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MME 467: Ceramics for Advanced Applications

Lecture 13
Dielectric Properties of
Ceramic Materials 1
1. Barsoum, Fundamental Ceramics, McGraw-Hill, 2000, pp.513–543
2. Richerson, Modern Ceramic Engineering, Dekker, 1992, pp.251–256.
3. Callister, Materials Science and Engineering- An Introduction.
Topics to discuss .......

 Basic theory of dielectrics


 Polarization mechanisms
 Dielectric constant
Introduction

 Materials that are good insulator but are not inert to an applied
electric field are called dielectric materials.

 The applied electric field causes a slight shift in the balance of


electric charge within the material to produce an electric dipole,
thus the term DIELECTRIC applied.

 Dielectric properties vary widely between the dielectric solids,


and are function of
 Temperature  Crystal structure
 Humidity  Frequency of applied field
Basic Theory of Dielectrics
 When a capacitor made of two metal plates of area A separated by
distance l in vacuum is attached to a simple electric circuit, a
transient surge of electricity will result which rapidly decays to zero.

 The total charge that has passed through the circuit and is now
stored on the capacitor plates is given by the equation

Q = ò I dt
 For different applied voltage V, the stored charge Q, which is
proportional to the applied voltage, can be written as

Q =CV
here the constant C is known as the capacitance and defined as

A
C 
l

 For an applied medium of vacuum between the plates

0 A 0 = permittivity of free space = 8.85x10–12 C2/J-m


Cvac  Cvac = Capacitance (farad, F) 1 F = 1 C/V = 1 C2/J
l
 When a dielectric materials (solid/liquid/gas) is introduced between
the plates, the charged stored between the plates is increased.

 In presence of a solid between the plates,

A
C   = permittivity of the material between the plates
l
 The relation between the
applied voltage V and the
stored charge Q is still
linear, but with a larger
slope than that for vacuum.

 The relative dielectric


constant of a material

e
k¢ = It is a measure of how much charge a solid
can store relative to vacuum
e0
 Since  is always greater than 0, k’min = 1 when  = 0.

k  0 A
A
C   k Cvac
l l
To summarize,

 When a voltage is applied to a parallel-plate capacitor in


vacuum, the capacitor will store charge

 In presence of dielectric material, additional “something”


happens within the dielectric, which allows the capacitor to
store more charge.
Polarization Charge

 The surface charge in vacuum

éQ ù CV  0V
s vac = ê ú   0E
ë A ûvac A l
E = applied electric field

 In presence of dielectric, the surface charge

Q  k  0V
 die      vac   pol
 A  die l
pol = excess charge per unit surface area
present on the dielectric surface which occur
due to polarisation of dielectric
 The polarization of the
dielectric, the surface charge D0 = 0 E
P = s pol
 According to
electromagnetic theory, the
dielectric displacement D E=V/d
is defined as the surface
charge on the metal plate

D = e0 E + P D0 = 0 E + P
D = displacement (C/m2)
E = applied electric field, (V/m)
P = polarization (C/m2) of material

 In vacuum, P = 0, and

D0 = e0 E
Thus, to summarize:

The total charge stored on the plates of parallel-plate capacitor D


is the sum of of the charge that would have been present in
vacuum 0E and an extra charge resulted from the polarization of
the dielectric material P.
s pol
 Dielectric susceptibility, c die =
s vac

Polarization in terms of dielectric susceptibility

D = e0 E + P
D = e0 E + P k ¢e0 E = s vac + s pol
k ¢e0 E s vac + s pol
P = k¢e0 E - e0 E = k¢ -1 e0 E ( ) e0 E
=
s vac
s pol
P = c die e0 E k ¢ =1+
s vac
s pol
k ¢ -1=
s vac
Microscopic Approach

 Something happens in the solid that


allows the parallel plate capacitors to
store more charge.

That something is called polarization.

P =q d

Thus understanding polarization is the key to


understanding dielectric properties.
 A dipole moment, m, is defined as m = qd
q = total charge, (±ze)
d = distance separating the centres of –ve and +ve charges

m is a vector quantity with its direction, when positive, is directed


from the negative to positive charge.

 If the total number dipole formed per unit volume is N, then the
total polarization

P = N m = Nqd
Fundamental equation to understand

P Nqd dielectric respond of a solid.


k¢ -1 = = The greater the separation of charges
of a dipole d, the greater the relative
e0 E e0 E dielectric constant k’.
In a microscopic sense,

 The polarizability of an atom or ion is defined as

P
a = C m2 V–1 or F m2
Eloc = local electric field
to which the atom/ion
N Eloc is subjected

 For dilute gas as dielectric medium, the molecules are far apart,
for which Eloc = E, and

Na
k ¢ -1 =
e0
 In solid dielectrics, polarization of surrounding media will affect
the magnitude of local electric field.

 For example, in case of cubic symmetry,

E
(
Eloc = k¢ + 2
3
)
 Then, we have

k   1 N

k   2 3 0
Clausius–Mossotti Relation
which provide the link between the macroscopic
property k’ and the microscopic property .
(Only applies to linear dielectrics)
Polarization Mechanisms

 Mechanisms of polarization, (i.e., the formation of electric dipole


due to application of electric field):

 Electronic polarization
 Dipolar (or, orientation) polarization
 Ionic (atomic) polarization
 Space charge polarization
Electronic Polarization
 Occurs in all dielectric materials.
 Electrons surrounding each molecule are shifted/displaced very
slightly towards the +ve electrode, and nucleus to –ve electrode.
 Very small polarization resulted, compared to those obtained by other
mechanisms.
 Polarization disappears when electric field removed.

a e » 4p e 0 r0
3
Zi e
E= 0
+ S0

Electronic polarizability is d E
+ +
proportional to the volume
Z i me
of an atom or ion
(a) (b) (c)
Orientation or Dipolar Polarization

 Example: Water molecule


 directional covalent bonds between H and O
 two H on one side of O
 H side  net +ve charge Hd+
O side  net –ve charge Od-
Hd+
Water molecule

 When E applied, molecules of H2O align with


+ve sides facing the –ve electrode, and vice versa.

 Much higher polarization resulted due to a larger


displacement within relatively large molecules

 Other examples: HCl, CH3Br, HF E


Atomic/Ionic Displacement Polarization

Displacement of ions or atoms within crystal when electric field is applied

 Wider ranges of polarization possible depending on:


 crystal structure
 presence of solid solution

 Materials exhibiting pyro-, piezo-, and ferroelectric properties


can undergo atomic/ionic polarization
Interfacial/ Space Charge Polarization

Not well understood.


Dielectric Constant

 The degree of polarizability or charge storage capacity of a materials


is identified by the term relative dielectric constant k’.
 The dielectric response of solids is a complex function of frequency of
vibration, temperature, and type of solid.
 Under DC conditions, all mechanisms are operative, and the dielectric
constant is at its maximum and is given by the sum of all the
mechanisms.
Frequency Effect
 The polarization requires time to respond to an applied field.
 As the frequency of applied field is increased, various mechanisms will
be unable to follow the electric field and will drop off.

 Electronic polarization
occurs very rapidly. So it
stays even at high
frequencies.
 At very high frequencies,
none of the mechanisms
is capable of following
the field, and the relative
dielectric constant
approaches 1.0.
Temperature Effect

 Temperature only influence the polarization mechanisms that


depend on long-range ionic displacement, such as dipolar
polarization.

 Molecular orientation or dipolar polarization is opposed by


thermal agitation, so the dielectric constant goes down with
increasing temperature.

 Atomic/ionic polarization tends to increase with temperature due


to an increase in charge carriers and ion mobility.

 Electronic polarization is relatively insensitive to temperature.


Materials Effect

 Dielectric constant varies in wider range for different materials.

Low dielectric constant (k’ is low)


 Used for electric insulator applications
 Example: Al2O3 (k’=8.6–10.6), BeO (k’=6.5),

High dielectric constant (k’ is high)


 Used as capacitor
 Example: rutile (k’=80), BaTiO3 (k’=1800), SrTiO3 (k’=100,000)
Effect of frequency and temperature on
dielectric constant of soda-lime glass
Effect of temperature on relative
dielectric constant at 4 GHz