Fundamentals of Corrosion

2014 INSTITUTE OF TECHNOLOGY PETRONAS SDN BHD

All rights reserved. No part of this document may be reproduced, stored in a retrieval system or transmitted in any form or by any means (electronic,
mechanical, photocopying, recording or otherwise) without the permission of the copyright owner.

Course Instructor
AP Ir. Dr. Mokhtar bin Che Ismail
B.E (Mechanical Engineering), University of Newcastle, Australia.
M.Sc (Materials Science and Engineering), National University of Singapore.
PhD (Corrosion Engineering), UMIST, England

8 years professional industrial experience (INTEL & PETRONAS) and 16 years

academic experience.

PART I An Introduction to the World of Corrosion

Why metals
corrode?

Introduction (what is/why)

Corrosion is a natural phenomenon and can be considered as extractive
metallurgy in reverse (Fontana).
Earth

Mineral Ores

Extraction/
Refining

Metal
(Fabrication)

Components

Corrosion

Earth

Several Definitions
Corrodere (Latin) means to chew away or to wear away.
The degradation of a material that occurs when it reacts with environment
(Fontana).
Physicochemical interaction between a metal and its environment which
results in changes in properties of the metal and which often lead to
impairment of the function of the metal, the environment, or the technical
system of which these form a part: ISO 8044-1986.
Destruction of a metal by chemical or electrochemical reaction with its
environment. Herbert H. Uhlig in Corrosion Handbook.

A Few More Definitions..

The deterioration of a material, usually a metal, that results from a reaction
with its environment. (NACE)
Corrosion is an irreversible interfacial reaction of a material (metal, ceramic,
polymer) with its environment which results in consumption of the material
or in dissolution into the material of a component of the environment.
(IUPAC).

Examples of Corrosion Phenomena

LP Riser

Onshore Pipeline Section

Corrosion Pits
due to SRB

Offshore 8" Pipeline

Examples of Corrosion Phenomena

Severe corrosion at risers

Examples of Corrosion Phenomena

Corrosion under Insulation

Example of Sample Background

Equipment No:
Material:

Equipment Description:
Carbon Steel

Plant:
Date of Failure:

Part:
Unit:

April 2005

Time to Failure:

4 Years

Photo:

Phenomenon:

Under Deposit Corrosion

Appearance:

Thin layer with dry and brown deposit and localized pitting corrosion.

Environment:

Process Fluid
: LPG
Working Pressure
: 15.9kg/cm2
Working Temperature : 40C

Remedy:

Pipe replacement with in kind material

Consequences / Cost

Cost in order of 4% of GNP in advanced countries. USA = $100 - $200 billion.

(recent data..??).
The effect can be in many ways:

Appearance/Aesthetic factor: Bad impression low morale to worker.

Maintenance and operating cost
Plant shutdowns
Contamination of products
Loss of product
Effect of safety and reliability

Cost of Corrosion Previous Studies

Year

Studies

GNP (%)

1950

H.H. Uhlig U.S

2.1

1970

T.P. Hoar U.K

3.5

1974

Japan

1.2

1975

Battelle/NBS U.S

4.5

What are the worries?

Humber Refinery, 16 April 2001; Public Report on HSE website.

The Failure

A release of gas followed by an explosion and fire destroyed a large

area of plant.

Luckily it was a Bank Holiday and few people were on site and
casualties were minor.

The leak came from the erosion/corrosion failure of a line downstream

of a wash water injection point.

How was it allowed to happen?

The Key Events

1981

A vent connection is modified to be a wash water injection point

to solve a process fouling problem

1992

A company advisory bulletin warns of problem with injection

points, but this point not reviewed as it was not on the list.

1994

An inspection found pitting at the injection point and

recommended frequent inspection.

1994

A corrosion probe down stream shows high corrosion rate.

1996

Not re-inspected as there was no access.

2000

RBI assumed point not in use but rated the line high risk and set
an IDD of July 2001

Corrosion expert reviews considered the problem but from 1994 wrongly
assumed the injection point was only intermittently used.
The refinery had no corrosion reporting scheme.
The WSE for piping made no reference to injection points.

Where did the System Fail?

Lack of linkage to management of change and process knowledge.

Lack of feedback and action on the 1994 inspection result.

Corrosion rate measurements not acted on.

Collapse of LPG Sphere

Failure Factors

Factors caused the collapse:

Water caps over the fire-proofing concrete of bad design letting water
penetrate between the steel beams and the concrete.
Vertical cracks on the concrete let water in.
Repairs had been done to the concrete, but without good workmanship.
The new concrete has not adhered to the old concrete, letting water in.
Deluge system had been tested with salt water, increasing the possibility
of corrosion.

Failure Factors

Root cause: bad and lazy maintenance system, added to a bad

administration and lack of knowledge in inspection and maintenance
services.

A proper maintenance and a suitable inspection plan are major factors on

the conditions of the equipment. Inspection should be performed by
qualified personnel, to avoid the sad happening which took place after a
series of inspections that approved the vessel conditions.

Prevention

Some actions to be taken to avoid future accidents:

Water caps shall be designed, fabricated and installed to ensure

tightness and avoid infiltration that will cause corrosion.

Fire protection shall be installed criterion to reduce the gap between the
leg beams and the concrete for a minimum.

Fire protection shall be of good quality and regularly inspected.

Peep holes at the top of the legs shall be seal welded before the water
cap is installed.

Legs shall be inspected by qualified companies and inspection reports

shall be verified and approved.

Forms of Corrosion
Environmentally Induced
Corrosion

Stress Corrosion Cracking

General Corrosion

Atmospheric corrosion

Mechanically Assisted Corrosion

Localised Corrosion

Pitting

Metallurgical Influenced Corrosion

Forms of Corrosion

When Metal Corrodes?

When there is Anode

When there is Cathode
When there is electron path connecting anode and cathode
When there is ionic path/electrolyte

When Metal Corrodes?

Electrodes
Electrodes are pieces of metal on which an electrochemical reaction is
occurring.

An anode is an electrode on which an anodic or oxidation reaction is

occurring.
A cathode is an electrode on which a cathodic or reduction reaction is
occurring.

Anodic Reactions

Examples:

Zn Zn2+ + 2eFe Fe2+ + 2eAl Al3+ + 3eFe2+ Fe3+ + 3eH2 2H+ + 2e2H2O O2 + 4H+ + 4e

Oxidation reactions

Produce electrons

Cathodic Reactions
Examples

O2 + 2H2O + 4e- 4OH2H2O + 2e- H2 + 2OHCu2+ + 2e- Cu

Fe3+ + e- Fe2+
Reduction reactions
Consume electrons

Chemical vs Electrochemical Reactions

Chemical reactions = elements are added or removed from chemical
species. No change in valence.

Electrochemical = chemical reactions + change in valence

Example:
Precipitation of iron hydroxide (Fe (OH)2) is pure chemical reaction.

Fe 2+ + 2 OH- --- Fe(OH)2

Atmospheric Corrosion: Brown Rust

Fe2O3H2O or hydrous ferrous oxide,

Fe3O4H2O or hydrated magnetite, also called ferrous ferrite (Fe2O3FeO),

is most often green but can be deep blue in the presence of organic
complexants.
Fe3O4 or magnetite is black.

White Rust

Gray/Black Film

Degradation / Corrosion Failures

Failures come in
many different
forms!

Method of Corrosion Protection

Corrosion
Control

Cathodic
Protection

Surface Coating

Inhibitor

Design/Material
Selection

Cathodic
Anodic

Pa
ge

Another Corrosion Cycle

The problems arising from short-sighted corrosion control strategies have

been particularly well articulated by Joe C. Bowles (a former president od
NACE International) in the so-called corrosion cycle. Four phases were
identified in this cycle:

Phase 1: Neglect
Corrosion control is ignored; this may be tempting to (poor) management
as corrosion problems may not show up immediately. It is easy to be lulled
into a false sense of security.
Phase 2: Panic
The previously hidden corrosion danger becomes apparent, possibly with
disastrous financial consequences and safety hazards. It is not easy to
combat corrosion rationally and effectively in a state of panic.

Another Corrosion Cycle

Phase 3: Learning Curve

In dealing with the serious corrosion problems, effective corrosion control
measures are eventually introduced and failure rates are reduced to
manageable levels. Considerable effort (and time) may be required before
effective solutions are found, qualified and implemented.
Phase 4: Unlearning Curve
Once the initial crisis is over, there is a risk that corrosion control will be
neglected again and that hard lessons learnt in the past will be forgotten.
This is when the corrosion cycle starts all over again, with the neglect stage
re-establishing itself.

Reference
General bibliography:
1. M. Fontana, Corrosion Engineering, 3rd edition, McGraw Hill
International Edition,New York, 1987, 556 pp.
2. H. H. Uhlig, R. W. Revie, Corrosion and Corrosion Control, 3rd edition,
JohnWiley, New York, 1985, 441 pp.
3. G. Wranglen, An Introduction to Corrosion and Protection, Chapman
and Hall,London, 1985, 288 pp.
4. Jones, Principles and Prevention of Corrosion, Prentice Hall

THANK YOU
2014 INSTITUTE OF TECHNOLOGY PETRONAS SDN BHD
All rights reserved. No part of this document may be reproduced, stored in a retrieval system or transmitted in any form or by any means (electronic,
mechanical, photocopying, recording or otherwise) without the permission of the copyright owner.