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Detail (definition, mechanism, prevention)

Corrosion
of 2 types of corrosion based on a given
case study. Unif orm Localized

Corrosion
Macroscopic Microscopic
Metal degradation process resulting from
interaction with its environment. The Stress
Intergranular
destructive electrochemical attack of a Galv anic Crev ice Corrosion
Corrosion
Cracking
material.
Corrosion agent Pitting
Erosion
Corrosion
 Water
 Moisture Forms of Corrosion
 Acids/Bases  Stress Corrosion
 Salts S&C work together at crack tips.
 Oils  Erosion-Corrosion
Disadvantage Break down of passivating layer by
erosion (pipe elbows).
 Higher expense to prevent corrosion or
for maintenance/replacement  Pitting
Advantage Downward propagation of small
pits & holes.
 Etching (The removal of wafer surface
layers during the process of  Crevice
manufacturing.) Between 2 pieces of the same metal.
 Surface corrosion forms oxide layer  Galvanic
which acts as a barrier for air and Dissimilar metals are physically
moisture and prevent the inner metal joined, anodic one corrodes.
from corrosion  Intergranular
Degradation may result in: C along grain boundaries, often
 Thinning of metal where special phases exist.
 Leaks  Selective Leaching
Preferred corrosion of 1 element
 Sudden failure/damage of eqp
(Zn from Cu-Zn)
 Loss in heat transfer rate
 Uniform Attack
 Brittle surface
Oxidation & reduction occur
 Surface softening uniformly over surface.
 Unpleasant appearance Uniform Corrosion
 Others: tarnishing of silver, iron rusting,  Uniform, regular removal from the
dissolution of metal in acid solution surface is usually expected on the mode
All metals/alloys are susceptible to of corrosion.
corrosion  Metal must metallurgically &
 Gold: excellent resistance to compositionally uniform.
atmosphere, corrode when exposed to  Predictable corrosion rate.
Hg at ambient T.
 Examples
 Fe: does not corrode in mercury but o Steel in HCl
rusts readily in atm
o Thinning and penetration of CS
Forms of Corrosion storage tank for sour crude oil
(H2 S)
o Atmospheric corrosion.
 Control:
o Select proper material
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o Coating o Transgranular morphology

o Use inhibitor  Material
o Anodic/cathodic protection o Steel containing aluminium
Galvanic Corrosion have better resistance.
 Occurs when dissimilar metallic o SS susceptible to SC in
materials are brought into contact in the presence of chlorides.
presence of electrolyte. Attacks at the Erosion-Corrosion (Impingement
junction between them. Attack)
 Can occur between metal+other  From rapidly flowing solutions
conduction materials: carbon &  At elbows, pumps, tubes constrictions
graphite. & other structural features that alter
 Corrosion greater at active metal flow direction/velocity and increase
 The more noble metal can be damaged turbulence.
by H.  Often when corrodent in l phase.
 Factors affecting  Suspended solids aggravate it.
o Electrode potential  Attack may be serious in 2 phase flow
o Surface characteristics where steam & water vap condensate
o Reaction kinetics droplets are present.
o Bulk solution properties  Lower strength less resistance alloys
o Geometry such as CS, Copper, Al are susceptible.
o Type of joint  SS, Nickel alloys & Titanium are
o Alloy composition usually resistant due to their tenacious
 Noble=more cathiodic, Active=more & durable passive films.
aniodic  Takes form of grooves/waves/teardrop-
 More significant if potential difference shape pits & horseshoe-shaped
is more than 250mV. So select alloys depression in the surface.
with close potentials.
 Area of effect: Unfavorable – large
cathode, small anode results in
corrosion that take place at high
current density.
 Distance affected depends on solution
conductivity.
Stress Corrosion
 Accelerate in certain env.
 Important & diff to predict failure. Electrochemical Consideration
 Cracking present due to corrosive env  Electron transfer from 1 chem species
& stress induced. to another
 Stress Corrosion Cracking (SCC)  3 important process in corrosion
(have brittle appearance) o Electrolyte (solution w ion)
o Internal tensile stress (cold o Anode (oxidation)
work) o Cathode (reduction)
o External stress  Oxidation – metal gives e
 Magnitude of stress that causes failure  Reduction – metal gains e
depends on Summary
o Corrosive medium  Corrosion occurs due to
o Structure of base metal o Natural tendency of metals to
 Cracks can have give up e
o Intergranular o E given by oxidation rxn
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o E are then part of reduction rxn
 More (-) metals are likely to corrode
relative to other metals.
 Galvanic Series ranks reactivity of
metals in seawater
 Increasing T, increase ox/re rxn.
Prevention Methods
 5 General Techniques
o Material Selection
o Environmental Alteration
o Design Consideration
o Coating
o Cathodic & Anodic Protection
Material Selection
 Depends on corrosion environment
o Freshwater – cast iron, steel,
Al, Cu, brass, some SS
o Seawater – Ti, brass, some
bronzes, Cu-Ni alloys, Ni-Cr-M
o Atmospheric – all alloys, Cu,
galvanized steel.
 Mechanical Properties
o Aggressive op condition –
combination 2/3 metals are
needed
o Effect of T – plain CS limited
to 316-343C due to loss of
strength & susceptibility to
oxidation & corrosion. Highly
alloyed Ni-Cr-Fe alloy are
adequate to corrosion resistance
at elevated T.
 Material Fabrication
o Should be selected based on
maintainability & fabrication
ability. Also consider ease of
modification or repair after
exposure to op condition.
 Availability of materials
o Consider future availability for
repairs/replacement/alternative
replacement materials.
 Material Cost
o Life cycle cost/Cost
Effectiveness rather than initial
cost
Environmental Alteration
 Decrease velocity of corrosive fluid
 Use lower T
 Remove O 2 from water solutiom
(deaeration process)
 Reduce conc of corrosive ions in
solution
 Add inhibitors
o Scavengers type – react w &
virtually eleiminate chemically
active species in solution such
as dissolved O 2
o Absorption type – attach
themselves acc to corroding
surface/interface w either
ox/red rxn to form v thin
protective coating.
Design Consideration
 Prevent formation of galvanic cell by
using similar metal/alloys or using
non-metallic connector (gasket/fitting)
to electrically insulate 2 dissimlar
metal.
 Weld rather than rivets or choose rivets
that are cathodic to materials being
joined.
 Increase anode area than cathode area.
 Avoid sharp bend in piping system.
 Design
o Components so that fluid
system are closed to avoid
continuously dissolve gas.
o Easy removal/replacement of
part that are expected to fail
rapidly.
o Should allow complete
drainage & easy washing.
Coating
 Def: physical barrier applied on
surface in form of films.
 To isolate anode/cathode region
 Conditions of coating
o Must be non-reactive in
corrosive env
o Resistant to mechanical
damage that exposes the bare
metal to corrosive env
 Types
o Metal
 As sacrificial anodes
instead of coated metal.
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Eg. Steel coated with

Zn-plated/Sn-plated.
 Plated by electro plating
process
 Metal as cathode.
Electrolyte is solution
of salt of metal to be
plated & direct current
is applied.
o Ceramic/Glass (Inorganic
Coating)
 Porcelain coating
consist of thin layer of
glass fused to steel
surface so that it
adheres well and has
coefficient of expansion
adjusted to base metal.
Eg: Teflon.
 Stable, adherent,
nonporous, non-
 Galvanic/sacrificial anode
conduction oxide later.
requires:
Eg: glass fused coating
o Sacrificial anode
a steel
o Direct welding to
o Organic Coating
structure/conductor
 Thin, tough, durable
connecting to anode of
barrier to protect
structure.
substrate.
 Polymeric material, o Secure & min resistance
connections between
pints, paints, varniches,
conductor & structure
lacquers. Cheaper.
and conductor & anode.
Cathodic Protection (widely used)
 Current flow in a loop so the
 Principle: connect external anode to
surface can be protected is the
metal to be protected and pass an
submerged surface (receive
electrical DC current so that all areas
protection current from anoted)
of the metal surface become cathodic
& do not corrode.  Criteria for SA
o Sufficiently negative
 Involves supplying e to metal
corrosion potential.
protected.
o High anode efficiency.
 Sacrificial Anodes Cathodic Protection
Impurities that results in
(SACP)
self-corrosion must be
o Use reactive metals as auxiliary
absent/min.
anodes that are directly
o Ability to remain active
electrically connected to metal
& corrode uniformly &
to be protected
not become passive.
o The SA corrodes, supplies e to
metal & prevent anode rxn at
metal.
o Eg: Al, Zn, Mg.
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 Impressed Current Cathodic
Protection (ICCP)
o From direct current source
between anode & metal to be
protected.
o Cause metal to be cathode.
o Anode usually surrounded by
high conductivity backfill
material such as
gypsum/bentonite which
improve electric contact
between anode & surrounding
soil.
o Protects large area.
 ICCP requires
o Inert anodes (clusters
connected in backfill
called the groundbed)
o DC Power Source
o Well-insulated, min
resistance, secure
conductors between
anode & power source.
o Secure & min resistance
between power source
& structure.
 Reasons to use ICCP
o Steel structure to protect
is large
o High protection current
req
o Coating quality varies
in large range
o High soil resistivity
o Electric current source
is available
o Available field for
ground bed
 Structures that are commonly
protected
o Pipelines, ships’ hulls,
storage tank bases,
jetties/harbours,
platforms.
o Protect internal surfaces
of – large d pipelines,
ships’ tanks (product &
ballast), storage tanks
(oil & water), water-
circulating systems).
 Advantages
o Simply application
(maintain dc circuit)
o Effectiveness can be
monitored
o Applied to existing
structure to prolong life
o Protect steel structures
buried in soil/immersed in
water
o For cases where small leaks
cannot be tolerated for
safety/env.
Anodic Protection
 Reduce corrosion rate in anode by
polarizing into a potential region
where dissolution rate is low.
 When CP is not practical –
alkaline/acidic env.
 Metal to be protected is made the
anode. Active-passive
metals/alloys. Protect eqp used to
store/handle sulfuric acid.
 Passivation occur by exposing
metal to highly conc oxidizing
solution
o Iron dipped in nitric acid
o Iron rapidly corrodes to
form thin protective iron
hydroxide coating
o Coating protects iron from
subsequent corrosion in
nitric acid.
 Can be controlled by potentiostat –
electronic device that maintains
metal constant potential with
respect to a ref electrode.
 Have 3 terminals – connected to
tank, auxiliary cathode, reference
cathode.
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 Advantages
o Current applied is equal to corrosion rate of protected system.
o Can decrease corrosion rate substantially (in extremely corrosive env & low
current req.)
o Protect eqp that store & handle sulphuric acid manufacturing plants.
 Disadvantages
o If proper control not implemented, accelerate corrosion.
o Requires complex instrumentation (not economic for small manufacturing
plant)
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Detail properties of 3 types of suitable SS  C is the most important commercial

materials based on given case study. steel alloy. High C, High Hardness,
Ferrous & Non-Ferrous Metals High Strength, High Brittleness, Low
 Steel Weldability.
o Plain C Steels
o Low C  Iron C alloys with less than 2.14% C
o Medium C  Microstructures normally ferrite,
o High C relatively soft & weak but good
o Stainless ductility & toughness.
o Tool Plain Carbon Steels
 Cast Iron  Less than 1% C alloy with small
o Gray amount of Mn, P, S, Si.
o Nodular (Ductile)  Disadvantages – low hardenability,
o White loss of strength & embrittleness,
o Malleable subjected to corrosion.
 Non-Ferrous Alloys  3 groups – low, medium, high.
o Al Low Carbon Steel (<0.25% C)
o Cu  Unresponsive to heat treatments
o Mg intended to form martensite.
o Ti  Microstructures consist of ferrite &
o Noble Metal pearlite
o Refractory Metals  Properties – soft & weak with high
 Metals are divided into 2 ductility & toughness, good
o Ferrous formability & weldability, low cost,
Has Fe as prime constituent, rated at 55-60% machinability.
steel, cast iron. Higher chance  Application – Auto-body components,
of corrosion. structural shapes, sheets for pipelines,
Advantages building, bridges, tin cans, nail, low
Stronger, Stiffer, Better for temperature pressure vessel.
Welding, Iron is abundant,
 High-strength low alloy (HSLA) steels
Versatile, Produced from are LCS + 10wt% Mn, Cr, Cu, V, Ni,
economical process: extraction,
Mo.
refining, alloying & fabrication
 Properties – higher strength than
techniques are available.
PLCS, ductile, formable, machinable,
Disadvantages
more resistance to corrosion.
Tends to corrode, High density,
Strengthening by heat treatment.
Low electrical conductivity.
 Application – bridges, towers, support
o Non-ferrous
columns in high rise building, pressure
Less or no Fe. Cu, Al, Mg, Ti
vessels.
& its alloys. Higher resistance
Medium Carbon Steel (0.25 – 0.6% C)
to corrosion.
Advantages  Advantages – 60-70% machinability
Good resistance to corrosion, (hot & cold rolled steels machine better
easy for casting/cold working when annealed), good toughness &
processes, high ductility, high ductility, fair formability, responds to
thermal/electrical heat treatment but often in natural
conductivities, colour. condition.
Ferrous Alloy  PMCS – low hardenability, heat
 Classified based on % of C treatment: quenching & tempering.
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 Heat treatable steel – containing Cr,
Ni, Mo. Heat treated alloy is stronger
than LCS, lower ductility and
toughness than LCS.
 Applications – Couplings, forgings,
gears, crankshafts other high-strength
structural components. Steels in the
0.40 to 0.60% C range are also used for
rails, railway wheels and rail axles.
High Carbon Steel (0.6 -1.4% C)
 Properties – hardest, strongest, least
ductile.
 Application –Used for withstanding
wear. A holder for a sharp cutting
edge: drills, woodworking tools, axes,
turning and planning tools, milling
cutters, knives. Used for spring
materials, high-strength wires, cutting
tools, and etc.
 Advantages – high hardness, wear
resistance and fair formability.
 Disadvantages – low toughness,
formability, not recommended for
welding, usually joined by brazing w
low T Silver alloy making it possible
to repair/fabricate tool steel parts w/o
affecting their heat treated condition.
Stainless Steels
 Primary alloying element is Chromium
(>11%)
 Others: Ni, Mn, Mo
 In presence of O 2 , they develop thin,
hard, adherent film of chromium oxide
(Cr2 O3 ) that protects metal from
corrosion.
 Highly resistant to corrosion
 Applications
o Decorative trim, nozzles.
o Springs, pump rings, aircraft
fittings.
o Cookware, chemical and food
processing equipment.
o Turbine blades, steam boilers,
parts in heating furnaces.
o Temporary implant devices
such as fractures plates, screw
and hip nails.
o The best choice for the walls of
a steam boiler because it is
corrosion resistant to the steam
and condensate.
 3 basic types – Martensite, Ferritic,
Austenitic. Identified by their
microstructure or predominant crystal
phase.
 Austenitic
o Have austenite as primary
phase (FCC).
o Contain Cr & Ni (sometimes
Mg & N) around T302
composition of Fe, 18% Cr, and
8% Ni.
o Not hardenable by normal heat
treatment but can be work
hardened.
o Non-magnetic
o Kitchen sinks (304D)
o Excellent corrosion resistance,
weldability, ductility & hygiene
characteristic.
 Ferritic
o Ferrite as main phase (BCC)
o Contain Fe & Cr between 12-
17%, low C content.
o Type 430 with 17% Cr.
o Less ductile than austenitic.
o Magnetic but not heat treatable.
o Hot water tanks (444)
o Moderate to good corrosion
resistance w increasing Cr
content.
 Martensitic
o Orthorthombic (BCT)
microstructure
o Considered supersaturated
solution of C in Fe.
o Acicular (needle-like) pattern
in microstructure
o Can be turned into austenite
when it is quenched & cooled
below 450˚F.
o May be tempered and hardened
by heat treatment.
o High strength and great
hardness but reduces toughness
& makes it brittle.
o Used in knives, cutting tools,
dental & surgical eqp.
o Moderate corrosion resistant
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Ferrous Non-Ferrous
Generally greater strength Good resistance to corrosion

Generally greater stiffness ( Much lower density

↑E)

Better for welding Casting is often easies ( ↓

melting points)

Cold working processes are

often easier (ductility)

Higher thermal and electrical

conductivities

Colours

Environment, expected part life and extent of acceptable corrosion all help determine what
type of stainless to use. In most cases, the primary factor is corrosion resistance, followed by
tarnish and oxidation resistance. Other factors include the ability to withstand pitting, crevice
corrosion and intergranular attack. The austenitic/higher chromium stainless steels, usually
required in very high or very low temperatures, are generally more corrosion resistant than
the lower chromium ferritic or martensitic stainlesses.