CHAPTER 1

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INTRODUCTION AND LITERATURE REVIEW
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1.1 Surface engineering

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Surface engineering refers to the alterations made to the surface of engineering
components with the intention to achieve improvement in properties such as high
hardness, wear resistance, high-temperature resistance and corrosion resistance,
without making any significant changes to bulk characteristics of the structures.
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1.2 Various surface engineering techniques

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Commonly practiced surface engineering techniques are carburizing, nitriding,

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flame/induction hardening, physical vapour deposition (PVD), chemical vapour

deposition (CVD), galvanizing, diffusion coating, plasma spraying etc. However,
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these techniques suffer from several limitations, e.g., high processing time, high input
energy, high material consumption, poor precision, lack of flexibility, lack in scope
for automation and requirement of complex heat treatment cycles. Further, the
respective thermodynamic and kinetic constraints of restricted solid solubility limit
and slow solid state diffusivity impose additional limitations for these processes
(Dutta Majumdar, 2003). In contrast, the surface engineering techniques based on
applications of laser beam are free from many of these limitations.
 1.3 Laser assisted surface engineering

A laser beam with a high energy density is capable of intensely heating and melting
most of the refractory metals and ceramics and deposits them on metallic substrates to
produce coatings, which possess high hardness and excellent wear and corrosion
resistance. The unique feature of laser beam leads to localized melting and
solidification within a shallow depth and hence makes it possible to modify the
surface layer without affecting the bulk of the as-received sample (Singh and Dahotre,
2004).

1.3.1 Advantages of laser assisted surface engineering

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Laser assisted surface engineering offers several advantages over other surface
modification techniques. It is a fast process and can be applied readily on many
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engineering surfaces without the requirement of elaborate support systems (like ultra-
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high vacuum environment etc). High cooling rates (103-108 K/s) attainable in laser
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heating can give rise to extremely fine grain structures and improved mechanical
properties. By employing a high power laser, extremely high temperatures can be
attained to melt both the metal substrate and sometimes, added ceramic particles. This
may promote chemical reaction and wetting between ceramic and metal, and, as a
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result, may lead to a strongly bonded ceramic–metal interface after solidification

(Agarwal and Dahotre, 1999b). The surface structure can be tailored to the
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requirements of the application by varying process variables such as laser traverse

speed, power, beam size, and precursor composition (Kulka et al., 2003). Another
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advantage of laser assisted surface engineering comes from the fact that laser beam
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can be transported to any remote corner through fiber optics.

1.3.2 Classification of laser assisted surface engineering techniques

A wide range of laser assisted surface engineering techniques are available today.
Usually, laser surface modification involves utilizing the high power laser beam to
heat the surface of a material up to a required temperature, followed by rapid cooling
by heat conduction to the bulk. Depending on the maximum temperature attained
during thermal cycle, Vilar (1999) classified laser surface modification as shown in
Table 1.1

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 Chapter 1

Table 1.1: Laser assisted surface engineering techniques classified according to the
power density and interaction time

Process Power density Interaction

(W/mm2) time (S)
Laser transformation hardening 10 -102 10-2-1

Laser melting 102 -104 10-3-1

Laser Alloying 102 -104 10-3-1

Laser cladding 10-103 10-2-1

Laser CVD 1-104 10-1-102

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Laser PVD 106-107 10-8

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ar t Laser shock hardening (peening) 107 10-8
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However, depending on the procedure of adding coating materials, mode of bonding
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with substrate material, laser power density, interaction time, type of laser used, laser
assisted surface engineering techniques can be classified as follows (Chattopadhyay,
2004):
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Laser assisted
surface engineering
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Laser transformation Laser surface Laser shot Pulsed laser

hardening (T<TL) alloying peening deposition
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Laser melting (T>TL) Laser cladding Hybridized process

Pre-placed powder Particle injection Fusion of thermal Laser assisted vapor

spraying coatings deposition process

Pre-placed powder Powder feeding Wire feeding

Fig. 1.1: Various type of laser assisted surface engineering technique

3
 1.3.2.1 Laser transformation hardening

Laser transformation hardening is a fairly efficient way of improving the wear

resistance of steels. As a result of laser heating and subsequent rapid cooling, a
specific austenitic to martensitic structure formation occurs on the surface of the steel.
This structure is extremely resistant to seizing, abrasion, and loss of strength in
friction (Burakov and Fedosienko, 1983).

Transformation Laser beam

hardening

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T < TL

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Laser hardened zone
ar th Substrate

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Fig. 1.2: Laser transformation hardening

Laser transformation hardening of steels or cast irons has the same effect as induction
or flame hardening, in that the beam heats only the surface layer to form austenite,
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which then forms hard martensite upon auto-quenching. Fig. 1.2 shows the schematic
of laser transformation hardening process where T and TL represent the temperature
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rise due to laser irradiation and melting temperature of the material respectively. This
technique has found applications where only selected areas of components need to be
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treated, such as the surface of large piston rings. Sometimes laser surface melting has
been applied to grey or spheroidal graphite cast irons, where a thin surface layer is
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melted and then resolidified at a rapid rate to form hard white cast iron. This has been
widely used in the hardening of spheroidal graphite cast iron automotive cam shaft.

1.3.2.2 Laser melting

If a thin surface layer is melted by high intensity moving laser beam, it solidifies
rapidly due to mass effect of the bulk material to form non-equilibrium structures.
Fig. 1.3 shows the schematic of laser melting process where temperature rise due to
laser irradiation (T) should be higher than the melting temperature (TL) of the

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 Chapter 1

material. Depending on the cooling rate, which largely depends on the laser power,
interaction time of laser beam with material, and thermal properties of the material,
rapid solidification from liquid state can result in the formation of following three
types of metastable metals and alloys.

Laser melting Laser beam

T > TL

Laser melted zone

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Substrate

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ar th Fig. 1.3: laser melting

Supersaturated solid solutions: If the cooling rate is high enough to prevent

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nucleation and growth of a second phase, solute atoms are retained in the parent
lattice in excess of equilibrium concentration.

Non-equilibrium crystalline phases: Rapid quenching from liquid can lead to the
formation of a crystalline phase that does not exist under equilibrium conditions.
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Surface can be melted and rapidly cooled to produce a non-equilibrium high

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temperature structure in the melted area.

Amorphous phases: The crystallization process can be suppressed by more rapid

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quenching from melt, vapor or solution, provided certain kinetic and structural
conditions are satisfied. The resulting unstable phases are therefore in amorphous
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state.

1.3.2.3 Laser surface alloying

Laser surface alloying (LSA) is a laser assisted surface engineering technique that
involves melting of a pre-/co-deposited layer of alloying element(s) along with a part
of the underlying substrate leading to the formation of an alloyed zone confined to a
very low depth from the top surface within a very short interaction time. Laser surface
alloying is usually carried out using a continuous wave (CW) laser beam normal to
the substrate. When the laser beam scans the surface, it creates a melt pool. Addition

5
 of alloying elements to the melt pool is done either as a pre-deposited layer on the
substrate, or by feeding powder into the melt pool. Once irradiation stops,
solidification occurs due to rapid heat transfer to the bulk. The solidification front
progresses rapidly from the bottom towards the surface, at a very high speed (mainly
depending on the scanning speed, depth and shape of the melt pool and material
properties). Fig. 1.4 shows the schematic of laser surface alloying with pre-deposited
alloying element “B”. Here “B” substrate material “A” mixed and forms an alloy of
“AB” with improved properties than those of the substrate material.

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Laser alloying Laser beam

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ar th Laser alloyed zone (AB)

Substrate (A)
B

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Fig. 1.4: Laser surface alloying

Laser surface alloying is used for increasing the strength of various materials (i.e. -
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steels, cast iron, titanium, nonferrous metals, alloys, etc.) with a wide range of
elements and their compounds because of the relative ease of introducing them into
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the zone of alloying. Laser surface alloying can be obtained with the aid of laser
treatment by two fundamentally different methods:
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(i) Introduction of hard particles into the alloying zone

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It is imperative to take into account the nature of the interaction between the particles
and the molten alloyed material, i.e., the possibility of their dissolution, the formation
of chemical compounds, wettability, the difference between coefficients of linear
expansion, specific volumes, etc.

(ii) Obtaining the strengthening phases directly in the process of laser alloying

This can be carried out by three methods:

a) Addition of a constituent element of the final strengthening phase to the substrate

surface, while other constituent element(s) are contained in the substrate

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 Chapter 1

b) Adding mixtures of the elements

c) Successive additions of the elements.

Here it is necessary to take into account the affinity of elements to each other, and the
possibility of the formation of complex chemical compounds.

Moreover, LSA is a non-equilibrium process because it occurs with high heating and
cooling rates, and it is also complicated by the formation of the heat affected zone. As
a result, compounds with non-stoichiometric composition, metastable and new phases
may form in the alloyed zone, i.e., deviations from the phase diagrams are possible.

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1.3.2.4 Laser cladding

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In laser cladding, laser beam energy is used to locally melt the coating material to
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form coating of low dilution, with low degree of porosity and crack formation. A thin
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layer of the substrate must be simultaneously melted to create a fusion bond between
the coating and substrate.
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The coating material can be supplied by pre-depositing a suitable thickness of the
coating material prior to the laser treatment or by depositing an appropriate amount of
material (in powder or wire form) directly into the laser beam at its point of incidence
on the surface, where it fuses onto the surface to form a clad layer.
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There are several advantages of laser cladding as compared to alternative processes

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such as conventional arc welding or thermal spraying. Thermal input can be precisely
controlled by laser cladding, thus yielding minimal dilution and a small heat affected
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zone. This lower amount of heat input prevents distortion and the base material
properties are not detrimentally affected. A clad layer of markedly dissimilar
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composition to the substrate can be deposited with very little mixing of the two, yet
with high bond strength.

Due to the high solidification rates involved, the resulting microstructures are fine and
frequently contain non-equilibrium phases and supersaturated solid solutions, leading
to high hardness and high wear and corrosion resistance. Depending upon the method
of powder application laser cladding can be further classified as:

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 (i) Laser cladding with pre-placed powder

Laser cladding with pre placed powder (Fig. 1.5) is performed by scanning the laser
beam over the substrate surface with a pre-placed layer of precursor powder applied
over it. The pre-placed powder is generally mixed with a binder and a volatile non-
reactive liquid (like alchohol or acetone) to form a slurry. When the laser beam is
incident on the powder surface, melting occurs almost immediately. The melt front
advances through the low conductivity powder layer. As the melt front reaches the
substrate, heat conduction increases drastically (due to higher conductivity of the
substrate material) causing solidification of the melt pool. Good adherence and low
dilution are obtained by supplying enough energy to melt a very thin layer of the

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substrate.

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ar th Laser cladding with
pre-placed powder
Laser beam

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Clad layer of B powder (B)

Substrate (A)
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Fig. 1.5: laser cladding with pre-placed powder

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(ii) Laser cladding by powder feeding

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In this process the clad material is delivered in powder form to the melt pool by
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means of a carrier gas. The powder jet is directed towards the melt pool surface and
impinges on the substrate at an angle (Fig. 1.6). The laser beam scans the substrate in
a continuous motion and melts the incoming powder and a thin layer of the substrate
to form a clad track. The laser processing parameters are chosen so that the clad
material is metallurgically bonded to the substrate, and dilution is sufficiently low to
avoid degradation of the clad material properties.

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 Chapter 1

Laser cladding Laser beam

Powder
Clad layer of B
B feeding

Substrate (A)

Fig. 1.6: laser cladding by powder feeding

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(iii) Laser cladding by wire feeding

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In this process, the clad material is supplied to the melt pool as a wire. It is a one-step
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process and the efficiency of material usage is high, but laser energy is poorly
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absorbed by wire. To make the process more efficient, the wire and laser beam (with a

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power density greater than plasma formation threshold) are usually directed at an
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oblique angle to the surface. A plasma cloud is created in the interaction zone, which
couples effectively with the laser beam radiation and transfers its energy to both the
wire and substrate. The process is more efficient than the powder interaction
technique; however dilution is much higher and extremely accurate alignment of the
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laser beam with wire is required to get good results.

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1.3.2.5 Pulsed laser deposition (PLD)

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Fig. 1.7: Pulsed laser deposition technique

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 PLD is a deposition process which uses high power pulsed laser to ablate material
from a target to be deposited onto a substrate in a vacuum atmosphere. PLD can be
used to deposit a wide range of materials from polymers to metals on substrates at low
temperatures. It is a fast process, produces stoichiometrically pure substances with
good adhesion but is not good for large area deposition. Fig. 1.7 shows the basic
schematic of PLD system.

1.3.2.6 Laser shot peening

Similar to peening by high velocity shots, the laser beam can be used to produce the
similar effects on the surface. Laser peening technique involves the generation of

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tamped plasmas at the component’s surface. High laser intensities of 200 J/cm2 with

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pulse duration of 30 ns can generate shock pressures up to 105 atmospheres when
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absorbed on a metal surface.
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Laser shot peening can induce residual compressive stresses on the surface to a level

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equivalent to that produced by conventional process i.e., approximately 60% of tensile
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strength of the material. The process is capable of producing compressive residual
stress to a greater depth than that of conventional peening without any significant
change in surface finish. Deep residual stress is important for safety of critical items
such as compressor and turbine blades. An important additional benefit of laser shot
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peening is the prevention of crack growth.

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1.3.2.7 Laser fusion of thermal sprayed deposits

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Metals and alloys deposited by thermal spraying are normally fused by oxy-acetylene
flame or induction heating. Ceramic and ceramic based composites with higher fusion
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temperatures compared to those of metals and alloys are difficult to melt by oxy-fuel
flame and these non-conductors cannot be fused by induction heating.

Laser glazing is extensively used for surface fusion and closure of open pores of the
thermally sprayed ceramics and related composites. The non-reflective ceramic
coatings have the capability of absorbing a large fraction of the laser beam energy.
Ceramics being poor conductors, the laser heat gets concentrated at the point of
application resulting in melting of the sprayed surface layer. The closing of surface
pores prevents ingress of corrosive chemicals & vapors and therefore improves the
corrosion resistance of the surface.

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 Chapter 1

1.3.3 Application areas of laser assisted surface engineering techniques

Typical applications of laser assisted surface engineering include:

1. Automotive industry:
• Hardening and cladding of engine cam shafts and valve seats
• Hardening of cutting and bending edges on press tools involved in
manufacture of automotive parts
• Surface modification for various tribo-components

2. Aerospace industry:
• Repairing of turbine blades by laser cladding

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• Hardening of bearing surfaces on rotating shafts

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• Promotion of adhesion between metallic and composite joints
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3. Mining, power generation, oil and gas industry:
•
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Wear protection of drilling tools or hydraulic cylinders in mining industry
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• Hardening of various parts of pumps, valves and tubular components
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• Hard-facing of steam turbine blades
• Coating of long drilling tools for oil rigs by laser cladding
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1.4 Laser assisted surface engineering for hard and wear resistance coating

A considerable amount of research work has been conducted by various research

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groups in the field of laser assisted surface modification techniques. With

improvements in laser systems in terms of power and beam quality, laser surface
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modification techniques are now finding increasing applications either in industry to

produce hard and wear resistance surfaces for specific applications or as a research
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tool to develop coatings with novel material combinations on various engineering

materials.

With the view to improve hardness and wear resistance of different materials (various
type of steel, Al and its alloys, Ti and its alloys), composite coatings of some alloys
with unique compositions or ceramic reinforced metal matrix composites have been
developed using laser assisted surface modification techniques that include laser
surface modification (Rabitsch et al., 1994; Gopalakrishnan et al., 2001; Kulka et al.,
2003), laser surface engineering (Agarwal, A., Dahotre 1999a ), laser cladding (Xibao

11
 et al., 2001; Manna et al., 2006), laser particle injection (Mehlmann 1990; Ocelik et
al., 2005) and laser surface alloying of pre-placed powders (Babu et al., 2006; Roy
Choudhury et al., 2007).

1.4.1 Laser coating by laser surface alloying

Laser surface alloying is used for increasing the strength of various materials (steels,
cast iron, titanium, nonferrous metals, alloys, etc.). Laser alloying provides an easy
way to introduce different phases into the zone of alloying and hence there is a wide
choice of elements and compounds that may be introduced into the surface of
materials by this method.

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Abrasion resistant coatings of Fe-Cr-Mn-C alloy on steel surface (Singh and

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Mazumdar, 1986) and in-situ Fe-Cr-C alloys on AISI 1018 steel (Dahotre and
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Mukherjee, 1990) have been developed by laser surface alloying (LSA). Due to
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higher solubility and almost equal melting temperatures of the alloying elements and
substrate, homogeneous alloying layers are formed with fine distributions of complex
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(M6C) carbides in solid solution. In the latter case, chromium powders of different
particle size ranges have been used together to obtain optimum packing density of the
powder deposited on the substrate. The processing conditions were related to solute
(chromium) content, microstructural refinement of the laser alloyed zone and the heat
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affected zone (HAZ).

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Burg et al. (1995) have produced a firmly bonded Cr2O3 coating on steel (SAF2205)
by high power laser processing. A spot size of 1.27 mm diameter with laser power of
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1 kW and laser scan speed of 20 mm/s and an overlap of 75% between the tracks have
been employed to develop the coating. By measuring the maximum strain energy
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release rate with a 4 point flexure test, it has been found that the actual interface
strength of the laser coating depends strongly on the composition of the substrate and
that of the coating material. Delamination occurred by fracture through the coating
and partially along the interface, indicating that the interface strength is similar to or
higher than the fracture strength of (Fe, Cr)-spinel.

Fishman et al. (2001) have developed functionally graded tungsten carbide (WC)
alloyed multilayer coatings on M2 high-speed steel by laser alloying with direct
injection of WC powder into the melt pool. The laser treatment was performed using a
continuous wave CO2 laser with beam power in the range of 2–7 kW, and a 5 mm

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 Chapter 1

beam diameter. The powder was injected with argon flow as a powder carrier at an
angle of 45° through a nozzle (outlet diameter 4 mm) at the distance of 12 mm from
the alloyed surface. Powder injection rate of 3 g/min was used in all experiments.
Depending on the degree of alloying four different types of structures in laser alloyed
coatings were observed. Micro-hardness values in the range of 1100–1200 HV with
40–50% W and 1600 HV with 75% W have been observed. The coating with 58 wt.
% tungsten showed a five fold increase in wear resistance as compared with that of
the unalloyed laser-melted M2 steel.

TiN-reinforced MMC layer on NiTi has been developed by laser (high-power CW

Nd:YAG) coating of pre-placed Ti powder in a nitrogen atmosphere (Man et al.,

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2006). Commercially available pure Titanium powder of particle size in the range of

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40–100 µm was mixed with a binder (4% polyvinyl alcohol) to form slurry and then
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pasted on the samples. The pasted specimen was dried in an oven at 100 0C for two
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hours. The specimens were laser irradiated inside a gas-tight chamber with a glass
window through which the Nd:YAG laser beam can pass inside. The chamber was
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constantly filled up and purged with a mixture of Nitrogen and Argon at a ratio of 2: 1
by controlling the flow rates of Nitrogen and Argon at 20 and 10 l/min, respectively.
The ranges of laser power and speed studied were 1–1.5 kW and 20–30 mm/s with a
laser spot of 1.5 mm diameter. The laser tracks were overlapped at 50% track width
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to achieve surfacing. The pre-placed Ti powder reacted with N2 to form an MMC

layer containing a gradient distribution of TiN and NiTi2 dendrites in a Ti rich matrix.
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The hardness was increased from 250 HV in the substrate to 600–900 HV in the
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modified layer due to the presence of the hard TiN phase. The large increase in
hardness in the coating was mainly due to the presence of TiN, and the change in
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hardness was consistent with the graded distribution of the hard TiN phase in the
matrix. The wear resistance against a diamond ball was correspondingly increased by
a factor of two. The higher wear resistance of the MMC layer could be attributed to
the complementary effects of the hard TiN phase and the tough metal matrix.

1.4.2 Laser assisted coatings consisting TiB2, TiC, Al2O3 and SiC phases

It is known that coatings based on borides, carbides, and oxides of some refractory
materials have high wear resistance. (TiC + steel) composite layer has been formed on
the surfaces of Armco iron and AISI 1045 steel by injecting the TiC powder into the

13
 molten surface layer (Ariely et al., 1995) with laser alloying process. Experiments
were carried out under a protective atmosphere of argon, which also served as the
carrier gas. Laser power of 1.7 kW with a laser-beam diameter 1.2 mm was used for
experimentation. Scanning speed of 10 mm/s, powder feed rate of 0.043 g/s, and
overlap of 50% between consecutive passes was selected as operating conditions after
performing some preliminary experimentation. From the analysis of microstructures
the authors have found that some of the TiC particles had partially melted during their
passage through the laser beam and had re-solidified, forming small and fine
dendrites. Phase identification by XRD and TEM revealed the presence of α-Fe,
martensite and Fe3C phases, as well as some amounts of stochiometric TiC and

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unknown phases. A correlation was found between the substrate composition,

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microstructures of the coatings and the different phases inside them.
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Carbides (SiC and WC) along with elements (Cr and Ni) have been employed as
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additive elements during laser surface alloying of AISI 4340 steel under different
processing speeds (McCay et al., 1999). The sand blasted surfaces of the substrates
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were coated with a slurry comprised of chromium (44 wt %), nickel (22 wt %), silicon
carbide (3 wt %) and tungsten carbide (8 wt %) powder, varnish and mineral spirits.
The laser treatment was performed with CW 3 kW Nd:YAG laser at an overlap index
of 2.5mm at 2000W laser power and 1000, 1500, 2250 and 3000 mm/min laser scan
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speeds. The resultant alloyed surface shows improved hardness, wear resistance and
corrosion resistance compared to those of the base AISI 4340 steel material. The
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added chromium and nickel altered the matrix alloy properties, improved the
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corrosion resistance, while the carbides increased the hardness as well as the wear
resistance. The dissociation of the original carbides (SiC and WC) into elemental
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silicon and tungsten supplemented the stabilization of ferrite and the reduction in
hardness. The presence of undissociated carbides and some martensite formation
provided substantial increase in the micro-hardness. The carbides sometimes initiated
some cracks. However, crack formation was minimized by achieving better
homogeneity during processing.

Agarwal and Dahotre, (1999b) have applied laser surface engineering (LSE) to
develop a uniform, continuous TiB2 reinforced Fe composite coating of 200 µm
thickness, on AISI 1010 steel. A 2.5 kW CW Nd:YAG laser equipped with a fiber
optic beam delivery system was employed for synthesis of laser assisted TiB2

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 Chapter 1

coatings. Laser beam power of 1.5 kW and varying laser traverse speed (150-200
cm/min) was used. Polygonal and needle shaped boride particles are uniformly
distributed in the laser melted zone. The interfacial microstructure consists of cellular
dendrites and fine equiaxed dendrites. Metastable phase(s) such as FexBy and TimBn
B B

are also observed which is a characteristic feature of non-equilibrium synthesis is by

laser energy. The coating exhibits knoop hardness up to 1772 (under 300 gm load)
and metallurgically sound interface with the substrate. Compared with the same
coating developed by pulsed electrode surfacing (PES) process (Agarwal and
Dahotre, 1999a,) the authors have found that LSE yields higher hardness and higher
interfacial bonding strength compared to those for coatings obtained through the PES

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technique. However, with LSE process some metastable phases have also been

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formed, which is a characteristic feature of non-equilibrium synthesis by laser energy.
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Babu et al. (2006) have investigated laser surface alloying with a mixture of 80 wt.%
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431-type stainless steel and 20 wt.% titanium carbide powders on 1020 steel substrate.
The laser deposition was made using 2430 W (Nd:YAG laser) laser power and 2.12
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mm/s laser scan speed with beam diameter of 5 mm. The powder material to be
melted by the laser process was pre-placed (1.5 cm thickness) on the substrate
surface. Shielding gas (N2) was delivered to the laser surface processing region at 300
reverse angle from the direction of processing. Microstructural characterization of the
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alloy indicated that titanium carbide melted and re-precipitated as fine carbides from
the liquid melt during cooling which enhances the hardness of the coating. The treated
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specimens exhibited a micro-hardness of 670 HV0.3. The properties of the alloyed

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region depended on the microstructure that evolved during melting and cooling,
largely depending on laser beam parameters and the amounts of the alloying
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constituents.

A uniform, continuous and crack-free composite coating of TiC particles embedded in

Al alloy–Ti matrix has been deposited on 6061 Al alloy by laser surface engineering
using Nd-YAG laser beam (Katipelli et al., 2000a). A 2-kW CW Nd:YAG laser
equipped with a fiber optic beam delivery system was employed for laser treatment of
the sprayed substrates. The lenses within the output-coupling module of fiber optic
were configured to provide a beam of 3.5 mm wide line in spatial distribution onto the
sample surface. Such configuration provides a rapid processing speed and reduces the
overlap between the laser passes. The laser beam power and traverse speed were

15
 maintained constant at 1.8 kW and 120 cm/min, respectively. The coated samples
were additionally cooled by mounting them on a water-cooled copper plate during
laser processing. The various reactions occurring during laser processing were
thermodynamically analyzed and related to the experimental observations. Micro-
hardness measurements suggested high hardness in the coating and a strong bonding
at the coating substrate interface. The investigators observed higher hardness at the
top portion of the coating and found evidence of Si at the top portion of the coating,
which apparently segregated there during laser processing. SiC, being less dens (3.1
to 3.2 g/cm3) in comparison to TiC (4.92 g/cm3), floats to the top of molten coating
during laser processing and remains at the top of the coating after resolidification. An

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attempt was made to semi-quantitatively determine the interfacial strength by

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performing some micro-hardness indentations along the interface at various loads (50,
100, 200, 300, 500, and 1000 g).
ar t Initiation or formation of any cracks or
delaminations at the site of indentations was not observed. Wear resistance of the
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coated surface was found to be high when compared to that of substrate. The
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coefficient of friction was found to be 0.64. In order to study the interfacial strength
of the coating, four-point bend test was carried out (Katipelli et al., 2000b). Strain
energy release rate and the stress intensity factor, were computed for this particular
coating-substrate system. From the results, the authors found that some cracks, which
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propagated from the surface, caused delamination of the coating from the surface.

Kadolkar and Dahotre (2002) have deposited TiC coating on aluminium 2024 and
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6061 alloy using Nd-YAG laser beam. The effects of laser processing parameters,
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such as power intensity and speed on the thickness, microstructure and morphology of
both the coating and the heat affected zone have been evaluated using a SEM. The
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authors have used a 2 kW Nd:YAG laser beam with energy density in the range 1714
- 3429 J/cm2 by changing the laser scanning speeds (100, 125, 150, 175 and 200
cm/min). From the experimental results they have shown that by controlling the
process parameters it is possible to produce varied microstructures according to the
requirement of the application. In case of 2024 Al alloy substrate, increase in laser
scan speed resulted in refinement of dendrites, attributed to the higher cooling rates.
Performance of these coatings depend on the particle size, shape and distribution of
the reinforcing phase as well as the processing parameters such as laser power, laser
scan speed and energy density due to laser interaction (Kadolkar and Dahotre, 2003).

16
 Chapter 1

SiC and Al was laser alloyed on nickel-based high-temperature alloy Inconel-625

(Jasim et al., 1993). A 2 kW continuous wave CO2 laser was used at 2 and 1.7 kW
laser power with a beam diameter of 5 mm, and traverse speeds of 1-22 mm/s.
Powder mixtures of aluminium with 10, 30 and 50 wt % SiC were used to produce
single tracks with powder feed rates in the range 2-8 g/min. Aluminium was studied
as a component for the functionally gradient region for its capability to form
aluminide with the nickel present in Inconel-625. SiC was chosen as the ceramic for
its potential for improving wear resistance when present in substantial volume
fractions in particulate form. Laser processing conditions, particularly powder feed
rate and interaction time have been studied in order to achieve proper control of the

r
compositional gradient involving dilution of the successive tracks and the dissolution

pu
of the ceramic particles in the matrix. Depending on the processing conditions a
number of complex microstructural features can appear, involving various phases
ar t
(e.g. silicon and intermediate phases such as A14C3.
h
Dutta Majumdar et al. (2006a) investigated the improvement in the hardness and wear
ag
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resistance of aluminum alloy by laser surface alloying that produces a MMC layer on
the top of the surfaces of the substrates. SiC and a mixture of Al + SiC (at a ratio of
1:1) were pre-deposited (200 µm) on the substrate by dispersing the powders (particle
size 25–50 µm) in alcohol with an organic binder and subsequently, applying the
y

coating on the surface using a brush. Laser composite surfacing was carried out by
irradiating the pre-deposited Al substrate using a continuous wave (CW) CO2 laser
IIT p

with laser power of 3 kW, a beam diameter of 3.5 mm, scan speed of 300-500
o

mm/min and Ar as the shrouding gas. The microstructure of the composite layer
consists of a dispersion of partially melted SiC particles in a grain refined Al matrix.
C

SiC particles are partly dissociated into silicon and carbon leading to formation of a
low volume fraction Al4C3 phase and free Si, redistributed in the Al matrix. The
volume fraction of SiC is maximum at the surface and decreases with depth. The
micro-hardness of the surface was improved by two to three times as compared to that
of the as-received Al. The presence of hard particles in the matrix is responsible for
improvement in the average micro-hardness of the coating. A significant
improvement in wear resistance in the composite surfaced Al is observed as compared
to the as-received Al, which is attributed to improvement in hardness due to grain
refinement.

17
 1.4.3 In-situ formation of composite coating consisting TiB2, TiC, Al2O3 and SiC
phases by laser coating process

Park et al. (2000) have made an attempt to produce in-situ TiC particulate composite
layer by laser irradiating over a thermally sprayed titanium coating on cast iron. The
effect of the laser scan speed on the solidification microstructure of the base metal and
titanium alloyed beads was examined. The precipitation morphology of TiC
particulates generated by the reaction with carbon contained in the cast iron matrix
was observed. From the results, it was revealed that composite TiC particulate has
been formed on the surface layer by direct reaction between carbon existing in the
cast iron matrix and thermally sprayed titanium coating by remelting and alloying

r
using laser irradiation. The microstructure of the alloyed layer consisted of three

pu
zones; the TiC particulate precipitate zone (HV 400–500), the mixed zone of TiC
particulate C ledeburite (HV 650–900) and the ledeburite zone (HV 500–700). TiC
ar t
particulates were precipitated as a typical dendritic morphology. The secondary TiC
h
dendrite arms were grown to a polygonized shape and were necking. After that
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separated arms became cubic crystal of TiC at the slowly solidifying zone. However,
in the rapidly solidified zone near the fusion boundary, the fine granular TiC
particulates were grouped like grapes.

Xibao et al. (2001) have developed Fe-Ti-B composite coating with TiB2 as whiskers
y

on austenitic stainless steel by laser cladding with a powder mixture of B4C and Fe-Ti
alloy. Both the hardness (maximum cross sectional micro-hardness of 1300 HV0.1)
IIT p

and cracking resistance of the Fe-B laser clad coating could be improved by the
o

formation of TiB2 whiskers. The experimental work shows that the needle-like TiB2
whiskers could be synthesized in situ using the laser cladding method in the
C

composite Fe-Ti-B coating. The size, shape and volume fractions of TiB2 whiskers in
the composite coating are greatly dependent upon contents of powder compositions,
the ratio of B and Ti elements and the laser energy density used. The average ratio of
width to length for the synthesized TiB2 whiskers increases with increasing laser
energy density and ratio of B and Ti in this coating.

Singh and Dahotre (2004) have synthesized a mixed carbide coating on plain carbon
steel with the Fe-Ti-Cr-C quaternary system employing laser surface engineering
(LSE). A mixture of commercially available Fe (55 wt %), Ti (20 wt %), Cr (20 wt %)
and C (5 wt %) powders, blended together and suspended in a water-soluble organic

18
 Chapter 1

binder was used as precursor. The slurry of precursor material was deposited by air
spray on the substrate for uniform green thickness and then dried at 75 0C for 30 min.
A 2.5 kW CW Nd:YAG laser equipped with a fiber optic beam delivery system was
employed with scan speed of 1500 mm/min and varying laser power (900-2100 W)
for laser surface engineering. In-situ formation of Ti and Cr based carbides using
LSE produces a coating with high hardness (five times that of the substrate material)
and wear resistance. From the analysis of the results it has been found that, the
hardness and wear resistance of the samples without chromium carbides were inferior
to those of the samples with both TiC and chromium carbides. A substitutional solid
solution of chromium in iron (Fe-Cr) was found in all the samples and the relative

r
estimated amount of the phase was higher for the samples without chromium

pu
carbides. Metastable phase (characteristic of non-equilibrium synthesis) like
martensite was present in the coating and the transition zone.
ar th
Liu and Zhang (2005) have synthesized in-situ TiB2/Ni multiphase metal-ceramic
composite coating on medium carbon steel surface by laser cladding. Laser irradiation
ag
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power 1.2–2 kW, laser spot diameter 3–4 mm, lens with focal length of 300 mm and
scanning speed 1–2 mm/s were employed for laser treatment. Results of
microstructural studies on the coating show that the composite coating is mainly
composed of γ-(Ni, Fe) and (Fe, C) solid solution, dendrites and eutectic structures of
y

TiB2/ γ -(Ni, Fe) or TiB2/(Fe, C) distributed in inter-granular spacing. The effect of

changes in chemical composition on the amount of ceramic, synthesized in-situ has
IIT p

been discussed. Hardness of the coating increases prominently (790- 1100 HV)
o

compared with that of the substrate (200-300 HV). This is the mutual result of solid
solution hardening in the dendrites and solid solution hardening and dispersion
C

hardening of the second phase in intergranular.

A composite layer of dispersed TiB2 particles in AISI 304 stainless steel matrix has
been deposited on AISI 304 stainless steel by laser surface modification from a pre-
placed mixture of K2TiF6 and KBF6 (in the weight ratio of 2:1) using Ar as shrouding
environment (Dutta Majumdar et al., 2007). Analysis of the micro-structure of worn
out debris confirmed that, the mechanism of wear is predominantly abrasion and
subsequently, three body abrasion in laser composite surfaced stainless steel. The
authors (Dutta Majumdar et al., 2006b) have also produced a composite layer of
uniformly dispersed TiB2 and TiB particles in Al matrix by laser composite surfacing

19
 on pure Al substrate using same precursor through an external feeder. The micro-
hardness and wear resistance of the surface was improved as compared to that of as-
received Al substrate.

Selvan et al. (1999) have investigated the formation of titanium boride (TiB2) and
titanium nitride (TiN) coating on Ti–6Al–4V by laser alloying of pre-placed BN
powder. The alloying was conducted using CW CO2 laser with different power levels
1.5, 2.0, and 2.5 kW, keeping beam diameter (1 mm ) and scan speed (0.5 m/min)
constant. To protect the alloy surface from oxidation during processing, argon gas
shield at a pressure of 1.5 kg /cm2 was fed through a coaxial nozzle. The formation of
TiB2 and TiN, investigated using energy dispersive X-ray diffraction (EDX) results

r
were related to the micro-hardness and microstructure. The surface hardness (1500–

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1700 HV) observed at the boronised layer was five to six times higher than that of
ar t
untreated Ti–6Al–4V alloy.
h
Tian et al. (2005, 2006) have produced composite coatings of titanium carbide and

ag
titanium boride by laser surface alloying of Ti and B4C powder mixture on pure
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titanium substrate or with mixture of Ti–6Al–4V with powder mixture of graphite and
boron on Ti–6Al–4V substrate. For the first case (Tian et al., 2005), a continuous
wave CO2 laser, with beam diameter of 4 mm, laser power of 1200 W and varying
scan speeds (0.85, 3.85 and 6.8 mm/s) with 40% track overlap was employed to melt
y

the surfaces of the samples. During the process of laser surface melting, the pre-
IIT p

placed B4C was decomposed and dissolved into the melted pool, leading to alloying
of the surface of pure titanium with boron and carbon. Argon gas shield at a pressure
o

of 3.0 kg/cm2 was fed through a coaxial nozzle with the laser beam. For the second
case (Tian et al., 2006) scan speeds of 2 and 4.5 mm/s were employed, keeping other
C

parameters unchanged. For both cases the coatings exhibited higher hardness (1600–
1700 HV0.1 on Ti-6Al-4V) and higher wear resistance compared to those of the
substrate materials. Laser scanning speed and the content of alloying elements have
an effect on both the microstructure and the wear resistance of the coatings. With the
increase in laser scanning speeds, formation of fine microstructure was observed in
the coating.

In order to improve the wear resistance of an aluminum alloy, particulate-reinforced

MMC coating with TiB2 particles synthesized in-situ, was formed on a 2024
aluminum alloy by laser cladding with a powder mixture of Fe-coated boron, Ti and

20
 Chapter 1

Al (Xu and Liu, 2006). The nano-hardness and the elastic moduli of the phases of the
coating have been examined. With the increase in the content of Ti and Fe-coated
boron powder in the mixture from 30% to 70%, the maximum hardness of the coating
increases from 265 HV to 908 HV. The dry sliding wear behaviour of the coating was
investigated using a pin-on-ring machine. It has been found that the wear
characteristics of cladding were completely dependent on the content and morphology
of the TiB2 particulates, intermetallics in the microstructure and the applied load. At
the lowest load (8.9 N), with increasing content of TiB2 particulate and intermetallic,
the weight loss of the laser cladding due to wear was reduced. At higher loads (17.8,
26.7, and 35.5 N), the 2024 Al alloy exhibited superior wear resistance to the particle-

r
reinforced metal matrix composite cladding as over a certain applied load, the particle

pu
and intermetallic compounds fall off and lose their ability to support the load.
ar t
Du et al. (2008a) have investigated the synthesis of hard composite coating reinforced
h
with TiB2-TiC on AISI 1010 steel using laser surface engineering. Micro-hardness of
the composite coating has been found three to four times than that of the steel
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substrate. Microstructural examination revealed micron sized blocky particles and
submicron-sized spherical particles in the matrix. Results show that TiB2 dissociated
when the Al content reached 30 wt % or more. The composite coating with the
presence of TiB2 shows acicular TiB2 particles embedded in the α-Fe matrix. Coatings
y

produced using precursor of high-Al content reveals a refined cellular structure due to
the high-cooling rate induced by short pulse duration. The authors (Du et al., 2008b)
IIT p

have also synthesized a wear, oxidation and corrosion resistant composite coating
o

consisting of TiB2 and iron–aluminide on AISI 1010 steel substrate using mixture of
Al and TiB2 powder as precursor. Compared with the steel substrate, micro-hardness
C

and wear resistance of the coating are improved significantly. Due to the presence of
hard reinforcements, such as TiB2 and iron–aluminide, the laser-coated samples
demonstrate considerably higher wear resistance than the steel substrate. The hard
reinforcements (TiB2, Fe3Al, Al2O3) can play the role of hard barrier to interrupt the
ploughing and scratching and therefore improve the wear resistance of the coating.
Processing parameters as well as the composition of the precursor have been
correlated to the phase composition and microstructure of the coating.

Manna et al. (2006) attempted to explore the feasibility of developing an amorphous

layer of Fe–B–C, Fe–B–Si and Fe–BC–Si–Al–C on AISI 1010 steel by laser surface

21
 cladding, with an objective to improve hardness and wear resistance. LSC was carried
out by melting the pre-deposited layer of elemental powder blends with nominal
compositions of 94Fe4B2C, 75Fe15B10Si and 78Fe10BC9Si2Al1C (wt %) due to
their known ability to form glass in rapid solidification. The beam 2.5 kW continuous
wave Nd:YAG laser equipped with a fiber optic delivery facility was optically shaped
to provide a focused rectangular irradiation spot with 3.5×0.6 mm2 area on the sample
surface. Excellent wear resistance with a micro-hardness up to 1150 HV0.3 was
reported, however no amorphous phase has been found.

1.5 Application of high power diode laser (HPDL) for laser surface engineering

r
Surface treatment may be carried out by the use of laser beam with uniform high

pu
power density. The success of the laser surface treatment depends on appropriate
ar t
combination of power density, speed and most particularly, spatial power density
h
distribution (De Damborenea, 1998).

ag
Diode lasers have been known for many years and have been used mainly in
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electronic devices and metrology. The progress in development of semi-conductor
materials allowed for the introduction of industrial high power diode laser (HPDL).
Diode lasers produced nowadays achieve power levels up to 20 kW. Diode lasers are
characterized by a rectangular or linear shape of beam focus having multi-mode
y

energy distribution (Dobrzan´ski et al., 2004). As surface modification processes

IIT p

involve wide area processing, high power diode lasers with multimode beam profile
having uniform intensity distribution with wider spot sizes facilitate large area surface
o

treatment with better control of heat input resulting in high integrity and uniformity of
the coatings. In contrast, complex and expensive focusing techniques are required for
C

tailoring the laser spot sizes in case of CO2 and Nd:YAG lasers to obtain uniform
beam intensity distribution profiles (Kennedy et al., 2004). In addition, Laser surface
engineering with CO2 and Nd:YAG lasers is relatively expensive as compared to that
with the diode laser due to the relatively lower efficiency of the CO2 and Nd:YAG
laser, and high capital costs (especially for Nd:YAG lasers). HPDL has approximately
70% absorption compared with 10-15% for the CO2 laser and 65% for the Nd:YAG
laser (Li, 2000). Fiber-coupled HPDL in the kilowatt range, with larger rectangular
beam profiles are extremely appropriate tools for laser surface engineering (Seifert et
al., 2004).

22
 Chapter 1

The interfacial phenomenon of wetting is often the primary factor governing whether
a coating will adhere and bond to a substrate in practical applications. Lawrence et al.
(1999a; 1999b) have shown that the wetting characteristics of a selected range of
ceramic, metallic and composite materials can be controlled or modified by high-
power diode laser surface treatments. The authors found a correlation between the
change in the wetting properties of mild steel and the laser wavelength. Ehlers et al.
(1998) have reported the use of a 2.4 kW HPDL with a linear shaped beam profile for
hardening medium carbon steel M1044 producing a constant hardened depth of 1mm
and a track width of 20 mm. Kugler et al. (1998) demonstrated the use of a 1.5 kW
diode laser for transformation hardening of tool steels. The work shows that higher

r
hardness and wider track can be achieved with the HPDL due to better beam

pu
absorption as a result of shorter wavelength than that achieved with a 2 kW Nd:YAG
laser (Gaussian beam).
ar th
Recently, Roy Choudhury et al., have utilized HPDL in order to produce nano-
structured metal matrix composite (MMC) coatings of TiB2-TiB (Roy Choudhury et
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al., 2007) and TiB2–Fe2B (Roy Choudhury et al., 2008) on steel substrates by
combined laser and sol-gel technologies. The authors uses a 1.5 kW continuous wave
diode laser (at 808 and 940 nm wavelengths) operated at 1.2 kW and at scan rates of
0.5, 1.25, 5 and 10 mm/s, with a rectangular beam spot of 2.5 mm×3.5 mm.
y

Dobrzan´ski et al. (2004, 2005) investigated the effect of alloying with tungsten
carbide on properties of X40CrMoV5-1 steel surface, using a high power diode laser.
IIT p

1.6 Application of sol-gel and laser technologies for ceramic/ceramic composite

o

coating

Sol–gel processing has been widely employed to synthesize amorphous or crystalline

C

oxide coatings on metallic substrates and it was found to be effective in increasing the
corrosion and oxidation resistance (Ezz et al., 2006a). The sol–gel method has also
been used for synthesis of amorphous or nano-sized crystalline oxides. The two main
chemical reactions involved in sol–gel technology are the hydrolysis of the precursors
with the formation of partially hydrolyzed products and their calcinations. The
chemical and structural transformations that take place in the system during the sol–
gel process are influenced by many factors. These include chemical composition,
nature of the precursors, presence and nature of special additives, chemical procedure
and heat treatment schedule (Brinker and Scherer 1990). The conventional methods

23
 for sol–gel coating have some limitations in their application. For example, cracks can
form due to stresses developing during drying and thermal treatment, caused by
shrinkage and thermal expansion mismatches. An alternative method for sol–gel
coatings of crystalline silica films on polymer substrates using ultraviolet laser
irradiation has been developed recently (Imai et al., 1999).
Ezz et al. (2006b) developed composite coatings consisting of nanostructured TiN and
titanium oxide by a novel laser/sol–gel synthesis procedure under non-vacuum
condition. Titanium isopropoxide (TTIP) was used as the precursor for titania gel
preparation. Sub-micron and nanosize crystals of pure TiN have been precipitated at
the interface approximately 2–3 μm on the coating side. Micro-hardness of the order

r
of 1800–2000 HV0.1 has been achieved. The authors (Ezz et al., 2007b) have

pu
developed a novel method for the in-situ production of TiN by the reaction of titania
sol-gel with a nitrogenous admixture under laser irradiation on EN43 (AISI 1050)
ar t
mild steel and 316L stainless steel substrates. The authors found a coating hardness of
h
17-21 GPa. The same research group (Ezz et al., 2007a) also synthesized a coating of
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SiC with Cr–Fe–C intermetallic compound in ferrite matrix by chemical reaction of
silica sol-gel with chromium oxide. Silica sol–gel prepared from a silicon alkoxide
compound (TEOS), typically used in sol–gel chemistry, was used as a liquid precursor
for chemical reaction with solid present. Very fine SiC particles ≤1 μm and M7C3
y

carbides were synthesized in-situ and dispersed in the ferrite matrix by this process.
Micro-hardness up to 1100 HV0.1 and wear rate of the order of 10-15 m3/N.m has been
IIT p

achieved.
o

In addition, Roy Choudhury et al. (2007) synthesized nano-structured metal matrix

composite (MMC) boride coatings by laser melting of a pre-placed mixture of B4C+
C

Ti–6Al–4V powders and sol–gel derived nano-particulate Ti(OH)4. Micro-hardness

values up to 1450 HV0.1 and high wear resistance as compared to that of the substrate
material has been achieved. The authors (Roy Choudhury et al., 2008) also developed
nano-structured metal matrix composite coating of TiB2-Fe2B on steel substrate by
laser melting of pre-placed powder mixture paste of B4C+sol–gel derived nano-
particulate TiO2 on AISI 1050 medium carbon steel and AISI 316L stainless steel
substrates. Nano-particulate and sub-micron level TiB and TiB2 are found dispersed
throughout the metal matrix. Micro-hardness in the range of 800-2000 HV0.1 with a
wear resistance up to 5 times than that of substrate material has been achieved.

24
 Chapter 1

1.7 Ceramic and ceramic matrix composite coating

From the review of the past research on laser surface modification techniques it has
been found that the laser coating process is capable of producing metal matrix
composites (MMC) involving dispersion of hard ceramic particles in a relatively soft
metal matrix. Due to the presence of the soft metal matrix, the maximum hardness of
such laser-treated coatings is generally limited to about 1500-2000 HV. The
properties of the laser surface modified region depend mainly on the chemical
composition and microstructure resulting from melting and rapid solidification.

1.7.1 Monolithic ceramic coating

r
pu
Ceramic materials (e.g., oxides, carbides, and borides of refractory metals) due to
their exceptional hardness, excellent wear resistance and stability at high temperature,
ar t
find extensive applications in surface modification or coating technology. Hard
h
ceramic phases like TiB2, TiC, Al2O3, and SiC have received considerable attention
ag B
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for surface modification in the past for their high hardness and wear resistance.
Density, melting point, modulus of elasticity, co-efficient of thermal expansion,
hardness and fracture toughness values of these ceramics have been summarized in
Table 1.2 and Table 1.3.
y

Table 1.2: Physical properties of Al2O3, TiB2, TiC, SiC, Al3Ti and Fe
IIT p

Material Density Melting Modulus of Coefficient of thermal

(g/cm3) expansion (°C–1) (°C)
o

point(°C) elasticity (GPa)

Al2O3 3.9 2015 345-409 9.08 x 10–6( 0 -1527)
C

TiB2 4.5 3225 367 4.6–8.1 x 10–6(25–1500)

TiC 4.93 3067 439 8.15–9.45 x 10–6(25–1500)

SiC 3.22 2730 401-410 5.48 x 10–6(25–1500)

Al3Ti 3.35 1350 110-145

Fe 7.87 1535 12.6 x 10–6

25
 Table 1.3: Hardness and fracture toughness values of the monolithic, binary and
ternary ceramic composite consisting Al2O3, TiB2, TiC and SiC

Material Hardness Fracture toughness Reference

1/2
(GPa) (MPam )
Al2O3 16.2 4 Shackelford and
Alexander, 2001
TiB2 32.4 3.5-5.75

TiC 31.4 3.8

SiC 27.5 4.6

Al2O3-TiC 20.5 4.9 (Lee et al., 2001)

r
Al2O3-TiB2 21.3 4-6 (Gu et al., 2008)

pu
Al2O3–SiC 23 5.2 (Ko et al., 2004)
ar t
SiC–TiC–TiB2
h
Al2O3-TiB2-SiC
22

21.4-22
5.7

8.42
(Wäsche et al., 1999)

(Jianxin et al., 2001)

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Al2O3-SiC-TiC 19-32 9.6 (Smirnov et al., 1998)

A considerable number of research works have been done to form monolithic TiB2,
y

TiC, Al2O3, and SiC coatings on various substrates.

IIT p

(i) A12O3 coating

o

Alumina (A12O3) posses a high potential for many engineering applications such as
surface modification for wear- and/or corrosion-resistant components. Due to the
C

unique property combination of high hardness, low weight, high strength, high
stiffness and temperature stability along with excellent resistance to wear and
corrosion, Al2O3 has become one of the most extensively used ceramics. The use of
alumina coatings, produced by different processes for various tribological
applications, especially in aerospace and automobile industries is steadily on the
increase.

Many research groups have studied the wear behaviour of plasma sprayed alumina
coatings (Bull et al., 1996; Tao et al., 2010; Mindivan et al., 2009). A number of
research groups have reported on the laser cladding of A12O3 on AISI 304 stainless

26
 Chapter 1

steel substrates (Feng et al., 1996) or on Mg alloy (Gao et al., 2007). The developed
coatings exhibit high wear resistance and corrosion resistance as compared to that of
the substrate or coatings developed by the plasma-spray process. However,
brittleness, lack of defect tolerance owing to low fracture toughness, and low
resistance to thermal shocks can cause severe problems in case of components under
mechanical and/or thermal loads. Microstructural parameters such as grain size,
porosity and particularly, the size and density of flaws, affect strength. Strength and
toughness of alumina ceramics can be enhanced by various energy-dissipating
mechanisms such as phase transformation, micro-cracking, grain bridging, and most
importantly, by particle or fiber reinforcement. Particle reinforcement of alumina has

r
been studied by adding, for example, TiB2 as fine dispersed phase in the Al2O3 matrix

pu
(Lee and Zum Gahr, 1994).
ar t
(ii) TiB2 coating
h
TiB2 is a refractory compound exhibiting a unique combination of many useful
ag
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properties. TiB2 is characterized by a high-melting point, low-specific weight, high
hardness, high strength to density ratio, excellent abrasive wear resistance and higher
thermal and chemical stability up to 1700 0C (Vallauri et al., 2008; Du et al., 2008a).
By virtue of its high hardness, good oxidation resistance and excellent strength at high
y

temperature, TiB2 is a potential component in many widely used wear and thermal
IIT p

shock resistant coatings. These coatings have potential applications in boiler, tool
materials and shoot-proof in the surface of arms (Fang et al., 2008; Wang et al., 2006;
o

Darabara et al., 2006; Xu and Liu, 2006). Hence, many research efforts have been
carried out to prepare TiB2 coatings on various engineering surfaces by different
C

coating processes. These processing methods include high velocity oxy fuel spraying
(HVOF), plasma spraying and magnetron sputter deposition.

Wear properties of electrodeposited TiB2 coatings on Molybdenum, Inconel and

Nickel at various sliding speeds against hardened steel as counter body have been
reported by Kirk et al. (1981). The authors observed that wear of TiB2 coatings at
high speed is not dependent on the type of substrate for either lubricated or
unlubricated test conditions. It also appears that TiB2 coatings (under lubricated
conditions) are not as wear resistant as either the steel ball bearing or the Al203 single

27
 crystal. However, under un-lubricated wear conditions TiB2 coating has higher wear
B

resistance compared to that of Al2O3 coating under high speed (~30 m/s).

TiB2 coatings have been deposited on various materials by ion-beam-assisted

deposition (Riviere et al., 1991) and d.c. magnetron sputtering (Berger et al., 2004)
processes. These works mainly deal with the investigations on the mechanism of
development of TiB2 film on the substrate material. Riviere et al., (1991) found ion-
beam-assisted deposition allows for the modification of the microstructural state of a
growing film by controlling the mixing parameters independently of the deposition
conditions. Berger et al., (2004) mainly investigated the influence of substrate bias on
the growth, morphology, grain size and texture of d.c. magnetron sputtered TiB2

r
coatings.

pu
Panich and Sun (2005) investigated the mechanical properties of TiB2-based
ar t
nanostructured coatings fabricated by magnetron sputtering. The authors attempted to
h
enhance the hardness and adhesion of the TiB2-based nanostructured coatings by

ag
controlling the deposition parameters. It has been found that by proper control of the
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biasing period, a TiB2 coating with high hardness and good adhesion strength can be
produced. Super-hard TiB2 coatings were deposited from stoichiometric TiB2 target
using an unbalanced d. c. magnetron on Silicon, stainless steel, high-speed steel and
tungsten carbide substrates (Mikula et al., 2008). Recently Rybakova et al. (2009)
y

have studied the corrosion behaviour of molybdenum and steel materials, protected by
IIT p

electrochemically plated TiB2 Coatings. The chemical resistance of the TiB2 coatings
B

on Mo cylinder was characterized by immersion tests in molten aluminium alloy (Al9-

o

Si3Cu and AlSi7Mg) in a furnace at air atmosphere under dynamic and static
conditions. The investigators observed that TiB2 coatings effectively protect Mo
C

surface against corrosion in molten Al alloys media.

Agarwal and Dahotre (2000) have deposited wear resistant TiB2 coating on AISI 1010
steel using high energy density processes such as pulse electrode surfacing (PES) and
laser surface engineering (LSE). The wear resistance of the TiB2 coating deposited by
LSE has been found to be higher than that of the PES deposited TiB2 coating.

Lotfi et al. (2003) investigated Ni(Cr)-TiB2 coatings deposited by high velocity oxy-
fuel (HVOF) spraying of SHS-derived cermet powders. Three cermets are prepared
with compositions namely Ni(Cr)–65 wt.% TiB2, Ni(Cr)–40 wt.% TiB2 and Ni(Cr)–

28
 Chapter 1

40 wt.% TiB2 with 5 at.% excess boron by SHS reaction. The SHS products were
milled and the resulting powders were deposited onto steel substrates by HVOF
thermal spraying. Coatings consisted primarily of TiB2 particles in a nickel-based
binder phase. Abrasive wear behaviour was examined with both alumina and silica
abradents. All the coatings had similar, low wear rates with silica abrasive whilst with
alumina abrasive significantly different wear rates were observed. The investigator
reveals that higher content of TiB2 improves the wear resistance of the coating,
though indentation fracture toughness reduces.

(iii) TiC coating

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Due to high hardness, high melting point, and resistance to thermal fatigue and

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erosion TiC coatings have a high potential for application in fusion reactor
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containment vessels components (Mathur and McKee, 1991) as well as in case of
h
cutting tools.

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A number of research groups have reported on the development of TiC coating by
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various methods on different engineering materials. Raman et al. (1985) have
produced TiC coatings on steels, prepared by argon plasma-spraying of dry Ti and
TiC powders in open air and have described the corrosion characteristics of the
coating. Pure TiC coating has been deposited by pulsed laser deposition (Zergioti et
y

al., 1997). The authors mainly investigated the formation mechanism of TiC coating
IIT p

with different processing conditions and have studied the morphology of the films
with SEM and EDS analysis and the crystal structure by XRD and TEM analysis.
o

Upadhya (1991) developed TiC coating by plasma-assisted physical vapor deposition

technique and investigated the morphology and tribological properties of the coatings.
C

Lee et al. (1981) and Kinkel et al. (1994) deposited TiC coating by chemical vapour
deposition (CVD) on cemented tungsten carbide and steel respectively. These works
mainly deal with the mechanism of development of TiC layer on the respective
substrate materials and studies the dependence of the morphology of the coating on
the process parameters. The authors found, that grain structure of TiC was much finer
when either the deposition temperature or the total pressure was decreased and the
carbon concentration in the reactant gas was increased. Recently Guo et al. (2006)
have produced TiC coatings using electro-thermal explosion directional spraying

29
 (EEDS) process and found that the coatings have compact structure, high micro-
hardness and good bonding with substrate.

Katipelli et al., (2000) have deposited hard and refractory TiC on 6061 Al alloy by
Laser Surface Engineering. A composite coating with TiC particles embedded in Al
alloy–Ti matrix has been obtained. Wear resistance of the coated surface was found to
be high compared to the substrate material and the coefficient of friction was found to
be 0.64.

(iv) SiC Coating

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SiC is a ceramic known for its good oxidation, corrosion and creep resistance along
with high hardness and wear resistance properties (Thawari et al., 2003). A number of

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research groups have reported the synthesis of monolithic SiC coating by various
ar t
methods on different substrate materials to improve wear and corrosion resistance.
h
Costa and Camargo (2003) deposited SiC films onto WC cutting tool in order to
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improve wear resistance from a commercial sintered SiC target by r.f. magnetron
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sputtering. Silicon carbide films were deposited on AISI 304 stainless steel and
carbon steel from a SiC target in a magnetron sputtering system (Ordine et al., 2000).
Riviere et al. (1996, 1998) have produced SiC coatings on AISI 321 stainless steel by
y

dynamic ion mixing (DIM) and by ion beam sputtering technique. The coatings
exhibited improved wear and corrosion resistance.
IIT p

1.7.2 Multi-component ceramic composite

o

A considerable amount of research has been carried out so far to develop monolithic
C

or single phase ceramic coatings by different techniques, and some of the coatings
exhibit acceptable performances.

However, the uses of single-phase ceramics, even when fully densified, are limited by
the variability of their mechanical strength and their poor fracture toughness in high
temperature structural or wear applications. Their susceptibility to brittle fracture can
lead to unexpected catastrophic failure. Considerable improvements in mechanical
properties of single-phase ceramic materials have been achieved by incorporating one
or more of other components into the base material to form ceramic-matrix
composites (CMC).

30
 Chapter 1

In this connection, mention may be made of ceramic-matrix composites (CMCs) or

multi-phase ceramic composites that are reported to possess higher fracture toughness
along with high hardness and wear resistance, compared to those of single component
or monolithic ceramics (Mestral and Thevenot, 1991).

In addition, multi-component ceramic composites containing reinforcing phases in

nano-particulate form can also enhance the fracture toughness of the composite
(Zhang et al., 2003). This raises the possibility of obtaining a coating of high hardness
with high fracture toughness. Hence, the development of multi-component ceramic
composite coatings on metal substrates has generated considerable interest in surface
science.

r
Recently, various research groups have successfully produced multi-component

pu
ceramic composites like Al2O3-TiC (Lee et al., 2001) Al2O3-TiB2 (Jianxin et al.,
ar t
2005; Gu et al., 2008), TiB2-TiC (Lee et al., 2002), TiB2-SiC (Zhang et al., 1995)
h
Al2O3–SiC (Ko et al., 2004), TiB2-SiC-TiC (Zhang et al., 1996), Al2O3-SiC-TiC

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(Smirnov et al., 1998), Al2O3-TiB2-SiC (Jianxin, 2001), etc by conventional hot
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pressing or by SHS. It has been found from these reported literatures, that the
mechanical properties of the ternary composites are superior to those of the binary
composites. Table 1.3 exhibits the hardness and fracture toughness values of
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monolithic ceramic i.e. Al2O3, TiB2, TiC, SiC and their binary and ternary
composites. From the table it is clearly seen that fracture toughness values of the
IIT p

ternary composites is higher than those of the monolithic ceramic or binary ceramics.
o

1.7.2.1 Two-phase ceramic composite

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(i) Al2O3-TiB2

Over the years, the Al2O3/TiB2 composite has drawn the attention of research groups
due to its high wear resistance. Addition of TiB2 particles to Al2O3 matrix improves
fracture toughness, hardness, and strength over monolithic Al2O3 and offers
advantages with respect to wear and fracture behavior.

A considerable number of publications on the processing techniques and

characterizations of this composite are available. Jianxin et al. (1996), Meyers et al.
(2001) and Wang (2009) have reported processing techniques for Al2O3-TiB2
composites using SHS routes. Jianxin et al. (1996) have studied the mechanical

31
 properties of TiB2-Al2O3 composite powders with respect to the TiB2 content and
determined the optimum percentage of TiB2 for the best mechanical performance.
Meyers et al. (2001) produced Al2O3–TiB2 composite by the SHS reaction using
(3TiO2+3B2O3+10Al), which was densified by uniaxial loading immediately
following completion of reaction. The densification was enabled by the high
temperatures produced by the combustion reaction (~2000°C) which rendered the
reaction product (~70% porosity) plastic. The microstructure was characterized by
columnar TiB2 grains embedded in equiaxed A12O3; the TiB2 phase tended to
agglomerate in clusters. A few of the TiB2 grains exhibited dislocations, while the
A12O3 was annealed. TiB2-Al2O3 ceramic cutting tools prepared by hot pressing

r
exhibit substantial improvement in dry high-speed machining of hardened steel

pu
(Jianxin et al., 2005). It was shown that both the wear rates and the friction coefficient
at the tool–chip interface of Al2O3-TiB2 ceramic cutting tools in dry high-speed
ar t
machining of hardened steel were lower compared with the corresponding values for
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the same tool in low-speed machining. The authors report the formation of a self-
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lubricating oxide film on the tool–chip interface, owing to the tribological–chemical
reaction by the elevated cutting temperature and attribute the improvement in wear
resistance and reduction in friction coefficient to its formation.
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(ii) TiB2-TiC
IIT p

TiC-TiB2 ceramic–matrix composites have been produced by SHS combined with

pseudo hot isostatic pressing using Ti, B4C and carbon powder (Xinghong et al.,
o

2002). The microstructure of synthesized products consisted of the clubbed TiB2

grains and equiaxed or irregular TiC grains. The optimal ratio of Ti:B4C=3:1 of the
C

reactant powder was determined by experiments. It has been found that the maximum
relative density (96.8 %), hardness (93.5 HRA), compression strength (2.68 GPa),
bending strength (450 MPa) and Fracture toughness (5.8 MPa.m1/2) attained for the
TiC–2TiB2 ceramic are higher than those of TiC–TiB2 and 2TiC–TiB2 ceramics.
Higher clubbing of TiB2 grains into TiC-TiB2 ceramics resulted in a drastic increase
in the fracture toughness for TiC–2TiB2 synthesized compacts.

In-situ toughened TiB2–TiC composites have been fabricated using reaction synthesis
of B4C and Ti powders at high temperatures (Wen et al., 2001). The resulting
materials possessed extremely high relative densities and microstructural examination

32
 Chapter 1

revealed well developed plate-like TiB2 grains (due to very high reaction
temperature), leading to improved mechanical properties. Higher flexural strengths
(453–680 MPa) and excellent fracture toughness (8.4–12.2 MPa.m1/2) were obtained
for these composites.

Vallauri et al., (2008) studied ceramic matrix composites based on TiB2-TiC. The
B

available data provide evidence that the combination of high wear resistance and
relatively high thermal shock and oxidation resistance renders TiC–TiB2 composites
an excellent candidate for cutting tools.

Dense nano-crystalline TiB2–TiC composites formed by field activation from high-

r
energy ball-milled reactants have been studied (Lee et al., 2002). Elemental powders
(Ti, C and B) were milled to produce nanometric powders without product formation

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or to effect a reaction during milling to produce nanostructured TiB2 and TiC. The
ar t
products of these two mechanical activations were reacted/consolidated or only
h
consolidated under the influence of a high current and a uniaxial pressure. Dense (up

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to 98.6%) nanocomposites were formed which exhibited micro-hardness of 20.6 GPa.
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The same composite has also been synthesized by reaction sintering and densify the
composites (Zhao and Cheng, 1999). Intermediate boride phases were formed and
their amount and stability were strongly dependent on the sintering temperature and
time. It was found that the chemical reaction between the starting Ti metal and B4C
y

particles could be complete after sintering at ~1500 0C for 1 h, producing a TiB2-TiC

IIT p

ceramic composite. TiC-TiB2 coatings were deposited on WC-Co cemented carbide

tool bits by non-reactive magnetron sputtering using hot-pressed targets with different
o

TiC: TiB2 molar ratios (Holleck and Lahres, 1991). Hardness values of the TiC-TiB2
layers found is a function of composition, constitution and heat treatment.
C

(iii) Al2O3-TiC

Budhani et al., (1984) deposited TiC-Al2O3 two-phase coatings on stainless steel and
molybdenum substrates by high rate physical vapor deposition. The micro-hardness of
TiC-Al2O3 coatings increases with increasing TiC content. Konyashin (1996)
investigated the physico-mechanical and performance properties of A12O3-TiC
ceramics thin films deposited by an arc-evaporation PVD technique. The processing
technique and composite nature of the coating improves fracture toughness, transverse

33
 rupture strength, hardness and wear resistance of the ceramic indexable cutting
inserts.

Al2O3-TiC ceramic composite were prepared by SHS followed by sintering, using

TiO2, Al and C as raw materials at 3:4:2.7 molar ratio (Lee et al., 2001). The effect
varying the amount of carbon source and cooling time on the products were studied.
The highest combustion temperature and combustion velocity were obtained for
activated carbon, however no significant changes in microstructure and mechanical
properties of sintered Al2O3-TiC composite were observed. Hot pressing was found to
be very effective in hindering the formation of pores and obtaining a dense sintered
body at 1650°C. The composite exhibited high hardness (17- 20 GPa) along with high

r
fracture toughness (4.9 MPa.m1/2)

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(iv) Al2O3-SiC
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Al2O3–SiC composites containing up to 30 wt. % of dispersed SiC particles, have

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been fabricated via hot-pressing and machined as cutting tools. The Al2O3–SiC
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particulate composites exhibit higher hardness (up to 23.4 GPa) in comparison to that
of monolithic Al2O3 because of the inhibited grain growth due to addition of SiC and
the presence of SiC as hard secondary phase. The fracture toughness (maximum 5.2
MPa.m1/2) of the composites remains constant up to 10 wt. % loading of SiC (Ko et
y

al., 2004). The improved performance of the Al2O3–SiC composite tools attributes to
IIT p

the transformation of fracture mode from intergranular fracture for Al2O3 to

intragranular fracture for Al2O3–SiC composites.
o

Al2O3-SiC micro/nano composites have been prepared by axial pressing of sub-

C

micron alumina powder (coated with poly-carbosilane) at elevated temperature with

subsequent pressure-less sintering in the temperature interval of 1700 to 1850 0C
(Galusek et al., 2007). Warm pressing at 350 0C and 50 MPa resulted in green bodies
with high mechanical strength and higher density than in green bodies prepared by
cold isostatic pressing of the same powder at 1000 MPa. Moreover the sintering of
warm pressed specimens yielded composites with higher final density with the
microstructure composed of micrometer-sized alumina grains with inter- and
intragranular SiC precipitates. High hardness (19.4±0.5 GPa) and fracture toughness
(4.8±0.1 MPam1/2) have been achieved for the composites containing 8 vol. % of SiC.

34
 Chapter 1

Bajwa et al. (2005) have investigated the mechanical properties of the nano-
composite ceramic Al2O3–SiC developed by ball milling and subsequent hot pressing.
The significant benefits in wear behaviour compared to that of monolithic Al2O3 have
been demonstrated, particularly for erosive and abrasive conditions. From the
experimental results authors found that the worn track on Al2O3–SiC nanocomposites
exhibit a surface covered in plastic deformation grooves, while for the same
conditions the monolith exhibits intergranular fracture. The dry sliding wear
behaviour of SiC–Al2O3 composites with 5, 10 and 15% SiC has been studied and
compared with monolithic alumina.

r
(v) TiB2-SiC

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Study was made of the reaction between silicon carbide and titanium diboride
ar t
compounds of high hardness and wear resistance occurring in the quaternary system
h
Ti-B-C-Si (Ordan'yan et al., 1986). Micro-hardness values measured on the alloys
varied depending on the particle size, in the range 20-25 GPa. TiB2-SiC composites
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have been produced by reaction synthesis from TiH2-Si-B4C system (Zhang et al.,
1995). The composite exhibited high hardness (16.5 GPa) with high fracture
toughness (8.67 MPam1/2).
y

(vi) SiC-TiC
IIT p

TiC–SiC composites were fabricated by spark plasma sintering (SPS) in vacuum

without additives (Luo et al., 2004). Vickers hardness of the SiC–TiC composites
o

reached upto 28 GPa and maximum fracture toughness value of 6.2±0.6 MPa m1/2 has
been achieved when content of the TiC rose to 30%.
C

Chen et al. (2009) fabricated TiC–SiC composites using TiC and SiC powders as
starting materials in the range of 1650–2000 0C in Ar atmosphere by arc-melting
technique. The hardness of the fabricated TiC–SiC composites was 25–27 GPa.

1.7.2.2 Three-phase ceramic composite

Smirnov et al. (1998) in their work have shown that the Al2O3-SiC-TiC composite
exhibits a three-fold increase in wear resistance as compared to that of monolithic
alumina. Moreover, significant toughening is imparted by SiC whiskers that

35
 subsequently improve the mechanical performance of the composite. The Al2O3–
SiC–TiC composite was fabricated by hot pressing 46.1 vol. % Al2O3 powder, 30.9
vol.% SiC whiskers and 23.0 vol.% TiC powder. Significant reaction occurred
between the Al2O3 and SiC during processing. The resultant composite consisted of
nearly unreacted TiC particles, Al2O3, plus smaller concentrations of SiC, mullite and
possibly a mixture of Al–Si–O–C. The composite exhibited at room temperature an
elastic modulus of 409.69 GPa, micro-hardness values of 19–32 GPa, indentation
fracture toughness of 9.69 MPa.m1/2, compressive strength as high as 2.8 GPa and
fracture strength in bending of 680–825 MPa.

Jianxin (2001) produced Al2O3-TiB2-SiCw ceramic composites with different volume

r
fraction of SiC whisker, and investigated their friction and wear behaviour sliding

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0
against cemented carbide at temperatures up to 800 C in air and nitrogen
ar t
atmospheres. The experimental results revealed a decrease in the wear rate of Al2O3-
h
TiB2-SiC ceramic composite with increasing SiC whisker content. Hardness and
fracture toughness of the composite increases with increasing SiC whisker content.
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Fracture toughness value up to 8.42 MPa.m1/2 has been achieved with 30 volume
percent of SiC content in the composite.

Zhang et al. (1996) developed a platelet reinforced ceramic composite of TiB-TiC-

SiC by reactive hot-pressing, using TiH, Si and B4C as raw materials. Experimental
y

results show that the growth of TiB2 platelets was different in different regions of the
IIT p

composite. The platelets grew very well in the TiC-rich regions and imperfectly in the
SiC rich regions, with agglomeration of TiB2 prohibiting the growth of TiB2 platelets.
o

The EDS results show that there is no reaction between TiB2 and SiC while reaction
between TiC and SiC, forming solid solutions. Fracture toughness value up to
C

6.90±0.18 MPa.m1/2 along with high hardness of the composite has been reported.

TiB2-AlN-SiC ternary composites have been prepared by reactive hot pressing at

2000 0C for 60 min in an Ar atmosphere using TiH2, Si, Al, B4C, BN and C as raw
powders. The distribution of elements Al and Si were found inhomogeneous, which
shows that to obtain a homogeneous solid solution of AlN and SiC in the composites
by the proposed reaction, temperatures higher than 2000 0C or time duration longer
than 60 min are needed. High fracture toughness values (6.35±0.74 MPa.m1/2 and
6.49±0.73 MPa.m1/2) have been obtained in samples with equal molar contents of AlN
and SiC (Yue et al., 1999).

36
 Chapter 1

1.7.2.3 Four-phase ceramic composite

Bulk ceramic composite Al2O3-TiB2-AlN-TiN consisting of 4 hard phases (Changxia

et al., 2007) fabricated by hot-pressing liquid phase sintering, during which AlN and
TiN phases are produced by chemical reactions taking place among Al, Ti and N2.
The relations of volume content of Al-Ti-B and Al-Ti-C master alloys and mechanical
properties of alumina matrix ceramic materials are analyzed. The influences of Al-Ti-
B and Al-Ti-C additions were studied by mechanical property evaluations and
microstructural observation. The developed composite exhibited hardness up to 20.1
GPa, and high fracture toughness (8.44 MPa.m1/2).

r
Ceramic composite powders of TiC-TiB2-hBN-SiC have been synthesized in-situ by

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the combination of two different SHS reactions in one step by Mossino et al. (2004a).
Simultaneous synthesis of TiC–TiB2 and hBN–SiC composites was achieved without
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the application of high pressure or high temperature. The process yielded high purity
h
powders with tailored compositions suitable for the fabrication of ceramic and cermet
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materials characterized by wear resistance and self-lubricant behaviour shown by the
presence of hBN intimately dispersed into the hard ceramic matrix. This process
allows avoiding the high temperature furnace technologies traditionally employed to
produce hBN composites. The addition of silicon carbide which is an important
y

ceramic for high-temperature applications represents a further improvement of the

properties of the final composite material developed. Reactants powders B4C, TiO2,
IIT p

Mg, TiC, C and α-Si3N4 were milled with a planetary mill for 2 h in a grinding vessel
of agate with ball-to-powder ratio of 1:1. The powders were uniaxially pressed into
o

green compacts showing a relative density of about 60%. The ignition of the reaction
was performed through a graphite rod electrically heated under inert atmosphere of
C

argon. The stoichiometry has been tailored in order to obtain 5–7% by weight of hBN
in the final powders after the leaching step (for the elimination of undesired MgO
phase and residual Mg).

Meng et al. (2006) have reported the formation of a Ni-matrix laser clad layer in
which three reinforcing phases, namely, TiB2, CrB and TiC are present. Tjong et al.
(2003) reported the formation of an aluminium-based composite with TiB2, A12O3
and Al3Ti multi-component phases. The composite has been prepared through
reactive hot pressing of TiO2, Al and B powders. Brittle Al3Ti blocks were also

37
 formed in situ when the B/TiO2 molecular ratio is smaller than 2. The experimental
results showed that the composite reinforced with in situ TiB2 and Al2O3 particles
exhibits a relatively stable cyclic response at low total strain amplitudes. The presence
of Al3Ti blocks led to a very slight cyclic hardening followed by softening at total
strain amplitude of 0.4%. Moreover, the intermetallic Al3Ti blocks reduced the fatigue
life of in situ composites as they promoted microscopic cracking during cyclic
deformation.

A variety of Alumina-based ceramic matrix composite cutting tool materials were

discussed by Like et al. (2007) such as ZrO2-A12O3-carbide with Mn and Ti oxides,
A12O3-TiC-TiB2-ZrO2 and A12O3-TiC-Mo-Ti.

r
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1.8 Self-propagating high temperature synthesis (SHS) and laser assisted SHS
ar t
Self-propagating high temperature synthesis (SHS) provides an attractive practical
h
alternative to the conventional methods for producing novel materials, such as

ag
ceramics, ceramic-composites and intermetallic compounds, since it offers advantages
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with respect to process economics and process simplicity.

The underlying basis of SHS relies on the ability of highly exothermic reactions to be
self-sustaining and, therefore, energetically efficient (Moore and Feng, 1995). It
y

generates sufficient thermal energy to sustain itself in the form of a propagating

reaction (combustion) wave through the extent of the powder mixture. The wave
IIT p

travels through the reactants, completely converting them to the final product. The
temperature of the combustion wave may be as high as 5000 K and the speed of wave
o

propagation can be around 25 cm/s. This process offers an opportunity to investigate

reactions at extremely high thermal gradients (~ 105 K/cm) (Subramanyam and
C

Vijayakumar, 1992; Borovinskaya, 1992; Mossino, 2004).

There are a number of reaction parameters which affect SHS reactions, e.g. reactant
particle size, stoichiometry, green density, thermal conductivity, ignition temperature,
combustion temperature, heating and cooling rates and physical conditions of
reactants (Mossino et al., 2004b). Many of these parameters are interdependent and
have significant effects on the final product morphology and properties. Particle size
of the reactant powder has a strong effect on SHS process. The particle sizes of the
reactants influences the degree of completion of the reaction, the temporal sequence

38
 Chapter 1

of the reaction, the temperature profile of the combustion zone and the velocity of the
combustion wave. The stoichiometry of the reactants is another important process
parameter. Generally the deviation from the stoichiometry results in a decrease of the
adiabatic temperature, any excess of either reactants or products will normally
decrease the exothermicity of the reaction with a consequent reduction of the
adiabatic temperature through a reduction in the heat liberated. The compaction or
green density of the powders plays an important role in the combustion synthesis
reaction. A green compact produced with significantly high or low densities will
ignite with difficulty. This effect of green density on the ignition and propagation of
the reaction was attributed to the balance between a good particle contact but not too

r
much to lead to excessive heat loss from the reaction zone due to increased thermal

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conductivity.
ar t
There are different techniques used to ignite SHS reactions, for example ignition by
h
means of radiant flux, resistance heating coil, spark, chemical oven and laser radiation
etc.
ag
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Laser-induced ignition provides a possibility to obtain high heat flux densities (up to
1011 W.m-2). Different types of lasers have been utilized, for example neodymium-
doped glass laser, ruby laser and cesium bromide laser. SHS of many systems such as
Ti + B, Ti + 2B, Ti + C, Ti + 2Si, Zr + C, Zr + 2Si, MO + 2Si, Al + Ni, 2Al + Fe2O3B
y

+ BaCrO4 and 2Cu + 3CuO were studied using laser-induced ignition (Moore and
IIT p

Feng, 1995).

Powders undergoing chemical reactions have been used in laser sintering and
o

cladding. Shishkovski et al. (1999) reported the laser sintering of aluminium and
nickel-base filler powders, titanium and nickel-base filler powders to obtain
C

intermetallics of the Ni-Ti and Ni-Al systems by SHS reactions between the
constituent powders. Tarasova et al. (2000) reported the synthesis of the ceramic PZT
(Lead zirconate titanate) as a monolithic composite by selective laser sintering (SLS)
of the oxides of lead, zirconium and titanium respectively. The laser treatment
induced chemical processes leading to the changes in phase content and lattice
structure of the material. Laser-assisted or laser-triggered SHS has also been
investigated to obtain in-situ synthesis and coating of hard composite materials
(Slocombe and Li, 2001; Kab, 2002).

39
 1.9 Reactions for present work

Zhang et al. (2004), in their paper suggested a series of probable SHS reactions using
boron carbide (B4C) and boron nitride (h-BN) as reactants, to produce ceramic
composites containing borides. From this literature a suitable reaction that can
produce Al2O3, TiB2 and TiC as final products from the reactants TiO2, B4C and Al
has been adopted as follows:

4 Al + 3TiO2 + B4C = 2 Al2O3 + 2TiB2 + TiC ...Eq(1)

ΔGθ T = −1291684 + 161.145T (J/mol)

r
In this respect it may be mentioned, Wang et al. (2004), employed this exothermic
reaction to develop a metal matrix composite (MMC) of Al2O3, TiB2 and TiC in

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aluminum matrix by the conventional sintering route.
ar t
Al2O3-SiC composite powder was prepared by the SHS process, using SiO2, Al, and C
h
powders as raw materials (Lee et al., 2000). Thermodynamic data calculated by the
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authors shows the possibility of reaction (2) and (3) at high temperature.
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SiO 2 + 2C → SiC + CO 2 Eq(2)

3SiO 2 + 4Al + 3C → 2Al2 O3 + 3SiC Eq (3)

y
IIT p

1.10 Wear characteristics of ceramics and laser alloyed/cladded coatings

Though, many researchers have developed laser-assisted wear resistant coatings with
o

some novel material compositions exhibiting promising hardness and microstructural

C

characteristics, very few (Ocelík et al., 2005, Xu and Liu, 2006) have assessed the
wear behaviour of the coatings developed by laser surface modification techniques.

There is no generalized rule that can be globally applied to a tribological phenomenon

for the prediction of amount of wear. Wear resistance of a material is the ability to
resist gradual removal of material caused by mainly following basic mechanisms
(Holmberg et al., 1994; Erdemir, 1994).

(a) Adhesive wear

Adhesive wear can be described as plastic deformation of very small fragments within
the surface layer when two surfaces slide against each other. The asperities found on

40
 Chapter 1

the mating surfaces will penetrate the opposing surface and develop a plastic zone
around the penetrating asperity. Dependent on the surface roughness and depth of
penetration the asperity causes damage on the surface layer or even the underlying
bulk material. In initial asperity/asperity contact, fragments of one surface are pulled
off and adhere to the other, due to the strong adhesive forces between atoms. It is
thereby clear that physical-chemical adhesive interaction between the surfaces plays a
role in the initial build-up process but the energy absorbed in plastic deformation and
relative movement is the main cause for material transfer and wear.

(b) Abrasive wear

r
Abrasive wear occurs when a hard rough surface slides across a softer surface. The
harder surface asperities are pressed into the softer surface which results in plastic

pu
flow of the softer material around the harder one. When the harder surface moves
ar t
tangentially, plouging and removal of softer material takes place resulting in grooves
h
or scratches on the surface. Depending on the geometry of the harder surface and the

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degree of penetration, the removal of material can take different forms, such as
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plouging, wedge formation or cutting. The two modes of abrasive wear are known as
two-body and three-body abrasive wear. Two-body wear occurs when the grits, or
hard particles, are rigidly mounted or adhere to a surface, when they remove the
material from the surface. Three-body wear occurs when the particles are not
y

constrained, and are free to roll and slide down a surface.

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(c) Fatigue wear and delaminating wear

o

Fatigue crack growth results from repeated loading and unloading of a surface, at a
stress level lower than its ultimate strength. Fatigue wear is produced when the wear
C

particles are detached by cyclic crack growth of micro-cracks on the surface. These
micro-cracks are either superficial cracks or subsurface cracks. Fatigue can initiate
large-scale cracking and may result in the liberation of surface material in the form of
wear debris. At the points of concentrated contact, the surface creates a stress field
beneath the contact zone where the maximum shear stress occurs. In rolling, where
the stress field moves repeatedly over the surface, fatigue of the near-surface material
takes place. Material voids or dislocation pile-ups may form the nuclei for the first
crack to occur. After that the crack will often propagate quite rapidly, unite with other
cracks and liberate surface material. This often results in large craters in the surface.

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 Delamination wear is a kind of fatigue wear that occurs on a more microscopic scale
in sliding contacts when surface asperities repeatedly slide over each other. Small
cracks are nucleated below the surface. Further loading and deformation causes cracks
to extend, propagate and join with neighboring cracks. The cracks tend to propagate
parallel to the surface, resulting in the delamination of long and thin wear sheets.

(d) Erosive wear

Erosive wear is caused by the impact of particles of solid or liquid against the surface
of an object. The impacting particles gradually remove material from the surface
through repeated deformations and cutting actions. It is a widely encountered

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mechanism in industry. A common example is the erosive wear associated with the
movement of slurries through piping and pumping equipment. The rate of erosive

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wear is dependent upon a number of factors such as shape of the particles, hardness,
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impact velocity and impingement angle along with the properties of the surface being
eroded.
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(e) Chemical wear

Chemical wear occurs due to detrimental chemical reactions in the contact, initiated
by the influence of the environment in combination with mechanical contact
mechanisms. Rubbing, in combination with the chemical reactions in the contact,
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results in removal of material and wear debris formation. The chemical reactions at
the surfaces may render them softer and weaker and thus decrease their resistance to
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new crack formation and liberation of surface material in the form of wear products.
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Oxidation wear is the most common chemical wear process. A thin layer of oxides
will be formed on metal surfaces. This is an important protective layer because
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without it both the friction and wear in metal contacts would be extremely high. If this
layer is continuously removed by rubbing action and the contact is exposed to a
humid environment, the formation of new oxide layers is speeded up and the result is
typical oxidation wear. In certain cases wear can be due to chemical instability of the
materials.

Most of the ceramics are brittle because of their covalent and ionic bonds. In the
presence of a hard particle or at high asperity contact pressure, fracture by radial and
lateral cracks can be the dominant wear mechanism (Wang and Hsu, 1996). For
polycrystalline solids, inter-granular fracture is a result of grain boundary cracking

42
 Chapter 1

(Breznak et al., 1985). Despite the fact that ceramics are considered brittle materials,
one of the wear mechanisms reported in the literature is “plastic deformation” (Cutter
and McPherson, 1973; Aghan and McPherson, 1973). Other wear mechanisms of
ceramic materials which appear in the literature are fatigue-induced wear (Bayer and
Sirico, 1970), chemical reaction induced wear (Sugita et al., 1984) and adhesive wear
(Mehrotra, 1987).

Wear resistance of brittle ceramics against abrasion is mainly determined by micro-

cracking. During unlubricated oscillation and abrasive sliding contact, friction and
wear of the ceramics are defined by inter-crystalline micro-fracture, spalling of grains
or particles of second phases, grain fragmentation, formation and quasi-plastic

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deformation of surface layers consisting of densified wear debris, detachment of these

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surface layers and delamination fracture due to subsurface cracking. Sensitivity of the
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ceramics to surface pressure can be reduced by steps which abate micro-cracking and
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spalling of grains or phases embedded in the matrix (Zawrah et al., 2002).

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The ceramic particles formed in-situ has a uniform dispersion in the matrix. This
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restricts removal or pulling out of grains in case of abrasive wear interface. In that
case, the wear mechanism appears to be mix-up of micro-cutting, ploughing and grain
pull-out (Sivaprasad et al., 2008).
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Jianxin (2001) has reported the wear behaviour of Al2O3-TiB2-SiC composites up to a

temperature of 800 0C. It was emphasized that oxidative wear was dominaing at
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higher temperatures. For sliding contact of materials at high operating temperatures,

oxidation plays a significant role, causing changes in the overall wear rate. The
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importance of oxidation during wear was identified by many researchers and the
classification of mild and severe wear was proposed based on measurement of contact
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resistance, wear debris analysis and microscopic examination.

The effect of applied load on the wear rate of the Al-based composites prepared by
other routes has been analyzed by many investigators (Xie et al., 2006; Basavarajappa
et al., 2006). It has been emphasized that the wear rate increases with the applied
load. Natarajan et al. (2009) investigated the dry sliding wear behaviour of the Al
6063/TiB2 composite by using a pin on disc method at different applied loads of 9.8,
19.6 and 29.4 N for various temperatures. The results indicate that the wear rate

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 decreases with the increase in the weight percentage of TiB2, while it increases with
the increase in the applied load.

Xu et al. (2006) have shown that the wear characteristics of cladding are completely
dependent on the content and morphology of the TiB2 particulates and intermetallics
in the microstructure and the applied load. At the lowest load (8.9 N) with increasing
content of TiB2 particulate and intermetallic, the wear weight loss of the laser
cladding is decreasing. At high applied load (>8.9 N), 2024 Al alloy displayed
superior wear resistance to the laser cladding coating, the dominant wear mechanism
of cladding coating is delamination and third-body abrasion.

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1.11 Modulus of elasticity (E) and fracture toughness (KIC) measurement of the

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coating

The modulus of elasticity (E) and fracture toughness (KIC) are the important properties
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for a coating material as these are strongly related to the mechanical strength of the
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coating. Residual stress of a composite coating is also dependent on the E value of the
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coating material. For a composite material, E is changed according to its composition
as well as the processing techniques employed. Measurement of modulus of elasticity
(E) is difficult by conventional methods for a “composite coating” of low area and
thickness.
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The nano-indentation technique is at present widely employed to determine various

mechanical properties, such as hardness, modulus of elasticity, scratch resistance,
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residual stress, based on the analysis of the indentation load-displacement curves

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resulting from the nano-indentation test (Bhushan, 1999).

Oliver and Pharr (1992) developed a mathematical model to measure nano-hardness

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and modulus of elasticity by analysis of the indentation load displacement curves

resulting from the nano-indentation test.

Most of the previous studies concerning the determination of hardness and modulus of
elasticity have been performed on either thin films (Barshilia et al., 2008; Fischer-
Cripps et al., 2006; Sjölén et al., 2007; Raju et al., 2008) or on bulk ceramics or
ceramic composite materials (Gong et al., 2003; Ichimura and Ando, 2001; Musil et
al., 2002).

44
 Chapter 1

Very few works have been done (Biswas et al., 2008; Agarwal and Dahotre, 2000b;
Xu and Liu, 2006) to measure modulus of elasticity (E) and nano-hardness (H) for
coatings developed by laser coating technology using nano-indentation technique.

Biswas et al., (2008) calculated the hardness and modulus of elasticity from a load–
displacement graph using the method proposed by Oliver and Pharr for the TiN
coating developed on Ti-6Al-4V alloy through laser surface nitriding. Modulus of
elasticity (E) and nano-hardness (H) have been evaluated using the nano-indentaion
technique for the composite boride coatings developed with various laser traverse
speeds (Agarwal and Dahotre, 2000b). E values have been correlated to the
reaction(s) occurring within the coating region for different laser scan speeds. The

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investigators also found that theoretical elastic modulus values are lower than the

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computed elastic modulus values, as the latter includes the effect of dissolution of fine
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TiB2 particles in the Fe matrix and metastable phase formation.
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Xu and Liu (2006) measure the nano-hardness (H) and the modulus of elasticity (E) of

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the phases of the TiB2 particulate-reinforced metal matrix composite coating
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developed on 2024 aluminum alloy by laser cladding.
Fracture toughness (KIC), a measure of a materials resistance to crack propagation, is a
critical parameter for a ceramic or ceramic composite used for coating. The
application of the Vickers indentation technique to measure the fracture toughness of
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brittle materials, particularly glasses and ceramics, has become widespread because it
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can be used on small sized samples of materials not amenable to other fracture
toughness tests.
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Lawn and Fuller (1975), Evans and Wilshaw (1976) and Lawn, Evans and Marshall
(1980) have developed mathematical models to determine fracture toughness through
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indentation technique. The models are as follows

⎛ P ⎞
K IC = 0.0515 ⎜ 3/ 2 ⎟ c / a ≥≈ 2 [Lawn and Fuller] …Eq(4)
⎝c ⎠

⎛ P ⎞
K IC = 0.079 ⎜ 3/ 2 ⎟ log(4.5a / c) 0.6 ≤ c / a ≤ 4.5 [Evans and Wilshaw] …Eq(5)
⎝a ⎠

1
⎛ E ⎞2 ⎛ P ⎞
K IC = α ⎜ ⎟ ⎜ 3/ 2 ⎟ [Lawn, Evans and Marshall] …Eq(6)
⎝H ⎠ ⎝c ⎠

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 Where P = applied normal load, a = half-indentation diagonal, c = (crack length +
half-indentation diagonal) and α depends on geometry of the indenter. A Schematic of
crack formation by Vickers indentation is shown in Chapter 2

Cantera et al. (1998) determined the fracture toughness of composite coating 86WC–
10Co–4Cr produced by the Detonation Gun (D-Gun) process and High Velocity Oxy-
fuel (HVOF) process. Fracture toughness of composite coatings deposited by HVOF
spraying of SHS-derived cermet powders of Ni(Cr)–TiB2 in different percentage
compositions have been measured (Lotfi et al., 2003). Bolelli et al. (2006) have
measured fracture toughness for thermally sprayed ceramic composite coating of

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(Al2O3, Al2O3–13%TiO2, Cr2O3) by indentation method. The indenter was positioned

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such that the two indent diagonals were parallel and perpendicular to the substrate–
coating interface, respectively.
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For all of the above cases, indentation load of 1 kgf have been used to produce
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parallel and transverse crack of the coating substrate interface. For first case (Cantera
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et al., 1998) both “Evans and Wilshaw” and “Lawn and Fuller” equations have been
employed whereas for other cases (Lotfi et al., 2003; Bolelli et al., 2006) only “Evans
and Wilshaw” equation has been used to calculate fracture toughness values.
However, no specific literature has been found that has employed indentation method
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to measure the fracture toughness of ceramic composite coating developed by laser

alloying/cladding.
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It has been found that there is no simple relationship between the mechanical response
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(like wear resistance) of the coating and H or E alone; however, this response is
strongly dependent on the ratio H/E. Leyland and Matthews (2000) discussed the
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importance of the elastic modulus E and the ratio H/E in determining the endurance
capability of a surface coating, especially its ability to accommodate substrate
deflections under load. Recent experiments, however, show that hard nano-composite
coatings with the same hardness, according to their chemical composition, can exhibit
different values of the effective Young’s modulus (E) (Musil et al., 2002). This means
that there is a possibility of tailoring the mechanical properties of a material for a
given application.

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 Chapter 1

1.12 Problem Definition and Objectives

From the review of the past research on laser surface modification techniques it has
been found that the laser surface modification technique is capable of producing hard
and wear resistance composite coatings involving dispersion of hard ceramic phases
in a relatively softer metal matrix. Due to the presence of the soft metal matrix, the
maximum hardness of such laser-treated coatings is generally limited to about 1500-
1800 HV. The properties of the laser surface modified region depend mainly on the
chemical composition and microstructure resulting from melting and rapid
solidification.

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From the literature it has also been found that ceramic-matrix composites (CMC) or
multi-component ceramic composites can enhance the values of fracture toughness of

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the composites along with high hardness. This raises the possibility of obtaining a
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coating of high hardness with high fracture toughness. Hence, the feasibility of multi-
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component ceramic coatings on metal substrates can be a new area of interest in

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surface engineering.
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A composite comprising of the constituents Al2O3, TiC and TiB2 may also combine
ceramic properties such as high melting point, high hardness, thermal and chemical
stability, wear and corrosion resistance with typical metallic properties such as high
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electrical and thermal conductivity. This advantageous combination can make these
materials promising candidates as constituents of a multi-component protective
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coating with enhanced resistance against thermal, corrosion and mechanical wear.
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Self-propagating high-temperature synthesis (SHS) technique leads to the in-situ

formation of refractory ceramics from reactants through exothermic reaction. Laser-
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assisted or laser triggered SHS has also been investigated by some researchers to
obtain in-situ synthesis and coating of hard composite materials.

From the literature it has also been found that, high power diode laser (HPDL) with its
specific advantages; i.e. uniform intensity distribution, high absorption by metallic
surfaces, low operating cost and easy to transport through fiber optics proves to be an
extremely appropriate tool for laser surface engineering.

Nano-sized precursors, with a high surface-to-volume ratio in the powder mixture,

ensure better mixing between the powder constituents. This causes a fast initiation
and completion of the SHS chemical reaction. Sol-gel technology is a chemical route

47
 to produce nano-sized TiO2 and SiO2, which could be used as precursor powder for
laser triggered SHS reaction.

In the case of multi-component ceramic composites, a number of research groups

have experimented with the addition of SiC to the matrix of coatings for
improvements in the coating properties. It is interesting to note that apart from the
increase in hardness, significant toughening can also be imparted by the addition of
SiC to a material. Ceramic composite powder consisting of four phases has been
synthesized in-situ by the combination of two different SHS reactions by some
research groups. Bulk ceramic composites consisting of four hard phases may exhibit
higher hardness with higher fracture toughness.

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Hence, after review of the aforementioned literature and progress in the field of laser

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assisted surface engineering, it has been decided to develop multi-component ceramic
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composite coatings with the novel compositions of Al2O3-TiB2-TiC and Al2O3-TiB2-
h
TiC-SiC in-situ through SHS reactions and subsequent laser cladding. The SHS

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reactions considered for the Al2O3-TiB2-TiC composite coating as per Eq(1) and for
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the Al2O3-TiB2-TiC-SiC composite coating as per combination of both Eq(1) and
Eq(2) as suggested by Zhang et al. (2004) and Lee et al. (2000) .

To the best of the authors’ knowledge these combinations of hard phases i.e. Al2O3-
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TiB2-TiC and Al2O3-TiB2-TiC-SiC in a coating have not been attempted earlier and
are going to be investigated in the present work for the first time.
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With these motivations, the major objectives of the present investigation are set as
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follows

1. To investigate the feasibility of the development of in-situ Al2O3-TiB2-TiC

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multi-component ceramic composite coating on mild steel (AISI 1020)

substrate, by combined SHS and laser cladding of pre-placed powder mixture.

2. Development of Al2O3-TiB2-TiC composite coating using high power diode

laser (HPDL) on AISI 1020 mild steel

3. To study the effects of sliding speed and normal load on the tribological
performance of the composite coating developed with different laser process
parameters (laser power and laser scanning speed).

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 Chapter 1

4. To measure the modulus of elasticity (E) nano-hardness (H) and fracture

toughness (KIC) of the composite coating.

5. To study the effects of variation in size of TiO2 powder in the precursor

powder mixture on the properties and performance of the coating.

6. To study the effects of substrate materials (AISI 1020 and AISI 304) on the
formation, properties and performance of coatings.

7. Development of Al2O3-TiB2-TiC-SiC composite by double SHS reactions and

to study the effect of additional SiC on the performance of the coating.

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