Introduction to functional ceramic
materials. Structure, properties,
preparation and applications
Vincenzo Buscaglia
Istituto per l’Energetica e le Interfasi
Consiglio Nazionale delle Ricerche
Via De Marini 6, 16149 Genoa
[email protected]
What a ceramic is ?
From Greek word “keramos” (pottery, potter’s clay)
Inorganic nonmetallic materials obtained by the action of heat and subsequent
Polycrystalline materials, single phase or multiphase (composites), sometimes with
an amorphous component (glass)
Traditional ceramics
•Whitewares: tableware, cookware, sanitary ware, etc.
•Refractories (kiln and furnace linings for steel and glass industry)
•Structural clay products (floor & roof tiles, bricks, etc.)
Fabricated from clay, quartz, feldspar (earthenware) and kaolin (porcelain)
Technical/advanced ceramics
•Structural ceramics (mechanical properties: strength, toughness, hardness,
creep resistance)
•Functional ceramics (electric, magnetic, optical properties)
Structural ceramics
Two Kyocera ceramic knives
Ceramic body armour plates
(Al2O3, SiC)
The Porsche Carrera GT's
silicon carbide disk brake
Ceramic Si3N4 bearing parts
Radial rotor made from Si3N4
for a gas turbine engine
Functional ceramics
SiC, MoSi2, LaCrO3
Heating elements for high temperature
Temperature sensors, self-regulating
heating elements
Dielectrics with very low
losses (r = 3 -10)
Al2O3, AlN,
Substrates for electronic circuits and
chip packaging
Dielectrics for microwave
applications (r = 30-80)
MW resonators, filters and antennas for
mobile communications and GPS
devices, tunable MW devices
Temperature stable dielectrics
(r  100)
CaTiO3, BaONd2O3-TiO2
Capacitors with temperatureindependent capacitance
Dielectrics with very high
dielectric constant (r  3000)
Multilayer ceramic capacitors
Piezoelectric ceramics
Pb(Zr,Ti)O3 (PZT)
Transducers, actuators and resonators
Pyroelectric ceramics
IR radiation detection and imaging
Functional ceramics
Ferroelectric memories (FeRAMs)
PbMg1/3Nb2/3O3 -PbTiO3
Magnetic ceramics
Spinels (Ni,Zn)Fe2O4
Y3Fe5O12 (YIG)
Permanent magnets
Microwave devices (radars)
Ionic conductors
Y:ZrO2 (YSZ)
Electrolytes for solid-oxide fuel cells
(SOFCs), oxygen sensors
YBa2Cu3O7-x (YBCO)
Superconducting cables for magnets
Al2O3, MgAl2O4, Y3Al5O12
Phosphors, optical materials for lenses
and laser systems, nose cones for heatseeking missiles, high-pressure sodium
street lamps
Waveguides, frequency doublers,
voltage-controlled optical switches,
Thick (left) and thin (right) substrates (alumina)
Pressed and extruded parts (alumina, mullite, zirconia)
Ferrites cores
Microwave dielectric components
Low Temperature Co-fired Ceramics
(LTCC) Ceramic Multilayer Substrates
Monolithic Multilayer Ceramic Capacitors
(modified BaTiO3)
Pyroelectric Infrared sensor (PZT)
SAW filter (SIO2, LiNbO3, LiTaO3)
Ceramic resonators (SiO2, PZT, BaMg1/3Ta2/3O3)
Thermistors (NTCR: spinels;
PTCR: modified BaTiO3)
Ceramic filters (BaMg1/3Ta2/3O3, Zr(Sn,Ti)O4)
Cheap ferrite beads
(hexaferrites BaFe12O19)
Multilayer piezoelectric ceramic
actuators for diesel injection
system (PZT – PbZrxTi1-xO3)
Multilayer technology used for higher performances and device miniaturization
Multilayer ceramic capacitors: most widely used ceramic components in ME
Microstructure of ceramics
Glossary: grains, grain boundaries, pores, secondary phases, domain walls, relative
density, grain size, grain size distribution, texture, etc.
Fully dense 99% Al2O3, transparent
Partially porous 99% Al2O3,
Liquid-phase sintered 96% Al2O3
with secondary glassy phase
Further details: Classification&Microstructure.ppt
Outlook of the course
 Introduction. Why a course on functional ceramics? (Introduction.ppt)
 Processing of ceramic materials: forming and sintering (Processing.ppt).
 Structure and properties of grain boundaries. Nanoceramics (GrainBoundaries.ppt).
 Ceramics for electronics: ferroelectric and piezoelectric ceramics, dielectrics with
high dielectric constants (BaTiO3, PbZrxTi1-xO3, (K,Na)NbO3)
(Ferroelectrics.ppt, Piezoelectrics.ppt)
-Multilayer ceramic capacitors. Miniaturization of devices and related issues.
-Piezoelectric actuators and transducers.
-Lead-free materials.
 Multiferroic materials (BiFeO3, magnetoelectric composites): a challenge for
materials science. (Multiferroics.ppt)
 Ceramics for energy: (SOFC.ppt, MIEC.ppt)
-Ionic and mixed high-temperature conductors (Y:ZrO2, Gd:CeO2, (La,Sr)MnO3)
-Solid-oxide fuel cells.
-Ceramic membranes for gas separation.
Required background
 General background in physics, chemistry and materials science.
 Knowledge of most common crystal structures (fluorite, spinel, perovskite).
 Defects and defect chemistry in oxides, extended defects, doping, p- and n- type
semicondutors, defect chemistry and electrical conductivity.
 Electric and dielectric properties of crystalline solids: polarization, complex
dielectric permittivity, ac dielectric properties, impedance, dielectric relaxation.
 Fundamentals of solid-state magnetism
Suggested readings
 A.J. Moulson & J.M. Herbert, Electroceramics, Chapman & Hall.
 W.D. Kingery, H.K. Bowen, D.R. Uhlmann, Introduction to Ceramics, John Wiley & Sons.
Review papers
 F. Ernst, O. Kienzle and M. Rühle, Structure and Composition of Grain Boundaries in Ceramics, J. Europ.
Ceram. Soc. 19,665-673 (1999).
 S. von Alfthan et al., The Structure of Grain Boundaries in Strontium Titanate: Theory, Simulation and
Electron Microscopy, Annu. Rev. Mater. Res. 40,557–99 (2010).
 G. H. Haertling, Ferroelectric Ceramics: History and Technology, J. Am. Ceram. Soc. 82,797–818 (1999).
 D. Damjanovic, Ferroelectric, dielectric and piezoelectric properties of ferroelectric thin films and
ceramics, Rep. Prog. Phys. 61,1267–1324 (1998).
 L. Jin, F. Li, S. Zhang, Decoding the Fingerprint of Ferroelectric Loops: Comprehension of the Material
Properties and Structures, J. Am. Ceram. Soc. 97,1–27 (2014)
 A.K. Tagantsev et al., Ferroelectric Materials for Microwave Tunable Applications, J. Electroceramics 11,
5–66 (2003).
 S. Zhang & F. Li, High performance ferroelectric relaxor-PbTiO3 single crystals: Status and perspective, J.
Appl. Phys. 111,031301 (2012).
 J. Rodel et al., Perspective on the Development of Lead-free Piezoceramics, J. Am. Ceram. Soc. 92,
1153-1177 (2009)
 T. R. Shrout & S. J. Zhang, Lead-free piezoelectric ceramics: Alternatives for PZT?, J. Electroceram.
19,111–124 (2007)
 C.A. Randall et al., High Strain Piezoelectric Multilayer Actuators—A Material Science and Engineering
Challenge, J. Electroceramics 14,177-191 (2005).
 M. Fiebig, Revival of the Magnetoelectric Effect, J. Phys. D.: Appl. Phys. 38,R123-R152 (2005)
 C.A.F. Vaz et al., Magnetoelectric Coupling Effects in Multiferroic Complex Oxide Composite Structures,
Adv. Mat. 22,2900-2918 (2010).
 J. van den Brink, D. I. Khomskii, Multiferroicity due to charge ordering, J. Phys.: Condens. Matter
20,434217 (2008)
M. Winter & M.J. Brodd, What Are Batteries, Fuel Cells, and Supercapacitors?, Chem. Rev. 104,42454269 (2004).
 A. J. Jacobson, Materials for Solid Oxide Fuel Cells, Chem. Mater. 22,660-674 (2010).
 A. Orera & P. R. Slater, New Chemical Systems for Solid Oxide Fuel Cells, Chem. Mater. 22,675-690
 J. Sunarso et al., Mixed ionic–electronic conducting (MIEC) ceramic-based membranes for oxygen
separation, J. Membrane Science 320,13–41 (2008)
 S. Baumann et al., Manufacturing strategies for asymmetric ceramic membranes for efficient separation of
oxygen from air, J. Europ. Ceram. Soc. 33,1251-1261 (2013).
 A. Feteira, Negative Temperature Coefficient Resistance (NTCR) Ceramic Thermistors: An Industrial
Perspective, J. Am. Ceram. Soc., 92, 967–983 (2009).
 W. Wersing, Microwave ceramics for resonators and filters, Current Opinion in Solid State & Materials
Science 1,715-731 (1996.)
I. Reaney & D. Iddles, Microwave Dielectric Ceramics for Resonators and Filters in Mobile Phone
Networks, J. Am. Ceram. Soc. 89,2063–2072 (2006).

Functional ceramics

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