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Chapter 1 Introduction

Chapter 1 Introduction

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Published by Udo Sam

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Categories:Types, Research, Science
Published by: Udo Sam on Oct 28, 2010
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11/23/2012

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1
INTRODUCTION
The word ceramic is derived from
keramos
, the Greek work for potter’s clay orware made from clay and fired, and can simply be interpreted as ‘pottery’.Pottery is based on clay and other siliceous minerals that can be convenientlyfired in the 900–1200
8
C temperature range. The clays have the property that onmixing with water they form a mouldable paste, and articles made from thispaste retain their shape while wet, on drying and on firing. Pottery owes itsusefulness to its shapability by numerous methods and its chemical stability afterfiring. It can be used to store water and food, and closely related materials formthe walls of ovens and vessels for holding molten metals. It survives almostindefinitely with normal usage although its brittleness renders it susceptible tomechanical and thermal shock.The evolution from pottery to advanced ceramics has broadened the meaningof the word ‘ceramics’ so that it now describes ‘...solid articles which have astheir essential component, and are composed in large part of, inorganic non-metallic materials[1]. Here the term will be restricted to polycrystalline,inorganic, non-metallic materials that acquire their mechanical strength througha firing or sintering process. However, because glass and single crystals arecomponents of many polycrystalline and multiphase ceramics, and because singlecrystals of some compositions are grown for special applications, discussion of them is included as appropriate.Thefirstuseofceramicsintheelectricalindustrytookadvantageoftheirstabilitywhen exposed to extremes of weather and to their high electrical resistivity, afeature of many siliceous materials. The methods developed over several millenniafor domestic potterywere refinedfor theproductionofthe insulatingbodiesneededto carry and isolate electrical conductors in applications ranging from power linesto the cores bearing wire-wound resistors and electrical fire elements.Whilst the obvious characteristic of ceramics in electrical use in the first half of the twentieth century was that of chemical stability and high resistivity, it was
Electroceramics: Materials, Properties, Applications
. 2nd Edition. Edited by A. J. Moulson and J. M. Herbert.
&
2003 John Wiley & Sons, Ltd: ISBN 0 471 49747 9 (hardback) 0 471 49748 7 (paperback)
 
evident that the possible range of properties was extremely wide. For example,the ceramic form of the mineral magnetite, known to the early navigators as‘lodestone’, was recognized as having a useful electrical conductivity in additionto its magnetic properties. This, combined with its chemical inertness, made it of use as an anode in the extraction of halogens from nitrate minerals. Also,zirconia, combined with small amounts of lanthanide oxides (the so called ‘rareearths’) could be raised to high temperatures by the passage of a current and soformed, as the Nernst filament, an effective source of white light. It wasrecognized that some ceramics, the ‘fast-ion conductors’, conduct electricity well,and predominantly by the transport of ions, and over the last two decadesinterest in them has intensified because of their crucial roles in fuel cell, batteryand sensor technologies.The development from 1910 onwards of electronics accompanying thewidespread use of radio receivers and of telephone cables carrying a multiplicityof speech channels led to research into ferrites in the period 1930–1950. Nickel– zincandmanganese–zincferrites,closelyalliedinstructuretomagnetite, wereusedas choke and transformer core materials for applications at frequencies up to andbeyond 1MHz because of their high resistivity and consequently low susceptibilityto eddy currents. Barium ferrite provided permanent magnets at low cost and inshapes not then achievable with ferromagnetic metals. From 1940 onwardsmagnetic ceramic powders formed the basis of recording tapes and then, as toroidsof diameter down to 0.5mm, were for some years the elements upon which themainframe memories of computers were based. Ferrites, and similar ceramics withgarnet-type structures, remain valuable components in microwave technology.From the 1920s onwards conductive ceramics found use, for instance, assilicon carbide rods for heating furnaces up to 1500
8
C in air. Ceramics withhigher resistivities also had high negative temperature coefficients of resistivity,contrasting with the very much lower and positive temperature coefficientscharacteristic of metals. They were therefore developed as temperature indicatorsand for a wide range of associated applications. Also, it was noticed at a veryearly stage that the resistivity of porous specimens of certain compositions wasstrongly affected by the local atmosphere, particularly by its moisture contentand oxidation potential. Latterly this sensitivity has been controlled and put touse in detectors for toxic or flammable components.It was also found that the electrical resistivity of ceramics based on siliconcarbide, and, more recently, zinc oxide could be made sensitive to the appliedfield strength. This has allowed the development of components that absorbtransient surges in power lines and suppress sparking between relay contacts. Thenon-linearity in resistivity is now known to arise because of potential barriersbetween the crystals in the ceramic.Ceramics as dielectrics for capacitors have the disadvantage that they are noteasily prepared as self-supporting thin plates and, if this is achieved, areextremely fragile. However, mica (a single-crystal mineral silicate) has been
2
INTRODUCTION
 
widely used in capacitors and gives very stable units. Thin-walled (0.1–0.5mm)steatite tubes have been extruded for use in low-capacitance units. The lowrelative permittivity of steatite (
e
r
6) has limited its use but the introduction of titania (
e
r
100) in the 1930s led to the development of capacitors having valuesin the 1000pF range in convenient sizes but with a high negative temperaturecoefficient. Relative permittivities near to 30 with low temperature coefficientshave since been obtained from titanate and zirconate compositions.The situation was altered in the late 1940s with the emergence of high-permittivity dielectrics based on barium titanate (
e
r
2000–10000). For a widerange of applications small plates or tubes with thicknesses of 0.2–1mm gaveuseful combinations of capacitance and size. The development of transistors andintegrated circuits led to a demand for higher capacitance and small size whichwas met by monolithic multilayer structures. In these, thin films of organicpolymer filled with ceramic powder are formed. Patterns of metallic inks aredeposited as required for electrodes and pieces of film are stacked and pressedtogether to form closely adhering blocks. After burning out the organic matterand sintering, robust multilayer units with dielectrics of thicknesses down to
5
5
m
m have been obtained. Such units fulfil the bypass, coupling and decouplingfunctions between semiconductor integrated circuits in thick-film semiconductorcircuitry. The monolithic multilayer structure can be applied to any ceramicdielectric, and multilayer structures for a variety of applications are the subject of continuous development effort. In particular ‘low temperature co-fired ceramic’(LTCC) technology is intensively pursued for electronics packaging, especiallyfor mainframe computer and telecommunications systems.The basis for the high permittivity of barium titanate lies in its ferroelectriccharacter which is shared by many titanates, niobates and tantalates of similarcrystalstructure.Aferroelectricpossessesauniquepolaraxisthatcanbeswitchedindirection by an external field. The extent of alignment of the polar axes of thecrystallites in a ceramic islimited by the randomness in orientation of the crystallitesthemselves but is sufficient to convert a polycrystalline isotropic body into a polarbody. This polarity results in piezoelectric, pyroelectric and electro-optic behaviourthat can be utilized in sonar, ultrasonic cleaners, infrared detectors and lightprocessors.Ceramicshavetheadvantage,overthesinglecrystalsthatprecededthemin such applications, of greater ease of manufacture. Ferroelectrics in thin film formare now becoming established as one type of digital memory element.Barium titanate can be made conductive by suitable substitutions and/or bysintering in reducing atmospheres, which has led to two developments: firstly,high-capacitance units made by reoxidizing the surface layers of conductiveplates and using the thin insulating layers so formed; secondly, high positivetemperature coefficient (PTC) resistors since the resistivity of suitably doped andfired bodies increases by several orders of magnitude over a narrow temperaturerange close to the transition from the ferroelectric to the paraelectric states. Usesfor PTC resistors include thermostatic heaters, current controllers, degaussing
INTRODUCTION
3

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