ENGM174 Ceramics & Ceramic

Coatings
Question 1
a) Describe the fracture mechanisms that occur within a ceramic
when impacted by a spherical projectile. In answering the
question you should describe the evolution of fracture as a
function of time as the projectile impacts the surface.
Due to their high hardness and relatively low density compared to metals,
ceramic materials are often used for the application of ballistic armour. When
impacted by a blunt projectile, such as a spherical object, a ceramic will form
cone cracks at the interface between projectile and ceramic. Figure 1 illustrates
an alumina specimen after impact from a spherical projectile at high velocity,
clearly showing the cone and radial cracks that have formed during the impact.
The cone cracks formed under impact from a
spherical projectile are similar to the fracture
mechanism due to quasi-static blunt indentation.
The cone cracks form following the maximum
tensile stress ring that occurs below the contact,
as described by Hertzian contact theory. The
crack continues to grow until the elastic strain
energy reduces below the surface formation
energy according to the Giffith criteria.
Furthermore, during the initial phase of the
impact, the area of high pressure caused by the
projectile impact reaches the rear face of the
ceramic causing cracks to initiate along with
deformation of the back plate supporting the
Figure 1: Cone & Radial cracks on ceramic
ceramic.
after projectile impact (Yamada, et al.,
2010)

As the cracks propagate through the material

they will coalesce and cause comminution, resulting in a cone of fractured
material as shown in Figure 2. Generally, intergranular fracture is preferable to
transgranular as the cracks will have to travel along a further distance therefore
lengthening the time to coalesce and comminution, although both mechanisms
are likely to occur during impact (Hazell, 2015).
The formation of the cone of fragmented material is advantageous as the force
of the impactor is spread over a large area, reducing the damage to the back
plate and objects that the armour is protecting. The main disadvantage is that
since most of the material has been fragmented the ability for the ceramic to
resist subsequent impacts is significantly reduced.

Figure 2: Ceramic fracture mechanism from projectile (Wadley, 2014)

b) Studies of the ferroelectric material BaTiO3 show that the

relative permittivity is not constant as a function of
temperature. With reference to the phase diagram explain the
changes in relative permittivity observed.
Ferroelectric materials are capable of holding spontaneous polarisation, or a
dipole moment. The dipole moment is as a result of the centre of the positive
and negative charges in an atomic structure being separated by some distance.
In order for this to be the case the centre atom in the structure cannot be
equidistance from the surrounding atoms, otherwise the symmetry would result
in a zero dipole moment, therefore the atomic structure cannot be symmetric
around the centre point, such as a cubic structure.
The overall dipole moment in a piece of bulk material is dependent on the
moment and orientation of the domains that comprise the material. Typically, a
ferroelectric material will be constructed of many different domains
perpendicular and parallel to each other, with a strong tendency to align the
positive end with the negative end of an adjacent domain. Where this occurs
there will be no net dipole moment as the domains will
cancel each other out. The direction of polarisation can
be changed in ferroelectric materials through external
application of an electric field. The change in
polarisation follows the hysteresis curves shown in
Figure 3, demonstrating how application of a strong
electric field in a single direction can produce a
homogenously polarised material. If the electric field is
subsequently reversed gradual nucleation and growth Figure 3: Hysteresis Curve
of dipole moments in the direction of the field will occur for Ferroelectric materials
(Mousharraf & Turjo, 2012)
resulting in the hysteresis curve shown.
Barium titanate (BaTiO3) has a perovskite structure, where the barium atom is
centred with oxygen and titanium atoms surrounding. The structure can exist in
different phases, shown in Figure 4 is the phase diagram illustrating how the
phase of the material changes as a function of temperature and pressure.

Figure 4: Pressure vs Temperature phase diagram for BaTiO3 (Hayward & Salje, 2002)

Above 120C, at atmospheric pressure, BaTiO3 has a cubic structure, where all
atoms are equally spaced resulting in no dipole moment. This is known as the
Curie temperature as no spontaneous dipole moment is exhibited above this
temperature. As the material cools it enters the tetragonal phase, where the
structure forms a rectangular cuboid characterised by a lengthening of one
dimension of the cubic structure. This causes a relative movement of the
Titanium and Oxygen atoms, as shown in Figure 5, resulting in a net dipole
moment in the vertical direction. Below approximately 5C, the orthorhombic
phase takes on the structure of an irregular cuboid where none of the
characteristic lengths are equal, as we can see in the figure this gives a net
dipole moment with a vertical and horizontal component. Finally, after further
cooling to below -90C, BaTiO 3 enters the rhombohedral phase whereby one axis
is no longer perpendicular to the others, resulting in a further movement of the
titanium atom relative to the oxygen atoms and increasing the dipole moment.

Figure 5: Barium Titanate spontaneous dipoles for each phase (DoITPoMS, 2006)

The effect that these phase changes has on the

relative permittivity, or dielectric constant, of the
material is illustrated in Figure 6. Relative
permittivity can be defined as the permittivity of a
material compared to the permittivity of a vacuum,
it is particularly important when designing
electronics components such as capacitors. The
peak relative permittivity is exhibited at 120C,
where the phase change to cubic takes place and
Figure 6: Dielectric Constant for
there is a general decrease in the value as the
BaTiO
3 as a function of temperature
material moves from the tetragonal through to
(Horiba, 2008)
rhombohedral phases.

c) Select the two most appropriate coatings and explain the

reasons for your choice
i)

Internal components of a pump exposed to an abrasive fluid

Internal pump components exposed to an abrasive fluid must be resistant to

corrosion and erosion whilst experiencing prolonged use. It is likely that once
fitted the pump components will be required to endure a long life cycle with little
opportunity for maintenance.
Carbide coatings with a cobalt matrices, such as TiC/Co, have been used as
coatings for pumps to effectively extend the life of the internal components.
When deposited using a thermal spray method, such as high velocity oxy-flame,
it is possible to get very thick coatings up to 600m. This large thickness and
good adhesive properties to substrates can extend the life of components by as
much as 12 times (Sulzer, 2001).
Alternatively, a titanium nitride coating offers good toughness and adhesion to
metallic substrates that are likely to be used for pump components, the metallic
bonding present in a TiN coatings ensures that there is a strong bond between
the coating and a metal substrate. The inclusion of the nitride coating would
increase the life of the component substantially against abrasive wear although
it is possible it may suffer in the presence of a corrosive fluid.

ii)

Dry cutting of a hardened steel

nc-(Al,Ti)N/a-Si3N4 is a nanostructured coating comprising of nanocrystalline

aluminium and titanium nitride embedded into an amorphous matrix of silicon
nitride. This structure provides a coating of superior properties compared to
(Al,Ti)N alone, including improved hardness of 40-50GPa which is sustained at
high temperatures as well as improved oxidation resistance (Cselle, et al., 2003).
The silicon nitride content has been found to stabilise the (Al,Ti)N against
decomposition and softening whilst remaining stable (Cavaleiro & De Hosson,
2006). As a result of the desirable properties of the coating, it has been shown
that tool lifetime can be increased significantly when dry machining very hard
steel using this nanostructured coating, with studies indicating life increases of 24 times (Cavaleiro & De Hosson, 2006). These properties make nc-(Al,Ti)N/a-Si 3N4
an excellent coating selection for this application.
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Aluminium chromium nitride is another coating suitable for the cutting of

hardened steel. This ternary coating provides good wear resistance and low
friction at high temperatures. This is largely due to the introduction of aluminium
which, when exposed to high temperature, forms a protective oxide layer helping
to protect the coating and tool (Zelinksi, 2005). The AlCrN coating offers a less
expensive alternative to the premium nanostructured coating of nc-(Al,Ti)N/aSi3N4.

iii)

Machining of a SiC whisker reinforced alumina

SiC whisker reinforced alumina is a very hard and tough material making
machining a challenging task. The high hardness will cause excessive wear in all
but the hardest and wear resistance materials and coatings.
The most obvious choice is a diamond coating deposited using chemical vapour
deposition. Diamond has the highest hardness (100GPa) of all the available
coatings, making it most suitable for cutting the hard ceramic matrix composite.
Diamond retains its properties even at very high temperatures, as would be
experienced during machining the material, furthermore it is only reactive with
ferrous metals at high temperature which would not cause any problems for
cutting a ceramic material. Diamond coatings deposited using CVD are very
expensive and the substrate choice is limited to materials that can withstand the
high temperatures such as carbide tool inserts.
Given that the wear rate for any tool and coating machining SiC whisker
reinforced alumina will be very high it might be favourable to select a coating
that offers a good compromise between wear rate and cost. Nitride coatings
have long been used for their wear resistant properties and can be deposited
using less expensive deposition methods. TiN offers oxidation resistance upto
only ~500C so it may be necessary to use AlCrN which provides oxidation
resistance up to much higher temperatures whilst also retaining its hot hardness.

iv)

Hip implant

In order for a coating to be suitable for use in a hip joint prosthesis it must be
biocompatible and offer excellent wear resistance properties. It is essential that
that the coatings exhibit good resistance to corrosion in a fluid environment and
that that adhesive or cohesive failure of the coating does not occur as a result of
impact fatigue. The two of the available coatings that satisfy the biocompatibility
requirement and have been successfully implemented as coatings for prosthetics
at titanium nitride (TiN) and diamond-like carbon (DLC). Both coatings display
high hardness and good wear resistance whilst showing little corrosion in a
simulated body fluid environment (Wang, et al., 2010). Titanium nitrides
corrosion resistance was due to formation of an oxide layer that protected the
coating whilst DLC is chemically inert in the fluid environment tested. DLC is the
most desirable coating given that it possesses better resistance to impact fatigue
and a smoother, harder surface leading to less wear during operation.

v)

Forming tool

Forming tools are required to have good wear resistance and low friction
coefficient but do not operate at the high temperatures experienced by
machining tools. Tungsten disulphide (WS 2) offers very low friction coefficient
which decreases as applied load increases up to around 2000MPa (Baumgarten,
et al., 2011) making it particularly suitable for use on forming tools. Disulphide
5

coatings have strong planar with weak inter-planar bonding, allowing sliding
between planes hence the low friction coefficient. Coatings are limited in
thickness due to the fact that the coating does not adhere well to itself.
Diamond-like carbon also offers excellent low friction properties coupled with a
high hardness. Use of a graded interface can be used to ensure that the coating
has good adhesive properties to the substrate and performance of the coating in
this type of application has been proven through use on punches and dies.

d) A set of 40 nominal identical bars are manufactured from an

oxide ceramic. 20 are ground then tested in four-point bending
using a slow rate of loading. The other 20 are ground then
polished before testing in three-point bending using a fast rate
of loading.
Figure 7 illustrates the tensile stress distribution of a specimen in 3-point and 4point bending. The area of maximum tensile stress in the 4-point bend test is
clearly much larger than the maximum stress are in the 3-point test. Since there
is a larger volume of material in the specimens at higher stress in the 4-point
test, there is a greater probability that a flaw of critical size will be encountered
resulting in failure of the specimen. This is reflected by a reduction in the Weibull
modulus, indicating a greater degree of variability in the results, along with a
reduction in the average strength.
Polishing the specimens will reduce the surface roughness of the material,
thereby removing stress concentrations and surface cracks that are present
during testing. Since the maximum tensile stresses occur at the surface during a
flexural test, the removal of surface flaws will act to increase the Weibull
modulus (reduce variability in the results) and increase the average
characteristic strength of the specimens.
Studies have shown that the dynamic fracture
toughness for a ceramic oxide, alumina, is higher
under dynamic loading than quasi-static testing
therefore indicating that a fast load rate will result
in greater characteristic strength (Duffy, et al.,
1987). However, the test in the study were
conducted using notched tensile specimens, a
similar correlation between load rate and fracture
toughness has been shown in flexural tests of
Silicon Carbide materials (Weerasooriya, et al.,
2006). Oxide ceramics are also susceptible to subcritical crack growth, where cracks can grow as a
result environmental attack thereby decreasing the
strength and Weibull modulus although it is
unlikely that this will have a significant effect over Figure 7: Tensile stress
distribution for 3-point and 4the duration of a typical flexural test.

point bend test (Richerson, et al.,

Overall, the polished specimens tested in 3-point 2006)

bending with a fast rate of loading will exhibit a higher characteristic strength
and Weibull modulus than the 4-point bend test with ground specimens and slow
6

load rate. This is a result of the significant increase in strength from 3 to 4 point
bending, which also reduces the variation in results, along with the reduction of
surface defects from polishing. Finally, the increased load rate is likely to result in
a higher characteristic strength with little effect on the Weibull modulus.

e) Ceramics are frequently used as cutting tools due to their high

hardness and temperature stability. Identify and explain the
design and materials requirements for such tools.
When selecting a cutting tool material it is important to consider the machining
processes and material that will be undertaken, the longevity of the tooling and
the quality of the finish after machining. In particular, it is essential that a cutting
tool has good wear resistance in order to ensure tools last as long as possible,
minimising machine down time and replacement tooling cost. Furthermore, a
high fracture toughness is desirable to prevent tool damage during interrupted
cutting or whilst manufacturing an inconsistent workpiece.
Modern engineering ceramics have been developed with material properties that
satisfy the requirements for cutting tooling. Ceramic materials typically exhibit
very high hardness compared to their metal counterparts, proving excellent
abrasive wear resistance while also giving better chemical inertness allowing
cutting of a wider range of materials. A key area where ceramic materials are
superior to metal cutting tool materials is their high temperature properties.
Since ceramic materials generally have higher melting points, they can be
operated at higher temperatures hence faster cutting speeds, improving
productivity whilst reducing machining costs.
Figure 8 shows an extract from the ASM Speciality Handbook: Tool Materials,
illustrating the approximate cutting speeds for a wide range of typical tooling
materials along with the materials they can generally be used to machine.
Amongst the top four materials given are ceramic materials such as Alumina and
Silicon Nitride based ceramics along with composite ceramics utilising whisker
reinforcement. The high temperature properties of the ceramic materials allow
cutting speeds many times faster than standard cutting steels and also ceramic
coated carbide materials, indicating the potential increases in efficiency that can
be gained from using ceramic materials over traditional tool materials. It is worth
noting, however, that whilst cutting speeds can be greatly increased the feed
rate used will be limited as a material of lower toughness is used.

Figure 8: Approximate speed ranges and applications for various cutting and tool materials (Davis,
1995)

There are a few limitations regarding use of ceramic tool materials. In particular,
ceramics lack fracture toughness compared to metal and carbide materials. This
makes ceramic tooling more prone to cracking, notching and chipping which,
given ceramic materials brittle nature, can lead to more frequent failure of
cutting tools. These problems have been alleviated to some extent through
introducing metallic particulates or whiskers and through edge preparation of
cutting edges. One example of this is the development of Alumina-based
ceramics through addition of metal particulates. Studies have shown that
Alumina reinforced with Titanium Carbide (Al 2O3-TiC) provides an increase in
hardness and toughness. Similarly, whisker reinforced alumina can provide an
increase of fracture toughness by as much as a factor of 2 as well as increasing
the thermal shock resistance (Burden, et al., 1988). The whiskers act to prevent
crack propagation through the material and toughness is increased through
whisker pull out.
A further limitation of ceramic cutting tools is their low thermal shock resistance.
Thermal shock can be an issue when cutting at high speeds, therefore at high
temperatures, and introducing cutting fluid. The large fluctuations in
temperature can lead thermal cracking in the material resulting in failure of the
tool (Brandt, 1985), although as discussed these issues can be alleviated by
adding particulates or whiskers.
The design on the cutting tool has a significant effect on the cutting
performance. The size and shape both effect the quality of the cut, the maximum
cut depth and the strength of the cutting tool. A larger cutting radius of a tool
insert will increase the strength at the cost of more power required to drive the
work piece or tool and increased vibration which will degrade the quality of the
finish. Figure 9 illustrates the effect the cutting shape has for turning cutting tool
inserts. Scale 1 indicates that the strength of the inserts increases to the left,
with increasing radius of cutting edge, while the accessibility of the insert is
increasing towards the right. The accessibility is indicating the inserts ability to
cut small radius edges or reach certain areas in more complex shapes, clearly for
the circular insert the radius of cut achievable is much more limited along with
the ability to cut into enclosed areas. The second scale is representing the
inclination for vibration to occur whilst machining, this increases in correlation
with the area of the cutting edge in contact with the workpiece. Finally, the
power requirement when machining is also directly related to the size of the
contact edge.

Figure 9: Various tool shapes with effect on Strength (S), Accessibility (A), Vibration (V) and Power
(P) (Sandvik Coromant, 2016)

The size of the insert will have an effect on the depth of cut achievable, with
larger inserts capable of deeper cuts than small ones. This will also have an
effect on the chip size generated during cutting, it is important that the chip size
is appropriate for the tooling material, workpiece and cutting technique in order
to achieve the most efficient process.

f)
i)

The benefits and drawbacks of the pull-off test

The pull-off test can be used as a qualitative or quantitative assessment of a

coatings adhesion to a substrate. In the case of a qualitative test, a piece of
scotch tape can be applied to the coating then removed. A visual inspection of
the tape will indicate if the coating has adhered to the substrate or been partially
or fully removed by the tape. Whilst providing an inexpensive and quick
assessment, this method offers only a rough indication of the coating adhesion
with a low degree of repeatability and little ability to compare coatings.
A quantitative approach utilises a
tensile test machine to measure
the pull off force applied to a
coating. Figure 10 illustrates the
setup for the pull-off test using a
tensile test machine. Rods are Cement
cemented to the coating and
substrate with a load applied to
each, the applied force is
gradually increased until there is
failure of the coating.

Coating

Substrate

This type of pull of test can

provide a comparable value
indicating the strength of the
F
adhesion between coating and substrate, also allowing for an assessment of the
consistency of adhesion for a particular coating/substrate combination. The only
measurements required are the
Figure 10: Schematic diagram of pull-off test setup
applied load and the crosssectional area of the test piece.
Whilst the test is easy to implement there are a number of potential drawbacks
from using this technique. Firstly, perfect alignment of the rods and cement onto
the coating is required in order to provide a uniform loading over the test area.
This could be difficult to achieve leading to a results that do not accurately
reflect the adhesive strength of the coating. Failure during the test can result
from fracture between the coating and substrate (adhesive), the cement and the
coating or within the coating itself (cohesive). Furthermore, whilst a tensile load
is applied, the stresses present may be a complex combination of tensile and
shear stresses making comparison between tests challenging (Stern, 1996). This
means that careful inspection of the test piece should be carried out to
determine the failure mechanism that has occurred. Where failure occurs
between the cement and coating, it is apparent that the applied load for the test
is limited by the strength of the cement, usually an epoxy. If the adhesion of the
coating to the substrate is greater than the available epoxies then the pull-off
10

test cannot be used to determine the ultimate adhesive strength. Finally, it is

possible that the epoxy may be permeate into coatings, degrading the adhesion
between coating and substrate.

ii) The meaning of Lc1 and Lc2 in the scratch test

Scratch testing is an alternative method to measure the adhesion of coatings. A
scratch test is performed by applying a load to a conical stylus with a defined tip
radius and cone angle. As shown in Figure 11, a linear motion is applied to the
stylus whilst gradually increasing the load and recording the normal load,
frictional force and penetration. The failure mode of the coating depends on the
mechanical and physical properties of the coating along with the strength of
adhesion to the substrate. In thin coatings it is common for buckling failure to
occur whilst thick coatings may exhibit wedge
spallation.
The concept of a critical load was introduced to
determine the normal force required on a stylus
that would result in failure in adhesion of the
coating to a substrate (Benjamin & Weaver,
1959). Furthering this concept, two critical loads
can be determined. Lc1 can be defined as the
normal load where first cracking or cohesive
11: Illustration of scratch test
failure of the coating occurs, usually Hertzian Figure
setup (CSM Instruments, 2016)
type cracks. Lc2 is the normal load where total
failure of the coating through adhesive failure or delamination occurs. Error:
Reference source not found below shows the progression of a scratch test in a
diamond-like carbon coating, with the location of L c1 and Lc2 indicated. The figure
clearly shows signs of a cohesive coating failure past the point of L c1 followed by
total failure of the coating above Lc2.

Figure : Micrograph of full scratch of DLC coating showing position of Lc1 and Lc2 (Nanovea, 2013)

g) What is the maximum short term four-point bending stress to

which a component of volume 2700mm3, made from the same
material, can be subjected if less than 2 in 300 failures can be
tolerated?
The ratio of the three point bending strength to the uniaxial tensile strength
(3/t) and the four point bending strength to the uniaxial tensile strength (4/t)
are respectively given by:
11

1
3
2 m
=[ 2 ( m+1 ) ]
t

4 4 ( m+ 1 )2
=
t
m+ 2

Equation 1

1
m

Equation 2

Table 1: Ceramic bar physical and mechanical properties

Dimensions
Flexural Strength,
3pt
Ps
Weibull Modulus

5x3x
36
360

Mm

0.5

MPa

The properties of the ceramic bars are shown in Table 2 below, where Ps
corresponds to the survival rate. To determine the maximum applicable stress for
a 4-point bend test of the same material with volume 2700mm 3 with a survival
rate of Ps = 99.3% (2 in 300 failures), the 4-point stress must first be calculated.
Rearranging Equation 1 for t and substituting in the values gives:

t =

360
1
2 8

=190.5957 MPa

Equation 3

[ 2 ( 8+ 1 ) ]
Therefore,

4 ( 8+1 )2 8
4=190.5957
=294.3956 MPa
8+2

Equation 4

The characteristic strength, 0 ,(stress for 27% survival rate) can be determined
from Equation 5, thereby enabling the calculation of the allowable stress in 4
point bending for the same volume of material and a survival rate, P s = 99.3%
shown in Equation 6.

ln ln

1
=m ln mln 0
P s(V 0)

0 =308.1968 MPa

12

Equation 5

ln ln
ln =

1
( 0.993
) +ln
8

Equation 6

=164.816 MPa

Finally, maximum allowable stress for the 2700mm 3 specimen is calculated using
the equation for the volume dependence of strength equation shown below and
given by

final .
2 V 1
=
1 V 2

( )

1
m

Equation 7

final=134.78 MPa

h) Compare and contrast sputtering and electron beam

evaporation as methods for the deposition of ceramic coatings.
Describe the advantages and disadvantages of each method,
explaining why evaporation is employed for the deposition of
thermal barrier coatings and sputtering is favoured for most
electronic/optical applications.
Sputtering uses high velocity particles directed at a target to eject atoms that
can be deposited onto a substrate as a coating. The high speed particles are
delivered in the form of plasma, a partially ionised gas. There are two common
methods for producing a plasma, these are direct current and radio frequency.
The direct current (DC) method supplies a high voltage (0.5 4 kV) current
across a cathode (target) and anode (substrate), random particles of the gas
between the anode and cathode will become ionised. The positive ions are
accelerated towards the negatively charged cathode with sufficient energy to
dislodge atoms, known as sputtering, along with the release of secondary
electrons which act to ionise more gas particles resulting in a self-sustaining
plasma.
The direct current methods relies on the use a conductive target, for nonconductive targets the radio frequency (RF) method must be used. In this case a
RF gun is used to initiate the glow discharge plasma, rather than an electrical
current, with a matching network used to ensure that the optimum power is
supplied by the RF generator. This method allows deposition of non-conductive
dielectrics and other functional ceramic coatings.
It is possible to effect the properties of the coating produced through sputtering
by application of heating or cooling to the substrate or by applying a substrate
bias. Heating the substrate can act to promote a larger grain size with increased
density as a result of increased surface diffusion as well as a columnar structure,
therefore improving the mechanical properties of the coating (Lee, et al., 2006).
On top of this, the impurity content of the coating is decreased at higher
substrate temperatures. A negative bias can be used before coating deposition
13

to clean the substrate by sputtering, removing any surface impurities that may
be present by bombardment my ions from the plasma glow discharge. The bias
can also be used during coating growth to improve the microstructure of the
coating by increasing density and surface diffusion. Re-sputtering will also
improve surface diffusion.
Electron beam evaporation (EB-PVD) uses an electron beam to evaporate the
target in a vacuum chamber and evaporated particles are deposited onto the
substrate. The use of an e-beam removes the need to heat target in a crucible
which can introduce contamination and impurities to the coating. For flat
substrates, planetary motion is required in order to ensure that an even
distribution of the deposited film is grown on the substrate. It is possible to grow
alloy or compound coatings using EB-PVD, either through evaporation of an alloy
target or by using separate targets. Since the constituent elements in an alloy
will evaporate independently the deposited coating will not have the same
chemical composition as the target material hence use of separate targets allows
for more control of the coating deposited.
Typically, EB-PVD exhibits a much higher deposition rate than sputtering, with
deposition rates of upto 100 A/s compared to around 10 A/s for sputtering (Chen,
2004). The use of the e-beam allows precise control of the evaporation rate,
allowing for careful construction of thermal barrier coatings (TBCs) that are
constructed from layers of ~100-400m thick. TBCs typically consist of a bond
coat, to provide excellent adhesion to the substrate followed by a thicker top
coat, usually a porous oxide with a high melting point and low thermal
conductivity (MRS, 2012). Sputtering is more suitable for electronic or optical
coatings where the coatings required are typically much thinner, and may require
many distinct layers to form a functional coating. The low deposition rate of
sputtering can be improved by introducing magnetron sputtering to control the
movement of the ions and electrons. Furthermore, sputtering is can be used to
deposit coatings from targets with high melting points that would require
excessive energy using evaporation methods.

i)

A manufacturer wishes to make at least 600,000

turbocharger rotors. Cy considering what properties are
required and by comparing the materials and manufacturing
routes, explain why injection moulding silicon nitride would
be preferable to slip casting Zirconia.

Turbocharger rotors require manufacture of a complex and intricate shape that

closely matches an aerodynamic profile. Few ceramic processing methods are
capable of producing the complicated shape that is essential, these are slip
casting and injection moulding. The performance requirements of a turbocharger
rotor necessitate a lightweight and durable design, able to cope with the stresses
imposed during operation with low mass to reduce the moment of inertia thereby
improving the response time for the turbocharger rotor (Shimizu, et al., 1990).
Slip casting is carried out by production of a mould of the desired shape, allowing
for shrinkage during sintering, into which a suspension of ceramic particles (slip)
is poured. The slip is formed of ceramic particles of the desired material, usually
of size in the order of micrometres, suspended in a liquid containing additives.
Deflocculant added to the slip acts to reduce the viscosity of the mixture,
14

allowing a slip with a low water content to be poured into the mould. The liquid
from the slip is absorbed into mould, forming a layer of ceramic material around
the surface. Once the solid layer has reached the desired thickness the excess
slip can be removed for reuse whilst the cast is left to dry further. Slip casting is
suitable for creating complex, thin walled structures however, the process takes
a long time and is difficult to automate so may not be suitable for producing the
large production volumes expected for the component.
Injection moulding is a plastic forming method that uses a mixture of a ceramic
powder and binder that, when heated form a viscous fluid that can be formed
into the desired shape. The binder used is normally a thermoplastic polymer
material. The granulated ceramic mixture is heated and pressurised in the
injection moulding machine, liquefying the mixture so that it is able to flow into
the mould of desired shape. After cooling, the component is removed from the
mould and undergoes the debinding process. Initially, any soluble binder can be
removed through soaking in a solution and subsequently the remaining binder is
removed through a heating. The injection moulding process can be heavily
automated making it suitable for the scale of production that is required for the
turbocharger rotors, although the binder removal process takes a substantial
amount of time.
Shown in Table 2 below are the mechanical properties for Silicon Nitride and
Zirconia. As discussed earlier, it is important for a turbocharger rotor to have a
low mass in order to increase performance. Silicon Nitride exhibits a substantially
lower density of the two materials. Although Zirconia has reduced stiffness
compared to Silicon Nitride, it offers greater flexural strength and fracture
toughness which both contribute to manufacture of a more durable component in
a high stress environment. Despite the mechanical properties of Zirconia, Silicon
Nitride is the more suitable material since the lower density allows for
manufacture of a lighter component, which is critical for performance, whilst
maintaining reasonable strength and toughness. Production of Silicon Nitride
turbocharger rotors has been demonstrated by Japanese car manufactures for a
number years (Shimizu, et al., 1990).

Table 2: Material and mechanical properties for Silicon Nitride and Zirconia (Ceratec, 2016)

Ceramic
Material
Properties
Density
Modulus of
Elasticity
Flexural Strength,
4pt
Compressive
Strength
Fracture
Toughness
Weibull Modulus

Silicon
Nitride (Si3N4)

Zirconia
(ZrO2) TZP

3.26
275

6.05
200

Silicon
Carbide
(SiC)
3.1
410

MPa

750

1000

410

MPa

>2500

2000

2200

MPa
m1/2
-

10

3.2

15

15

10

Units
g/cm3
GPa

15

The uniaxial pressing procedure feeds ceramic powder into a die which is then
compressed into the desired shape. Figure 12 shows a schematic illustrating the
procedure. Uniaxial pressing is suitable for manufacture of simple, low aspect
ratio shapes such as mechanical seals and the process can be easily automated
for rapid production of components. A significant drawback from the process is
that the density of the compressed ceramic is not uniform throughout the
component, resulting from the friction between particles and the die walls.
Furthermore, it is possible that cracks may form in the component when pressure
is released and during ejection.
The mechanical properties shown in Table 2 show that whilst Silicon Carbide
exhibits high stiffness, it has reduced strength and fracture toughness compared
to Silicon Nitride. The lower Weibull modulus indicates that there is greater
variability in the properties for the Carbide.
The uniaxial pressing of Silicon Carbide is most suitable for producing mechanical
seals. The requirement for a seal is that it must be string under compressive
stress, which is satisfied by the carbide material. It is likely that the seals will be
produced in large numbers, hence a cheap automated manufacture process is
desirable to reduce the cost, making uniaxial pressing the more suitable process
despite the fact that injection moulding will produce a higher quality finished
product.

Ceramic Powder

Figure 12: Schematic of uniaxial pressing process (OFA Advanced

Ceramics, 2016)

j) Explain bonding and nanostructural differences of Diamond

and Diamond-Like Carbon (DLC) and the reasons why they are
used in very different applications
Carbon can exist as bulk material in the form a number of allotropes including
Graphite, Diamond and Diamond-Like Carbon (amorphous Carbon).
Diamond has the highest hardness and thermal conductivity of any known bulk
material, with a hardness of 100GPa and thermal conductivity of 2000Wm -1K-1.
These mechanical properties are the result of the bonding and nanostructure
present in the material. Diamond is bonded with sp 3 hybridised bonding, which
consists of one s atomic orbital to 3 p atomic orbitals to form 4 distinct
hybridised bonds in a tetrahedral shape, as shown in Figure 13. The figure also
illustrates the equal angle between each bond, 109.5, and bond length, 0.15nm.
The nanostructure, comprised of short, covalent bonds all of equal strength, is
what gives Diamond such high hardness as the bonds are incredibly difficult to
break. The high thermal conductivity can be explained by the very short bond
16

length, meaning that any energy is quickly transferred across particles.

Production of bulk Diamond material can only be achieved at very high
temperatures and pressures, >1400 and >5GPa (Capper, 2005).

Figure 13: sp3 hybridised bonding (left) crystal structure (right) (Peshcel, 2011)

Diamond-Like carbon is the name given to carbon allotropes with an amorphous

structure, which can take several different forms. DLC utilises a combination of
sp2 and sp3 hybridised bonding and the nanostructure and properties are
dependent on the relative quantity of bond types. Figure 14 illustrates bonding
content for a variety of DLC materials with the sp 2, sp3 and H corners of the plot
corresponding to Graphite, Diamond and Hydrocarbons respectively. The large
range of bonding encompassed by the DLC family can be controlled through the
deposition method used for coating growth, in particular the ion energy used
during physical vapour deposition methods will have a significant effect on the
proportion of sp2/sp3 bonding present.

Figure 14: Ternary diagram showing bond content for various DLC (left) with key (right) (Robertson,
1994)

It is not possible to deposit diamond coatings using physical vapour deposition as

the conditions are not adequate to create fully sp 3 hybridised bonding. Therefore,
coatings are typically grown using chemical vapour deposition (CVD). The
temperatures involved when using CVD are very high, much higher than the
softening temperature for tool steel making diamond an unsuitable coating for
tooling purposes. This issue is circumvented by using metal carbide inserts in
cutting equipment that have a much higher melting point, therefore allowing
deposition of diamond using CVD. Although diamond is generally unreactive, at
moderate temperatures experienced during machining diamond will react with
ferrous metals to form FeC (Davis, 1995). As a result, diamond coated tooling is
17

only suitable for use on non-ferrous components. Diamond coatings are

extremely useful for optical applications, given that they offer transparency over
an extensive spectral range along with scratch resistance and corrosion
resistance from hardness and chemical inertness respectively.
DLC exhibits very desirable mechanical properties including high hardness, very
smooth surface, low friction coefficient, low electrical conductivity and biological
compatibility. The hardness of the coating is positively correlated to the sp 3
content, however very high sp3 content can cause poor adhesion or cohesion of
the coating due to the residual stress present after deposition although this can
be improved by use of High Power Impulse Magnetron Sputtering (Richter
Precision , 2016). Hardness can reach values of 40GPa, along with the smooth
surface give good wear resistance suitable for manufacture tooling such as Drills,
Punches and Dies. Since DLC can be deposited using PVD techniques such as
sputtering or evaporation at temperatures ranging from 100-500C, it can be
directly deposited on to tool steel without the need for carbide inserts as
required for diamond coatings. The low friction coefficient, typically <0.1 (Bonelli,
et al., 2000), and biological compatibility makes DLC ideal for use in prosthetic
joint replacements.

18

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