The consequences of corrosion are many and varied and

the effects of these on the

safe, reliable and efficient operation of equipment or structures are often more serious than the simple loss of a mass of metal. Failures of various kinds and the need for expensive replacements may occur even though the amount of metal destroyed is quite small.

Economic Impact
Corrosion a most serious problems of industry Corrosion causes damage in the billions of dollars each year. Apporx. 10% world metal production is completely lost due to corrosion each year.

According to estimate national annual costs of corrosion to a country vary from 1 % to 4 % of GNP.

Economic Impact
A study showed that for 1998 the total annual direct cost of corrosion in the US was $276 billion ( 3.1% of the US GDP. 15% to 25% of this loss can be saved if available knowledge and techniques are used.

How much does corrosion really cost?

Highways and Bridges

Before

After

Silver Bridge Collapse December 15, 1967 in Kanauga, OH

How much does corrosion really cost in USA ?

Highways & Bridges1: $8.3 Billion per year + safety issues

Economic losses
Costs of corrosion are divided into direct & indirect losses Direct losses

include costs of replacement of corroded structures & machinery / their components, e.g., condenser tubes, pipelines, metal roofings, repainting of structures against rusting.
These losses also include the extra cost of using - corrosion-resistant material in place of Carbon steel or other cheaper materials, - adding inhibitors to enclosed systems, - protective systems for metal structures.

Economic losses
Indirect losses Loss of product

Loss of production
Loss of efficiency Product contamination Over design Maintenance of stand-by Machinery & Equipment

General loss e.g., loss of health & life which can not be computed in terms of money.

Types of Corrosion
Dry corrosion or oxidation of metals Atmospheric corrosion Pitting Corrosion

Wet corrosion or electrochemical oxidation Galvanic Corrosion

Electrode Potential Examples of Galvanic Corrosion

Erosion / Cavitation corrosion

Fretting corrosion

Crevice Corrosion
Stress Corrosion Intergranular Corrosion Microbial Corrosion

Dry Corrosion or Oxidation of Metals

(scaling of iron at high temperature)

Many metals tend to oxidize to some extent at all temp. When iron heated in the presence of oxygen it becomes coated with a film of black scale as per following reaction: 2Fe + O2 = 2FeO Iron is oxidized as its atoms lose electrons.

Wet Corrosion or Electrochemical Oxidation

Iron does not rust
in a completely dry atmosphere,

nor will it rust

in completely pure, O2-free water,

but in a moist atmosphere, as a result,

reddish-brown deposit of ferric hydroxide soon begins to develop, as :

4Fe + 6H2O + 3O2 = 4Fe(OH)3

Contd

Wet Corrosion or Electrochemical Oxidation

The fundamental principle is that atoms of iron in contact with oxygen and water oxidize, i.e., they lose electrons and enter into solution as ferrous ions (Fe++) which are further oxidized to ferric ions (Fe+++).

Galvanic Series
Ranks the reactivity of metals/alloys in seawater
Platinum Gold Graphite Titanium Silver 316 Stainless Steel Nickel (passive) Copper Nickel (active) Tin Lead 316 Stainless Steel Iron/Steel Aluminum Alloys Cadmium Zinc Magnesium
8

Electrode Potential for some metals

Galvanic Corrosion
Galvanic Corrosion occurs when two dissimilar metals electrically contact each other and are immersed in an electrolyte. In order for galvanic corrosion to occur, an electrically conductive path and an ionically conductive path are necessary. This affects a galvanic couple where the more active metal corrodes at an accelerated rate and the more noble metal corrodes at a retarded rate

Requirements for Corrosion:

In order for galvanic corrosion to occur, an electrically conductive path and an

ionically conductive path are necessary.

Ionic Current Path

ANODE

CATHODE

Where Corrosion Occurs!!!!

Electronic Path

Anodic & Cathodic Reactions

Examples of Galvanic corrosion

Galvanic corrosion of pearlite

Galvanic corrosion an examples of bad plumbing

Atmospheric Corrosion
Most common & economically most costly form. The atmospheric corrosion process depends not only on the moisture content of air but also on the gaseous impurities, dust particles and other

contaminants

which

favour

condensation

of

moisture on the metal surface. Atmospheric corrosion rates vary markedly all over the world depending upon the climatic region, season of the year, time of the day etc.

Contd

Atmospheric Corrosion

Approaching the sea coast, air is laden with increasing amount of sea salt. At industrial areas, appreciable amounts of SO2 which is converted into H2SO4, and to lesser amounts of H2S, NH3,

NO2 and various suspended salts are encountered.

A metal resisting one atmosphere may lack effective resistance elsewhere and hence relative performance of metals changes with location.

Pitting Corrosion
Pitting is a localized attack, in the form of pits, such as observed on stainless steel immersed in chloride ion solutions.This causes premature failure. The main causes of pitting are
galvanic corrosion,

low or high oxygen concentrations and

applied stresses.

Erosion corrosion
Erosion is acceleration of

corrosion because of relative

movement between corrosive fluid and material as may occur in pumping equipment.

Cavitation corrosion
Cavitation corrosion is a form of velocity effect caused by the explosion of bubbles formed where the local pressure in the flowing fluid drops below the vapour pressure of the

liquid.
It is observed on ship propellers, pump impellors

etc.

Fretting corrosion

Fretting corrosion is a surface damage produced by vibration which results in striking or rubbing at the interface of close fitting, highly loaded surfaces. It is common at surfaces of clamped or press fits, splines, keyways, and other close-fitting parts subject to minute relative movement.

Fretting corrosion ruins bearings, destroys dimensions, and reduces fatigue strength.
This type of corrosion is a mechanical-chemical phenomenon.

Crevice Corrosion
It is a intense

localized corrosion at
a crevice under a bolt head or flanged connections usually due to concentration cells.

Crevice Corrosion

Stress Corrosion
Stress corrosion is caused by simultaneous presence of tensile stress and a particular corrosive medium e.g., cracking of cold worked Cu or brass in ammonia or stainless steel in chloridecontaining water. The magnitude of stress necessary to cause failure depends on the corrosive medium and on the structure of base metal.

Intergranular Corrosion
It occurs in the vicinity of grain boundaries Due to elevated temperature Chromium Carbides can form in the grain boundaries of SS.

This Chemical reaction depletes the Cr in the HAZ near the grain boundary, making those areas much less resistant to corrosion. This creates a galvanic cell which leads to weld decay.

Intergranular Corrosion
Preferential attack along grain boundaries
Results from localized differences in chemistry Common in SS, nickel some Al alloys

Sensitive Regions precipitates

Microbial Corrosion
Microbial or Bacterial Corrosion is caused or promoted by microorganisms. It can apply to both metals and nonmetallic materials, in both the presence and lack of Oxygen.

Sulfate reducing bacteria are common in lack of oxygen; they produce hydrogen sulfide causing sulfide stress cracking.
In the presence of oxygen, some bacteria directly oxidize iron to hydroxide.
Titanics bow exhibiting microbial corrosion damage in the form of rusticles

Corrosion of plastics
This dished end of a vessel is made of glass fibre reinforced PVC. Due to internal stresses and an aggressive environment it has suffered

environmental stress
cracking.

Some examples of corrosion

Galvanic corrosion

This rainwater guttering is made of aluminium and would normally resist corrosion well. Someone tied a copper aerial wire around it, and the localised bimetallic cell led to a knife-cut effect.

Galvanic corrosion
This polished Aluminium rim was left over Christmas with road salt and mud on the rim. Galvanic corrosion has started between the chromium plated brass spoke nipple and the aluminium rim.

Galvanic corrosion
Galvanic corrosion can be even worse underneath the tyre in bicycles. Here the corrosion is so advanced it has penetrated the rim thickness.

Erosion corrosion

Erosion-Corrosion

Intergranular Corrosion Occurs in specific alloys precipitation of corrosive specimens along grain boundaries and in particular environments

e.g. : Chromium carbide forming in SS, leaving adjacent areas depleted in Cr

Solutions:

High temp heat treat to redissolve carbides Lower carbon content (in SS) to minimize carbide formation Alloy with a material that has formation (e.g., Ti or Nb)

stronger carbide

Intergranular Corrosion Intergranular stainless steel Corrosion

Influence of corrosion on value

A very slight amount of corrosion may not interfere with the usefulness of an article, but can affect its commercial value. At the points where these scissors were held into their plastic case some surface corrosion has occurred which would mean that the shop would have to sell them at a reduced price.

Motor vehicle corrosion and safety

The safety problems associated with corrosion of motor vehicles is illustrated by the holes around the filler pipe of this petrol tank. The danger of petrol leakage is obvious. Mud and dirt thrown up from the road can retain salt and water for prolonged periods, forming a corrosive poultice.

House Drain and Drain Cap

1 year old cap

30 year old cap

METAL: Cast Iron ENVIRONMENT: Residential basement water exposure FORM OF CORROSION: General METHOD TO CONTROL! Surface is painted for protection. Note the 1 year old cap shows significant corrosion already!

Corrosion at sea

Sea water is a highly corrosive electrolyte towards mild steel. This ship has suffered severe damage in the areas which are most buffeted by waves, where the protective coating of paint has been largely removed by mechanical action.

Aluminium Corrosion
The current trend for aluminium vehicles is not without problems. This aluminium alloy chassis member shows very advanced corrosion due to contact with road salt from gritting operations or use in coastal / beach regions.

Corrosion: an extensive, expensive materials degradation process

Corrosion in a high temperature pipeline

A rusted shipwreck

Forms of Corrosion

Stainless screw v cadmium plated steel washer

Forms of Corrosion

Stress Corrosion Cracking (SCC) in a U-bend sample of 316 stainless steel exposed to Supercritical Water Oxidation (SCWO) environment

Exfoliation in aluminum aircraft alloy

Corrosion control / prevention

Combating Corrosion
Following are the most important methods used in industry for protection of corrosion: Use of high purity metals Use of alloy additions

Use of special heat treatments

Proper design Cathodic protection Use of Inhibitors Surface coatings

Proper Design

Cathodic Protection
It is a technique to control the metal surface by making that surface the cathode of an electrochemical cell. By means of an externally applied electric current, corrosion is reduced virtually to zero, and metal surface can be maintained in a corrosive environment without deterioration for an indefinite time . It is most commonly used to protect steel, water and fuel pipelines and tanks, ships and offshore oil platforms.

Sketch of Cathodic Protection showing pipe, auxiliary anode and rectifier

Reactive Coatings by using Inhibitor

If the environment is controlled in re-circulating systems, corrosion inhibitors (chromates, phosphates, long change organic molecules) are added to it. These form an electrically insulating and / or chemically impermeable coating on exposed metal surfaces, to suppress electrochemical reaction. Thus corrosion is reduced or eliminated.

Inhibitors are added to the antifreeze mixtures used in automobile radiators.

Anti-corrosive surface Coatings

Metal surface can be protected by the provision of following surface coatings:

Paints,
Oxide films and Metallic coatings Note: Prior to applying coatings, pretreatments (such as shot/sand blasting, cleaning, pickling, rinsing, drying etc) of substrate is essential.

Paints
Paints and other organic coatings are primarily used to improve to appearance of the surfaces and structures. Its use for corrosion protection only is secondary. Paints [which are mixture of pigments (metallic oxides e.g., TiO2, Pb3O4, Fe2O3 or other compounds ZnCrO4, PbCO3, BaSO4 etc) suspended in organic or aqueous vehicle] provide a protective film to the metal and is effective only as long as the film is unbroken.

Anodizing

Aluminum alloys often undergo a surface treatment. Electrochemical conditions in the bath are carefully adjusted so the uniform pores several nanometers wide appear in the metals oxide film. These pores allow the oxide to grow much thicker then passivating. At the end of the treatment, the pores are allowed to seal, forming a harder-than-usual surface layer. If the coating is scratched, normal passivation processes take over to the protect the damaged area

Metallic Coatings
Metallic coating may be obtained by a variety of methods such as:

Diffusion (Carburizing, Cyaniding, Nitriding, Chromizing)

Hot dipping (mainly coating of Zn, Sn, Pb, Al & Cd on steel)

Galvanizing / Znic coating; used for the protection of nuts, bolts, screws, nails etc. Electroplating

Metallic Coatings
Cladding Coating becomes the integral part of the metal. In this process, sheets of cladding material are strapped to an ingot of the base material. After heating to the rolling temp, the straps are removed and the entire assembly is rolled.

The heat and pressure during rolling weld the two

materials together, e.g., Alclad or GMCS.

Thanks

Corrosion prevention