CORROSION OF METALS

A deterioration/ destructive of material by chemical, electrochemical, or metallurgical interaction between the environment and the material

i.e the tarnishing of silver, iron rusting, dissolution of metal in acid solution Corrosion agent to metal
1. 2. 3. 4. 5. 6.

Water Moisture Acids Bases Salts Oils

Disadvantage: economic terms higher expense to spent for corrosion prevention and maintenance/ replacement Advantage: etching, dry cell batteries

ELECTROCHEMICAL CONSIDERATION

Corrosion process is normally electrochemical process

Involve chemical reaction

transfer from one chemical species to another

3 important process in corrosion

Electrolyte (any solution that contains ion) Anode (oxidation) Cathode (reduction)

Anode

Oxidation process occurs Oxidation metal atom lose/ give up

M M n+ + n i.e ; Fe Fe 2+ + 2

CATHODE

Reduction reaction occurs Gains of ( from metal atom that is oxidized) The reaction at cathode
M n+ + M n-1 Or M n+ + n M i.e Mg 2+ + 2 Mg

It is possible for two or more of reduction reaction occurs

Corrosion in acid solution which have a high concentration of hydrogen ions.

2H+ + 2 H2

For an acid solution having dissolved oxygen. The reduction follows

O2 + 4H+ 4 2H2O

For a neutral or basic aqueous solution

O2 + 2H2O + 4 4(OH- )

Individual oxidation and reduction are termed half reaction

Zn Zn2+ + 2 2H+ + 2 2H+ (gas) Zn + 2H+ Zn2+ + 2H+ (gas)

Electrode potential

The potential of metallic materials oxidize to form ions do not have the same degree of ease

two half-cell reactions for A

Fe Fe2+ + 2 Cu2+ + 2 Cu Fe + Cu2+ Fe2+ + Cu Overall cell potential V = V2 - V1 = 0.340-(- 0.440 ) = 0.780

V1 anode = -0.440 V2 cathode = +0.340

two half-cell reactions for B

Zn Zn2+ + 2 Fe2+ + 2 Fe Zn + Fe2+ Zn2+ + Fe Overall cell potential V = V2 - V1 = -0.440+0.763 = 0.323

V1 anode = -0.763 V2 cathode = -0.440

Various electrode pair have diff. voltages

The Standard EMF series

Measured cell voltage

Represent only diff. in electrical potential from reference cell Reference cell : using standard hydrogen electrode

Hydrogen electrode and a standard half cell

A standard half cell an electrochemical cell consisting of pure metal immersed in a 1M aqueous solution of its ions, which is electrically coupled to the standard hydrogen electrode.

Standard EMF series

One half an electrochemical cell consists of a pure iron electrode in a solution of Fe2+ the other is the tin electrode immersed in the Sn2+ solution. Write the spontaneous overall reaction and calculate the voltage that is generated

Galvanic series represents the relative reactivity of a number of metals and commercial alloys in seawater

Galvanic series

Corrosion rate

The rate of material removal as a consequence of the chemical action the weight loss can be converted to corrosion rate in units

mm/yr mpy (mils per year)

Corrosion current is used to generate a corrosion rate

CR = Icorr K EW / A
CR = The corrosion rate. Its units are given by the choice of K Icorr = The corrosion current in amps K EW =A constant that defines the units for the corrosion rate =The equivalent weight in grams/equivalent

= Density in grams/cm3
= Sample area in cm2

EW = m / n

m= Atomic mass of the species n = is the number of electrons transferred per molecule or atom Current density i ; I/A

Corrosion Rate Constants

Corrosion Rate Units mm/year (mmpy) millinches/year (mpy) 3272

Units mm/(amp-cmyear) milliinches(ampcm-year)

1.288x105

Types/ Form of corrosion

Uniform corrosion Galvanic corrosion Stress corrosion Erosion corrosion Crevice corrosion Pitting corrosion

Uniform corrosion

when the entire surface of the metal is attacked to same degree.

easily measured and predicted

Effect can be a tarnishing colour or rough surface of metal

The reaction starts at the surface and proceeds uniformly.

Galvanic corrosion

Occurs at the interface where two metals are in contact in a corroding medium

So three conditions must be present: Electrochemically dissimilar metals must be present; These metals must be in electrical contact; and The metals must be exposed to an electrolyte.

When a galvanic couple forms, one of the metals in the couple becomes the anode and corrodes faster than it would all by itself, while the other becomes the cathode and corrodes slower than it would alone.
It is this potential difference that is the driving force for galvanic current flow area ratio of metal also influence the galvanic corrosion rate Normally occurs at joining i.e fastener, welded

aluminum helicopter blade has corroded near where it was in contact with a steel counterbalance.

Stress corrosion

acceleration of corrosion in certain environments

important and difficult to predict the failure

Cracking present due to corrosive environment and stress induce

A.k.a Stress corrosion cracking (SCC) stress either internal tensile stresses (cold work) or external stressed

The magnitude of stress necessary to cause failure depends on the corrosive medium and on the structure of the base metal
In the microstructure, these cracks can have an intergranular (fig. A) or a transgranular (fig. B) morphology.

Macroscopically, SCC fractures have a brittle appearance.

Figure A

Figure B

i.e material:

steel containing aluminium have better resistance to stress corrosion Stainless steels are susceptible to stress corrosion cracking in the presence of chlorides

Erosion corrosion

an acceleration in the rate of corrosion attack in metal due to the relative motion of a corrosive fluid and a metal surface It is characterized by surface features with a directional pattern which are a direct result of the flowing media. Erosion corrosion is most prevalent in soft alloys (i.e. copper, aluminum and lead alloys). factors such as turbulence, cavitation, impingement or galvanic effects can add to the severity of attack.

Erosion corrosion mechanism

Crevice corrosion

a localized form of corrosion usually associated with a stagnant solution on the microenvironmental level

Concentration differences of ions or dissolved gases in the electrolyte solution can accelerated the corrosion
Corrosion occurs in the local that has the lower concentration

Screws and fasteners have are common sources of crevice corrosion problems. The stainless steel screws shown below corroded in the moist atmosphere of a pleasure boat hull.

Occurs in crevice or under deposits of dirt or corrosion product where the solution become stagnant.
The crevice must be wide enough for solution to penetrate, yet narrow enough for stagnancy It may occur at washers, under barnacles, at sand grains, under applied protective films, and at pockets formed by threaded joints.

Pitting corrosion

localized form of corrosion by which cavities or "holes" are produced in the material more dangerous than uniform corrosion damage because it is more difficult to detect, predict and design against A pit may be initiated by a localized surface defect such as scratch. Fatigue and stress corrosion cracking may initiate at the base of corrosion pits.

Trough Pits

Narrow, deep

Shallow, wide

Elliptical

Vertical grain attack

Sideway Pits Subsurface Undercutting

Horizontal grain attack

The various types of corrosion are listed in the following table:

Intergranular corrosion Localized corrosion (pitting corrosion)

Wide pitting corrosion

Imperceptible or barely perceptible from outside, since the corrosion proceeds at the grain boundaries.

The basis metal is eaten away and perforated in places in the manner of holes, the rest of the surface being affected only slightly or not at all. Transgranular or intragranular corrosion

The corrosion causes localized scarring.

Selective corrosion

Interfacial corrosion

Corrosive attack on structural constituents

The grain boundary material is retained, since the corrosion proceeds preferentially within the grain.

Frequently observed at water-air interfaces.

Underground corrosion

Buried gas or water supply pipes can suffer severe corrosion which is not detected until an actual leakage occurs, by which time considerable damage may be done.

Electronic components

In electronic equipment it is very important that there should be no raised resistance at low current connections. Corrosion products can cause such damage and can also have sufficient conductance to cause short circuits. These resistors form part of a radar installation.

Corrosion influenced by flow-1

The cast iron pump impeller shown here suffered attack when acid accidentally entered the water that was being pumped. The high velocities in the pump accentuated the corrosion damage.

Corrosion influenced by flow 2

This is a bend in a copper pipe-work cooling system. Water flowed around the bend and then became turbulent at a roughly cut edge. Downstream of this edge two dark corrosion pits may be seen, and one pit is revealed in section.

Safety of aircraft

The lower edge of this aircraft skin panel has suffered corrosion due to leakage and spillage from a wash basin in the toilet. Any failure of a structural component of an aircraft can lead to the most serious results.

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.

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.

Damage due to pressure of expanding

rust
The iron reinforcing rods in this garden fence post have been set too close to the surface of the concrete. A small amount of corrosion leads to bulky rust formation which exerts a pressure and causes the concrete to crack. For structural engineering applications all reinforcing metal should be covered by 50 to 75 mm of concrete.

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

The tubing, shown here was part of an aircrafts hydraulic system. The material is an aluminium alloy and to prevent bimetallic galvanic corrosion due to contact with the copper alloy retaining nut this was cadmium plated. The plating was not applied to an adequate thickness and pitting corrosion resulted.

Galvanic corrosion
This polished Aluminium rim was left at 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 used all winter. Here the corrosion is so advanced it has penetrated the rim thickness.

Corrosion prevention and protection

4 general techniques to consider:

Material selection and treatment Environmental alteration Design consideration Coating and cathodic protection

Material selection and treatment

Selection of material depends on the corrosion environment:

i.e application in fresh water

Suitable metal: cast iron, steel, Al, Cu, brass and some stainless steel.

Application for seawater environment Titanium, brass, some bronzes, cooper-nickel alloys, nickel-chromium-molybdenum alloys,

Suitable metal for atmospheric application

Al alloys, cu alloys, galvanized steel

Heat treatment for relieve the residual stress induce in metal that formed into finished shapes by bending Another factors that will be consider

Mechanical properties Material fabrication Availability of materials Material cost

Mechanical properties

When operation condition become aggressive, material from combination 2/3 metal are needed Effect of temp. will influence the mechanical properties i.e application of plain carbon steel is limited to 316-343oC due to loss of strength and susceptibility to oxidation and corrosion. Highly alloyed Ni-Cr-Fe alloy are adequate to corrosion resistance at elevated temp. compare to 18Cr-12Ni. 18Cr-12Ni sustain oxidation resistance at temperature up to 816oC and strength reduce above 650

Material fabrication

Material should be selected on the basis of their maintainability as well as their fabrication ability Need to consider the ease of modification or repaired after exposure to operating condition.

Availability of materials

Consideration for future availability for repairs or replacement or alternative replacement materials

Material cost

Life cycle cost or cost effectiveness rather than initial cost

Environmental alteration

Decrease the velocity of corrosive fluid Use lower temperature Remove O2 from water solution by deaerated process Reduce the concentration of corrosive ions in a solution Adding inhibitors in system

Scavengers type- react with and virtually eliminate a chemically active species in solution such as dissolved O2 Absorption type- attach themselves to the corroding surface and interface with either oxidation/reduction reaction or form a very thin protective coating

Design consideration

Prevent the formation of galvanic cell by using similar metal or alloys or using non metallic connector ( fitting, gasket) to electrically insulate the two dissimilar metal
Weld rather than rivets. Or choose rivets that are cathodic to the materials being joined Make the anode area larger than the cathode area

Avoid sharp bends in piping system when flow occurs. Erosion corrosion will occur at areas in which the fluid direction changes sharply. Design components so that fluid system are closed to avoid continuously dissolve gas.
Easy removal and replacement of parts that are expected to fail rapidly in service, must be design The design should allow for complete drainage and easy washing

Coating

Physical barrier applied on surfaces in the form of films Used to isolate anode and cathode region Important condition:

coating must be nonreactive in the corrosive environment Resist to mechanical damage that exposes the bare metal to corrosive environment

Types of material for coating

Metals Ceramic Polymers

Metallic coating

Acts as sacrificial anodes instead of coated metal i.e: steel are coated with Zinc-plated or tin-plated Metal coating are plated by electro plating process metal./ part to be plated is made as cathode. The electrolyte is a solution of a salt of the metal to be plated and direct current is applied.

Inorganic coating/ceramic coating

i.e reaction vessels can also be lined with corrosion-resisitant teflon Stable, adherent, nonporous, noconducting oxide layer i.e glass fused coating a steel

Organic coating

Polymeric material, pints, varnish Cheaper

Cathodic protection

The principle of cathodic protection is in connecting an external anode to the metal to be protected and the passing of an electrical dc current so that all areas of the metal surface become cathodic and therefore do not corrode.
Cathodic protection can use a sacrificial anode or an impressed current

Sacrificial anode

employ reactive metals as auxiliary anodes that are directly electrically connected to the metal to be protected. The sacrificial anode corrodes, supplies to the metal and thereby prevents an anode reaction at metal The metals commonly used, as sacrificial anodes are aluminium, zinc and magnesium.

A galvanic or sacrificial anode system requires: i) Sacrificial anodes ii) Direct welding to the structure or a conductor connecting the anode to the structure iii) Secure and minimum resistance connections between conductor and structure, and between conductor and anode.

Impressed current

Obtained from a direct current source connected between anode and the metal to be protected
A connection from a current source to make electron flow to metal, to cause the metal to be cathode Anode is usually surrounded by high conductivity backfill material such as gypsum or bentonite which improve the electric contact between anode and surrounding soil Add: it will protected large area

An impressed-current system requires:

i) Inert anodes (clusters of which, connected together often in a backfill, are called the groundbed). ii) A dc power source.

iii) Electrically well insulated, minimum resistance and secure conductors between anodes and power source.
iv) Secure and minimum resistance connections between power source and structure.

Structures that are commonly protected by cathodic protectionare the exterior surfaces of:

Pipelines Ships hulls Storage tank bases Jetties and harbour structures Steel sheet, tubular and foundation pilings Offshore platforms, floating and sub sea structures

Cathodic protection is also used to protect the internal surfaces of:

Large diameter pipelines Ships tanks (product and ballast) Storage tanks (oil and water) Water-circulating systems.

The main advantage of cathodic protection is;

that it is applied simply by maintaining a dc circuit

its effectiveness may be monitored continuously.

Can applied to a coated structure to provide corrosion control to areas where the coating may be damaged.
may be applied to existing structures to prolong their life. will avoid the need to provide a corrosion allowance to thin sections. It may be used to afford security where even a small leak cannot be tolerated for reasons of safety or environment. In practice, its main use is to protect steel structures buried in soil or immersed in water. It cannot be used to prevent atmospheric corrosion on metals.

Anodic protection

Reduction of the corrosion rate in an anode by polarizing it into a potential region where the dissolution rates low. In circumstances where cathodic protection is not practical, such as in strongly alkaline or acidic environments, anodic protection is a useful corrosion control technique In anodic protection, the metal to be protected is made the anode

corrosion products protective

active-passive metals/alloys The passivation metal corrode at slower rates than normal

The primary advantages of anodic protection are its applicability in extremely corrosive environments and its low current requirements.
Anodic protection has been most extensively applied to protect equipment used to store and handle sulfuric acid.

Passivation occur by exposing the metal to highly concentrated oxidizing solution

i.e:

iron is dipped in very concentrated nitric acid. Iron rapidly and uniformly corrodes to form a thin protective iron hydroxide coating The coating will protects the iron from subsequent corrosion in nitric acid

Cathodic or Anodic ? A Comparison:

Cathodic Protection Advantages
can

Anodic Protection
can

be used for all metals installation cost is low corrosion rate can be reduced to zero

be used in extremely aggressive environment applied current is direct measure of corrosion rate operating conditions can be easily controlled operation cost low
only

Limitations

can

only be used in weak to moderate environment operating conditions must be determined by empirical testing.

applicable to active-passive metals installation cost is high