Advanced Ceramics - 4th Year - Lecture Notes

Advanced Ceramics 4th year Lecture notes
2014-2015
Part 1: Functional and Engineering Ceramics
1. Insulating/ Thermal Conductive Ceramics
2. Semi-conductive Ceramics
3. Piezoelectric Ceramics
4. Dielectric Ceramics
5. Magnetic Ceramics
6. Opto-electro-ceramics
7. High-Temperature High-Strength
Ceramics
8. Porous Ceramics for Filtration
9. Ceramic Bearing
10. Cutting Tools
11. Ceramic-Matrix Composites
12. Ceramic Materials for Energy Systems
13.
Functionally Graded Materials
Dr. Saad B. H. Farid
Part 2: Bio-Ceramics
1. Introduction to Bio-Ceramics
2. Alumina and Zirconia in Surgical Implants
3. Bioactive Glasses - Materials
4. Bioactive Glasses - Clinical Applications
5. A/W Glass-Ceramics
6. Machinable and Phosphate GlassCeramics
7. Porous Hydroxyapatite
8. Hydroxyapatite Coatings
9. Pyrolytic Carbon Coatings
10. Bioceramic Composites
11. Calcium Phosphate Cements
12. Radiotherapy Glasses
13. Dental Glass-Ceramics and ZrO2Ceramics
1. Insulating Ceramics/High Thermal Conductive Ceramics

Materials for PKG
Because of its high thermal conductivity, high mechanical strength, good insulation
characteristics, moderate dielectric properties, and high chemical durability, Alumina (HTCC:
high-temperature co-fired ceramics) is the most popular ceramics material for semiconductor
packages.
However, for power devices like power amplifier for base station or for satellites, higher
thermal conductivity ceramic materials is required to dissipate the heat generated in the
devices. To meet this requirement, aluminum nitride (AlN), which has high thermal
conductivity (TC) and a low thermal expansion coefficient comparable to that of Si, has been
adopted for packages requiring high thermal dissipation.
Another market trend, toward higher power, higher working frequencies, and lower power
consumption, requires reduction of the resistivity of conductors in co-fired packages. To meet
this requirement, glass ceramics (LTCC: low-temperature co-fired ceramics) with silver or
copper conductors have been developed.
New materials have been developed such that a novel AlN that can co-fired at low
temperature to reduce cost. The second is a novel LTCC that has a high thermal coefficient of
expansion. The third is also a novel LTCC that has low permittivity and low loss tangent at
high frequency.
Process Flow
Figure 1 shows the process flow for a co-fired multilayer ceramic package. There are many
steps to produce a multilayer package; however, there are only a few differences among
different materials. Of course, material composition, metallize composition and process
condition is different for each. Among these steps, metallizing is an especially critical
technology for package production.
Aluminum Nitride AlN: Material Properties
AlN has a characteristic dielectric dispersion at high frequencies. Figure 2 shows the
frequency dependence of the dielectric loss (tan ) of AN75W and AN242. The dielectric loss
of AlN shows a maximum at a few gigahertz. This phenomenon is due to the piezoelectricity
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of AlN, and the peak frequency inversely depends on the crystallite size. As the crystallite
size of AN75W is smaller than that of AN242, the peak (dispersion) frequency of AN75W is
correspondingly higher.
LTCC with High Thermal Coefficient of Expansion
Due to the ever-increasing I/O counts for the IC devices, packaging trends
have been changing to surface mountable area array second-level
interconnection, namely ball grid array (BGA) and chip scale package (CSP).
The motivations for these types of secondlevel mounting are described as follows:
1. Higher wiring density: smaller packages,
thinner packages, lighter packages,
2. Higher performance: electrical performance,
thermal performance, higher I/O counts,
3. Lower cost.
A surface mounting technology (SMT)
package, such as BGA, has low height
interconnection between the substrate and the
printed wiring board PWB (also called printed
circuit board PCB).
BGA
Figure 1: Process flow for multilayer

ceramic package fabrication.
When we have a big difference of TCE

between the substrate and the PWB, BGA, and
CSP packages, they receive more severe shear
strain, damaging the reliability of solder joints,
compared with Pin grid array PGA. This shear
strain is a big problem, since alumina ceramics
has TCE of 7 ppm/C while the TCE of a typical
PWB is 1216 ppm/C.
The observations suggest that the reliability
largely depends on the TCE mismatch between
the substrate and the potting compound.
A new ceramics is developed with TCE of 13
ppm/C, which is in the range of PWBs (1216
ppm/C) and that of the potting compounds (10
30 ppm/C).
Hint: it is done by incorporating glass in a
composite.
The dielectric constant is 5.3 at 1 MHz, which
is lower than 9.8 of alumina. The Youngs
modulus is 110 GPa, approximately one-third
that of alumina. Also, copper conductor is cofirable.
It is found that the equivalent plastic strain
generated by the TCE mismatch among Si-die,
substrate, potting compound and PWB
drastically decreases as TCE of the substrate
increases from 11.5 to 13 ppm/C.
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Figure 2: Frequency dependence of

dielectric loss of AlN.

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LTCC with Low Permittivity and Low Loss Tangent at High Frequency
The ceramic package used for microwave applications requires following properties;
(a) Lower dielectric constant and lower loss tangent in the radio frequency range;
(b) Lower resistivity conductor;
(c) Thermal expansion coefficient of the ceramic material close to that of semiconductor
chips;
(d) High reliability of hermeticity (airtight).
A new LTCC material was designed to be able to sinter at less than 1000C because of cofiring with copper conductor. The LTCC is composed of lead-free, SiO2Al2O3MgOZnOB2O3
system glass and ceramic fillers. In order to satisfy electrical and thermal properties, the
amount of crystalline phases precipitated after sintering is adjusted.
The coefficient of thermal expansion is 7.5 ppm/C in the range of 40300C. This value is
close to that of GaAs chips that are mainly used for microwave applications. Thermal
conductivity and flexural strength and volume resistivity are as good as conventional LTCC
material. The dielectric constant is 6.0, which is lower than that of alumina in the range of 2
60 GHz. The loss tangent increases as frequency increases and close to that of alumina,
which is good for microwave applications.
Copper metallization
Copper was used for metallization material because of excellent migration resistance. It is
important for co-firing process to match the shrinkage behavior of copper metallization to
that of LTCC material. Since the shrinkage of copper starts at lower temperature than that of
LTCC material, glass and ceramic fillers are added to copper paste to control the shrinkage
behavior of copper metallization. After co-firing, copper metallization, the LTCC material is
plated with nickelgold or coppergold.
Squares are the unit-less
dimension of length divided by width.
Adhesion strength of the metallization was
measured, and no change was observed after
1000 h aging at 150C.
Sheet resistance of the metallization was 2.5m/ (12m thickness), where and no
increase was observed after 1000 h aging at 150C. The insulation resistance between lines
separated by 100m space was more than 1012 after 1000 h of High Humidity Biased Test
HHBT (semiconductor component reliability test) (85C, 85% RH, 5.5 V).
2. Semiconductive Ceramics
a- PTC Thermistors
Barium titanate (BaTiO3) is a ferroelectric material with a high dielectric constant and high
insulation resistance. Therefore, it has been widely used in the electrical industry for ceramic
capacitors since its discovery in 1943. The insulating BaTiO3 ceramic is converted into a
semiconductor by adding a small amount of rare earth metal oxide such as Sm 2O3, CeO2,
Y2O3, and La2O3. In 1955, unusual temperature dependence of resistance above the Curie
temperature of semiconductive BaTiO3 ceramics was discovered.
The resistance of this semiconductor called the positive
temperature coefficient (PTC) thermistor drastically
increases above the Curie temperature (TC), up to the
temperature (Tn) where the resistance reaches its maximum
value. The characterized temperature is divided into three
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regions (I, II, and III in Figure 4) according to the resistance
behavior.
Conduction Mechanisms
The conduction mechanisms in the regions IIII are
explained as follows. In the temperature region I(T < TC),
the resistivity of PTC thermistor is in the range of 10106
cm. To produce semiconductive BaTiO3, a small amount of
rare earth metal ions (e.g. Sm3+ or La3+) are substituted at
the Ba2+ site, or Nb5+ and Ta5+ ions are substituted at the Ti4+
site. These ions provide conductive electrons.
In the region II above the Curie temperature, resistance across the grain boundary
increases exponentially with increasing temperature. The increase of resistance corresponds
to the decrease of spontaneous polarization (Ps) of BaTiO3 due to the phase transition from
the ferroelectric tetragonal phase to the paraelectric cubic phase. The gradual decrease of Ps
and dielectric constant cause the potential barrier height to recover. This recovery results in
an increase of resistance in region II.
In the temperature region III (T > Tn), the electrons that overcome the double Schottky
barrier increase with temperature, and resistance decreases from maximum resistance.
Manufacturing Process
Additives and their effects on PTC
characteristics are listed in Table 1. The
transition temperature TC can be lowered or
elevated from its original value (120C) by
substitution of Sr2+ and Pb2+ at the Ba2+ site.
BaCO3, SrCO3, Pb3O4, TiO2 and donor dopant
(e.g. La2O3, Sm2O3, Y2O3 and Nb2O5) are used as
starting materials. Manufacturing processes of
PTC thermistor are almost the same as those in
the electronic ceramics industry.
To control the resistance and the temperature
coefficient within the exact range, much attention is
paid to the firing temperature and ensuing cooling
rate. The impurity of rare materials and
contamination in manufacturing process must be
decreased, because these increase the resistance at
room temperature. In particular, Fe and Al strongly
affect the resistivity of PTC thermistor.
Non-precious metal electrodes such as Ni, Zn,
and Al provide ohmic contact with PTC thermistor,
which is n-type semiconductor ceramics. InGa alloy
also makes ohmic contact, and is used for
experimental samples.
Applications
Table 2 shows three basic functions and
applications of PTC. PTC thermistors are used in a
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Figure 3: Characterized
temperature regions of
PTC ceramics

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lot of electric products, such as color televisions,
refrigerators, hot-wind heaters, and personal
computers.
b- NTC Thermistors
The negative temperature coefficient (NTC)
thermistors are semiconductive materials whose
resistance decreases with increasing temperature
as shown in Figure 4 with other thermistors.
R = A exp(B/T), B = E/k, where A is a constant, B a
thermistor constant, E the activation energy, and k
Boltzmanns constant.
Conduction Mechanism
NTC thermistor usually consists of transition
metals (Cu, Fe, Co, Ni, etc.) spinel manganites. The
conductivity is due to the transfer of electrons
between Mn3+ and Mn4+ ions. The resistance and
thermistor constant is dependent on the
composition, purity, cation distribution, and crystal
structures.
Mn3O4, NiO, Co2O3, and Fe2O3 are used as
starting materials. NTC thermistors are produced
by the general method of the manufacturing of
electroceramics. Precious metals such as Ag, Pd,
and Pt are used for electrodes of NTC thermistor,
which is mainly p-type semiconductor ceramics.
Applications
NTC thermistors are used as temperature compensation, temperature sensing, and surge
current suppression devices. All of these applications are based on the resistance
temperature characteristics of NTC thermistors.
Although various thermistor constant B and resistivity are required for many applications,
these values are obtained within certain limits, because the thermistor constant B is
Figure 4 Temperature dependence of
dependent on the resistivity.
different types of thermistors in
contrast to a platinum
Ceramic Varistors
Metal oxide varistors are ceramic semiconductive devices having highly nonlinear current
voltage characteristics, as shown in Figure 5, expressed as I = (V/C).
is the nonlinear exponent, C the constant

corresponding to the resistance, and V1 and V2 are the
voltages at the currents of I1 and I2, respectively. C is
convenient1y given by Vc called varistor voltage, that
is, a voltage per unit length (V/mm) when 1 mA/cm2 of
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current flows through the body. Thus, the ceramic
varistor is characterized by the non-linear exponent
and varistor voltage Vc.
Two types of ceramic varistors are manufactured.

Zinc oxide based ceramic varistors were developed in
1970. They exhibit a high non-linearity on voltage
current characteristics. Their value is in the range of
4050, and the Vc adjustable to values in the range
from 50 to 250 V/mm. Strontium titanate based
varistors were developed in 1980. The feature of these
varistors is their larger electrostatic capacitance
compared with ZnO varistors. The SrTiO3 ceramics are
essentially dielectrics with a die1ectric constant of 320,
which is much higher than that of ZnO.
The effect of additives on varistor
properties of ZnO varistors are listed in
Table 3. The varistor voltage Vc is
dependent on the number of grain
boundaries between a couple of
electrodes, because the varistor voltage
across a single grain boundary is constant
value (3V) at each boundary. To obtain the
varistors with the various voltages Vc, the
grain size are controlled by firing
temperature or additives, such as B and
Sb.
Figure 5 Typical VI characteristic of

ceramic varistor
Strontium titanate based varistors are manufactured by firing in a reducing atmosphere

and re-oxidized on only grain boundary, like a boundary-layered ceramic capacitor.
Applications
Metal oxide varistors are mainly used in circuits for
protection against inductive surges, very short spike
noise, or power surges. They result to protect circuit
simply by inserting between surge entrance line and
ground lines shown in Figure 6. A varistor should be
chosen that have a varistor voltage Vc slightly higher
than the signal voltage applied to the load to be
protected. The varistor is insulator in normal operation
where the applied voltage is lower than Vc.
Figure 6 Typical application of ZnO

varistor as a transient
protective device.
If a transient pulse, whose voltage is higher than Vc, is incident, the current through
varistor rapidly increases, resulting in a conducting shunt path for the incident pulse.
ZnO-based varistor have become popular because of the high non-linearity on voltage
current characteristics.
3. Piezoelectric Ceramics
Certain materials produce electric charges on their surfaces as a consequence of applying
mechanical stress. The induced charges are proportional to the mechanical stress. This is
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called the direct piezoelectric effect and it was discovered in quartz by Piere and Jacques
Curie in 1880. Materials showing this phenomenon also conversely have a geometric strain
proportional to an applied electric field. This is the converse piezoelectric effect. The root of
the word piezo means pressure; hence the original meaning of the word piezoelectricity
implied pressure electricity.
Piezoelectricity is extensively utilized in the fabrication of various devices such as
transducers, actuators, surface acoustic wave devices, frequency control and so on. In this
chapter, we describe the piezoelectric materials that are used, and various potential
applications of piezoelectric materials.
Piezoelectric Materials
This section summarizes the current status of piezoelectric materials: single-crystal
materials, piezoceramics, piezopolymers, piezocomposites and piezofilms.
i- Single Crystals
Although piezoelectric ceramics are widely used for a large number of applications, singlecrystal materials retain their utility, being essential for applications such as frequency
stabilized oscillators and surface acoustic devices. The most popular single-crystal
piezoelectric materials are quartz, lithium niobate (LiNbO3), and lithium tantalate (LiTaO3).
The single crystals are anisotropic, exhibiting different material properties depending on the
cut of the materials and the direction of bulk or surface wave propagation. Quartz has a cut
with a zero temperature coefficient.
ii- Polycrystalline Materials
Barium titanate (BaTiO3) is one of the most thoroughly studied and most widely used
piezoelectric materials. Just below the Curie temperature (120C), the vector of the
spontaneous polarization points in the [001] direction (tetragonal phase), below 5C it
reorients in the [011] (orthorhombic phase) and below 90C in the [111] direction
(rhombohedral phase). The dielectric and piezoelectric properties of ferroelectric ceramic
BaTiO3 can be affected by its own stoichiometry, microstructure, and by dopants entering
onto the A or B site in solid solution. Modified ceramic BaTiO3 with dopants such as Pb or Ca
ions have been developed to stabilize the tetragonal phase over a wider temperature range
and are used as commercial piezoelectric materials. The initial application was for Langevintype piezoelectric vibrators. Piezoelectric Pb(Ti,Zr)O3 solid solutions (PZT) ceramics have
been widely used because of their superior piezoelectric properties.
iii- Polymers
Polyvinylidene difluoride, PVDF or PVF2, is piezoelectric when stretched during fabrication.
Thin sheets of the cast polymer are then drawn and stretched in the plane of the sheet, in at
least one direction, and frequently also in the perpendicular direction, to transform the
material to its microscopically polar phase. Crystallization from the melt forms the non-polar
-phase, which can be converted into the polar -phase by a uniaxial or biaxial drawing
operation; the resulting dipoles are then reoriented through electric poling.
iv- Composites
Piezo-composites, comprised of a piezoelectric ceramic and a polymer phase, are
promising materials because of their excellent and readily tailored properties. A piezocomposite, such as the PZTrod/polymer composite is a most promising candidate. The
advantages of this composite are high coupling factors, low acoustic impedance, good
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matching to water or human tissue, mechanical flexibility, broad bandwidth, and low
mechanical quality factor. Piezoelectric composite materials are made by forming a
composite structure, that is, by replacing some of the heavy, stiff ceramic with a light, soft
polymer. Piezoelectric composite materials are especially useful for underwater sonar and
medical diagnostic ultrasonic transducer applications.
v- Thin Films
Both zinc oxide (ZnO) and aluminum nitride (AlN) are simple binary compounds with a
Wurtzite-type structure(hexagonal crystal system), which can be sputter-deposited as a caxis oriented thin film on a variety of substrates. ZnO has large piezoelectric coupling and
thin films of this material are widely used in bulk acoustic and surface acoustic wave devices.
The fabrication of highly oriented (along the c-axis) ZnO films have been studied and
developed extensively. The performance of ZnO devices is limited, however, due to their low
piezoelectric coupling (2030%). PZT thin films are expected to exhibit higher piezoelectric
properties. At present the growth of PZT thin films is being carried out for use in
microtransducers and microactuators.
Application:
a- Pressure Sensors/Accelerometers/Gyroscopes
One of the very basic applications of piezoelectric ceramics is a gas igniter. The very high
voltage generated in a piezoelectric ceramic under applied mechanical stress can cause
sparking and ignite the gas. There are two means to apply the mechanical force, either by a
rapid, pulsed application or by a more gradual, continuous increase.
Piezoelectric ceramics can be employed as stress sensors and acceleration sensors,
because of the direct piezoelectric effect. A three-dimensional (3D) stress sensor can be
designed by combining an appropriate number of quartz crystal plates (extensional and shear
types), the multilayer device can detect 3D stresses.
b- Piezoelectric Vibrators/Ultrasonic Transducers
Piezoelectric Resonance
When an electric field is applied to a piezoelectric material, deformation (L) or strain
(L/L) arises. When the field is alternating, mechanical vibration is caused, and if the drive
frequency is adjusted to a mechanical resonance frequency of the device, large resonating
strain is generated. This phenomenon can be understood as a strain magnification due to
accumulating input energy, and is called piezoelectric resonance. Piezoelectric resonance is
very useful for realizing energy trap devices, actuators, etc.
Electromechanical Coupling Factor, k: corresponds to the rate of
electromechanical transduction.
k2 = (stored mechanical energy/input electrical energy)
k2 = (stored electrical energy/input mechanical energy) = d2/0 s
The general processes for calculating the electromechanical parameters (k31, d31, sE11, and
33) are:
X
1. The sound velocity in the specimen is obtained from the resonance frequency fR
2. Knowing the density , the elastic compliance sE11 can be calculated.
3. The electromechanical coupling factor k31 is calculated from the value and the
antiresonance frequency fA
4. Knowing the permittivity X33, the d31 is calculated
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Piezoelectric Vibrators
In the use of mechanical vibration devices such as filters
or oscillators, the size and shape of a device are very
important, and both the vibrational mode and the ceramic
material must be considered.
The resonance frequency of the bending mode in a centimeter-size sample ranges from
100 to 1000 Hz, which is much lower than that of the thickness mode (100 kHz). For these
vibrator applications, the piezoceramic should have a high mechanical quality factor (Q M)
rather than a large piezoelectric coefficient d; that is, hard piezoelectric ceramics are
preferable. For speakers or buzzers, audible by humans, devices with a rather low resonance
frequency are used (kilohertz range).
c- Ultrasonic Transducers
Ultrasonic waves are now used in various fields. The sound source is made from
piezoelectric ceramics as well as magnetostrictive materials. Piezoceramics are generally
superior in efficiency and in size to magnetostrictive materials. In particular, hard
piezoelectric materials with a high QM are preferable. A liquid medium is usually used for
sound energy transfer. Typical applications are ultrasonic washers, ultrasonic microphones for
short-distance remote control and underwater detection, such as sonar and fish finding, and
non-destructive testing. Ultrasonic scanning detectors are useful in medical electronics for
clinical applications ranging from diagnosis to therapy and surgery.
One of the most important applications is based on ultrasonic echo field. Ultrasonic
transducers convert electrical energy into mechanical form when generating an acoustic
pulse and convert mechanical energy into an electrical signal when detecting its echo. The
transmitted waves propagate into a body and echoes are generated which travel back to be
received by the same transducer. These echoes vary in intensity according to the type of
tissue or body structure, thereby creating images. An ultrasonic image represents the
mechanical properties of the tissue, such as density and elasticity. We can recognize
anatomical structures in an ultrasonic image since the organ boundaries and fluid-to-tissue
interfaces are easily distinguished.
The ultrasonic imaging process can also be done in
real time. This means we can follow rapidly moving
structures such as the heart without motion distortion.
In addition, ultrasound is one of the safest diagnostic
imaging techniques. It does not use ionizing radiation
like X-rays, thus, it is routinely used for fetal and
obstetrical imaging. Useful areas for ultrasonic imaging
include cardiac structures, the vascular systems, the
fetus, and abdominal organs such as liver and kidney. In
brief, it is possible to see inside the human body
without breaking the skin by using a beam of
ultrasound.
Figure 7 Piezoelectric
buzzer.
Figure 8 Basic transducer geometry

d- Resonators/Filters
for acoustic imaging
When a piezoelectric body vibrates at its resonant frequency, it absorbs considerably
more energy than at other frequencies resulting in a dramatic decrease in the impedance.
This phenomenon enables piezoelectric materials to be used as a wave filter. A filter is
required to pass a certain selected frequency band or to block a given band. The band width
of a filter fabricated from a piezoelectric material is determined by the square of the coupling
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coefficient k, that is, it is nearly proportional to k2. Quartz crystals with a very low k value of
about 0.1 can pass very narrow frequency bands of approximately 1% of the center
resonance frequency. On the other hand, PZT ceramics with a planar coupling coefficient of
about 0.5 can easily pass a band of 10% of the center resonance frequency. The sharpness of
the passband is dependent on the mechanical quality factor QM of the materials. Quartz also
has a very high QM of about 106, which results in a sharp cut-off to the passband and a welldefined oscillation frequency.
e- Surface Acoustic Wave Devices
A surface acoustic wave (SAW), also called a Rayleigh wave, is essentially a coupling
between longitudinal and shear waves. The energy carried by the SAW is confined near the
surface. An associated electrostatic wave exists for a SAW on a piezoelectric substrate, which
allows electro-acoustic coupling via a transducer.
There is a very broad range of commercial system applications which include front-end
and intermediate frequency (IF) filters, community antenna television (CATV) and video
cassette recorder (VCR) components, synthesizers, analyzers and navigators.
f- Piezoelectric Transformers
When input and output terminals are fabricated on a piezo device and input/output
voltage is changed through the vibration energy transfer, the device is called a piezoelectric
transformer. Piezoelectric transformers were used in color TVs because of their compact size
in comparison with the conventional electromagnetic coil-type transformers. Recent lap-top
computers with a liquid crystal display require a very thin, no electromagnetic-noise
transformer to start the glow of a fluorescent back-lamp.
g- Piezoelectric Actuators
Piezoelectric and electrostrictive devices have become key components in smart actuator
systems such as precision positioners, miniature ultrasonic motors and adaptive mechanical
dampers.
Piezoelectric actuators are forming a new field between electronic and structural
ceramics. Application fields are classified into three categories: positioners, motors and
vibration suppressors.
The manufacturing precision of optical instruments such as lasers and cameras, and the
positioning accuracy for fabricating semiconductor chips, which must be adjusted using solidstate actuators, are generally in the order of 0.1m. Regarding conventional electromagnetic
motors, tiny motors smaller than 1 cm3 are often required in office or factory automation
equipment and are rather difficult to produce with sufficient energy efficiency. Ultrasonic
motors whose efficiency is insensitive to size are considered superior in the mini-motor area.
Vibration suppression in space structures and military vehicles using piezoelectric actuators
is another promising field of application.
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4. Dielectric Ceramics
A material with high electric resistivity is categorized as an insulator material. When we
pay attention to their dielectric polarization and apply the materials to the electronics
circuits, we usually call them "dielectrics". Dielectric ceramics are essential electrical
materials for today's advanced electronics devices. Production quantity of the dielectric
ceramic is the largest among the other electronics ceramics such as magnetic,
semiconductors, insulators, resistors and piezoelectric, and electro-optic materials. Main
applications are for ceramic capacitors and microwave resonators. The dielectric ceramics is
classified into two groups based on their dielectric properties.
Classification of the dielectric ceramics
1- High-Q materials
The dielectrics of this group are called temperature compensating dielectrics, because
they can compensate the temperature dependence of other components. Dielectric constant
changes linearly with temperature. Ceramic capacitors with these materials stabilized the
resonant circuits in which a high quality factor (Q value) and a resonant frequency are
extremely important. In some cases, the ceramics also called linear dielectrics, because the
polarization changes linearly with an applied electric field.
Dielectric constant of this group ranges from about 4 to 400. The temperature coefficient
is in the range from +120 to 4700 ppm/C. Q value (defined as a reciprocal number of a
dissipation factor tan ) is in the range from 1000 to 100 000. These characterized values are
intrinsically given by the compositions, and are modified with kinds and contents of the
composed elements. Typical dielectrics are TiO2, MgTiO3, and CaTiO3.
Titanate-based materials are dominant compositions, which sinter at normally higher than
1100C. Some of the high Q materials for microwave application need very high soaking
temperature (>1400C). Today, glass ceramics are widely used for ceramic multilayer
substrate with Ag and Cu as an inner conductor. About 4050% of the basic oxides such as
Al2O3, SiO2, MgO and alkali-earth oxides compose the dielectrics, which can sinter at relatively
lower temperature (<900C).
2- High-r Materials
Barium titanate (BaTiO3) is the main dielectric in this category, which provides the
dielectric constant r higher than 1000. Stabilizing the high dielectric constant at wider
temperature range has been the principal work for the capacitor engineers.
Lead-based dielectrics have been also developed, which have much higher r of 30000 at
room temperature, and provide better temperature and bias voltage performances than
BaTiO3-based dielectrics.
Ceramic Capacitors
The manufacturing process flowchart
of the Multi Layer Capacitors MLCs is
shown in the figure. Green sheet process
is suitable to prepare the defect-free thin
ceramic film. Thickness reduction of the
dielectric layer is a most effective
method to design the higher capacitance
capacitor with given dielectrics and chip
dimension.
Dielectric Resonator
Dielectric resonators have gained a
position as key elements in microwave
components for size reduction in microwave
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filters and as frequency stabilizing elements in
oscillator circuits. Dielectric resonators reduce
the physical size of resonant systems because
the electromagnetic wavelength is shortened
in dielectrics to 1/ r of its value in free
space, where r is the dielectric constant of
the resonator.
The required properties for dielectric resonators

are:
High dielectric constant;
Low dielectric loss tangent tan ;
Low temperature coefficient of resonant frequency f
Many kinds of dielectric resonator materials have been developed since the 1970s. See
the above table.
5. Magnetic Ceramics
Classification of magnetic materials according to their properties;
1. Diamagnetic materials: These have relative permeabilities slightly below 1, e.g. Copper.
2. Paramagnetic materials: These have relative permeabilities slightly greater than 1, e.g. Aluminum.
3. Ferromagnetic and ferrimagnetic materials: These have relative permeabilities considerably greater than 1.
The relative permeability for a ferromagnetic or ferrimagnetic material is not constant, depending on the size
of magnetizing field used.
a. Ferromagnetic materials being metallic elements (only iron, cobalt and nickel).
b. Ferrimagnetic materials being ceramics like iron oxide Fe3O4 and nickel ferrite NiFe2O3 and Barium
ferrite BaO.6Fe2O3.
Although initial permeability and magnetic flux density of metal and alloy magnetic materials are high, loss by
eddy current is large at high frequencies because of their lower electrical resistivity. Moreover, metallic
materials suffer from oxidation.
Classification of magnetic materials according to their magnetization;
1. Soft magnetic materials: it is very easily demagnetized and little energy dissipated in magnetizing it. They
are used for inductors or core materials of transformers.
2. Hard magnetic materials: it is difficult to demagnetize and needs high energy for magnetization. They are
used as permanent magnets like speakers and motors.
Example: Which of the following applications (a) a compass needle, (b) the core of an electromagnet, requires a soft
and which a hard magnetic material?
Answer: (a): A hard magnetic material is required since the compass needle is required to be a permanent magnet.
(b): soft magnetic material is required since the electromagnet is required to lose its magnetism when the
energizing current is switched off.
The following are mainly mentioned as magnetic characteristics required for high-frequency materials:
1. High permeability,
2. Low loss (high effective permeability),
3. High permeability at high frequency,
4. Stable permeability against temperature,
5. Stable permeability against time,
6. Higher magnetic flux density
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The above properties are usually met by the ferrites. It is important to achieve stable permeability. Permeability is
strongly affected by the composition and the microstructure because it is a structure sensitive characteristic.
The factors that affecting permeability is as follows:
1. Chemical composition and a small amount of ingredient: high permeability can be obtained by the composition.
2. Grain size: the number of domain walls increase when grain size is larger, and permeability becomes higher due to
a superior magnetizing process by the movement of domain walls.
3. Sintered density (pore): pore becomes a pinning site of domain wall that prevents domain wall motion.
4. Inclusions: a precipitate becomes a pinning site of domain wall, and prevents its movement.
5. Completeness of a crystal: the permeability is reduced by the imperfection of the crystal (defect, dislocation, etc.)
because it can lower the mobility of domain wall or increase the induced magnetic anisotropy.
In soft ferrite, there are two chemical formulas, spinel type (MeFe2O4) and the garnet type (Me3Fe5O12). The spineltype ferrite is the most useful material (next table).
Yttrium iron garnet (YIG) is a kind of synthetic garnet, with chemical composition Y3Fe2(FeO4)3, or Y3Fe5O12. It is a
ferrimagnetic material with a Curie temperature of 550 K. YIG is used in microwave, optical, and magneto-optical
applications, e.g. microwave YIG filters. It is transparent for infrared light wavelengths over 600 nm. It also finds use
in solid-state lasers in Faraday rotators, in data storage, and in various nonlinear optics applications.
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6. Opto-electro-ceramics
Electro-optic and magneto-optic effects
In the modern information age,

new technology is developed by
combining optics and electronics
to produce the new field of
optoelectronics. In this field, work
is under way to find functions that
can be performed by exploiting
phenomena to which electrons and
photons both contribute, and to
develop new systems based on
these functions.
General Electric in 1973, succeeded in developing a transparent sintered solid-state laser
(NDY) by sintering a system of Y2O3 including 10% ThO2 and 1% Nd2O3 at 2170C in hydrogen
atmosphere. Since then, developments in the field of opto-electro-ceramics have taken place
at an ever-increasing rate. Recently, Y3Al5O12 (YAG) transparent sintered materials are being
produced with characteristics better than that of single-crystal ceramics in some respects,
and have been successfully used in laser devices.
Processes for preparation of opto-electro-ceramics (Different processes in order to making
ceramic transparent)
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Engineering Ceramics
7- High-Temperature High-Strength Ceramics
Since the late 1980s, the efficient utilization of resources and the protection of
environments have been widely recognized as the most crucial issues in the global scale. As
one of the most promising solutions to the problems, attention has been given to ceramics
with high temperature durability due to their highly probable contribution to the heat-engine
efficiency improvements. From this point of view, great efforts have been carried out in the
area of science and engineering of structural ceramics for high-temperature applications
through the late 1970s to 1990s.
Silicon-based ceramics as high-temperature high-strength materials
The improvements in the efficiency of heat-engines generally require the structural
materials to be utilized under severer operation conditions. Typically in the case of gas
turbine engines, the temperature has already far exceeded the melting point of the superalloys.
The general requirements to the high-temperature structural materials for heat-engines
such as gas turbines and diesel engines are as follows:
1. high fracture strength from
ambient to high temperatures,
especially high strength per
density;
2. high fatigue strength from
ambient to high temperatures;
3. high thermal shock and thermal
fatigue resistance;
4. high creep resistance to high
temperatures;
5. high oxidation and corrosion
resistance;
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6. high wear resistance;
7. high impact resistance
Although many kinds of materials are classified as ceramics, only limited materials are
capable of simultaneously satisfying the conditions listed above. Silicon nitride and silicon
carbide are the most promising ceramic materials from this point of view. Table 9.1.1
summarizes the characteristics of silicon nitride and silicon carbide as high-temperature highstrength ceramics.
Fabrication and microstructure control of silicon-based monolithic ceramics
Silicon Nitride
Silicon nitride is a highly covalent material, which means bulk diffusion rate is too low to
give densification. Therefore, sintering additives are used to obtain the fully densified
material. The added metal oxides (MgO, Al2O3, Y2O3, rare earth oxides, etc.) and metal nitride
form a liquid phase by the reaction with Si3N4 and surface SiO2 on Si3N4 powder at high
temperatures.
The application of mechanical and gas pressure during sintering is also effective to
increase density and control the microstructure. Hot-pressing (HP), where an uniaxial
pressure is applied, is one of the most effective sintering method of simple shape parts.
Complex shape parts can be densified by hot-isostatic-pressing (HIP), which utilizes isostatic
pressure of gas.
The other important point is the temperature limitation due to the decomposition of Si 3N4,
which depends on the temperature. Serious decomposition occurs at a temperature of
1800C under ambient nitrogen atmosphere. Gas pressure sintering (GPS) is often applied to
suppress the decomposition at higher temperatures.
Silicon Carbide
Although silicon carbide has a covalent bond, SiC can be densified by solid state sintering.
A combination of boron and carbon is used as typical sintering additives. The added carbon is
considered to react with SiO2 on the surface of silicon carbide particles, and boron is thought
to increase grain boundary diffusion rate.
The liquid phase sintering is also applied by using the similar additives as Si3N4.
SiC produced by solid state sintering has no heterogeneous phase at the grain boundary,
which leads to better oxidation resistance and high temperature strength than SiC produced
by liquid phase sintering. However, SiC by the solid state sintering has lower toughness and
lower thermal shock resistance, compared to SiC or Si3N4 having the heterogeneous phase at
the grain boundary.
Mechanical properties of Si-based monolithic ceramics
1. Spontaneous fracture
Monolithic ceramic materials, as typical brittle materials, possess very limited plastic
deformation capability. The lack of the capability of release of local stress concentration
results in extremely high sensitivity of the materials to the microstructure defects. Besides
the typical defects, that is, voids, inclusions, or surface flaws, the heterogeneities in the grain
microstructure such as elongated grains also have to be carefully taken into consideration.
2. Time-dependent deformation and fracture
Many ceramic materials also show time-dependent mechanical behavior. Glasses are
known to show sub-critical crack growth (SCG) in the presence of humidity. Silicon nitrides
with metal oxide additives also show SCG at elevated temperatures where the crack growth
occurs along the grain boundaries. SCG under static stress is often called as static fatigue.
While sintered silicon nitrides show noticeable static fatigue, silicon carbides with B and C
show little SCG even at high temperatures.
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Many ceramic materials also show creep deformation at elevated temperature. Among the
several creep mechanisms studied or proposed for ceramic materials, sintered silicon nitride
with metal oxide additives is considered to show creep with grain boundary sliding
mechanism.
3. Inelasticity
In the case of fracture of polycrystalline materials, grain boundaries generally play a role
of crack branching or bowing, which results in higher fracture toughness of polycrystalline
materials than that of single crystals. Especially in the case of polycrystalline silicon nitride,
the grains of high aspect ratios play an important role in enhancement of the fracture
toughness.
4. Oxidation
Silicon nitride and silicon carbide are thermodynamically unstable in oxygen rich
atmosphere, although they are exceedingly oxidation resistant compared with super-alloys.
Their oxidation resistance relies on the oxidation product layer on the surface. The oxidation
of silicon-based ceramics under relatively high oxygen partial pressure is called passive
oxidation, where silica or silica-based oxide layer formed on the surface plays the role of
oxidation protection and high durability of the materials are expected.
Toughening of Si-based ceramics by fiber reinforcement
Considerable efforts have been made in order to improve the toughness of Si-based
ceramics especially by whisker and fiber reinforcement. Silicon nitride reinforced with silicon
carbide whisker is one of the material systems that have been most extensively investigated,
because superior mechanical properties and heat resistance can be expected. An example is
the enhancement of the fracture toughness of silicon nitride with SiC whisker reinforcement.
The whiskers are of different orientations that achieved by cold-pressing or extrusion in
powder forming.
As whisker reinforcement usually inhibits the growth of the matrix grains, this approach
has a potential to simultaneously achieve higher strength and toughness.
Laminated composite structure with enhanced fracture resistance
Multilayered ceramic composites have attracted attention in recent years to overcome the
brittleness of ceramic materials. An alternate layered composite composed of different
materials has enhanced fracture resistance and/or damage tolerance, as reported in
ZrO2/Al2O3, SiC/C systems and so forth. The large difference in the layer properties leads to
improved mechanical properties. On the other hand, the difference of shrinkage and thermal
expansion coefficient causes the subsequent de-lamination or cracking through the sintering
stage. Different procedures have been adopted to override this problem, such that using
different additives and graded materials.
8- Porous Ceramics for Filtration
A general definition of a
membrane is that it is "a
selective barrier between two
phases". Therefore, using
membranes, the feed is
separated into two streams, that
is, the retentate and permeate
streams, as shown in Figure
10.1.1. Either the retentate or the
permeate could be product
stream, depending upon types of
membranes used and the feed
stream.
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The permeate stream is the product stream, if the solvent is purified by removing solutes
using a membrane which allows the permeation of solvent and retains the permeation of
solutes, such as in the desalination of seawater. If the purpose of the separation process is
the concentration of solutes, then the retentate becomes the product.
Membrane separation, which is a relatively new separation process, has been
commercialized in the last two decades. The majority of membrane materials, which have
been commercialized thus far, are polymeric. Porous ceramic membranes have great
potential for opening up new types of applications to which polymeric membranes cannot be
applied. This review will summarize the present status and a potential application of porous
ceramics as materials for membrane separation.
Preparation of porous ceramic membranes
Porous membranes must
have pores, which are
connected continuously from the
feed stream to permeate
stream, otherwise no
permeation through the
membranes is possible. Figure
10.1.2 shows a SEM photo and a
schematic representation of a
typical structure of porous
membranes: asymmetriccomposite membranes.
Porous supports, which are usually manufactured using powders by extrusion or slipcasting, have large pore sizes in excess of 1 m and a thickness of the order of millimeters,
and are designated for purposes of mechanical strength. The intermediate layer is coated on
the support layer to reduce pore sizes for the further coating of the top layer. The separation
top layer has separation ability and needs to have controlled pore sizes suitable for the
specific separation. It is formed as thin as possible on the intermediate layer. In this way, the
pore size of asymmetric composite membranes shows a gradient structure from porous
supports to the separation layer, so as to minimize the resistance to permeation across a
membrane.
Membranes can be classified into two groups based on differences in their morphology:
porous or nonporous membranes. In powder sintering methods, ceramic powders, which have
been pre-ground to several micrometers in diameter, can be formed in various types of
membrane shapes such as tubes, plates, and monoliths, by extrusion, tape casting, and slip
casting. Since there is a low limit of particle diameters at approximately several hundred nm,
the pore sizes of the membranes are approximately 0.1m at a minimum, which is in the
microfiltration range, and are not small enough for molecular separation. Therefore,
membranes prepared by powder sintering have been used as supports for preparing
membranes of small pore sizes by further coating.
Porous membranes have been prepared by the solgel process from a variety of metal
oxides and composite oxides. The solgel process is divided into two main routes: the
polymeric solgel route and the colloidal solgel route. An inorganic salt (or metal alkoxide) is
hydrolyzed and a simultaneous condensation reaction occurs to form polymeric or colloidal
sols. In the colloidal sol route, the hydrolysis and condensation reaction is fast, in comparison
with the case of the polymeric sol route, which is achieved by adjusting the reaction
conditions (type of salt, solvent, catalyst, composition of reactants, molar ratio of water,
temperature, etc.), resulting in a fully hydrolyzed alkoxide (highly branched polymer)
other techniques exist.
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Inorganic microfiltration MF
and ultrafiltration UF
membranes have been used in a
wide variety of processing. MF,
which has pore sizes larger than
100 nm, can be applied to
remove or concentrate particles
or microorganisms, while UF
membranes have been used for
the separation of components,
the sizes of which are from 2 to
100 nm, such as proteins and
colloidal solutes. The
applications include Liquid
Phase Separations (table) and
Gas Phase Separations.
9- Ceramic Bearing
As a result of recent
technological progress, the
environments and condition
under which rolling bearings are
used are becoming severe as well
as diverse. Therefore, bearings
made of bearing steel are not
operating in severe conditions.
Engineering ceramics such as
silicon nitride (Si3N4), zirconia
(ZrO2), silicon carbide (SiC) and
alumina (Al2O3) are excellent at
heat resistance, corrosion
resistance and wear resistance.
Accordingly, engineering
ceramics are developed for
applications of bearings.
Applicability of Ceramics to Bearings
Table 11.1.1 shows the features of various ceramic materials. Ceramic materials include
silicon nitride (Si3N4), zirconia (ZrO2), silicon carbide (SiC), and alumina (Al2O3). General
comparison is as the following:
1.
2.
3.
4.
5.
Mechanical strength is in the order alumina < silicon carbide < silicon nitride < zirconia
Corrosion resistance is in the order silicon nitride < zirconia < silicon carbide < alumina
Thermal Expansion is in the order silicon nitride < silicon carbide < alumina < zirconia
Density is in the order silicon carbide silicon nitride alumina < zirconia
Silicon nitride and zirconia are sintered by hot isostatic pressing (HIP).
Table 11.1.2 shows the

suitability of each type of
ceramic for use in bearings
based on the characteristics of
each type of ceramic materials
and the results of the rolling life
test. This table is the standard
when selecting ceramic
materials for bearings. Because
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the load capacity and rolling life
of silicon nitride are equal to or
better than those of high-carbon
chrome bearing steel, silicon
nitride is commonly used as a
bearing material. Silicon nitride,
however, has a problem with
corrosion resistance in high
temperature corrosive
environments such as acid or
alkali, and therefore zirconia or
silicon carbide is the best
material for such applications.
However, it is necessary in such cases to limit bearing load because the load capacity and
rolling life of zirconia and silicon carbide are lower to those of silicon nitride. Because the load
capacity (strength) of alumina is low, it cannot be used basically as a bearing material.
Fitting of Ceramic Bearings
It is necessary to think about two kinds of fitting: fitting between the inner ring and the
shaft; and fitting between the outer ring and the housing. For all-ceramic bearing, in the case
of fitting between the silicon nitride inner ring and the steel shaft, the linear expansion
coefficient of steel is four to five times greater than that of silicon nitride. Consequently, if
temperature rises, the shaft expands, and there is a possibility of the silicon nitride inner ring
being failed. Meanwhile, in the case of fitting between the silicon nitride outer ring and the
steel housing, with an expansion of the housing an excessive clearance occurs between the
outer ring and the housing, and it is possible that this will adversely affect the rotation
performance of the bearing.
Composition of Ceramic Bearings
Ceramic bearings can be divided into all ceramic type and hybrid ceramic type. For the
all-ceramic type bearings, all the outer rings, inner rings, and rolling elements are made of
ceramics. For the hybrid type bearings, only the rolling elements are made of ceramics, and
the outer and inner rings are made of high-carbon chrome bearing steel or other special
steel.Some applications require that the hybrid type bearings run at high speeds. In such
applications, problems may occur because of inner ring expansion due to the centrifugal
force produced by high-speed running and hence the interference between the inner ring and
shaft will loosen. In such cases, rolling elements and inner rings made of ceramics are used.
The retainers are made of
metallic material or plastic
material, depending upon the
intended use of the bearings.
Characteristics of Ceramic Bearings
The characteristics of the
ceramics (silicon nitride, Si3N4)
used in ceramic bearings are
compared to those of high
carbon chrome bearing steel
(SUJ2) used for conventional
types of bearings. The result is
given in Table 11.1.11,
together with the advantages
of ceramic bearings. Because
of the preferable
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characteristics of ceramic
material (silicon nitride),
ceramic bearings are
considered useful in a variety
of applications.
For example, the higher

heat resistance of ceramic
bearings allows them to be
used in high-temperature
environments. Further, their
lower density greatly reduces
the mass of the bearings and
contributes to the reduction in
centrifugal force generated by
the rolling elements (balls or
rollers) when the bearings run
at high speeds. In addition,
covalent bonding of ceramic
material gives higher
resistance to seizure (attack)
caused by discontinued oil film
during high-speed rotation.
10- Cutting Tools
Cutting method has been widely used as precession machining operation. Significant
increases in manufacturing productivity can be achieved by increasing metal-removal rate.
However, when cutting hard or abrasive materials at high speed, productivity is severely
limited by cutting tool edge wear.
The cutting tool material determines at what rate the chip (manufactured part) can be
made. Machine cutting tools and procedures have always been designed around the
maximum capabilities of new tool materials as they were developed. The use of ceramic tools
in the machining of steel and cast iron may achieve speeds up to 3000 m/min (50 m/s). The
utilization of ceramics cutting tools overcomes the problem encountered at the high
temperature generated under these conditions, in addition, even less wear on the ceramic
cutting tool per unit of metal cut.
1.
2.
3.
4.
5.
Favorable properties that promote increased metal removal rates include:

Good hot hardness
Low coefficient of friction
High wear resistance,
Chemical inertness
Low coefficient of thermal conductivity
Thus, materials for cutting tools are classified into three categories by virtue of their
cutting speed:
1. Usage of high-speed steels is comfortable for speed below 100 m/min (1.67 m/s)
2. Cemented carbides such as WC(Ti,Ta)CCo and Ti(C,N)Mo2CNi are mainly used in cutting
speed between 100 and 300 m/min (i.e. between 1.67 and 5 m/s)
3. Intrinsic ceramic tools are suitable for higher speed than 300 m/min (5 m/s).
Thus, for high-speed cutting, ceramic materials of III, IVa, Va, and VIa group elements in
periodic table play the leading part. That is because they have high hardness, low thermal
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expansion, and high thermal conductivity and excellent oxidation and corrosion resistance,
thus, they are candidate for high speed cutting tool materials.
Among these compounds, alumina Al2O3, silicon nitride Si3N4, titanium carbide TiC or
titanium carbonitride Ti(C,N), diamond and cubic boron nitride cBN are actually used as the
ceramic tool. Silicon carbide SiC, which have high hardness in high temperature, is not
suitable material for cutting of metals, especially steels or ferrous alloys, because of thermal
reaction with the work metals during cutting process. However, silicon carbide whiskers are
used as additive of alumina composite tool for cutting of nickel based super alloys such as
Inconel and Waspaloy. Low thermal conductivity of zirconia ZrO2 controls usage as main
cutting tool material.
The fundamental requirement to the tool development is the ability to control
microstructure in tool materials to maximize those physical and mechanical properties
responsible for optimum machining performance.
Physical Properties
Some physical properties of various cutting tools materials are shown in the next table.
This table can aid in materials selection for cutting tools in given conditions. The material
conditions required for cutting tool materials at the high-temperature region (high-speed
cutting) are:
1.
2.
3.
4.
5.
Deformation resistance,
Thermal crack resistance
Oxidation resistance
Good thermal shock parameter R > 10
The Parameter R = (1 ) / E. is the transverse rupture strength, the thermal
conductivity, is the Poissons ratio, is the thermal expansion coefficient and E is the
Youngs modulus.
11- Ceramic-Matrix Composites

It is widely known that controlling the microstructure of materials can modify their
physical properties. In this section, a brief illustration of ceramic-matrix composites is
presented.
Toughening Mechanisms in Ceramics
1. Ceramic materials are in general brittle. So, according to the fracture mechanics, the
strength is governed by the flaw size and the fracture toughness.
2. General approaches for producing strong ceramics are to reduce the maximum size of
processing flaws or to enhance the fracture toughness.
3. The former approach is limited by the nature of the microstructure of ceramics, since a
grain boundary itself can be a flaw responsible for brittle fracture, and surface flaws
generated in use may reduce the strength of ceramics.
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4. The fracture toughness of ceramics is improved by introduction of secondary phases into
matrix materials when the secondary phases are chosen to act as barriers to crack
propagation.
5. As an example, Whiskers introduced into a ceramic matrix, for example, can retard the
crack propagation because the stresses in a whisker spanning the crack plane will tend to
pull the crack shut "crack bridging".
Ceramic matrix composites may be classified into two categories:
1. One is a group of toughened ceramics reinforced with particulates and whiskers. These
materials exhibit brittle behavior in spite of considerable improvements in fracture
toughness and strength. The maximum in fracture toughness is around 10MPa.m1/2 or
more.
2. The second consists of continuous-fiber composites exhibiting quasi-ductile fracture
behavior accompanied by extensive fiber pull out. The fracture toughness of this class of
materials can be higher than 20MPa.m1/2 when produced with weak interfaces between
the fibers and matrix.
Toughening mechanisms in ceramics explored in recent years may be summarized as
follows:
1. Crack Bowing (Bend): Brittle materials containing secondary phase dispersions can
possess higher strength than those of homogeneous materials. The strength increases
with an increase in the volume fraction of dispersed particles and decreases with
dispersed particle size. The strength therefore depends on the particle spacing. the
strengthening is achieved in a manner analogous to the bowing of a dislocation between
pinning points.
2. Crack Deflection: The crack deflection can enhance the fracture toughness. The most
effective morphology for deflecting a propagating crack has been found to be rod-shaped
grains having a high aspect ratio, and this can account for fourfold increase in fracture
toughness. This was demonstrated in rod-shaped grains of silicon nitride and lithiumalumino-silicate glass ceramic.
3. Microcracking: In composites containing secondary fine particles, the local residual
stress due to mismatch of thermal expansion coefficients is generated during cooling
from the processing temperature. The residual stresses cause spontaneous
microcracking. However, when the residual stress is less than the local strength of the
material, the internal stress remains in the material. The volume expansion of the cracked
layers leads to the generation of compressive stresses to the crack interface, resulting in
an increase in the fracture toughness.
4. Transformation Toughening: The microstructure of partially stabilized zirconia (PSZ) in
a system such as CaO-ZrO2 consists of metastable tetragonal ZrO2. The stress-induced
transformation of tetragonal zirconia to monoclinic contributes to the toughening because
all particles within several microns of the cracks become monoclinic while all other
particles remain tetragonal. As a result, a compressive stress is generated at the crack
interface due to the volume expansion accompanying phase transformation, in a similar
way to microcracking. High fracture toughness is achieved by controlling the size of the
precipitates, e.g. ZrO2 ceramics doped with around 3 mol% Y2O3 exhibit high strength
when fabricated from an ultrafine powder to produce fine-grained materials.
5. Bridging: The frictional stress between the fiber and the matrix resists crack propagation
in the pullout process. The bridging stresses are generated by a variety of microprocesses, such as frictional interlocking, fiber bridging and sliding pullout. A weak
interface leading to de-bonding of fibers from the matrix is essential for producing
toughened composites. Example is the toughening of alumina and silicon nitride with
silicon carbide whiskers.
Carbon Fibers
Sic Fibers
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Oxide Fibers
Whiskers
Processing of Ceramic Composites
Hot Pressing
Chemical Vapor Impregnation
Liquid Impregnation and Pyrolysis
Novel Techniques
Other advanced ceramics

12- Ceramic Materials for Energy Systems
Ceramic materials also play an important role in the field of battery technology. The Li-ion
battery is a typical case in which ceramic materials are applied. Here, only the case of Li-ion
battery is presented. Other examples of ceramics in energy systems such as solid oxide fuel
cell SOFC may be found in literature.
Li-ion battery
In Li-ion batteries, lithium oxides are used for a positive active material, and carbons for a
negative active material. Both of the active materials are considered to be ceramics prepared
by normal ceramic production processes. They are used in powder form in Li-ion batteries.
One of the important parameters in evaluating a battery is its capacity to store electric
energy. Coulomb capacity is normally expressed as a unit of ampere-hour. One ampere-hour
capacity delivers 1 A current for 1 h (3600 s); that is, it has energy of 3600 C. Therefore, 1
molar active materials can give 26.8 A h capacity (= 96 500/3600), if they have monovalence. When the mean voltage of a battery is in volts V, energy capacity is expressed to be
V A h, which is Wh. Therefore, a higher voltage gives higher energy, and also higher power
because power is proportional to V squared.
Another important parameter for battery is C. C-rate can normalize current density for a
battery. One C-rate current for a battery with 1 A h capacity is 1 A. Battery engineers often
compare performance of batteries with C-rate when the batteries have the same chemistry of
electrode active materials.
Positive Electrode (Cathode)
The most popular positive electrode material for Li-ion batteries is LiCoO 2. This material is
a kind of ceramic (discovered by Mizushima et al. in 1988) that delivers 4 V potential. During
charging, Li-ion/electron pairs are extracted electrochemically from LiCoO2 ceramic particles.
Electrons come to the negative electrode through an external circuit, while Li-ions also come
to the negative electrode through the electrolyte inside the battery. The valence of trivalent
Co ions in the particles increases tetra-valence to maintain electrostatic neutrality after the
extraction of Li-ions and electrons. The equation of this reaction can be expressed as follows:
Li+Co+3O2 nLi+ + ne + Li+(1n)Co+3(1n)Co+4n O2, where, n is the number of ions and
electrons.
This valence change in the positive electrode is so-called solid-state reductionoxidation
(redox) reaction. For this reaction, positive electrode active material must contain a transition
element. This reaction is characteristic for Li-ion batteries. Oxygen deficiency in the LiCoO 2
affects the Co valence and keeps electrical neutrality. Therefore, control of oxygen partial
pressure is very important for producing LiCoO2 ceramic material.
Negative Electrode (Anode)
Carbon is normally used as the negative electrode active material of Li-ion batteries. It is
widely known that the use of carbon for negative electrode generated great advances in Libased battery technologies. Generally, lithium metal is too reactive for practical use.
During charging, electrons extracted from positive electrode transport to the negative
carbon electrode through an external circuit. At the same time, Li-ions also extracted from
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positive electrode transport to the negative through liquid electrolyte. These two particles
form a pair and exist in the carbon material in charged state. The equation of this reaction
can be expressed as follows:
C + nLi+ + ne CLin
Negative electrode carbon is normally
powder with particle size range of 520m. As
carbon particles must receive electrons from
external circuit and Li-ions from liquid
electrolyte, the carbon particles have to
contact both the metal current collector and
the electrolyte liquid. Carbon powder is mixed
with PVDF binder and then coated by a
machine onto a thin metal copper foil.
Battery Reaction
Battery reaction of Li-ion battery is
illustrated in the next figure. Electrochemical
reactions in the positive and negative
electrodes during charging are expressed by
the following equations:
Positive electrode: LiCoO2 nLi + ne + Li(1n)CoO2
Negative electrode: C + nLi + ne CLin
Overall reaction is as follows.
LiCoO2 + C Li(1n)CoO2 + CLin (charging reaction)
Where is the discharging reaction?
Chargedischarge reaction of Li-ion
13- Functionally Graded Materials
Functionally graded materials (FGM's) are a new generation of engineered materials
wherein the microstructural details are spatially varied through non-uniform distribution of
the reinforcement phase(s).
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Phase B
particles with
phase A matrix
Transition
zone
Phase A
particles with
phase B matrix
Schematic representation of FGM
1.
2.
3.
4.
5.
Schematic of a ceramic/metal
FGM for the relaxation of
thermal stress
The volume fraction of the reinforcement phase is increased gradually replacing the
matrix phases.
FGM's is accomplished using reinforcements with different properties, sizes, and
shapes.
The produced microstructure has varying thermal and mechanical properties
continuously or discretely at the macroscopic scale.
Many techniques are involved in the fabrication of FGM's. E.g. mechanical mixing or
powder deposition then compaction, tape casting, chemical vapor deposition CVD,
physical vapor deposition PVD, and electrophoretic deposition EP.
Functionally graded materials are ideal for applications involving severe thermal
gradients, e.g. thermal structures in advanced aircraft and aerospace engines to computer
circuit boards.
The FGM concept was originated in an effort to reduce thermal stress for thermal barrier
materials. Subsequently, much research has been done focusing on the thermal and
mechanical aspects of FGMs. Recent research has revealed that the concept of FGM can also
be advantageously extended to electronic, optical, biomedical and other fields. Many
interesting and unique concepts and experimental results have been forthcoming to appear
not only in structural materials but also in other various fields.
Generally, the most popular applications of the FGM concept are based on combining two
or more incompatible functions into a given material (such as high thermal resistivity and
excellent mechanical properties) in order to suit a particular circumstance. Example is High
order step wise functionally graded materials Al2O3-Ti. These materials combine the high fracture toughness of Ti
phase and the relatively low density of Al2O3 and stand for candidate materials for harsh mechanical and thermal
environments.
However, many phenomena and experimental results, such as the control of electrical
properties of perovskite oxide and the optical filter characteristics of graded TiO 2/SiO2 film
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mentioned above, cannot be explained by such simple combination of two functions. In
addition, recent research has revealed that natural plants and living bodies have many
intelligent properties due to their graded structures. This encourage us to create new
functions through gradation techniques.
Part 2: Bio-Ceramics
1- Introduction to Bio-Ceramics Chp1
Most clinical applications of
bioceramics relate to the repair of
the skeletal system, composed of
bones, joints and teeth, and to
augment (enhance) both hard and
soft tissues. Ceramics are also
used to replace parts of the
cardiovascular system, especially
heart valves. Special formulations
of glasses are also used
therapeutically for the treatment
of tumors.
Bioceramics are produced in a
variety of forms and phases and
serve many different functions in
the repair of the body, which are
summarized in Fig. 1.1 and Table
1.1.
In many applications ceramics
are used in the form of bulk
materials of a specific shape,
called implants, prostheses, or
prosthetic devices. Bioceramics
are also used to fill space while the
natural repair processes restore
function. In other situations the
ceramic is used as a coating on a
substrate, or as a second phase in
a composite, combining the
characteristics of both into a new
material with enhanced
mechanical and biochemical
properties.
Bioceramics are made in many
different phases. They can be
single crystals (sapphire),
polycrystalline (alumina or
hydroxyapatite), glass (Bioglass),
glassceramics (apatitewollastonite A/W glass-ceramic) or
composites (polyethylenehydroxyapatite). The phase or
phases used depend on the
properties and function required.
For example, single crystal
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sapphire is used as a dental
implant because of its high
strength. A/W glass-ceramic is
used to replace vertebrae because
it has high strength and bonds to
bone. Bioactive glasses have low
strength but bond rapidly to bone,
so are used to augment the repair
of boney defects.
Ceramics and glasses have

been used for a long time
outside the body for a variety of
applications in the health care
industry. Eye glasses, diagnostic
instruments, chemical ware,
thermometers, tissue culture
flasks, chromatography
columns, lasers, and fiber optics
for endoscopy are commonplace
products in the multi-billion
dollar industry.
Ceramics are widely used in dentistry as restorative materials: gold porcelain crowns,
glass-filled ionomer cements, endodontic treatments, dentures etc. However, use of ceramics
inside the body as implants is relatively new: alumina hip implants have been used for just
over 40 years.
Many compositions of ceramics have been tested for potential use in the body but few
have reached human clinical application. Clinical success requires the simultaneous
achievement of a stable interface with connective tissue and an appropriate, functional
match of the mechanical behavior of the implant with the tissue to be replaced. Few
materials satisfy this severe dual requirement for clinical use.
Types of BioceramicsTissue Interfaces
There are four general types
of implanttissue response, as
summarized in Table 1.3. It is
critical that any implant material
avoids a toxic response that kills
cells in the surrounding tissues
or releases chemicals that can
migrate within tissue fluids and
cause systemic damage to the
patient. One of the main reasons
for the interest in ceramic
implants is their lack of toxicity.
The most common response of tissues to an implant is formation of a nonadherent fibrous
capsule. The fibrous tissue is formed in order to wall off or isolate the implant from the
host. It is a protective mechanism and with time can lead to complete encapsulation of an
implant within the fibrous layer. Metals and most polymers produce this type of interfacial
response; the cellular mechanisms which influence this response are described in a later
section.
The second type of response is that for biologically inactive, nearly inert ceramics.
Alumina or zirconia, also develop fibrous capsules at their interface. The chemical inertness
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of alumina and zirconia results in a very thin fibrous layer under optimal conditions. More
chemically reactive metallic implants elicit thicker interfacial layers. However, it is important
to remember that the thickness of an interfacial fibrous layer also depends upon motion and
fit at the interface.
The third type of interfacial responseis when a bond forms across the interface between
implant and the tissue. This is termed a "bioactive" interface. The interfacial bond prevents
motion between the two materials and mimics the type of interface that is formed when
natural tissues repair themselves. This type of interface requires the material to have a
controlled rate of chemical reactivity. An important characteristic of a bioactive interface is
that it changes with time, as do natural tissues, which are in a state of dynamic equilibrium.
The fourth type of interfacial responseis is as follows: When the rate of change of a
bioactive interface is sufficiently rapid the material "dissolves" or "resorbs" and is replaced by
the surrounding tissues. Thus, a resorbable biomaterial must be of a composition that can be
degraded chemically by body fluids or digested easily by macrophages. The degradation
products must be chemical compounds that are not toxic and can be easily disposed of
without damage to cells.
Types of BioceramicTissue Attachments
The mechanism of
attachment of tissue to an
implant is directly related to
the tissue response at the
implant interface. There are
four types of bioceramics,
each with a different type of
tissue attachment,
summarized in Table 1.4 with
examples.
The relative level of
reactivity of an implant also
influences the thickness of
the interfacial layer between
the material and the tissue.
Nearly inert, implant forms a non-adherent fibrous layer at the interface, while a bioactive
material undergoes chemical reactions in the body, but only at its surface.
2- Alumina and Zirconia in Surgical Implants Chp2
The potential of ceramics as biomaterials relies upon their compatibility with the
physiological environment. Bioceramics are compatible because they are composed of ions
commonly found in the physiological environment (calcium, potassium, magnesium, sodium,
etc.) and of ions showing limited toxicity to body tissue (zirconium and titanium). This section
deals with the two nearly inert ceramics most used in surgical implants: alumina and zirconia.
Nearly inert bioceramics undergo little or no chemical change during long-term exposure
to the physiological environment. Even in those cases where these bioceramics may undergo
some long-term chemical or mechanical degradation, the concentration of degradation
product in adjacent tissue is easily controlled by the bodys natural regulatory mechanisms.
Tissue response to immobilized inert bioceramics involves the formation of a very thin,
several micrometers or less, fibrous membrane surrounding the implant material. Inert
bioceramics may be attached to the physiological system through mechanical interlocking,
by tissue ingrowth into undulating (wavy) surfaces, or by cement fixation. The nearly inert
ceramic most used for surgical implants is alumina.
Alumina Ceramics as Implant Materials
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High- density, high purity (> 99.5%) Al2O3 is used in load-bearing hip prostheses and
dental implants because of its combination of excellent corrosion resistance, good
biocompatibility, high wear resistance, and high strength. Although some dental implants are
single-crystal sapphire, most Al2O3 devices are very fine-grained polycrystalline -Al2O3,
produced by pressing and sintering at temperatures ranging from 16001800C, depending
upon the properties of the raw material. A very small amount of MgO (<0.5%) is used as a
grain growth inhibitor and is essential in order to achieve a fully dense sintered body with a
fine grain microstructure. It is very important that the amount of SiO2 and alkali oxides be
below 0.1%, because they impede densification and promote (enhance) grain growth. It is
also essential that the amount of CaO be below 0.1% since its presence leads to a lowering of
the static fatigue resistance.
Strength, fatigue
resistance, and fracture
toughness of polycrystalline
-Al2O3 are a function of grain
size and percentage of
sintering aid, i.e., purity. Al2O3
with an average grain size of
<4 m and >99.7% purity
exhibits good flexural strength
and excellent compressive
strength. Extensive testing
has shown that alumina
implants which meet or
exceed ISO standards have
excellent resistance to
dynamic and static fatigue,
and resist subcritical crack
growth and impact failure.
An increase in average grain size to >7 m can decrease mechanical properties by about
20%. High concentration of sintering aids must be avoided because they remain in the grain
boundaries and degrade fatigue resistance.
These and other physical
properties are summarized in
Table 2.1 for a commercially
available implant material, along
with the International Standards
Organization (ISO) requirements
and the proposed new standards
for alumina implants.Other
typical properties of commercially
available alumina implant
materials are listed in Table 2.2.
Methods exist for lifetime predictions and statistical design of proof tests for load bearing
ceramics. Applications of these techniques show that specific prosthesis load limits can be
set for an Al2O3 device based upon the flexural strength of the material and its use
environment.12 Load bearing lifetimes of 30 years at 12,000 N loads or 200 MPa stresses
have been predicted. Results from aging and fatigue studies show that it is essential that
Al2O3 implants be produced with the highest possible standards of quality assurance,
especially if they are to be used as orthopedic prostheses in younger patients.
Use of Zirconia Ceramics in Surgical Implants
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Medical grade alumina has
outstanding biocompatibility and
wear resistance. However, it
exhibits moderate flexural strength
and toughness. For this reason,
the diameter of most alumina
femoral head prostheses has been
limited to 32 mm. Zirconia is also
exceptionally inert in the
physiological environment, and
zirconia ceramics have an
advantage over alumina ceramics
of higher fracture toughness and
higher flexural strength and lower
Young's modulus.
Zirconia ceramics suggested for surgical implants fall into two basic types: tetragonal
zirconia stabilized with yttria (TZP) and magnesium oxide partially stabilized zirconia (MgPCZ). Properties of zirconia are compared with alumina ceramic implant materials in Table
2.4.
Zirconia may be suitable for bearing surfaces in total hip prostheses. However, there are
three major drawbacks (disadvantages) regarding zirconia. One is the reported strength
reduction with time in physiological fluids. The second is its wear properties, and third is the
potential radioactivity of the material.
The deleterious (harmful) martensitic (non-diffusional) transformation from tetragonal to
monoclinic phase in yttria-doped zirconia is due to aging in water and the accompanying
reduction in toughness. However, tests in simulated body fluids and in animals have shown
only slight decreases in fracture strength and toughness. The observed strength after two
years is still much higher than the strength of alumina tested under similar conditions.
Zirconia is often accompanied by radioactive elements with a very long half-life, such as
thorium and uranium. These elements are difficult and expensive to separate from zirconia.
There are two types of radiation of concern in zirconia ceramics: gamma and alpha. The
gamma radioactivity of alumina, zirconia and Co-Cr-alloy femoral head prostheses has been
measured. Alumina was found to have the lowest gamma radioactivity and zirconia and the
Co-Cr-alloy were found to be approximately the same. The gamma radioactivity for the Co-Cralloy and zirconia were found to be of the same order of magnitude as the national ambient
radioactivity in France. The data suggest that the level of gamma radiation in commercially
available zirconia bioceramics is not a major concern. However, significant amounts of alpha
radiation have been observed with zirconia ceramics intended for surgical implants.
Alpha particles, because of their high ionization capacity, destroy soft and hard tissue
cells. The alpha emission observed from zirconia ceramic femoral head prostheses is a
concern. Although the activity is small, questions concerning the long-term effects of alpha
radiation emission from zirconia ceramics must be answered.
Summary
Alumina and zirconia ceramics are both exceptionally biocompatible, due to their chemical
stability in the physiological environment. Zirconia ceramics have a higher fracture strength,
toughness and lower modulus of elasticity than alumina ceramics. The phenomena of slow
crack growth, static and cyclic fracture, low toughness, stress corrosion, deterioration of
toughness with time, and sensitivity to tensile stresses are all serious concerns for both
ceramics in high load bearing applications. Both alumina and zirconia ceramics undergo
slight reduction in fracture strength with time in the physiological environment. Alumina and
zirconia bioceramics should be restricted to designs involving compressive loading or limited
tensile loads.
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As a consequence of a mismatch in elastic modulus is that a bioceramic implant will shield
a bone from mechanical loading, allowing nearly all the mechanical load to be carried by the
implant. Living bone must be under a certain amount of tensile load in order to remain
healthy; if it is unloaded or is loaded in compression it will undergo biological changes which
lead to resorption, weakening of the bone, and deterioration of the implantbone interface.
The high modulus of elasticity of alumina and zirconia limit their effectiveness as load
bearing bone interface materials. Metal alloys suffer the same limitation. The high modulus of
elasticity of alumina does not limit its ability to serve as an articulating surface.
Alumina is an excellent material for certain orthopedic applications, such as the ball in an
artificial hip joint, because of its excellent biocompatability, low friction, high wear resistance,
and high compressive strength. The tribological properties of alumina ceramics are far
superior to zirconia ceramics. Alumina or alumina-articulating surfaces in total joint
replacements have the best tribological properties and the best clinical results.
3- Bioactive Glasses - Materials Chp3
It was discovered by Hench and colleagues in 1969 that bone can bond chemically to
certain glass compositions. This group of glasses has become known as bioactive glasses,
based upon the following definition:
"A bioactive material is one that elicits (obtains) a specific biological response at the interface
of the material which results in the formation of a bond between the tissues and the material"
Bioactive glasses have numerous applications in the repair and reconstruction of diseased
and damaged tissue, especially hard tissue (bone). One aspect that makes bioactive glasses
different from other bioactive ceramics and glass-ceramics is the possibility of controlling a
range of chemical properties and rate of bonding to tissues. The most reactive glass
compositions develop a stable, bonded interface with soft tissues. It is possible to design
glasses with properties specific to a particular clinical application. This is also possible with
some glass-ceramics, but their heterogeneous microstructure restricts their versatility.
Compositions of Bioactive Glasses
The base components in
most bioactive glasses are
SiO2, Na2O, CaO, and P2O5.
The first, and most wellstudied composition, termed
Bioglass 45S5 contains
45% SiO2, 24.5% Na2O, 24.4%
CaO and 6% P2O5, all in
weight percent. The
Bioglass 45S5 (Registered
trademark University of
Florida, Gainesville,
FL),composition in mole
percent is given in Table 3.1,
along with many other
compositions investigated for
surface reaction kinetics.
Hench and coworkers have
studied a series of glasses in
this four-component system
with a constant six weight
percent P2O5 content.
Properties of Bioactive Glasses
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The primary advantage of
bioactive glasses is their rapid
rate of surface reaction, which
leads to fast tissue bonding.
Their primary disadvantage is
mechanical weakness and low
fracture toughness due to an
amorphous two dimensional
glass network. The tensile
bending strength of most of
the compositions is in the
range of 4060 MPa, which
make them unsuitable for
load-bearing applications. For
some applications low
strength is offset (balanced)
by the glasses low modulus of
elasticity of 3035 GPa. The
importance of this value is
that it is close to that of
cortical bone.
The low strength does not influence the utility of bioactive glasses as a coating, where
interfacial strength between metal and the coating is the limiting factor. Low strength also
has no effect on use of bioactive glasses as buried (masked) implants, in low-loaded or
compressively loaded devices, in the form of powders or as the bioactive phase in
composites. A new generation of highly bioactive glass-ceramics that also have high strength
is thus studied.
Notes on Preparation Processing of Bioactive Glasses
1. Bioactive glasses are produced by conventional glass manufacturing methods.
2. Contamination of the glass must be avoided in order to retain the chemical reactivity of
the material.
3. Purity of raw materials must be assured.
4. Analytical grade compounds are typically used for most components.
5. Silica can be added in the form of high purity (flint quality) glass sand, since chemically
prepared silicas are difficult to handle without adsorption of water and agglomeration.
6. The choice of raw materials can affect the properties of the glass.
7. Crystal-water free compounds are used. This is due to the dissolution of OH ions in the
glass structure and the associated decrease of viscosity.
8. Preferential vaporization of fluxes will also affect glass viscosity and tendency to
crystallize or phase separate, as well as alter the final glass composition.
9. Weighing, mixing, melting, homogenizing and forming of the glass must be done
without introducing impurities or losing volatile constituents, such as Na2O or P2O5.
10.
Melting is usually done in the range of 13001450 C, depending on composition.
Notes on Shaping Processing of Bioactive Glasses
1. Bulk specimens can be formed by casting or injection molding in graphite or steel
molds.
2. Annealing is crucial, 450550 C, because of the high coefficient of thermal expansion
of the bioactive glass compositions. Each type of device (composition) must have its
own annealing schedule established.
3. Bioactive glasses are soft glasses and final shapes can be easily made by machining.
Standard machine tools or dental handpieces can be used.
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4. Diamond-cutting tools are preferred with copious irrigation (with plentiful water
washing), although dry grinding is also possible.
5. If a granulated or powdered material is required, the melt can be rapidly quenched in
water or air before grinding and sieving into the desired particle sizes. The glass frit
should be rapidly dried to avoid corrosion while in contact with water.
Other processing methods used for bioactive glass coatings are exists
4- Bioactive Glasses - Clinical Applications Chp6
The bioactive glasses had valuable properties. When in contact with body fluids and
tissues, they would develop a reactive layer at their surfaces. Due to the gel-like structure of
the bioactive glass, it provided a compliant interface between bulk glass and tissue. It was
found that the 45S5 formulation of Bioglass and related compositions did not break-up
when drilled with standard surgical drilling equipment. The glass was relatively soft and
extremely suitable for microsurgical drilling techniques, opening up its use in certain
otolaryngological applications.
Particles possibly will appear after implantation of a bioactive glass if it were to become
damaged in some way; however, cells found in blood and tissues are programmed to pick up
and digest all unusual particles. Tests showed that these bioactive glasses in solid or
particulate form were not toxic to any of the tissues or systems with which they were in
contact.
Applications of bioactive glass have required several different forms of the material:
1. Solid shapes.
The glasses can be fabricated by casting into shaped implants for specific purposes where
mechanical strength is of secondary importance. E.g. middle ear device.
2. Particulates of various size ranges.
Bioactive glass in the form of particulate has found application in the treatment of e.g.
periodontal disease; where it is essential to replace lost bone and soft tissue connections
if teeth are to be saved.
3. Particulates combined with autologous bone particles.
The success of particulate material in restoring bone in the periodontal area, where the
surgical site preparation releases bone fragments and associated growth factors to
combine with the bioactive glass, has led to a series of investigations in which the glass
has been mixed with autologous bone before implanting.
4. Particulates delivered via an injectable system.
A group of applications that depend on the soft tissue adhesion of bioactive glass; which
are introduced by injection. The particle size and shape, characteristics of the vehicle and
needle size and length provide many problems which need to be solved in advance.
Preclinical experiments in animals have concentrated on the treatment of two urological
conditions which occur in children and some adults.
5- A/W Glass-Ceramic Chp13
Glass can be converted by heat treatment into glass-crystal composites containing
various kinds of crystalline phases with controlled sizes and contents. The resultant glassceramic can exhibit superior properties to the parent glass and to sintered crystalline
ceramics. Generally, monophase bioactive ceramics such as Bioglass-type glasses and
sintered HA (hydroxyapatite Ca5(PO4)3OH) do not show as high a mechanical strength as
human cortical bone. Natural bone is a composite in which an assembly of HA small crystal
particles is effectively reinforced by organic collagen fibers. Kokubo et al. attempted to
prepare a similar composite by a process of crystallization of glass in 1982. In this attempt, wollastonite (CaOSiO2), consisting of a silicate chain structure, was chosen as the reinforcing
phase. This type of glass ceramics is called A/W glass ceramic (apatite/wollastonite glass
ceramic).
Advantages of A/W Glass Ceramics
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1. A/W glass-ceramic can easily be machined into
various shapes, even into screws, by diamond
tools.
2. The mechanical properties is superior to both
glass and glass ceramics, see table 13.1. When
loaded in an aqueous body environment, this
glass-ceramic shows a decrease in mechanical
strength, i.e. fatigue, by slow crack growth due
to stress corrosion, similar to other ceramics.
The magnitude of its fatigue is, however, much
lower than those of glass and glass-ceramic.
3. The parameter, n, of slow crack growth, which is derived from the dependence of the
bending strength upon the stressing rate, is 33 for A/W glass-ceramic, whereas it is 9 and
18 for glass and glassceramic, respectively.
4. When a bending stress of 65 MPa is continuously applied in the body, A/W glass-ceramic
should withstand it for over ten years, whereas glass, glass-ceramic, and dense sintered
HA would survive only one minute.
5. The magnitude of the fatigue of A/W glass-ceramic can be further decreased by a surface
modification such as Zr+ ion implantation (a type of coating).
Summary (AP formation)
The mechanism of apatite formation on the surfaces of CaOSiO2-based glasses and glassceramics, including A/W glass-ceramic, in the body can be interpreted as follows. The calcium
ion dissolved from the glasses and glass-ceramics increases the ion activity product of the
apatite in the surrounding body fluid, and the hydrated silica on the surfaces of the glasses
and glass-ceramics provides favorable sites for apatite nucleation.
Consequently, the apatite nuclei are rapidly formed on their surfaces. Once the apatite
nuclei are formed, they spontaneously grow by consuming calcium and phosphate ions from
the surrounding body fluid.
In the case of A/W glass-ceramic, although the presence of the silica gel layer on its
surface could not be detected even under the high resolution transmission electron
micrographs, the dissolution of an appreciable amount of the silicate ion from the glassceramic into the simulated body fluid indicates the formation of a large number of silanol
groups (SiOH) at the surface of the glass-ceramic in the body.
It is expected that the bone-like apatite layer could be formed on the surfaces of various
kinds of materials including metals, ceramics and organic polymers by the following
biomimetic method at ordinary temperature and pressure. When a material as a substrate is
placed on or in granular particles of a CaOSiO2-based glass soaked in the simulated body
fluid for a certain period, a large number of apatite nuclei can be formed on the surface of the
substrate, as well as on the surfaces of the glass particles, by the calcium and silicate ions
dissolved from the glass particles. When the substrate is then soaked in another solution
supersaturated with respect to the apatite, the apatite nuclei grow spontaneously in situ on
the substrate by consuming the calcium and phosphate ions from the surrounding solution to
form the apatite layer.
A dense and uniform layer of bone-like apatite
was formed on various kinds of materials, including
stainless steel, titanium metal, platinum, gold,
silicon, carbon, alumina, zirconia,
polymethylmethacrylate, polyethylene, polyethylene
terephthalate (PET), and polyethersulfone (PES), by
this method. The thickness of the apatite layer
continued to increase with increased soaking time in
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the second solution. The rate of growth of the
apatite layer increased with increasing temperature
and the degree of the supersaturation of the second
solution.
6- Machinable and Phosphate Glass-Ceramics Chp16

In a living tissue, the bioactive materials are not regarded as foreign bodies and
encapsulated by fibrotic tissue; instead, direct bonding takes place. The special combinations
of properties required for medical indications can be adjusted and varied in glasses and
glass-ceramics.
Glass-ceramics consist of at least one glassy and at least one crystalline phase. The
processing to develop a glass-ceramic is characterized by a formation of a base glass and an
additional heat treatment of the glass. During this heattreatment process, nucleation and
crystallization has to be controlled to form the crystals in the base glass.
Biomaterials for bone substitution are called bioactive if a stable bond to the bone is
formed. Hench et al showed that Bioglass can bond to bone in animals. The interface
reactions between Bioglass and bone, the formation of different Ca-, P-, and SiO2-rich
layers, the dependence on the composition of the implant, the environment, and reaction
time were studied. It was shown that the preferred bonding of bone and biomaterial (glassceramic or sintered ceramic) can be achieved if the biomaterial contains apatite crystals in
the basic material or develops an apatite layer. Mica crystals will permit predictable
mechanical machining properties. It is believed that for a material to be machinable and
bioactive, it should contain both mica and apatite crystals; thus, the glass-ceramics
developed for medicine is derived from different base glasses.
Compositions and Processing
BIOVERIT products is taken here as case study.
BIOVERIT I is a mica-apatite glassceramic with a chemical composition from
the SiO2-(Al2O3)-MgO-Na2O-K2O-F-CaOP2O5 base glass system. These glasses are
from the silico-phosphate type. The key to
the development of BIOVERIT I was to
form a phase-separated base glass
consisting of three glassy phases and to
control the nucleation and crystallization
by heat treating the glass. BIOVERIT II
glass-ceramic contains mica as the main
crystal phase and secondary crystals, e.g.
cordierite crystals.
The base glass is derived from the SiO2-Al2O3-MgO-Na2O-K2O-F system, called silicate
glasses. The base glass is phase separated into two glassy phases and micas were formed
during heat treatment of the glass. Because of the high mica content, BIOVERIT I and II are
machinable glass-ceramics.
The chemical composition of BIOVERIT III glass-ceramic is characterized by glasses from
the CaO-Al2O3-P2O5-Na2O (ZrO2-FeO/Fe2O3) system, so called "invert" glasses of a phosphate
type. In comparison to BIOVERIT I and II, the base glass of BIOVERIT III does not show phase
separation. Apatite, AlPO4 crystals, and other phosphate crystals grow via a special process in
the base glass during heat treatment.
Machinable mica-based glass-ceramics were developed for technical applications by Beall
et al. The composition of the base glasses are characterized by the alkali-fluoroboro-silicate
system. The glass-ceramic implants known as Dicor have been used for dental restorations.
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Typical chemical compositions of BIOVERIT-type glass-ceramics are shown in Tables 16.1
16.3, with the range of possible chemical compositions given.
7- Porous Hydroxyapatite Chp19

The natural bone is approximately 70% HA by weight and 50% HA by volume. The basis
for making the material macroporous is not so obvious, and require an approval for the
architecture of tissues and its effect on regeneration and repair, e.g. throught SEM photos.
Processing
Sintered HA
The most widely-used process to fabricate porous HA implants utilizes isostatic
compaction and sintering of calcium phosphate powders that contain naphthalene particles.
Volatilization of the naphthalene particles leaves a porosity which consists of spherical voids
communicating by a narrow-necked aperture wherever the particles were in contact. To
permit bone in-growth of any depth, these apertures must exceed 100 m or they will
represent blind ends and discontinuities in bone. Another sintering process for creating a
macroporous structure utilizes pretreatment with hydrogen peroxide. Other techniques to
produce porous ceramis exists.
HA Cement
More recently, water-setting HA cements have been employed to create HA materials with
various porosities. The most completely-characterized HA cement in this group is made by
reacting tetra-calcium phosphate and calcium hydrogen phosphate in an aqueous
environment.
Ca4(PO4)2 + CaHPO4 Ca5(PO4)3OH
Under in vitro conditions at 37C, the HA cement sets in approximately 15 minutes and
the isothermal chemical reaction is completed in 4 hours. Porosity is obtained by mixing the
cement prior to set with sucrose granules and then dissolving the granules in water.
Composition
The chemical compositions of the different HA preparations are traditionally evaluated
with X-ray diffraction. X-ray diffraction typically show a crystalline structure which is
essentially pure HA with trace levels of beta tri-calcium phosphate. This beta form of
tricalcium phosphate is also present within human bone at similar low concentrations.
8- Hydroxyapatite Coatings Chp21
Ceramic coatings are used on metallic substrates in a variety of applications, including
enhancement of corrosion resistance of a metal or the creation of a more refractory surface
for high temperature service. In the biomedical field, coatings have been used to modify the
surface of implants, and in some cases to create an entirely new surface, which gives the
implant properties which are quite different from the uncoated device.
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Because of its similarity to the inorganic component of bone and tooth structure, synthetic
hydroxyapatite [Ca10(PO4)6(OH)2] was one of the first materials considered for coating metallic
implants. As bulk HA is brittle and relatively weak when compared to common implant metals
and alloys and high strength ceramics like aluminum and zirconium oxides, the best use of
HA in load-bearing implant applications is as a coating on one of these stronger implant
materials. In spite of the relatively good tissue response to metallic implant surfaces, such as
the passive titanium oxide layer present on titanium, with the use of calcium phosphate
materials as coatings it is possible to present a surface which is conducive to bone formation.
One reason for the use of HA or a similar calcium phosphate surface is to cause earlier
stabilization of the implant in surrounding bone. This is the case, for example, in a dental
implant, where the healing time is reduced and the prosthetic attachment can be placed
earlier. Another reason to use an HA coating is to extend the functional life of the prosthesis,
as in the case of a cementless hip prosthesis, stabilized by the HA coating in the surrounding
femur without the use of polymethylmethacrylate bone cement. Under the proper conditions
a cementless prosthesis should remain functional longer than a cemented device in which
stability is threatened by fracture of the bone cement after a limited number of years in
service.
Processing
Industrial and laboratory techniques used for coating HA and other ceramic materials onto
metallic substrates include plasma spraying, electrophoretic deposition, sputtering and hot
isostatic pressing. The plasma spray method is currently the most widely-used method for
coating. There exist a number of alternative ways of HA coating.
Plasma Spraying: Plasma spraying, the most common means of applying HA coatings to
implant devices, employs a plasma, or ionized gas, partially to melt and carry the ceramic
particulate onto the surface of the substrate. In flame spraying, another thermal spraying
technique, the carrier gasses are not ionized and the temperatures generated are
considerably lower than in plasma spraying. (Details can be found in the course of powder
technology)
Pure, 100% crystalline HA particles in the 2040 m range are typically used as the
starting material for plasma spraying. When the softened particulate impinges on the
substrate surface, individual particles deform into characteristic shapes called "splats". Three
passes of the HA spray are typically made for any given area of the implant surface.
Deformation and spreading of individual particles takes place on impact with the substrate,
and the final coating thickness typically averages 4060 m. The flow of the softened HA is
usually sufficient to form a dense coating with less than 2% residual porosity.
HA coatings produced by the plasma-spraying process typically contain considerable
amorphous calcium phosphate material and small amounts of crystalline phases other than
HA. It is possible to increase the crystallinity and in some cases the bond strength of plasmasprayed HA coatings by a post-deposition heat treatment. However, this extra step is usually
not feasible commercially because of factors such as the adverse effects of the annealing
temperature on the mechanical properties of the substrate metal or alloy, the time and
expense of the additional operation and the contamination of the HA surface.
Other Coating Techniques: Because of the difficulty in producing highly-crystalline
coatings and reproducibly high bond strength using the plasma-spraying technique, other
coating methods have been investigated for commercial applications as follows:
1. An electrophoretic deposition process, in which HA particulate is suspended in an
alcohol or other suitable solution and then subjected to an electric field, is a method
which deposits the HA on an implant surface with minimal alteration of the starting
material. This is a useful technique for placing HA on porous surfaces which cannot be
completely coated other techniques such as plasma spraying. However, as the HA is
only weakly deposited and the individual particles are not bonded together, high
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2014-2015
temperature sintering is necessary after deposition. Because of low bond strength,
electrophoretically-deposited coatings are perhaps best used for porous implant
designs where the presence of an HA coating is only necessary for a limited time
period.
2. Hot isostatic pressing (HIP) can be used to densify HA powder placed on the surface of
a metallic implant. In order to achieve a uniform application of pressure on the
particulate mass, an encapsulation material (e.g., a noble metal foil) is necessary. The
advantage of the method is that lower sintering temperatures (less than 900C) are
required to attain densification and bonding of the HA coating, thus the chances of
altering the microstructure or mechanical properties of the metal substrate are
reduced.
3. Ion beam sputtering and radio frequency (RF) sputtering are thin film deposition
techniques in which a target material is bombarded with an ion beam in a vacuum
chamber, and atomic-sized fragments of sputtered material form coatings on suitably
placed substrates. The typical coatings sputtered from an HA target are amorphous on
deposition, as the sputtered components from the HA target (Ca, P, O and H) do not
possess enough energy to recombine into HA. A heat treatment in the order of 500C is
usually sufficient to provide enough thermal energy to form a crystalline coating that is
predominantly HA. Although sputter-deposited coatings generally have better bond
strength and mechanical properties than thick coatings, the durability of thin 1 m
coatings in the body has not yet been demonstrated.
4. Thermal spray techniques other than plasma spraying are also potential candidates for
the production of commercial HA coatings on implants. One approach involves the use
of the high velocity oxy-fuel (HVOF) technique. In this method the much higher velocity
of the particles causes them to fuse and flow into irregularities on the metal surface
more easily, in spite of being subjected to much lower temperatures than plasma
spraying, thus the initially high crystallinity of the HA can be maintained.
Composition: The composition of plasma-sprayed HA coatings is somewhat different to that
of the starting material, as might be expected because of the high degree of melting
experienced by the ceramic particulate.710 There are several analytical techniques which
are useful for evaluation and analysis of HA coatings. Observation of the coating surface by
scanning electron microscopy (SEM) or light microscopy (LM) can be useful prior to the use of
other techniques which determine the composition and physical properties.
XRD has been widely used as a means of determining the composition and structure of
plasma-sprayed HA coatings as well as for estimating the percentage of crystallinity and
identifying secondary crystalline phases generated as a result of the high temperature
spraying process. Several changes in the diffraction pattern can be noted, including an
increase in the background area under the peaks. A slight bulge (hump) in combination with
peaks indicates a material which is partly crystalline and partly amorphous. A second change
in the pattern would be the appearance of new peaks, as indicated by arrows to the left.
These new peaks are indicative of one or more crystalline phases which have been generated
by the plasma-spraying process, such as and -tri-calcium phosphate, calcium
oxyphosphate, calcium pyrophosphate, or calcium oxide. Finally, lattice parameters may also
alters depending on impurities.
9- Pyrolytic Carbon Coatings Chp24
The carbon can exist in a number of forms. The advantages of using carbon are, some of
its forms, offer the most outstanding biocompatibility, chemical inertness and thromboresistance compared with any of the ceramics used in biomedical applications. These
properties have, for example, made various forms of carbon the preferred material where
interface to blood flow is required. Alternatively, they can be attached to both soft and hard
tissue, which is a prerequisite for a wide range of biomedical devices.
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2014-2015
Three types of carbon are commonly used for biomedical devices: the low temperature
isotropic (LTI) form of pyrolytic carbon, glassy (vitreous) carbon and the ultralow-temperature
isotropic (ULTI) form of vapor-deposited carbon. These three forms of carbon have a
disordered lattice structure and are collectively referred to as turbostratic carbons. While the
microstructure of turbostratic carbon might seem very complicated due to its disordered
nature, it is in fact quite closely related to the structure of graphite. It can be described as
randomly oriented hexagonal graphite layers
Although pyrolytic carbons were developed originally for elevated temperature
applications (e.g., as coatings for nuclear fuel particles), LTI pyrolytic carbon has found wide
appeal in the biomedical materials industry, in particular for mechanical cardiac valve
prosthetic devices, as it has been shown to be highly thromboresistant and to have inherent
cellular biocompatibility with blood and soft tissue. Moreover, it displays excellent durability,
strength and resistance to wear, and had been thought to be immune to cyclic fatigue failure.
Processing
Dense and high strength LTI pyrolytic carbon components are typically made by codepositing carbon and silicon carbide on a polycrystalline graphite substrate via a chemical
vapor-deposition, fluidized-bed process (in vaccum) using a gas mixture of a silicon
containing carrier gas with a hydrocarbon (e.g., propane, methyltrichlorosilane and helium
gas mixtures) at elevated temperatures. The resulting material contains typically 10 wt%
silicon, often in the form of discrete submicron -SiC particles randomly dispersed in a matrix
of roughly spherical micron-size subgrains of pyrolytic carbon; the carbon itself has a
subcrystalline turbostratic structure, with a crystallite size of typically less than 10 nm.
The solid products of these pyrolysis reactions are carbon and silicon carbide, which
deposit as a coating on everything in the bed, including the fluidizing particles and the
graphite components to be coated. The fluidizing bed system is equipped with metering
devices so that the quantity of carrier gas, hydrocarbon and silicon-containing hydrocarbon
can be controlled to give the proper concentrations for deposition.
The ULTI vapor-deposited carbons can be produced with much higher densities and
strengths but only as a thin coating, typically in the range of 0.11.0 mm in thickness. The
coating is formed by a hybrid vacuum process by using a catalyst to deposit carbon from a
carbon-bearing precursor. With variations in processing parameters, the density, crystallite
size and isotropy of the coating can be varied within quite wide ranges.
The adhesion of the ULTI coating to the substrate is naturally an important design
consideration, particularly when used on flexible substrates. When used as a coating on
certain clinical stainless steels and titanium ( Ti-6Al-4V) alloys, a bond strength exceeding 70
MPa is achieved. This excellent bond strength is, in part, due to the formation of carbides at
the carbon/metal interface. The bond strength with other materials that do not form carbides
is typically lower.
Mechanical Properties
The mechanical properties of the
various turbostratic carbons are
closely related to their
microstructures, with a strong
correlation of most of these
properties with coating density. Other
microstructural features such as
crystallite size, structure and
orientation, grain size and
composition are also important in
determining the resulting properties.
Some of the more important
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2014-2015
mechanical properties of the
clinically useful turbostratic carbons,
together with a typical
polycrystalline graphite substrate
onto which coatings might be
deposited, are presented in Table
24.1.
10- Bioceramic Composites Chp26

Numerous studies were
conducted to develop reliable
composites of bioactive glasses and
ceramics reinforced with a metallic
phase. Structural failures occurred
due to attack of the metalglass
phase boundaries in the composite
material and the materials never
became clinically important and
therefore only an abbreviation is
presented here. Seer table 26.1.
It seems that Functionally
graded materials FGM is the
solution. In our department, there is
a current PhD research on AluminaZirconia FGM to produce allceramic prosthesis components for
Hip Joint by electrophoretic
deposition.
11- Calcium Phosphate Cements Chp28
Bone grafts are frequently required for surgical procedures in bone regeneration. A large
proportion of the bone grafts are derived from autologous bone, which remains the gold
standard despite the numerous synthetic bone substitutes that are commercially available
because autologous bone has all the prerequisites for new bone formation. However, it has
its own limitations, such as the amount of autogenous bone available, increased morbidity,
increased anaesthesia time, blood loss and postoperative donor site complications. For this
reasons, the majority of bone substitutes are based on calcium phosphates ceramics, calcium
sulphates and bioactive glasses, presented in the form of granules, blocks, pastes and
putties.
Calcium phosphate cements comprise a promising group that are mouldable and undergo
in situ setting, which may or may not produce a resorbable material depending on the
composition. Current synthetic bone grafts are primarily made either from calcium phosphate
ceramics or selfsetting calcium phosphate cements and composite materials. Calcium
phosphates are applied for bone tissue engineering and bone substitute materials.
Current strategies in developing calcium phosphate bone substitutes are focused towards
in situ setting of the cements under physiological conditions with adequate mechanical
properties, which can be tailored to resorb by controlling structure and composition. Calcium
phosphates show excellent biocompatibility and are able to integrate biologically with bone in
the living body due to their similarity to poorly crystalline carbonated hydroxyapatite (HA),
which forms the mineral component of bone and teeth. This is one of the main reasons for
their widespread use as a bone substitute or bone repair material and thus has been widely
researched and used in orthopaedics, dental applications and increasingly they are being
applied in spinal surgery.
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2014-2015
Calcium phosphate biomaterials can be divided in two major categories: the ceramic
calcium phosphates and the calcium phosphate cements. The ceramic calcium phosphates
are clinically applied in the form of blocks or granules, which exhibit excellent
biocompatibility that is able to support bone growth and osseointegrate mainly at the
surface. Ceramic calcium phosphates are thus limited by poor resorbability, lack of
adhesiveness, require pre-shaping and are brittle in nature. These limitations led to the
development of self-setting calcium phosphate cements (CPCs), which was a significant step
towards the clinical application of calcium phosphates. The self-setting cements confer the
ability to mould the material into any desired shape, such that it can be easily introduced in
irregularlyshaped bone cavities. Excellent cytocompatibility, bioactivity, mouldability and
resorbability make calcium phosphate cements a unique group of materials which have made
a significant impact in the field of bone regeneration.
Calcium phosphate cement is a generic term that describes hydraulic cements formed
from a mixture of precursors that constitute one or several calcium phosphate powders and a
liquid or aqueous component that sets to a hardened mass, with the end product being a
calcium phosphate material. CPCs generally consist of a concentrated mixture of one or
several calcium phosphate powders and an aqueous solution and only those transformations
that can occur at physiological temperature under aqueous conditions can be considered for
in vivo applications.
Calcium phosphate (or orthophosphate) cement is a generic term to describe chemical
formulations in the ternary system Ca(OH)2 H3PO4 H2O which can experience a
transformation from a liquid or pasty state to a solid state and in which the end-product is a
calcium orthophosphate (contains Ca2+ & orthophosphates PO43)
12- Radiotherapy Glasses Chp29
1. Radiotherapy glasses are defined as radioactive glasses used for in situ irradiation, beta
or gamma radiation, of targeted organs inside the body.
2. Glasses used for this purpose must not only be biocompatible, but also chemically
insoluble in the body during the time that the glass is radioactive, to prevent the
unwanted release of the radioisotopes from the targeted site.
3. The development of radiotherapy glasses was motivated by the need to deliver large
(>10,000 rads), localized doses of beta radiation to diseased organs in the body in such a
way as to minimize, and ideally avoid, damage to adjacent healthy tissue.
4. Irradiating malignant tumors inside the body by external beam radiation is limited in
several important ways.
a. A major limitation is that the maximum dose which can be safely delivered is
constrained by the need to protect surrounding healthy tissue and is usually too small
(3,000 rads) to be therapeutic.
b. Furthermore, external irradiation with energy radiation such as gamma often causes
damage to healthy tissue.
c. The lower energy beta radiation is not well suited for delivery by external means
because its smaller range in tissue may be too small for it to reach the target site.
5. Since beta radiation is preferred in many cases, a means of in situ radiation is
advantageous.
Yttrium aluminosilicate (YAS) glasses have been successfully used clinically for 25 years.
This application uses YAS glass microspheres, containing Y-90, to irradiate malignant tumors
in the liver. Depending upon the size of the liver, desired dose, and diameter of the
microspheres, the surgeon injects 115 million microspheres of radioactive YAS glass, 1535
m in diameter, into the hepatic artery, the primary blood supply for the target tumors.
Microspheres are sized so that the blood carries them into the capillary bed of the liver, but
they are too large to pass completely through the liver and enter the circulatory system.
Since the distribution of the radioactive microspheres follows the blood flow, the
microspheres will concentrate in the tumor, which has a greater than normal blood supply,
42

2014-2015
and irradiate the tumor with beta rays. Typically, 80% of the dose reaches the tumor. Since Y90 has a half-life of 64.1 hrs, the radioactivity decays to a negligible level in about 21 days.
Radiotherapy glasses can be made in a variety of shapes, such as irregular particles,
fibers, or spheres. Microspheres are the shape of choice since the diameter can be carefully
controlled and the smooth spherical surface helps with easy injectable delivery of the
particles to the target.
Processing
A typical manufacturing sequence for
preparing radiotherapy glass microspheres is
given in Fig. 29.1. The first step is the melting
of a homogeneous mixture of high purity
powders, such as Y2O3, Al2O3, and SiO2, in a
platinum crucible. Melting typically occurs at
15501650C for the RE aluminosilicate glass
forming compositions, Fig. 29.2.
After melting, the chemically-homogeneous
melt is quenched to room temperature and
crushed to a powder of the desired size. This
powder is spheriodized by passing the
particles through a gas/oxygen flame, where
each particle is melted, forms a sphere by
surface tension forces, and becomes solid
during cooling. The microspheres are then
screened to obtain microspheres of the
desired size.
Fig 29.2. Glass formation region (<1,600C) for Y2O3,

Ho2O3, or Sm2O3 aluminosilicate
The final step is the irradiation of the glass microspheres with neutrons to form the
desired quantity of radioisotope. YAS glasses are easily irradiated, forming Y-90, to a specific
activity up to 5 mCi/mg of glass. After irradiation the microspheres are ready for packaging
and shipment. It is important that high purity raw materials, free of neutron-activatable
impurities, be used and that care is taken during the various manufacturing steps to avoid
chemical contamination of the glass.
The maximum time which these glass microspheres will remain in the body is currently
unknown, but YAS microspheres have been in one patient for more than four years with no
reported problems. There are other opportunities where microspheres of YAS and other RE
aluminosilicate glasses can be used as in situ radiation devices to destroy malignant tumors
in other organs in the body.
13- Dental Glass-Ceramics and ZrO2-Ceramics Chp30
Biomaterials used in restorative dentistry are important products for humans who want to
regain the full range of their chewing functions or improve the aesthetic appearance
(malposition) of their teeth. Therefore, dental biomaterials are products which considerably
enhance the quality of human life. Typical products are dental inlays, onlays, crowns, veneers
bridges, posts or abutments for implant therapy. This category of materials must fulfill a
combination of properties. They must be able to match or even surpass the optical
(translucency, opalescence, fluorescence), chemical and mechanical properties of natural
teeth. For the first time, materials capable of meeting the challenges of metal-free tooth
replacements became available.
1. Mica-Type Glass-Ceramics
DICOR (Corning Inc./Dentsply Int., USA) was the first glass-ceramic developed for
restorative tooth replacements. Mica crystals of the type of tetrasilicic mica, KMg2.5Si4O10F2,
were precipitated by means of controlled crystallization in the SiO2MgOK2OF system.
43

2014-2015
2. Leucite-Type Glass-Ceramics
At the end of the 1980s, special molding technology which eliminated the need for
additional heat treatments became available, allowing the fabrication of inlays and crowns
from leucite, KAlSi2O6, glass-ceramics. The principles of controlled surface nucleation and
surface crystallization in base glasses of the SiO2Al2O3K2ONa2O system were applied in
these glass-ceramics. The resulting product is IPS Empress (Ivoclar Vivadent AG,
Liechtenstein).
3. Lithium Disilicate Glass-Ceramics
Lithium disilicate (Li2Si2O5) glass-ceramics expand the range of indications of glassceramic biomaterials to include dental bridges. Wide-ranging developments have been
undertaken in conjunction with this material system. To develop the new material, the main
crystal phase was produced in the special base glass of the SiO2Li2OK2OZnOP2O5Al2O3
La2O3 system by means of heterogeneous nucleation and crystallization. In the process, an
interlocking microstructure with a crystal content of more than 60% vol. was achieved. The
resulting product was called IPS Empress2 (Ivoclar Vivadent AG).
4. Fluoroapatite Glass-Ceramics
The needle-like fluoroapatite crystals, Ca5(PO4)3F, contained in glassceramics (IPS e.max
Ceram, IPS e.max ZirPress, Ivoclar Vivadent AG) may produce a favorable light-scattering
effect, such that the resulting translucency corresponds to that of natural teeth. The objective
was to develop a veneering ceramic that offered tooth-like optical properties.
This, however, does not mean that the material should be bioactive. The tooth-like
translucency and the CTE of 9.5106 K1 enabled the resulting glass-ceramic to be used on
lithium disilicate glass-ceramics as well as on high-toughness 3Y2O3ZrO2 sintering ceramics.
Sintered ceramic devices are achieved by machining open-pore materials and
subsequently sintering them to a high density. The high toughness of 4.5 MPam1/2 allows the
fabrication of metal-free long-span bridges.
5. ZrO2-Containing Glass-Ceramics
With the objective to achieve high levels of toughness and a CTE that is adjusted to that
of ZrO2 sintered ceramics, a ZrO2-containing glass-ceramic (IPS Empress Cosmo Post,
Ivoclar Vivadent AG) was developed. Controlled crystallization was used to produce
Li2ZrSi6O15 as the main crystal phase.
This glass-ceramic offers the advantage over other products that it can be pressed onto
ZrO2 posts by means of a molding process. The resulting dental posts are suitable for the
build-up of devitalized teeth and offer metal-free, highly aesthetic solutions for patients.
6. Leucite- Apatite Glass-Ceramics
Glass-ceramics were also developed to veneer dental metals frameworks, e.g. long-span
bridges. A preferred material is a leucite-apatite glass-ceramic (IPS d.SIGN, Ivoclar Vivadent
AG) from the SiO2Al2O3K2ONa2OCaOP2O5F system. The leucite content enables this
glassceramic to attain the required CTE of 12106 K1. The fluoroapatite needles provide the product
with the required translucent qualities.
7. ZrO2 Ceramics
Sintered ceramics of Al2O3 and ZrO2-type are widely used in dentistry. The preferred
processing technology is machining by milling. The ZrO2 ceramic of the type IPS e.max Zir
CAD (Ivoclar Vivadent AG) is characterized by a K1C value of 4.5 MPam1/2. Based on this very high
toughness, the biomaterial is used to produce dental copings, frameworks of dental bridges and
dental abutments.
44

Advanced Ceramics - 4th Year - Lecture Notes

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Advanced Ceramics - 4th Year - Lecture Notes

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Advanced Ceramics 4th year Lecture notes

Functionally Graded Materials

Dr. Saad B. H. Farid

1. Insulating Ceramics/High Thermal Conductive Ceramics