MKM6144

ADVANCED MATERIAL
FACULTY OF MECHANICAL ENGINEERING
UNIVERSITI MALAYSIA PAHANG

INTRODUCTION
Corrosion is a natural phenomenon and can be considered as
extractive metallurgy in reverse( Fontana).
Earth
Mineral Ores
Extraction/Refining
(Fabrication)
Components
Corrosion

Metal
Earth

CORROSION ENGINEER

HIGH TEMPERATURE DEGRADATION

Chlorination
OXIDATION
Carburation
Flue gas and deposit corrosion
Nitridation
Sulphidation

Tube Supports Escatron (Spain)

Replaced RA253MA
Pressurized Fluid Bed
Boiler
6.8% Sulfur Lignite
Earlier Units <3.6%
Sulfur
TIDD, Vartan
RA253MA successful

Coupon Testing

11 months
1475-1650F
RA353MA 0.1 mm
RA253MA 1.1 mm

Metal Ores
Hematite (AE) or haematite (BE) is the
mineral form of Iron(III) oxide, (Fe2O3),
one of several iron oxides.

Magnetite is a ferrimagnetic mineral with

IUPAC name iron(II,III) oxide and with
chemical formula Fe3O4, one of several
iron oxides and a member of the spinel group.

PENINSULAR CRUDE AND GAS EVACUATION

Legend
Oil Fields
MTJDA

Gas Fields
Existing Gas Pipeline

Bunga Raya

Cakerawala
Songkhla

Existing Condensate Pipeline

PM 302
Jerneh

Lawit

PM 301

LARUT
30"X240 km
900 mmscf/d

RESAK
28" X 135 km
800 mmscf/d ANGSI

28" X 232 km
750 mmscf/d

O
S
C

32" X 160 km
1200 mmscf/d

(2000
mmscf/d)

GPPs

OGT

(2000 mmscf/d
(1300
Sales Gas) mmscf/d)

30" X 156 km
550 mmscf/d

GUNTONG
D
SELIGI
BEKOK
DUYONG

SCP
MASA

WEST
NATUNA-B
Not to scale

OFFSHORE SARAWAK CRUDE EVACUATION

M1 SADERI
M1
JINTAN

M4

SERAI
M5

F12

M3

F11
BIJAN

BARAM DELTA

F14
G7

F27

F29

C .PADI

CENTRAL LUCONIA

MAWAR

F9

KUMANG

F6

JERONG
MARINE

K5

SHALLOW

E6

E8

SELAR
MARINE

SIWA

E11
COMPLEX

MIRI

SAPIH
D12

A21

HELANG LAYANG
FAIRLEY BARAM
BARONIA
BARAM
BERYL
FATIMAH
BETTY LAILA BAKAU
BOKOR HASNAH SALBIAH
W. LUTONG ASAM PAYA
TUKAU
SIKAU
REBAB

CLASTICS

A3

TENGGIRI
MARINE

J1

BUNGA
PELAGA

B11

F13

E4

KANOWIT

S W LUCONIA

F22

F23 SELASIH

F28
K4

B12

J4

E2

D21

GAMBANG
GEDUK

D30

J5

J12

T3

D18

D35

SERUNAI
PATRICIA

J32
J2

SOMPOTAN
D51

BALINGIAN

BAYAN

D2

C13
C2

GAS FIELD (to be developed)

OIL FIELD
OIL PIPELINE

MLNG PLANTS

TEMANA

GAS FIELD (producing)

BINTULU

EXISTING GAS P/LINE

Corrosion Disaster

Atlantic Southeast 529, 8-21-1995

Lead wool added for
balancing
Cork stopper

FORMS OF CORROSION by Fontana

Group 1
readily
identifiable by
ordinary visual
examination:
uniform
corrosion
pitting
crevice
corrosion
galvanic
corrosion

Group 2
may require
supplementary means
of examination:
erosion corrosion
cavitation
fretting corrosion
intergranular
corrosion

Group 3
verification is usually
required by microscopy
(optical, SEM):
dealloying
stress corrosion cracking
corrosion fatigue

Corrosion of material can be by a combination of

modes driven by intertwined mechanisms

FORMS OF CORROSION
C O R R O S IO N FO R M S

U N IF O R M / G EN E R A L
M a c r o - c o r r o s io n c e lls
> G a lv a n ic
> P it t in g
> C r e v ic e & D e p o s it

LO C A LIS E D
M ic r o - c o r r o s io n c e lls
> I n t e r g r a n u la r
> S t r e s s C o r r o s io n C r a c k in g
> S e le c t iv e D is s o lu t io n

UNIFORM / GENERAL CORROSION

Characterised
Characterised by
by corrosive
corrosive attack
attack proceeding
proceeding evenly
evenly over
over
entire
entiresurface
surfacearea
area@
@large
largefraction
fractionarea.
area.

General
General thinning
thinning takes
takes place
place until
until failure.
failure. Anode
Anode and
and cathode
cathode
areas
areasdistributed
distributedevenly
evenlyover
overthe
theservice
serviceby
byshifting.
shifting.

Easily
Easilymeasured
measuredand
andpredicted.
predicted.Measurable
Measurablein
inmm/yr.
mm/yr.

Affect
Affectentire
entiremetal
metalin
incontact
contactwith
withelectrolyte.
electrolyte.

Corrosion
Corrosionallowance
allowanceisisapplicable.
applicable.

Examples:
Examples:Rusting
Rustingof
ofsteel
steelin
inatmosphere.
atmosphere.

Breakdown
Breakdown of
of protective
protective coating
coating systems
systems often
often leads
leads to
to this
this
form
formof
ofcorrosion.
corrosion.

Practically
Practically controlled
controlled by
by cathodic
cathodic protection,
protection, use
use of
of coatings
coatings
or
orpaints,
paints,or
orsimply
simplyby
byspecifying
specifyingaacorrosion
corrosionallowance.
allowance.

FORMS OF CORROSION: Localized Corrosion

Sources of Localized Corrosion:

Environment
oxygen concentration
chloride ion concentration
pH
flow rate

Material
segregation
inclusions
different phases
grain boundaries

Mechanical
static stress
fluctuating stress

CORROSION OF ZINC IN
ACID
Two reactions are necessary:
-- oxidation reaction:
-- reduction reaction:

Zinc

Zn

flow of e- 2e in the metal

Zn Zn 2 2e
2H 2e H2 (gas)

H+
Oxidation reaction
Zn 2+
H+
H+
H+

Acid
solution

H+

H 2 (gas)

H+

reduction reaction

H+

Adapted from Fig. 17.1, Callister 7e.

(Fig. 17.1 is from M.G. Fontana,
Corrosion Engineering, 3rd ed., McGrawHill Book Company, 1986.)

Other reduction reactions:

-- in an acid solution

O2 4H 4e 2H2O

-- in a neutral or base solution

O2 2H2O 4e 4(OH)
28

Corrosion Rate Expression

Corrosion Penetration Rate (CPR)
CPR = K W/DAT
K= constant (534 for mpy, 87.6 mm/yr)
W= weight loss,mg
D= density, g/cm3
A = Area,in2 or cm2
T = time,hr

Faradays Law

The atomic weight

in grams,
i.e. 55.8 g
Consider the
reaction
Fe Fe
for2+Fe+ 2 e For every atom of iron reacting, two electrons
will be produced.
One mole contains Avogadros number
(61023) atoms
The charge on each electron is 1.610-19 C
Hence each mole produces 296500 C
Faradays constant (F) = 96500 C/mole

Faradays Law
According to Faradays Law, when ni moles of a given substance
react, a proportional electric charge Q passes across the electrodeelectrolyte interface

More accurately
nFm
relative atomic
Q
M
mass, but still with
where Q charge passed
units(C)
g/mole
n number of electrons for each metal atom

F Faraday' s constant (C/mole)

m mass of metal oxidised (g)
M atomic weight of metal (g/mole)

Faradays Law Divide by time

nFK
I
M
where I corrosion current (A)
n number of electrons for each metal atom
F Faraday' s constant (C/mole)
K rate of corrosion (g/s)
M atomic weight of metal (g/mole)
Faradays law thus states that the rate of an electrode
reaction is proportional to the magnitude of the
electrical current that crosses the electrode-electrolyte
interface.

Faradays Law
Divide by area:
nFk
i
M
where i corrosion current density (A/cm 2 )
n number of electrons for each metal atom
F Faraday' s constant (C/mole)
k rate of corrosion (g/s m )
2

M atomic weight of metal (g/mole)

Electrochemical Potential

Corrosion of zinc in acid

Then
Thenthe
thecorrosion
corrosionrate
ratemay
may
be
expressed
as
the
be expressed as the
corrosion
corrosioncurrent
currentdensity,
density,icorr
i 2+

Zn Zn
Corrosion
2eCorrosionRate
Rate

corr

At
, we
Atthe
theCorrosion
CorrosionPotential,
Potential,EEcorr
corr, we
have
aastable
mixed
have
stable
mixedequilibrium
equilibrium
Corrosion
Potential
Corrosion Potential

EEcorr
corr

2H+ + 2e- H2

icorr
i

corr

Rate
of Reaction
Current
density

 Examples of equilibria in the iron Pourbaix diagram

(numbered on the plot):
Fe2++2eFe(s)(pure redox reaction - no pH
dependence)
Fe3++eFe2+(pure redox reaction - no pH
dependence)
2Fe3++3H2OFe2O3(s)+6H+(pure acid-base, no redox)
2Fe2++3H2OFe2O3(s)+6H++2e(slope = -59.2 x 6/2
= -178 mV/pH)
2Fe3O4(s)+H2O3Fe2O3(s)+2H++2e(slope = -59.2 x
2/2 = -59.2 mV/pH)

Coupon Testing

Exposure conditions test

Kinds of Coupons

Welded Coupon

Stressed Coupons
ASTM G 58, G39, G 513

Corrosion Product on Coupons

Specimen - Standard corrosion coupon from Metal Samples. ASTM 1010 mild carbon steel.
Exposure - 15 Days
Original Wall Thickness - 0.066 in.
Wall Loss - 0.0023 in. at two surfaces / Corrosion Rate - 28.0 MPY

Specimen - 1-1/2 in. ASTM A795 Grade A mild carbon steel pipe, schedule
10.

Exposure - 15 Days

Original Wall Thickness - 0.104 in.

Wall Loss - 0.0025 in. at two surfaces / Corrosion Rate - 30.4 MPY

Specimen - CorrView Model # P3S1-NF1-BC, 1-1/2 in. NPT,

1018 mild carbon steel
Front Wear Thickness - 0.050 in.

Exposure - 15 Days

Original Wall Thickness - 0.099 in.

Wall Loss - 0.0009 in. at one surface / Corrosion Rate - 21.9

Preferred Flow
Direction

Placement coupon

http://www.alspi.com/bypass.htm

Advantages coupon
testing

Coupon tests are low in cost

Simple to conduct
Simultaneous evaluation of numerous materials and
variations of a single material
Alloy chemistry variations and metallurgical variations
(ie., the effect of heat treatment, microstructure,
welding and stress) can be considered
Coupon tests are easily adapted to evaluate specific
types of corrosion, such as crevice corrosion and
galvanic corrosion.

Flow-Induced Corrosions
Research Studies with
Multiphase Flow Loops
Study of Oil/Water Transport
Evaluation of Corrosion
Inhibitors

Flow loop

In situ corrosion monitoring online

ASTM G96 - 90(2008) Standard Guide for Online

Monitoring of Corrosion in Plant Equipment
(Electrical and Electrochemical Methods)
Online Corrosion Monitoring in the Oil and Gas
Industry

In situ corrosion
monitoring

In situ CORROSION POTENTIAL

ASSESSMENT

Half Cell Potential Survey of

corrosion activity

Corrosion Sensor for Monitoring the Service

Condition of Chloride-Contaminated Cement Mortar

CORROSION POTENTIAL Resistivty

Mapping:

Sensor to assess corrosion in concrete

An integrated electrochemical sensor system

High Temperature High Pressure Corrosion Testing

Autoclave Experiments Equipment

High Temperature and/or High

Pressureprobe of reference electrode
Probe Type

Temperature Rating

Pressure Rating*

Ag/AgCl Reference Probe

0 to 305oC(32 to 581oF)

up to 5100 psi (350 atm)

High Temperature and/or High

Pressureprobe of corrosion measurements

High-P and High-T CMAS

Corrosion Probe

up to 305oC(581oF)

up to 5100 psi (350 atm)

High Temperature and/or High Pressureprobe of

pH meter

Glass-Based pH
Probe

0 to
120oC(32 to
248oF)

2000 psi (136 atm)

HPHT probes corrosion monitoring

mechanism

Electrical potential
Type
Instantaneous
confirmation of
state, rather than
rate
Principle
Measure corrosion
potential

Electric junction box badly corroded only four years after a

new residence was completed

Factors Affecting Atmospheric Corrosion

he most important factor

inatmospheric corrosion,
overriding pollution or lack of it, is
moisture, either in the form of
rain, dew, condensation, or high
relative humidity (RH). In the
absence of moisture, most
contaminants would have little or
no corrosive effect.

 Rain also may have a beneficial effect in

washing away atmospheric pollutants that
have settled on exposure surfaces. This
effect has been particularly noticeable in
marine atmospheres. On the other hand,
if the rain collects in pockets or crevices,
it may accelerate corrosion by supplying
continued wetness in such areas as
illustrated in the following Figure.

Galvanized bolting assembly after ten years

of exposure to a deicing salt environment.

REINFORCEMENT
CORROSION
Passivity
High pH leading to formation of
passive layer
Chemical binding of chlorides
Dense and impermeable structure of
concrete

Depassivation
Chloride ingress
Carbonation

MECHANISMS OF REINFORCEMENT
CORROSION

What is CUI?

Corrosion under insulation

(CUI) the corrosion of steel or
other material under thermal
insulation due to the presence
of water, oxygen or other
corrosive atmospheric
contaminants such as SO2 (in
the form of H2SO4) and
Figure Example of corrosion under insulation in a chemical plant.
chlorides.

Calcium cilicate insulation

CUI Cases
Photo 1:Steam sprayed at the leaking area to
disperse remaining Hydrocarbon released to
atmosphere during depressurization of crude tower
for pipe spool replacement

Photo 2: Rupture at thinned section of 3/4 Sch 80

ASTM A106 Gr B short pipe due to CUI exposed
after removal of insulation material.

CO2 corrosion
Principle and prediction

Oil & Gas Industry Presentation

Business Overview

What is natural gas?

Conventional
Unconventional
Shale gas

November 21, 2012

Canadian Oil & Gas Industry

Presentation

BUS 417

Exploration and Production (5): Enhanced

Recovery
Although oil and gas are less
dense than water and naturally
rise up a well to the surface,
in reality only 40-50% of the
total will do so.
To enhance recovery, a hole
is drilled adjacent to the well
and steam is pumped down. The
hot water helps to push the oil out
of the rock and up into the well.

California Department of Conservation

Exploration and Production (7):

At the Refinery
Distillation
Plant

Oil refinery

Car fuel
Jet fuel

Road tar
en.wikipedia.org/wiki/Image:Anacortes_Refinery_31911.JPG

en.wikipedia.org/wiki/Image:Crude_Oil_Distillation.png

Before it can be used crude oil must be refined.

Hydrocarbons can be separated using distillation, which
produces different fractions (or types) of oil and gas

Exploration and Production (2): Reservoir

Rocks
The permeable strata in an oil trap
is known as the Reservoir Rock
Reservoir rocks have lots of
interconnected holes called pores.
These absorb the oil and gas like a
sponge

This is a highly magnified picture of

oil migrates
fills up
the pores
aAs
sandy
reservoirit rock
(water-filled
(oil-filled
in black)
pores
are pores
shownshown
in blue)
Earth Science World Image Bank Image #h5innl

Oil and Gas Black Gold!

NASA
http://en.wikipedia.org/wiki/Image:Moscow_traffic_congestion.JPG
en.wikipedia.org/wiki/Image:Ceratium_hirundinella.jpg

http://upload.wikimedia.org/wikipedia/commons/c/ce/Oil_well.jpg
en.wikipedia.org/wiki/Image:Oil_platform.jpg

Origin (1): Chemistry

en.wikipedia.org/wiki/Image:Petroleum.JPG

en.wikipedia.org/wiki/Image:Octane_molecule_3D_model.png

Hydrocarbon
Oil and gas are made of a mixture of
different hydrocarbons.
As the name suggests these are large
molecules made up of hydrogen atoms
attached to a backbone of carbon.
Crude Oil

Oil & Gas Industry Presentation

Oil Industry Outline

Proven Oil Reserves by Geographic Region

8% 2%
9%
48%

13%

Middle East
Central & South
America
North America
Europe
Africa
Asia Pacific

20%

November 21, 2012

Canadian Oil & Gas Industry

Presentation

BUS 417

Oil & Gas Industry Presentation

Oil Industry Outline

Global Oil Production: 76.2% Crude Oil, 23.8% Gas

1. Saudi Arabia 11.15 Million Bbl/day
2. Russia 10.23 Million Bbl/day
3. United States 10. 23 Million Bbl/day
4. China 4.234 Million Bbl/day
5. Canada 3.6 Million Bbl/day
OPEC produces ~30 million bbl/day, but level of influence lowered
from 1970s, when they produced close to 50% of worlds supply

November 21, 2012

Canadian Oil & Gas Industry

Presentation

BUS 417

Oil & Gas Industry Presentation

Oil Industry Outline

Crude Oil Properties

Light/Heavy Has to do with the viscosity of the oil. The
heavier/thicker it is, the harder it is to transport.
Bitumen from Canadian Oilsands requires to be blended with
condenstate

Sweet/Sour Oil with high Sulfuric content (sour) requires

further processing or else damages to pipes and refineries
will occur

November 21, 2012

Canadian Oil & Gas Industry

Presentation

BUS 417

1.0 INTRODUCTION

CRUDE AND GAS TERMINALS

Provided at end of Crude and Gas Pipelines,
respectively
Process/Treat Crude/Gas Streams to meet Customers
Specifications
Provide Crude Storage Facility
Ensure Continuous, uninterrupted Supply of Crude/Gas
to Customers
Perform Custody Transfer Metering prior to Changing
Ownership of Crude/Gas

Biocorrosion and biofouling of water

pipe materials and other
infrastructures

Corroded section

Corroded section

Microbial Influenced Corrosion

Classic generalized steel corrosion

Ship hull corrosion

Buried pipelines
Bridges

HIGH TEMPERATURE CORROSION

Chlorination
OXIDATION
Carburation
Flue gas and deposit corrosion
Nitridation
Sulphidation

The mostly encountered corrosion reaction

occurred in high temperature is oxidation.
Forced by diffusion mechanisms most of these
corrosion are very rapid reaction that involve
almost all alternative electrochemical processes.

PillingBedworth ratio

The PB ratio is defined as:

where:
RPB is the PillingBedworth ratio,
M the atomic or molecular mass,
n number of atoms of metal per one molecule
of the oxide
density, and
V the molar volume.

High temperature corrosion mechanisms in

cases when an oxide layer is first formed

IRON
Pic. 2.1 Oxide layer

Oxide layer 550C

900C

Oxide layer

250

y (g/mm)

200
150

Fe 900C
Fe 550C

100
50
0
0

10

20

30
Time (min)

40

50

60

 At 550C a thin and compact protective layer

consisting out of Magnetite (Fe3O4) and Hmatite
(Fe2O3). The oxygen richer oxide is always
formed at the outer layer due to the higher
oxygen pressure. These layers protect the base
metal from further rapid corrosion attack.
At 900C the oxide layer consists out of 3
different oxides. Wstite (FeO) has a very high
concentration of vacancies, which leads to very
high diffusion and corrosion rates.

y (g/mm)

MOLYBDENUM
500
0
-500
-1000
-1500
-2000
-2500
-3000
-3500
-4000
-4500
0

10

20

30

40

50

60

Time (min)

Comparison of oxidation rates of Mo at 550C

and 900C

 At 550C a protective layer will establish

immediately. There is still some MoO3 that
undergoes the transformation into the
vaporous phase, but the rate is very low.
At 900C the evaporation rate is so high
that all formed oxide evaporates
immediately due to the liquid state in
conjunction with MoO2 (Tmelt eutectic
MoO3/MoO2: 795C).

NIOBIUM
y (g/mm)

500
450
400
350
300
250
200
150
100

Nb 900C
Nb 550C

50
0
0

10

20

30

40

50

60

Time (min)

Comparison of oxidation rates of Nb at 550C and 900

 At 550C -Nb2O5 and at 900C -Nb2O5 is

present. These scales have a very high
porosity. Another problem is the generated
stress in the oxide layer caused also by this
ration, which derives out of the nature of
the metal and the oxidation mechanism (ntype). The oxygen diffuses across the scale
and builds up an inner oxide layer, located
directly at the interface (Nb/Nb-oxide).

STAINLESS STEEL

STAINLESS STEEL

 Stainless steel is expected to form a protective

Cr2O3 within these parameters (900C). Due to the
inherent properties of an chromium oxide scale
the transport of species across the scale must be
very slow (very few vacancies). The problem is the
oxide growth. This takes place by inward diffusion
(Oxygen) and simultaneously an outward diffusion
(Chromium). The new oxide is mostly established
in the middle the bulk oxide layer causing some
disconnections between the interfaces.

SUMMARY
Iron can be used within temperature ranges up to 550C

due to the formation of a slow growing oxide layer

(Magnetite) but is unsuitable above this temperature due to
the formation of Wstite (FeO) .
Molybdenum and Niobium belong to the refractory metals.
The instability (volatile oxides; MoO3)or different volume
ratios can affect the behaviour intensively. Molybdenum can
not be used (in the presence of Oxygen) in high
temperatures and Niobium plays almost the same part. But
due to internal stresses, it is also prone to catastrophic.
Stainless steel was expected to be resistant in this
temperature range (due to Chromium oxide formation) but
the effect of thermal cycling caused spallation and pointed
out some significances of considering every possibility of
negative side effects (1).

SUMMARY
There are two steps, which
govern the poor corrosion
behaviour. Initially a build up of
protective scale and followed by a
breakaway oxidation.

CORROSION PROTECTIONS

Cathodic Protection:
Impressed current.
Sacrificial anode.
Surface modification:
inhibitor
coating:
painting
nitriding

Cathodic Protection
This can be achieved in two ways:
1.) Impressed current
2.) Sacrificial Anode

Impressed Current
(ICCP)
Involves the use of an external power
source metal to be protected is made
cathodic to its surroundings inert
anodes used which are virtually nonconsumable insulated from structure
Early anodes made from scrap steel
but most modern ICCP systems use
lead silver alloy, titanium or niobium

Sacrificial Anode
Use of sacrificial anodes Zinc, lead,
etc.
Used on small structures
Anodes welded or bolted to fixtures
Need regular checks for wastage
Recently aluminium oxides have
become more popular due to better
performance to weight

Contd
Has been used in the protection of
steel reinforcement in concrete
The use of modern electronics makes
the system self regulating
Very costly to run mainly used in
marine applications oil rigs large
anodes placed on sea bed
approximately 100m away

INHIBITOR
IS A CHEMICAL SUBSTANCE THAT, WHEN
ADDED IN A SMALL CONCENTRATION TO AN
ENVIRONMENT, EFFECTIVELY DECREASES
THE CORROSION RATE
In the oil extraction and processing industries
inhibitors have always been considered to be the
first line of defense against corrosion

Inhibitors decrease corrosion

process by:
Increasing the anodic or cathodic

polarization behavior (Tafel slopes)

Reducing the movement or diffusion of
ions to the metallic surface
Increasing the electrical resistance to
the metallic surface
Inhibitors are chemicals that interact
with a metallic surface, or the
environment this surface is exposed,
giving the surface a certain level of
protection.
Inhibitors often work by adsorbing
themselves on the metallic surface by

 The efficiency of inhibitor can be

expressed by a measure of this
improvement :

Inhibitor efficiency (%) =

x 100%
[CRuninhibited CRinhibited]
CRunhibited
or
x 100%
[Rp,inhibited Rp, uninhibited]
Rp,inhibited
CR : corrosion rate ; Rp = polarization resistance

CLASSIFICATION OF INHIBITOR
Passivating (anodic)
inhibitors
Cathodic inhibitors
Organic inhibitors
Precipitation inhibitors
Volatile corrosion inhibitors

Passivating (anodic)
inhibitors
Passivating inhibitors cause a large anodic
shift of the corrosion potential, forcing the
metallic surface into the passivation range.
There are two types of passivating inhibitors:
- oxidizing anions, such as chromate, nitrite
and nitrate that can passivate steel in the
absence of oxygen.
- nonoxidizing ions, such as phosphate,
tungstate and molybdate that require the
presence of oxygen to passivate the steel

Electrochemical effect

pitting
Zone 1

cracking
zones

Usual region for TGSCC,

mostly is initiated by
pitting corrosion
(transgranular cracking
propagation needs
higher energy)

passive

Zone 2

active

Usual region for IGSCC,

SCC usually occurs where
the passive film is relatively
weak

The reduction potential of

chromate ion to solid Cr2O3
is possible to increase the
corrosion potential of steel
into its passivation region
but not for molybdate and
tungstate.

INHIBITING MECHANISM OF NITRITES

The formation of ferric oxides with the

participation of nitrite ions takes place
according to the following reactions
(Joseph et al):
Formation of a lower oxide:
NO2-+8H++6e = NH4++2H2O
9 Fe(OH)2 = 3Fe3O4+6H2O+6H++6e
2H2O = 2H++ 2OH9Fe(OH)2+NO2- = 3Fe3O4+NH4++2OH-+6H2O

Cathodic Inhibitors
Cathodic inhibitors either slow the cathodic
reaction itself or selectively precipitate on
cathodic areas to increase the surface
impedance and limit the diffusion of reducible
species to these area.
Cathodic inhibitors can provide inhibition by
three different mechanisms: 1. as cathodic
poisons; 2. as cathodic precipitates, and 3.
as oxygen scavenger.

Volatile Corrosion
Inhibitors
Volatile corrosion inhibitors (VCIs), also vapor phase

inhibitors (VPIs), are compounds transported in a

closed environment to the site of corrosion by
volatilization from a source. In boilers, volatile basic
compounds, such as morpholine or hydrazine , are
transported with steam to prevent corrosion in
condencer tubes by neutralizing acidic carbon dioxide
or by sifting surface pH toward less acidic and corrosive
values.
In closed vapor spaces, such as shipping containers,
volatile solids such as salts of dicyclohexylamine,
cyclohexylamine, and hexamethylene amine are used.
On contact with the metal surface, the vapor of this
salt condenses and hydrolyzed by any moisture to
liberate protective ions.

Electrochemical Tests to Monitoring

inhibitors effectiveness
While all laboratory corrosion tests require
accelerating corrosion processes, only
electrochemical tests can directly amplify the impact
of corrosion processes. The main reasons why this is
possible is that all electrochemical tests use some
fundamental model of the electrode kinetics
associated with corrosion processes to quantify
corrosion rates. The amplification of the electrical
signals generated during these tests has permitted
very precise and sensitive measurements to be
carried out.
Potentiodynamic polarization methods
Linear polarization resistance (LPR)
Electrochemical impedance spectroscopy (EIS)

Introduction to Paint
Paints are mixtures of many raw materials. The major
components are:
Binder (other terms used include: vehicle, medium,
resin, film former,
polymer)
Pigment or Extender.
Solvent.
The first two form the final dry paint film.
Solvent is only necessary to facilitate application and
initial film formation,
it leaves the film by evaporation and can therefore be
considered an
expensive waste product.

 Binders (or Resins) are the film

forming components of paint.
They determine the characteristics of
the coating, both physical and
chemical.
Paints are generally named after
their binder component, (eg. Epoxy
paints, chlorinated rubber paints,
alkyd paints etc).

Pigments and
extenders
Used in the form of fine powders which
are dispersed into the binder to
various particle sizes.
These materials can be divided into the
following types: Anticorrosive pigments
Barrier pigments
Colouring pigments
Extenders

Anticorrosive pigments
These prevent corrosion of
metals by chemical and
electrochemical means (chemical
inhibition):
Red lead
Zinc
Zinc phosphate
Zinc chromate

Protective Coatings / Wrapping

Provide barrier between metal and environment.
Coatings may act as sacrificial anode or release
substance that inhibit corrosive attack on substrate.
Metal coatings :
Noble silver, copper, nickel, Cr, Sn, Pb on steel.
Should be free of pores/discontinuity coz creates
small anode-large cathode leading to rapid attack at
the damaged areas.
Sacrificial Zn, Al, Cd on steel. Exposed substrate
will be cathodic & will be protected.
Application hot dipping, flame spraying, cladding,
electroplating, vapor deposition, etc.

Protective Metallic Coatings

Metallic coatings provide a layer that
changes the surface properties of the
workpiece to those of the metal being
applied. The workpiece becomes a
composite material exhibiting properties
generally not achievable by either
material if used alone.
The coatings provide a durable,
corrosion resistant layer, and the core
material provides the load bearing
capability.

 Metal Cladding
The corrosion resistance of a substrate can be improved
by metallurgically bonding to the susceptible core alloy a
surface layer of a metal or an alloy with good corrosion
resistance. The cladding is selected not only to have good
corrosion resistance but also to be anodic to the core alloy
by about 80 to 100 mV. Thus if the cladding becomes
damaged by scratches, or if the core alloy is exposed at
drilled fastener holes, the cladding will provide
cathodic protection by corroding sacrificially.
Cladding is prevalently applied at the mill stage by the
manufacturers of sheet, plate or tubing. Cladding by
pressing, rolling or extrusion can produce a coating in
which the thickness and distribution can be controlled
over wide ranges and the coatings produced free of
porosity. Although there is almost no practical limits to the
thickness of coatings that can be produced by cladding,
the application of the process is limited to simple shaped
articles that do not require much subsequent mechanical
deformation.

Aluminum Cladding
Among the principal uses are aluminum cladding in the aircraft industry, lead and cadmium sheathing
for cables, lead-sheathed sheets for architectural applications and composite extruded tubes for heat
exchangers. The thickness of the cladding is usually between 2% and 5% of the total sheet or plate
thickness, and since the cladding is usually a softer and lower strength alloy, the presence of the
cladding can lower the fatigue strength and abrasion resistance of the product

Cladding and Weld Overlaying

Compared to carbon and alloy steels, all corrosion resistant alloys are expensive. In many cases,
corrosion resistance is required only on the surface of the material and carbon or alloy steel can be
clad with a more corrosion resistant alloy. Cladding can save up to 80% of the cost of using solid
alloy.
Clad materials are widely used in the chemical process, offshore oil production, oil refining and
electric power generation industries. The use of clad steel is not new. Corrosion resistant alloy clad
steel has been available for over 40 years. Almost any corrosion resistant stainless steel or nickel
alloy can be bonded to steel. The steel can be clad on both sides or on one side only. The hot roll
bonding process is used to produce over 90% of clad plate products.

Nitriding
In many engineering applications, it is desirable that
a steel being used should have a hardened surface to
resist wear and tear. At the same time it should have
soft and tough interior or core so that it is able to
absorb any shocks (deformation, thermal etc). This
is achieved by hardening the surface layers of the
articles while the rest of it is left as such. This type
of treatment is applied to gears, bearings, railway
wheels, etc.
These also led to the development of the types of
Thermochemical treatments such as nitriding,
carburizing, Boriding and other processes which are
based on the Thermal activated diffusion processes
which are carried out at specific temperatures. So
far, These treatments have been successfully
conducted by advanced techniques including plasma
nitriding, ion beam nitriding and ion implantation.

EXPERIMENTAL PREPARATION

CH4 C Fe+ 2H2

2 NH3 2[N]Fe + 3H2
C

C
N

5 m

Substrate Material
AISI 304 and API X-52

 Traditional gaseous
thermochemical treatments
for Surface Engineering are
typically carried out in
carbon and/or nitrogen
bearing gases and are
usually associated with
temperature above 450 oC.
The improvement of wear
properties (and hardness)
relies on development of a
compund layer and an
underlying diffusion layer
in the surface adjacent
region of the sample.

Electroless plating
Electroless nickel (EN) plating is a chemical
reduction process which depends upon the
catalytic reduction process of nickel ions in an
aqueous solution (containing a chemical
reducing agent) and the subsequent
deposition of nickel metal without the use of
electrical energy. Due to its exceptional
corrosion resistance and high hardness, the
process finds wide application on items such
as valves, pump parts etc., to enhance the life
of components exposed to severe conditions
of service ,particularly in the oil field and
marine sector.

Electroless Plating

Due to its unique properties of excellent corrosion resistance, combined

with a high wear resistance and uniformity of coating, EN finds
extensive applications in a number of fields. Some of the prominent
areas of application are :-Oil & Gas: Valve components, such as Balls, Gates, Plugs etc. And
other components such as pumps, pipe fittings, packers, barrels etc.
Chemical Processing: Heat Exchangers, Filter Units, pump housing
and impellers, mixing blades etc.
Plastics: Molds and dies for injecting and low and blow molding of
plastics components, extruders, machine parts rollers etc.
Textile: Printing cylinders, machine parts, spinneret's, threaded guides
etc.
Automotive: Shock Absorbers, heat sinks, gears, cylinders, brake
pistons etc.
Aviation & Aerospace: Satellite and rocket components, rams
pistons, valve components etc.
Food & pharmaceutical: Capsule machinery dies, chocolates molds,
food processing machinery components etc.

Alteration of Environment
Typical changes in medium are :

Lowering temperature

but there are

cases where increasing T decreases attack. E.g
hot, fresh or salt water is raised to boiling T and
result in decreasing O2 solubility with T.

Decreasing velocity

exception ; metals &

alloys that passivate (e.g stainless steel) generally
have better resistance to flowing mediums than
stagnant. Avoid very high velocity because of
erosion-corrosion effects.

 Removing oxygen or oxidizers

e.g
boiler feedwater was deaerated by passing it thru a
large mass of scrap steel. Modern practice
vacuum treatment, inert gas sparging, or thru the
use of oxygen scavengers. However, not
recommended for active-passive metals or alloys.
These materials require oxidizers to form protective
oxide films.

Changing concentration

higher
concentration of acid has higher amount of active
species (H ions). However, for materials that exhibit
passivity, effect is normally negligible.

Design Dos & Donts

Wall thickness allowance to accommodate for
corrosion effect.
Avoid excessive mechanical stresses and stress
concentrations in components exposed to corrosive
mediums. Esp when using materials susceptible to
SCC.
Avoid galvanic contact / electrical contact between
dissimilar metals to prevent galvanic corrosion.
Avoid sharp bends in piping systems when high
velocities and/or solid in suspension are involved
erosion corrosion.
Avoid crevices e.g weld rather than rivet tanks and
other containers, proper trimming of gasket, etc.

THANKS