Chapter 3.

Corrosion of Metals
Occurs all the time
Attacks many structures in a plant
Shortens useful life of plant equipment
Increases maintenance requirements
Creates safety and environmental problems
Increases production downtime

Costs you money!!!

Corrosion causes catastrophic failures !!

Corrosion caused
leakage which
triggered the fire
that destroyed this
Nypro Reactor
Chevron 2001

The leak caused by corrosion at this elbow

started the fire that destroyed this refinery
Phillips
Phillips -- Pasadena
Pasadena –– 1989
1989:: Ethylene
Ethylene rreactor
eactor explo
explosion
sion
TYPES OF CORROSION
 
There are many different ways of looking at real case s of metallic corrosion:
• low-temperature corrosion and high-temperature corrosion
• dry corrosion and wet corrosion:
atmosphere, industrial gases
aqueous solutions, liquid chemicals
• chemical corrosion and electrochemical corrosion
• types of metals: steels, aluminium alloys, ceramics, etc.
• types of environment: sulphuric acid, alkalis, marine, etc.
 
One classification regards industrial metallic corrosion in 10 categories:
• uniform attack
• galvanic corrosion
• crevice corrosion
• pitting
• intergranular corrosion
• selective leaching
• stress-corrosion cracking and corrosion fatigue
• hydrogen damage
• oxidation
• high temperature corrosion
 UNIFORM CORROSION
uniform removal of metal over the entire surface

• it is the most common type of corrosion; it is most metal-consuming

• all metals are attacked by uniform corrosion
• it could be either chemical or electrochemical
• steady corrosion over the entire surface exposed to the corroding media
• least objective in engineering design: easy testing, easy inspection, easy
prediction of failure
 
Uniform corrosion is dealt with most effectively by
• proper selection of materials
• application of protective coatings
• addition of inhibitors
• cathodic protection

Question: do you know how the rate of

uniform corrosion is determined? This is an
important parameter for both the design
and maintenance
 corrosion products
of the unprotected
re-bars expend in
volume and cause
cracking to the
concrete

Coating holidays
cause localised
corrosion
GALVANIC CORROSION
 
The corrosion of one metal caused by another in an electrochemical process driven by
the potential difference between the two metals.

In this process, the corrosion in one metal is accelerated (the anode) while in the
other suppressed (the cathode)
 
Three Essential Conditions
• potential difference
• presence of an electrolyte
• electrical connection between the two electrodes
 
Factors Influencing Galvanic Corrosion
• potential difference:
electromotive force (emf) of pure elements
galvanic series of alloys
• environment: electrolyte conductivity, temperature, etc.
be aware that under certain environment conditions a galvanic coupling may
reveres their cell potential difference:  galvanised steel in hot water systems
• cathode-to-anode area ratio
• distance effect
Galvanic series, the
driving force of
galvanic corrosion
Restoration of the Statue of Liberty in
1986, due to galvanic corrosion damage
 Prevention Techniques
• selecting metals of similar electrode potentials to minimise the driving force
of the process
• protection against moisture condensation to eliminate the chance of
forming an electrolyte
• insulation between dissimilar metals to avoid electrical connection
• coating for electrical insulation or isolation of metal from electrolyte
• installing a third metal which is anodic to both metals
• designing for easy replacement of the anode metal or thicker section for
longer service life
 
Beneficial Applications of Galvanic Corrosion
• Cathodic protection, sacrificial anode protection
Galvanised steels: Zn coating is anodic to steel, act as a sacrificial metal
• Cleaning silver
blackened surfaces: silver sulphide
rubbing with an abrasive? bad for silver plates
Ag in Al pan: soda solution:
cathodic reaction reduces silver sulphide to Ag
CREVICE CORROSION

Crevice corrosion is a localised attack occurring within crevices or other shielded

areas where a small volume of stagnated solution presents

Mechanism
In a seawater environment: H2O, O2, Na+ and Cl-
Metal oxidises in balance with the reduction of oxygen:
 
M  M+ + e- (the anodic reaction)
O2 + 2H2O + 4e-  4OH- (the cathodic reaction)
M+ + OH-  MOH

Under stagnant conditions, the concentration of M+ increases due to a

decreasing concentration of O2. The positively charged crevice attracts
negatively charged ions: Cl- and OH-. Being a smaller ion, Cl- travels faster than
OH- into the crevice.
 
The increased concentration of Cl- in the crevice promotes production of M +,
encourages M+ + OH-  MOH, and more hydrolysis of H2O, leading to
increased [H+] concentration.

Increased concentrations of [H+] and [Cl-] accelerate the corrosion  crevice

corrosion is self-catalytic.
 Crevice corrosion on the face
of a flange caused by
absorbent gasket, also known
as gasket corrosion

Crevice corrosion is auto-catalytic

Crevice corrosion of a bolt

Characteristics
• crevices of the width of 25 - 100 m are most effective
• concentration of Cl- in a crevice is found to be 3-10 times higher than that in
surrounding areas in a case of dilute neutral NaCl solution: pH value drops from 7
to 2-3.
• crevice corrosion is characterised by an initiation period with a very slow start and
an ever-increasing corrosion rate.
• the oxygen reduction reaction provides cathodic protection in surrounding areas,
making the attack inside the crevice very difficult to inspect.
• it occurs in many mediums and is most intense in Cl- solutions.
• metals and alloys having corrosion-resistant oxide films or passive layers are
susceptible to crevice corrosion:
films destroyed by high concentration of Cl- and H+
stainless steels and Al alloys are typical examples
 
Typical Conditions
• holes on surfaces
• gaps underneath bolt head or between lapping parts
• porous mediums: gaskets, wood, fabrics, sand
• deposition of dirt or corrosion product
• water droplets, waterline
Example: an 18-8 stainless steel tank for a saline solution was safe in a dyeing plant; but
when a stainless steel bolt accidentally fell to the bottom of the tank, rapid attack developed
under the bolt after a brief period, causing leakage.
Minimising Crevice Corrosion
• use welded butt joints instead of riveted or bolted joints
• seal crevices: continuous welding/soldering
• regular and thorough cleaning or complete draining to remove deposits or avoid
stagnation
• filter or screen flow to remove solids in suspension
• use non-absorbent gaskets, such as Teflon, whenever possible.
• use crevice corrosion resistant alloys
 
Maximum crevice corrosion resistance is achieved in alloys of
• a narrow active-passive transition
• a small critical current density
• an extended passive region
 
Titanium and high nickel alloys are examples of such materials.
 
Type 430 stainless steel has a large critical current density, a wide active-passive
transition and a limited passive region. It is extremely susceptible to crevice
corrosion. Stainless steels as a family are very poor in resisting crevice corrosion.
Minimising Crevice Corrosion – tutorial questions

Due to the similar mechanism many other forms of corrosion are also considered
crevice corrosion. These include:

Deposition corrosion
Most corrosion is found in the
Waterline corrosion splash zone, where wet-dry
Inlet corrosion conditions alternate
Gasket corrosion
Droplet corrosion
Differential aeration corrosion

What are these forms of corrosion?

Why are they considered similar to crevice

corrosion?

How is crevice corrosion resistance

(or tendency) evaluated for materials?

What about pitting resistance?

PITTING
Pitting is a highly localised form of corrosion. It is characterised by pits or holes of
various sizes:

• small diameters and depth-to-diameter ratio of >>1

• often in clusters
• fail because of perforation with small weight loss
• most destructive
• very difficult to detect
• difficult to evaluate by laboratory tests
• develop and grow in the direction of gravity
• undercut surface as they grow

Corrosion pits
Factors Affecting Pitting
• Solutions
solutions containing chloride or chlorine-containing ions: sea water
hypochlorites (HClO3) have strong pitting tendencies; oxidising metal ions with
chlorides are extremely aggressive pitters:
cupric (CuCl2) and ferric (FeCl3) chlorides
• Flow
Pitting is associated with stagnant conditions. Increasing flow velocity
decreases pitting attack.
• Alloys
As a class, stainless steels are more susceptible to pitting corrosion than are
any other group of metals or alloys.
Solution-quenched austenitic SS exhibit better pitting resistance.
Cold working increases pitting attack of 18-8 steels, preferentially on edges.
Surface finish affects pitting resistance. Polished surfaces are more resistant
than etched or ground surfaces.
Cr, Ni, Mo and N as alloying elements increase pitting resistance of SS.
 
Type 316 SS is more resistant to pitting than type 304 due to the addition of 2%Mo.
Type 304 is considered unsuitable for applications in seawater whereas type 316 is
sometimes recommended. Ti has excellent resistance to pitting, owing to its
protective film being inert to Cl- and H+.
The Mechanism
The process of pitting corrosion consists of two stages: the initiation and the growth.
 
Initiation:
Pitting starts with an initiation period of very slow corrosion rate. Pitting selectively
initiates at areas of surface irregularities  chemical, microstructural, physical.
• a surface scratch or other mechanically induced break
• en emerging dislocation or slip step
• a compositional heterogeneity such as an inclusion, segregate or precipitate
The initiation of pitting is very fragile and young pits are unstable.
 
Growth:
Following the initiation, a pit grows at an ever-increasing rate with an identical
mechanism to crevice corrosion. It is an autocatalytic process. The same
mechanism implies that alloys that show pitting attach are also susceptible to
crevice corrosion.
EROSION CORROSION

Erosion corrosion is a result of the combined effect of chemical attack and mechanical
abrasion.
 
The Attack:
The damage appears as groves, waves or holes, following the direction of the flow.

• Typical conditions:
submarine propellers
interior of slurry pumps
exterior parts of high speed boats and ships
high flow rate pipelines

• Special locations:
elbows and junctions, extra angular acceleration
sudden reduction of pipe diameter, high velocity
sudden increase of pipe diameter, turbulence
valves, high velocity + turbulence

• Alloys:
Most alloys are susceptible to erosion corrosion, particularly those that have low
hardness and rely on protective surface films for corrosion resistance, such as
Al, Pb and Cu alloys, and stainless steels.
 Liquid impingement and
impingement erosion

Solid erosion corrosion of Erosion corrosion at

impellers in slurry media pipeline elbow
Factors Affecting Erosion Corrosion

• Medium
Many mediums can cause erosion corrosion. These include gases, aqueous
solutions, organic systems, and liquid metals. Solid particles in suspension in
fluid are most destructive by destroying surface films.
 
• Velocity
Increasing velocity generally increases erosion corrosion rate. There usually
exists a critical velocity beyond which the rate of corrosion is suddenly increased.
 
- laminar flow moving at a velocity removes metal ions from metal surface
and break local equilibrium balance, encouraging further dissolution of metal
 
- low flow velocity helps avoid stagnant conditions, replenish oxygen and bring
inhibitors to metal surface, leading to a decrease in corrosion rate
 
- corrosion tests under static or slow motion conditions often do not represent
the real situation.
• Turbulence
Turbulence provides a greater agitation of the fluid and greater mechanical impact to the
surface of the metal. Instantaneous high pressure pulses associated with the
formation and explosion of microbubbles cause most damage to metal surfaces.
 
• Impingement
Impingement create a local environment of very high velocity, very strong turbulence,
and very high pressure pulses and thus is very destructive in causing erosion corrosion.
 
• Cavitation
Cavitation damage is a special form of erosion corrosion, commonly observed on
components moving at very high velocities through fluid. It is caused by the formation and
collapse of liquid vapour bubbles, which may create local pressure pulses as
high as 400 MPa, causing local plastic deformation and destruction of surface films to
the metal.
 
Typical cases of cavitation damage:

- leading edge of the wing of supersonic airplanes caused by rain droplets

- leading edge of propellers of sea going vessels
- body of high speed boats
- liner on the coolant side of vehicle engines caused by vibration
Cavitation damages
Minimising Erosion Corrosion

• Materials
Solid solution hardening is effective in improving resistance to erosion corrosion.
Solution hardening is more effective than other hardening methods in improving
corrosion resistance is due to the fact that other methods tend to produce
heterogeneous microstructure or cause mechanical instability to surfaces.
 
- High silicon iron is an improvement to cast irons and it is widely used in severe
erosion corrosion conditions, such as slurry carrying pipelines.
- Alloying with noble metals to be inherently more resistant to corrosion
80%Ni-20%Cr alloy
ferritic stainless steels (80%Fe-20%Cr)
- Alloying to form more stable and impermeable surface films
316 stainless steel to improve 304
aluminium brass to improve Cu-Zn brass
- Stainless steel is considered to have the greatest resistance towards cavitation

Shape memory alloys are excellent in resisting cavitation, due to their ability to
deform non-destructively during impact.
• Design
Erosion corrosion is closely related to the structure of a system and the flow pattern of the
liquid; thus, many erosion corrosion situations may be avoided or minimised by proper
design.
Increasing tube diameter to reduce flow velocity and ensure laminar flow
- Increasing tube diameter to reduce flow velocity and ensure laminar flow
- Using streamline bends and expanded junction section to minimise impingement effect
- Lining with second metal at high risk locations (galvanic corrosion !!!)
- Easy to replace
- Protruding pipe ends at inlet and out let, delivering turbulence away from the vessel wall
into the middle of liquid.
- Very smooth surface to minimise the chance of vapour nucleation as against cavitation
 
• Environment
Settling and filtering to remove solids in suspension are helpful. Inhibitors may also be
added to the liquid. Decreasing temperature always reduces the rate of corrosion.
 
• Surfacing
Some surface coatings are effective to prevent other forms of corrosion, but may not have
satisfactory mechanical properties to stand against erosion corrosion, particularly when a
heavily suspended slurry solution is involved. Hard facings, welded overlays and
replaceable inserts are widely used.

proper design is the most effective way of preventing erosion corrosion

INTERGRANULAR CORROSION

Intergranular corrosion is a localised corrosion that occurs preferentially along

grain boundaries inside a metal.

• Grain Boundary Attack

Grain boundary regions are generally subjected to a higher degree of corrosion,
because of the relatively higher free energy state, chemical segregation and
impurity concentration. However, in most cases grain boundary corrosion does
not impose a serious problem to the performance of a structural component.
 
• Sensitisation of Austenitic Stainless Steels
Austenitic stainless steels tend to form carbide precipitates (Cr23C6) along
grain boundaries at 400-850 °C, causing a local depletion of Cr. The sensitised
regions are anodic to the grains and are attacked preferentially. A common
cause of sensitisation is welding, known as weld decay.
 
Common heat treatments of austenitic stainless steels:
(i) stress relieving at 350-450 °C to avoid sensitisation
(ii) solution annealing at 1000-1100 °C followed by quenching to eliminate the
effect of sensitisation; more problems with cast austenitic stainless steels
 The problem of weld decay may be avoided by using:
- L grades: 304L, 317L, 316L: <0.03%C , standard 18-8 steels: 0.06-0.15%C
-  Stabilisers: strong carbide forming elements: Nb, Ta (type 347), Ti (type 321)
- Electric arc welding instead of flame welding: more rapid heating cycle,
narrower heat affected zone, lower tendency to form carbides in HAZ
- Laser cutting instead of oxy-flame cutting
 
• Other Alloys Susceptible to Sensitisation
Some high strength Al alloys are also susceptible to sensitisation. For example,
the strengthening precipitates CuAl2 in Al-Cu alloys cause local depletion of Cu,
reducing their corrosion resistance.

Acceperated grain boundary Heat affected zones provide a Fusion cutting is another
corrosion due to Cr depletion condition for SS sensitisation case
caused by formation of Cr carbides
SELECTIVE LEACHING

Selective leaching, also known as dealloying and parting, is the selective preferential
removal of one elemental spices in an alloy system.

dezincification of yellow brass

dealuminification of aluminium bronze
graphitisation of grey iron
dechrominification
 
• Dezincification
zinc dissolves in pure water by a hydrolytic reaction.
Better resistance to dezincification:
red brass: 85-15%Zn
alloying: "inhibitors", such as Sn, As and P
 
Al bronze and Si bronze are attacked by selective leaching
Al, Si and Zn are anodic to Cu
 
• Graphitisation
Graphitisation is the selective removal of iron from the surface of grey cast iron
due to a galvanic reaction between the graphite and iron. It is the most costly
damage large-diameter underground water mains.
 
- Graphite is cathodic to iron, forming excellent galvanic cells
- Moist soil under the ground and aqueous solution it carries inside provide the
environment for selective leaching
- Earth movement may cause failure as a result of reduced strength
- Use of nodular or malleable iron is effective in avoiding graphitisation

Dezincified yellow brass

showing red Cu colour
STRESS CORROSION CRACKING
 
The Attack
Stress corrosion cracking (SCC) is a cracking failure of materials caused by the
combined action of tensile stresses and corrosive environments. SCC occurs to
many different materials, including plastics, Al alloys, Cu alloys, Mg alloys, carbon
steels, stainless steels, Ti
 
It occurs only with specific material-environment combinations:
stainless steels in 50-60 °C chloride-containing solutions
carbon steels in caustic solutions
Al alloys in chloride solutions
Cu alloys, particularly brasses, in ammonia atmosphere
 
The environments in which SCC occurs sometimes are not highly corrosive to the
metals in question. When SCC happens the metal may be virtually unattacked over
most of its surfaces. The stress that induces SCC is also often very much lower than
the failure stress of the metal. It is the combination of the two that causes the attack.
 
Morphology of cracks
Wedging effect of corrosion products
Intergranular and transgranular cracks
Factors Affecting Stress Corrosion Cracking

• Stress:
residual stresses: welding, cold working, heat treatment and casting
applied stresses: gravitation, mechanical assembling stresses, temperature
variation, etc.
a critical stress seems to exist for SCC for each metal-environment combination
 
• Time
Materials fail by SCC in brittle fracture manners - corrosion is responsible for
nucleation of cracks and failure occurs by mechanical cracking.
short time SCC tests
decreasing stress and temperature increases failure time
 
• Metallurgical Factors
Generally speaking, pure metals have lower tendency towards stress corrosion
cracking than alloys. Single phase structure better than multiphase structures.
Segregation of precipitates raises the susceptibility to stress corrosion cracking.
However, a soft phase inclusion, such as ferrite domains in austenite stainless
steel matrix, may relax the stress concentration at crack tips and slow down their
propagation.
 • Environment
No general rules to what environments cause SCC
Specific metal - environment combinations
Refer to the list of established data for known
combinations
Conduct new tests for combinations

Cracks may propagate in

intergranular or
transgranular manner.

Chloride SCC. SCC always occurs at the tensile

stress site
The Process of Stress Corrosion Cracking
unclear mechanism - complex interplay of metal, environment, stress states and interface
properties
 
• Initiation
Corrosion is the primary reason for crack initiation - cracks are observed to start at the
base of a pit.
A tensile stress assists breaking up protective films and enhance the elastic energy of
surface atoms.

• Propagation
In the intermediate stages, stress corrosion cracking proceeds by the conjoint action of
stress (concentration) and corrosion at crack tips. Cracks have been observed to
propagate in discontinuous steps, emitting acoustic waves when jumping. The contribution of
corrosion to crack propagation is evident in experiments when acoustic waves are
stopped at the application of cathodic protection and resumed after the removal of the
cathodic protection.
 
preferential attack at crack tips:
local plastic deformation, increased defect density,
emerging slip steps, decreased resistance to chemical attack
 
• Cracking
The final failure caused by unstable propagation of cracks is basically a mechanical
process. However, the presence of corrosive chemicals and water molecules at the crack tips
lowers the critical stress for cracking.
Summary

Stress corrosion cracking is an electrochemical-mechanical process. It initiates

at small but chemically active areas such as a stress induced film rupture, a high
energy grain boundary, and chemical segregation sites.
 
Stress corrosion cracks propagate in discontinuous steps. The slow motion of
corrosion builds up stress concentration at a crack tip until a critical moment
when the crack propagate to a new location and stopped when the stress
concentration is relaxed.
 
Stress corrosion cracks may follow intergranular and transgranular paths. In
materials having complex slip systems or high stacking-fault energies, cracks
propagate along intergranular paths.
 
The role of corrodant in the mechanism of stress corrosion cracking is the least
understood.
Prevention
Avoid dangerous metal-environment combinations by using a different metal.
Carbon steels sometimes are used in preference to stainless steels due to their
higher resistance to stress corrosion cracking. Inconel is used to replace type
304 SS for the same reason.
 
Eliminate the tensile stress component whenever possible. More than often a
tensile stress is from residual sources; thus stress relieving heat treatment is
commonly recommended. Furthermore, creating a compressive surface residual
stress condition is highly effective in suppressing stress corrosion cracking. A
compressive surface stress state may be achieved by various means including
thermal treatment, blasting, ion implantation.
 
Reduce the corrosivity of environment, such as to change the pH of a fluid, to
eliminate oxygen or chloride from a solution. Inhibitation, cathodic protection and
design modification may also render the environment less harmful.
 
Cathodic protection is effective. It may be applied either with an external power
supply or consumable anodes. Precautions must be taken when applying
cathodic protection to guard for hydrogen embrittlement.
Corrosion Fatigue
The presence of a corrodant, or the action of corrosion, tends to reduce the
fatigue life, or decreases the fatigue limit, of a metal.
 
Little is known about corrosion fatigue beyond the knowledge of stress corrosion
cracking.
 
Corrosion fatigue is characterised by transgranular cracks that do not show much
branching. The final cracking is largely a mechanical process.
 
• Factors Affecting Corrosion Fatigue
Fatigue life in the case of pure mechanical loading is determined by the number
of cycles; the effect of cycling frequency is negligible. In the case of corrosion
fatigue, however, stress-cycle frequency has a strong influence on the fatigue life
of a metal. Corrosion fatigue is most pronounced at low stress frequencies. Low
frequencies allow a better contact of corrodant to the metal at crack tips.
 
• Prevention
In addition to those applied to stress corrosion cracking, vibration should clearly
be avoided to prevent corrosion fatigue, by, for instance, proper designs.
Fretting corrosion is a special
form of corrosion fatigue
HYDROGEN DAMAGE
Hydrogen in environment is damaging to metals
Damage is associated with hydrogen absorption
Forms of damage: embrittlement, blistering & decarburisation
Sources of atomic hydrogen:
corrosion process
application of cathodic protection
welding
electrolysis & electroplating
 
• Hydrogen Blistering
Hydrogen blistering is caused by the formation of micro-bubbles of high
pressure hydrogen gas inside the metal
 
The most damaging fact is that the equilibrium pressure between H2 and
H is very high - several 100,000 atm, sufficient to rupture any known
engineering material.
 
Hydrogen blistering is most prevalent in petroleum industry. It occurs in
storage tanks and in refining processes.
• Hydrogen Embrittlement

Hydrogen embrittlement is the brittle cracking of metals caused by

hydrogen absorption. The actual embrittling mechanism is not clear.
 
Ti alloys: formation of brittle hydrides
Irons & steels: interaction of H & crack tips
Different from SCC: cathodic current suppresses SCC but encourages
hydrogen embrittlement
 
Hydrogen embrittlement is a more serious problem in high strength
materials:
- HSLA steels
- high strength grades of carbon steels
- Ti alloys
- Cu alloys
• Prevention

• "Clean" steels:
rimmed steels: high % microvoids
killed steels: voids-free structure
• Coating & lining:
impervious to hydrogen penetration
electroplating, cladding with ASS or nickel
porous materials: brick lining
• Resistant alloys:
Ni-containing steels & Ni alloys
low diffusion rate of H in Ni
• Baking:
absorption of H in metals is reversible
baking at 100-150°C removes dissolved H in steels
• Process control:
pickling, plating & welding
Low-H or H-free welding techniques
• Decarburisation & Hydrogen Attack

Removal of C in C-containing alloys at high T:

[C] + 4[H] = CH4
CH4 formed in microvoids exerts a high pressure to the matrix of steels,
causing embrittlement – known as hydrogen attack
Hydrogen attack occurs in
- petrochemical plants
- oil refineries
- processing lines for ammonia & methanol synthesis
- conventional power stations

• Environmental Effect

Hydrogen attack occurs in carbon steels at 250 - 600 °C with critical

hydrogen partial pressures of 1 -75 MPa. Increasing temperature
decreases the critical hydrogen partial pressure required for the attack. At
temperatures below 200°C, carbon steels are not attacked by hydrogen gas
even under relatively high pressures.
 
• Metallurgical Factors

The sensitivity of carbon steels to hydrogen attack increases with carbon

content:
- commercial pure iron (0.004%C) resisted attack at 540°C & 4.8 MPa
for 500 hrs
- steel (0.009%C) was attacked under the same conditions
 
Alloying with carbide-forming elements (Ti, V, Cr, Mo and W) improves
resistance to hydrogen attack. These elements stabilise C in the matrix,
mostly by forming complex alloy carbides, such as (Fe,M)3C or M7C3.

Processing
- Cold worked steels embrittle easily in high-T, high-P hydrogen
- Surface stresses accelerate H absorption and cause hydrogen attack
- HAZ in a weldment is more susceptible to hydrogen attack
- Quench and tempered steels are more resistant than normalised ones
- Spheroidising improves resistance to hydrogen attack
OXIDATION
Reaction between a metal and O2 at the absence of water.

Dry oxidation is only a process of appreciable rate at elevated temperatures

for most metals

Pilling-Bedworth Ratio
It is suggested that oxidation resistance of a metal depends on the
properties of the metal oxide on the surface, as determined by the Pilling-
Bedworth Ratio:
  volume(oxide)
PB ratio =
  volume( metal )
PB ratio ~ 1 gives good oxidation resistance
Requirements on protective film:
- good adherence, coherent to base metal
- good mechanical properties: strength, ductility and toughness, no
rupture under applied or thermal stresses
- high melting temperature
- similar thermal expansion coefficient to metal
- low diffusion coefficient for oxygen and metal ions
Electrochemistry of Oxidation

Oxidation process of metals in gaseous oxygen is effectively an

electrochemical process rather than a simple chemical reaction, in analogy
to aqueous galvanic process, for example:

Cu + O2 = CuO

Anodic reaction at metal-scale interface:

Cu = Cu2+ + 2e-
Cathodic reaction at scale-gas interface:
O2 + 2e- = O2-
Most metal oxides conduct electrons and ions to some extent
Morphology of Oxides
Diffusion of either metal ions or oxygen ions through the oxide controls the
oxidation rate
 
Fe, Ni, Cu, Cr, Co: oxides grow preferentially at the scale-gas interface by
outwards cation diffusion certain protection of the scale
 
Ti, Ta, Zr, Hf: oxides grow inwards at the metal-scale interface, non-
protective due to scale fracturing
 
Oxidation Rate
Controlling factor: conductivity of oxide
Anion deficient oxides: n-type oxides
Cation deficient oxides: p-type oxides
 
Alloying with higher valence metals reduces anion vacancy concentration of
n-type oxides & reduces the rate of diffusion-controlled oxidation
 
Alloying with lower valence metals reduces cation vacancy concentration of
p-type oxides & reduces the rate of diffusion-controlled oxidation
Oxidation Kinetics
Different metals show different oxidation kinetic behaviour
 
- Linear: W = kt
metals having non-protective surface films
Na, K PB ratio ~0.5
Ta, Nb PB ratio ~2.5

- Parabolic: W2 = kt + C
metals having protective surface films
Fe, Co, Cu, Ni

- Logarithmic: W = klog(Ct + A)
empirical observation
thin oxide layers at low temperatures
Al, Cu, Fe

- Catastrophic:
oxidation with continuously increasing rate
ignition and self-sustained combustion of metals
Mg, Al (powder), Zn
Oxidation Resistance of Fe-Ni-Cr Alloys

Fe, Ni and Co exhibit only moderate oxidation resistance. Alloying with Cr,
Si and Al enhances their resistance. Fe-Ni-Cr alloys are the most commonly
used alloys for general purpose high temperature oxidation resistance
applications, largely due to their relatively low costs, moderate oxidation
resistance, and good mechanical properties