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3.1 Introduction
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An Introduction to Conductive Polymer Composites
J = E
Real materials are more or less anisotropic and the conductivity is not a single value,
but a matrix. In spite of this physical reality, conductivities are mainly presented using
only a single value. Electrical resistivity, , is the inverse value of the conductivity,
namely:
= 1/
The unit of volume resistivity is ohm.metre (.m) and the unit of conductivity is the
unit of inverse ohms (1). The latter is usually called Siemens per unit distance; in
the SI system it is expressed as Siemens per metre (S/m) but is usually expressed as
Siemens per centimetre (ohm1).
There are several technical solutions and commercial applications to measure the
electrical conductivity of plastic samples. Many of them are designed for a particular
type of sample and/or materials. The electrical circuit models are needed to understand
these measurements in detail. This approach is outside the scope of this book, and
only the practical principles of the measurements are presented here.
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Testing of Conductive Materials
To determine the conductivity of the sample the resistivity is measured. The resistivity
of the material is defined by the resistance (R) of the sample. The resistivity can be
calculated by using the dimensions of the measurement arrangements (the distance
between the electrodes used to measure the voltage and the sample dimensions).
The in-plane conductivity is a measure of how the current flows on the sample
surface. Therefore, the terms surface conductivity and surface resistivity (S) are
frequently used.
There are several types of electrode structures (e.g., ring-type constructions) but here
we describe the measurement principles using the four-point method.
The four-point method is the most commonly used method to determine surface
conductivity. There are application-oriented variations of the concept. The method
was developed by Smits [2]. The method includes a correction factor (c) describing
the geometry of the experimental arrangement. The influence of this factor is usually
minimal and therefore it is usually not used in calculations.
The four-point method involves four electrodes (Figure 3.1). In the system, a constant
current (I) flows between two outer electrodes and the change in potential (V) between
the inner electrodes is measured. The following equations are used:
V = IR
= (R.A)/l
S = (R.w)/l
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An Introduction to Conductive Polymer Composites
The resistance of the sample, R, is also called the sheet resistance or surface
resistance, and sometimes noted as RS. A is the area of the sample cross-section and
l is the distance between the electrodes to measure the voltage. In these equations,
is the volume resistivity (or bulk resistivity) and S is the surface resistivity [3].
Current
source
In a particular case where the sample width is equal to the distance of the measurement
electrodes, w = l, surface resistivity is equal to the surface resistance. Therefore, a
frequently used term for this value is the resistance of a surface, expressed by the unit
ohm/square or ohm/sq, to distinguish this surface resistance from a volume resistance.
This term is common in datasheets of plastic films.
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Testing of Conductive Materials
known (mean) thickness t, is closed between two electrodes with an area A (Figure
3.2). The volume resistivity can be calculated by the equation:
= (A/t).R
where R is the measured resistance. Again, the volume conductivity is the reciprocal
value of the resistivity.
SAMPLE
The contact resistance is a serious issue in the through-plane method. When rigid
electrodes are used, flatness of the sample and electrodes are essential. A typical risk
is that the real electrode area is smaller that the nominal area of the electrodes. If
electrodes are compressed on the sample surface to attain good contacts (low contact
resistance) the result is that measured resistances follow an inverse function of the
compression pressure. An approach to minimise the contact resistance is coating
of the specimen surface by a highly conductive material using conductive paints or
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An Introduction to Conductive Polymer Composites
sputtering. These types of coated electrodes are useful for soft and uneven sample
surfaces. Although the method seems to be a simple and straightforward solution,
the concept includes the risk of the right electrode and other issues.
The van der Pauw method is a four-point method to measure volume resistivity (or
conductivity) where the contact resistance is eliminated [4]. The method is frequently
used in the semiconductor industry. The method is also known as the resistivity or
Hall effect measuring system.
In this method, the electrodes are placed at the circumference of the sample (Figure
3.3). The shape of the sample could be almost arbitrary, but the surface of the sample
should not include isolated holes. The thickness of the sample should be constant.
According to the preconditions for the method, the sample should be homogeneous.
However, if the samples are composites, this is not exactly valid. According to the
original concept, the areas of the electric contacts should be small.
This method does not require information about the area of the sample or the distances
between electrodes: only the accurate thickness of the sample is necessary. However,
there are two preconditions:
(2) The location of the contacts on the edge of the surface are technically complicated
to realise.
Technical arrangements and correction methods to eliminate these problems are stated
in the literature. Also various standard geometries for electrode configurations are
presented.
Figure 3.3 shows four electrodes: A, B, C and D. In the system, a current (IA-B) flows
between the electrodes A and B and the voltage drop (VC-D) between electrodes C and
D is recorded. According to van der Pauw, the resistances RA and RB are expressed as:
RA = (VC-D/IA-B + VA-B/IC-D)/2
RB = (VD-A/IB-C + VB-C/ID-A)/2
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Testing of Conductive Materials
The thickness of the sample is t [m] and the conductivity (S/m). The conductivity
of the sample is calculated by the equation:
The van der Pauw method is usually applied for semiconducting samples (i.e., plastic
composites with relatively high conductivities).
Polymers and non-metallic fillers are dielectric. They are polarised by an applied
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An Introduction to Conductive Polymer Composites
electric field and the dielectric constant is >1; the dielectric constant of a vacuum
is one. The polarisation is based on electronic polarisation, which is a fast response
of electron clouds. If the conductivity is based on ions the response to the electric
field is slow.
Some additives for plastics are ionic and dielectric behaviour is a method to analyse
these types of materials. If the electric field is accelerating, the direction of polarisation
follows the field, but the resistance to motion of atoms creates a phase difference
between the field and polarisation: this is called the phase angle (). The power factor
is defined as sin and the dissipation factor as tan . The product sin is the loss
factor. The loss factor describes the energy absorbed per cycle from the field in the
dielectric material.
C = 0A/d
The impedance Z and the phase angle are measured. The complex dielectric constant
(*), the real part of the complex dielectric constant (') and the imaginary part of
a complex dielectric constant ('') can be calculated using the following equations:
' = Zi/2fCZ2
'' = Zr/2fCZ2
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Testing of Conductive Materials
AC = 2f0''
We have discussed above the contact resistance-related issues which usually are more
typical in the through-plane measurements than in-plane measurements. However,
surface conductivity measurements are also influenced by the contact resistance.
These types of measurement are sensitive to undesired electric noise. Also, the qualities
of all electric connections are essential. Careful construction of the measuring unit,
sample preparation and quality management of testing procedures with reference
samples are preconditions for reliable results. The environment has effects on the
conductivity values and temperature, but humidity in particular may cause inaccurate
results.
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An Introduction to Conductive Polymer Composites
A part of incident energy reflects; absorption and multiple internal reflections decrease
the intensity of the radiation in the material and the rest will be transmitted through
the material (Figure 3.4). The EMI SE is the result of reflection, absorption and internal
multiple reflections [6]. SE is expressed in decibels (dB). The decibel information is a
logarithmic scale in which 20 dB means a drop of 90% in the radiation strength, 40
dB is a drop of 99% and 60 dB is a drop of 99.9%. In many applications, the values
of SE from 40 dB to 70 dB fulfil the requirement.
where SER, SEA, and SEM are the attenuations by reflection, absorption, and multiple
internal scattering, respectively. The sum equation is usually used in the form:
where PI, EI and HI are incident power, electric field, and magnetic field, respectively,
and PT, ET and HT describe the transmitted power and fields.
3.3.2 Reflection
The primary mechanism for shielding is usually reflection [7]. The physical background
for reflection is based on interaction of radiation with free charge carriers (i.e.,
with electrons and holes). These same mobile charge carriers also create electric
conductivity, and therefore highly conductive materials are usually excellent reflective
materials for EMI-shielding purposes. A typical application is metal-coated plastic
housings. Other types of materials with mobile charge carriers are carbon nanotubes,
carbon fibres and graphene. In the group of organic polymers, inherently conductive
polymers such as polyaniline have these free carriers. However, high conductivity of
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Testing of Conductive Materials
the material itself is not a direct measure of the high reflection term in SE: the high
concentration of mobile charge carriers (electrons) is the key issue. Plastic composites
with a non-conductive matrix and conductive fillers may have good SE even though
electric conductivity is only moderate.
A
R
T
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An Introduction to Conductive Polymer Composites
where n is the refractive index of the shielding material. The refractive index and
dielectric constant are related: ~ n2. Here we can find the relationship between the
dielectric characteristic of the shielding material and the SE performance.
3.3.3 Absorption
where Im(k) is the imaginary part of the wave vector in the shielding material and d
is the thickness of the shielding material. The absorption loss is proportional to the
thickness of the material.
The physical phenomena causing the multiple reflections are the inhomogeneus
morphology of the shielding material. Internal surfaces and interfaces in the material
cause reflections, and examples of this kind of material are foams (porosity) and
composites (interfaces between filler and matrix). The general term for multiple
reflection shielding efficiency is:
The multiple reflection shielding term is usually small compared to the two other
terms and therefore it is usually neglected.
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Testing of Conductive Materials
To analyse SE, a useful concept is the skin depth (). At high frequencies,
electromagnetic radiation penetrates only the surface of an electrically conductive
material. The intensity of the radiation drops exponentially, and the skin depth is
the depth when the intensity is proportional to 1/e of the value on the surface. The
skin depth is expressed by the following equation:
= 1/(.f..)1
The equations detailed above are general equations. More detailed information
is necessary for the purposes of research and development. In many commercial
applications, EMI shielding is realised by multilayer structures such as metallised
plastic housings. For this type of structure, the complexity of mathematical expressions
of SE increases.
The near-field and the far-field concepts are based on the distance from the radiation
source (antenna) to the object of interest measured by the used wavelength of the
radiation, . The far-field region covers distances 2 or longer from the antenna, and
distances between and 2 are located in the transition zone. The near-field region
covers distances less than . The near-field region is divided into two sub-regions: the
reactive near-field region is the region immediately close to the antenna, and longer
distances below 1 are located in the radiative near-field region.
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An Introduction to Conductive Polymer Composites
Shielded rooms
SIGNAL RECEIVER
GENERATOR
Sample
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Testing of Conductive Materials
To measure SE of materials, two common methods are used. The shielded box
method is based on a sealed box with a hole in it. The sample is placed on the hole.
Electromagnetic signals are measured outside and inside of the test box and the ratio
of intensities represent SE. The method is not usually employed for higher frequencies.
An example of a frequently used test method is the military standard, IEEE 229 [8].
The standard ASTM 4935-99 [9] describes a version of the coaxial transmission line
test method. Published variations of this method for high frequencies (18 GHz) reveal
the upper limit of the ASTM standard version to be ~1.5 GHz. The method uses a
coaxial line holder for the planar sample. The system includes a signal generator, a
coaxial sample holder and a receiver (Figure 3.6). SE is calculated by comparing the
intensities measured by the test sample and the reference.
SAMPLE HOLDER
ATTENUATOR ATTENUATOR
SIGNAL
RECEIVER
GENERATOR
INNER CONDUCTOR
OUTER CONDUCTOR
WITH FLANGE
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An Introduction to Conductive Polymer Composites
References
6. K. Hong, C.Y. Lee, C.K. Jeong, D.E. Lee, K. Kim and J. Joo, Review of
Scientific Instruments, 2003, 74, 1098.
9. ASTM D4935 -10, Test Method for Measuring the Electromagnetic Shielding
Effectiveness of Planar Materials, 2010.
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