Basics of Corrosion

Aasem Zeino
Senior Water Treatment Specialist
Dammam – Saudi Arabia
Topics to be Discussed ..

 Corrosion’s Definition
 Corrosion Mechanism
 Corrosion & Environment
 Engineering Materials
 Forms of Corrosion
 Corrosion Control
 Open Discussion
Corrosion Definition

What is corrosion ?!
The deterioration of a metal or its properties because
of a reaction with its environment (NACE).

Corrosion Affect You !

Your Your Your Your

Environment Your Job
Company Safety Pocket
 Corrosion Costs !

Direct Costs … Indirect Costs …

Excessive Maintenance Safety
Replacement Water
Loss of production / downtime Consumer Confidence
Product contamination Toxic Releases
Accidents Structural Collapse
Capital costs Appearance

Direct Losses > 300 $ Billion / Year in U.S.

$ 300 Billion = $ 300,000,000,000
3 % of Gross National Product of the U.S.

Corrosion Cost & Preventive Strategies in U.S., Sep 2001, FHWA

Corrosion Mechanism
Anode = Oxidation = Corrosion

Galvanic Cell – Spontaneous

Item Function
Anode (Metal) Oxidation: Fe to Fe+2
Cathode (Metal) Reduction: O2 to OH-
Water Droplet Electrolyte
Corrosion Reactions

Anodic Reactions: Cathodic Reactions:

Generic: M0 Mn+ + n e- Generic: R + + e- R0

Iron: Fe Fe++ + 2 e-
• Hydrogen Reduction
Fe Fe+++ + 3 e-
Fe++ Fe+++ + e- 2H+ + 2e- H2

• Oxygen Reduction
Aluminum: Al Al+++ + 3 e-
2 H2O + O2 + 4e- 4 (OH)-
O2 + 4 H+ + 4e- 2 H2O
All anodic reactions make the
metal more positive and produce
electrons All cathodic reactions make the
metal more negative and
consume electrons
Corrosion Reactions
4 Requirements …..

• Area that • Area that

give up receives or
electrons consume
electrons

Anode Cathode

Electrolyte
Metallic
Path

• Area that • Area that

transport transport
ions electrons

Corrosion can be controlled by controlling one of the 4 requirements

Where is the Anode ?!

B
A

A
B

A
Corrosion Potential

Facts
 Energy naturally flows from sites with high energy to sites with low energy.
 Thermodynamics can predict if corrosion will happen under specific conditions.
 Kinetics can predict the rate of corrosion reactions.
 A corrosion potential is made by comparing a metal site’s voltage to a reference
electrode’s potential.
 Applying thermodynamics (Nernest Equation) & kinetics (Farady’s law) will
determine the corrosion rates.
Galvanic Series

Different for different environment

S-48
Pourbaix Diagrams

Benefits ….

 It is available for each metal

 Predicting stability of substances
 Consider potential & pH
 Predicts corrosion products
 Predicts stability of metal
 Evaluate effects of pH
 Passivity

What is Passivity ?!
A relatively inactive state in which the metal displays a more
noble behavior than thermodynamic conditions predict or simply
defined as Formation of passive films of reaction products

• Stainless Steel
Occur Naturally • Nickel Alloys
• Titanium
No Corrosion

Formed • Corrosion Inhibitors

Chemically or
Electrochemically • Applied Current
Passivity
Oxidizing Power

Corrosion Rate
Environment

Major Types of Corrosive Environments

 Atmospheric
 Underground
 Liquid (Submerged)
 High Temperature
Atmospheric Environment

Industrial • Corrosive gases

(SO2,Nox, CO)
Atmospheres • Solids & Soot

Marine • Sea Salts (NaCl,

MgCl2)
Atmospheres • High Rltv. Humidity

Rural • Dusts & corrosive

gases (NH3)
Atmospheres • Temperature
• Can be controlled
Indoor • Some aggressive
Atmospheres conditions

Can you give an example for each case? Let us do it !

 Underground Environment

Factors affect the corrosion underground …

 Physical Soil Characteristics (grain size & distru, Moisture retention)
 Chemical Soil Characteristics (pH, Water soluble salts, alkalinity)
 Moisture Content (1-100% is possible)
 Electrical Resistivity (ohm.cm, reciprocal of conductivity)
 Aeration (more oxygen)
 Bacteria (Aerobic – less problems, Anaerobic – more aggressive such as SRB)

More High More More

Acidic pH
aeration conductivity bacteria Moisture Corrosion
 Liquid Environment

Factors affect the corrosion in liquids …

 Physical configuration (surface smoothness, etc.)
 Chemical make-up (Dissolved solids, dissolved gases)
 Flow rate (new surfaces, destroying protective film)
 Temperature & pressure (more diffusion & dissolved gasses)
 Biological Organisms (Microbiological Influenced Corrosion – MIC)

Qurayyah Case ?!!

 High Temperature Corrosion

High Temperature High temperature

Oxidation Reduction

Oxidizing Atmosphere Reducing Atmosphere

e- are lost
Oxygen not necessary In presence of reducing
Oxygen + Sulfur gases
increases the rate H2, CO, CO2
(Sulfidation)

Factors should be in materials have oxide films:

 Physical Stability & low volatility (don’t melt – don’t boil)
 Maintenance of good mechanical integrity (don’t crack)
 Slow growth kinetics (don’t allow rapid corrosion)
Engineering Materials

Metals

Ceramics Concrete

Elastomers Plastics
 Metals Metallurgy Concepts

Crystalline Structure:
 Repeating pattern of atoms called Unit Cells (Crystals = Grains)
 In each grain the crystal structure is fairly uniform (0.025 – 0.25 mm)
 Grain boundaries is area of disorder (less purity – Imperfection)
Metals Metallurgy Concepts

Alloys:
 Mixture of two or more metals, 2 types: Solid Solution, Multiphase
 Solidification by slow cooling produces large grains
 Solidification by fast cooling produces large grains

Solid Solution Alloys Multiphase Alloys

Two solid metals Insolubility of metals

Properties related to mixture Properties depends on phases

Phase diagrams show phase

Uniform structure changes

Brass Cast Iron

 Metallurgy Cells

Quenching Problems:
 Stresses may be produced during quenching which will produce
corrosion cells
 Non-uniform structures may produce corrosion cells caused by
non-uniform cooling rates
 Some of the problems can be corrected by heat treatment after
quenching.
Metallurgy Cells

Causes of Metallurgy Cells:

 Stressed areas
 Imperfections & impurities
 Alloy additions
 Unequal Cooling rates
 welding
 Welding

Welding Benefits:
 Low cost solution
 High strength
 High corrosion resistance
 Wide range of materials (Filler Rod)
 Some materials are unweldable

How you can avoid corrosion due to

welding & cutting?

SS 316
Carbon & Low Allow Steel (CS)

Inexpensive & available materials

Wide range of properties

Weldable

Commonly 0.2% Carbon

Tensile strength range 40 – 200 ksi (275-1,400 Mpa)

Few % of alloying elements (Cr, Ni, Cu, Mo, P, V)

Similar corrosion resistance & some additions improve it

 Cast Iron (CI)

 Higher Carbon content 2 – 4%, in the form of graphite

 Low cost of castings
 Relatively brittle
 Has six types

High Silicon
Gray CI Malleable CI White CI Ductile CI CI Alloy CI

• Carbon as • Carbon as • Carbon as • Carbon as • Highly • Ni

Flakes rosettes Iron spheroids corrosion resistant –
• Less brittle carbide • Ductile resistant pumps &
• Brittle turbines
than gray • Hard & • Used as
brittle anodes in • Ni hard –
• Not CP erosion
weldable • Si > 14% resistant
Cast Iron (CI)

Gray CI Malleable CI White CI

Ductile CI High Silicon CI Alloy CI

 Cast Iron (CI)

Cast Iron Corrosion

 Atmospheric corrosion is slower than Carbon steel
 De-alloying corrosion is possible & also graphitization

Brittle Failure
 Copper Alloys

Copper Alloy Benefits

 Good corrosion resistance
 High heat & electrical conductivity
 Good mechanical properties – ductility
 Can form passive films in aqueous environments
 Wide range of alloys in a variety of applications

Brass: copper-zinc alloys Bronze: copper-tin alloys

Principle : Always use UNS & ASTM numbers for alloys, No common names
Copper Alloys

90% Cu, 10% Cu, Sn, Pb,

99% Cu Zn Zn

70% Cu, 30% 60% Cu, 40%

Zn Zn Cu, Zn, Pb, Fe

Cu, Zn, Si Cu, Zn = Ni Cu, Ni

 Copper Alloys

Technical Points
 Copper corrodes in the presence of oxidants such as Nitric acid, hydrogen
peroxide .. etc.
 Copper alloys are generally subject to erosion-corrosion in high velocity
flow conditions.
 Poor resistance to CO2, acids, chlorides, sulfides and ammonia
compounds.
 Patina: a thin protective layer of corrosion products.
Stainless Steel

Stainless Steel Benefits

 Highly corrosion resistant in specific environments
 Forms passive films of chromium oxide
 Corrosion resistance depends on passive film stability
 Alloying elements increases passive film stability (Mo, Ni)
 Wide range of alloys in a many applications (families & groups)
 Stainless Steel Groups

Martensitic Austenitic
Ferritic SS Duplex SS
SS SS
• AISI 400 series • AISI 400 series • AISI 200 & 300 • 20-30% Cr + 3-
• 12-30% Cr • 17-25% Cr + 9- 10% Ni + 1-5%
• 12-17% Cr Mo
• Better corrosion 10% Ni
• Moderate • High corrosion
corrosion resistance • 200 use Mn
partially of Ni % resistance
resistance • Resistance to Cl
stress cracking • High corrosion • Resistance to Cl
• Weldable resistance (Ni) stress cracking
• Difficult to weld
• Used for valves, • Mo addition is • Good ductility &
• Used for furnace high strength
cutlery parts, exhaust good for Sea
systems water • Used for marine
• Weldable tanks, heat
exchangers

Magnetic Magnetic Nonmagnetic Magnetic

Nickel Alloys

Nickel Alloys
 Highly corrosion resistant
 Corrosion resistance depends on alloy & environment
 Resistant to alkaline environments
 Highly resistant to pitting & crevice corrosion
 Must be carefully selected & specified
 Not universally immune
 Aluminum Alloys

Aluminum Alloys
 Used for low weight applications
 Reactive metal (Amphoteric metal)
 Corrosion resistance due to passive film (Al2O3)
 Exfoliation problems
 Stable in neutral solutions & oxidizing acids (why?!)
 Unstable in acids, alkaline & Cl solutions.
 Titanium & Its Alloys

Titanium & Its Alloys

 Reactive metal
 High Corrosion resistance due to passive film (TiO2)
 Low weight, high strength, high strength to weight ratio
 Difficult to form & fabricate
 Very stable & resistant to chloride, chlorine & sea water.
Corrosion Science

Forms of Corrosion
Forms of Corrosion

There are 16 types of Corrosion !!!

Corrosion Types
General Corrosion Corrosion Fatigue
Pitting Corrosion (Localized) Erosion corrosion
Crevice Corrosion (Localized) Impingement Corrosion
Filiform Corrosion (Localized) Cavitation Corrosion
Galvanic Corrosion Intergranular Corrosion
Stress Corrosion Cracking (Environ) Dealloying Corrosion
Hydrogen Induced Cracking (Environ) Fretting Corrosion
Liquid Metal embrittlement (Environ) High-temperature Corrosion
Forms of Corrosion

Principle:
More than one form of corrosion can, and usually dose,
occur within a system, even on a single alloy at different
points
General Corrosion

 It is a corrosion that proceeds more or less uniformity over the

entire exposed surface.
 It is forming anodic & cathodic sites
Pitting Corrosion

 It is a form of localized corrosion appears as deep narrow attack

& rapid penetration.
 Interior is anodic, exterior is cathodic. QCCPP Story ?!
 Pitting Corrosion

Performance of Metals & Alloys

 Aluminum alloys (Halides)
 Stainless Steel (Chlorides)
 Copper alloys (NH3, Hot O2 water, Soft water, Sulfides, oxidizing acids)
 Carbon Steel

What are the solutions ?!

Crevice Corrosion

 It is a localized attack that occurs in areas where access to

surrounding environment is restricted
 Crevices: Metal-to-Metal, Metal-to-nonmetal, deposits of depris or
corrosion products
 Anodic sites will be concentrated in the crevice.
Crevice Corrosion

 Crevice corrosion is initiating under deposit attack.

 Most metals could face this problem
 Materials selection is very important
 Eliminate crevices during design
 Cathodic protection reduces its effects
 Avoid skip welds & provide drainage.
 Use seal joints
Filiform Corrosion

 It is a special localized corrosion occurring beneath a metallic or

organic coating (Corrosion Under coating)
 Driven by potential difference between head of attack and area
behind (oxygen concentration cell)
 Associated with surface contamination (coating quality &
selectivity).
 Filiform Corrosion

Solutions
 Proper surface preparation (ex. Sand blasting)
 Clean & dry surfaces for coatings
Which corrosion is that?

1- General Corrosion 2- Pitting Corrosion

3- Crevice corrosion 4- Filiform Corrosion

Pitting General Filiform

Crevice
Galvanic Corrosion

 It is a classical electrochemical cell.

 Corrosion accelerated by the potential differences between
metals when they are in electrical contact and exposed to
electrolyte (Atmosphere or immersion).

S-10
Galvanic Corrosion

Anode Effects Cathode Effects

Corrosion accelerated Corrosion reduced

Different forms of attack Hydrogen effects

Affected by …
 Nature of the Environment
 Potential difference (metals) Why ?!
 Resistivity of electrolyte
Corrosion Fatigue

 It is a fatigue in a corrosive environment. It is the mechanical

degradation of a material under the joint action of corrosion
and cyclic loading. Nearly all engineering structures
experience some form of alternating stress, and are
exposed to harmful environments during their service life.
Corrosion Fatigue
 Erosion Corrosion

 Erosion corrosion is a degradation of material surface due

to mechanical action, often by impinging liquid, abrasion by
a slurry, particles suspended in fast flowing liquid or gas,
bubbles or droplets, cavitation, etc.

Called in some cases: Flow assisted corrosion

It is the most common case for Cupper tube failure

Erosion Corrosion

Brass pump Brass tube

Erosion Corrosion

The recommended maximum velocity for water in a copper tube

system is 5 - 8 feet per second (1.5 – 2.4 m/s) for cold water
systems,

&

4 - 5 fps (1.2 – 1.5 m/s) for hot water systems < 140º F, and 2-3
fps (0.61 – 0.91 m/s) for hot water systems with a temperature
greater than 140º F.

Erosion Corrosion damages even noble metals … as Titanium,

Monel, Stainless Steel
 De-Alloying Corrosion

Called also: Selective leaching

 It is selective removal of one element from an alloy by
corrosion processes. A common example is the
dezincification of unstabilized brass, whereby a weakened,
porous copper structure is produced.

Dezincification

Graphitization
De-Alloying Corrosion

 Active metal selectively removed (corroded)

 Less active metal is residue
 It is known in brass, copper-zinc alloys (dezincification)
 Bronze is subjected to the selective removal of tin
(destanification)
 Aluminum bronze is subjected to dealuminification
 Cast Iron is subjected to graphitization
Corrosion Science

Methods of Corrosion
Control
Corrosion Science

Call Mohammed, Asaad, Ahmed … don’t be late

Methods of Corrosion Control

 Design Parameters
 Materials Selection
 Modification of Environment
 Chemical Solutions
 Cathodic Protection
 Protective Coating
Design Parameters

 Materials Selection during design

 Understanding process parameters (chemistry, T, P, velocity ..)
 Construction Parameters (welding)
 Dissimilar Metals
 Avoid crevices (skip welds)
 Geometry for drain (avoid stagnancy & accumulation)
 Using coating materials for some parts
Design Parameters

Cooling Basin,
Tank, …

Drain
Drain
Drain

What is the best design ?!

Cathodic Protection
Chemical Solutions

 Corrosion Inhibitors
 Dispersants
 Biocides
 Coating Materials
Thank You
Questions ?!