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INTRODUCTION

Fulfilling customer needs are essential for business success. The activities of
an automobile manufacturer have to be oriented towards the customer’s expectation
and customers delight. Nowadays, needs like functionality, comfort, safety, reliability,
as well as high level of quality are taken for granted. Design, material quality and
their perception are reflected. Correct material selection is essential in order to
guarantee functionality or grace fullness of the multitude components of an
automobile. The piston, cylinder liner and valves are the important parts of the
internal combustion engine to be given more attention.
In baseline engine, the liner undergoes a severe wear at high temperatures of
combustion which results in seizure of the liner. Due to heat losses through the
cylinder walls, the thermal efficiency of the engine decreases. Reduction of emissions
from diesel engine is becoming increasingly important, because of promulgation of
stringent emissions legislation. Particulate and NOx emission are the primary concern
for diesel engine owing to the nature of the compression ignition process and diesel
fuel consumption. The challenging problems occurring are due to the presence of
solid particulates in the exhaust, in addition to gas phase pollutants. In order to
minimize these pollutants, it is necessary to go for an alternate method to design
engine cylinder and its combustion chamber components. The rapid increase in fuel
expenses, the decreasing supply of high grade fuels in the market and environmental
concerns stimulated research for more efficient engines.
To increase wear resistance, thermal efficiency, and minimize pollutants in the
exhaust of the engine, a thermal barrier and wear resistant coating is applied to inner
walls of the cylinder which replaces conventional liner.
Thermal barrier Coating (TBC), a new technique used at present scenario.
TBC is a thin layer of ceramic coating applied to combustion chamber components, mainly
for piston crown, valves, cylinder cover and cylinder walls. By using this technique, the
present problems could be solved to some extent.

Thermal barrier coatings becoming increasingly important in providing thermal


insulation for heat engine components. Thermal insulation reduces in-cylinder heat
transfer from the engine combustion chamber and also components structural
temperature. Containment of heat also contributes to increase in cylinder work and offers
higher exact temperature for energy recovery. Lower component structural temperature
will result in greater durability.

The problem faced by gas turbine engineers was the failure of components
exposed to not combustion gases. This problem was exacerbated by oxidizing
components of combustion gas (C02 and O2), high pressure (4 MPa) and the very high
loads experienced by gas turbine blades. Common causes of failure in hot end of
component even to date are creep, oxidation and thermo-mechanical fatigue.
There have been three major engineering advances in dealing with problem:
1. The development of the super alloys( 1950 to 1980)
2. The development of air cooling system( 1960 to present)
3. The development of durable thermal barrier coatings (1980 to present).
The gains in gas temperatures obtained were of the order of about 2000 c for the
development of super alloys, 5000C for air cooled system and 3000C for thermal barrier
coatings. Hence in the hot end of modem gas turbine engines most components are
made of super alloys with air cooled system and an increased number of components
now have thermal barrier coatings.
Modem TBCs are required not only to limit the heat transfer through the coating
but also to protect the engine components from oxidation and corrosion. No single
coating composition appears to satisfy these multifunctional requirements. As a result, a
"coating system" needs to be evolved. Research in the last 20 years have led to a
preferred coating system, consisting of three separate layers to achieve long term
effectiveness in the high temperature, oxidative and corrosive environment in which
they are to function.
First, a thermally protective TBC layer with a low thermal conductivity is
required to maximize thermal drop across the thickness of coating. This coating is likely
to have a thermal expansion co-efficient which differs from that of the component
material. This layer should therefore have a high in-plane compliance to accommodate
the thermal expansion mismatch between the TBC and the underlying super alloy
component. In addition to this it should be able to retain this property and its low
thermal conductivity during prolonged environmental exposure. A porous, columnar,
100-200µm thick, yttria stabilized zirconia (YSZ) layer is currently preferred for this
function.
Second, an oxidation and hot corrosion resistant layer is required to protect the
underlying component from environmental degradation. This layer is required to remain
relatively stress free during long term exposure and remain adherent to the substrate to
avoid

Thermal mismatch which mainly occurs due to improper adhesion and


difference in thermal expansion, coefficients between bond coat and cylinder material. TBC
must also withstand wear and tear. There is a need to over come these problems for
employing TBC to engine cylinder as a liner. In present work an attempt has been made to
develop a TBC which is also a wear resistant coating to be used in IC engine as a liner.

For last 100 years, engineers have searched for the best materials for
cylinder, pistons and rings. In the early years of automotive engines. the choice of
materials was cast iron. Engineers used cast iron in pistons, rings and cylinders. Cast
iron worked fine for cylinders and rings, but pistons made of cast iron were heavy, Cast
iron pistons were replaced by aluminum pistons due to the lower density of the
aluminum alloy. Due to the combination of cast iron cylinders and rings, aluminum
pistons are still in use in most automotive engines today. In the present investigations,
Aluminium-6061 (AI-606J) and Cast Iron are selected as engine cylinder materials.
These are also called as substrates of TBC system developed in the present work. Bond
coating is an intermediate layer of the TBC system. It is mainly used to bond a
subsequent over coat design for a particular function. The bond materials are specially
designed to provide optimal properties for both adherence of the top coating and
integrity of the interfacing substrate. Grading the TBC system from the bond coat to top
ceramic coat by incorporating one or more intermediate layers into the coating system
can minimize ceramic metal thermal expansion coefficient. The bond coat materials are
selected considering coincidence of thermal expansion coefficient values of the coating
and the relative elastic moduli, good wettability of the coating material at the surface of
support during its applications, suitable chemical affinity between the two systems. In
the present work, commercially available three bond coat materials, viz., Al25Fe7Cr5Ni
(Metco 446 metal powder), Ni9Cr3Si (Metco 451) and Fe38NilOAl (Metco 452, metal
powder) are selected. On AI-6061 substrate, two coating systems are developed. The
first coating system consists of two bond layers (A125Fe7Cr5Ni as Bond coat I-BCI and
Ni9Cr3Si as Bond Coat 2-BC2) and a top coat. The second coating system consists of
one bond coat (BC I) and a top coat. Similarly, two more coating systems are developed
on cast iron substrate. In this, the first coating system consists of two bond layers
(Fe38Ni10Al as bond coat l and Ni9Cr3Si as bond coat 2) and a top coat. The second
coating system consists of one bond coat and a top coat.
The performance of a TBC system as a liner in IC engine mainly depends on top
coat. Top coat should have characteristics of high wear and erosion resistance, low
thermal conductivity and high expansion coefficient. A significant amount of research
activities have been carried out on coating systems which utilizes alumina (Al2O3) and
Zirconia as top coats. The survey of the published literature shows that alumina is used
as a wear and erosion resistant coating where as Zirconia is used as thermal barrier
coating to minimize heat loss. The thermal conductivity of alumina is significantly high
compared to that of Al-6061. Also alumina has high hardness. Due to this, alumina can
be used as thermal barrier as well as wear resistant coating with AI-606 I substrate. The
addition of CaO, MgO, Y2O3 to zirconia decreases both the cubic to tetragonal and
tetragonal to monoclinic transformation temperatures. Thus, with sufficient additions of
various oxides to zirconia, the cubic phase can be stabilized. At concentrations less than
this limit, partial stabilization occurs, and all three phases i.e. cubic, tetragonal and
monoclinic can be retained on cooling to room temperature. The resulting ceramic is
referred as Partially Stabilized Zirconia (PSZ). The thermal shock resistance of PSZ has
been found to be superior to that of a fully stabilized and pure zr02. Thus partially
stabilized zirconia can be used as thermal barrier coating in both AI-6061 and cast iron
engine cylinders. In the present work, commercially available two materials viz.,
alumina (Metco 105SFP) and ZrO225CeO2 (Metco 205 NS) are selected as top coat
materials. The first coating system of AI-606 I and cast iron consists of alumina as a top
coat and second systems consists ZrO225CeO2 as top coat. The top coat thickness in all
the coating systems is varied as 100 ,200 and 300.
The performance of TBC coating system depends upon top layer morphology as
well as the coating technique. A manifest of this is seen when TBC top layers are
deposited using Atmospheric Plasma Spray ( APS) or Electron Beam-Physical Vapour
Deposition (EBPVD)Techniques. Coatings produced by APS have a thermal
conductivity in the range of 0.8-1.0 W/mK at 25°C. This is significantly lower than the
1.5-1.9 W/mK reported for EBPVD coatings at 25°C and as a result, the APS coatings
provide superior thermal protection. However the spallation resistance of these layers
is less than that of EB-PVD TBC layers (S to 10 time's shorter spallation lifetimes).
This arises because of the superior in-plane compliance of EB-PVD coating. As a
result, EB-PVD TBC layers are preferred for aerospace gas turbine applications. But
thicker TBCs are applied using plasma spraying technique. Plasma spraying can be
used to deposit a wide range of ceramics and metals and any combinations of these. It
is possible to deposit alloys and mixed ceramics with components of widely differing
vapor pressures without significant changes in composition. Very homogenous
coatings can be formed that display no significant changes of composition with
thickness. High deposition rates are possible without extreme investments in capital
equipment. Plasma spraying can be carried out in virtually any environment, air,
encoded inter low and high-pressure environment (relative to ambient) or underwater.
Thus in the present investigation, atmospheric plasma spraying method is selected for
coating the materials on substrate.
LITERATURE SURVEY
2.1 Coating Techniques
The following block diagram gives the different techniques used for depositing metal, cermet
and ceramic non-metallic powders.

Fig: 2.1 Classifications of Coating Techniques


2.1.1 Chemical Vapor Deposition (CVD)
CVD method ensures dense coating deposits on the materials due to the
decomposition of relatively high pressure gases. Gaseous compounds of the materials to
be deposited are transported to the substrate surface to achieve deposition due to thermal
reaction process. Reaction byproducts are then exhausted out of the system. It is a very
versatile process to produce varieties of coatings, powders, fibers and monolithic parts. It
is possible to produce almost all types of metallic or non-metallic elements, including
carbon and silicon, as well as compounds such as carbides, nitrides, borides, oxides,
intermetallics and many others using this technique.
Specific advantage of this process is attributed to the reactants which are gases
with wide type of characteristics. CVD is not a line-of-sight process as is the case with
other plating/coating techniques. Coatings can be made on porous bodies, blind holes,
large L/D tubes, etc. The various advantages this process are versatility of the process,
high levels of purity and density of the coatings, deposition occurring below the melting
point of the deposits, economical operation to cite a few.

2.1. 2 Physical Vapor Deposition (PVD)


It is functionally, a vaporization coating technique, involving transfer of material
at an atomic level.
The process involves the following four stages.
Evaporation: The material to be deposited is bombarded by a high-energy source such
as beam of electrons or ions dislodging the atoms from the surface of the target before
vaporizing them.
Transport: The movement of vaporized atoms from the target to the substrate to be
coated.
Reaction: Coatings of metal oxides, nitrides, carbides new metal targets. The metal
atoms react with appropriate gases during the transportation stage.
Deposition: Coating build up on the substrate surface.
Fig: 2.2 PVD Process

2.1.3 Flame Spraying Process


Combustion flame is the heat source to melt the coating material, which may
either be in rod, wire or powder form. In case of the wire and rod systems, a feed
mechanism drives the stock material into the combustion chamber where the flame melts
and propels (due to the high flow rates of the gases) the particles as a spray deposit. It is
possible that the powder used carried by an additional gas (generally nitrogen) from a
hopper unit to the gun for combustion and deposition.
Fig: 2.3 Flame Spraying

2.1.4 Spray and Fuse Process

This process is a modification of the powder flame spraying process explained in


the previous section. The process is a combination of two steps, where the coating
material is firstly sprayed by a flame spray gun (or a plasma spray gun) and
immediately after spraying, fused by an oxy-acetylene torch, induction heating or heat
treatment in a furnace (which is generally held under a reducing atmosphere or in a
vacuum). The fusion temperature is high, often up to 1300 0C, but can produce thicker
coatings up to 2000 μm with a high hardness The advantages of this process is the
production of fully dense microstructure and high bond strength between the coating and
the substrate. The major disadvantage is due to the high temperatures experienced by
the substrate during the fusion step.

2.1.5 HVOF Thermal Spray Process


HVOF (High Velocity Oxy-Fuel) thermal spray process is another variant of
form of the flame spraying process. The coating material is in the powder form. The
process can be categorized as Detonation Gun (pulse) HVOF system and Continuous
Combustion HVOF system. The difference between the two systems is related to type of
fuel gases and cooling systems employed in the process. Further, in detonation gun
system, combustion is maintained by a timed spark which is used to detonate the particle
and gas mixtures.
(A) Detonation-Gun Spraying
The process consists of a gas mixture, generally a mixture of oxygen and acetylene,
which is ignited by a spark plug to ensure a controlled detonation (or explosion) wave
(which heats the individual particles to temperatures of 4500 0C) which would accelerate
the particles and subjects them at subsonic speeds of 800 mS-1. Fig. 2.4 shows the
schematic of a typical detonation-gun system. A uniform, closely packed, laminar type of
structure of a coating can be obtained from the process due to the high temperature and
kinetic energy of the particles, which would also ensure higher hardness, density and
bond strengths of the coatings in comparison with those of plasma spray coatings.
Coatings up to 0.5 mm thickness can be produced by multiple detonations, but high
sound levels of 150 decibels are also produced. Double walled sound-proofing is
essential and the process is controlled from outside this housing.

Fig: 2.4 TAFA TJ-4000 HVOF Detonation Gun-Schematic

(B) Diamond Jet HVOF Thermal Spraying is a flame deposition technique wherein
powder material is melted by the combustion of oxygen with a fuel gas and it is propelled
at a high velocity with the help of compressed air, towards surface to be coated. In the
combustion zone, the powder material enters the flame, where it becomes molten or
semi-molten, depending upon the melting temperature and the feed rate of the material.
The flame temperature for the HVOF process is about 2300 – 3000 0C. The molten or
semi-molten particles are then propelled out of the gun nozzle at supersonic velocities,
exceeding 1350 mS-1 towards the substrate or forming die.

Fig: 2.5 Diamond Jet Spray Gun-Schematic

In comparison with other thermal spraying techniques such as plasma spraying,


this process allows very low thermal residual stress, thus enabling the deposition of
higher thicknesses of coatings. The DJ HVOF system exhibits the highest bond strengths
and lowest porosity of all the other thermal spraying processes, due to the high kinetic
energy experienced by the impinging particles.

2.2 Plasma Spray Coating Technique


2.2.1 Process Characteristics
Plasma, often called as the fourth state of matter, consists of neutral atoms,
positive ions and free electrons. Plasma is generated when sufficient energy is transferred
to a gas, which is capable of ionizing it, thus making the electrons and ions to act
independently of one another. It has been estimated that 98 % of visible universe exists in
the form of plasma. Natural plasma occurs in earth as the aurora borealis and lighting.
Examples for common man made plasma include neon and fluorescent tubes and bulbs.
Thermal plasma is a state wherein energy levels of electrons, heavy particles and
ions are similar. Higher levels of ion transfer significantly enhances the kinetic energy of
the gas in comparison with that observed during electron collisions. Higher electron
temperature plasma though energetic, is found to be not enabling higher levels of energy
transfer which is attributable to their lower mass particles. Energy sources for the creation
of thermal plasma used in the thermal screen devices are usually electric arcs, DC or RF
discharges. Thermal plasma can also be generated using micro waves, gamma radiation
and electric arcs based on alternating current.
In plasma arc spraying process also known as plasma spraying process, the
thermal energy of an electric arc (40 kW or 80kW) together with a plasma forming gas,
which would be either nitrogen or argon, are utilized in melting and propelling of the
deposit material at high velocities (600 mS-1) onto a substrate. This process is capable of
generating very high temperature, exceeding 16,000 °C, which can be gainfully employed
in the deposition of materials with high melting points. The deposited material is
generally in a powder form and requires a carrier gas to feed it into the combustion
chamber. The process enables discharging high bond strengths of the coatings due to the
very high propulsion velocities of the impinging particles.
In a DC plasma arc process, gas heating is enough to generate core plasma
temperatures exceeding 20000 °C depending upon the properties of gas and its electrical
break down characteristics. Enthalpy of the gas is an indicator of its heating potential
while it is getting translated to plasma state.
The basic components of a DC plasma arc gun is shown in Fig. 2.6
It consists of an axially aligned cathode and an anode. Tungsten is used as the
cathode because of its high melting point and good thermionic emittance as well. The
thoriated tungsten tip is found to operate around its melting point due to high current
densities which locally heats tip of the cathode. The water cooled copper anode
constricts and spatially stabilizes the arc and accelerates the expanding heated gases.
Cathode relies on conduction and the high melting point of tungsten to survive the high
temperature of the arc since they are not directly water cooled. Direct current plasma arc
guns are intensely water cooled not only to prevent melting but also to minimize the
erosion of cathode and nozzle.
In working, plasma forming gases are introduced through the rear region of the gun.
They enter the arc chamber through a gas rim that imparts a spin or vortex to the gas
flow. The arc is stabilized at the cathode tip which in the low pressure region of the
vortex and rotates the arc attachment or arc route at the anode. Rotation of the anode arc
attachment minimizes its erosion. The heated gases expand radially and axially,
accelerating as they expand before exiting through the nozzle. Depending upon the
pressure ratio between the upstream arc region and the down stream nozzle exit of the
gun the gases either expand sub-sonically or super sonically. Many gun designs employ a
converging/diverging type of nozzle to achieve super sonic expansion which in turn
increases particle velocity.

Fig: 2.6 Plasma Spray Gun


2.2.2 Plasma Spraying Equipments
Plasma arc spray systems are made up of components similar to other thermal spray
systems.
Direct current plasma arc spray systems are the most complex and the most flexible
of all thermal spray processes. Plasma guns are designed for 144 to 720 MJ input power.
Water cooling is essential because of high temperature and enthalpies. Pressure of water
exceeding 1MPa is needed to suppress the localized film boiling in the gun which would
reduce the component life and coating contamination. This necessitates the use of high
pressure co-rings seals and passage ways inside the gun. Ceramic gas injectors and high
temperature insulators are required to separate the electrodes. The high power density of
DC plasma arc can produce relatively high erosion rates of the anode and the cathode.
Gun design is a significant factor in determining the component life. Designs that use a
closely coupled anode and cathode possess shorter life than those that employ wide
spacing and a flow nozzle. Operational procedures particularly start up and shut down
sequences shall significantly affect the electrode life. Mono atomic gases are also found
to extend the electrode life due to their lower enthalpy. Arc erosion of anode and erosion
of powder ports and powder feed tube are the factors to be considered while deciding
about the anode replacement. The cathode is generally replaced after effecting nozzle
changes about 2-5 times and is governed by its geometry and current density.
Powder ports contribute significantly to ensure consistency in coating process. Adjustable
and removable powder ports need to be monitored and controlled. Alignment tools
should be used to ensure precise and repeatable positioning when powder ports installed
replaced or adjusted.

2.2.3 Special Features of Plasma Spraying Technique


The following are some of the unique features of the plasma spraying process.
• The technique can be used to deposit a wide range of ceramics and metals and
their combinations as well.
• It is possible to deposit alloys and mixed ceramics with components of widely
differing vapor pressures without significant changes in composition.
• Homogenous coatings can be formed for any composition while maintaining
uniformity in their thickness.
• Fine microstructures with equiaxed grains and without any type of columnar defects
are the characteristics of this process.
• High deposition rates are possible without huge investments on capital equipment.
• The process can be carried out virtually in any environment such as air, encoded
inert low and high-pressure environments, or underwater.\

2.3 Plasma Sprayed Ceramic Coatings


Ceramic coatings can be readily formed employing a wide variety of techniques
(e.g. sputtering, electron-beam deposition). The technique being used since the middle of
previous century, to form metal alloys, ceramic and cermet coatings on a range of
metallic substrates. These types of coatings mostly greater than 50 µm in thickness are
used for varieties of engineering applications to realize enhances, wear/erosion and
corrosion resistance of thermal barriers; electrical magnetic components and so on.
Plasma spraying technique has been playing a significant role in depositing a
variety of ceramic materials on conventional metallic substrates. These coatings are
generally employed to realize enhances wear resistance of abradable seals as well as
thermal barriers, thus permitting hot sections of gas turbine engines to function at
increased operating temperatures in aircraft industries. Plasma sprayed refractory ceramic
coatings are also used in handling liquid metals and in electrically insulated metal
substrates in the automotive electronics industry.
A number of inter dependent parameters are found to describe the characteristics
of the plasma sprayed ceramic coating process. Some of them are gas type, pressure and
flow rate, spray distance to cite a few. The physical features of the feed stock powder
appear to influence the quality of the coating. Particle size, shape and its distribution, and
the level of chemical uniformity of the constituents in a mixed oxide are the parameters
but to be neglected in this analysis. Particle size influences the meltability whereas its
shape determines the extent of flowability of the powder into the flame.
The microstructure and phase distribution of plasma sprayed coatings are
dissimilar in composition with that of the substrate. Material properties of the coating
such as thermal diffusivity, mechanical strength in tension and shear and wear
characteristics are found to be different in comparison with that of bulk material.
2.4 Thermal Barrier Coatings for Internal Combustion Engines
Chrome plated cylinder liners were used in Internal Combustion (IC) Engines till
70s. Hard chromium was electroplated directly on to the bore of the aluminum cylinder.
Honda cars of late 70s exclusively used this process. Kawasaki employs a process referred to
as electro-fusion for the said purpose. Leading auto manufacturers such as Yamaha, Honda,
and KTM utilize a technique wherein the Nikasil material is applied directly on the aluminum
bore. On the liner Suzuki employs a boron composite material for the purpose. These
processes are found to enable the designers to reduce the clearance between the piston and
cylinder which results in enhanced power from the engine.
A Poeton Max Power, Wiscons [1] in is considered to be the leader in the
technologies related to engine cylinder plating and coatings. The company has devised a
system to coat cylinders, pistons, rings and combustion chambers of IC engines with a Nickel
composite loaded with ceramic particles. The process was first developed for its application
in aircraft industries but later on made its way into automotive environments.
Y.Miyairi [2] has investigated the performance and exhaust emission characteristics
of a thermally insulated single cylinder diesel engine. The cylinder head and piston crown are
thermally insulated with sintered silicon nitride (SSN) whereas the upper part of the cylinder
liner with Partially Stabilized Zirconia (PSZ). He has shown that volumetric efficiency of
engine with insulated cylinder head and liner is higher in comparison with the engine which
has an insulated piston cavity. It is also examined that the gas temperature in the cylinder
with insulated piston crown, cylinder head and cylinder liner is much higher than that of
other types of engines such as baseline engine, engine insulated with piston crown, engine
with insulated cylinder head and cylinder liner which is mainly due to formation of Nitrogen
Oxide in large amount. Local insulation of combustion chamber walls with ceramics has
resulted in improved engine performance with decreased volumetric efficiency. Insulation of
the piston cavity, cylinder head and cylinder liner upper part together is found to reduce the
emission of hydrocarbons under natural aspirated conditions at low speeds. On the other, a
reduction in Brake Specific Fuel Consumption (BSFC) is reported under both naturally
aspirated and turbo charged condition when the cylinder head and liner upper parts were
thermally insulated with ceramics. Further insulation of the piston cavity has contributed the
increased in BSFC partly due to the increase in the reciprocating mass.
Osawa [3] has conducted tests on coatings made on small aluminium bore of an air
cooled diesel engine. He has reported that coatings possessing high thermal insulation and
low friction characteristics perform best albeit with a 10% reduction in fuel consumption.

Morel [4] has analyzed that a significant part of the retained heat is directly converted
to positive work. He has also examined that a typical highway truck engine with a practical
zirconia coating able to achieve a 5% performance benefit over that of an engine cooled
baseline at rated conditions.

Wong [5] has considered different combinations of coatings with different thermal
characteristics and coating thicknesses to predict the pattern of fuel consumption in IC
engines. The simulation model developed by him considers the influence of transient heat
transfer into and out of the combustion chamber surface throughout the entire engine
operating cycle. The simulation also included an advanced liner friction model which
accounts for the effects of liner surface temperatures and lubricating oil viscosity. Results of
the analysis showed that all thermal barrier coating materials provided a performance benefit
that is strongly dependent on the coating thickness. Most coatings for the piston and head
face surfaces provided a maximum benefit at a coating thickness of 0.1mm. The predicted
maximum benefit in thermal performance is found to range from 1 to 2%. It is predicted that
a coating thickness of 0.5 mm in the liner would provide an optimum oil viscosity and a
reduced friction with a 5% increase in performance.

Dennis Assanis and Kevin Wiese [6] have carried out work on zirconia band TBC coated
on to the piston of diesel engine with a coating thickness of thickness of 0.5 mm and 1mm.
They have compared the performance and exhaust emission of coated piston engine with that
of base line piston engine. They have found that 0.5mm thick ceramic coated piston engine
has in comparison with that of the metal piston engine. On the other, the thermal efficiency of
1mm thick ceramic coated piston was only 4% higher than that of base line engine piston.
Due to more complete combustion in the insulated configuration, exhaust CO levels are
found to be 30 to 60% lower than that of base line engines. Similarly unburned hydrocarbon
levels were 35 to 40% lower than that of baseline engine. The NOx concentration is also
found to 10 to 30% lower than that of baseline engine due to the changes in the nature of
combustion. The variation in thermal efficiency and BSFC as a function of engine speed is
shown in Fig. 2.7.

Fig: 2.7 Thermal Efficiency and BSFC as a Function of Speed for Baseline and Ceramic Coated Engines [6]

Hideo Kawamura [7] has worked on Si3N4 monolithic ceramic coatings


which are applied to combustion chamber walls. A combustion chamber with thermos
structure made of sintered Si3N4 was used for this purpose. He has reported that the pre-
combustion chamber exhibits a good potential for LHR (Low Heat Rejection) engine due to
capability of combustion chamber wall temperature resulting in improved fuel consumption
and controlling of exhaust emission. The NOx emissions are also found to be low due the
presence of rich mixture in the pre-chamber in spite of the prevalent high temperature. It is
mainly due to the diffusion of air and fuel mixture near the cylinder wall which reduces the
temperature of the combustion gas. The fuel consumption in case of new type of energy
recovery system is found to be 180 g/kWh or less for 2 liters cylinder light duty diesel engine
with the proposed new combustion chamber. The LHR engine consisting of a thermos
structure having good heat insulation layer is found to eliminate the need for cooling system,
and found to improve the heat insulation ratio upto 75% or more.
Masaki Tanaka [8] has conducted experiments on Cr2O3+Mo coated piston and
cylinder liners and found that that the ceramic coated piston rings and cylinder liner
possesses superior wear resistant characteristics.
F.Rastegar [9] has worked on High Velocity Oxygen Fuel (HVOF) cermet coatings
employed in high horse power diesel engines. He has used Cr3C2/NiCr as the coating
material. He has found that the highly dense chrome carbide based HVOF coatings develop
crack resistance during their service life. The liner wear is found to be almost three times
higher in comparison with chrome under severe service conditions.
Roy Kamo [10] had carried out work on TBC for improving the engine performance
considering three engine configurations such as Metal base line builds, coated cylinder liner
builds and fully insulated builds wherein the cylinder liner, piston top and cylinder head faces
were coated with thin layers of thermal barrier ceramic composite materials. He has used
Zirconia slurry and chrome oxide for piston and head face coatings, Zirconia for cylinder
liner post densified with chrome oxide using plasma spraying technique with the thickness of
coatings as 0.127 mm and 0.508 mm for piston and liner respectively. He has reported that
the coated liner build exhibits about 1% improvement in performance over that of the metal
base line while the fully insulated configuration would produce about 2% loss in fuel
consumption. Heat rejection results indicate that the coated liner did not produce any
significant reductions while the fully insulated configuration produced a full load reduction
of 10% at 1400 rpm and no reduction at all with the increase in engine speed.
M.Vittal [11] had studied emission characteristics of indirect diesel engines with TBC
applied to their combustion chamber. The piston crown, cylinder head and valves were given
a thin thermal barrier coating (thickness 300 µ m). The parts were given a bond coat of
NiCoCrAly followed by top coat of Yttria stabilized Zirconia. He had reported that the
thermal barrier coatings minimize the CO emissions marginally, increase the exhaust
temperature, and decrease specific fuel consumption, decreases with the air fuel ratio with
reduced particulate emissions. Further, thermal analysis of the particulate matter had
demonstrated that the ceramic coated engine shifts the composition of the particulate matter
towards more dry soot and less volatile content (Fig. 2.8).
Fig: 2.8 Compositional Differences between Exhaust Particulates from the Baseline and Ceramic Coated
Engine Configurations

Hejwowski [12] has suggested that TBC with NiCrAl bond coat and Alumina –
Titania or yttria partially stabilized ZrO2 can be used to constitute a durable and efficient
thermal barrier coating on gasoline and diesel engine piston crowns. An optimum thickness
for TBC is slightly below 0.5 mm according to him. Further, he has also found that, that the
Specific Fuel Consumption (SFC) is lowered by 15 to 20 % with the use of coated piston
crown with 8% increase in power (Fig. 2.9). TBC with alumina –titania shows good
resistance to conditions prevailing in a gasoline engine combustion chamber. The fuel
consumption of a modified engine is found to reduce by 4.2 % at a speed of 1100 rpm, 11.7
% at 4000 rpm and 20.7% at 2500 rpm. Temperatures of cooling water and oil are slightly
higher in a modified engine.

Fig: 2.9 Variation of Brake Power and BSFC with Speed (1) Baseline Engine (2) Ceramic Coated Engine
Computer aided modeling and analysis carried out by Melvin Woods [13] has shown
that the conventional thermal spray coatings (slurry densified Zirconia) experience thermal
fatigue and does not provide the desired durability. He has also reported that a coating
thickness of 1.25 mm of zirconia can produce same insulation level that of 2.5 mm thick
coating by changing the piston material to titanium alloy.
Prasad and Ravindra [14] have carried out an investigation on heat transfer in an oil
cooled piston with and without ceramic insulation on crown face. A 2 mm thick oxide based
ceramic insulation material is coated on the piston crown of diesel engine. They have
predicted the isothermal distribution in the piston body and the heat flow rate through the
different cooling media at different engine loads for both the cases with and without
insulation coating and found that there is a reduction in heat loss of 12 to 30% for the piston
with insulation coating, assuming that both the heat transfer and temperature of the
combustion products remain unchanged.
Kulkarni and Jagdish. R [15] has indicated that ceramics, a family of heat resistant
super tough materials, contribute to energy savings. Cylinder head liners, valve train
components and exhaust ports with ceramic coatings are form to retain heat and eliminate the
need for cooling systems.
Poola and Ramesh. B [16] have characterized the TBCs that are applicable to SI
engines. Improving the fuel economy while reducing the exhaust emissions of a conventional
carbureted two stroke spark ignition engine was the main thrust of their investigations. An in
cylinder catalyst in the form of coating is found to provide a moderate thermal insulation in
the combustion chamber by deposition of thin ceramic material.
Ashok Kumar [17] has evaluated the performance of aluminum-titanate coated piston
crown of a CI engine. The insulating piston crown is found to increase the temperature of
cylinder wall which in turn contributes to reduction in volumetric efficiency which has a
significant impact on the power developed. The aluminum-titanate coating is found to
increase the temperature of combustion chamber, reducing the amount of lubrication and an
increase in friction. He has also proposed that the increase in the energy content of the
exhaust gases can be effectively utilized for turbo compounding.

2.5 Surface Texture of Plasma Sprayed Coatings


Earlier research activities on TBCs are most related to surface topography
charactertion at micrometric and nanometric scales to address the issues related to the
evaluation of quantitative parameters over profile and surface data points, which can be
acquired by means of roughness measurement instruments and/or atomic force
microscopes [18]. Quantitative parameters are typically designed to be representative of
mean properties of a surface topography; Ra, the arithmetic mean roughness of a profile,
or its 3D equivalent, Sa, one .he well known examples of such an approach. The wear
and friction performance of ceramics haw been studied by earlier investigators [23, 24].
It has been found that low wear rates can sometimes be obtained at low surface
roughness of materials, but with high friction coefficients which is in contrary with the
general view that the friction coefficients are low because of their high hardness.

2.6 Effect of Surface Roughness and Chemistry of Bond Coat on


Surface Roughness of Coatings
Effect of bond coat roughness by subjecting it to different treatments before
spraying of the top coat has been investigated [19]. It has been found that roughening of
the bond coat raises the fracture energy of the bond coat/top coat interface up to a certain
level of roughness beyond which a plateau is reached. Study of the crack paths followed
in different cases indicated that, while cracking occurs largely within the interface when
it is relatively smooth, it tends to occur within the top coat, close to the interface, at
higher roughness levels of the interface.
The effect of creep in the bond coat has also been studied . It is anticipated that
some systematic work on the role of bond coat creep could be undertaken using
proprietary Sulzer powders with high creep resistance, but no decision has yet been taken
on the provision of powder for this purpose.

The roughness [20] on the surface of work pieces increases with the thickness of
the inial oxide layer. It is maximum at the final removal of oxide layer. The bonding or
adhesive strentgth of the sprayed surface also is maximum in such a condition. Bonding
strength increases with the arithmetical mean height of the surface roughness due to the
thickness of the initial oxide layer. Further, when the arithmetical mean height of the
surface which is pre-treated by the cathode spots is the same, bonding strength is also
increases which are due to the narrow mean spacing of profile irregularities.

O. Sarikaya [21] has reported that the increase in the roughness of substrate
surface also increases the porosity and roughness of coatings. Higher hardness, lowest
porosity and the lowest coating roughness has been obtained by him at a substrate
roughness of 3.28IJm. Roughness of the coating also increases with enhanced thickness
of the coating. He has examined the coatings prepared at 500°C substrate temperature and
found that their microhardness increased at 28% level, where as porosity and coating
roughness decreased at 86 and 36% levels respectively. It has also been reported that the
thicker top coat is mechanically weakened with the increase in volume of pores and
magnitude of residual stresses.

Z. Liu [22] has reported that plasma sprayed Zr02 8%Y203 coatings on mild
steel substrate possess surface roughness of 4.51Jm in as-sprayed condition. The
surface quality is found to improve upon laser treatment. He has shown the roughness
of the coating increases with the increase in traverse speed of the laser beam, where as
the roughness decreases with the increase in the pulsing frequency. Further there is a
marginal increase in the roughness levels with the increase in the fluence. This is
attributed to simultaneous occurrence of ablation and thermal effects during the
sealing process of an excimer laser

C. Batista [23] has carried out an investigation on surface topography of


plasma sprayed and laser assisted zr02 thermal barrier coatings using triangulation
technique. He has found that there is a significant decrease in surface roughness of the
coatings upon laser treatment which is due to the increase in crack density which is a
function of both scanning speed and over lap of the beam.

R. Krishnan et.al. [24] Have examined the surface texture of as-sprayed and
CO2 infra red laser treated alumina air plasma sprayed coatings on copper substrate.
They have reported that the surface roughness of as-sprayed coatings is about 5µm
The surface roughness is found to 2.5 µm at 50 W powers and minimum at l.0 µm at
100 Wand increases to 1.3 µm at 150W power. The reduction in surface roughness of
laser treated coatings is mainly due to the transformation of γ-AL 2O3 to α-Al 2O3 and
densification through elimination of pores.

2.7 Porosity of Plasma Sprayed Coatings


Porosity is one of the disadvantages of plasma sprayed ceramic coatings. It
occurs in ceramic coatings due to i. Retrained gases with in the splats which introduce
spherical porosity ii. Early solidification or incomplete melting resulting n irregular
pores iii. Incomplete filling of interstices between previously deposited particles
resulting in fine planar pores which are observable between individual splats and at
locations of incomplete contact between lamellae.

Porosity can be classified into three distinctive groups such as; oblate, oriented
with high aspect ratios and volumetric pores. The oblate pores originate from incomplete
contact locations of adjacent splats due to insufficient wetting. These voids are generally
flat with high aspect ratios and their dominant orientation is parallel to the substrate.
Vertically oriented voids are present between horizontally (i.e. parallel to the substrate
surface) adjacent splats. The oblate pores mainly contribute to the inner surface area
porosity but they are only a small fraction of the total porosity . Due to their high aspect
ratios, these voids have a major effect on the elastic constants of the coatings since they
effectively decrease the crosssectional area of the coatings . Volumetric or globular pores
are fonned not only because of trapped gases but also due to incomplete filling of surface
pits and gaps left by solidified splats. It has been found that their contribution to the inner
surface area is small but they contribute up to 30% of the total porosity . The aspect ratio
of the pores is small and there is no preferred orientation for them. Globular pores are
found to decrease the Young's modulus of the coatings in small volume fraction .
Depending upon the spray conditions, some fraction of the pores can be surface-
connected. Network pore structure is found to reduce the elastic modulus. Factors such
as speed and temperature of the particles have a strong influence on all aspects of the
porosity .

Residual stress in coatings is an important issue since it enables the coating to get
debonded from the substrate . Residual stresses are introduced in the coatings during the
impact quenching of the molten particles causing a difference in the magnitudes of
coefficients of thermal expansion between the coating and the substrate. Pore structure
also contributes to the residual stresses since they are influenced by elastic modulus and .
The strains mainly determined by the thermal conditions during the deposition process.
Portinha [25] has carried out the characterization of plasma sprayed thermal
barrier coatings possessing porosity gradients while using Zr02+8%Y203 as top coat and
NiCoCrAlY bond coat on Nickel super alloy inconel 738 LC substrate. Samples are
initially annealed at 11000 C for 100hurs in air and are subjected to a thermal shock
heating at 10000 C and cooling in water, for 100 cycles. The as-sprayed coatings are
found to exhibit a porous and lamellar structure with porosity in the range of 12 to 15%.
Upon annealing in air, all coatings present a sintered structure with reduction in their
porosity levels. The porosity of sintered coatings is found to be in the range of 7 to 8%.
The sintering effects are found to increase the thermal conductivity, elastic modulus with
a loss in their strain tolerant behavior. Thermally shocked coated samples showed no
spallation and only exhibited some densification at the surface with the appearance of
small cracks which are perpendicular to the coating plane found to enhance the strain
accommodation. The porosity is found to increase from the bond coat interface towards
the surface of the top coat. In as-sprayed condition, the absolute porosity is found to vary
from 3 to 5% from interface to top coat surface and in annealed condition is from 1 to
2%. The reduction is due to the sintering effects at high temperature. Porosity is also
found to depend on deposition parameter. It increases with increase in the working
distance and decreases significantly at higher powers of the plasma gun. It is mainly due
to the reduced velocity of the melted particles in the first case when they reach to the
coating in growth and in the second case the particles have more velocity at higher
temperatures.

2.8 Bond strength of sprayed coatings


Bond strength (adhesive bonding) is one of the important properties of plasma
sprayed coatings. The main mechanism of adhesion can be described as mechanical
keying, physical, diffusive and chemical in natur. According to sobolav et al. [26]
Mechanical interlocking, due to rughness of the substrete surface, high pressures
developed on the droplet impact and soldification of the lower part of the splat is found
to be prominent mechanism for introducing the bond strength.
Compostion of the substrate and that of the bond coat as well are found to affect
the adhesion of alumina formed during the oxidation of bond. With the spalling of
alumina, zirconia layer is found to disintegrate contributing the failure of TECs.
Migration, segregation and stress generation are key issues of concern in the thermally
grown oxide regions. Migration of aluminum ions from bond coat to metal alloy substrate
occurs due to a concentration gradient. Similarly, migration from both the substrate and
bond coat into the thermally grown oxide region also happens. It appears that limited
yttrium ion migration to the alumina improves adhesion; however, contaminants in the
alumina generally lead to additional stresses, which decrease the adhesion during thermal
expansion process. High temperature diffusion of bulk yttria ions to the YSZ surface is
found to destabilize the top coat enabling the transformation of zirconia phase to
monoclinic resulting in an undesirable volume expansion which may contribute to
spallation. It has also been suggested by earlier researchers that both neutral and ionic
aluminum diffusion into the YSZ layer induces spallation . Diffusion controlled
migration in the TEC is found to promote h harmful phase transitions besides enhancing
the thermal stresses. Though a concentration gradient is found to enable the migration via
diffusion, the oxygen chemical potential gradient, occurring during oxidation is found to
supply another driving force. Studies have also shown that, this chemical potential
gradient is found to penetrate the top coat, bond coat and the metal substrate. It also
affects the oxygen reactive species in all these layers, including those which were
initially in the form of stable oxides, nitrides, carbides and sulphides . For example,
sulfur is found to segregate the interface, which can prove to be detrimental to the life of
TBC. The interfacial sulfur is found to increase the thickness of the oxidation layer,
decrease the adhesion of the oxide layer to the metal, besides enhancing the
transformation of metastable alumina to the alpha phase and hence pore formation at the
interface and also within the oxide layer. It also increases interfacial roughening and
formation of voids. The formation of voids is found to be problematic since they act as
stress concentration sites within the oxidation layer .

2.9 Parameters Affecting the Wear Rate of Plasma Spray Coatings


a) Effect of Intra-Lamellar Microcracking
The vertical cracks present in the plasma sprayed ceramic coatings playa
significant role in the formation of wear debris . The presence of pre-existing cracks
within the individual splats provides low energy pathways for the crack growth during
the abrasive processes including scratching and erosion.

b) Effect of Material Hardness

It is established that the wear resistance of a material is closely related to its micro
hardness, toughness, microstructure, defect content and the ratio of its hardness to the
hardness of the abrasive. Hardness has a large effect on the wear of materials through
the mechanisms of plastic deformation, while fracture toughness is a dominant factor in
wear involving brittle fracture. In case of plasma sprayed coatings, better correlations are
found between the hardness of the worn material and the modes of wear where plastic
deformation is a major mechanism. the relationship between hardness and wear is in the
form of W=k/Hn where W is the wear rate, k and n are constants and H is the hardness of
the surface. Exponent n is varied form 2.8 for adrasion and 1.6 foe small particle and low
angle erosion. Many studies have suggested that a high hardness is desirable for both
brittle and ductile materials, while a brittle material benefits father from a high
toughness there is no simple relationship between the abrasive wear resistance and
hardness of the coating. The abrasive wear mechanism of the coating IS found to be not
only .dependent on coating hardness and density, but also on particle size, type of
powder used, coating microstructure, as well as micro structural changes occurring
during the process of wear. The wear resistance of alumina coatings can be changed
significantly by selecting different powder process methods or by adding different
additives, even if the hardness is almost similar.

c) Effect of Fracture Toughness


Fracture mechanics concepts have been used to explain and predict the wear of
brittle materials[27]. The models are based on ideal brittle materials such as glasses,
single crystals such as sapphire with an assumption about the formation of lateral and
radial crack systems. However, when these models are applied to more typical
polycrystalline materials such as coarser grained alumina, where lateral cracking does
not always occur, the model predictions are found to be inaccurate. These models suffer
from the simplifying assumptions and are applicable to either ideal or brittle materials
and only one type of wear mechanism operates at a time viz. plastic deformation or
brittle fraction. However engineering materials are rarely ideal and it has been
demonstrated clearly that the wear of ceramic plasma sprayed coatings by hard particles
usually involves both plastic flow and brittle fracture occurring at the same time. The
effect of fracture toughness on the wear resistance of brittle materials is usually related
to hardness.

d) Effect of Load
Load or the contact stress is the most obvious and easily monitored parameter that
can affect wear. The magnitude of the normal load or the contact stress is important since
it increases both the area of contact and the depth below the surface at which the
maximum shear stress occur as well as the elastic or plastic deformation states.
e) Effect of Residual Stress
Wear behavior of APS and VPS coatings have been found to be dependent on the
levels of residual stress in the coatings. The resistance of materials to abrasive wear has
often been correlated with hardness and the levels of residual stress in thin films have
also been correlated with hardness, clearly indicating that the resistance of the coating to
deformation process must play an important role in the wear tests. The wear resistance of
plasma sprayed alumina increases with the increase in levels of compressive residual
stress in the coatings. To obtain the best wear performance it is therefore necessary to
maximize these stresses without compromising on the coating-substrate adhesion.

f) Effect of Microstructure and Grain Size


Wear is acomplex process and many factors are found to influence it. In certain
situations one or more factors will dominate the vwear process of the materials. In
addition to hardness and toughness, the microstruture of cermics especially grain size has
an ammense infuluence on its wear resistance the changes in microstruture are more
vsignificant in the nanostructure coatings than in the conventional coating. It is belived
that the phase transformation has an important effect on the process of wear.
I P.Psyllaki [28] has carried out investigations to examine the wear behavior of
APS and Detonation Gun (DG) sprayed alumina coatings on cast iron and Haste alloy X
substrates having a bond coat of 60Ilm thickness. He has conducted the wear test on both
APS and DG coatings (1ON load and sliding speed 0.1 m/s, 6mm dia. Ab03 ball,
1900HV) in which the friction coefficient at the contact of Al203 coating/sintered Ab03
ball is 0.78 and had remained constant until the coating was totally worn out. He has
reported that the wear has taken place mainly by adhesion mechanism and is enhanced by
the exfoliation of the surface splats. According to exfoliation mechanism, friction can
result in the imitation of crack between two splats of the same lamella. During cyclic
loading of the surface, the crack is propagating along the splat boundary, leading to its
final exfoliation from the worn surface.
In the case of APS Al2O3 coatings, the weak interfaces between the successive
lamellae are found to have failed, leading to the delamination of the coating which is
extended for long distance from the axis of loading. This degradation mechanism is
found to induce the rapid wear of the ceramic coating and hence increased wear rate. In
the DG Al2O3 coating, the stress field developed during sliding led to theinitiation of
cracks perpendicular to the coatings/substrate interface and their propagation through the
coating’s thickness.

Fig : 2.10 Exfoliation Mechanisms during Sliding Friction Testing


3. OBJECTIVES
Thermal barrier coatings(TBC) in internal combustion engine have advantages
such as improved thermal efficiency and combustion, reduction in weight by eliminating
cooling systems, etc. however, practical problems are faced in implementing these
coatings in internal combustion engines, A significant amount of research activities
shows the implementation of TBC to different parts of IC engine. At present TBCs are
applied to combustion components of IC engines, mainly for pistons crow, valves,
cylinder cover, and cylinder liner. However, the extended application of TBC to cylinder
liner has not been explored practically. Cylinder liner is one of the important components
of IC engine which severely under goes wear and tear due to reciprocating motion of
piston. At the same time, linear as subjected to thermal stresses caused by hot gasses of
combustion. TBC in the place of linear has to play very important role in minimizing
wear and tear, heat transfer from cylinder to surroundings. The problem presently faced
in implementing of TBC as engine cylinder is thermal mismatch which mainly occurs
due to improper adhesion and difference in thermal expansion coefficient between bond
coat and cylinder materials. TBC must also withstand wear and tear. There is a need to
overcome these problems for employing TBC to engine cylinder as a liner the present
work is undertaken with the following main objects.
1. To search a proper bond coatings and top coat materials based on
composition of substrates.
2. Selection of proper coatings techniques.
3. Preparation of plasma sprayed coated samples for various tests.
4. To check the microstructure and Topology of coating.
5. To check the surface texture parameter of coating.
6. To determine the bond strength of coating.
7. To determine micro hardness of coating.
8. To determine abrasive wear of coating .
9. To determine erosion wear of coating.
10. To establish the suitability of coatings for its application in internal
combustion Engine as a linear.
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