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Ceramic Materials Science and Engineering [Chapters 3-8]

Ceramic Materials Science and Engineering [Chapters 3-8]

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Published by Emmanuel Alemaka
Resource for students and researchers in the field of Ceramic materials Science and Engineering
Resource for students and researchers in the field of Ceramic materials Science and Engineering

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Published by: Emmanuel Alemaka on Mar 01, 2013
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3
Background You Need to Know
CHAPTER PREVIEW
In this chapter we will summarize three concepts fundamental to all materials science: atomicstructure, thermodynamics, and kinetics. You should be familiar with these topics from intro-ductory chemistry, physics, and materials science classes so we give only a brief review here.Books are written on each of these topics. In ceramics, you can often avoid such books, butthe details become more critical as you delve deeper into the subject.The properties of a material are determined, to a large extent, by how the constituent atomsbond together. The nature of this bonding is determined by the electron configuration of theatoms. The electron configuration of an atom alsodetermines the properties of the atom andmaterials that contain it. For example, the ceramic magnetite (Fe
3
O
4
) is magnetic due to thepresence of unpaired electrons in the 3d level of Fe; you need to know what the 3, the d, and“unpaired” denote. To understand why Mn ions can exist with many different charge states butwe invariably find only Al ions with a 3
+
charge, you must know the electron configuration of the respective atoms.Knowledge of boththermodynamics and kinetics is necessary to understand how ceramicmaterials behave and what happens when they are processed. Thermodynamics tells us whatis possible while kinetics tells us how long we have to wait for the inevitable. Thus, thermo-dynamics tells us if a specific chemical or physical reaction can occur. In ceramics thesechanges are often brought about because samples are routinely heated and cooled. Ceramicsmay be processed at temperatures above 1800°C and then cooled to 25°C. Some processes mayoccur at 1800°C, but may continue or change as we cool the sample. Conversely, some ceramicschange their properties at quite low temperatures: BaTiO
3
changes from the paraelectric cubicphase to the ferroelectric tetragonal phase at 120°C. Kinetics tells us how rapidly these reac-tions will proceed. Diamond is thermodynamically unstable atroom temperature and atmo-spheric pressure, but the phase change occurs much too slowly to worry jewelers.
3.1 THE ATOM
The bases for understanding the structure of the atom arequantum theoryand wave mechanics, which were devel-oped in the early 1900s. The important conclusions of these studies, particularly as they relate to materials, areas follows:
᭿
Electrons in atoms can move only in certain stableorbits, that is, only certain energy values are possible.We expand on this fact when we describe energy bands,which are usedto explain electron conductivity.
᭿
Transition between orbits involves the emission orabsorption of energy. These transitions can be thesource of color and we use them to analyze chemistryby spectroscopy.
᭿
No two electrons in the same atom can have the samefour quantum numbers. This requirement led to theintroduction of the spin quantum number. Atomscontaining electrons with unpaired spins will havemagnetic properties.
᭿
It is impossible to know simultaneously the positionand momentum of an electron with certainty. We usethis property intunnel diodes.
᭿
Electrons have wavelike properties. This means thatthey can be diffracted. Electron diffraction, like X-raydiffraction, gives us the crystal structure.In the following sections we summarize how theseconclusions lead to our present view of the structure of theatom and, in particular, the nature and arrangement of theelectrons in the atom. We are not attempting to summarizemodern physics, but only the concepts that we use in thistext. You need to understand the main aspects of thenature of the chemical bond in ceramic materials: what isan ionic bond, what is a covalent bond, and why do most
3.1
The Atom
..................................................................................................................................................................
35
 
36
................................................................................................................................
Background You Need to Know
bonds show a mixture of the two. In spectroscopy andmicroscopy we willprobe the electronic structure todetermine the local chemistry of the ceramic.
3.2 ENERGYLEVELS
The quantization of energyis a key aspect in under-standing atomic structure.Bohr’s model involveselectrons moving only incertain stable orbits. Theangular momentum of theorbiting electrons is quan-tized so thatonly specificorbits are allowed and onlycertain energy values arepossible.These orbits are known as stationary states, and theone with the lowest energy is called the ground state.The quantization of angular momentum is
nh
 /2
π
,where
n
is the principal quantum number. As the principalquantum number increases1. The radius,
, of the electron orbit increases, that is,the electron is further from the nucleus.2. The energy,
 E 
, of that electron is also increased.The first five Bohr orbits, thatis,
n
=
1 through 5, are alsoreferred to as shells; we define a shell as a group of statesthat have the same
n
. A letter is used to denote eachshell:Shell K L M N O . . .
n
1 2 3 4 5 . . .Charles Barkla, anearly X-ray spectroscopist, intro-duced this terminology for electron shells in 1911. We stilluse it today to designate characteristic X-rays in both X-ray diffraction and in chemical analysis using electronmicroscopy. Barkla named the two types of characteristicX-ray emissions he observed as the K-series and L-series.He later predicted that an M-series and a J-series mightexist. An M-serieswas subsequently discovered, but noJ-series. The K shell is hence the first shell.The other aspect of Bohr’s theory is that while anelectron is in a stationary state, the atom does not radiate.Electrons can be excited into higher energy orbits if theatom is stimulated(thermally, electrically, or by theabsorption of light). These orbits are the excited states andare more distant fromthe nucleus. The residence time of an electron inthe excited state may be very short (
1 ns)before it spontaneously descends to a lower energy stateand eventually the ground state. Duringeach transition theexcess energy is emitted in the form of a photon. Anytransition between orbits involves either the emission orabsorption of energy. Understanding this concept is neces-sary in, for example, appreciating how a laser works. If the energy emitted is in thevisible part of the electro-magnetic spectrum (Table3.1), then we will be ableto observe the emission.The emission from theruby laser (ruby is aceramic) is at694 nm (inthe red). A frequencydoubled Nd-doped yttriumaluminum garnet (YAG)laser (YAG is anotherceramic) operates in thegreen part of the spectrumat 530 nm.Bohr’s model was quitepopular at the time because an electron circling the nucleusis conceptually similar to the earth circling the sun. Theidea that orbiting electrons did not radiate was less easyto accept, Bohr simply insisted they did not and that wasthat! Most importantly, the model explained a number of physical phenomena. Bohr’s assumption that electrons areparticles with well-defined orbits was not consistent withthe concept of “simultaneous interdeterminacy” of posi-tion and momentum as propounded inthe Heisenberguncertainty principle.What you should remember from this discussion is theorigin of KLMNO and the terminology. We will use thisagain in Chapter 10.Electron energy levels and the Bohr model are impor-tant for understanding the following:
᭿
Atomic radii—as we fill shells going down a particularperiod the atoms get bigger (
increases).
᭿
Ionization energy—as we fill shells going down a par-ticular period it becomes progressively easier to removethe outer electron(s) (
 E 
increases with respect to theground state).
᭿
Covalent bond formation—ionization energies must behigh (
 E 
large).
THE BOHR ATOM
Quantization of angular momentum
mvrnh
e
=
2
π
Box 3.1Radius of possibleelectron orbits
nhme
=επ
0222e
Box 3.2Energy of the electron
 E menh
=
e4022
8
ε
Box 3.3
TABLE 3.1 The Visible Part of the ElectromagneticSpectrum
Energy, E (J) Wavelength,
λ 
(nm) Color 
2.84
×
10
19
700 Red3.20
×
10
19
620 Orange3.42
×
10
19
580 Yellow3.75
×
10
19
530 Green4.23
×
10
19
470 Blue4.73
×
10
19
420 Violet
 
᭿
Magnetic ceramics—we needto have an Mshell.
᭿
X-ray spectroscopy—we use the Barkla nota-tion, the energy of thecharacteristic X-raysdepends on the electronenergy levels involved.
3.3 ELECTRON WAVES
Demonstrating electron diffraction (a property associatedwith waves) was proof of their wave nature. In 1927 C.J.Davisson and L. Germer in the United States and, inde-pendently, G.P. Thomson and A. Reid in the UnitedKingdom showed that electrons could be diffracted inmuch the same way as X-rays. We carebecause wecannotexplain the properties of electrons and X-rays without thisunderstanding.The wavelike natureof electrons enables electron dif-fraction studies of materials. Most electron diffractionpatterns are obtained in a transmission electron micro-scope, which allows us to obtain structural informationfrom very small regions. This is of particular importancein many new ceramics where we are often dealing withthin interface layers (suchas at grain boundaries)and very small grains(nanopowders).One of the most impor-tant consequences of thedual nature of electrons isHeisenberg’s uncertaintyprinciple, which states thatit is impossible to knowsimultaneously both themomentum and position of a particle withcertainty.If we are describing themotion of an electron of known energy or momen-tum, we can speak only in terms of the probability of finding that electron at a particular position. This leads tothe electron-density or electron-cloud representation of electron orbitals.The Schrödinger equation, as central to quantummechanics as Newtons equations are to classical mechan-ics, relates the energy of an electronto its wave properties.The equation describes the likelihood that a single elec-tron will be found in a specific region of space. The wavefunction,
Ψ
, depends on
 E 
and
, the total energy and thepotential energy of the electron, respectively.The importance ofthe wave function has beenexpressed by Atkins and de Paula (2002): “A wave func-tion contains all there is to know about the outcome of experiments that can bedone on a system.” Thus,the Schrödinger waveequation includes informa-tion about the chemicalbehavior of all atoms andcompounds and the answerto whether any proposedchemical reaction will takeplace or not.Mathematically,
Ψ
describes the motion of an electronin an orbital. The modulus ofthe wave function squared,|
Ψ
(
)|
2
, is a direct measure of the probability of findingthe electron ata particular location. The Schrödinger waveequation can be solved exactly for hydrogen. To apply ityou must first transform it into polar coordinates (
,
θ
,
φ
)and then solve using the method of separation of variables(described in, e.g., Kreyszig, 1999).The solution of these equations leads to three quantumnumbers:
n
,
l
, and
m
l
.The Schrödinger wave equation can be set for atomswith more than one electron, but it cannot be solvedexactly in these cases. The second and subsequent elec-trons introduce the complicating feature of electron–electron repulsion. Nevertheless, the basic characteristicsof the orbitals do not change and the results obtained forhydrogen are applied to many-electron atoms.Methods are nowbecoming available thatallow us to calculate thestructure of some “bulk”materials. Generally, thisis still done only rarelyby startingwith theSchrödinger equation. Thecalculations are just toodifficult or too time-consuming. Actually, it isworse than it looks becausewe also have to deal withcharge.
3.4 QUANTUM NUMBERS
Four quantum numbers are necessary to specify the stateof any electron:
᭿
n
principal quantum number
᭿
l
orbital shape, or orbital angular momentum, quantumnumber
᭿
m
l
orbital orientation, or orbital magnetic, quantumnumber
᭿
m
s
spin, or spin magnetic, quantum numberA shell is a group of states that has the same
n
andcorresponds to Bohr’s
n
. A subshell is a smaller group of 
THE DE BROGLIE HYPOTHESIS
All matter possesses wave properties. Every movingparticle can be associated with a wavelength,
λ 
, givenby
λ = =
hmvh p
SCHRÖDINGER WAVE EQUATION
The time-independent form is
2
Ψ +
8
π
2
m
 / 
h
2
(
 E 
)
Ψ =
0 Box 3.4
2
is the operator
 
2
 / 
 x 
2
+ ∂
2
 / 
 y
2
+ ∂
2
 / 
 z
2
Box 3.5In polar coordinates
Ψ
has the form
Ψ
(
,
θ
,
φ
)
=
 R
(
)
Θ
(
θ
)
Φ
(
φ
) Box 3.6
 R
(
),
Θ
(
θ
),
Φ
(
φ
) are each only functions of 
,
θ
, and
φ
.
3.4
Quantum Numbers
.................................................................................................................................................
37

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