PIEZOELECTRIC MATERIALS

References:
• Edited by L. Nowotny, “Electronic Ceramic Materials”, Trans Tech Publications.
• J. Unsworth, “Piezoelectricity and Piezoelectric Materials”, Key Engineering
Materials, Vols. 66&67 (1992), pp.273-310.

MECHANISMS FOR PIEZOELECTRICITY

• The crystals which were piezoelectric lack internal spatial symmetry in their unit cells.
• In some materials, the centres of the positive and negative ionic charges are
displaced from the unit cell planes either with no pressure applied or when
pressure is applied giving rise to dipole moments. The dipole moment for each of
the ionic charges can be considered to be the charge times the distance the centre
of the ion is displaced from the plane.
• Some crystals possess these dipole moments without pressure being applied (eg. lead
titanate), whilst others only develop the dipole moments when forces are applied (eg.
quartz).
• To calculate the dipole moment the sign of the charge and the displacement has to be
considered for each ionic charge. For example if we have a negative ion displaced
downwards in a Cartesian geometry system the dipole moment would be positive. If

1
 another ionic charge is positive and it is displaced upwards the dipole moment would
be also positive.
• The algebraic sum of the total dipole moments per unit volume of the unit cell is
equal to the polarization.
• From electromagnetic theory it can be shown that this polarization creates an electric
field with both internal (net internal charge zero for perfectly aligned polarization) and
surface contributions. The surface contribution manifests itself as surface charge which
is exactly equal to the internal polarization. An alternate yet equivalent view is that the
charge generated at the top of each cell cancels with the opposite charge on the bottom
of the next cell above it at the interface. Obviously the charge on the bottom of an
internal unit cell also cancels exactly the charge on the top of the cell immediately
beneath it. If we assume that we have a perfectly polarized single crystal this
cancellation process occurs throughout the internal region of the crystal leaving only
surface charges so that the charge per unit area is exactly equal to the polarization.
• The establishment of this surface charge can be extremely fast since the charge takes
place at the velocity of sound in the crystal.
• Many of the applications of piezoelectric materials involve use as dynamic transmitters
or sensors eg. Ultrasonic transducers.

2
QUARTZ
Quartz occurs naturally and can be man made. Suppose we consider a unit cell of quartz
between parallel plates. In the undeformed state the centre of gravity of the positive
silicon ions and the negative oxygen ions coincide and so there is no resultant dipole
moment and the effective charge distribution throughout the crystal and on the
surface is zero.

Let a slab or disc of quartz be cut as shown in figure 1. If the unit cell is deformed by
compression or extension because of the anisotropic elasticity, the centres of gravity no
longer coincide and dipole moments are created due to the change of the ionic charge
distribution. This results in charges appearing at the parallel planes.

Figure 1.
Quartz unit cell.
(a) cell unstressed;
(b) cell in
compression; (c)
cell in extension

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We can cut the crystal in such a way that the applied strain is parallel to the resulting
electric field E=V/t, where t is the thickness of the crystal and V is the resulting
potential difference due to the charge q developed, such that q = CV where C is the
capacitance.

When mechanical vibrations such as acoustic or ultrasonic waves are applied to the
cut crystal, the sinusoidally varying strains set up an alternating electric field. The
cut crystal can hence be used as a detector. When an electric field is applied the ionic
charges will be acted upon by forces acting in the opposite direction causing the unit cell
to deform. We can cut the quartz in such a way that the strain is parallel to the
applied electric field and apply an alternating electric field to the cut crystal which
will expand and contract at the same frequency as the field. The cut quartz crystals
can be used as generators of acoustic or ultrasonic waves.

AXES OF SYMMETRY

Quartz, tartic acid, tourmaline, Rochelle salt, ammonium dihydrogen phosphate (ADP),
lithium sulphate and potassium dihydrogen phosphate (KDP) are some of the
piezoelectric single crystals which have to be cut in a special way in order to
maximise the piezoelectric properties.

4
These crystals lack a centre of symmetry and
are characterised by three axes x, y, and z, as
seen in Figure 2. It is on the crystal surfaces
parallel to the x and y planes that the charges
are established when the crystal is subjected to
forces. The z axis is the optical axis along which
the crystal is birefringent and can be located by
finding the direction such that no variation in
polarized transmitted light occurs as the crystal is
rotated about the axis.

Figure 2. X-cut rectangular and circular plates

from a quartz crystal

ELECTROSTRICTION

In electrostrictive materials, dimensional changes occur in all directions as the result of

an applied electric field E. The strain is small and proportional to E2. In contrast to
piezoelectricity the converse effect does not occur, that is the application of a stress
does not produce an electric field. For comparison a field of 104Vm-l produces 23 nm
per metre in x cut quartz whereas electrostrictive glass produces only 1 nm per metre.

5
FERROELECTRICITY

Ferroelectric materials exhibit self polarization, that is adjacent dipoles align

themselves by mutual interaction and these parallel dipoles arrange themselves into
domains. All have high dielectric constants and high refractive indices. The polarization
of these materials is not proportional to the applied electric field as for paraelectric
materials (i.e. polarization is proportional to applied electric field) but instead
exhibits hysteresis. There is a coercive field required to reduce the polarization to
zero and a remanent polarization which remains when the field is reduced to zero.
These materials are called ferroelectric by analogy with ferromagnetic materials which
also have domains and exhibit hysteresis.

There are many piezoelectric materials which are not ferroelectric but all ferroelectric
materials are piezoelectric. In some ferroelectrics the spontaneous polarization creates
part of the piezoelectric effect.

If a ferroelectric material is heated up above a critical temperature Tc called the

Curie point, it changes its crystal structure and becomes paraelectric. This behaviour
is described by the Curie-Weiss equation

Ω = K-1 = Cc /(T – Tc) (2)

6
where the Curie constant Cc is about 105oC, Ω is the electric susceptibility and K is
the dielectric constant (relative permittivity), T is the operating temperature and Tc
is the Curie temperature. The Curie temperature for barium titanate is 120oC at which
temperature it goes through a first order transition and changes from ferroelectric to
paraelectric and the domains disappear. This is associated with a crystal structure change
from tetragonal to cubic.

POLING

To be able to use the

piezoelectric effect associated
with ferroelectric materials
(egs: barium titanate BT, lead
titanate PT, lead zirconate titanate
PZT and polyvinylidene fluoride
PVDF) they have to be put
through a process called poling
which aligns the domains and
hence the dipoles so as to
achieve saturation polarization.
Figure 3. Poling methods for piezoceramic

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One method is to place the sample of material in an heated oil bath (eg 90oC) which is
well below the curie temperature and then applying an electric field. The oil bath is used
to obtain even heating of the ceramic discs or polymer film and to prevent surface electric
discharges and surface tracking which would occur in air.

The increased temperature agitates the ions and hence the dipoles and allows the domains
to be rotated more easily in the electric field, and thus the saturation polarization
associated with the hysteresis loop is more easily achieved. The oil bath is allowed to
cool down to room temperature whilst the electric field is maintained. once it has cooled
down the electric field is removed and the domains and hence the dipole moments are
aligned corresponding to saturation polarization.

Poling Effect on Application

Hard PZT (Type I) used for transmitters can withstand higher poling and driving fields
without electric breakdown whilst soft PZT (Type II) which has higher sensitivity and
dielectric constants cannot withstand high driving fields and so is used mainly for
receivers.

PZT can be poled up to 165oC (Type I) or 135oC (Type II). Aging follows the poling
process which set up internal stresses which later relax - it is a time dependent domain re-

8
orientation process which reduces the dielectric and piezoelectric properties. It is
therefore good practice to leave the ceramic for a period of several days before
characterisation and use. Depoling can also occur reducing the properties caused by heat
or by using large driving fields.

CERAMICS vs QUARTZ CRYSTAL

A big advantage of these polycrystalline ferroelectric materials compared with the
single crystal materials is that they do not need to be sliced in a particular direction in
order to maximise the piezoelectric properties. Also one does not need optical facilities
or X-ray diffraction equipment to locate any special planes or directions.

Ceramic Processing
PT and PZT are man-made materials and are manufactured by conventional ceramic
processing methods. Oxides or carbonates of the elements as powders are mixed dry or as
a wet slurry. Often a binding agent such as poly(vinyl alcohol) is added as an aid to
processing. The mixture is then subjected to high pressure in a mould to achieve the
desired shape, removed and subjected to a programmed rise of temperature as it passes
through a high temperature furnace. The moisture is driven off first, then the polymer is
burned off and then the carbonates break down to oxides which then chemically react.
This is referred to as firing and sintering the ceramic.

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CALCULATION OF THE POLARIZATION OF BARIUM TITANATE
The structure of tetragonal barium titanate is presented in Figure 4.

Figure 4. Tetragonal BaTi03. Below 120°C the ions shift with

respect to the corner Ba2+ ions. Since the Ti4+ and the O2- ions
shift in opposite directions, the centres of positive and negative
charges are not identical

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The values of the charges and the displacements of the centres for each of the ions from
the planes for each of the ions barium, titanium and oxygen are given in Table l. Also the
calculated values of the dipole moments for the ions is presented allowing for the sign
and magnitude of charge and the displacement of each of the ions.

Table 1: Calculation of Barium Titanate Polarisation of unit cell.

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The algebraic sum of the dipole moments per unit volume is the total polarization which
equals the magnitude of the charge per unit area of the crystal surface at right angles to
the poled direction. The value estimated of 27 µC/cm2 compares well with the value of 26
µC/cm2 for the saturation polarization obtained experimentally.

PIEZOELECTRIC RELATIONS
Consider a piezoelectric solid cylinder of cross sectional area A and thickness t with
electrodes on opposite parallel surfaces. Suppose a voltage difference V is applied so
electric field is E = V/t and a constant tensile stress σ is also applied to the surface. If
γ is the resulting mechanical strain and P the polarization and assuming that we are
keeping within the elastic limit,

where d' is the effective piezoelectric constant, s is the compliance (which is the
reciprocal of the Young's Modulus) and d is the piezoelectric strain constant which is the
charge per unit area (charge density) divided by the applied stress and Ω is the electric
susceptibility.

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Table 2.
Definition of
piezoelectric
constants

13
If we short circuit the surface electrodes with one another, so that E = 0, we obtain,

If stress is removed, so that σ = 0 and

From the conservation of energy d = d' ( or you can treat this as one of the
properties of piezo-materials) and so

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If the piezoelectric effect is zero, so that d = 0

which is what is expected for a paraelectric elastic solid, that is that strain is proportional
to stress and polarization is proportional to the electric field.

From (6) and (11) we have

when stress is of such a value that strain is zero, that is the crystal is clamped, from
(14) we have

15
where e is called the piezoelectric stress constant and can be expressed in units of
Coulombs per metre2 (C/m2) or Newtons per volt per metre (N/Vm).

Two other coefficients that are frequently used to describe the behaviour of piezoelectric
materials are the piezoelectric coefficients g and h. Where g is the electric field produced
per unit applied pressure (V-m/N) and h is the electric field produced per unit applied
strain (N/C) with,

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In order to clarify the convention of axes and constants of piezo ceramics, please refer
to the following book: Edited by R.C. Buchanan, “Ceramic Materials for Electronics –
Processing, Properties, and Applications”, Marcel Dekker Inc. pp 133- 135.

CONVENCTION

A convenient method of uniquely specifying such directional properties is by the use of

subscripts which define orientation directions as described in Figure 5. The 3 direction is
usually taken as the poling (polar) axis and the 1 and 2 directions as orthogonal
axes. Shear effects are indicated by the subscripts 4, 5, and 6. Coefficients that relate
two variables (e.g., a d constant) are indicated with two subscripts, the first of which
refers to the electrical direction (electric field or dielectric displacement) and the
second to the mechanical direction (stress or strain).

The applied tensile stresses are σ1, σ2 and σ3 and the shear stresses are σ4, σ5 and σ6
parallel to or about the axes respectively.

Also, when a given property is being measured while holding another quantity
constant, a superscript symbol is used to indicate the quantity held constant.

Typical examples of often used properties with appropriate subscripts or superscripts are
given below:

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Figure 5. Notation
of axes for poled
ceramic element

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s31 = mechanical compliance, lateral, m2/N
g31 = voltage coefficient, lateral, V-m/N (open-circuit field/applied stress)
g15 = voltage coefficient, shear, V-m/N (open-circuit field perpendicular to 1
axis/applied shear stress around 2 axis)
K3 = relative dielectric constant, longitudinal, no units (K3 =K33=εε33/εε0)
ε0 = dielectric constant of free space, ε0=8.85 x 10-12 F/m
k33 = electromechanical coupling factor, longitudinal, no units
k31 =electromechanical coupling factor, lateral, no units
kt=electromechanical coupling factor, thickness, no units
kp = electromechanical coupling factor, planar (radial), no units (thin disk only)
σ = Poisson's ratio of cross contraction, -0.3 approx., no units
ρ = material density, kg/m3

Poled ferroelectric ceramics symmetry shows that all coefficients are zero except d31
= d32 , d33 and d15 = d24

The piezoelectric charge coefficients (d33 and d31) and the voltage coefficients (g33,
g31, and gl5) describe the electromechanical parameters of the piezoelectric ceramic
material. For both the direct and the converse effects, the d coefficient is the
proportionality constant between displacement and stress, or strain and electric
field, according to the relationships

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 d = D/T =S/E

where d is a piezoelectric coefficient,

D is the dielectric displacement (consider it equal to polarization),

T is the stress,
S is the strain,
E = V/t, where V is the voltage difference applied to a thickness t.

where the d coefficient is numerically identical for both effects. High d coefficients are
desirable for those materials which are utilized in motional or vibrational devices such as
sonor and sounders. The g coefficient is related to the d coefficient via the dielectric
constant according to

g = d/(Kε0) = E/T = S/D

High g coefficients are desirable for materials intended to produce voltages in response to
mechanical stress, such as in gas igniters and phonograph pickups.

The piezoelectric coupling factor (k33, k3l, kt and kp) is a convenient and direct
measurement of the overall strength of the electromechanical effect (i.e., the ability of the
ceramic to convert one form of energy to another). It may be defined as the square root of

20
the ratio of energy available in electrical form to the total mechanical energy input (direct
piezoelectric effect) or the square root of the ratio of energy available in mechanical form
to total electrical energy input as in the converse effect. Since the conversion of electrical
to mechanical energy (or vice versa) is always incomplete, k is always less than unity.
For ceramics, kp is a typical measurement in comparing materials, values ranging from
0.35 for barium titanate to 0.72 for lead zirconate.

ELECTROMECHANICAL COUPLING COEFFICIENT

If we eliminate the stress from equations (4) and (10) we have,

P = rd/s - Ed2/C + ΩE

P - rd/s + ΩE(1 - d2)/(Ωc)

P = rd/s + ΩE(1 - kc2) (20)

where the electromechanical coupling coefficient is,

kc2 = d2/(Ωs) = e2s/Ω

21
The mechanical energy Wm stored in a transducer when an applied force produces a strain
r is,

Wm = (½)Frt = (1/2)F2Cm = (1/2)aT2 = (1/2)V2C (22)

where C is the
capacitance and Cm
is the mechanical
compliance and is
the reciprocal of
the Hooke's
constant. aT is
called the
transformation
factor. Hence

AT2 = C/Cm (23)

The electrical
energy stored in a
capacitor is,

22
 We = (1/2)Co V2 (24)

and Wm /We = C/Co = aT2Cm/Co= e2C/Ω = kc2

where kc2 is the electromechanical coupling factor and is a measure of the efficiency of
the piezoelectric material.

PIEZOELECTRIC MATERIALS

• Piezoelectric materials are currently being considered in a number of actuator

applications including precision positioning, vibration suppression, and noise control.
• While piezoelectric materials such as lead zirconate titanate ceramics (PZT) have been
commercially available since the 1950's, they have been predominantly characterized
for sensor applications and not for the more demanding applications required of
actuator systems.
• To effectively design and fabricate piezoelectric actuators, one must evaluate and
understand the material's response under conditions simulating the operating
environments which are representative of the application.

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Basics of Piezoelectric Materials
The piezoelectric effect is often encountered in daily life. For example, in small butane
cigarette or gas grill lighters, a lever applies pressure to a piezoelectric crystal creating an
electric field strong enough to produce a spark to ignite the gas. Furthermore, alarm
clocks often use a piezoelectric element. When AC voltage is applied, the piezoelectric
material moves at the frequency of the applied voltage and the resulting sound is loud
enough to wake even the strongest sleeper.

The word "piezo" is derived from the Greek word for pressure. In 1880, Jacques and
Pierre Curie discovered that pressure applied to a quartz crystal creates an electrical
charge in the crystal; they called this phenomena the piezo effect. Later they also
verified that an electrical field applied to the crystal would lead to a deformation of
the material. This effect is referred to as the inverse piezo effect. After the discovery
it took several decades to utilize the piezoelectric phenomenon. The first commercial
applications were ultrasonic submarine detectors developed during World War I and in
the 1940's scientists discovered that barium titanate ceramics could be made piezoelectric
in an electric field.

As stated above, piezoelectric materials can be used to convert electrical energy into
mechanical energy and vice versa. For nanopositioning, (nano = 10-9) the precise
motion which results when an electric field is applied to a piezoelectric material is of

24
great value. Actuators using this effect first became available around 20 years ago and
have changed the world of precision positioning.

Piezoelectric actuators (PZTs) offer the user several benefits and advantages over other
motion techniques:

• Repeatable nanometer and sub-nanometer sized steps at high frequency can be

achieved with PZTs because they derive their motion through solid state crystal
effects. There are no moving parts (no "stick-slip" effect due to inertia). PZTs can
be designed to move heavy loads (several tons) or can be made to move lighter
loads at frequencies of several 10 kHz.
• PZTs act as capacitive loads and require very little power in static operation,
simplifying power supply needs.

• PZTs require no maintenance because they are solid state and their motion is
based on molecular effects within the ferroelectric crystals.

With high-reliability PZT materials a strain on the order of 1/1000 (0.1 %) can be
achieved; this means that a 100 mm long PZT actuator can expand by 100 micrometers
when the maximum allowable field is applied.

25
The unique characteristics of piezoelectric materials permit them to be employed as
actuators or sensors which can be exploited in the synthesis of smart materials utilizing
electrical energy for the sensing, communication and actuation functions. Indeed, the
deployment of piezoelectric materials in the synthesis of smart materials involves the
exploitation of a bio-mimetic (mimetic→imitation) philosophy. For example, both skin
and bone have piezoelectric properties. Thus, our sensing system at the fingertips
involves the generation of an electric potential at the surface of the skin, which is then
transmitted to the brain by the nervous system prior to evaluation, interpretation and
subsequent action.

Currently, piezoelectric materials are employed in a variety of conventional commercial

applications such as phonographic pickup cartridges, where the vibrational motion of the
phonograph stylus is converted into a time-varying electrical signal; microphones, where
sound pressure waves are converted into dynamic voltages; and devices for controlling
the frequency of electrical signals, where the shape of the crystal is carefully shaped in
order to ensure that only signals of a specific frequency pass through them.

The direct and converse piezoelectric phenomena, involving an interaction between the
mechanical and electrical behaviour of a material, can be usefully modeled by linear
constitutive equations involving two mechanical variables and two electrical variables.
Thus in matrix form the equations govern the direct piezoelectric effect and the converse
piezoelectric effect are written respectively,

26
Where {D} is the electric displacement vector; [e]T the transpose of [e], the dielectric
permittivity matrix; {S} is the strain vector; [αS] is the dielectric matrix at constant
mechanical strain; {E} is the electric field vector; {T} is the stress vector, and [cE] is the
matrix of elastic coefficients at constant electric field strength.

Figure 6.

27
FUNDAMENTALS OF PIEZOELECTRICITY AND PIEZO ACTUATORS

Material Properties
Since the piezo effect exhibited by natural materials such as quartz, tourmaline, Rochelle
salt, etc is small, polycrystalline ferroelectric ceramic materials such as Barium Titanate
(BaTi03) and Lead Zirconate Titanate (PZT) have been developed with improved
properties. Ferroelectric ceramics become piezoelectric when poled. PZT ceramics are
available in many variations and are still the most widely used materials for actuator or
sensor applications today. PZT crystallites are centro-symmetric cubic (isotropic) before
poling and after poling exhibit tetragonal symmetry (anisotropic structure) below the
Curie temperature. Above this temperature they lose the piezoelectric properties, because
the positive and negative ions' symmetric centers are coincident.

+ Pb

O2-
− Ti, Zr
Centro-symmetric cubic Tetragonal symmetry Figure 7.
(isotropic) (anisotropic)

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Charge separation between the positive and negative ions is the reason for electric dipole
behavior. Groups of dipoles with parallel orientation are called Weiss domains. The
Weiss domains are randomly oriented in the raw PZT material, before the poling
treatment has been finished. For this purpose an electric field (> 2000 V/mm) is applied
to the (heated) piezo ceramics.
The material now has a permanent polarization (which can be degraded by exceeding the
mechanical, thermal and electrical limits of the material). As a result, there is a distortion
that causes
growth in the
dimension
aligned with
the field and
a contraction
along the
axes normal
to the electric
field.

Figure 8. The dipole rearrangement of the piezoelectric effect

29
When an electric voltage is applied to a poled piezoelectric material, the Weiss domains
increase their alignment proportional to the voltage (see figure 8). The result is a change
of the dimensions (expansion, contraction) of the PZT material.

PZT-based ceramics have two principal benefits:

• They furnish materials with a high piezoelectric activity.
• These materials can be molded during their preparation into a wide variety of shapes,
and, of these, plates and hollow cylinders are particularly useful. The ceramic
processing also enables the fabrication of piezoelectric stacks (Figure 9).

Figure 9. Some possible shapes for

piezoelectric elements.

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The ceramic is inherently isotropic so that the polarization axis may be determined by the
polarization process itself; for example, radial polarization of the hollow cylinder is very
simple to arrange.

Figure 10. The D-E loop for

piezoelectrics

Where C = coulomb (electrical

charge)

The polarization processing involves applying an electric field across the sample in
excess of the coercive field of the material (Figure 10), which is typically of the order of

31
1 MV/m, raising the temperature of the material above the Curie point and cooling the
material below this point to "lock" the domain structure.
Piezoelectric ceramics are extensively used as strain sensors and as mechanical sources.
Careful impedance matching both at the mechanical and electrical sides of the circuit is
necessary.

The great majority of sensing applications based upon piezoelectrics use either
piezoceramic or polymer transducers. Both these materials are essentially isotropic.

The polarization axis is defined by the polarizing field (that is, the "3" axis). Even with
this relatively simple system, great care is required in the use of piezoelectric transducers
and the interpretation of the consequential results.

32
PIEZOELECTRIC ACTION

(a) (b)
Figure 11.

• Poling, or application of a large coercive field on the order of 50 volts/mil, aligns

crystalline subdomains in the ceramic.
• Poling causes the ceramic to grow in the field direction and to shrink laterally, roughly
according to Poisson's ratio.
• Subsequent application of field in the poling direction also causes the ceramic to grow
in that direction.

33
• Application of reverse field
causes the ceramic to shrink
until a negative coercive field
level is reached. Poling action
then switches and the ceramic
grows again. Hence the
"butterfly" curve (Figure 11b).

Since the spontaneous

polarization can be reversed by
an electric field Ez, it is possible
to switch the piezoeectric
polarity. Therefore, the converse
piezoelectric effect exhibits a
quadratic hysteresis loop
("butterfly loop") as indicated in the figure 12.
Figure 12.

The figure 12 shows the quadratic hysteresis of the converse piezoelectric effect of an
untwined BaTi03 crystal in the tetragonal phase. Expansion z, versus electric field EZ
(schematic).

34
The slope of AB and EF represents the piezoelectric strain coefficient d33. Between O and
D (O and G) the field E, opposes the spontaneous polarization, but is not big enough to
switch it; at D (G) the coercive field is reached, the spontaneous polarization is reversed
and the piezoelectric effect changes its sign.

PEROVSKITE STRUCTURE AND PHASE DIAGRAM OF PIEZOELECTRIC

MATERIALS

Perovskite crystal structure: the structure of many piezoelectric materials chemically

represented by ABO3, where A and B are arbitrary elements.
The figure 13 shows the Perovskite structure which
is common in ferroelectrics. Below the Curie
temperature, the oxygen ions are displaced below
the crystal canter, resulting in a net dipole moment.

Figure 13.

35
 Figure 14. Simplified phase diagram
for PZT

The vast majority of ceramic piezoelectrics are in the PZT family. Figure 14 shows the
phase diagram for lead Zironate titanate system.

36
PZT Phase Boundaries

PZT is a solid
solution of lead
zirconate (PbZr03)
and lead titanate
(PbTiO3). The ratio
of these two
molecules and
addition of other
trace compounds
determines the phase
transition
boundaries, and
15.
hence the properties.
• PZT and Barium
Titanate are
Perovskite ceramics. PZT has somewhat better piezoelectric and dielectric properties.
• The electric offsets in the crystal lattice also cause very high mechanical strains when
subjected to a field, and conversely.

37
PHASE DIAGRAM

A phase means a matter having certain definite composition and structure.

For a single-component system, a phase diagram in which pressure is plotted versus

temperature exhibits the existence ranges for the different phases of a system comprising
only one component.

For a two-component system, the chemical composition is plotted versus one of the
variables (pressure or temperature) with the other unchanged. A phase diagram is usually
a plot of the composition versus temperature at normal pressure.

The phase diagram is determined experimentally using the method described in the
following. In differential thermal analysis (DTA), a sample of a given composition is
heated or cooled slowly together with a thermal different reference substance, and the
temperatures of both substances are monitored continuously. When a phase transition
occurs in the sample, the enthalpy of conversion is released or absorbed, and therefore a
temperature difference shows up between the sample and the reference, thus indicating a
phase transition.

DTA is a very useful technique for phase determination, but its accuracy depends on the
precision of temperature measurement and rate of heating or cooling. In fact, phase

38
transition automatically introduces a change in crystal structure. Therefore, x-ray
diffraction is usually used to identify the phase.

Fully understanding the intrinsic connections among a variety of phases is critically

important for constructing new materials.

FERROELECTRICITY

Definition of a Ferroelectric, Outstanding Properties

• The outstanding property of ferroelectrics is the reversibility of the permanent
polarization by an electric field.
• This reversibility is a consequence of the fact that the polar structure of a ferroelectric
is a slightly distorted nonpolar structure. The reversal of the permanent polarization
gives rise to a nonlinear dielectric behavior.
• In most cases a temperature exists, i.e. the Curie temperature, at which the crystal
undergoes a phase transition from a nonpolar state into a polar state. Therefore, the
polarization is called spontaneous polarization.

39
Ferroelectric Property
• The ferroelectric property originates from electric dipole moment induced by
spontaneous polarization of the crystal. In ionic compounds the tetrahedra and/or the
octahedra usually are the basic building blocks of the unit cells.
• However, in some cases the centers of gravity of positive and negative charges do not
coincide and uncompensated charges form a permanent electric dipole in the unit cell.
If these dipoles can be canceled by the randomly oriented ferroelectric domains, the
material does not exhibit a macroscopic dipole. We call it paraelectric. If these dipoles
cannot cancel each other, the residual dipoles add up, forming a macroscopic dipole,
which is ferroelectricity.
• Ferroelectricity generally disappears if the specimen temperature is higher than a
critical value (Curie temperature).

Piezoelectric Property
Figure 16 shows the mechanism of the
piezoelectric effect. An external
pressure causes the deformation of a
coordination tetrahedron, resulting in a
shift of the gravity centers of the
electric charges, creating a local
polarization dipole. Figure 16.

40
• To illustrate piezoelectricity, consider an atom with a positive charge surrounded
tetrahedrally by anions (- ions) (Figure 16). The center of gravity of the negative
charges is at the center of the tetrahedron. By exerting pressure on the crystal on the
corners of the tetrahedron, the
tetrahedron undergoes distortion
and the center of gravity of the
negative charges no longer
coincides with the position of the
positive central atom, and an
electric dipole is generated.

• If all of the tetrahedra in the

crystal have the same orientation
or some other mutual orientation
that does not allow for
cancellation among the dipoles,
the crystal has a macroscopic
dipole. The two opposite faces of
the crystal have opposite electric
charges.
Figure 17.

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• Piezoelectricity refers to a reverse process in which contraction or elongation is created
in the crystal once it is positioned in an electric field

• Piezoelectric effect can convert a mechanical vibration into an electric signal, or vice
versa. It is widely used in quartz resonators, controlling tip movement in scanning
probe microscopy, sensors for vibration waves in air and under sea, and other
applications.

Definition of Piezoelectric Coefficients and Directions

• Because of the anisotropic nature of PZT ceramics, effects are dependent on direction
(see Fig.). To identify directions the axes, termed 1, 2, and 3, are introduced
(analogous to X, Y, Z of the classical right hand orthogonal axial set). The axes: 4, 5
and 6 identify rotations (shear).
• The direction of polarization (3 axis) is established during the poling process by a
strong electrical field applied between two electrodes. For actuator applications the
piezo properties along the poling axis are most essential (largest deflection).

Notes:
It should be clearly understood that the piezoelectric coefficients described here are not
independent constants. They vary with temperature, pressure, electric field, form factor,

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mechanical and electrical boundary conditions etc. The coefficients only describe
material properties under small signal conditions. Compound components such as PZT
stack actuators, let alone preloaded actuators or lever amplified systems cannot be
described sufficiently by these material parameters. This is why each component or
system manufactured by PI is characterized by specific data such as stiffness, load
capacity, displacement, resonant frequency, etc., acquired by individual measurements.

Piezoelectric materials are characterized by several coefficients:

Examples are:
• dij : Strain coefficients [m/V] : i --- direction of excitation, j --- direction of
response
strain developed (m/m) per electric field applied (V/m)
or (due to the sensor / actuator properties of PZT material).
• Charge output coefficients [C/N]:
charge density developed (C/m2) per given stress (N/m2).
• gij: Voltage coefficients or field output coefficients [Vm/N]:
open circuit electric field developed (V/m) per applied mechanical stress
(N/m2)
or (due to the sensor / actuator properties of PZT material)
strain developed (m/m) per applied charge density (C/m2).
• kij: Coupling coefficients [no dimensions].

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 The coefficients are energy ratios describing the conversion from mechanical to
electrical energy or vice versa.
k2 is the ratio of energy stored (mechanical or electrical) to energy (mechanical
or electrical) applied.

Other important parameters are the Young's modulus Y (describing the elastic properties
of the material) and the relative dielectric coefficients (permittivity) ε (describing the
capacitance of the material).

To link electrical and mechanical quantities double subscripts (e.g. dij) are introduced.
The first subscript gives the direction of the excitation, the second describes the direction
of the system response.

Example:
d33 applies when the electric field is along the polarization axis (direction 3) and the strain
(deflection) is along the same axis. d31 applies if the electric field is in the same direction
as before, but the strain is in the 1 axis (orthogonal to the polarization axis)

In addition the superscripts "S, T, E, D" are introduced. They describe an electrical or
mechanical boundary condition.

Definition:

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S → strain = constant (mechanically clamped)
T → stress = constant (not clamped)
E → field = constant (short circuit)
D → electrical displacement = constant (open circuit)

The individual piezoelectric parameters are related by several equations that are not
explained here because they are not important for the user of piezo actuators.

PIEZOELECTRIC CONSTANTS & PROPERTIES

A. Physical Properties
• Curie Temperature: The curie temperature is that temperature above which
spontaneous polarization and piezoelectric behavior cease to exist.
• Maximum Operating Temperature: The safe use temperature for piezoelectric
materials to ensure continued piezoelectric behavior. Generally, the operating
temperature is 50-60% of the curie temperature.
• Youngs' Modulus: Defined as the stress on the material divided by the strain in the
direction of the applied stress.
• Mechanical Quality Factor Q: A dimensionless number that describes the merit of the
material as a harmonic oscillator. The mechanical Q is the reciprocal of the mechanical
damping factor. Large Q means small mechanical loss of the material.

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B. Dielectric Properties
• Dielectric Constant: The relative dielectric constant or permittivity of a material is the
ratio of the amount of charge a material can store as compared to the charge so stored
by a comparable vacuum.
The relative dielectric constant K is given by K=4.44CT/A,
where C --- capacitance in pf at 1 kHz,
T --- thickness in inches;
A -- the area in square inches
Dielectric Constant ε = CT/A, unit of ε --- pf/inch
• Aging: The polarization of the material gradually decreases with time, and aging is the
time decay given as a percent per decade of time.

C. Piezoelectric Properties
Coupling Coefficient: The coupling coefficient is a measure of converting electrical to
mechanical energy and vice versa. It is the square root of the ratio of the stored
electrical energy to the mechanical energy input.

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Figure 18. Properties of typical commercial piezoelectric materials.

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48
COMPARISON BETWEEN PIEZOCERAMICS AND PVDF
• Piezoceramics (e.g. PZT) are brittle materials, which are manufactured as small
simple-shaped parts with a relatively small surface area. These brittle piezoelectric
elements are typically manufactured in 2 inch by 3 inch (50mmx75mm) sheets in
thickness varying from 4 x 10-3 to 12 x 10-3 inches (0.1mm to 0.3mm).
• In sharp contrast to the mechanical characteristics of piezoceramics, PVDF materials
are flexible plastic materials that are manufactured in thin sheets, which can be readily
cut into a wide variety of different shapes and sizes.
• This tough lightweight plastic material is manufactured in various thicknesses from
0.4x 10-3 to 30 x 10-3 inches (0.01 to 0.725mm), and it is easily shaped prior to bonding
to a substrate with commercial adhesives.
• The significantly different mechanical properties of these two classes of piezoelectric
materials can have different applications.
Thus, for example, the high rigidity of ceramic elements ensures that electrical energy
is efficiently converted into mechanical energy, which ensures good actuation
capabilities. On the other hand, Polyvinylidene Fluoride, PVDF, plastic materials are
electromechanically weak compared with the piezoceramic elements in low frequency
applications and near resonant frequencies.
• However, PVDF elements are more sensitive to mechanical loads over a wider range
of loading conditions than piezoceramics, consequently they are good candidates for
sensor applications.

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For example, the wide range sensitivity of polymeric films to mechanical deformation
has permitted PVDF materials to measure the impact of micron-sized particles in
space, and also the stresses developed in ballistic tests by armorpiercing shells. The
pressure sensitivity of these polymeric materials ranges from micro-torr (10-
6
x1.33322x102 Pa) to Mega-bar (109xl05Pa).
(Torr → mm Hg, 0oC, =1.33322x102 Pa)
• Polyvinylidene fluoride (PVDF) films also have wide-band frequency dependent
characteristics from near D.C. to frequencies in the GHz range depending upon the
thickness of the film. For example, a 28 µm-thick sheet has a fundamental resonant
frequency near 40 MHz; very thin films have resonant frequencies in the GHz range.
• The relative dielectric permittivity (ε/εo) of PVDF's is typically of the order of 12
while piezoceramics are of the order of 1200 or higher. Consequently the
piezoelectric stress constant g31 is approximately 216 x 10-3 (V/m)/(N/m2), which is
typically 20 times greater than that of a piezoceramic material.
• PVDF materials possess dielectric strengths of the order of 40 V/µm while the
dielectric strengths of typical piezoceramics are of the order of 2 V/µm.
Thus polymeric materials can be exposed to much higher electric fields than their
piezoceramic counterparts.
• PVDF films are approximately one-third the weight of piezoceramic materials.
Furthermore, because they are extremely compliant, PVDF film sensors can be
bonded to lightweight flexible structures undergoing large dynamic deflections

50
 without significantly distorting the elastodynamic characteristics of the original
structure.
• However, because PVDF materials are so compliant they are not as effective as the
piezoceramics in the role of electromechanical actuators for smart material
applications, especially at low frequencies.
• Polyvinylidene fluoride films (PVDF) are extremely robust when subjected to
various chemical environments with high humidity, solvents, acids, and ultraviolet
radiation, but the material is quite sensitive to electromagnetic radiation, mandating
appropriate shielding in certain applications.
• In addition, PVDF films are temperature sensitive, resulting in decreasing
piezoelectric performance with increasing temperature. A typical limiting
temperature for PVDF applications is 100°C, however, piezoceramic elements may
generally be employed in environments twice this temperature.

PZT Ceramics Manufacturing Process

• The process starts with mixing and ball milling of the raw materials. Next, the
mixture is heated to 75% of the sintering temperature to accelerate reaction of the
components.. The polycrystalline, calcinated powder is ball milled again to increase
its reactivity. . Granulation with the binder is next to improve processing properties.
After shaping and pressing the (green) ceramics is heated to 750° to burn out the
binder.

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 • The next phase is sintering at temperatures between 1250° C and 1350° C. The
ceramic block is cut, ground, polished, lapped, etc., to the desired shape and
tolerance. Electrodes are applied by sputtering or screen printing processes. The last
step is the poling process which takes place in a heated oil bath at electrical fields up
to several kV/mm.
• Multilayer PZT actuators require a different manufacturing process. After milling a
slurry is prepared. A foil casting process allows layer thickness down to 20 µm.
Next, the sheets are screen printed and laminated. A compacting process increases
density of the "green" ceramics and removes air trapped between the layers. The
final steps are the binder burnout, sintering (co-firing) at temperatures below 1100°
C, end termination and poling.

SUMMARY

Piezoelectric material
material exhibiting coupling between strain and electric field, typically restricted to linear
behavior.

Direct effect
electrical polarization is produced by mechanical stress (Curie Brothers).

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Converse effect
crystal becomes strained by an electric field (Lippman).

Ferroelectric material
crystal exhibiting spontaneous polarization.

Perovskite crystal structure

the structure of many piezoelectric crystals; chemically represented by AB03, where A
and B are arbitrary elements.

Ferroelectric effect
when spontaneous polarization can be induced due to an electric field.

Ferroelastic effect
when spontaneous polarization can be induced due to a mechanical load.

Ferroelectric switching
Either 180 ° or 90 ° polarization reversal caused by an electric field is termed
ferroelectric switching

Dielectric strength

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The maximum electric field a material can be subjected to without breaking down or
discharging, analogous to mechanical failure.

180° switching
When electric field is applied opposite to the polarization direction, material undergoes
180° switching, producing characteristic strain-electric field butterfly loop.

90° switching
• 90° polarization reversal may be achieved by applying sufficiently large electric field
in a direction normal to the polarization vector.

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 • The process is considerably more complicated than 180 ° switching involving both
switching and growth within the crystal.
• The process occurs over a range of values and is not represented by a critical value.
• There is a permanent deformation upon removal of electric field.

Ferroelactic switching
Polarization may also be reversed 90° due to Ferroelastic switching compressive
mechanical load.

PUBLICATIONS
• Park, S.B., Park S.S., Carman, G.P., and Hahn, H.T., "Measuring Strain Concentrations
During Macroscopic Domain Reorientation in a Ferroelectric Material," Transactions of
the ASME. Journal of Engineering Materials and Technology, Jan. 1998, vo1.120,
(no.l):1-6.
• Wang, D., Fotinich, E., and Carman, G.P., "Influence of temperature on the Electro-
mechanical Fatigue Behavior of Piezoelectric Ceramics," Journal of Applied Physics,
May 1998, V 83, pp.5342-5350.
• Park, S.B. and Carman, G.P., "Minimizing Stress Levels in Piezoelectric Media
Containing Voids," Transactions of the ASME. Journal of Applied Mechanics, Jan
1998, vol.64, (no.3):

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• Park, S.B. and Carman G.P., "Tailoring the Properties for Piezoelectric Ceramics:
Analytical International Journal of Solids and Structures, Sept. 1997, V. 34 (no. 26), pp.
3385-3399.
• Chen, Q., Yao, D., Rim, C.J., & Carman, G.P.,"Mesoscale Actuator Device with Micro
Interlayer Mechanism," Eleventh IEEE International Workshop on MICRO ELECTRO
MECHANICA SYSTEMS", January 25-29,1998, Heidelbery, Germany.

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