MATS 64532: Surface Engineering and Materials Design

Surface Engineering Part 1

Dr Zhu Liu
Corrosion and Protection Centre
School of Materials
The University of Manchester

Lecture Arrangement
L1 Surface Engineering I

Introduction to SE
Hot-dipping
Electroplating
Chemical plating
Thermal spray
Overlay coating
Cold spray
Diffusion coating

L3 Surface Engineering III

Introduction to LSE

Heat-treatment
Surface re-melting
Surface alloying
Cladding
Shock-peening

L2 Surface Engineering II
Physical vapour deposition
Chemical vapour deposition
Ion implantation
Sol-gel coating

L4 Surface Engineering IV
Surface texturing
Surface modification of
polymers
Surface finishing

Definition of Surface Engineering

1. Treatment of the surface and near-surface regions of
a material to allow the surface to perform functions
that are distinct from those functions demanded from
the bulk of the material [defined by ASM handbook]
2. The design of a surface and a substrate together as a
system, to give a cost effective performance of which
neither is capable alone [defined by CEST]

Surface Engineering
Surface Properties
Improved corrosion resistance
Improved wear resistance
Improved thermal insulation
Improved high-temperature oxidation resistance
Improved adhesion (for polymers)
Improved wettability (both polymers and metals)

Economic Benefits

Classification of Surface Engineering

Changing surface
metallurgy

Localised surface

hardening: Flame,
Induction, Laser and
Electron-beam
Rapid solidification:

Laser surface melting

Shot peening
Laser shock peening

Changing surface
chemistry

Ion

implantation
Laser surface

alloying

Adding
coatings
Hot-dip coating
Electroplating
Chemical plating
Diffusion coating
Thermal spray
Overlay coating
Cold spray
Physical vapour

deposition
Chemical vapour
deposition
Sol-gel
Laser Cladding

Changing surface
structure

Laser surface

texturing
/patterning
/structuring

Classification of Coatings
For applications of corrosion protection:
Metallic coatings

Anodic coating
Cathodic coating
Neutral coating

Ceramic, polymer coatings

Anodic Coatings
Coating material is less nobel than the substrate to be protected.

Cathodic or sacrificial protection

A barrier to the environment
Examples: zinc-coatings on steel (galvanised steel)
Features: at breaks or pores
or cut edges the coating
corrodes preferentially and
provides sacrificial protection
to the underlying steel
http://www.gordonengland.co.uk/corrosion.htm

substrate.

Cathodic Coatings
Coatings is more noble to the substrate to be protected

Examples: nickel-coatings on steel, copper-coating on steel

http://www.gordonengland.co.uk/corrosion.htm

Limitation: the coating

must provide a complete
barrier to the substrate from
the environment; otherwise,
at breaks, pores or cut edges
the steel will corrode,
causing severe pitting
because the anodes will be
small while the cathode area
is much larger.

Arrangement of metals in Galvanic Series

Corrosive End (Anodic or less noble)
-----------------------------------------------Magnesium
Zinc
Aluminium
Cadmium
Iron/steel
Stainless steel (active)
Tin
Nickel
Copper
Stainless steel (passive)
Gold
-------------------------------------------------Protective End (Cathodic or most noble)

Protection of carbon steels:

Anodic coatings

Zn
Al (exceptional cases)
Cd
Mg (too reactive)
Cathodic coatings

Tin
Nickel
Copper

Hot-dipped Coatings
Definition: A metallic coating obtained by dipping the substrate

metal into a molten metal.

* coating with lower melting temperature
Stages:

1) Pre-treatment: degreasing, descaling and rinsing

2) Fluxing: wetting
3) Dipping:
4) Post-treatment: annealing, or rolling, or rapid coling
Typical hot-dipping processes:

Galvanized steel
http://www.youtube.com/watch?v=c2J07n5hSbs

Typical Surface Appearance of Galvanized Steel

Surface appearance: 100% Zn bright, polycrystalline structure with

visible crystalline grains of zinc, some times several centimetres in
size.

Typical Microstructure of Galvanized Steel

Out-layer (20-30 m) : 100% Zn

Metallurgical bonding: various Zn-Fe intermetallics
Zn-Fe intermetallics is brittle limited additional shaping

Other Zinc-based Coatings

To improve formability and ductility of coatings by addition of other elements into the molten zinc bath.

"Galfan" (Zn-5%Al):

Continuous coil-coating, much improved ductility

Better corrosion resistance than Zn coating
Similar function of sacrificial protection
"Galvalume (Zn-55%Al):
Continuous coil-coating, much improved ductility
Even better corrosion resistance than Zn-5%Al coating
Limited sacrificial protection
"Galvanneal":
Full Zn-Fe intermetallic layer by heat-treatment
Similar function of sacrificial protection

Corrosion Protection of Galvanized Steels

Zn provides:
Physical barrier (corrosion rate of Zn

Zn

is 5-10% that of steel): When exposed

Steel
to the atmosphere, zinc reacts with
oxygen to form zinc oxide, which further reacts with water
molecules in the air to form zinc hydroxide. Finally zinc
hydroxide reacts with carbon dioxide in the atmosphere to
yield a thin, impermeable, tenacious and quite insoluble dull
grey layer of zinc carbonate which adheres extremely well to
the underlying zinc, so protecting it from further corrosion.
Cathodic protection: Zinc coatings prevent corrosion of the

protected metal by forming a physical barrier, and by acting as a

sacrificial anode if this barrier is damaged.

Applications of Galvanized Steels

Galvanized
steel pipe

Galvanized
Steel bucket

Galvanized Steel
Guard Rail System

Lifetime of galvanized steel: up to 50 years

Extended lifetime by duplex system: up to 75 years.

Electro-deposition/Electroplating
Principles how it works

Consist of: anode, cathode,

aqueous-metal solution and

power supplier
Corrosion process in reverse
Example: Ni plating
Anode:

Ni Ni2+ + 2e-

Cathode:

Ni2+ + 2e- Ni
(2H+ + 2e- H2)

Surface Preparation and Electroplating

Procedure

Degreasing
Etching/chemical pre-treatment
Washing/rinsing
Pre-plating or other surface treatment
Washing/rinsing
Plating
Washing/rinsing
Post-treatments (annealing, polishing, passivating, etc.)
Importance of surface cleanliness: In real world, surface

preparation is more crucial than plating to ensure good

adhesion and surface quality

Electrodeposition/Electroplating
Structure of plating

Epitaxial growth for a few

hundred atomic layer
(clean and oxide-free surface)
Coating thickness

Proportional to the current density

and length of deposition time, leading
to one of the majors drawbacks in
electroplating inability of achieving uniform deposition for
irregular shaped components
* Throwing power: ability of a plating solution to produce a
uniform metal distribution on an irregular shaped object.

Electrodeposition/Electroplating
Major drawbacks

Poor thickness uniformity on complex components

Hydrogen embrittlement for steels
Not applicable to insulating substrates
Possible environmental concerns with plating baths
Advantages:

Low temperature treatment (< 100 C) no distortion and

no metallurgical changes
Coatings are dense with excellent adhesion to the substrate
No technical limitation to coating thickness - thick layers
possible
Selective deposition possible by applying masks
Applicable to a wide range of metal substrates
Low cost

Applications of Specific Coating Systems

Nickel plating: corrosion protection, undercoat for

electroplating chromium for decorative purpose of

automotive, consumer products and office furniture
Chromium plating: Chromium easily passivated cannot be

used as soluble anode. Decorative (tarnish-resistant), hard,

wear-resistance coatings (always need nickel as undercoat).
Note a problem with cracks and pores within the chromium
coating, leading to limited corrosion protection.
Cadmium and Zinc plating: Cadmium for marine

environment, and zinc (<6 m) for industrial environment.

Tin plating: for non-aggressive environment, tin coating

(0.5-1 m) is required, such as tin plated steel cans.

Applications of Specific Coating Systems

Micro- and Nano-composite Coatings

Metal Matrix Composite (MMC) Ceramic particles

(carbides, oxides) in metal matrix (cermet)
Size of ceramic particles: a few micron, submicron, or nano-.
Ceramic particles suspending

in an electrolyte
Co-deposit ceramic particles

into metal matrix

Application Examples of Electrodeposition

Gold plating

Chromium Coating for

Superior Metal
Protection

Polished electroplated chrome or multi-layer

Mild steel core and

electroplated with Cu

Environmental concerns

Chemical Plating
Chemical plating: deposition of metal on substrate

without applying external current.

Two forms

(1) Immersion plating

Cu2+ + Fe = Fe2+ + Cu
(2) Electroless plating
Ni2+ + 2HPO2- = Ni + H2 + 2PO2 Mechanisms: Electrochemical in nature, involving

both oxidation and reduction reactions

Immersion Plating
Immersion plating

Oxidation: Zn Zn2+ + 2e-, anodic,

E0 = 0.76 V
Reduction: Cu2+ + 2e- Cu, cathodic,
E0 = 0.34 V
-----------------------------------------------------------------------------Overall reaction: Zn + Cu2+ Zn2+ + Cu
E0 = 1.1 V
A simply displacement reaction between an anodic substrate

and a more noble metal ion in solution with the deposition

reaction driven by local dissolution of the substrate
Limited plating thickness (1m): Displacement process

continues until almost the entire substrate is covered with

copper.

Electroless Plating
Electroless plating

Reduction: Ni2+ + 2e- Ni

E0=-25 mV
Oxidation: H2PO2- + H2O H2PO3- + 2H+ + 2e- E0 = +50 mV
-----------------------------------------------------------------------------Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+ E0 = +25 mV
* Sustainable oxidation reaction
Autocatalytic mechanism

Plating thicker coating layers

Chemical Coating/Electroless plating

Advantages:

Low temperature treatment

More corrosion resistant than electrodeposited Cr
Can coat complex shapes uniformly
Hard particles can be incorporated to increase Hv
PTFE can be incorporated to reduce friction
Can coat most metals and some insulators
Disadvantages

More expensive than electroplated Cr

Heat-treatment
is needed to develop optimum properties

Thermal Spray Coatings

What is a thermal ( flame ) spray coating?

A coating produced by a process in which molten or

semi-molten particles are applied by impact onto a
substrate.

Thermal Spray Coatings

A common feature of all thermal spray coatings is their

lenticular or lamellar grain structure resulting from the

rapid solidification of small globules, flattened from
striking a cold surface at high velocities

http://www.gordonengland.co.uk/

Thermal Spray Coatings: Bonding

Thermal Spray Coating Bonding Mechanisms:

1) Mechanical keying or interlocking

2) Diffusion bonding or Metallurgical bonding
Factors affecting bonding and subsequent build up of

coating:
1) Cleanliness; 2) Surface area 3) Surface topography or
profile; 4) Temperature ( thermal energy); 5) Time (reaction
rates & cooling rates etc. ); 6) Velocity ( kinetic energy ); 7)
Physical & chemical properties; 8) Physical & chemical
reactions.

Thermal Spray Coatings

Coating structure

Lamellar or flattened grains, oxide inclusions

outlining the grains or particle boundaries
Porosity: 1-25%

Low impact energy ( un-melted particles / low

velocity )
Shadowing effects ( un-melted particles / spray
angle )
Shrinkage and stress relieve effects

Various thermal spray coating processes

Low-energy processes:
Combustion wire thermal spray
Combustion powder thermal spray
Arc wire thermal spray

High-energy processes:
Plasma thermal spray
HVOF thermal spray

Combustion Thermal Spray (Flame Spray)

http://www.gordonengland.co.uk/

Coating Material in powder, or wire form

Flame (oxy-acetylene or hydrogen most common)
Flame velocity: 50 m/s; and Temperature achieved < 3000 C
Low performance coatings (high porosity, poor bonding)

High Velocity Oxygen Fuel (HVOF) Thermal Spray

http://www.gordonengland.co.uk/

Similar to combustion thermal spray, but with special

design on torch
Flame velocity up to supersonic values
Well-adhered and dense coating

Plasma Spray

http://www.gordonengland.co.uk/

Formation of plasma
Material in the form of powder - injected into a very high

temperature plasma flame - rapidly heated and accelerated

to a high velocity
High velocity and high temperature (up to 5500 C)
Well-adherent and dense coatings

Comparison of Various Thermal Spray Processes

Thermal
process

Velocity
m/s

Tempera
-ture, C

Max. spray
rate, kg/h

Porosity,
%

Bonding

Combustion
powder

30

2200

6-20

poor

HVOF

610-1500

3100

14

< 0.5

welladherent

Plasma
spray

240

5500

<2

welladherent

Applications of Thermal Sprayed Al Coatings

Thermal spray metallic coatings, with and without sealers

and topcoats, as a means to prevent corrosion of steel

surfaces.
Types of metallic coatings included are pure zinc, pure

aluminum, and zinc/aluminum alloy, 85% zinc/15%

aluminum by weight.
Applications

High temperature resistant

Excellent resistance to polluted and marine environments
Forms oxide layer
Reduces corrosion

Examples of Thermal Spray Coatings

Example 1: Metal Matrix Composite (MMC) Coatings

MMC coatings, comprised of a hard ceramic phase

embedded in a metallic matrix, are increasingly being
applied for many industrial components in the petrochemical
industry, power generation and offshore applications to
provide cost effective protection against wear and corrosion.
Typical examples:
WC + CoCr
WC + NiCrBSi
Cr2C3 + NiCr
Typical coating technique: HVOF

Examples of Thermal Spray Coatings

Nanoparticles cannot be sprayed directly;
Reconstitution of NPs into spherical micro-sized granules
Coating properties:
Hardness of n-WC/Co

Nano-WC/Co feedstock powder

coating is higher than that of

the conventional one.
Corrosion resistance of n-

WC/Co coating is higher than

that of the conventional one.
Potential problems:
Conventional WC/Co feedstock powder

De-carburization of WC

due to higher surface to

volume ratio.

Examples of Thermal Spray Coatings

Example 2: Plasma sprayed thermal barrier coatings
Coating material: Y2O3-ZrO2 (120-250

m), plus metallic bond-coat (50-120 m)

Coating characteristics:
Porosity (interconnected), microcracks
and layered-structure
High-temperature corrosion behaviour:
Penetration of corrosive gas, fuel and
liquid through the inter-connected pores
to get contact with metallic substrate
oxidation spallation of coatings

Applications of Thermal Spray Coatings

HVOF spraying Tungsten Carbide / Cobalt Chromium Coating

(WC/10Co4Cr) onto Roll for the Paper Manufacturing Industry
http://www.youtube.com/watch?v=k-T_PBmhs3M
http://www.youtube.com/watch?v=ZgkSY8hYbH4

Application Examples of Surface Engineering

Gas turbine blades
Environment: High-temperature, corrosive.
Coatings: Ceramic coatings as thermal barrier
Bond coat: MCrAlY alloy

Typical Applications of Thermal Spray Coatings

Plasma spray: Ceramic, metal,

carbide coatings to solve

industrial problems and wear,
abrasion, corrosion, thermal
barriers.

HVOF: Serving all industries

requiring extreme wear resistant,

dense carbide and metal coatings

Overlay Coatings
Melting of a layer of material on the substrate to

form a coating
Heating source: welding torch, arc, plasma,
electron-beam.
Bonding: metallurgical fusion
Main applications:
Hardfacing: engine valve seats
Corrosion protection
Repairing of damaged components

Compared with thermal spray coatings

Comparison

Overlay coatings

Thermal spray

Thickness

2-6 mm

Normally < 1
mm

Number of
layers

Can be multilayers

Normal single
layer

Bonding

Fusion

Mechanical
interlocking

Microstructure

Solidification

Laminar and
pan-cake like

Cold Spray (Kinetic Spray)

Powder size: 1 50 m
Powder particle velocity: 450 1000 m/s (supersonic)
Powder impinging on the substrate in solid form at

temperature well below melting temperature

How Cold-spray Coating Builds

Stage 1: Substrate cratering and first

Van Steenkiste, T.H., et al, Surface and Coatings

Technology 154 (2002) 237-252.

layer built up of particles (initial

cratering, deformation of substrate,
spat formation, fracturing of surface
oxides on metal particles and
substrates and first particle layer
formation
Stage 2: Particle deformation and
realignment (multilayer coating
build-up)
Stage 3: Metallic bond formation
between particle/particle and void
reduction
Stage 4: Further densification and
work hardening of the coating

Important Parameters of Cold Spray Process

A critical value of powder particle velocity (Vc)
Determining factors for powder particle velocity:

gas temperature
particle size
molecular weight of gas
(Lower gas molecular
weight, the faster the
powder particle velocity)

Microstructural Characteristics of
Cold-spray Coatings
Top layer:

porous
microstructure
Inner layer:

denser
microstructure
Tamping effect
Van Steenkiste, T.H., et al, Surface and Coatings Technology 154 (2002) 237-252.

Ti on steel substrate

Diffusion Coatings
Metals and alloys are used at high-temperature environment.
Protection mechanism: Protective elements lead to
formation of chromia, alumina and silica scales respectively,
for oxidation and corrosion protection.
Process: A protective element (or elements), like Cr, Al or
Si, is deposited on the surface of the base metal, and diffused
into the base metal at high temperature
Diffusion coatings processes:
Aluminizing;
Chromizing;
Above-the-pack or out-of-pack chemical vapour deposition

Aluminising
Process: carried out by a pack cementation process.
Pack: Al or Al alloy powder,
halide salt (activator), e.g. NH4Cl, to form metal halide
with high vapor pressure
inert filler (alumina)
Temperature required: above 650 to 1100C for several hours
Pack

Substrate to be
coated

Aluminising
Chemical reactions and diffusion:
on heating: activator reacts with the metallic component of the
pack to form metal halides, e.g.
NH4Cl NH3 + HCl
HCl + Al AlClx + H2
AlClx has high vapour pressure which diffuse through the pack,
to form Al deposit on the substrate, then diffuse into the
substrate to form Fe-Al (or Ni-Al) intermetallics
Typical microstructures of aluminised carbon steels: layers
of -Fe2Al5, -FeAl and/or Fe3Al along the depth.

Aluminising
Activity of aluminising process depends on: the amount
and type of Al source alloy, the amount and type of
halide activator, the amount of inert oxide and process
temperature.
For aluminising of Ni base alloys:
High-activity aluminising: high concentration of
aluminium-rich vapour at the surface of the part
and coatings grow mainly by inward diffusion of
aluminium
Low-activity aluminising: the coatings are formed
mainly by outward diffusion of nickel; the
formation of higher aluminide phases is suppressed.

Low-activity aluminizing
The pack contains aluminium alloy powder .
The concentration of aluminium-rich vapor is low.
The coatings grow mainly by outward diffusion of nickel.
The processing temperature is 1000-1150C, i.e. the high end.
Microstructure: NiAl, no post-coating heat treatment required
The coatings have coarse-grained columnar microstructures
with limited ductility.
The coatings thickness is less than high-activity coating
thickness.

The effect of substrate materials on aluminizing: e.g.

1)Ni
2)Ni-Cr (variation of Cr content)

Low-activity aluminizing
Aluminising on pure Ni substrate

Inclusions

Original
interface

1)

Coating grows outward

2)

Original surface

3)

Ni diffuses outward faster

than Al diffuses inward

Kirkendall Ni
porositydiffusion

formation of Kirkendall
porosity at the interface.
4)

Formation of inclusions by
trapping pack particles in
the coating.

Low-activity aluminizing
Aluminising on Ni-Cr substrate
Region below the original
Inclusions

surface:
1) Depletion of Ni

Original
interface

2) Enrichment of Cr
Kirkendall Ni
For Ni-10Cr alloy:
porositydiffusion

Cr is still in solid solution

For Ni-20Cr alloy:
Cr precipitates out of the solid
solution to form Cr (reduce
ductility).

High-activity aluminizing
The pack contains pure aluminium powder.
The concentration of aluminium-rich vapour is high.
The coatings grow mainly by inward diffusion of aluminium.
The processing temperature is 700 - 900C.
The coatings is then heat-treated, typically 4h at 1050-1100C,
to convert brittle aluminium-rich phases, such as -NiAl3 and Ni2Al3, to -NiAl.
High-activity aluminizing is more common than low-activity
aluminizing.

Comparison between low- and highactivity aluminizing

Aluminising Ni-Cr superalloy
for gas turbine engines

Comparison of the following aspects:

1. Original surface
2. Diffusion direction (Ni, Al)
3. Microstructures: Kirkendall porosity, embedded pack particles,
4. Mechanical properties

Chromising
Process: carried out by a pack cementation process.
Pack: Cr powder, ammonium chloride and inert alumina filler
Temperature required: typically to 1150C for several hours;
Fe-Cr equilibrium diagram

Weight % Chromium

55

Temperature, C

b)

a)

12
0

te
Distance into substrate

1400

900
0

12
Weight % Chromium

Microstructures:
Low-carbon steels: the chromium deposits on the surface to form a solid
solution alloy of ferritic iron-chromium;
Medium-high carbon steels: tend to result in the formation of a layer of
chromium-iron carbide preventing Cr diffusion process.

Above-the-pack processes
Substrate to be coated is positioned above the pack in a retort
Gas-phase process
Aluminising or Chromising

Advantages over pack processes:

ability to uniformly coat internal passages and holes
coating without pack particle entrapment (no direct contact

with the pack)

better mechanical properties in terms of lower transition

temperature (NiAl)

Out-of-pack chemical vapour deposition

Chamber: a gas mixture of aluminium chloride and hydrogen (AlCl 3 is

created externally by passing HCl or Cl2 gas over Al)

Chemical reactions and diffusion:

6HCl + 2Al --- 2AlCl3 + 3H2;

2AlCl3 + 4Al --- 6AlCl
6AlCl + 6Ni + 3H2 --- 6NiAl + 6HCl (g)
Temperature: 1000 C for 4 hours

Low aluminium activity: microstructure

is similar to low-activity pack aluminising.
The use of molten aluminium is to increase
aluminium activity by forming lower
chlorides of aluminium when passing the
inlet gas mixture over liquid aluminium.

Comparison of vapour-phase aluminising

with pack cementation aluminising
Vapour-phase aluminizing is more costly;

In large retorts, variations in the concentrations of vapour-

phase reactants can result in non-uniform coating thickness;

Vapour-phase aluminizing is effective for coating complex-

shaped parts, and dust hazards associated with handling

large amounts of powder are avoided.

Typical Applications of Pack Cementation

Majority of aero-engine turbine

blade aerofoils are aluminised to

improve their resistance to high
temperature oxidation or surface
preparation prior to deposition of TBC.

Modified Diffusion Coatings

Adding Cr into aluminide coatings to improve resistance

to Type II hot corrosion, HT oxidation and ductility.

Deposition of Cr-enriched layer prior to aluminising and
then aluminising of chromium coated substrate
Pack containing Al and Cr powders
Adding Si into aluminized coatings to improve resistance

to Type II hot corrosion, and high temperature oxidation.

Deposition of metallic Si layer prior to aluminising
*Silicon-containing coatings are susceptible to basic fluxing, i.e. by Na 2O,
leading to Type I hot corrosion, but have good resistance to sulphidation. In
addition, it may be prone to cracking during thermal cycling due to the formation
of brittle intermetallics.

Modified Diffusion Coatings

Adding Pt into aluminised coatings

1) to improve resistance to oxidation and type I hot

corrosion; but 2) resistance to type II hot corrosion is
marginally better than conventional aluminides. In addition,
3) resistance to cyclic oxidation is poor as Pt aluminides are
less ductile than ordinary aluminides.
Depositing a layer of Pt (5-10 m), and followed by
diffusion heat treatment, and then aluminizing

Microstructure: a matrix of nickel aluminide with Pt present

in solid solution [(Ni,Pt)Al], and as intermetallic phases, (PtAl 2

or Pt2Al3 near the outer surface).
continue

Modified Diffusion Coatings

Protection mechanism:
to promote formation of pure alumina scale and reduce scale

growth rate
to act as a phase stabiliser and prevent the detrimental
convertion from to on thermal cycling
to improve alumina scale adherence, including mechanical
keying, as a possible mechanism due to the formation of an
irregular oxide-alloy interface;
to improve self-healing of the alumina scale after modest
spalling
to suppress interfacial void formation
to tie up Al as Pt-Al compounds, thus lowering Al activity, in
turn, to reduce the driving force for the diffusion of Ni from the
substrate into the coating;
* During service, PtAl2 can transform to PtAl to cause cracking and void formation.

Failure of Metallic coatings

Defects in the coating or at the coating/substrate interface

Loss of protective elements from the coating in service:

by spallation of scale.

by vaporization into a gaseous atmosphere, e.g. Cr2O3 can

be further oxidized above 1000C to become volatile CrO3.

by dissolution into molten salt deposits: Molten salt has

Na2O reacting with Al2O3 + O2 become NaAlO3 (aluminate)

Failure of Metallic coatings

Coating-substrate interactions in service (interdiffusion)

(compositional difference between coating and substrate
provides driving force at high temperature).
1) Formation of detrimental phases within the coating, e.g.

brittle intermetallics reduces ductility of the coating.

2) Dilution of the coating in the protective elements, e.g. Mo

and V from alloy substrate migrate to the coating, leading

to reduction of resistance to hot corrosion.
3) Kirkendall porosity at the coating/substrate interface

reduces the adhesive strength, leading to spallation of the

coatings.

Failure of Metallic coatings

Coating-substrate interactions in service (interdiffusion):

4) Loss of Al to the substrate by interdiffusion; and Diffusion
of refractory elements from the superalloy into the coating,
leading to degradation of oxidation resistance of protective
aluminide coatings on high temperature superalloy
components.
Coating (20 40 at%) Al

Superalloy
(5 -10 at% Al)

Al

Cr, Ta,
W, Mo

Failure of Metallic coatings

Weight gain

Example 1: Aluminized Nickel-base superalloys

C

B
A
Time

AB
BC

~ 2000 hours at 1000oC in air.

~ 500 hours at 1200oC in air

Failure mechanism:

Al2O3 scale tends to spall easily in service;

Interdiffusion between the coating and the substrate

leads to dilution of the coating in aluminium. If Al is
less than a critical value, it is no longer protective.
Note the effect of temperature in service.

Failure of Metallic coatings

Example 2: Chromized carbon steels, note the effect of C

Low carbon steel

loss of chromium due to:
spallation of Cr2O3 scale, diffusion of chromium
into the steel substrate and volatilization of CrO3
High carbon steel
forms a lot of Cr23C6 precipitates
during chromizing; these are an effective source of
chromium, thereby increasing the time to breakaway
oxidation that arises from loss of chromium from the
coating.

Improving lifetimes of coating/substrate

Incorporating a barrier layer between coating

and substrate: to reduce the rates of interdiffusion

between coating and substrate.
Alumina scale
Diffusion
barrier layer

Aluminide coating

Superalloy

*Ni-Hf compound, Pt-Hf compound used at interface of

superalloy/aluminide coating

Incorporating a reactive element, such as Y or

Ce, into the coating: to improve scale adhesion on

thermal cycling (needs to understand the effect of
reactive element in high temperature oxidation).