Chapter 4:

Functional Ceramics

Outline of Chapter 4
4-1 Introduction to Functional Ceramics 4-2 Fabrication Processes for Functional Ceramics 4-3 Application of Ferroelectric Ceramics

Questions for Chapter 4

1 What are Ceramics and Functional Ceramics? 2 What are the application fields of Functional Ceramics? 3 The types of Functional Ceramics and their applications. 4 How to fabricate functional ceramics? 5 The crystal structure of ferroelectric ceramics (BaTiO3 ceramics). 6 Why are ferroelectric ceramics so important? 7 The applications of ferroelectric ceramics.

4.1 Introduction to Functional Ceramics

What are Ceramics?
comes from the Greece word keramicos, which means burnt stuff broadly classed as inorganic, non-metallic materials usually a compound, or a combination of compounds, between metallic and nonmetallic elements (mainly O, N, C, B) always composed of more than one element (Al2O3, SiO2, SiC, etc.) bonds are either totally ionic, or combination of ionic and covalent. A ceramic is an inorganic, nonmetallic solid prepared by the action of heat and subsequent cooling. Ceramic materials may have a crystalline or partly crystalline structure, or may be amorphous (e.g., a glass) .

4.1 Introduction to Functional Ceramics

Ceramic artware Ceramic components

Ceramic knife

Piezoelectric ceramics Bioceramics Ceramic components

Classification of Ceramics

Traditional ceramics Clay based products

Ceramic dishware

Structural ceramics Used for their mechanical properties

Ceramic bearing and bolts

Functional ceramics Used for other properties than mechanical strength, i.e. electrical, optical, magnetic properties

Piezoelectric ceramic components

Classification of Functional Ceramics

Based on Chemical composition:
Silicate Ceramices: presence of glassy phase in a porous structure Clay ceramics (with mullite - 3Al2O3.2SiO2) Silica ceramics (with cordierite 2MgO.2Al2O3.2SiO2) Oxide Ceramics: dominant crystalline phase, with small glassy phase Single oxide (Al2O3), doped oxide, mixed oxide (BaTiO3) Non-oxide Ceramics: Carbon, SiC, BN, Ti3N4, sialon(Si3N4-Al2O3 )

Properties and Applications of Functional Ceramics

Properties Optical Electronic and ion conducting Catalytic Magnetic et al. Applications of functional ceramics Information and communication technology Energy technology Process technology - catalysis Environmental technology Medical technology Sensor technology

Types of Functional Ceramics

Ceramic insulators Ferroelectric Ceramics Piezoelectric ceramics Thermosensitive ceramics Pressure-sensitive ceramics Gas-sensitive ceramics et al.

Ceramic insulators
electrical resistivity (> 109 cm) Functions: The primary function is physical separation of conductors and regulation or prevention of current flow between them. Other functions are to provide mechanical support, heat dissipation, and environmental protection for conductors. Classification: Oxide-based Ceramics: SiO2, Al2O3, MgO-Al2O3-SiO2, BaO-Al2O3-SiO2 Nitride-based Ceramics: BN, AlN, Si3N4, Ti3N4

Ceramic insulators
Advantages: The advantage of ceramics as insulators is their capability for hightemperature operation. High voltage insulators of ceramic materials are mainly used in outdoor switching stations and outdoor lines.

Ceramic insulator supporting a power line

Different shaped ceramic insulators

Disadvantages: brittle and easily chipped or broken

Ferroelectric Ceramics
Ferroelectric ceramics is a special group of minerals that have ferroelectric properties: the strong dependence of the dielectric constant of temperature, electrical field, the presence of hysteresis and others. The ferroelectric effect: the polarity can be reversed under the influence of an electric field of the appropriate orientation.

Crystal Structure: The ABO3 perovskite type materials are by far the most important category for ferroelectric ceramics. For example, BaTiO3, CaTiO3, PbTiO3, KNbO3

Ferroelectric Ceramics
Applications: Ferroelectric random access memory (FRAM): this offers very fast storage and retrieval of data, with the advantage that the stored data is preserved when there is no power supply. Ferroelectric ceramics are suitable for use in capacitors, for example in ultrasound imaging and high sensitivity infrared cameras. Thin-film ferroelectric ceramics, which can be used in optical waveguides and optical memory displays.

Piezoelectric Ceramics
Piezoelectricity is the charge which accumulates in certain solid materials in response to applied mechanical stress. A ceramic, such as lead zirconate titanate (PZT), that converts an electrical field to a mechanical strain or a mechanical strain to an electrical charge. Applications: Actuators Sensors Generators Transducers

Other Functional Ceramics

Thermosensitive ceramics: PTC ((Ba2Pb)TiO3, (Sr,Ba)TiO3) NTC (MnO-CuO-O2, Mn-Nio-O2) Pressure-sensitive ceramics: (ZnO ceramics) Humidity sensitive ceramics: (Si-Na2O-V2O5, ZnO-Li2O-V2O5 ceramics) Gas-sensitive ceramics: (SnO2, ZnO, Fe2O3 ceramics)

4.2 Fabrication Processes for Functional Ceramics

General Fabrication Processing for Functional Ceramics
Synthesis of powder (critical step: monophasic powders, with fine and homogeneous particle size distribution) Milling, usually with additive mixing (lubricant, plasticizers, binders) Drying Forming Sintering (the reduction of the porosity) Finishing (including slicing, lapping, polishing, electroding, encapsulation and poling) Evaluation

Outline of fabrication process for multi-layer ceramic capacitor

Capacitors could provide functions such as interdicting DC current, storing charges, filtering waves, differentiating frequencies and resonating circuit for electronic circuits. Therefore capacitor ceramics are the most often used materials among all functional ceramics, in which Multilayer Ceramic Capacitors (MLCCs) are the most often used devices among all capacitors. BaTiO3

Outline of fabrication process for PZT pieoelectric ceramics

lead zirconate titanate (PbZrTiO3, PZT),

Raw Materials and Powder preparation

Raw materials should be properly selected to meet demands from functional ceramic performance, production processing and facilities, as well as economical concern. (raw materials are the foundation for ceramics of excellent performance.) purity reaction activity

Powder preparation methods oxide synthesis (solid state reaction) co-precipitation sol-gel method hydrothermal methods spray pyrolysis

Ball mill mixing and grinding

a conventional and often used technique

agent balls (higher density induce more remarkable effect of impacting and grinding)

types of mills Normal ball mills, Stirring ball mills, Planetary ball mills, Jet mills.

Powder preparation methods

Powder preparation by oxide synthesis Synthesis is generally conducted in solid states, and thermal analysis and X ray diffraction analysis could be used to analyze composition of synthesized powders and phase evolution during synthesis.

impurity, particle size > 0.5-2.0 um low reactive activities

 Powder preparation by co-precipitation Solutions of metal ion salt are mixed according to mole ratio, and precipitators are then introduced in the solution to precipitate metal ions. Powders of specific composition could be obtained by drying and firing the sediments. Co-precipitation of BaTiO3 powder: 1. Inorganic salts of Ba and Ti as precursors:

Fabrication of BaTiO3 by co-precipitation method

 Powder preparation by co-precipitation

2. Co-precipitation in oxalate is the major technique for mass production of BaTiO3 powder. Advantages and disadvantages of co-precipitation method: Satisfy the features including high purity, high fineness, high homogeneity, and low sintering temperature. Problem of possible residue of Cl- and particle agglomeration. 3. Organic metal salts as precursors:

 Powder preparation by hydrothermal method Example of BaTiO3 powder:

Where TiO2 could be replaced by as-prepared Ti(OH)4 gel.

Advantages: fine grain size (<100nm), highly dispersion, no agglomeration, so that sintering temperature could be reduced.

 Comparison among the above preparation methods

Precipitation of oxalate and hydrothermal methods are very important wet chemical techniques for powder preparation. Hydrothermal method is promising in the mass production of ferrite powders.

 Powder preparation by sol-gel method Powder obtained with sol-gel technique is more homogeneous and its additive dispersion is also more homogeneous, thus composition could be better controlled and thin films could be easily obtained. Example of BaTiO3 powder:

Synthesis temperature (550~600 oC) Oxide processing (900~1000 oC)

 Powder preparation by spray pyrolysis

newly developed technique for fabricating multi-element powders. provide higher homogeneity than other wet chemical methods. ZrO2, PZT, superconductor, mullite.

Questions:
1 What is sintering and what is the role of sintering in fabrication process? 2 Comparison of the sintering mechanisms? 3 Hysteresis loop of ferroelectrics. 4 Which materials can be used for ferroelectric ceramics? 5 Why are ferroelectric ceramics so important? 6 The applications of ferroelectric ceramics.

Shaping and Forming of Functional Ceramics

Forming is a significant fabricating process for ceramic materials.

Conventional film processes

Current film processes Sputtering CVD

Conventional forming processes for powder compression

Conventional forming processes for powder compression

Spray granulation

Mechanisms of two types of spray drying (a) Pressure spray nozzle dryer; (b) High speed rotary spray dryer

Spherical particles from spray drying

Sintering
The densification process of ceramic powders at a high temperature is called sintering. Sintering could eliminate most pores in porous green body and compress residual pores, and bring grain growth and improve binding among grains. Energy is required during sintering to advance mass transfer. Heat energy is the major source of energy, while energy gradation from particle contact and surface tension could also provide energy.
Sintering

mechanisms

Gas phase sintering Solid phase sintering Liquid phase sintering Activated liquid phase sintering

Gas phase sintering

The driving force: the differentiation in vapor pressure. the curvature is larger for smaller particles, and the driving force for vapor transfer is correspondingly larger. could enhance material strength and reduce open pores, but it does not lead to contraction. densification can not be achieved with only gas phase transfer.

Solid phase sintering

the driving force for solid phase sintering lies at the differentiation of free energy or chemical potential between free surface of particles and its interface with neighboring particle. The diffusion could be gas phase diffusion, surface diffusion, grain boundary diffusion or internal diffusion. the factors for enhancing sintering

small particle size and narrow distribution a properly wide distribution of granularity to allow dense packing and to
reduce interstitial volume green body should have a uniform distribution of density an optimal pre-calcining temperature

Liquid phase sintering

If liquid phase is generated to wet powder particles at sintering temperature, liquid phase sintering will occur. Liquid phase surrounding particles will bring capillary pressure, and it could promote densification. Particles could be better realigned to achieve denser packing Contact pressure between particles will be improved to promote mass transfer through dissolution and precipitation. Liquid phase sintering strongly depends on temperature since slight increase of temperature might produce a large amount of liquid phase. liquid phase sometimes will promote densification, but sometimes will lead to abnormal grain growth or deformation that impedes densification.

Activated liquid phase sintering

is also called as transient liquid phase sintering. liquid phase promotes densification during sintering, but its composition would be altered or the liquid phase could totally disappear at the end of sintering. Particles could be better realigned to achieve denser packing Three methods could be used to obtain transient liquid phase sintering. proper powders or additives could be added to generate one or more liquid intermediate products after various chemical reactions, but the final products are solid state certain powders could be added to generate liquid phase and turn into solid solution finally. glass phase could be crystallized with heat treatment to eliminate liquid phase products.

Sintering Mechanism Summary

Sintering Process
Sintering is a key process during fabrication of functional ceramics.

During sintering, the shrinkage and porosity decreased, and the density increased. Sintering is actually a process of densification through mass transfer mechanism.

Sintering Process

Sintering process could be divided into four stages: 1. Linear expansion stage (25~400 oC) 2. Solid reaction stage (400~1000 oC) 3. Shrinkage stage (700~above 1000 oC) 4. Grain growth stage

Effects of Pressure and Atmosphere on Sintering

Pressure

Almost all ceramics have pores that mainly contain air (O2 and N2),
thus sintering under reduced pressure or vacuum could promote the elimination of pores. Sintering in vacuum: PLZT, ferrite, Al2O3. Atmosphere

Perovskite materials (ABO3): sintering in oxygen could promote oxygen

diffusion via oxygen vacancy and increase densification. Sintering in oxygen: PZT, PLZT and some niobate ceramics.

Pressure Sintering
Hot pressing (HP): 10000~30000 kPa Hot iso-static pressing (HIP): 150000 kPa Ordinary sintering: 100~700 kPa large pressure could facilitate elimination of pores and vacancies through diffusion along grain boundaries.

Microwave sintering
Microwave sintering could bring uniform densification and promote ionic diffusion without causing abnormal grain growth. Advantages of microwave sintering Semiconductor doping range is broader, which could facilitate the fabrication of ceramics with a low resistivity. Sintering temperature could be decreased to avoid abnormal grain growth, which could improve dielectric strength Sintering time could be shortened from 8~10 h to 0.5~1.5 h. Lead volatilization could be reduced.

4.3 Application of Ferroelectric Ceramics

Ferroelectric ceramics were born in the early 1940s with the discovery of
the phenomenon of ferroelectricity. Ferroelectricity is a property of certain materials which possess a spontaneous electric polarization that can be reversed by the application of an external electric field.

Variety of ferroelectric ceramics used in piezoelectric and electrostrictive applications, such as sonar, accelerometers, actuators, and sensors.

Abbreviations Used for Ferroelectric Ceramics

PZT: Lead zirconate titanate PLZT: Lead lanthanum zirconate titanate PMN: Lead magnesium niobate PT: Lead titanate PZN: Lead zinc niobate PSZT: Lead stannate zirconate titanate PZ: Lead zirconate BST: Barium strontium titanate SBT: Strontium bismuth titanate

Ferroelectrics: Ferroelectric domains

Ferroelectric domains are generated by coupling between dipole moments of atoms. When subjected to electric field, the domains pointing towards its direction start to grow over its neighbouring domains.

Ferroelectrics: hysteresis loop

Saturation and remanent polarization Coercive field Possibility to reverse the polarization Smart material: it keeps information (remanent poalrization)

Ferroelectrics: phase transition

Ferroelectricity is a phase transition (Curie point) Ferroelectric phase has always lower symmetry Example: BaTiO3, PbTiO3 (cubic changes into tetragonal)

Piezoelectricity in Ferroelectric Ceramics

two effects are operative in piezoelectric crystals, in general, and in
ferroelectric ceramics, in particular.

Piezoelectric effects in ferroelectric ceramics

Basis for Ferroelectricity in Ceramics

The ABO3 perovskite type materials are by far the most important category for ferroelectric ceramics. For example, BaTiO3, PZT, PLZT, PT (lead titanate), PMN, (Na,K)NbO3

Perovskite ABO3 unit cell for PZT or PLZT, illustrating 180polarization reversal for two of the six possible polarization states produced by displacement of the central cation in the tetragonal plane

Properties of Ferroelectric ceramics

Mechanical: poor toughness (under study) Electrical: semiconductors, superconductors, piezoelectrics, pyroelectrics, ferroelectrics (BaTiO3, PZT) High resistance to abrasion Excellent hot strength Chemical inertness We can tailor properties for specific applications

Why are ferroelectric ceramics so important? Ferroelectrics

High permittivities Spontaneus polarization Electric conducticity can be controlled Piezoelectric and pyroelectric effect Optical anisotropy, electrooptic an photorefractive deffect

Ceramics
Broad range of chemical composition Control of grain size, porosity Possibility of varying its shape and size. High resistance to abrasion Excellent hot strength Chemical inertness

All this properties lead to a lot of potential aplications!

Applications of Ferroelectric Ceramics

Ferroelectric ceramics are used in a very broad range of functional ceramics and form the materials base for the majority of electronic applications. These electronic applicators account for more than 60% of the total high technology ceramics market worldwide.

Applications of bulk and film ceramic electronic materials

Applications of Ferroelectric Ceramics

Why ferroelectric ceramics have been so successful over the years in finding an increasing number of applications? Their simplicity, compact size, low cost, and high reliability are very attractive features to the design engineer. Why the trend in the industry is toward film devices? (1) lower operating voltages (2) size and weight compatibility with integration trends (3) better processing compatibility with silicon technology (4) ease of fabrication (5) lower costs through integration

Capacitors
Basic principle

( 0 r A) C= t

'C' is the capacitance, 0 is the permittivity of free space, r is the relative dielectric permittivity, 't' is the distance between the electrodes, 'A' is the area of the electrodes.

To get a high volumetric efficiency (capacitance per unit volume), the dielectric material between the electrodes should have a large dielectric constant, a large area and a small thickness. BaTiO3 ceramic based disk capacitors have captured more than 50% of the ceramic capacitor market.

Multilayer Ceramics (MLC)

the volumetric efficiency can be further enhanced . consists of alternate layers of dielectric and electrode material. MLC capacitors are made by the tape casting process.

( n 0 r A) C= t

Ferroelectric Memories
FRAM (Ferroelectric Random Access Memory) is a non-volatile memory combining both ROM and RAM advantages in addition to nonvolatility features. It has higher speed in write mode, lower power consumption and higher endurance. PZT thin film

Pyroelectric Detectors
Pyroelectric detectors are current sources with an output proportional to the rate of change of its temperature. PbTiO3, (Pb,La)TiO3 and PZT

Surface Acoustic Wave Substrates

An elastic wave generated at the input interdigital transducer (IDT) travels along the surface of the piezoelectric substrate and it is detected by the output interdigital transducer. These devices are mainly used for delay lines and filters in television and microwave communication applications LiNbO3, or LiTaO3 were used as SAW substrates

Gas Ignitors
It consists of two oppositely poled ceramic cylinders attached end to end in order to double the charge available for the spark. Usually PZT ceramic disks are used for this application

A piezoelectric spark generator

Accelerometers
An accelerometer is a device which gives an electrical output proportional to the acceleration. The transducer is a piezoelectric cylinder which is poled along its axis but has its poling electrodes removed and the sensing electrodes applied to its inner and outer surfaces. PZT ceramics

A shear mode accelerometer

Piezoelectric Transformers
Low voltage to high voltage transformation can be done by using a piezoelectric plate. A length mode resonance is excited by applying a low AC voltage source between the larger face electrodes.

A piezoelectric transformer with the arrows indicating the poling directions

Impact Printer Head

the printing pin element consists of a piezoactuator, a stroke amplifier operated on the lever principle and a printing wire

Schematic of a printing pin element

Summary of Functional Ceramics

Definition of functional ceramics. Application fields of functional ceramics. General fabrication processing for functional ceramics. The synthesis methods of raw powders. Sintering mechanism and process. Ferroelectricity of ferroelectric ceramics. Applications of ferroelectric ceramics.