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)
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)
ii)
iii)
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.
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.
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)
Coating
Substrate
Figure : Micrograph of full scratch of DLC coating showing position of Lc1 and Lc2 (Nanovea, 2013)
1
3
2 m
=[ 2 ( m+1 ) ]
t
4 4 ( m+ 1 )2
=
t
m+ 2
Equation 1
1
m
Equation 2
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
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)
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 13: sp3 hybridised bonding (left) crystal structure (right) (Peshcel, 2011)
Figure 14: Ternary diagram showing bond content for various DLC (left) with key (right) (Robertson,
1994)
18
References
Baumgarten, B. A., Tordonato, D. S. & Kepler, W. F., 2011. Investigation of
Molybdenum Disulfide and Tungsten Disulfide as Additives to Coatings for Foul
Release Systems , Denver: Materials Engineering and Research Laboroatory,
Technical Service Center.
Benjamin, P. & Weaver, C., 1959. Measurement of adhesion of thin films. London,
Royal Society, pp. 163-176.
Bonelli, M. et al., 2000. Structural and Mechanical Properties of Diamond-Like
Carbon Films Prepared By Pulsed Laser Deposition With Varying Laser Intensity.
Materials Research Society, Volume 593.
Brandt, G., 1985. Thermal Shock Resistance of Ceramic Cutting Tools. Surface
Engineering , 2(2), pp. 121-132.
Burden, S. J., Hong, J., Rue, J. W. & Stormsborg, C. L., 1988. COMPARISON OF HOTISOSTATICALLY-PRESSED AND UNIAXIALLY HOT-PRESSED ALUMINA-TITANIUMCARBIDE CUTTING TOOLS.. American Cermaic Society Bulletin, 67(6), pp. 10031005.
Capper, P., 2005. Bulk Crystal Growth of Electronic, Optical and Optoelectronic
Materials. s.l.:John Wiley & Sons.
Cavaleiro, A. & De Hosson, J. T. M., 2006. Nanostructured Coatings. 1st ed.
s.l.:Springer.
Ceratec, 2016. Materials. [Online]
Available at: http://www.ceratec.nl/materials.html
[Accessed 07 04 2016].
Chen, E., 2004. II. Thin Film Deposition, s.l.: Materials Research Science and
Engineering Center, Harvard.
Cselle, T. et al., 2003. Nanostructured Coatings for High Performance Tools, s.l.:
Wekzeug Technik.
CSM Instruments, 2016. Scratch Test. [Online]
Available at: http://www.csm-instruments.com/Scratch
[Accessed 06 April 2016].
Davis, J. R., 1995. ASM Speciality Handbook: Tool Materials. 1st ed. s.l.:ASM
International.
DoITPoMS, 2006. Ferroelctric Materials. [Online]
Available at: http://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.php
[Accessed 10 April 2016].
Duffy, J., Suresh, S., Cho, K. & Copp, E. R., 1987. A Method For Dynamic Fracture
Initiation Testing Of Ceramics, Providence: Brown Univeristy, Division of
Engineering .
Hayward, S. A. & Salje, E. H., 2002. The pressure-temperature phase diagram of
BaTiO3: a macroscopic description of the low-temperature behaviour. Journal of
Physics: Condensed Matter, 14(36), pp. 599-604.
19
Hazell, P. J., 2015. Armour: Materials, Theory and Design. s.l.:CRC Press.
Horiba, 2008. Electronic Ceramics The Importance of Particle Size for Multilayer
Ceramic Capacitors (MLCC) by Horiba Scientific - Particle Products. [Online]
Available at: http://www.azom.com/article.aspx?ArticleID=4154
[Accessed 10 April 2016].
Lee, J. W., Thomas, B. & Rabiei, A., 2006. Microstructural study of titanium
palladiumnickel base thin film shape memory alloys. Thin Solid Films, 500(1-2),
pp. 309-315.
Mousharraf, A. & Turjo, R. M., 2012. The World of Ferroelectric Ceramics. Cermaic
Industry, 1 August.
MRS, 2012. Thermal-barrier coatings. Materials Research Society Bulletin, 37(10).
Nanovea, 2013. Undertsanding Coating Failures Using Scratch Testing, s.l.: s.n.
OFA Advanced Ceramics, 2016. Processing. [Online]
Available at: http://ofaceramics.com/company
[Accessed 07 04 2016].
Peshcel, G., 2011. Carbon-Carbon bonds: Hybridisation, s.l.: s.n.
Popovici, D., Okuyama, M. & Akedo, J., 2011. Barium Titanate-Based Materials a
Window of Application Opportunities. In: M. Lallart, ed. Ferroelectrics - Material
Aspects. s.l.:s.n.
Richerson, D., Richerson, D. W. & Lee, W. E., 2006. Modern Ceramic Engineering:
Properties, Processing, and Use in Design. Third ed. s.l.:Taylor & Francis Group .
Richter Precision , 2016. DLC Coatings - Diamond-like Carbon. [Online]
Available at: http://www.richterprecision.com/dlc-coatings.html
[Accessed 08 04 2016].
Robertson, J., 1994. Diamond-like carbon. Pure & Appl. Chem., 66(9), pp. 17891796.
Sandvik Coromant, 2016. Insert Shape. [Online]
Available at:
http://www2.coromant.sandvik.com/coromant/pdf/Metalworking_Products_061/te
ch_a_5.pdf
[Accessed 08 04 2016].
Shimizu, T., Takama, K., Enokishima, H. & Mikame, K., 1990. Silicon Nitride
Turbocharger Rotor for High Performance Automotive Engines. SAE International.
Stern, K. H., 1996. Metallurgical and Cermaic Protective Coatings. 1st ed.
s.l.:Springer Netherlands.
Sulzer, 2001. Protecting Pumps against Abrasive Wear , s.l.: Sulzer Technical
Review.
Wadley, H., 2014. Ballistic Impact Mechanisms Of Materials. [Online]
Available at: http://www.virginia.edu/ms/research/wadley/ballistic-impact.html
[Accessed 10 April 2016].
20
Wang, L., Su, J. F. & Nie, X., 2010. Corrosion and tribological properties and
impact fatigue behaviors of TiN- and DLC-coated stainless steels in a simulated
body fluid environment. Surface and Coatings Technology, 205(5), pp. 15991605.
Weerasooriya, T., Moy, P. & Casem, D., 2006. A Four-Point Bend Technique to
Determine Dynamic Fracture Toughness of Ceramics. Journal of the Americn
Ceramic Society, 89(3), pp. 990-995.
Yamada, M., Sekine, K., Kumazawa, T. & Tanabe, Y., 2010. Relationship between
the cone crack and fracture mode in ceramics under high-velocity-projectile
impact. Journal of the Ceramic Society of Japan, pp. 903-908.
Zelinksi, P., 2005. The Case For A Chromium-Based Coating. [Online]
Available at: http://www.mmsonline.com/articles/the-case-for-a-chromium-basedcoating
[Accessed 10 April 2016].
21