Analysis of internal stresses in Thermal

Spray Coatings
by
Dr. Ramesh M.R.
NATIONAL INSTITUTE OF TECHNOLOGY KARNATAKA,
SURATHKAL

Contents
Developments in Coatings
Residual Stresses, Fracture Toughness
and Adhesion Strength of Coatings
Case Study
Design modification to coated piston head

Thermo Mechanical Fatigue analysis of

coatings
2

Surface Engineering
Surface Engineering is a branch of Science deals with
modification of near

surface structure, chemistry or

property of a surface in order to achieve superior

performance and durability.
Definition as per ASM Handbook states that:
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
Surface

engineering

engineering

contributes

disciplines

which

to

include

physics, mechanical engineering,

materials science.

virtually

all

chemistry,

metallurgy and

Surface Damages

Chemical

Thermal

Environmental

Mechanical

Acids

Direct flame

Humidity

Wear

Alkalis

High Temp

Oxidation

Erosion

Salts

Arcing

Rain

Friction

Solutions to Surface Damages

Sl.
No
1

Surface Treatment

Changing the
surface metallurgy

Changing the
surface chemistry

Adding a surface
layer or coating

Methods

Property Benefits

Surface hardening,
Laser melting

Wear resistance

Shot peening

Fatigue strength
and stress relieve

Carburizing

Wear & fatigue resistance

Nitriding

Wear, fatigue and corrosion resistance

Boriding
Laser alloying
Ion implantation

Oxidation and surface fatigue

Wear resistance
Friction and wear resistance

Organic coatings

Aesthetic appearance and linings

Thermal Spray
coatings

Hot Corrosion, Erosion, Wear and TMF

Electroless-plating

Corrosion resistance and electrical

properties

Physical vapour
deposition

Improved wear (tools and dies), erosion

and corrosion resistance

Chemical vapour
deposition

Improved wear (tools and dies) and

Improved optical and electronic
properties
5

Characteristics of Surface
Engineered Components
Improved corrosion resistance through
barrier or sacrificial protection.
Improved oxidation and/or sulfidation
resistance.
Improved wear resistance.
Improved mechanical properties, for
example, enhanced fatigue or toughness.
Improved
electronic
or
electrical
properties.
Improved thermal insulation.
Improved aesthetic appearance.
Reduced frictional energy losses.
6

Coatings
Coating - a layer of material, formed
naturally or deposited artificially on the
surface of another material(substrate),
with the aim of obtaining required
technical and tailored properties.
Coating
protects
the
component
effectively from a variety of environmental
degradation factors such as abrasion,
erosion, wear, fretting, oxidation and
corrosion.
No modification to the properties of the
substrate.
7
Wide range of applications in all the fields.

Why Coatings?
Produce most protective oxide layer
Self healing type
Helps trade off in material selection
Maximize efficiency of plant or
machine
Cost effective

Adding Surface Layer or Coating

Thermal Spray Coatings

The behavior of material at elevated temperature is becoming of
increasing technological importance, yet it is a problem man has to
face and solve from the very beginning of his existence.

It is important to understand the nature of all types of environmental

degradation of metals and alloys as vividly as possible so that
preventive measures against metal loss and failures can be
economically devised to ensure safety and reliability in the use of
metallic components.
The materials used for high temperature applications are subjected
to high temperature erosion, wear and corrosion under
multicomponent gaseous industrial environment and problem has
been observed in boilers, internal combustion engines, gas turbines,
fluidized bed combustion and industrial waste incinerators etc
Strong erosion and corrosion resistance is required for high
temperature materials, in addition to excellent mechanical properties
such as high temperature strength, good creep resistance and
microstructure stability. However, these requirements some times
cannot be achieved simultaneously by alloy development alone
An alternate approach, where mechanical strength is accomplished
by alloy development and corrosion or erosion resistance by surface
coating is now generally acceptable practice in industrial processes.
10

The thermal spray techniques include arc spray, plasma

spray, high velocity oxy-fuel and detonation spray, among
which HVOF is the most popular and effective technique
used to prepare metal matrix composite coatings (MMCs),
such as WCCo-NiCr, Cr3C2NiCr or TiB2NiCr, due to
its
exibility, low cost and high velocity. The moderate
temperature for HVOF can also effectively reduce the
decomposition of the carbide/ boride ceramic reinforcement
phase and maintain its good mechanical properties such as
high hardness and mechanical strength

11

Some of the examples of surface damage due to

Erosion -Hot Corrosion- includes
Accelerated high-temperature fire-side corrosion associated with the
presence of molten alkali-containing salts of super heater and reheater
tubing in boilers
Steam-side oxidation of tubing, piping, and valves in boilers
Fireside erosion in coal-fired boilers; fly ash erosion and soot-blower
erosion
Accelerated high-temperature corrosion of land and marine based gas
turbine vanes and blades: normally associated with alkali salt
deposits.
Erosion of combustion turbine components in dusty environments;
e.g. expander turbines in pressurized fluidized bed combustors.
Rollers, hot working punches, heat exchangers of steel making plants
Piping in petro chemical industries
Reformer baffle plates/tubes in fertilizer plants
Nuclear parts viz. feed valves, combustion chambers etc.
Large size piston rods, high temperature springs and other
components of IC engines
Industrial waste incinerators
Chemical and food processing equipments
Ship propellers
12
Aircraft - Windshield Wings Propellers Rotors

Coatings Types
Thermal Spray Process
1.Flame spraying with a powder or wire
2.Plasma spraying
3.High Velocity Oxy-fuel (HVOF) spraying
4.Detonation Gun

13

HVOF process parameter

COATING MATERIAL
(Powder/Wire)

HEAT GENERATION
(Combustion)
Acceleration of
particles to high
velocity

Deposited Coating

SUBSTRATE

* LPG fuel gas is cheap and readily available as compared to other fuels

14

15

16

Carbides

Optical micrographs

Back scattered electron image

Coatings Properties

*
*

Coating Type

Average
Thickness
(m)

Porosity
(%)

Surface
Roughness
(m)

Density
(g/cm3)

Average
Micro
hardness,
(Hv)

WCCo/NiCrFeSiB

290

<0.5

7.26

1223

seemingly dense laminar structured coating

Thickness in the desired range of 260-295 m
Porosity less than 2 % has been achieved
The higher hardness value of 1223Hv obtained for WC-Co/NiCrFeSiB coatings
17

Why HVOF spraying?

The high-velocity oxy-fuel (HVOF) processes belong to the family of thermal
spraying techniques, uses the kinetic energy and the output of a supersonic
flow of burned gases, to soften and to propel the spray powder, producing
dense, very low porosity, good inter-particle cohesion and well-bonded
coatings.

Homogeneous and dense coatings

Greater bond strength and inter-particle cohesion
Lower porosity(< 1%)
No limitation on coating material
Less degradation of powder
Metallurgical properties of substrate remain unchanged
Unique microstructure
Wide range of coating thickness

On-site application and repair of components

Large size components can be coated
Lower cost/performance ratio

18

Detonation Gun Deposition Process

19

Plasma Spraying

20

Process Variants of Plasma Spraying. The plasma spray process can take place in different
atmospheres at different pressure levels and the resulting various process variants of plasma
spraying
Atmospheric Plasma Spraying (APS), Low Velocity.
Economically, most important is atmospherical plasma spraying (APS) in air. The powder particles
can interact with the air atmosphere, which may limit the choice of the spray materials, since the
originating oxides are built into the coating. The major fields for APS applications are coatings for
wear- and corrosion (liquid and gaseous) protection, often based on oxide ceramic materials. Other
typical coating materials are metals, and some alloys especially insensitive to oxidation. The
porosity of APS-coatings is generally between 1 and 5%. The spraying distance between substrate
and plasma torch is about 100 to 150 mm, depending on the materials and spraying parameters.
Atmospheric Plasma Spraying: High Velocity, High Power Plasma Spraying (HPPS, High
Velocity Plasma Spraying).
A further development of APS is the HPPS process. This development was necessary to meet the
requirements/demands for better coating densities and bond strengths of high melting ceramic
materials. This process variant leads to advantages when spraying with high power levels (ca. 200
kW), higher gas flows, deposition rates, and efficiencies. A typical example for a HPPS application
is the advanced coating of chromium oxide Cr2O3 on printing rolls.
Vacuum Plasma Spraying (VPS, Low Pressure Plasma Spraying, LPPS).
The coating process of VPS takes place in a closed chamber with reduced pressure. The coating
process, started after the chamber is evacuated to pressures < 10-1 mbar and refilled with an inert
gas atmosphere, takes place at about 50 to 400 mbar. To be able to constantly follow the working
chamber pressure, efficient pump systems have to be employed in order to remove the steadily
injected plasma gases. The advantages of VPS processes compared to APS are:
Through reducing the chamber pressure to about 10-1 mbar the largest part of the oxygen is
removed. Therefore, it is possible to process materials (feedstock and substrate) that are highly
sensitive to oxygen, e.g., refractory metals.
Due to the lower pressure inside the chamber, the less oxidized particles and substrates result in
better bond strengths, dense, and low oxide coatings.
21

There are, however, also some disadvantages of VPS technologies:

The rather high technical effort/expense for achieving the vacuum conditions.
The time necessary for one VPS process/coating is longer than for APS and there is a deposition
of overspray materials inside the chamber that has to be removed thoroughly.
For some applications using low melting point materials as substrates, there is insufficient
convective heat transfer within the chamber
Shrouded Plasma Spraying (SPS).
This plasma spray variant has been developed to reduce the effort for chamber and pumping
system for less expensive applications. Similar to shrouded welding processes an envelope of an
inert gas, which is not ionized, protects the plasma jet from the surrounding oxygen containing
atmosphere and also improves substrate cooling.
Controlled Atmosphere Plasma Spraying (CAPS).
Combining vacuum plasma spraying, and inert-gas plasma spraying in one system leads to
controlled atmosphere plasma spraying (CAPS). For a pressure range from 50 to 400 mbar VPScoatings are produced,at pressures around 1 bar IPS-coatings, and with pressures up to 4 bar high
pressure, plasma spray coatings are deposited. The advantage of a CAPS system is the possibility to
coat with APS- and VPS-coating systems in one step, and additionally to use materials with high
vapor pressures. Furthermore, reactive plasma spraying is possible.

22

Thin Films Types

23

Physical Vapour Deposition

24

25

26

27

CVD Process
28

Post Coating treatment

Homogenize the structure of coating
Induce oxide layer, which increase the wear and
corrosion resistance of coating
The interconnected network of voids and oxides at the
spalt boundaries will be destroyed and the corrosion
resistance of the coating was significantly improved
It increase coating adhesion strength

Laser remelting treatmentFurnace heat treatment

Ion Beam treatment
29

Ongoing research at NITK, Surathkal

on thermal spray coatings to over come environmental
degradations such as oxidation, hot corrosion and erosion in
various industrial applications
HVOF coatings in improving resistance to fireside corrosion and
erosion, both in the furnace wall and in the super heater and
reheater areas of power station boilers
Coating powder

Chemical Composition
(wt %)

Particle size

WC-Co / NiCrFeSiB
35/65

29.2W - 4.2Co - 9.4Cr - 47.6Ni

1.9B - 2.8Si - 2.8Fe - 2C

-45 + 15 m

[Cr3C2-35%(NiCr)]+5%Si

[Cr - 30Ni - 9.5C] + 5%Si

-45 + 15 m

[WC-12%Co]+65%[NiCrAlY]

28.49W - 4.55Co 14.95Cr 42.12Ni 7.15Al 1.96C

0.78Y

-45 + 5 m

WC - 20CrC - 7Ni

W - 19Cr 7.25Ni - 6.8C

-45 + 15 m

B. Somasundaram, Ravikiran Kadoli, and M.R. Ramesh, Evaluation of Cyclic Oxidation and Hot
Corrosion Behavior of HVOF-Sprayed WC-Co/NiCrAlY Coating,
Journal of Thermal Spray
Technology, August 2014, Volume 23, Issue 6, pp 1000-1008
M.R. Ramesh, S. Prakash, S.K. Nath, Pawan Kumar Sapra, B. Venkataraman, Solid particle erosion of
HVOF sprayed WC-Co/NiCrFeSiB coatings, Wear, Volume 269, p197205, 2010
M.R. Ramesh, S. Prakash, S.K. Nath, Pawan Kumar Sapra, and N. Krishnamurthy, Evaluation of
thermocyclic oxidation behavior of HVOF-sprayed NiCrFeSiB coatings on boiler tube steels, Journal of
30
Thermal Spray Technology, Volume 20, Issue 5, p992-1000, 2011
Mr. B. Somasundaram. Registered for PhD at NITK, Surathkal Awarded PhD Degree in 2015

Super heater zone of coal fired boiler

31

Failed Boiler Tubes as a result of Erosion-Corrosion

32

33

CHARACTERISATION
MICROSTRUCTURE
RESIDUAL STRESSES
BOND STRENGTH
FRACTURE TOUGHNESS
MICROHARDNESS
PHASE COMPOSITION
34

RESIDUAL STRESSES IN
COATINGS
Stress which persist in the absence of external force, which are internal and
therefore locked in, are contained in materials that are produced by nearly
every mechanical, chemical, and thermal process, either alone or in
combination.
The stress can be either compressive or tensile - compressive stresses in
coatings are more favorable than tensile stresses, because they increase
resistance to fatigue failure.

Extremely high compressive stresses may cause either coating separation

from the base metal or intracoating spallation.
If a tensile stress causes strain that exceeds the elastic limit of the coating,
then it will cause cracking.
Understanding the formation of residual stress in the coating is important to
prevent the coating from peeling or cracking during service.
Residual stresses have significant influences on the mechanical and physical
properties of the coatings, particularly electrical resistivity, optical
reflectance, fatigue, brittle fracture and stress corrosion cracking.
35

36

Origins of Residual Stress

Residual macrostress in a coating combines the intrinsic stress and

the thermal stress acting in the coating plane parallel to the
coating/substrate interface
t = i + th
At elevated temperatures, thermal stress araise because of the
difference in the coefficients of thermal expansion between the
coating and the substrate
th = (c - s) (T2 - T1) Ec/(1 - u c)
Intrinsic stress results from the growth processes, depending
primarily on deposition parameters

Incorporation of residual gas atoms in the coating

Grain size, microvoid, and dislocation density in the coating
Energetic particle bombardment during coating growth
Lattice misfit between the substrate and the growing coating
Combined effect of surface tension and growth process at grain boundaries
Deposition temperature relative to the melting temperature of the coating
material
Annealing and shrinkage of disordered material buried behind the advancing
surface of a growing coating
37

38

X-Ray Diffraction Technique

X-Ray beams collide with a
solid and interaction with
electrons of the particular solid
takes place. Interference is
possible when the wavelength of
the
incoming
X-ray
is
comparable to the separation
between the atoms. When an
ordered array of scattering
centres are present, the reflected
X-rays will show interference
maxima and minima. Typical
wavelengths used for X-ray
experiments lie between 0.6 and
1.9.
39

Diffraction Principle
Braggs Law
n = 2 d sin

Incident ray

atoms

n= order of diffraction, = x ray wavelength

d= inter planer distance, = angle between sample and detector
40

General Uses

Macrostress measurement

Nondestructive surface residual stress measurement for quality

control
Determination of subsurface residual stress distributions
Measurement of residual stresses associated with failures caused
by fatigue or stress corrosion

Microstress measurement
Determination of the percent cold work at and below the surface
Measurement of hardness in steels in thin layers

The strain in the crystal lattice is measured, and the

residual stress producing the strain is calculated, assuming
a linear elastic distortion of the crystal lattice.
applicable to materials that are crystalline, relatively fine
grained, and produce diffraction for any orientation of the
sample surface. Samples may be metallic or ceramic,
provided a diffraction peak of suitable intensity and free of
interference
41

The position of the diffraction peak undergoes shifting as the specimen is

rotated by an angle . The magnitude of the shift is related to the
magnitude of the residual stress. The relationship between the peak shift
and the residual stress () is given

where E is Young's modulus, is Poisson's ratio, is the tilt angle, and

di are the d spacing measured at each tilt angle.
42

43

Diffraction-Peak Location

44

HVOF sprayed Fe3Al coatings

45

Line Broadening
Diffraction peak broadening caused by microstresses in the crystal lattice
can be separated into components due to strain in the crystal lattice and
crystallite size.
The diffraction-peak width can be quantified precisely as the integral
breadth (total area under the peak divided by diffraction peak height) or
the width at half the height of the diffraction peak.

Significance and Use- measuring residual stress directly and nondestructively on a

product component- Portable diffractometers are commercially available for on-site
measurement- coating with a thickness ranging from 0.5 to 350 m- difficult to
measure residual stresses in extremely thin coatings and, in some cases, highly
textured coatings- inapplicable to amorphous coatings, and a large scatter in46stress
measurement is often encountered in coatings with large grain size.

Neutron Diffraction
Compared to low-energy X-rays the main
advantage of working with neutrons is the
possibility to analyze greater depths, i.e., higher
coating thicknesses. Neutrons have the following
advantage over X-ray photons for wavelengths
comparable to the atomic spacing, their penetration
into engineering materials is in the range of several
millimeters, due to their interaction only with nuclei
instead of electrons.

47

Deflection Method
It involves measuring the amount of bending in a strip that is
due to the deposition of the coating.
A mismatched force at the coating/substrate interface results in
residual stress in the coating, which bends the strip either
upward (concave) or downward (convex).

In the first the substrate is fashioned into the shape of a cantilever beam.
The film is deposited on one surface, and the deflection of the free end of
the bent beam is then determined
To measure the deflection of cantilever beams, various techniques have
been
developed,
including
optical,
capacitance,
mechanical,
electromechanical, interferometric, and electromechanical or magnetic
48
restoration.

Disks. The average stress in the coating on a disk

substrate can be determined from the amount of
deflection, , at the center of the disk caused by the
deposition of a coating on one side. This value can be
measured optically by interferometry or microstylus
profilometry.

where x and y are deflection changes measured

before and after coating deposition, and r is the radius
of the disk. Whether the stress is tensile or
compressive, it is determined by the curvature of the
disk, as determined by a depth microscope.
the measured defection, , is equal to the wavelength
of monochromatic light multiplied by the number of
light fringes

49

Hole-Drilling Method
Involves drilling a shallow hole in the test specimen to a depth
approximately equal to the hole diameter.
The creation of the hole redistributes the stresses in the material
surrounding the hole.
The inplaneresidual stresses that originally existed at the hole location can
then be calculated from the measured strain reliefs using the method
described in ASTM E 837-92

These coefficients A & B can be determined by either experimental calibrations

using known externally applied stresses or finite-element calculations
Significance and Use- semidestructive technique for measuring residual
stress on a coating with a thickness of at least 0.1 mm- can apply to test
samples as well as to actual components with complex geometries- on-site
measurements.

50

Modified layer removal method

Determine the through-thickness residual stress distribution in the coating.
The procedure involved gluing a strain gage to the uncoated side of the
specimen and then measuring the strain change after removing successive
layers by mechanical polishing
Strain and thickness changes were recorded simultaneously as layers were
removed, and used for the residual stress determination using the backcomputation procedure

51

Nano indentation technique

The indentations extend only to extremely shallow depths, often as low as
nanometers.
A hard indenter, usually an accurately ground diamond(triangular pyramid ),
is gradually pressed into the film, which is deformed first elastically and then
plastically. Analysis of the load-displacement curves provides information
not only on the hardness, but also on the elastic properties of the films. In
contrast to traditional hardness measurements, the nanoindentation
technique furnishes a continuous record of both load and indentation depth
during loading and unloading, so that imaging of the indentation is no longer
required.
Less tedious, less time consuming, utilized for the estimations of the
residual stresses, plastic strains, global properties such as Young's
modulus, yield strength, strain- hardening exponent, tensile strength and
nanohardness
The high spatial resolution of the indentations--less than 1 m2
The most common means of applying the load in nanoindentation
equipment is through electromagnetic or piezoelectric devices, in which the
resolution obtained is often better than 0.01 N.
The displacements are typically measured by a capacitive device giving
resolutions as small as 0.1 nm.
52

Nano indentation technique

The nano indentation experiments were carried out in depth
sensitive indentation machine
The shear presence of a residual compressive stress will
oppose the penetration of the indenter into the coating.
the presence of a residual tensile stress will aid the penetration
of the indenter into the coating.
the ratio of the projected contact area is related to the possible
residual tensile stress present in a coating by the following Eq.

the ratio of projected area is linked to the possible residual

compressive stress present in a coating by the following Eq

is the residual stress of the coating. A is the projected area, A0 represents the
projected area of the free standing coating, h stands for the final depth of penetration,
H is nano hardness of the coating and the is the angle complimentary to the
53 semiapex angle of the indenter.

Ductility measurement from nano indentation

Ductility of a material is its ability to deform permanently without fracture. As the cermet
coatings consist of hard carbide phase and matrix phase, good ductility of the matrix phase
allows the material to deform plastically and resist to erosion. [17]. Ductility of the thermal
sprayed cermet coatings differs from bulk materials due to the nature of thermal spray
process. Load verses displacement curves obtained from nano indentation were used to
measure the ductility. It is measured by the ratio of the plastic work, Wp to the total work,
Wt. Wp was obtained from the area enclosed by the loading and the unloading curve and
Wt was the area below the loading curve in a LD plot. Wp/Wt varies between 0 and 1 for
perfectly elastic and perfectly plastic materials respectively. The Wp/Wt ratio for the binder
in CoCrAlY/WC-Co and CoCrAlY/Cr3C2-NiCr as-sprayed coating is 0.80 and540.86
respectively Thus, it shows binder has good ductility.

Nano Indentation on Ti/TiC/TiN coatings

(a) Load-penetration plot during indentation tests

(b)Hardness- penetration plot during indentation tests
(c) Elastic modulus- penetration plot during indentation tests
(d)Displacement-scratch distance plot during nano scratch tests

Nano Indentation on Ti/TiC/TiN coatings

(a)

(b)

(a)Nano indents image and (b)Nano

Scratch image of the TiCC coatings.

Nano Indentation on Ti/TiC/TiN

coatings
Mechanical properties of Ti/TiC/TiN coatings
Hardness
(GPa)

Coatings
Ti/TiC/TiN

Elastic
Modulus
(GPa)

Thickness
(m)

Surface
Roughness

SEM

STM(nm)

297.6

1.79

2.56

4.98

Nano scratch properties of Ti/TiC/TiN coatings

Coatings

Critical
load
(mN)

Ti/TiC/TiN 47.704

COF Depth
(nm)

0.42

568

Scratch
width
(m)

Groove
Height
(nm)

Pile-up
height
(nm)

Scratch
wear vol
(m3)

135

790

156

31995

57

Finite Element Analysis

Several studies on a layer deposition model
have been investigated to predict the
quenching and thermal mismatch stresses
To implement peening stresses into the layer
deposition model, The impact of a single
particle has been extensively studied using
FE modeling for the shot-peening process
The thermomechanical process associated
with particle impingement is a nonlinear
dynamic contact event, modeled via a
thermomechanical coupled dynamic transient
analysis.
58

59

Method Comparison
The mechanical-deflection method is capable of
measuring the average stress throughout the coating
thickness, but requires the stress to be uniform over
large distances in the in-plane directions. In contrast,
the x-ray diffraction and holedrilling methods can
make a much more localized measurement in-plane,
but they have a significantly more limited depth
capability. A user can select the most suitable method
based
on
economics,
environment,
coating
microstructures, and the geometry of the component
to be measured.
60

Fracture toughness
Brittleness refers to the ease with which fractures can propagate within a
material. Brittleness is quantified through a parameter known as toughness
(denoted Kc), which describes the resistance of the material to fracture
propagation.

2d

The indentation was carried out on the traverse section of the coating in
the midplane region to minimize the edge and interface effects. Due to the
characteristics of the thermally sprayed coatings, the cracks parallel to the
coatingsubstrate interface are more easily formed in comparison to the
perpendicular direction
The indenter was loaded so that one of the horizontal diagonals was
parallel to
the coating substrate interface.
The crack length from the center of the indent, c, was used for determining
the fracture toughness of the coatings.The fracture toughness, KIC, 61was
calculated through the following equation

Where HV is the
Vickers hardness, E
is
the
Youngs
modulus, d is the
half-diagonal of the
Vickers indentation.
The radial crack
length, a, is equal to
c, the indentation
crack length minus
d, the half diagonal
of
the
Vickers
indentation. Both the
crack length and
Vickers
diagonal
were measured from
the optical images or
SEM.
Youngs modulus of
the
coating
was
measured by Nanoindenter.

Coating type

Vickers
Micro
hardness
(Hv)

Youngs
Modulus
(GPa)

Fracture
Toughness
KIC
(MPa m1/2)

10% Al2O3 + CoCrAlTaY

526

300

4.8

25% (Cr3C2-25(Ni20Cr))
+75% NiCrAlY

416

Stellite-6

543

373
200

3.0
62

6.8

Interfacial indentation

interfacial toughness

63

Film - Substrate Interfaces

Different interfacial layers formed between film and substrate:

(1)abrupt interface; (2) compound interface;
(3) diffusion interface; (4) mechanical anchoring at interface.

64

Direct Pull-off
The coated sample is glued to an uncoated similar counterpart that is just
grit blasted and then tested in tension in an universal testing machine.
The value of the tensile load, in which the separation of the coated
uncoated parts occurs, is registered
The bond strength, by calculating the load/area relation.
The failure region indicates the type and characteristic of the failure

65

Coating Type

Bond Strength (N/mm2)

Trial 1

Trial 2

Observation
Average

WC-Co/NiCrAlY

65.68

58.71

62.19

Coating-Bond Failure

WC-CrC-Ni

72.16

70.8

71.48

Coating-Bond Failure

Cr3C2-NiCr+Si

77.97

81.02

79.49

Glue Failure

bond strength tester in accordance with ASTM C633 standard- Fig1 and 3 ,behavior
indicates that the coating cohesive strength is superior to the coating adhesive strength.
The bond strength between individual structure parts (splats and phases) is higher than
66
the bond strength of the coating to the base material.

scratch test

the magnitude of coefficient K

depends on the model details (
K can range from 0.2 to 1). H,
is the Vickers hardness, and R
is the
radius of the stylus tip, critical
load F, that just causes
adhesion failure.

67

VDI 3198 Adhesion Test

HF
1

HF
3

HF
2

HF
4

HF
5

HF
6

Qualitative Analysis of the

Adhesion of THIN FILMS

VDI 3198 Adhesion Test

Ti/TiC/TiN coatings

HF1-Acceptable coatings

The peeling test

The blister test

70

Case Study
Design Modification on Coating Surface and
its Thermal Analysis for Plasma Sprayed
Ceramic Coated Piston for its Performance
Improvement

Thermal Barrier Coating:

Thermal fatigue protection
Reduces heat rejection
Protects piston from corrosion attack, thermal
stress, high heat emissions and it reduces heat
flux.
TBC allows using low quality fuels by making the
piston temperature much higher than uncoated
one due to which proper combustion of fuel
occurs.
TBC mainly consists three layers of substrate,
bond coat and top coat

Coating material: Yittria Stablized Zirconia

Yttria-stabilized zirconia (YSZ) is a ceramic in which the
crystal structure of zirconium dioxide is made stable at room
temperature by an addition of yttrium oxide. These oxides
are commonly called "zirconia" (ZrO2) and "Yttria" (Y2O3),
hence the name.

Bond Coat : NiCrAl

Bond coat is used to provide bonding between substrate
and top coat surface. It also helps to reduces stresses
occurring during thermal shock. Provide Corrosion
resistance

Coating Process: Plasma Spraying

Material properties
Material

Thermal
conductivity
[w/mC]

Thermal
expansion
in 106
[1/C]

Specific
heat [J/
kg C]

Modulus
of
elasticity
(GPa)

Poissons
ratio

Density
[kg/m3]

Piston
(aluminum
alloy)

155

21

910

71

0.33

2700

Rings (cast
iron)

58

12

460

200

0.30

7200

Bond coat

16.1

12

764

90

0.27

7870

Y-PSZ

1.4

10.9

620

46

0.20

6080

FINITE ELEMENT MODELING

Software: UG NX 10.0
Bore -95mm
Stroke length:120mm
Engine rating :300 kW
at 1500 rev/min
Compression Ratio: 19:1

Thermal Analysis
A thermal analysis was performed to determine the
temperature distribution and thermal stresses for
uncoated and coated piston which will be compared
with the modified coated surface for performance
improvement.
Import model
Assign material to every part
Make connections
Meshing setup and Meshing

Static thermal analysis

Convection is taken as a major phenomenon of heat
transfer in the piston. Different temperature and heat
transfer coefficient are applied to the different areas of
piston which is calculated using

Hohenberg Equation:
hgas(t)=VC(t) -0.06P(t)0.8T(t) -0.4 (s+b) 0.8

Before applying the boundary conditions, some assumptions are made:

The effect of piston motion on the heat transfer is neglected.
The rings do not twist.
The rings and skirt are fully engulfed in oil and there is no cavitation.
The conductive heat transfer in oil film is neglected.

Results
Temperature distribution for uncoated part

without coating (Tmax=345.65 C)

Temperature distribution for Coated part

Fig. (a)Top surface with YSZ Coating (Tmax=384.65 C),

Fig (b)Substrate with YSZ coating (Tmax=320.4 C)

Modification on coating surface:

Chamfer Hole
Temperature distribution of modified coating surface

Fig. 3a)Top surface with Coating and hole (Tmax=406.71C),

Fig (b)Substrate with coating and hole (Tmax=314.8C)

Result Table
Type

Top surface
Substrate
Temperature Temperature
( C)
( C)

Uncoated piston

345.75

--

Coated Piston

384.65

320.4

Coated piston
with chamfer
hole

406.71

314.8

Case Study

Fatigue analysis on thermal barrier coating

(TBC) using FESAFE conventional high
temperature fatigue

Courtesy: ProSim

Fatigue
Fatigue is a process in which damage is accumulated in a
material undergoing fluctuating (cyclic) loading, eventually
resulting in failure even if the maximum load is well below the
elastic limit of the material.
Fatigue is responsible for 90% of mechanical engineering
component failures
Very little plastic deformation associated with failure
Fatigue is the process of progressive localized permanent
structural change occurring in a material subjected to
conditions that
produce fluctuating stresses and strains at some point or
points and that may culminate in cracks or complete fracture
after a sufficient number of fluctuations ASME definition for
fatigue

Three stages of fatigue failure

1.Crack initiation
Cracks may initiate from surface, Occupies most of fatigue
life
2. Propagation
Crack growth takes place in a direction normal to applied
stress
3. Fracture
Unstable fracture occurs suddenly 1

loa
d

loa
d

Fig. shaft tested in bending

Modern diesel piston

Crack initiation
site

Problem: Crack at root

of valve pocket radius

fe-safe fatigue contours

Solution: ABAQUS and

fe-safe used to
accurately predict
location and time to
crack initiation

Objective and Methodology

Objective
To find the fatigue life of the Thermal barrier coated
specimen

Methodology
Coupled thermal analysis is carried out using
ABAQUS for TBC specimen
Stresses and strains along with temperature data is
imported to FESAFE
Using conventional high temperature fatigue in
FESAFE fatigue analysis is carried out

Introduction
Finite element models are used to analyze engineering
components
FE results include stress, strain, temperature, Displacement,
deflections , frequency, etc.., These results are used for fatigue
analysis

Many fatigue analysis uses linear elastic FE results

Surface stresses are required for the analysis of fatigue crack
initiation from the surface
Nodal stresses are used for fatigue calculation rather than
integration point stresses
Nodal averaged stresses are best recommended

Role of FESAFE in Fatigue Analysis

FESAFE is a highly effective tool for fatigue
analysis of finite element analysis stress
results

Input/output
ABAQUS .fil
ABAQUS .odb
NASTRAN f06

Loading

NASTRAN op2
ANSYS .rst
I-DEAS .unv

Design

FEA
ABAQUS, ANSYS
I-DEAS,
NASTRAN, Pro/E

Stress
results

Fatigue
fe-safe

Pro/M s01..., d01

General .csv

Output
Hypermesh
.hmres
PATRAN
FEMVIEW

Redesign

CADFIX
FEMAP
Life
contours

fe-safe durability analysis from FEA

Configuration of TBC system

100

20
100

570

500

Four layer TBC specimen is taken for analysis as shown

Note: Figure not up to
above
scale

Coupled thermal analysis using ABAQUS

Uniform Temperature is applied at top of the specimen using
amplitude curve (Amplitude curve is shown in next slide)

Insulated, x
translation
constrained

Insulated, x
translation
constrained

X
Z

Heat convection, x&y translation constrained

(Bottom)

Amplitude curve (Loading Cycle)

1400

2100, 1373

Time
(sec)

300, 1373

1300

Temperature
(k)

Temperature (K)

1200

1100

313

1000
900

300

1373

2100

1373

3900

573

800
700
600

3900, 573
500
400

0, 313
300

400

800

1200

Time
(SEC)
1600 2000
2400

2800

3200

3600

4000

Temperature is applied on top of the specimen (load

history in FEM)

Material Properties

Materials
Propertie
s
Youngs
modulus
(N/m^2)

Substrate

Bond coat
(BC)

Thermal grown
oxide layer
(TGO)

2.1E11

2E11

4E11

1E11

0.3

0.2

0.2

1.2E10

1.1E9

Poisson's
ratio

0.3

UTS (Pa)

9E8

1E9

80

60

Thermal
conductivity

(W/mK)

Thermal
barrier
coating
(TBC)

20

Temperature plots (Kelvin)-FEM

Maximum
temperature is at top
of the specimen (1382
Kelvin)
Minimum
temperature
is
at
bottom of specimen
(1087 Kelvin)

FEM Results-Displacement plots

Displacements in meter
for maximum temperature
Maximum displacement
is found to be 2.5E-05
meter

Strain Result at Maximum Temperature

Maximum strain is at
Substrate region(0.035)
Minimum strain
TGO(0.011)

is

at

Stress Result at Maximum Temperature

Stresses are in Pascal

Maximum stress of
3.64E9Pascal is observed at
thermal grown oxide (TGO)
layer

Fatigue analysis using FESAFE

Elastic plastic results (stress, strain, temperature)

are imported to FESAFE

Different element groups were created for different

layers
Four different materials were created in FESAFE
using material approximation function
Fine machined surface finish is defined
Plastic stresses and strains were paired and
analysis is carried out

Fatigue results

Element
421

The element where minimum life of

computed for element 421
Reliability at 1500 cycles is 50%

1522 cycles is

Life contours from FESAFE

Life contour shows

that minimum life in
the
component
Is
103.183= 1524 cycles
Note: life
component
scale

of
in

the
log

Reliabilty at 100 cycles

Reliability at 100
cycles is 77% at
substrate
Note: Reliability is
shown
as
percentage

Reliabilty at 2000 cycles

Reliability at
2000 cycles is
46% at substrate

Conclusion
Fesafe results shows that crack can initiate at 1522
cycles at the interface between Thermal Grown Oxide
layer and Bond coat
More accurate results can be obtained by using
temperature dependent SN data

Note: Fatigue analysis is carried out using conventional

high temperature fatigue in FESAFE

Room temperature SN curve properites are considered

To carry out analysis using Thermo mechanical fatigue
(TMF) in FESAFE at least two strain rate and two
temperature data is required for all materials

High temperature fatigue vs TMF

Conventional high temperature fatigue is included in
standard Fe-safe
Conventional high temperature fatigue is used where
time-dependent effects are not Significant
In conventional high temperature fatigue at each node
material data is adjusted once to maximum temperature
TMF addresses transient stress and temperature
histories where time effects are critical
In TMF material data is adjusted continuously as the
temperature varies with time

Thermo Mechanical Fatigue (TMF)

Fatigue cracks are caused by the repeated application of
loads
Thermo mechanical fatigue occurs when both stress and
temperature fluctuate eg.Pistons
The following are the parameters to be considered during
TMF analysis
1.Effect of strain rate and instantaneous temperature on
fatigue damage
2.Phase relationship between stress and temperature in
each cycle
3.Bulk stress relaxation
4.Effect of strain ageing(Pre-soaking) on fatigue strength
5.Superimposition of high frequency stress cycles

Stress-strain response varies with strain-rate and

temperature

e
cycle

cycle

Time
A

we can identify the small cycles which can be removed

and analysed separately

Stress-strain response varies with strain-rate and

temperature

temperature

Time
Strain rate

Temperature and strain rate varies during fatigue

cycle

Effect of strain rate and temperature on stress-strain

hysteresis loop

800

Stress (MPa)

600
400
200
0
-6000

-4000

-2000

-200

2000

4000

-400
-600
Strain (u e)

Stress-strain response

6000

Effect of Strain Rate and

Temperature on Fatigue Damage

Instantaneous

Strain life curves are defined as follows

/2 = f'/E (2Nf)b + f ' (2Nf)C

coefficient
coefficient

E- Youngs modulus
f' Fatigue strength
f' Fatigue ductility
b Fatigue strength

exponent
c
exponent

reversals

Fatigue

ductility

- strain amplitude
2Nf

Number

of

For TMF analysis these curves are defined at a series of

strain rate and temperatures (minimum two different
temperatures and two different strain rates)
Total strain

Total = elastic + plastic + thermal + .

Effect of Phase Relationship

Fatigue damage is dependent
on phase relationship between
strain and temperature
Effect is material dependent
and is most pronounced in Low
cycle fatigue regime

Fig. In-phase

Fig. Out of
phase

In general, both in-phase and

out-of-phase stress and
temperature cycles are more
damaging than iso thermal stress
cycles
Fig. Effect of phase
relationship on fatigue
strength

Bulk Stress Relaxation

Bulk stress relaxation is a time dependent and
temperature dependent phenomenon.
It is the cumulative effect of transient stress relaxation
and recovery over consecutive cycles, which leads to a
change in the mean stress over the cycle as shown below
(Figure)

Fig.Bulk stress
relaxation

Strain Ageing/Pre-Soaking
With prolonged time at elevated temperatures, material
strength properties tend to degrade due to strain-ageing,
oxidation, etc.

This effect is most significant early in the life of the

component, and is known as strain ageing or presoaking.
Time based properties
can be combined in to
Presoak factor (Pf)
Pf = Fatigue strength (at
time t and temperature T) /
Short term fatigue strength
at temperature T

Application Areas
POWER GENERATION:

Deregulation resulted in
gas turbines and boilers
are
cycling
more
frequently

AUTOMOTIVE:

Emissions
and
fuel
consumption
requirements
caused
many
engine
components to operate
at higher temperatures
and loads

Erosion
According to ASTM standard G76-95, erosion is the
progressive loss of original material from a solid surface due to
mechanical interaction between that surface and a fluid/a multicomponent fluid or impinging liquid or solid particles.
Solid particle erosion is the loss of material that results from
repeated impact of small solid particles.
Solid particle erosion refers to a series of particles striking and
rebounding from the sliding of abrasive particles across a
surface under the action of an externally applied force.
solid particle erosion is expected whenever hard particles are
entrained in a gas or liquid medium impinging on a solid at any
significant velocity (greater than 1m/s).

114

The free oxygen content in power plant boiler

atmospheres is sufficient to account for a combined
erosioncorrosion process, consisting of an oxidizing
gas at elevated temperature carrying erosive fly-ashes
which impact against metallic surfaces. These erodent
particles can deposit or embed themselves on the test
surface in quite significant quantities, and chemical
reactions of erodent particles and oxide scales can
develop on the eroding surface, so that the erosion rate
is also dependent on the oxidation kinetics and erodent
particle reactivity.
The extent of attack in such environments is dependent
on
Erodent particles shape, size, density, velocity,
hardness etc.
Environment -atmosphere composition and
corrosiveness, temperature etc

115

Erosion mechanisms of ductile materials

Hutchings has proposed the
best mechanism using the
impact of single particle on to
metals at 30 impact angle and
subdivided the cutting type
into two basic types of impact
damages,
as
illustrated.
According to him rounded
particles deform the surface by
ploughing, displacing material
to the side and in front of the
particle. Further impacts on
neighbouring areas lead to the
detachment of heavily-strained
material from the rim of the
crater or from the terminal lip.
He further reported that this
type of deformation embraces
both the ploughing and
wedges-forming modes of
abrasion shown
116

Erosion mechanism of brittle materials

Simplified Schematic drawing of crack formation from a single

particle impact
117

Erosion mechanisms at high temperature

Several
studies
concerning the interaction
between erosion and a
surface oxide film have
been
conducted
Mechanisms of material
removal
have
been
proposed which include
oxide
fracture
and
chipping, oxide spallation
at
the
metal-oxide
interface
and
plastic
deformation
of
metal
substrate resulting in both
oxide and metal loss.

Schematic diagram showing the

types of degradation that can occur
under
conditions
of
combined
oxidation-erosion
118

FACTORS AFFECTING EROSION

impact velocity
impact angle
particle concentration
particle shape & size
particle density
temperature
particle hardness
material hardness
toughness
microstructure
chemical composition
119

Erosion tester

Erodent material
Erodent average
size
Particle velocity
Erodent feed rate
Impact angle
Temperature
Test time
Standoff distance
Nozzle diameter

Alumina
50 m
30 m/s
2 g/min
30,60 and 90
Room temp,
200,400 and
600C
15 min
10 mm
1.5 mm

120

Scanning electron micrograph of WC-Co/NiCrFeSiB powder

Coating powder

Chemical Composition
(wt %)

Shape

WC-Co / NiCrFeSiB
35/65
(MEC-1031C)

29.2W - 4.2Co - 9.4Cr - Spherical

47.6Ni 1.9B - 2.8Si 2.8Fe - 2C

Particle size

-45 + 15 m

121

Carbides

Optical micrographs

Back scattered electron image

Coatings Properties

*
*

Coating Type

Average
Thickness
(m)

Porosity
(%)

Surface
Roughness
(m)

Density
(g/cm3)

Average
Micro
hardness,
(Hv)

WCCo/NiCrFeSiB

290

<0.5

7.26

1223

seemingly dense laminar structured coating

Thickness in the desired range of 260-295 m
Porosity less than 2 % has been achieved
The higher hardness value of 1223Hv obtained for WC-Co/NiCrFeSiB coatings
122

WC-Co/NiCrFeSiB Coating
56.96% W
07.24% Co
01.03% Ni
00.35% Cr
00.43% Fe
02.01% Si
25.69% B
04.95% C
01.33% O

01.53% W
00.75% Co
52.84% Ni
09.25% Cr
03.27% Fe
02.08% Si
21.22% B
07.72% C
01.33% O

123
*Retention of higher amount of WC in matrix with a minor amount of W2C brittle phase

Solid Particle Erosion

Studies

124

125

Bar chart indicating volumetric steady state erosion rate for uncoated and
HVOF coated GrA1 steels at 30 and 90 impact angle

WC-Co/NiCrFeSiB > NiCrFeSiB > NiCrAl > NiAlCrFeMo

126

WC-Co/NiCrFeSiB Coating

127

WC-Co/NiCrFeSiB Coating

128

129

WC-Co/NiCrFeSiB Coating

130

NiCrFeSiB Coating

131

NiCrFeSiB Coating

132

NiCrFeSiB Coating

SEM micrographs showing the surface morphology

of NiCrFeSiB coated steels eroded at 90 impact
angle
133

Elevated Temperature Erosion at 600 C

134

Elevated Temperature Erosion at 600 C

3-D profile of
CoCrAlY/Al2O3
coating at 90 and
30

135

Elevated Temperature Erosion at 600 C

3-D profile of
CoCrAlY/CeO2
coating at
90 and 30

136

Elevated Temperature Erosion at 600 C

CoCrAlY/Al2O3/YSZ coating
showing eroded region with
an impact angle of
90 (a) and 30

137

Elevated Temperature Erosion at 600 C

CoCrAlY/CeO2 coating at
an impact angle of
90 (a) and 30 (b)

138

Questions

Thank You

Structure-Property Relations

Internal Structure
Macrostructure
Microstructure
Substructure- SEM, TEM

Crystal

StructureElectronic Structure- Spectroscope

Nuclear Structure- NMR, Mossbauer
X-ray/neutron/electron diffraction

142

Electron Microscope
TECHNIQUE

LIMITS

RESOLUTION

eye

retina

700,000

optical microscope

diffraction of
light

3000

scanning electron
microscope

transmission electron
microscope

diffraction of
electrons

diffraction of
electrons

30

Magnification

10X to
2000X
10X to
200,000X

up to
1,000,000
X

143

Electron Microscope

144

Electron Microscope

High energy electrons are focussed to a fine

probe on a sample (bulk or specially prepared
thin)

The interaction between high energy electrons

and the atoms of the sample gives rise to a
variety of signals.

Detection and quantitative characterization of

the signals form the basis of SEM and TEM.

145

INFORMATION AVAILABLE

Morphology size, shape and distribution of

phases and their relationship to one another,
high resolution, m to nm (or fraction of it)
level

Crystallography - arrangement of atoms and

their degree of order, detection of equilibrium
and metastable precipitates, orientation
relationship

Composition elements present in the sample

and their local variation - high resolution

146

Electron/Specimen Interactions
When the electron beam strikes a sample, both photon and electron signals are
emitted.

X-rays
Through thickness
composition info

Incident Beam

Primary backscattered
electrons
Atomic number and
topographical

Cathodoluminescence

Secondary electrons
Auger electrons

Topographical

Surface sensitive
compositional

Specimen

Specimen Current
147

Detectors

A number of different detectors can be incorporated into the chamber

surrounding the specimen. Detection and quantitative characterization of
148
the signals form the basis of SEM and TEM

Region of excitation
Resolution in an SEM is ultimately
determined by the size of the region from
which signal is produced. Thus for the
same region of excitation the resolution
from the three signals differs and
decreases from secondary to backscatter
to X-rays
Factors affecting size of the interaction
region:
Diameter of the primary beam
Energy of the primary beam
Atomic weight of the specimen
Coating of specimen

149

Secondary electrons
Secondary electrons are usually the
result of an inelastic collision in which
the transferred energy of the primary
beam is transferred to an electron that is
then emitted from the atom.
Loosely bound electrons near the
surface of the sample ejected by the
incident high energy electrons
Secondary electrons typically have an
energy between 10 eV - 50 eV
Although secondary electrons are
produced throughout the interaction
region they can only escape from the
uppermost portion due their low energy

Microstructure

150

SE and reflected light micrographs

of Fe-1.0%C steel

151

Backscattered electrons
Backscattered electrons are the result of
elastic collisions with atoms of the specimen.
They result in emitted electrons that have an
energy of 80% or more of the original energy
of the primary beam electron
Electrons deflected by the nuclei of the
atoms
Yield increases with increase in atomic
number of the elements in the sample and
with increasing tilt
Backscattered electrons are also produced
throughout the interaction region but because
of their greater energy can escape from
deeper in the specimen.
Energy : ~ 100 eV to Ep

Chemical composition, microstructure

152

SE and optical images of HVOF sprayed

NiCrAl coating

153

BSEI

Backscatter image of a composite (polished cement fragment)

in which low atomic weight particles appear dark and high
atomic weight particles are white.
154

BSEI

SE

BS

Blood cells with nuclei stained with a silver compound are visible
in backscatter mode even though they are beneath the surface of
155
the cell membrane

Characteristic X-Rays
X-rays are indirectly produced when an
electron is displaced through a collision with a
primary beam electron and is replaced by
another electron. The resultant loss of energy is
given off in the form of an X-ray. The energy
will always be less than the energy of the
primary beam electron
Because of their high energy X-rays can
escape from very deep in the specimen
Energy is specific to the element emitting Xrays; e.g. Al K 1.48 keV. Energy generally lies
in the range 1 keV to 10 keV for K radiation of
common elements and L and M radiation for
heavier elements.
Basis of EPMA; chemical analysis, line
mapping, area mapping; high resolution and
localized chemical analysis

156

EDS - Energy Dispersive Spectroscopy

analytical tool for chemical characterization

identify the elements present
quantify their relative or absolute concentration and
map their distribution
fundamental principle: each element of the periodic table has a unique
electronic structure and, thus, a unique response to electromagnetic
waves
release of X-rays creates spectral lines that are highly specific to
individual elements
Quantification by Semi standard methods
Elements of low atomic number are difficult to detect by EDX
Poor peak seperation
Poor peak/background ratio (100:1)
Detection efficiency depends upon x-ray energy

But Very Rapid

157

Wavelength Dispersive Spectrometer (WDS)

Filtering of X-rays: only X-rays of chosen wavelength are
allowed
Time-consuming but higher resolution(~5 eV) for quantitative
analysis
Operates using diffraction principles (Braggs law)
Good light elements capabilities
High peak/background ratios (1000:1)
Good detection efficiency for all x-rays
High counting rates
Complex mechanical devices, operator intensive
Specimen height dependent focus
Quantification requires standards

158

Characteristics of WDS and EDS

Characteristic

EDX

WDX

Method of analysis

Entire
spectrum Analysis of wavelength
analysed
at a time
simultaneously

Ease of fitting

Easily fitted to TEM, Bulky,

stringent
SEM,
EPMA,
no focusing requirement,
focusing required
SEM and EPMA only

Time to collect full 1 min

spectrum

30 min

Artefacts

Escape and sum peaks

Higher order lines

Field of usefulness

Good for quick, readily Very good for precise

interpreted qualitative quantitative analysis
analysis
and line scans

Probe current

10-11 -10-9 A

10-9 - 10-6 A

159

Analysis

Qualitative analysis
Which elements are present? Measure energy or wavelength of
each characteristic X-ray

Quantitative analysis

How much of an element is present? Measure how many X-rays

of any type are emitted
Quantitative analysis involves the measurement of characteristic Xray intensities from the specimen (CsI) and a standard (Is) (which
may be a pure element or a compound)
C = CsI /Is
The equation does not take into account a number of phenomena
occurring in the sample before and after the excitation of the Xrays. For this purpose, it is necessary to apply the "ZAF" ( Z atomic number, A - absorption and F - fluorescence) correction.

160

56.61% NiO
14.83% Cr2O3
11.73% WO3
06.84% CoO
06.89% Fe2O3
01.33% SO3
02.13% V2O5

Enlarged in Fig. b

EDS analysis at point 1

(a)

58.94% NiO
18.39% Cr2O3
04.13% WO3
05.30% CoO
08.29% Fe2O3
00.74% SiO2
02.77% SO3
03.55% V2O5

EDS area analysis of Fig. b

(b)
Surface scale morphology and EDAX analysis for WC-Co/NiCrFeSiB coated steels subjected to hot corrosion161
for 50
cycles in Na2SO4-60%V2O5 at 900C:
(a) T11 steel
(b) Enlarged area of Fig. a

4
5

Back scattered electron image and EDAX point analysis (wt %) across the
162
cross-section of the NiCrAl and NiAlCrFeMo coated steels subjected to
hot
corrosion in Na2SO4-60%V2O5 environment for 50 cycles at 900C :

Output- Line Scan

Cu concentration across a section of Al-Cu alloy

163

Propagation of crack

164

BSEI and elemental X-ray mapping at the cross-section of the NiCrAl

coated T22 steel subjected to cyclic oxidation in air at 900C

Ni diffusion

165

BSEI and WDS elemental X-ray mapping across the cross-section of the WCCo/NiCrFeSiB coated GrA1 steel subjected to cyclic oxidation in air at 900C

Magnification

Magnification is accomplished by scanning a progressively smaller portion of

the specimen and displaying the image on the CRT.
Thus linier magnification is the side length of the CRT divided by side length
of the raster on the sample
166

Magnification

10X
An SEM focused at high magnification will still be in focus at low
magnification

167

110X

200X

168

400X

4K

169

4K

16K

45K

170

Resolution
The ability to discern fine details. It is represented by
the minimum distance between two points such that the
two points are perceived as separated image

= 0.61/N.A.
N.A. = sin , Numerical
aperture
refractive index of the
lens
Wavelength of light
- the half acceptance
angle of the lens.
171

Advantages of the SEM

Long depth of focus - 3D effect
Large specimen size
Simpler column design
Simple and rapid specimen preparation
Large range of magnification: 3X 150,000X

172

Limitations of SEM
Less

resolution than TEM

High vacuum environment for specimen
Metal coating of specimen
Only surface of specimen can be viewed

173

Specimen Electron Beam Interaction

Electron beam
Auger electrons
Cathodoluminescence
Bremsstrahlung

Characteristic x-rays

Secondary electrons
Backscattered electrons

SEM
Heat

Specimen
current

Elastically
scattered electrons

Transmitted and inelastically

scattered electrons

TEM
174

Comparison of OM, TEM and SEM

175

Transmission Electron Microscope

uses
omicrostructural analysis
ointerfacial analysis
ocrystal structure
omagnifications up to 1,000,000 X => atomic resolution
osmall region elemental analysis

samples

othinned to about 0.1 micron (1000 )

ominimum size: 1 mm; maximum size varies with instrument
osample preparation is very time consuming
TECHNIQUE

LIMITS

RESOLUTIO
N

Magnification

eye

retina

700,000

optical microscope

diffraction of
light

3000

10X to
2000X

scanning electron
microscope

diffraction of
electrons

30

10X to
200,000X

transmission electron
microscope

diffraction of
electrons

up to
176
1,000,000
X

TEM sample preparation

Bulk ceramics
Mechanical grinding, polishing, dimpling
Ion erosion, focused ion thinning
Metals
Mechanical grinding, polishing
Electrolytic thinning
Organic Materials
Freeze drying, embedding,
ultramocrotomy

177

Formation of Diffraction Spots from Different Planes

Unscattered primary electrons, E = Ep; very thin specimens
178

Elastically scattered low loss electrons, E ~ Ep; very thin specimens

Common Modes of Operation of TEM

Bright Field (BF) Microscopy

Selected Area Diffraction

Dark Field (DF)

179

Formation of Diffraction Spots from

Different Planes

Imaging in (a) BF mode, (b) DF mode with shift of

objective aperture and (c) DF mode with beam tilting

180

a) BF, (b) DF and (c) high resolution mode

(axial illumination) of imaging

181

Nature of Electron Diffraction Patterns

From crystalline materials - continuos rings, spotted rings or

spot patterns with well defined spacing and angles

continuos rings arise from very fine grain material; spotted

rings from coarser grains and spot patterns from single
crystals ( in the region defined by intermediate aperture)

From amorphous materials - fuzzy rings

Kikuchi lines - diffraction of inelastcially scattered

electrons - pair of lines (one dark and the other bright
corresponding to each diffraction spot

Provide information on specimen orientation

variation from exact Bragg diffraction conditions (s)

and

182

Changes in diffraction pattern spots to rings

183

Ring 1
Ring 2
Ring 3
Ring 6
Ring 7

Fe2O3
Fe2O3
Fe2O3
Fe2O3
Fe2O3

(111)
(220)
(311)
(511)
(440)

Ring 4
Ring 5
Ring 8
Ring 9

-Fe
-Fe
-Fe
-Fe

(111)
(200)
(220)
(311)
184

185

Diffraction Pattern from Amorphous Material

diffused rings reflecting short range order;
often seen on contamination layer or C support186

Electron Scattering Pattern from Amorphous Co Film

187

Well crystallized

Nanocrystalline

Phase identification

188

Hot Corrosion

Hot corrosion is defined as an accelerated oxidation, resulting

from the presence of salt contaminants such as Na2SO4, NaCl,
and V2O5 that combine to form molten deposits, which will
damage the protective surface oxides

Molten salt deposits react with protective oxides to form porous

non-protective oxide scale which results in penetration of
sulphides and chlorides on to the base metal results in further
corrosion.

The source of salts results from combustion of low quality fuels,

direct ingestion of sea salt in a marine environment etc

High-temperature corrosion varies widely depending on the kind

and grade of fuel and the operational conditions of the utility
boilers, many studies are aimed to understand the corrosion
mechanism of a particular system and to solve the practical
problem for it.

Hot corrosion mechanism can be separated in to initiation and

propagation stages.
The initiation of hot corrosion is often attributed to failure of the
protective oxide layer and repair of oxide layer by itself.
189

190

Hot Corrosion
When the salt arrives on a surface already covered with a
protective oxide, there is initially no reaction. In order for
accelerated oxidation to occur, the protective oxide must be
destroyed. This can happen in four distinct ways.
The first is the mechanical disruption of the oxide; i.e. by
erosion, thermal cycling, and by elastic strain of the substrate
putting the oxide in tension.
A second method is by diffusion of sulfur through the oxide
until chromium-rich sulfides form within the metal
The third method is dissolution (or fluxing) of the protective
oxide by the salts.
Finally during ignition, a local reducing environment may
form due to incomplete burning of fuel. Such a reducing
atmosphere can damage the protective surface oxide layer,
especially in the presence of contaminants such as Na2SO4
Once repair of the oxide is no longer possible, the propogation
phase results in the rapid consumption of the alloy. As soon
as oxide penetration occurs, the propagation stage often
results in catastrophic corrosion rates

191

EXPERIMENTS
Oxidation studies in Air for 50 cycles at
9000C.Each cycle consist of 1 hr heating
followed by 20 min cooling at ambient
conditions.
Hot
corrosion
studies
in
an
aggressive
environment of molten salt (Na2SO4-60%V2O5)
at 9000C for 50 cycles. Each cycle consist of 1 hr
heating followed by 20 min at ambient
conditions.
solid
particle
erosion
studies
at
room
temperature as per ASTM-G76 standard. The
impingement angles of 30 and 90 were
selected to provide the maximum erosion
condition for both ductile and brittle materials
under silica sand erodent.
Erosion-corrosion studies in the superheater
zone of coal fired boiler. The flue gas
temperature in this region is about 77820C.
The experiments were conducted for 10 cycles,
each cycle consisted of 100 hours exposure
192
followed by cooling at ambient conditions.

Super heater zone of coal fired boiler

193

EROSION-CORROSION STUDIES
IN INDUSTRIAL ENVIRONMENT
Bar chart indicating cumulative
weight gain and thickness loss
for HVOF coated steels after
1000 hours of exposure to
superheater zone of coal fired
boiler.

194

Erosion-corrosion studies in
coal fired boiler environment

(a)

(b)

(c)

Macrographs of the WC-Co/NiCrFeSiB coating exposed to superheater zone of coal fired

boiler for 1000 hours:
(a) GrA1 steel
(b) T11 steel
(c) T22 steel
195

Weight change plot for

WC-Co/NiCrFeSiB coated
steels exposed to super
heater zone of coal fired
boiler for 1000 hours

196

Bar chart indicating the

thickness lost in mm for the
uncoated
and
WCCo/NiCrFeSiB coated steels
after 1000 hours of exposure
to super heater zone of coal
fired boiler.

X-ray diffraction patterns

for
WC-Co/NiCrFeSiB
coated GrA1, T11 and T22
steels exposed to super
heater zone of coal fired
boiler for 1000 hours.

197

44.92% SiO2
32.39% Al2O3
10.23% TiO2
04.96% Na2O
03.33% Fe2O3

+1

EDS analysis at point 1

Open pore

+2

26.72% Cr2O3
14.29% NiO
18.29% SiO2
15.24% WO3
04.83% CoO
05.65% Fe2O3
06.06% Al2O3
02.66% SO3

(a)

EDS analysis at point 2

Surface scale morphology and EDAX analysis for

WC-Co/NiCrFeSiB coated steels exposed to super
heater zone of coal fired boiler for 1000 hours:

198

199

200

Weight change plot for

NiCrFeSiB coated steels
exposed to super heater
zone of coal fired boiler
for 1000 hours

201

Bar chart indicating the thickness lost in mm for the uncoated and
NiCrFeSiB coated steels after 1000 hours of exposure to super
heater zone of coal fired boiler.
202

204

Oxidation and Hot

Corrosion in Laboratory
Experiments
NiCrFeSiB Coating

205

OXIDATION IN AIR

Bar chart showing cumulative weight gain (mg/cm2) for uncoated and HVOF
coated steels subjected to cyclic oxidation in air

NiCrFeSiB > WC-Co/NiCrFeSiB > NiCrAl > NiAlCrFeMo

206

HOT CORROSION IN MOLTEN SALT

Bar chart showing cumulative weight gain (mg/cm2) for uncoated and HVOF
coated steels subjected to hot corrosion in Na2SO4-60%V2O5 salt environment

NiCrFeSiB > NiCrAl > NiAlCrFeMo > WC-Co/NiCrFeSiB

207

NiCrFeSiB Coating

208

NiCrFeSiB Coating
4

NiCrFeSiB coated GrA1

3.5

NiCrFeSiB coated T11

NiCrFeSiB coated T22

Weight gain/Area (mg/cm )

2.5

1.5

0.5

0
0

10

15

20

25

30

35

40

45

50

Number of cycles
25

NiCrFeSiB coated GrA1

NiCrFeSiB coated T11
20

Weight gain/Area (mg/cm )

NiCrFeSiB coated T22

15

10

0
0

10

15

20

25

30

35

40

45

50

Number of cycles

Weight gain vs. number of cycles plot for NiCrFeSiB coated steels subjected
209
to oxidation and hot Corrosion for 50 cycles in Na2SO4-60%V2O5 at 900C
*Rapid waight gain in the early cycles

*No SiO2 identified

210
X-ray diffraction patterns for NiCrFeSiB coated GrA1, T11 and T22 steels
And SEM/EDAX for coated GrA1 subjected to cyclic oxidation in air for 50 cycles at 900C

BSEI

Si + 2NiO = SiO2 +2Ni

Substrate

Silicon depleted region

Ni K

O K

Cr K

Ni K

Fe K

Mo K
Mo K

211

Elemental X-ray mapping at the cross-section of the NiCrFeSiB coated T22 steel subjected to oxidation

NiCrFeSiB Coating

*Uppermost layer-Continious SiO2

Subscale-rich in Cr2O3
212

XRD and SEM/EDAX point analysis (wt %) across the cross-section and on the surface of the213
NiCrFeSiB
coated steels subjected to hot corrosion in Na2SO4-60%V2O5 environment for 50 cycles at 900C :

NiCrFeSiB Coating

214

WC-Co/NiCrFeSiB
Coating

215

Oxidation Studies in Air

(a)

(b)

(c)

Macrographs of the WC-Co/NiCrFeSiB coating subjected to cyclic oxidation in air for 50 cycles at 900C:
(a) GrA1 steel
(b) T11 steel
(c) T22 steel

*In case of coated T22, iron oxide protrusions are observed after 26 cycle

216

WC-Co/NiCrFeSiB coated GrA1

5

WC-Co/NiCrFeSiB coated T11

Weight gain/Area (mg/cm )

WC-Co/NiCrFeSiB coated T22

4

0
0

10

15

20

25

30

35

40

45

50

-1

Number of cycles

Weight gain vs. number of cycles plot for WC-Co/NiCrFeSiB coated steels
subjected to oxidation for 50 cycles in air at 900C
13

WC-Co/NiCrFeSiB coated GrA1

11

WC-Co/NiCrFeSiB coated T22

Weight gain/Area) mg cm

-4

WC-Co/NiCrFeSiB coated T11

10

15

20

25

30

35

40

45

50

-1

Number of cycles

(Weight gain/area) vs. number of cycles plot for WC-Co/NiCrFeSiB coated steels
subjected to oxidation for 50 cycles in air at 900C
217
*Protective oxides of Si and Cr stabilized the formation of volatile tungsten oxide

57.25% SiO2
30.34% Cr2O3
04.47% NiO
05.88% WO3

1
EDAX at point 1
2
28.84% SiO2
16.46% Cr2O3
37.50% CoO
11.31% NiO
03.64%
Fe2O3

(a)

EDAX at point 2

SEM//EDAX for WC-Co/NiCrFeSiB coated T11 steels and XRD analysis

after subjected oxidation
*Discontinious,Amorphous silica along with the oxides of Cr and Co

218

219

2
3

4
5

2
3
4
5

Back scattered electron image and EDAX point analysis (wt %) across the cross-section of the
WC-Co/NiCrFeSiB coated steels subjected to cyclic oxidation for 50 cycles in air at 900C:
(a) T11 steel
(b) T22 steel

220

Hot corrosion studies in

Na2SO4-60%V2O5 environment

(a)

(b)

(c)

Macrographs of the WC-Co/NiCrFeSiB coating subjected to Hot corrosion

in salt for 50 cycles at 900C:
(a) GrA1 steel
(b) T11 steel
(c) T22 steel

221

222

223

WO3 + O2- = WO42-

224

225

226

WC-Co/NiCrFeSiB Coating

227