Beruflich Dokumente
Kultur Dokumente
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.
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
BGA
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
3
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
4
Figure 3: Characterized
temperature regions of
PTC ceramics
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.
Manufacturing Process
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).
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
6
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.
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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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13
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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;
15
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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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).
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
20
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
21
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.
22
25
Phase B
particles with
phase A matrix
Transition
zone
Phase A
particles with
phase B matrix
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
26
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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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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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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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.
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