Documente Academic
Documente Profesional
Documente Cultură
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
Surface Engineering
Surface Engineering is a branch of Science deals with
modification of near
engineering
engineering
contributes
disciplines
which
to
include
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
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
Nitriding
Boriding
Laser alloying
Ion implantation
Organic coatings
Thermal Spray
coatings
Electroless-plating
Physical vapour
deposition
Chemical vapour
deposition
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
11
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
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
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
18
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
22
23
24
25
26
27
CVD Process
28
Chemical Composition
(wt %)
Particle size
WC-Co / NiCrFeSiB
35/65
-45 + 15 m
[Cr3C2-35%(NiCr)]+5%Si
-45 + 15 m
[WC-12%Co]+65%[NiCrAlY]
-45 + 5 m
WC - 20CrC - 7Ni
-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
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.
36
38
Diffraction Principle
Braggs Law
n = 2 d sin
Incident ray
atoms
General Uses
Macrostress measurement
Microstress measurement
Determination of the percent cold work at and below the surface
Measurement of hardness in steels in thin layers
43
Diffraction-Peak Location
44
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.
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.
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
50
51
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 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.
(a)
(b)
Coatings
Ti/TiC/TiN
Elastic
Modulus
(GPa)
Thickness
(m)
Surface
Roughness
SEM
STM(nm)
297.6
1.79
2.56
4.98
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
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)
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
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
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
67
HF
1
HF
3
HF
2
HF
4
HF
5
HF
6
HF1-Acceptable coatings
70
Case Study
Design Modification on Coating Surface and
its Thermal Analysis for Plasma Sprayed
Ceramic Coated Piston for its Performance
Improvement
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
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
Hohenberg Equation:
hgas(t)=VC(t) -0.06P(t)0.8T(t) -0.4 (s+b) 0.8
Results
Temperature distribution for uncoated part
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
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
loa
d
loa
d
Crack initiation
site
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
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
Output
Hypermesh
.hmres
PATRAN
FEMVIEW
Redesign
CADFIX
FEMAP
Life
contours
100
20
100
570
500
Insulated, x
translation
constrained
Insulated, x
translation
constrained
X
Z
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
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
Maximum
temperature is at top
of the specimen (1382
Kelvin)
Minimum
temperature
is
at
bottom of specimen
(1087 Kelvin)
Displacements in meter
for maximum temperature
Maximum displacement
is found to be 2.5E-05
meter
Maximum strain is at
Substrate region(0.035)
Minimum strain
TGO(0.011)
is
at
Fatigue results
Element
421
1522 cycles is
of
in
the
log
Reliability at 100
cycles is 77% at
substrate
Note: Reliability is
shown
as
percentage
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
e
cycle
cycle
Time
A
temperature
Time
Strain rate
800
Stress (MPa)
600
400
200
0
-6000
-4000
-2000
-200
2000
4000
-400
-600
Strain (u e)
Stress-strain response
6000
Instantaneous
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
Fig. In-phase
Fig. Out of
phase
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.
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
115
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
Coating powder
Chemical Composition
(wt %)
Shape
WC-Co / NiCrFeSiB
35/65
(MEC-1031C)
Particle size
-45 + 15 m
121
Carbides
Optical micrographs
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
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
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 Coating
127
WC-Co/NiCrFeSiB Coating
128
129
WC-Co/NiCrFeSiB Coating
130
NiCrFeSiB Coating
131
NiCrFeSiB Coating
132
NiCrFeSiB Coating
134
3-D profile of
CoCrAlY/Al2O3
coating at 90 and
30
135
3-D profile of
CoCrAlY/CeO2
coating at
90 and 30
136
137
138
Questions
Thank You
Structure-Property Relations
Internal Structure
Macrostructure
Microstructure
Substructure- SEM, TEM
Crystal
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
145
INFORMATION AVAILABLE
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
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
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
153
BSEI
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
157
158
EDX
WDX
Method of analysis
Entire
spectrum Analysis of wavelength
analysed
at a time
simultaneously
Ease of fitting
30 min
Artefacts
Field of usefulness
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
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
(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
(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 :
163
Propagation of crack
164
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
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
172
Limitations of SEM
Less
173
Characteristic x-rays
Secondary electrons
Backscattered electrons
SEM
Heat
Specimen
current
Elastically
scattered electrons
TEM
174
175
samples
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
177
179
180
181
and
182
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
Well crystallized
Nanocrystalline
Phase identification
188
Hot Corrosion
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.
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)
196
197
44.92% SiO2
32.39% Al2O3
10.23% TiO2
04.96% Na2O
03.33% Fe2O3
+1
+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)
198
199
200
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
205
OXIDATION IN AIR
Bar chart showing cumulative weight gain (mg/cm2) for uncoated and HVOF
coated steels subjected to cyclic oxidation in air
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 Coating
208
NiCrFeSiB Coating
4
2.5
1.5
0.5
0
0
10
15
20
25
30
35
40
45
50
Number of cycles
25
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
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
Substrate
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
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
(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
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
Weight gain/Area) mg cm
-4
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
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
(a)
(b)
(c)
221
222
223
224
225
226
WC-Co/NiCrFeSiB Coating
227