Lecture by

Dr. V. BALASUBRAMANIAN, M.E., Ph.D (IITM)

Professor,
Centre for Materials Joining & Research (CEMAJOR)
Department of Manufacturing Engineering
(DST FIST Level II sponsored & UGC SAP Level II Assisted Department)

ANNAMALAI UNIVERSITY
Email: visvabalu@yahoo.com
 COATING-SUBSTRATE SYSTEM

• Roughness • Electronic properties

• Erosion • Frictional characteristics
• Corrosion / Oxidation • Porosity

• Residual stress • Multilayers

Coating • Cohesion • Graded composition
• Cracking /defects • Adhesion
c/s Interface
• Adhesion • Interdiffusion
Substrate • Substrate properties • Diffusion mismatch
• Expansion mismatch • Cleanliness / roughness

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 TYPES OF THE COATINGS

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 COATING PROCESSES

CHEMICAL

ELECTROCHEMICAL

THERMOCHEMICAL

THERMAL SPRAY COATING

VAPOR DEPOSITION

MECHANICAL

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 THERMAL SPRAYING PRINCIPLE

Powder Powder particle Molten particle Particle impact coating

feed stock melting acceleration
 Thermal Spraying Methods

With kinetic With From molten With gas or liquid With electrical
energy Radiation material fuel discharge in gas

Cold gas Flame spraying (FS) Arc Spraying (AS)

Laser Molten –metal
spraying spraying(LS) flame spraying
(CGS) 1. Powder flame Plasma Spraying (PS)
spraying (PFS) Atmospheric plasma
spraying (APS)
2. Wire flame spraying
Vacuum plasma spraying
(WFS) (VPS)

High pressure plasma

3. High velocity wire spraying (HPPS)
flame spraying(HVWFS)
Inductively coupled
plasma spraying (ICPS)
HVOF
Liquid Stabilized plasma
spraying (LSPS)
Detonation gun
Shrouded plasma
spraying (DGS) spraying (SPS)
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COATING’S MICROSTRUCTURE

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 THERMAL SPRAY FEEDSTOCKS

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 FLAME SPRAY
 To apply abradable coatings or nickel/chrome self-
fluxing alloys which are subsequently heat treated to
metallurgically bond them to the substrate (Fused
coatings).

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 SCHEMATIC DIAGRAM

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11

A Flame Spray gun uses oxygen and fuel gases to produce a flame
into which powder is injected.

The resultant molten particles of powder are projected on to the
work piece to produce the coating.

Many coatings sprayed by this process are then heat treated at
around 1000ºC to 'fuse' the coatings to the substrate surface.

Fused coatings produced by this process are hard and corrosion
resistant and are able to withstand wear by abrasion, fretting,
cavitation and other hard surfaces.

The addition of different proportions of carbon, silicon and boron
to the basic nickel/chromium alloy results in the formation of
hard phases of carbides, silicide and borides.

They can be applied 1 - 5 mm thick; much thicker than hard ware
coatings applied by the plasma or HVOF processes.

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 FLAME SPRAYING
- flame temperature:
• acetylene/oxygen 3160 ºC;
• propane/oxygen 2850 ºC;
• hydrogen/oxygen 2660 ºC.
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- sprayed materials:
• wire: metals and metal
alloys;
• powder: pure metals, alloys,
oxides, cermets, composite
powders.
 ARC SPRAYING
Two conductive wires are melted as they are acted upon
by an arc. The arc produces such a temperature that it
transforms the wires into a molten state, then atomized
into small particles and ultimately propelled onto the
desired substrate by ultra-clean, compressed air.

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 ARC SPRAYING

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 ARC SPRAYING

 temperature inside the arc: 6500 ºC;

 voltage 18 – 40 V, current 50 – 150 A;
 sprayed materials: electroconductive alloys,
 ceramics can be deposited, when using core wires.
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 ADVANTAGES - LIMITATIONS

Lower operating costs,

Higher material output per hour,

Production of a more coarse coating than the
Plasma or HVOF coating methods. dimensional
restoration of both mis-machined and worn parts.,

Overall, the wire arc spray coating method is a cost
efficient and easily repeatable process that allows
for a tremendous variety of highly reliable,
material-coatings solutions.

Produces a highly concentrated spray pattern and
can spray at extremely high speeds.

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 PLASMA SPRAYING

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20
 PLASMA SPRAYING

• Plasma temperature: up to 30000 ºC.

• virtually all existing materials.
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 PLASMA SPRAYING
 Key characteristics
 Quickly produces thin, dense, full-coverage
coatings
 Capable of applying the full range of coating
materials, including metals, ceramics, and
cermets
 Keeps the environment clean and safe as it’s a
chambered process with full filtration package
 Typical applications
 Combustion chambers
 Blades and vanes
 Solid oxide fuel cells

22 Medical implants
 HIGH-
HIGH-VELOCITY OXY FUEL SPRAYING (HVOF)

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 HIGH-
HIGH-VELOCITY OXY FUEL SPRAYING (HVOF)

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25
 HVOF COATING FEATURES

High Density (Low Porosity <1%)

Optimum Hardness (1250VHN)

Smooth(as-sprayed) Surface (3-5Ra)

High Bond Strengths(above10000psi)

Excellent Wear Resistance

Reduced Oxide Content than Plasma Coating
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#Depends on type of powder & parameters

 HVOF Spraying-
Spraying- Limitations

Fine powders can be sprayed

Low deposition efficiency (<50%)

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 HVOF SPRAYING-
SPRAYING- APPLICATIONS

Aerospace: Hard Surfacing; Hard Chrome replacement
etc.

Turbine engine fan blade, compressor blades, bearing
journals, stator, rotor disk snap diameters, landing gears,
actuators, flaptracks, helicopter rotor, rotor joints &
sleeves.

Power Generation: HardSurfacing, AntiCorrosion

Industrial gas turbines, hydro electric pelton buckets,
nozzles and blades, exhaust fans.

Automotive: SeffLubricating,HardChromereplacementetc.
Transmission shifter forks, hydraulic rods, pistons,piston

Rings, ship steering rams

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 DETONATION GUN SPRAYING

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 DETONATION GUN SPRAYING

Flame temperature: 4000 ºC.

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 COLD SPRAYING

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 COLD SPRAYING

• gas temperature: under the

phase transition temperature;
• sprayed materials: pure Al, Zn, Cu, Ni
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and babbites.
 THERMAL ENERGY VS. KINETIC ENERGY
IN THERMAL SPRAY

WARCS Wirearc Spray

PS Plasma Spray
Thermal Energy

FS Flame Spray

HVOF High velocity oxy fuel

Melt or partially melt

Solid CS Cold Spray

Kinetic Energy

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 COATINGS’ PROPERTIES (1).
INFLUENCE OF VELOCITY AND TEMPERATURE

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 COATINGS’ PROPERTIES (2).
ADHESION AND POROSITY

SPRAY TECHNOLOGY VELOCITY, m/s POROSITY, % ADHESION, MPa

Flame spraying
• powder 30 17 – 70
6 – 15
• wire 180 15 – 20

Arc spraying 240 2–8 40

Plasma spraying
240 – 1200 (2 to 5) 20 – 70
(different modifications)

Detonation gun spraying 910 <1 ≥ 100

HVOF, HVAF 610 – 1500 < 0,5 62 – 83

Cold spraying 500 – 1200 1–3 30 – 100

 COATINGS’ PROPERTIES (3).
OBTAINABLE HARNDESS.
SPRAYED MATERIAL SPRAYING TECHNOLOGY HARDNESS, HV

Flame spraying (wire) 500 – 600

Chrome steel
PTA 800 – 850

NiAl alloy Flame spraying 200 – 250

Copper Flame spraying (powder) 150

Flame spraying (powder)/HVOF 460 – 770

Stellite
PTA 290 – 590

MCrAlY Plasma spraying 400

Flame spraying/HVOF 250 – 780

Self-fluxing alloy (NiCrSiB)
PTA 360 – 820

WC-Co Plasma spraying (powder)/HVOF 1100 – 1300

Al2O3 Plasma spraying 1800 – 382000

 Coatings’ properties (4).
Microhardness of WC-
WC-17Co coating, sprayed using different technologies.
Microhardness – DPH 300 gram
1800
1600
HV 0.3
1400

1200

1000

800

600

400
Comb Plasma HVOF HVOF D-Gun JP-5000 Pressed and
powder Air Water sintered (for
Cooled Cooled comparison)

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 COATINGS’ PROPERTIES (4).
WEAR VS. SPRAY METHOD
7PSZ
800

700

600

500
Weight Loss (mg)

400

Al2O3
300
Cr2O3

200

100
22x
32x 21x
0
APS
1
HVOF
2
APS
3
HVOF
4
APS
5
HVOF
6
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 APPLICATIONS OF SPRAYED MATERIALS
MATERIAL EXAMPLES OF
EXAMPLE PROPERTIES
GROUP APPLICATION
Metal structures in
Pure Metals Zn Corrosion Protection
bridges
High hardness nearly
Self-Fluxing alloys Ni-Cr-B-Si Shafts, sleeves, seals
poreless after fusing
Low cost material, wear
Steels Fe-13Cr Repair, wear protection
resistant
High temperature
Blades and vanes in gas
MCrAlY alloys Ni-Cr-Al-Y corrosion and oxidation
turbines
resistance
Nickel-graphite Clearance control, Sealing of air inlet
Ni-25C
composites abradable coatings channels in compressors
Parts in textile
Al2O3, Cr2O3 High Hardness, good
Oxides machinery, paper
temperature stability
machine cylinder
WC.12CO,
Hardmetal Cr3C2. Wear resistance, high Valves, wear parts,
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(carbides) 25NiCr
hardness paper machine cylinders
 CASE STUDY - 1

IMPROVING SLURRY EROSION RESISTANCE OF AISI

304L AUSTENITIC STAINLESS STEEL BY HVOF
SPRAYED COATINGS

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 Material C Mn P S Si Cr Ni O Fe Co W
SS 304 L 0.017 1.81 0.025 0.04 0.22 18.59 8.66 - Bal -
WC-Cr3C2 - Ni 7.0 - - - - 20 7.0 0.2 0.3 Bal
WC–Co–Cr 4 10 Bal

OM of Stainless
Steel SS 304L

OM of WC-CrC- OM of WC-Co-Cr
Ni Powder Powder
 Optimized Processing Conditions for WC-CrC-Ni on ASS
oxygen flow Spray Powder Feed Carrier Gas
LPG flow rate
Process Parameters rate distance rate flow rate
(lpm)
(lpm) (mm) (g/min) (lpm)
Values 252 64 230 32 13
Deposition Adhesion Bond Shear
Porosity Hardness
Responses Efficiency Strength, Strength,
Vol % Hv
% Mpa Mpa
64.98 64.0 9.38 1.4 1349.5
 Pores Impurities

CO- Cr metal matrix

WC grains

Optimized Processing Conditions for WC-Co-Cr on ASS

oxygen flow Spray Powder Feed Carrier Gas
LPG flow rate
Process Parameters rate distance rate flow rate
(lpm)
(lpm) (mm) (g/min) (lpm)
Values 253 61 227 35 13
Responses Porosity (Vol %) Hardness (Hv)
1.38 1318

Evaluating the individual effect of various parameters such as

Effect of impingement angle

Effect of Water jet Velocity

Effect of Erodent discharge and

Effect of Stand off Distance
On the erosion rate of SS 304 and HVOF coated WC – CrC- Ni,
WC-Co-Cr coatings.
Parameters Units Minimum Maximum
Angle of Impingement Degree 15 90
Slurry jet Velocity m/s 10 50
Erodent Discharge g/cc 300 2500
Stand off Distance mm 35 55
 Parameters
Angle of
Impingement
(Degree ) 45
Slurry jet Velocity
(m/s ) 10
Erodent Discharge
(g/cc) 340
Stand off Distance
(mm) 45

Minimum Wear Rate Condition- BM Minimum Wear Rate Condition- COAT

WC-CrC-Ni

SS

WC-Co-Cr
 Parameters
Angle of
Impingement
(Degree ) 45
Sluury jet Velocity
(m/s ) 50
Erodent Discharge
(g/cc) 340
Stand off Distance
(mm) 45

Maximum Wear Rate Condition- BM Maximum Wear Rate Condition- COAT

WC-CrC-Ni

SS

WC-Co-Cr

The erosion mechanism was significantly affected by
the velocity and angle of impingement.

At high velocity, removal of material in the form of
fragments through plastic indentation mechanism
was also observed.

Erosion resistance of ASS is increased by 59% using
WC-CrC-Ni coatings.
CASE STUDY - 2
MoB–CoCr as alternatives to WC–12Co for
stainless steel protective coating and its
corrosion behavior in molten zinc

The present study evaluates a MoB–CoCr coating applied by

the high velocity oxy fuel (HVOF) process, used to replace
WC–12Co for anticorrosion to molten zinc. The
microstructure, mechanical properties and corrosion
behaviors in molten zinc of those two kinds of coating were
contrastively studied.
 Hot-dip galvanizing is known as the most efficient and economical method to
prevent steels in atmospheric environment from corrosion.

Fig. 1. The schematic diagram of hot-dip galvanizing

procedure.
 Feedstock

Fig. 2. Microscopic view of thermal spray powder: Fig. (a) WC–12Co, (b)
MoB–CoCr.
HVOF SPRAY PARAMETERS USED
 EXPERIMENTAL SETUP
 Specimens were repeatedly
immersed in molten zinc at
temperatures of 450–480 °C. The
specimens rotate and orbit in the
molten metal to come into contact
with a fresh molten metal as well as
to preserve liquid uniformity during
the test.
 Two groups of samples immersed for
360 h and 720 h, respectively, were
taken out to study the corrosion
mechanism by SEM observation and
EDAX analysis.

Fig. 3. Schematic graph of the corrosion device: 1 — thermocouple, 2 —

electrical resistance furnace, 3 — resistance wire, 4 — graphite crucible, 5
— molten zinc,
6 — samples , 7 — swivel plate, 8 — furnace lid, and 9 — electric motor.
CROSS SECTIONAL MICROSTRUCUTRE
FEATURES

Fig. 4. SEM micrograph of as-sprayed coating: (a) across-section

morphology of WC–12Co, (b) surface morphology of WC–12Co,

WC–12Co coating exhibited the areas with gray contrast (rich in

Co) and white contrast (rich in WC).
CROSS SECTIONAL MICROSTRUCUTRE
FEATURES

Fig. 4. SEM micrograph of as-sprayed coating: (c) across-section

morphology of MoB–CoCr, (d) surface morphology of MoB–CoCr.

MoB–CoCr coating exhibited three areas such as white contrast (A), gray
contrast (B) and dark contrast(C), those areas rich in Mo, MoB and CoCr
 PHASE ANALYSIS

Fig. 5. X-ray diffraction patterns of the powders and corresponding as-sprayed

HVOF coatings.

WC–12Co coatings contain WC, W2C, Co6W6CandCo6W3C phase. The
WC is hard-phase and the CoxWyC (η-phase) is bonding-phase, while a
small amount of W2C were formed by loss of carbon during spraying
process.

For the MoB–CoCr coating, it was composed of CoMo2B2 and CoMoB
phases, which were the same to the powder and no oxide was observed,
indicating that the powder was stabile when sprayed by HVOF.
 THERMAL SHOCK TEST ANALYSIS

Fig. 6. The microscopic view of the coatings after 300 times thermal shock
test: (a) surface morphology of WC–12Co, (b) across-section morphology of
WC–12Co
 THERMAL SHOCK TEST ANALYSIS

Fig. 6. The microscopic view of the coatings after 300 times thermal shock test
(c) surface morphology of MoB–CoCr, and (d) across-section morphology of
MoB–CoCr.
 Co-efficient of thermal expansion –
Stainless steel – 19.3X10-6/ K;
WC-12Co- - 7.2X10-6/ K;
MoB-CoCr - 9.2X10-6/ K;
 Thermal expansion mismatch on cooling is an major issue
 Corrosion Behavior in Molten Zinc

SEVERELY ATTACKED REGION

Fig. 7. The photograph of specimens after immersion in molten zinc: (a) MoB–
CoCr immersed for 360 h, (b) WC–12Co immersed for 360 h, (c) MoB–CoCr
immersed for 720 h, and (d) WC–12Co immersed for 720 h.
 EDS ANALYSIS

Fig. 8. SEM images and EDAX analysis of the coatings after immersing in molten zinc for 360 h: (a) MoB–CoCr coating, (b) WC–12Co coating, (c) energy
dispersive spectra generated from spot A in panel a and (d) energy dispersive spectra generated from spot B in panel b.

Fig. 8. SEM images and EDAX analysis of the coatings after immersing in molten zinc for 360 h: (a)
MoB–CoCr coating, (b) WC–12Co coating, (c) energy dispersive spectra generated from spot A in
panel a and (d) energy dispersive spectra generated from spot B in panel b.

Zinc diffuses in to the crack and extends the crack direction in different
zones
 SEM ANALYSIS AFTER IMMERSION

Fig. 9. SEM images of coatings after immersing in molten zinc for 720 h:
(a) MoB–CoCr coating and (b) WC–12Co coating .
 SUMMARY

Molten zinc corrosion test showed that the lifetime
of samples with MoB –CoCr coatings in molten
zinc was an average of about 26 days while the
lifetime of samples with WC–12Co coatings was
about 22 days.

Micro -cracks will inevitably produced in the

coatings after a long-term immersion. Along the
micro-cracks, molten zinc will permeate toward
the substrate, eventually form penetrating-cracks
and corrode the substrate, causing spalling of the
coatings. 2
 CASE STUDY -3

COLD SPRAYING FOR

HOT CORROSION
PROTECTION
This study presents an incremental and novel
attempt in which cold spraying process has
been used to develop the coatings.

The outcome of this study shall be useful to

explore the possible use of the developed
nanostructured coating for boiler tube
protection in power plant boilers.

Source: ARCI, Hyderabad

 FEEDSTOCK CHARACTERISATION

Fig. 1. SEM/EDS analysis of ball milled Ni-20Cr alloy powder showing XRD diffraction pattern (inset) and
particle size distribution (inset)
FEEDSTOCK CHARACTERISATION

Fig. 2. TEM image of ball milled Ni-20Cr alloy powder for 20 h showing grain size
COLD SPRAY PARAMETERS
XRD ANALYSIS OF AS COLD SPRAYED
COATINGS

Fig. 3. X-ray diffraction profiles of cold-sprayed Ni-20Cr coatings on (a) T22 and (b) SA 516
steels.

 Nickel Phase is dominant

Fig. 4. Surface SEM/EDS analysis of cold-sprayed Ni-20Cr coating on (a) T22 (b) SA 516
boiler steels.

 Original feedstock chemical composition is preserved after deposition

 ELEMENTAL ANALYSIS

Fig. 5. SEM back scattered image and variation of elemental composition across the cross section of cold-
sprayed Ni-20Cr coating on (a) T22 and (b) SA 516 boiler steels

Uniform composition observed throughout the coating.

No evidence of “O’ in this coatings.
 MICROHARDNESS ANALYSIS

Fig. 6. Cross-sectional microhardness profiles of cold-sprayed Ni-20Cr coating on T22 and SA 516 boiler
steels.

 Improved microhardness values were observed due to high packing

efficiency of CGDS system.
 CYCLIC OXIDATION TEST RESULTS

Fig. 8. Weight change per unit area vs. number of cycles’ plots for bare and cold-spray Ni-20Cr coated T22 and
SA 516 boiler steels subjected to cyclic oxidation in air at 900 ◦C for 50 cycles.

Reduced oxidative weight gain observed in cold spray coatings when

compared with bare steel.
 HOT CORROSION TEST SEM ANALYSIS

Fig. 9 Surface SEM/EDS analysis for bare and cold-spray coated steels subjected to cyclic
oxidation in air at 900 ◦C for 50 cycles (a) bare T22 steel, (b) bare SA 516 steel (c) Ni-20Cr
coated T22 steel, (d) Ni-20Cr coated SA 516 steel.

 Bare substrate shows granular scale whereas coating shows pyramidal

structure.
 SUMMARY

Initial feedstock chemical composition was retained

in cold spray process.

Formation of granular oxide shows rich in FeO
phase, Pyramidal shape shows formation of
protective oxides over the surface.

Adhesive strength of the coatings were similar
irrespective of the substrate materials

Higher hot corrosion resistance was observed in
boiler grade steels, which could be attributed to the
presence of protective phases such as Cr2O3 ,
NiCr2Oand NiO in its oxide scale.
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 Centre for Materials Joining & Research (CEMAJOR)

A 3 storey building with 9 Laboratories under one roof

Fusion Welding Laboratory
Solid State Welding Laboratory
Plasma Processing Laboratory
Laser Processing Laboratory
Modelling & Simulation Laboratory
Physical Metallurgy Laboratory
Mechanical Testing Laboratory
Corrosion Testing Laboratory
Tribology Laboratory

Centre has completed 25 R&D projects worth of Rs. 600 lakhs

Centre has 10 on-going R&D projects worth Rs.250 lakhs from DST,
DRDO,
UGC, AICTE
25 scholars completed and 20 scholars are pursuing Ph.D program
FACILITIES AVAILABLE AT CEMAJOR
MATERIALS JOINING
Pulsed TIG Welding Machine
Pulsed MIGWelding Machine
PTA Hardfacing Machine
Friction Welding Machine
Diffusion Bonding Machine
Resistance Spot Welding
Friction Stir Welding (Manual)
Friction Stir Welding (CNC)
Welding Emission Chamber
OM with Image Analyser
MicrohardnessTester
Universal Testing Machine (20Ton)
Rotary Fatigue Tester (INSTRON)
Tensometer (2Ton)
Servo Hydraulic Fatigue Testing Machine
SEM with EDS and EBSD
SURFACE ENGINEERING
Atmospheric Plasma Spraying
High Velocity Oxy Fuel Spraying
Powder Flame Spraying machine
Twin Wire Arc Spraying machine
500 W Laser Surfacing Machine
Physical Vapour Deposition (PVD)
Chemical Vapour Deposition (CVD)
Pin-on-Disc Wear Tester
Air Jet Erosion Tester
Dry Sand Abrasion Tester
Gill AC Potentiostat
Salt Spray Tester
Microwave Furnace
HighTemperature Furnace (1600 C)
Thermal Conductivity Meter
Water Jet Erosion Tester
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