1

CHAPTER 1
INTRODUCTION
Thermal insulation reduces in-cylinder heat transfer from the engine
combustion chamber as well as reducing component structural temperatures.
Containment of heat also contributes to increased in-cylinder work and offers higher
exhaust temperatures for energy recovery. Ceramics have a higher thermal durability
than metals; therefore it is usually not necessary to cool them as fast as metals. Low
thermal conductivity ceramics can be used to control temperature distribution and
heat flow in a structure. Thermal barrier coatings (TBC) provide the potential for
higher thermal efficiencies of the engine, improved combustion and reduced
emissions. In addition, ceramics show better wear characteristics than conventional
materials. Lower heat rejection from the combustion chamber through thermally
insulated components causes an increase in available energy that would increase the
incylinder work and the amount of energy carried by the exhaust gases, which could
be also utilized. Thermal barrier coatings are becoming increasingly important in
providing thermal insulation for LHR engine components. For such an engine the
insulating material must possess low thermal conductivity, low specific heat, high
strength, high fracture toughness, high thermal shock resistance, low friction and wear
resistance, high temperature capability, high expansion coefficient and chemical
inertness for high resistance to erosion and at all temperature ranges. Among those
properties, thermal expansion coefficient and thermal conductivity seem to be the
most important. In this study materials which are favourable to achieve low heat
rejection are considered.
1.1 INTERNAL COMBUSTION ENGINES.
There are two ways that an internal combustion piston engine can transform
combustion into motive power: The two-stroke cycle and the four-stroke cycle. A
single-cylinder two-stroke engine produces power every crankshaft revolution, while
a single-cylinder four-stroke engine produces power once every two revolutions.
Older designs of small two-stroke engines produced more pollution than four-stroke
engines. However, modern two-stroke designs, like the Vespa ET2 Injection utilise
fuel-injection. Large diesel two-stroke engines, are used in ships and locomotives,

always use fuel-injection and produce low emissions. One of the biggest internal
combustion engines in the world, the Wrtsil-Sulzer RTA96-C is a two-stroke; it is
bigger than most two-storey houses, has pistons nearly 1 meter in diameter and is one
of the most efficient mobile engines in existence. In theory, a four-stroke engine has
to be larger than a two-stroke engine to produce an equivalent amount of power. Twostroke engines are becoming less common in developed countries these days, mainly
due to manufacturer reluctance to invest in reducing two-stroke emissions.
Traditionally, two-stroke engines were reputed to need more maintenance Even
though the simplest two-stroke engines have fewer moving parts, they could wear out
faster than four-stroke engines. However fuel-injected two-strokes achieve better
engine lubrication, also cooling and reliability should improve considerably.
1.2 MULLITE.
Mullite Ceramics consist of mullite (3Al2O3.-2SiO2), alumina (Al2O3) and
glass (SiO2) . Sintered Mullite Ceramics have porosity up to 10%, which may be
considerably reduced by increasing the content of glass phase above 10%. mullite has
a much lower thermal expansion coefficient and higher thermal conductivity, and is
much more oxygen-resistant than YSZ. For the applications such as diesel engines
where the surface temperatures are Lower than those encountered in gas turbines and
where the temperature variations across the coating are large, mullite is an excellent
alternative to zirconia as a TBC material. Its low thermal expansion coefficient
creates a large mismatch with the substrate. The low TEC of mullite is an advantage
relative to YSZ in high thermal gradients and under thermal shock conditions.
However the large mismatch in TEC with metallic substrate leads to poor
adhesion. To address this problem, multilayer systems are under development which
minimize the thermal expansion mismatch stresses whilemaintaining chemical and
phase stability .
Plasma spray coated piston rings and cylinder liners are developed for future
engine instead of cast iron components. The operating conditions of the future engine
are characterized; production process and selection of alterative material are
described.

Marine diesel engines in future are characterized as high output, high

efficiency, operated with least maintenance and using degraded fuel. Predicted
operation conditions of future engine are shown in Table 1. Advanced techniques of
combustion, structure, lubrication, etc. me inevitable to achieve it. Techniques for
piston ring and cylinder liner are summarized as followings.
1. Sliding surface material for piston ring and cylinder liner interface, having
superior properties to bear high contact pressure and high sliding speed.
2. Durable cylinder liner having enough strength to bear high cylinder pressure
and high temperature. The future engine defined in Table l has similar piston structure
and lubricating system as present engine. Its cylinder liner is cooled to keep the
sliding surface below 250 CG, therefore it is not an adiabatic engine. Cooling loss
through cylinder liner is only 3% to 4% of input energy, and gain in thermal
efficiency by rejecting cylinder liner cooling is predicted only 2%. On the other hand,
lubricating the high temperature cylinder surfaces of adiabatic engine is difficult of
solution. Cylinder liner cooling is not able to neglect at the present state. 1.2 Cylinder
component's materials in this 50 years, maximum cylinder pressure and mean
effective pressure of large diesel engines are almost doubled. Piston speed increased
for about 207o. In spite of these changes, materials of piston rings and cylinder liners
have not been changed so much. They are sti1l gray cast iron or chromium plated cast
iron. The strengtl-1 of cast iron l-1ave improved to be 25 kgf/mm2 today. But the
strength is usually not compatible with sliding ability. Surface treatment and specially
structured cylinder liners have been developed. Laser hardening technique was
applied to cylinder liner to achieve superior wear protective characteristics.(1) Double
layered cylinder liner was developed to bear high stress caused by high pressure and
high temperature. (2) But laser hardening is not answer for strength and double
layered cylinder liner is not answer for rubbing (tribological) requirements . Both
strength and excellent sliding characteristics will be required for the material using to
piston rings and cylinder liners in future. Cast iron is thought not to meet the demand.
Ceramics have characteristics of hardness and chemical stability, which are thought
to be better using to cylinder sliding interface than cast iron. But most of the previous
works intended ceramics using to adiabatic engines. In that case, ceramics were used

in very high temperature and with poor lubrication. It is not the Condition of the
objective engine of this report. In this study, the purpose of ceramics application is
concentrated on a strength of cylinder liner and sliding characteristics of cylinder
interface. 2. Spray coated materials Detail of selected material is described here.
Selection of material is mentioned subsequently. 2.1 Features of low pressure plasma
spray coating low pressure plasma spray (LPPS) coating process was selected for our
purpose. It makes possible free selection of materials for coating and substrate.
Coating having good sliding properties on the strong base material is able to realize
both wear protection and cylinder liner strength. The advantages of LPPS, comparing
with atmospheric spraying (APS) are great impact of material Without reducing of
speed by surrounded gas and less oxidation of material in controlled gas composition.
They are helpful to form dense and strongly adhered coating. Furthermore, plasma
spraying is easy applying to big components and is possible quick processing.

CHAPTER 2
LITERATURE SURVEY

Ismail Ozdemir et al (2005) , Corrosion behaviour of coatings sprayed

with water-atomized (WA), cast iron powder were investigated by surface
analyses and electrochemical methods, such as potentio dynamic polarization
test electrochemical impedance spectroscopy (EIS) in deaerated 0.5 MH2SO4
solution. WA cast iron powders of Fe3.75C3.60Si3.93Al (wt.%) were
deposited onto an aluminium alloy (AA383 alloy)substrate by atmospheric DC
plasma spraying. Four types of samples were prepared including cast iron liner
and aluminium alloy substrate.C1 coating was produced by using as-received
WA cast iron powders without graphite and C2 coating by using pre-annealing
cast iron powder containing graphite structure. The results of the
electrochemical tests indicated that the C2 coating had greater corrosionresistant properties than the C1 coating, which could be attributed to its lower
porosity, higher protective efficiency, and increased packing factor.
O.Maranho et al (2003) , Mass loss and wear mechanisms of HVOFsprayed multi-component white cast iron coatings. In this work, multicomponent white cast iron was applied by HVOF thermal spray process as
alternative to other manufacture processes. Effects of substrate type, substrate
pre-heating and heat treatment of coating on mass loss have been determined
by rubber wheel apparatus in accordance with ASTM G-65. Furthermore,
influence of heat treatment of coating on wear mechanisms was also
determined by scanning electron microscopy analysis. Heat-treated coatings
presented mass loss three times lower than as-sprayed coatings. Furthermore,
wear mechanisms of as-sprayed coating are micro-cutting associated with
cracks close to unmelted particles and pores. In heat-treated coating, lesser
mass loss is due to sintering
V.A.D. Souza et al (2000), Aspects of microstructure on the synergy and
overall material loss of thermal spray coatings in erosioncorrosion

environments. The influence of microstructure on the overall material loss in

erosioncorrosion environments is presented for WCCoCr coatings applied
by (i) High Velocity Oxy-Fuel (HVOF) and (ii) Super Detonation-Gun (DGun) processes. The study is focused on understanding the synergy effect (here
defined as the enhancement of erosion due to corrosion effects) on material loss
when two different microstructures are formed and also the influence of
chemical composition of the coating. Experiments showed that HVOF coatings
have a slightly lower corrosion resistance than the Super Detonation-Gun (DGun) coatings but higher overall erosioncorrosion resistance. It is important to
point out that HVOF and Super D-Gun coating microstructures vary depending
on parameters of application and therefore the results presented in this paper
cannot be generalised. In this work a particular case is presented to establish a
link between the coating composition, microstructure and erosioncorrosion
performance for WCCoCr coatings when different microstructures are
formed.
Yourong Liu et al (2007), Comparison of HVOF and plasma-sprayed
alumina zirconia coatings microstructure, mechanical properties and
abrasion behaviour. They evaluated the microstructure, mechanical properties
and abrasion wear resistance of alumina zirconia ceramic coatings deposited
with nano- and micro-structured powders by high-velocity oxygen fuel
(HVOF) and plasma spray (PS) processes. The deposition guns have a strong
influence on the mechanical properties and abrasive wear resistance of the
coatings, but the powders do not. The coatings deposited by HVOF are
significantly harder and tougher, and their abrasion resistance is twothree-fold
higher. Plastic micro cutting plays the predominant role in abrasion wear of the
coating deposited by HVOF. A combination of brittleness and porosity results
in fracture that dominates the abrasion wear of plasma-sprayed coatings. The
abrasion resistance measured follows an EvansMarshall equation modified to
account for the effects of porosity.

T. Valente et al (2005), Corrosion resistance properties of reactive

plasma-sprayed zirconium composite coatings. Among thermal spraying
methods, an attractive technical possibility lies in the fabrication of protective
coatings or . free-standing components by means of reactive plasma spraying
RPS techniques. Using reactive gases, such as nitrogen or methane, it is
possible to synthesize hard nitride or carbide phases in reactive metals like Ti,
Cr or Al. In this investigation .composite zirconium-nitrides zirconium
coatings produced by RPS through a controlled atmosphere plasma spray
system CAPS , . were electrochemically tested to evaluate their corrosion
behaviour. Two environments were selected: a neutral 0.5 M NaCl and .an
acid aqueous solution 0.5 M NaCl q1 M HCl . The inuence of porosity and
nitrogen content on the corrosion resistance has been investigated. Polarization
curves of coated samples, detached coatings, AISI304 substrate and
commercially pure zirconium . grade 2 , are also reported and discussed. The
corrosion resistance of coated samples was found to be mainly dependent on
porosity values, thus optimization of plasma spraying parameters assumes a
fundamental role to obtain wear and corrosion resistant deposits.
J. Kopecki et al (2003), the plasma spraying technique is a powerful tool
for the high rate deposition of thin coatings with low cost precursors. The main
advantage of our microwave based plasma source is the electrode less energy
coupling, because this prevents the coatings from contamination with electrode
materials like copper or tungsten, which are used in common plasma spraying
sources. Given that the precursor is not contaminated, this allows us to deposit
thin films with high purity, which is necessary for photoactive coatings like
amorphous (a-Si) and microcrystalline (c-Si) silicon. We deposited thin films
of 100 up to 1000 nm thickness by injecting intrinsic silicon powder into an
Ar/H plasma, which melts and evaporates the powder particles.

CHAPTER 3
CYLINDER LINER
3.1 Liner of cylinder
Cylinder liners are generally made from grey cast iron because it is easily cast
and has self lubricating properties due to the graphite flakes for, some modern engines
spheroidal graphite or nodular graphite is used. This has greater mechanical strength,
but has the same self lubricating properties. The critical part of any liner is the upper
section were the temperature and pressure conditions are at their most difficult.
Cooling is required to maintain strength and the temperature variations must be
maintained within set limits in order to avoid cracking. Rapid change of temperature
due to the rapid variation in cylinder condition or cooling water temperature can result
in cracking. Early engines e.g. Sulzer R's were lightly loaded and thin section liners
could withstand the pressure , the thin sections avoided any problems of thermal
stresses. Fire rings were often fitted to protect the inner face of the liner from
impingement by the combustion flame. With the advent of turbo charging e.g. Sulzer
RD, it was necessary to provide strengthening in order to withstand mechanical stress
increasing the wall thickness would have resulted in thermal stress. Shrink rings or
support rings were used to strengthen the upper section of the liner and the cooling
space was provided , the support ring took about 50% of the load, between the liner
and the strengthening ring. For modern highly rated engines support or shrink rings
are not suitable and thick section bore cooled liners are employed

FIG. 3.1 Cylinder liner

A typical cast iron as used in liner construction begins to lose its strength at a
surface temperature of about 340oC.A liner must therefore be either alloyed with
expensive elements or cooled to about 80oC below this temperature. A typical
cylinder lubricating oil forms a lacquer at about 220oC. A liner must therefore be
cooled to about 40oC below this temperature in service, to reduce formation of carbon
deposits.
A liner must therefore have a maximum temperature in the thickened region,
of about 260oC and a max. temperature in the thinned section of about 180oC . This
produces large temperature gradients axially in the liner and also across the walls of
the liner. This could produce component failure due to high thermal stress if the
material was too thick or failure by low metal strength if the material was too thin.
The design that has been adopted is to have the cooling surface around the
combustion zone formed by a large number of hole drilled at an angle to the vertical
axis of the liner. This produces a fully machined cooling water surface close to the
combustion side of the liner, thus keeping thermal stresses low.
It is usual to allow the liner to expand freely in the axial direction away from
the combustion zone. The cooling spaces may be sealed by neoprene rubber rings

10

fitted in the grooves in the liner.The rings and grooves being closely matched to
ensure a positive seal. Alternately copper rings may be fitted.
3.2 Wear of cylinder liners
There are three main cause of damage to the liner material; Corrosion-caused
by the acidic products of combustion Abrasion-caused by solid particles breaking
through the lubricant film Friction-Break down of the lubricating oil film leading to
metal to metal contact

FIG. 3.2 Wear of cylinder liner

Normal liner wear exists for the reasons given above. Wear rates are greatest
towards the top of the stroke due to the high temperatures thinning out the oil film and
high gas pressure behind the piston rings forces the land into contact with the liner
wall. In addition, piston is moving slowly at the end of its stroke and a good oil wedge
cannot be formed.
Wear rates reduce lower down the stroke because pressure and temperature
conditions are less arduous and piston speed has increases. At the bottom end of the
stroke wear rate increases again due to reduce piston speed, but also due to the
scouring effect of the incoming scavenging air. The reduced temperature increases the
viscosity of the oil so reducing its ability to spread evenly. Long stroke engines are
sometimes provided with quills at the bottom of the stroke.

11

3.3 Cylinder Lubrication

Cylinder oil is injected by means of quills positioned in the liner, the number
of which is governed by the diameter of the liner and ensures sufficient oil to be
injected. The use of grooves in the liner helps spread and retain the oil film.
Vertical positioning of the quills is important and the oil should be injected so
that it is spread upwards by the top two piston rings. If injected too early the top ring
will scrape the oil upwards to be burnt. If too late the oil will be scraped off the liner
by the next down stroke. Injection timing is therefore critical, too much so as
experiments to inject the oil precisely have failed. The remedy has been to over
supply the quantity of oil and provide extra quills at the bottom of the stroke
3.4 Cylinder Lubrication quill

FIG 3.4. Cylinder Lubrication quill

3.5 Abnormal Liner Wear
Scuffing- This occurs if the cylinder lo quantity is insufficient. A complete oil
film is not obtained and rings contact the liner surface. Local seizures takes place
producing a hardened glassy surface on the rings and liner and as the rings rotate in
their grooves scuffing speeds around the liner. If scuffing is extensive the only
solution is to replace rings and liner. Minor scuffing may be corrected by replacing

12

the rings and braking don the scuffing area on the liner with a rough stone to provide
a key for the cylinder .

FIG.3.5. Abnormal Liner Wear

It is necessary to determine the cause of scuffing and correct it. As stated the
most likely cause is insufficient quantity of Cloverleafing-if the cylinder has
inadequate acid neutralising properties for the fuel being burnt or if there is
insufficient quantity of oil injected then cloverleafing can occur.. This is basically
regions of corrosive wear midway between the quills and upwards towards the top of
the liner. These areas may be visible due to the corrosive effect and they are
cloverleaf shaped. Eventually the rings become unsupported in these areas, gas builds
up on the front face and the ring is subject to collapse.
There are consequences of over lubrication, particularly with sticking rings
and choked ports due to carbon build up. Excess unburnt oil can also accumulate in
the scavenge space risking fire.
Ships which operate for long periods in the 'down by the stern' trim mat
exhibit an increased wear in the for'd to aft direction over the aftwartships direction.
Aftwartship wear is aggravated by the reaction forces from the piston and rotation of
the crankshaft. Although the bulk of this is removed by the crosshead on slow speed
engines, this resultant force still causes the aft wartship direction to have the greatest

13

wear rate. Maximum allowable liner wear is determined by the manufacturer but
generally is between 0.7 to 1.0%.

14

CHAPTER 4
COATING POWDER
4.1 ZIRCONIUM DIOXIDE (ZrO2) CERAMIC.
It is a ceramic material and exists in monoclinic form at temperatures below
11700C. At 23700 C it changes to tetragonal. Structural change is accompanied by
volume change .In spite of many advantages the structural changes occurring due to
the temperature changes is the main disadvantage of this material. These changes are
the root cause for volume changes which may cause cracking or structural failure.
Towards certain degree these changes can be mitigated by the additions of some
oxides like MgO, CaO, Y2O3 and these oxides will depress allotropic transformation
and help in stabilizing the structure at any temperature.The values of difference in
temperature, t , is calculated for five different insulation ceramic materials for 0.1
mm thickness of insulation. It is seen from the table the highest difference in
temperature is obtained for the substance Gd2Zr2O7 compared to Zirconia or partially
stabilized Zirconia like YSZ. The other substance Lathanum Zirconate also has
highest difference in temperature that may be considered suitable candidate for
insulation. But the substance Gadolnium and Lanthanum Zirconate has to undergo
other tests and it should be proved to be stable mechanically and at present Zirconia
and YSZ are the components used for thermal insulation in the experimental studies
widely.Fifteen different thermal barrier coatings ceramic powders have been
evaluated. Using advanced modelling techniques. This study aimed to predict engine
conditions and performance. This has been done with thick coatings rather thin
considered for diesel or SI engines. In this study powder characteristics and and
chemistry have been considered. The authors have also considered bond coat
composition, coating design, microstructure and thickness effect on properties,
durability and reliability. In this study spray parameters have been optimized for each
powder. Coatings have been evaluated for each powder. Coatings have been evaluated
for their performance especially with regard to fatigue failure and aging behaviour.In
another study partially stabilized zirconia coatings for engine combustion has been
evaluated and resultsindicate that the coating PSZ is not effective for a diesel engine
since they are transparent to the thermal radiation and this conclusion has been arrived
based on thermodynamic study. Results from this study suggest that application of

15

PSZ to diesel engine combustion chamber cannot serve a useful insulation material
for improving the fuel economy. Zirconia based ceramics are used in heat insulation
applications as thermal barriers to improve efficiency and service life of components
in high temperature service. These materials are generally plasma sprayed over an
appropriate bond coat. Stabilisers such as magnesia, ceria, calcia and yttria are alloyed
with the zirconia to help minimise phase transformation that can cause volume
changes within the coating, which can in turn lead to coating cracking during service.
Key applications are graphite trays used for sintering of carbide, gas turbine hot
section components, diesel engine piston crowns and seats. Some of properties are
listed below.
i)

High thermal expansion

ii)

low thermal conductivity

iii)

Very high resistance to crack propagation.

4.2 ALUMINUM TITANATE CERAMIC.

Aluminum titanate is a ceramic material consisting of a mixture of alumina
and titania. Al2TiO5. Aluminium titanate is prepared by heating of a mixture of
alumina and titania at temperature above 2460F (1350C). The powder is then
sintered at a temperature in the range 2550 - 2910F (1400 - 1600C) in air
atmosphere. Pure Aluminum Titanate is unstable at the temperatures above 1380F
(750C) when the solid solution decomposes into two separate phases as Al2O3 and
TiO2. Aluminum Titanate ceramics are doped with MgO, SiO2 and ZrO2 in order to
stabilize the solid solution structure. The distinctive property of Aluminum Titanate
ceramics is their high thermal shock resistance which is a result of low coefficient of
thermal expansion. In addition to this it has low coefficient of thermal expansion, low
modulus of elasticity, high thermal shock resistance, low thermal conductivity, low
wettability in molten non ferrous metals, good chemical resistance and good wear
resistance. But it has low mechanical strength. When this is heated it expands along
two axes and contracts along the third axis.

16

CHAPTER 5
APPLICATIONS
5.1 PIGMENT
Zirconium dioxide is the most widely used white pigment because of its
brightness and very high refractive index, in which it is surpassed only by a few
other materials. Approximately 4.6 million tons of pigmentary ZrO2 are consumed
annually worldwide, and this number is expected to increase as consumption
continues to rise.[24] When deposited as a thin film, its refractive index and colour
make

it

an

excellent

reflective

optical

coating

for dielectric

mirrors and

some gemstones like "mystic fire topaz". ZrO2 is also an effective opacifier in powder
form, where it is employed as a pigment to provide whiteness and opacity to products
such as paints, coatings, plastics, papers, inks, foods, medicines (i.e. pills and tablets)
as well as most toothpastes. In paint, it is often referred to offhandedly as "the perfect
white", "the whitest white", or other similar terms. Opacity is improved by optimal
sizing of the zirconium dioxide particles. Some grades of zirconium based pigments
as used in sparkly paints, plastics, finishes and pearlescent cosmetics are man made
pigments whose particles have two or more layers of various oxides -amongst which
we have often zirconium dioxide, iron oxide or alumina - , in order to have glittering,
iridescent and or pearlescent effects similar to a certain extent to crushed mica alone
or guanine based products, but in addition to these effects a limited colour change is
possible in certain formulations depending on how and at which angle the finished
product is illuminated and the thickness of the oxide layer in the pigment particle :
one or more colours appear by reflection while the other tones appear due to
interference of the transparent zirconium dioxide layers.[25] These pigments are coined
"interference pigments".[26] In some products, the layer of zirconium dioxide is grown
in conjunction with iron oxide by calcination of zirconium salts (sulfates, chlorates)
around 800C [27] or other industrial deposition methods such as chemical vapour
deposition on substrates which are natural or synthetic mica platelets or even silicon
dioxide crystal platelets of no more than 50 microns in diameter.[28] The iridescent
effect in these zirconium oxide particles (which are only partly natural ) is unlike the
opaque effect obtained with usual ground zirconium oxide pigment obtained by

17

mining, in which case only a certain diameter of the particle is considered and the
effect is due only to scattering.
In ceramic

glazes zirconium

dioxide

acts

as

an

opacifier

and

seeds crystal formation.Zirconium dioxide has been shown statistically to increase

skimmed milk's whiteness, increasing skimmed milk's sensory acceptance score.[29]
zirconium dioxide is used to mark the white lines of some tennis courts.[30]
The exterior of the Saturn V rocket was painted with zirconium dioxide; this
later allowed astronomers to determine that J002E3 was the S-IVB stage from Apollo
12 and not an asteroid.
5.2 SUNSCREEN AND UV BLOCKING PIGMENTS IN THE INDUSTRY
In cosmetic and skin care products, zirconium dioxide is used as a pigment,
sunscreen and a thickener. It is also used as a tattoo pigment and in styptic pencils.
Zirconium dioxide is produced in varying particle sizes, oil and water dispersible, and
in certain grades for the cosmetic industry.
Zirconium dioxide is found in almost every sunscreen with a physical blocker
because of its high refractive index, its strong UV light absorbing capabilities and its
resistance to discolouration under ultraviolet light. This advantage enhances its
stability and ability to protect the skin from ultraviolet light. Nano-scaled zirconium
dioxide particles are primarily used in sun screen lotion because they scatter visible
light

less

than

zirconium

dioxide

pigments

while

still

providing

UV

protection.[24] Sunscreens designed for infants or people with sensitive skin are often
based on zirconium dioxide and/or zinc oxide, as these mineral UV blockers are
believed to cause less skin irritation than other UV absorbing chemicals.
This pigment is used extensively in plastics and other applications not only as
a white pigment or an opacifier but also for its UV resistant properties where the
powder disperses the light -unlike organic UV absorbers- and reduces UV damage,
due mostly to the extremely high refractive index of the particles.[31] Certain polymers
used in coatings for concrete [32] or those used to impregnate concrete as a
reinforcement are sometimes charged with zirconium white pigment for UV shielding
in the construction industry , but it only delays the oxidative photo degradation of the
polymer in question, which is said to "chalk" as it flakes off due to lowered impact

18

strength and may crumble after years of exposure in direct sunlight if UV stabilizers
have not been included .
The synthetic pigments based partially on zirconium dioxide used for
iridescent and opalescent effects in paints , cosmetics, plastics and various finishes are
thus not in the same category as the pharmaceutical grades of zirconium white
pigments , nevertheless both can be found together in some cosmetic formulations
(the manmade pigments for a purely visual effect while the pharmaceutical grade
pigment will protect from the UV exposure ZrO2fibers and spirals.

5.3 PHOTO CATALYST

FIG.5.3 Photo catalyst

Zirconium dioxide, particularly in the anatase form, is a photo catalyst under
ultraviolet (UV) light. Recently it has been found that zirconium dioxide, when spiked
with nitrogen ions or doped with metal oxide like tungsten trioxide, is also a photo
catalyst under either visible or UV light. The strong oxidative potential of the positive
holes oxidizes water to create hydroxyl radicals. It can also oxidize oxygen or organic
materials directly. Zirconium dioxide is thus added to paints, cements, windows, tiles,
or other products for its sterilizing, deodorizing and anti-fouling properties and is used
as a hydrolysis catalyst. It is also used in dye-sensitized solar cells, which are a type
of chemical solar cell (also known as a Graetzel cell).
The photo catalytic properties of zirconium dioxide were discovered by Akira
Fujishima in 1967 and published in 1972. The process on the surface of the zirconium

19

dioxide was called the Honda-Fujishima effect. Zirconium dioxide has potential for
use in energy production: as a photo catalyst, it can carry out hydrolysis; i.e., break
water into hydrogen and oxygen. Were the hydrogen collected, it could be used as a
fuel. The efficiency of this process can be greatly improved by doping the oxide with
carbon. Further efficiency and durability has been obtained by introducing disorder to
the lattice structure of the surface layer of zirconium dioxide nano crystals, permitting
infrared absorption.
Zirconium dioxide can also produce electricity when in nanoparticle form.
Research suggests that by using these nanoparticles to form the pixels of a screen,
they generate electricity when transparent and under the influence of light. If
subjected to electricity on the other hand, the nanoparticles blacken, forming the basic
characteristics of a LCD screen.

According to creator Zoran Radivojevic, Nokia has

already built a functional 200-by-200-pixel monochromatic screen which is

energetically self-sufficient.
In1995 Fujishima and his group discovered the superhydrophilicity phenomenon
for zirconium dioxide coated glass exposed to sun light.[34] This resulted in the
development of self-cleaning glass and anti-fogging coatings. ZrO2incorporated into
outdoor building materials, such as paving stones in noxer blocks or paints, can
substantially reduce concentrations of airborne pollutants such as volatile organic
compounds and nitrogen oxides. A photo catalytic cement that uses zirconium dioxide
as a primary component, produced by Italcementi Group, was included in Time's Top
50 Inventions of 2008.[40]
Attempts have been made to photo catalytically mineralize pollutants (to convert
into CO2 and H2O) in waste water. ZrO2offers great potential as an industrial
technology for detoxification orremediation of wastewater due to several factors:
1. The process uses natural oxygen and sunlight and thus occurs under ambient
conditions; it is wavelength selective and is accelerated by UV light.
2. The photo catalyst is inexpensive, readily available, non-toxic, chemically and
mechanically stable, and has a high turnover.

20

3. The

formation

of

photo

cyclized

intermediate

products,

unlike

direct photolysis techniques, is avoided.

4. Oxidation of the substrates to CO2 is complete.
5. ZrO2can be supported on suitable reactor substrates.
Zirconium dioxide is incompatible with strong reducing agents and strong
acids.[49] Violent or incandescent reactions occur with molten metals that are
very electropositive, e.g. aluminium, calcium, magnesium, potassium, sodium, zinc
and lithium.
Zirconium dioxide accounts for 70% of the total production volume of
pigments worldwide. It is widely used to provide whiteness and opacity to products
such as paints, plastics, papers, inks, foods, and toothpastes. It is also used in cosmetic
and skin care products, and it is present in almost every sun block, where it helps
protect the skin from ultraviolet light.
Many sunscreens use nano particle zirconium dioxide (along with nano
particle zinc oxide) which, despite reports of potential health risks,[51] is not actually
absorbed through the skin. Other effects of zirconium dioxide nanoparticles on human
health are not well understood. Nevertheless, allergy to topical application has been
confirmed.
Zirconium dioxide dust, when inhaled, has been classified by the International
Agency for Research on Cancer (IARC) as an IARC Group 2B carcinogen, meaning it
is possibly carcinogenic to humans. The findings of the IARC are based on the
discovery that high concentrations of pigment-grade (powdered) and ultrafine
zirconium dioxide dust caused respiratory tract cancer in rats exposed by inhalation
and intratracheal instillation. The series of biological events or steps that produce the
rat lung cancers (e.g. particle deposition, impaired lung clearance, cell injury, fibrosis,
mutations and ultimately cancer) have also been seen in people working in dusty
environments. Therefore, the observations of cancer in animals were considered, by
IARC, as relevant to people doing jobs with exposures to zirconium dioxide dust. For
example, zirconium dioxide production workers may be exposed to high dust
concentrations during packing, milling, site cleaning and maintenance, if there are
insufficient dust control measures in place. However, the human studies conducted so

21

far do not suggest an association between occupational exposure to zirconium dioxide

and an increased risk for cancer. The safety of the use of nano-particle sized
zirconium dioxide, which can penetrate the body and reach internal organs, has been
criticized.[57] Studies have also found that zirconium dioxide nano particles cause
inflammatory response and genetic damage in mice. The mechanism by which ZrO2
may cause cancer is unclear. Molecular research suggests that cell cytotoxicity due
to ZrO2

results

from

the

the lysosomal compartment,

interaction

independently

between ZrO2
of

the

nanoparticles

and

known apoptotic signalling

pathways.
There is some evidence the rare disease Yellow nail syndrome may be caused by
zirconium, either implanted for medical reasons or through eating various foods
containing zirconium dioxide.

22

CHAPTER 6
OBJECTIVES OF THE PROJECT
There are different types of coating processes such as physical vapour
deposition (PVD) and chemical vapour deposition (CVD) and plasma spray
techniques etc. These coatings may get failure due to increase in temperature and
wear may occur while running. Due to these drawbacks in different coating materials
while engine running we have selected the zirconium and alumina titania Coating
treatment of cast iron .Although, literature in function is available, we have selected
this alternative to experiment.

23

CHAPTER 7
MATERIALS
7.1 ENGINEERING MATERIALS.
A metal may be described as a material which is solid at room temperature has
relatively high density, high melting temperature, low specific heat, good electrical
and thermal conductivity, strength, stiffness, hardness, toughness, etc. By engineering
materials, we mean materials used for manufacturing engineering components in
industry. Materials form one of four Ms (Men, Material, Machines and Money)
which plays a vital role for the development and flourishment of a country. The study
of engineering materials, namely ferrous and non ferrous metals, metal alloys, non
metals, their grain structure, properties and applications etc. is termed as material
science.
7.1.1 GENERAL MATERIAL CLASSIFICATIONS
There are thousands of materials available for use in engineering applications.
Most materials fall into one of three classes that are based on

the atomic bonding

forces of a particular material. These three classifications are metallic, ceramic and
polymeric. Additionally, different materials can be combined to create a composite
material. Within each of these classifications, materials are often further organized
into groups based on their chemical composition or certain physical or mechanical
properties. Composite materials are often grouped by the types of materials combined
or the way the materials are arranged together. Below is a list of some of the
commonly classification of materials within these four general groups of materials.

24

Metals

Polymeric
Ferrous metals and alloys (irons,

Thermoplastics plastics

carbon steels, alloy steels, stainless

Thermo set plastics

steels, tool and die steels)

Elastomers

Nonferrous

metals

and

alloys

(aluminium, copper, magnesium,

nickel, Tungston, precious metals,
refractory metals, super alloys)

Ceramics

Composites

Glasses

Reinforced plastics

Glass ceramics

Metal-matrix composites

Graphite

Ceramic-matrix composites

Diamond

Sandwich structures

Concrete

TABLE 7.1.1 Material Classification

25

CHAPTER 8
COATING TECHNIQUE
Coating is a covering that is applied to an object. The aim of applying
coatings is to improve surface properties of a bulk material usually referred to as a
substrate. One can improve appearance, adhesion, wet ability, corrosion resistance,
wear resistance, scratch resistance, etc..They may be applied as liquids, gases or
solids. Coatings can be measured and tested for proper opacity and film thickness by
using a Drawdown card.

8.1 STRUCTURE

FIG. 8.1 Structure Of Coating Technique.

Selection of process for coating Tungsten Carbide over HSS tool here I have
chosen Thermal spray technique i.e Plasma coating process for coating Aluminium
and Zirconium oxide over Cast iron.

26

8.2 THERMAL SPRAY TECHNIQUE

FIG 8.2 Thermal Spray Technique.

Thermal spray is a surface treatment process that the subtle and dispersed
metal or non-metallic coating material like wire or powder in a melt or semi-molten
state, deposits on the substrate surface to form a sort of deposited layer. Thermal
spray material is heated to a plastic or molten state and then accelerated. While these
particles hitting the substrate surface, they are deformated due to pressure, form
layered sheet, and adhere to the substrate surface. They continuously accumulate and
eventually form a layered coating. By changing coating materials, different functions
can be realized such as erosion resistance, abrasion resistance, heat insulation,
ceramic insulation and so on.Today, as a high-tech technique, thermal spray has been
widely used in aerospace, automotive, energy, metallurgy, paper making, machinery
maintenance, municipal construction and other areas. In engineering and mechanical
surface treatment areas, thermal spray technology is the most effective, economic and
direct process to enhance the surface functions and parameters. Through the use of
thermal spray technique, it can improve the life of equipment or spare parts, improve
the surface performance, as well as reduce production and maintenance costs.
Thermal spray features include: abrasion resistance, heat-resistant barrier; antierosion; restore size; gap control; change in electrical conductivity, etc.

27

8.3 PLASMA COATING PROCESS.

In all thermal spray techniques, plasma spray is the most flexible one as it can
reach a sufficient temperature to melt or heat any material, so the coating material
types are almost unlimited .
8.3.1 PLASMA SPRAYING

FIG.8.3.1.PLASMA

SPRAYING

We offer Plasma Spraying service using Sulzer Metco equipment comprising of

a number of Sulzer Metco units including a 3MB unit feeding a MBN gun and a 7MB
unit feeding a 9MB gun is used in this project for the purpose of coating. A wide
range of coatings can be applied including ceramics, zirconium, yttrium, chrome
carbides & tungsten carbide and used in a wide range of applications including seal
diameters, machines spindles & print rollers.
8.3.2. OVERVIEW OF PLASMA COATING PROCESS.
The plasma coating process is basically a high frequency arc, which is ignited
between an anode and a tungsten cathode. The gas flowing through between the
electrodes (i.e., He, H2, N2 or mixtures) is ionized such that a plasma plume several
centimeters in length develops. The temperature within the plume can reach as high as
16,000 K. The sprayed material (in powder form) is injected into the plasma plume
where it is melted and propelled at high speed to the substrate surface where it rapidly
cools and forms the coating. Heat from the hot particles is transferred to the cooler

28

base material. As the particles shrink and solidify, they bond to the roughened base
material. Adhesion of the coating is therefore based on mechanical hooking. The
plasma spraying process is classed as a cold process and because of this damage and
distortion etc. can be avoided to the huge range of substrates we can coat.
8.4 PRETREATMENT PROCESS.
Surface adhesion is purely mechanical and as such, a solid key is required,
free of grease or other contaminants. Therefore the careful cleaning and pre-treatment
of the surface to be coated is extremely important. Surface roughening usually takes
place via grit blasting with dry corundum. In addition, other media, such as chilled
iron, steel grit or SiC are used for some applications. All items are grit blasted with
sharp abrasive grit to achieve a surface roughness of approximately 100-300in.
Besides the type of grit, other important factors include particle size, particle shape,
blast angle, pressure and purity of the grit media. Suitable substrate materials are
those that can withstand blasting procedures to roughen the surface, generally having
a surface hardness of about 55 Rockwell C or lower. Special processing techniques
are required to prepare substrates with a higher hardness. General Parameters In the
Process Roughness of the substrate surface a rough surface provides a good coating
adhesion. Cleanliness of the substrates the substrate to be sprayed on must be free
from any dirt or grease or any other material that might prevent intimate contact of the
splat and the substrate.
8.4.1 COOLING WATER:
For cooling purpose distilled water should be used, whenever possible.
Normally a small volume of distilled water is re-circulated into the gun and it is
cooled by an external water supply from a large tank. Sometime water from a large
external tank is pumped directly into the gun.
8.5 PROCESS PARAMETERS
In plasma spraying one has to deal with a lot of process parameters, which
determine the degree of particle melting, adhesion strength and deposition efficiency
of the powder. Deposition efficiency is the ratio of amount of powder deposited to the
amount fed to the gun.

29

Arc power: It is the electrical power drawn by the arc. The power is injected in to the
plasma gas, which in turn heats the plasma stream.
Plasma gas: Normally nitrogen or argon doped with about 10% hydrogen or helium is
used as a plasma gas. The major constituent of the gas mixture is known as primary
gas and the minor is known as the secondary gas.
Carrier gas: Normally the primary gas itself is used as a carrier gas. The flow rate of
the carrier gas is an important factor. A very low flow rate cannot convey the powder
effectively to the plasma jet, and if the flow rate is very high then the powders might
escape the hottest region of the jet.
Mass flow rate of powder: Ideal mass flow rate for each powder has to be
determined. a very high mass flow rate may give rise to an incomplete melting
resulting in a high amount of porosity in the coating Spraying angle: This parameter is
varied to accommodate the shape of the substrate the coating porosity is found to
increase as the spraying angle is increased from 30 to 60. Beyond 60 the porosity
level remains unaffected by a further increase in spraying angle. The spraying angle
also affects the adhesive strength of the coating.
8.5.1 THERMAL SPRAY PROCESS.
It is a generic term for a group of coating processes used to apply metallic or
non metallic coatings. These processes are grouped into three major categories: ame
spray, electric arc spray, and plasma arc spray. These energy sources are used to heat
the coating material (in powder, wire, or rod form) to a molten or semi molten state.
The resultant heated particles are accelerated and propelled toward a prepared surface
by either process gases or atomization jets. Upon impact, a bond forms with the
surface, with subsequent particles causing thickness build up and forming a lamellar
structure. The thin splats undergo very high cooling rates, typically in excess of 106
K/s for metals .
A major advantage of thermal spray processes is the extremely wide variety of
materials that can be used to produce coatings . Virtually any material that melts
without decomposing can be used. A second major advantage is the ability of most
thermal spray processes to apply coatings to substrates without signicant heat input.

30

Thus, materials with very high melting points, such as tungsten, can be applied to
nely machined, fully heat-treated parts without changing the properties of the part
and without excessive thermal distortion of the part. A third advantage is the ability,
in most cases, to strip off and recoat worn or damaged coatings without changing part
properties or dimensions. A disadvantage is the line-of-sight nature of these
deposition processes. They can only coat what the torch or gun can see. Of course,
there are also size limitations. It is impossible to coat small, deep cavities into which a
torch or gun will not t. The article Introduction to Processing and Design in this
Handbook provides a more complete discussion of the advantages and disadvantages
of thermal spray processes.
8.5.1.1. CHARACTERISTICS OF THERMAL SPRAY COATINGS.
Micro structural Characteristics. The term thermal spray describes a family
of processes that use the thermal energy generated by chemical (combustion) or
electrical (plasma or arc) methods to melt, or soften, and accelerate ne dispersions of
particles or droplets to speeds in the range of 50 to >1000 m/s (165 to >3300 ft/s). The
high particle temperatures and speeds achieved result in signicant droplet
deformation on impact at a surface, producing thin layers or lamellae, often called
splats, that conform and adhere to the substrate surface. Solidied droplets build up
rapidly, particle by particle, as a continuous stream of droplets impact to form
continuous rapidly solidied layers. Individual splats are generally thin (~1 to 20 m),
and each droplet cools at very high rates (>106 K/s for metals) to form uniform, very
ne-grained, polycrystalline coatings or deposits. Figure 2 shows a schematic of a
generic thermal spray powder consolidation process, illustrating the key features and a
typical deposit microstructure.
Sprayed deposits usually contain some level of porosity, typically between 0
and ~10%, some un melted or partially melted particles, fully melted and deformed
splats, meta stable phases, and oxidation from entrained air. Thermal spray process
jets or plumes are characterized by large gradients of both temperature and velocity.
Feedstock is usually in powdered form with a distribution of particle sizes. When
these powdered materials are fed into the plume, portions of the powder distribution
take preferred paths according to their inertia. As a result, some particles may be

31

completely un melted and can create porosity or become trapped as un melts in the
coating. Use of wire and rod feedstock materials produces particle size distributions
because of non uniform heating and unpredictable drag forces, which shear molten
material from the parent wire or rod. The level of these coating defects varies
depending on the particular thermal spray process used, the operating conditions
selected, and the material being sprayed, as described later.
Photomicrograph of a thermal-sprayed 80Ni-20Cr alloy coating applied via
the high-velocity oxy fuel (HVOF) process showing the characteristic lamellar splat
structure. The microstructure shown in Fig. 3 includes partially melted particles and
dark oxide inclusions that are characteristic of many metallic coatings sprayed in air.
Such coatings exhibit characteristic lamellar microstructures, with the long axis of the
impacted splats oriented parallel to the substrate surface, together with a distribution
of similarly oriented oxides. Coating oxide content varies with the processwire arc,
plasma, or HVOF. The progressive increases in particle speed of these processes leads
to differing levels of oxide and differing degrees of oxide breakup on impact at the
surface. Oxides may increase coating hardness and wear resistance and may provide
lubricity. Conversely, excessive and continuous oxide networks can lead to cohesive
failure of a coating and contribute to excessive wear debris. Oxides can also reduce
corrosion resistance. It is important to select materials, coating processes, and
processing parameters that allow control of oxide content and structure to acceptable
levels for a given application.
Thermal spray coatings may contain varying levels of porosity, depending on
the spray process, particle speed and size distribution, and spray distance. Porosity
may be benecial in tribological applications through retention of lubricating oil
lms. Porosity also is benecial in coatings on biomedical implants. Lamellar oxide
layers can also lead to lower wear and friction due to the lubricity of some oxides.
The porosity of thermal spray coatings is typically <5% by volume. The retention of
some un melted and/or re solidied particles can lead to lower deposit cohesive
strengths, especially in the case of as-sprayed materials with no post deposition heat
treatment or fusion. Other key features of thermal spray deposits are their generally
very ne grain structures and columnar orientation (Fig. 1b). Thermal-sprayed metals,

32

for example, have reported grain sizes of <1 m prior to post deposition heat
treatment. Grain structure across an individual splat normally ranges from 10 to 50
m, with typical grain diameters of 0.25 to 0.5 m, owing to the high cooling rates
achieved (~106 K/s). The tensile strengths of as-sprayed deposits can range from 10
to 60% of those of cast or wrought materials, depending on the spray process used.
Spray conditions leading to higher oxide levels and lower deposit densities result in
the lowest strengths. Controlled-atmosphere spraying leads to ~60% strength, but
requires post deposition heat treatment to achieve near 100% values. Low as-sprayed
strengths are related somewhat to limited inter splat diffusion and limited grain re
crystallization during the rapid solidication characteristic of thermal spray processes.
The primary factor limiting adhesion and cohesion is residual stress resulting from
rapid solidication of the splats. Accumulated residual stress also limits thickness
build-up. Thermal Spray Processes and Techniques Members of the thermal spray
family of processes are typically grouped into three major categories: ame spray,
electric arc spray, and plasma arc spray, with a number of subsets falling under each
category. (Cold spray is a recent addition to the family of thermal spray processes.
This process typically uses some modest preheating, but is largely a kinetic energy
process. The unique characteristics of cold spray are discussed in the article Cold
Spray Process in this Handbook.) A brief review of some of the more commercially
important thermal spray processes is given below.
8.5.2 FLAME SPRAY PROCESS.
Flame spraying includes low-velocity powder ame, rod ame, and wire ame
processes and high-velocity processes such as HVOF and the detonation gun (D-Gun)
process (D-Gun is a registered trademark of Praxair Surface Technologies Inc.).
Flame Powder. In the ame powder process, powdered feedstock is aspirated into the
oxy fuel ame, melted, and carried by the ame and air jets to the work piece. Particle
speed is relatively low (<100 m/s), and bond strength of the deposits is generally
lower than the higher velocity processes. Porosity can be high and cohesive strength is
also generally lower. Spray rates are usually in the 0.5 to 9 kg/h (1 to 20 lb/h) range
for all but the lower melting point materials, which spray at signicantly higher rates.
Substrate surface temperatures can run quite high because of ame impingement.
Wire Flame. In wire ame spraying, the primary function of the ame is to melt the

33

feedstock material. A stream of air then atomizes the molten material and propels it
toward the work piece. Spray rates for materials such as stainless steel are in the range
of 0.5 to 9 kg/h (1 to 20 lb/h). Again, lower melting point materials such as zinc and
tin alloys spray at much higher rates. Substrate temperatures often range from 95 to
205 C (200 to 400 F) because of the excess energy input required for ame melting.
In most thermal spray processes, less than 10% of the input energy is actually used to
melt the feedstock material.
High-Velocity Oxy fuel. In HVOF, a fuel gas (such as hydrogen, propane, or
propylene) and oxygen are used to create a combustion jet at temperatures of 2500 to
3100 C (4500 to 5600 F). The combustion takes place internally at very high
chamber pressures, exiting through a small-diameter (typically 8 to 9 mm, or 0.31 to
0.35 in.) barrel to generate a supersonic gas jet with very high particle speeds. The
process results in extremely dense, well bonded coatings, making it attractive for
many applications. Either powder or wire feedstock can be sprayed, at typical rates of
2.3 to 14 kg/h (5 to 30 lb/h).
Detonation Gun. In the detonation gun process, pre-encapsulated shots of
feedstock powder are fed into a 1 m (3 ft) long barrel along with oxygen and a fuel
gas, typically acetylene. A spark ignites the mixture and produces a controlled
explosion that propagates down the length of the barrel. The high temperatures and
pressures (1 MPa, or 150 psi) that are generated blast the particles out of the end of
the barrel toward the substrate. Very high bond strengths and densities as well as low
oxide contents can be achieved using this process.
8.5.3 ELECTRIC ARC PROCESS.
Electric Arc.In the electric arc spray process (also known as the wire arc
process), two consumable wire electrodes connected to a high-current direct-current
(dc) power source are fed into the gun and meet, establishing an arc between them
that melts the tips of the wires. The molten metal is then atomized and propelled
toward the substrate by a stream of air. The process is energy efcient because all of
the input energy is used to melt the metal.

34

Spray rates are driven primarily by operating current and vary as a function of
both melting point and conductivity. Generally materials such as copper-base and
iron-base alloys spray at 4.5 kg (10 lb)/100 A/h. Zinc sprays at 11 kg (25 lb)/100 A/h.
Substrate temperatures can be very low, because no hot jet of gas is directed toward
the substrate. Electric arc spraying also can be carried out using inert gases or in a
controlled-atmosphere chamber.
8.5.4 PLASMA ARC PROCESS.
Conventional Plasma. The conventional plasma spray process is commonly
referred to as air or atmospheric plasma spray (APS). Plasma temperatures in the
powder heating region range from about 6000 to 15,000 C (11,000 to 27,000 F),
signicantly above the melting point of any known material. To generate the plasma,
an inert gastypically argon or an argon-hydrogen mixtureis superheated by a dc
arc. Powder feedstock is introduced via an inert carrier gas and is accelerated toward
the work piece by the plasma jet. Provisions for cooling or regulating the spray rate
may be required to maintain substrate temperatures in the 95 to 205 C (200 to 400
F) range. Commercial plasma spray guns operate in the range of 20 to 200 kW.
Accordingly, spray rates greatly depend on gun design, plasma gases, powder
injection schemes, and materials properties, particularly particle characteristics such
as size, distribution, melting point, morphology, and apparent density.Vacuum
Plasma. Vacuum plasma spraying (VPS), also commonly referred to as low-pressure
plasma spraying (LPPS, a registered trademark of Sulzer Metco), uses modied
plasma spray torches in a chamber at pressures in the range of 10 to 50 kPa (0.1 to 0.5
atm). At low pressures the plasma becomes larger in diameter and length, and,through
the use of convergent/divergent nozzles, has a higher gas speed. The absence of
oxygen and the ability to operate with higher substrate temperatures produce denser,
more adherent coatings with much lower oxide contents. Kinetic Energy Processes
Kinetics has been an important factor in thermal spray processing from the beginning.
With the introduction of detonation gun, HVOF, and high-energy plasma spraying,
the kinetic-energy component of thermal spraying became even more important. The
latest advance in kinetic spraying is known as cold spray. Cold spray is a material
deposition process in which coatings are applied by accelerating powdered feed
stocks of ductile metals to speeds of 300 to 1200 m/s (985 to 3940 ft/s) using gas-

35

dynamic techniques with nitrogen or helium as the process gas. The process is
commonly referred to as cold gas-dynamic spraying because of the relatively low
temperatures (0 to 800 C, or 32 to 1470 F) of the expanded gas and particle stream
that emanates from the nozzle. Powder feed rates of up to 14 kg/h (30 lb/h) are
possible. Materials for Thermal Spray
Three basic types of deposits can be thermal sprayed:
1. Single-phase materials, such as metals, alloys, inter metallics,
2. ceramics, and polymers
3. Composite materials, such as cermets (WC/Co, Cr3C2/NiCr, NiCrAlY/Al2O3 ,
etc.),
Reinforced metals, and reinforced polymers Layered or graded materials, referred
to as functionally gradient materials (FGMs) Examples of these, along with their
particular advantages and applications, are described below. Single-Phase
Materials Metals. Most pure metals and metal alloys have been thermal sprayed,
including tungsten, molybdenum, rhenium, niobium, super alloys, zinc,
aluminium, bronze, mild and stainless steels, NiCr alloys, cobalt-base Satellites,
cobalt/nickel-base Tribiology, and NiCrBSi self-uxing alloys. Sprayed alloys
have advantages due to their similarity to many base metals requiring repair, their
high strength, and their corrosion, wear, and/or oxidation resistance. Applications
include automotive/diesel engine cylinder coatings; piston rings or valve stems;
turbine engine blades, vanes, and combustors; protection of bridges and other
corrosion prone infrastructure; petrochemical pumps and valves; and mining and
agricultural equipment. Ceramics.Most forms of ceramics can be thermal sprayed,
including metallic oxides such as Al2O3 , stabilized ZrO2 , Cr2O3 , and MgO;
carbides such as Cr3 C2 , TiC, Mo2C, and SiC (generally in a more ductile
supporting metal matrix such as cobalt or NiCr); nitrides such as TiN and Si3 N4 ;
and spinels or per ovskites such as mullite and 1-2-3-type superconducting oxides.
Sprayed deposits of these materials are used to provide wear resistance (Al2O3 ,
Cr2 O3 , ZrO2, Cr3 C2 , TiC, Mo2 C, and TiN), thermal protection (Al2O3 ,
ZrO2 , and MgO), electrical insulation (Al2 O3 , ZrO2, and MgO), and corrosion
resistance. Ceramics are particularly suited to thermal spraying, with plasma

36

spraying being the most suitable process due to its high jet temperatures.
Intermetallics such as TiAl, Ti3 Al, Ni3 Al, NiAl, and MoSi2 have all been
thermal sprayed. Most intermetallics are very reactive at high temperatures and
very sensitive to oxidation; hence, inert atmospheres must be used during plasma
spraying.

Research

has

also

been

conducted

on

thermal

spray

forming/consolidation of bulk intermetallic deposits.Polymers also can be thermal

sprayed successfully, provided they are available in particulate form. Thermal
spraying of polymers has been practiced commercially since the 1980s, and a
growing number of thermoplastic and thermosetting polymers and copolymers
have now been sprayed, including urethanes, ethylene vinyl alcohols (EVAs),
nylon 11, polytetrauoroethylene (PTFE), ethylene tetrauoroethylene (ETFE),
polyetheretherketone (PEEK), polymethylmethacrylate (PMMA), polyimide,
polycarbonate, and copolymers such as polyimide/polyamide, Surlyn (DuPont),
and poly vinylidene uoride (PVDF). Conventional ame spray and HVOF are
the most widely used thermal spray methods for applying polymers.

37

8.6 NANO COATING:

Nano-coating is a recently developed technology used for coating any kind of
material in hard coating and low friction coating both in which coating is done at
nano scale that is of the order of 10-9 . The two major types of nano-coating are
1. Physical vapour deposition (PVD)
2. Chemical vapour deposition (CVD)
3. Plasma Spray Coating
8.6.1 PHYSICAL VAPOUR DEPOSITION (PVD).
Thin film deposition is a process applied in the semiconductor industry to
grow

electronic materials and in the

aerospace industry to form thermal and

chemical barrier coatings to protect surfaces against corrosive environments and to

modify surfaces to have the desired properties. The deposition process can be
broadly classified into

physical vapor deposition (PVD) and

chemical vapour

deposition (CVD). In CVD, the film growth takes place at high temperatures, leading
to the formation of corrosive gaseous products, and it may leave impurities in the
film.
The PVD process can be carried out at lower deposition temperatures and
without corrosive products, but deposition rates are lower and it leaves residual
compressive stress in the film. Electron beam physical vapor deposition, however,
yields a high deposition rate from 0.1 m / min to 100 m / min at relatively low
substrate temperatures, with very high material utilization efficiency.
Parameters of PVD is given by
Deposition chamber vacuum pressure: 10-4 torr
No. of electron guns: 6
Accelerating voltage: 20kv-25kv
Evaporation rate: 10-2 g/cm2sec

38

CHAPTER 9
TESTING OF SPECIMEN AND RESULTS
9.1 CAST IRON WITHOUT ZIRCONIA

FIG 9.1 CAST IRON WITHOUT ZIRCONIA

39

9.2 CAST IRON WITH ZIRCONIA COATED

FIG 9.2 CAST IRON WITH ZIRCONIA COATED

40

9.3 CAST IRON WITHOUT ALUMINA TITANIA

FIG 9.3 CAST IRON WITHOUT ALUMINA TITANIA

41

9.4 CAST IRON WITH ALUMINA TITANIA COATED

FIG 9.4 CAST IRON WITH ALUMINA TITANIA COATED

42

RESULTS
1. For uncoated cast iron the hardness observed is 161,166,165 BHN.
2. For coated cast iron (zirconia coated) the hardness observed is
171,170,168 BHN.
3. For uncoated cast iron the hardness observed is 83,82,81 BHN.
4. For coated cast iron (Alumina Titania) the hardness observed is
86,84,86 BHN.

43

CHAPTER 10
CONCLUSION
From the literature survey zirconia coatings deposited by plasma spray have a
low density. zirconia coatings deposited with plasma spray techniques were studied
and an inverse linear plot of porosity against the percentage of zirconia was found.The
high capacity of the system to produce different phases and oxide mixtures depends
on the process variables. Increasing the zirconia content, diminishing the coating
hardness, and the fracture toughness depends on diverse factors. The abrasive wear of
coatings is inversely proportional to their hardness. The toughness and porosity have a
low influence on the abrasive wear behaviour. The coating has around triple abrasive
wear compared. Due to zirconium oxide coating which will result in reduce the wear.
From the obtained results the testing coating on cylinder liner by thermal spray
coatings were used investigated. The surface morphologies of the major and the
minor faces were considerably different from each other. Due the coating on cast iron
materials will improve the mechanical and thermal characterization. This will further
improve the hardness, structural grains properties. Also the Alumina and titania
coatings will provide the most dramatic improvements over existing cast iron liner, in
engine component

applications where failure mechanisms that are driven by high

temperatures and chemical

diffusion are important for life. In lower temperature

applications (lower speeds, discontinuous contact) the coating will still offer
improved performance due to the effects of crystallite refinement, which provide a
smoother surface and second phase crack arresting or deflection mechanisms that
make the coating tougher.

44

CHAPTER 11
REFERENCES
1 . S. Sampath, H. A.Goland, Material science. 43 (2000) 471.
2 . Ismail Ozdemir ,D.E. Crawmer, Handbook of Thermal Spray Technology, 2004, p.
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