Polymer Testing 4 (1984) 195-209

Electrical Resistivity Measurements of

Polymer Materials

A. R. B l y t h e
BICC Research and Engineering Ltd, Wood Lane, London W12 7DX, UK

SUMMARY

Basic methods of measuring volume and surface resistivities are

reviewed in relation to the wide range of values encountered in plastics
and rubbers, including antistatic grades, conducting composites and
intrinsically conductive polymers. The application of conventional
electrode configurations of 2, 3 and 4 terminal types is considered first.
Then the performance and reliability of various probe techniques are
analysed. Finally, the observation of charge decay rates is discussed
as a means of determining resistivities, and its limitations are defined.

1. INTRODUCTION

Polymers have electrical resistivities that are characteristically very

high, and in most electrical applications they are essentially used as
insulators. 1 There are, however, requirements for conductive grades,
and base polymers are frequently modified to meet this need. Thus
antistatic treatments are applied to surfaces to prevent u n w a n t e d
accumulation of charge, and carbon black composites are used as
flexible heating elements. Variants incorporating carbon fibres afford
low resistivities too, and these are valuable for screening purposes.
Polymers which possess a high degree of intrinsic electronic conduc-
tivity, usually derived from d o p e d polyacetylene, are also u n d e r
195
Polymer Testing 0142-9418/84/$03-00 © Elsevier Applied Science Publishers Ltd,
England, 1984. Printed in Northern Ireland
196 A. R. Blythe

1018 _

PTFE
POLYTHENE
1015 - POLYPROPYLENE

NYLON
1012 - PVC

Volume 109 _ CELLULOSICS (PAPER, COTTON ETC.)

Resistivity AT ABOUT 50% RH
(f~ rn)

106-- 1
I0~ - COMPOSITES WITH"
C - BLACK
METALLISED FIBRES
I - C - FIBRES

J
70 -3 -- DOPED POLYACETYLENE

GRAPHITE
10 -6 _
Ag Cu

Fig. 1. Chartof volume resistivities.

development. Hence the measurement requirements for resistivity

cover an exceptionally wide range as indicated in Fig. 1.
This paper, in addition to briefly reviewing the conventional
methods of measuring resistivities, using specially shaped specimens
and electrodes, discusses the applicability of various probe methods.
The latter are attractive from the point of view of making simple
measurements on moulded objects in situ, etc., but, unless used with
great caution, they give unrealiable results. Consideration is also
given to observations of the rate of decay of charge in a material as a
way of determining resistivity. Although this principle is adopted in
 Electrical resistivity measurements of polymer materials 197

certain standard test methods, it is difficult to obtain o t h e r than

comparative values by this means.

2. DEFINITIONS AND UNITS

The simple definition of volume or bulk resistivity O (l~m) of an

isotropic material is the resistance, as determined in accord with
O h m ' s law, b e t w e e n opposite faces of a unit cube. W h e n c e the
resistance R b e t w e e n opposite ends of a block of uniform cross-
sectional area A and length l is given by:

R =0/ (1)
A
Alternatively, volume resistivity may be expressed by means of a
generalised form of O h m ' s law:
E = od, (2)
w h e r e E and J represent the electric field and current density,
respectively, at any point in the material. M o r e generally still, for an
anisotropic material, resistivity is a second rank tensor that relates
the two vector quantities:
]Ei = Pik]k (3)
Being symmetric, the resistivity tensor has three principal values
w h e n referred to its principal axes. A c o m m o n case of anisotropy
occurs with oriented conducting fibre composites w h e r e the resistivity
c o m p o n e n t in the fibre direction (taken along the z-axis), is lower
than those in the perpendicular directions, i.e.

p= <<Px~, Pv~
Volume conductivity is the reciprocal of resistivity, l/p (~-1 m-l). (It
should be noted that the unit of conductance, the reciprocal ohm
(l-l-l), is now often called the siemen (S).)
Where current flow is confined to a surface, it is convenient to
define an analogous surface resistivity (~ (l-l) as the resistance be-
tween opposite edges of a square. The resistance across a square is
independent of the size of the square, so that the unit of surface
resistivity is properly the ohm, occasionally written rather superflu-
ously as ohm per square. A conducting surface must in reality be a
198 A. R. Blythe

layer with a finite thickness t, and we have only an effective surface

resistivity, which is related to the true volume resistivity of the layer
by:

P
~r=- (4)
t

In s o m e contexts it is convenient to divide materials into three

categories: conductors, antistatic materials and insulators. T h e r e is no
strict definition of these terms with respect to resistivity, although as
a guide we can take the ranges to b e <103, 103-109 and >109 ~-~m,
respectively. T h e concept of an antistatic material is that it can b e
used to m a k e c o m p o n e n t s that are low e n o u g h in resistance to allow
rapid dissipation of static charges b u t high e n o u g h to provide safe
insulation from mains electricity. P e r f o r m a n c e is specified 2 in m o r e
detail for certain applications.

3. CONVENTIONAL MEASUREMENT OF RESISTIVITY

In the laboratory, resistivities are most usually m e a s u r e d with spe-

cially shaped specimens and electrode configurations that are chosen
in such a w a y that uniform electric fields (or field gradients) are
generated in the material. Resistivities are then easily calculated from
the o b s e r v e d currents and voltages b e t w e e n the electrodes.

3.1. Low volume resistivity

The simplest arrangement of all consists of a rectangular or cylindri-

cal block with two electrodes applied, one at either end, as shown in
Fig. 2(a). T h e resistance is t a k e n from the ratio of the applied voltage
to the series current. T h e main p r o b l e m in accurate m e a s u r e m e n t is
o n e of the uncertain contact resistances, b e t w e e n the electrodes and
the specimen, that are included. Contact resistance may be r e d u c e d by
replacing simple pressure contacts to metal plates and foils by silver
paint, colloidal graphite (water or alcohol D A G ) or v a c u u m -
e v a p o r a t e d metal, but it is much better to use the four-terminal
m e t h o d , as shown in Fig. 2(b). A current density J is established in
the central region (cross-sectional area A ) by passing a k n o w n
current I b e t w e e n the o u t e r electrodes, and the electric field E is
 Electrical resistivity measurements of polymer materials 199

(a)

l----]l

(tl)

IF~. 2. Measurement of low volume resistivity: (a) two-terminal method; (b) four-
terminal method.

d e t e r m i n e d by measuring the potential drop Av across the two inner

electrodes (separation Ax). The resistivity is given by:
E AWAx
o - - - - (5)
J I/A

A n y effect of contact resistance is t h e r e b y avoided, provided that the

contact resistances of the voltage electrodes are much smaller than
the input resistance of the voltmeter. In practice, the m e t h o d is
generally restricted to resistivities below a b o u t 10 6 glm, otherwise
currents b e c o m e too small to measure accurately and voltmeter
resistances b e c o m e significant.
200 A. R. Blythe

3.2. High volume resistivity

In order to facilitate current m e a s u r e m e n t on high-resistivity materi-

als, thin disc specimens are used (see Fig. 3), w h e r e b y the overall
resistance b e t w e e n the current electrodes is much reduced. T h e main
p r o b l e m b e c o m e s o n e of leakage current from the high-voltage
source to the a m m e t e r via routes o t h e r than the intended one through
the specimen; the surface of the specimen itself is liable to provide a
low resistance path through the accumulation of dirt and moisture on
it. F o r this reason, a three-terminal m e t h o d is used, w h e r e the extra
guard electrode is applied a r o u n d the low-voltage electrode and its
connection to the ammeter, so as to intercept and divert any leakage
currents which are then excluded from the a m m e t e r reading. W h e r e
very high resistivities are involved and the direct conduction current
is very small, one must b e aware of various transient components,
e.g. a displacement current due to dipolar orientation. If the current
does not reach a constant equilibrium value, then a genuine resistivity
cannot be obtained in this way.

gurdrn

v~o[fcl V disc
specimen
high- ge ' -r"
e[ecfrode

T
F~. 3. Measurement of high volume resistivity: three-terminal method.
 Electrical resistivity measurements of polymer materials 201

3.3. Surface resistivity

Concentric ring electrodes are the easiest to use for m e a s u r e m e n t of

surface resistivity. The resistance R belween them is the sum of the
resistances of the elemental annuli (mean radius r) in series (Fig. 4):
Ir~ Or
R = , ~dr (6)

where rl and r2 are the radii of the inner and outer electrodes,
respectively. Hence:

cr = 2wR In (r~) (7)

This electrode g e o m e t r y completely defines the area of m e a s u r e m e n t .

If the surface is flat and not too hard, sufficiently good contact can be
m a d e by pressure against knife-edged metal electrodes. Otherwise it
m a y be necessary to use conductive rubber electrodes or to paint the
electrodes onto the surface. W h e r e contact resistance remains a
problem, a four-terminal m e t h o d may be applied to a rectangular
strip. It should be m e n t i o n e d that surface conduction p r o d u c e d by
most antistatic agents is ionic in nature and very sensitive to ambient

II

Fig. 4. Measurement of surface resistivity.

202 A. R. Blythe

humidity. Therefore control of relative humidity becomes an impor-

tant part of surface-resistivity measurements.

4. RESISTIVITY P R O B E T E C H N I Q U E S

Some idea of the resistivity of a material may be obtained by simply

probing the surface of a sheet or block with a pair of metal points
connected to an ohmmeter. The result is rather difficult to interpret
quantitatively, however, because the electric field patterns are com-
plex, with large gradients near the electrode tips. As long as Ohm's
law is obeyed, the local current density is still linearly related to the
electric field at any point, but the current density and field vary in
direction and magnitude from place to place. There is a strict analogy
between the field equations of current flow with the equations of
electrostatic fields, since they both comply with Laplace's equation:
V2V = 0 (8)

where V is the electric potential at any point in the field. Thus

electrodes which inject or drain current from the material are equi-
valent to positive and negative charges. For example, the potential at
a distance r from a point electrode supplying a current I inside a
conductor is given by:
Ip
v= (9)
4,n'r '

which may be compared with that due to a point charge q in a

dielectric medium of relative permittivity e:

V= q (10)
4~eoer
where eo is the permfftivity of free space. Since analytical solutions
have been obtained for many charge distributions, we have a conve-
nient fund of data for solving current-flow problems. This principle is
applied below to various point probe measurements.

4.1. Xwo-point volmne-resistivity measurement

The field equations have been solved analytically for charged prolate
and oblate spheroids, 3 and this enables expressions to be devised for
 Electrical resistivity measurements of polymer materials 203

"I[AIBI_~ 1
Resistance Between Pairs of Simple Electrodes

ELECTRODETYPE ~ RESISTANCEFORMULA
(fi)
'='r d ::::~.~

Hemispheres : d

w//~//~/ / i. . . . . . d v//
1/ / A R =

~ . Discs: d >>'r / '

2

edtes" d >>( >>v i

the resistance b e t w e e n pairs of electrodes of several simple shapes.

Table 1 summarises the results for various forms of electrode con-
tacting the surface of a semi-infinite block of material having an
isotropic volume resistivity. Considering the results for hemispherical
e l e c t r o d e s - - t h e s e roughly correspond to blunt metal electrodes pres-
sed into the s u r f a c e - - i t can be seen that the theoretical resistance is
independent of the electrode separation (always provided that d >> r, i.e.
we are dealing with fine electrodes). The physical explanation is that
the m a j o r part of the voltage drop occurs in the immediate vicinities
of the electrode tips: we may think of the resistance as the sum of a
'spreading' resistance from the source electrode, and a 'convergence'
resistance to the drain electrode.
In this treatment we have totally ignored contact resistance. W e
expect, and indeed find, great variability in resistance m e a s u r e m e n t s
made in this w a y d u e to the difficulty in making good reproducible
ohmic contact with electrode tips. Furthermore, the theory shows
that the m e t h o d only really measures the resistivity of the material in
the small region around the electrode tips, where the voltage drop
occurs. W h e n pointed or r o u n d e d electrode tips are pressed onto a
204 A. R. Blythe

pliable material the area of contact is difficult to control with preci-

sion and, in addition, the material b e c o m e s d e f o r m e d by the pressure
from the electrodes in just that region to which the m e a s u r e m e n t is
most sensitive. A n y surface skin which is less conductive than the
main b u l k - - a c o m m o n feature of s o m e composite materials--will
greatly increase the apparent resistivity too. A n o t h e r spurious effect
that is liable to occur in the all-important region near an electrode tip
is sample overheating due to the high current density there.
F o r the a b o v e reasons a t w o - p o i n t - p r o b e m e a s u r e m e n t of resistiv-
ity is most unreliable and cannot be r e c o m m e n d e d . If such a m e t h o d
is, however, especially required for some reason, it w o u l d b e better to
use disc-shaped electrode tips, lightly pressed onto the surface,
because the material distortion w o u l d be r e d u c e d and the area of
contact m o r e precisely defined than with p o i n t e d tips.

4.2. Two-point surface resistivity measurement

In o r d e r to calculate the resistance b e t w e e n two electrodes contacting

a conductive surface, solutions of the two-dimensional Laplace e q u a -
tion 4 are required. It m a y then be shown that the resistance b e t w e e n
two circular electrodes of radius r at distance d apart on an infinite
sheet of uniform surface resistivity is given by:

R = - - cosh -1 (11)
"n-

Unlike the volume-resistivity case, the resistance is not i n d e p e n d e n t

of electrode separation, even when the electrode separation is much
larger than the electrode size.
Figure 5 illustrates an experimental check on this b e h a v i o u r using
Teledeltos paper, a type of recording p a p e r that is conductive on o n e
side by virtue of a graphitic coating. (The mean surface resistivity as
d e t e r m i n e d by four-terminal m e a s u r e m e n t s on strips cut from the
p a p e r was 4.5 + 7 % kl) with a 2 0 ± 5 % higher value in the transverse
direction than in the longitudinal direction with respect to the origi-
nal roll.) T w o circular electrodes 2 m m in diameter were painted
50 m m apart on a large sheet, and the resistance b e t w e e n them
m e a s u r e d with an A V O meter. The electrodes were then increased in
size, without shifting their centres, and the resistance re-measured. In
this w a y the effect of variable resistivity of the p a p e r was avoided as
 Electrical resistivity measurements of polymer materials 205

Ag - paint "~
etecfrode 2r~
®
F-

/"
Yetedetfos paper
C

6
R
(k~)
/,

1 2 3 4 5
cosh-1 (d/2r)

Fig. 5. Two-point-probe resistance on Teledeltos paper.

much as possible, whilst the effect of changing the electrode

separation-to-diameter ratio was studied, l~he linearity of the graph
confirms the theoretical relationship. The m e a n surface resistivity
calculated from the slope is 4"9 kl~, which is satisfactory when the
variability of the p a p e r itself is taken into account.
The m e t h o d is again sensitive to contact. Use of sharp points on
soft materials is therefore unsuitable because the line of contact will
d e p e n d on h o w far the points are pushed through the surface. Small
ring electrodes gently pressed onto the surface give better control of
this. Generally there is no advantage over concentric ring electrodes,
206 A. R. Blythe

except where the surface is sharply curved and two small electrodes
can m a k e better contact.

4.3. Four-point resistivity measurement

Figure 6 shows the simplest form of four-point probe m e a s u r e m e n t

of volume resistivity. A row of pointed electrodes, equi-spaced
distance d apart, rest on the plane surface of a semi-infinite conduc-
tor. A k n o w n current I is injected at electrode 1 and collected at
electrode 4, whilst the potential difference AV b e t w e e n electrodes 2
and 3 is measured. For this a r r a n g e m e n t Valdes 5 derived the follow-
ing equation:
AV
O = 2wd - - (12)
I
The result is i n d e p e n d e n t of electrode contact area so long as the
radius of contact area r << d. The m e a s u r e m e n t of volume resistivity by
this m e t h o d is also i n d e p e n d e n t of contact resistance, provided that
AV is m e a s u r e d with a sufficiently high resistance meter that AV is

poinl probes

///
~ /
~ /
/
\ /
\ /
\ / /
\ /

Fig. 6. Diagram of four-point resistivity probe.

 Electrical resistivity measurements of polymer materials 207

not significantly affected b y the meter. Consequently, the m e t h o d is

very reliable and is used extensively in the solid-state-electronics
industry.
W h e n the electrodes are applied to a specimen with finite b o u n d -
aries the apparent resistivity Oa that is m e a s u r e d is higher than the
true resistivity, and this is usually expressed in terms of a 'correction
divisor' (CD):

0 = (13)
CD
Uhlir 6 has derived expressions for this p a r a m e t e r by the m e t h o d of
images and has tabulated them for various geometries. For a very
thin conductive sheet, i.e. thickness t << d, the expression for the C D
reduces to:

C D = 2 d In 2 (14)
t

Since the effective surface resistivity is 0/t (see eqn. (4)), we obtain:
-rr AV
o- = (15)
ln2 I
Hence, w h e n the four-point p r o b e is used to measure a surface
resistivity, the result is independent of electrode spacing.
A more general treatment of four-point p r o b e measurements,
which includes alternative electrode arrangements and takes into
account anisotropic resistivities, has been presented by van der
Pauw.7

5. CHARGE DECAY METHODS

Observation of the rate of decay of charges by leakage to earth has

f o r m e d the basis for other m e t h o d s of determining high resistivities,
especially of antistatic films or sheets. The specimen is first charged to
a high potential by o n e of several methods: (1) exposing the surface
to a corona source of air ions; (2) rubbing with another material to
p r o d u c e charge transfer; or (3) connecting the edges to a high-voltage
source. T h e charge on the material is then m o n i t o r e d as a function of
time by means of an electric field meter facing the surface.
208 A. R. Blythe

Quantitative interpretation of the rate of charge dissipation by

conduction over a surface is complex, for it depends on the product
of the system's effective resistance and capacitance to earth. These
two quantities are separately distributed over the surface and related
to the particular geometrical a r r a n g e m e n t that is employed. H e n r y e t
al. 8 have carried out a detailed theoretical analysis which shows that,
in general, the decay is not strictly exponential. Their calculation of
the half-life of charge on the basis of a simple model serves, however,
to indicate the typical relationship with resistivity. T h e y consider a
strip of film bridging, at right angles, two conducting planes; initially,
the charge is deposited on the mid-line of the strip and the conduc-
tors are c o n n e c t e d to earth. T h e half-life tl/z of the initial charge is
t h e n given approximately by:
tl/2 = 3"9 x 10-12(e + 1)(ra (16)
w h e r e o-, e are the surface resistivity and relative permittivity of the
film, and a is the width of the strip. T h e y f o u n d good experimental
a g r e e m e n t for a film held b e t w e e n concentric rings, taking a to be
the annular gap. F r o m this w o r k 8 it is clear that m e a s u r e m e n t s of
charge decay rate on a particular apparatus cannot easily be used to
d e t e r m i n e resistivity in any absolute way, but that the apparatus can
be calibrated by means of a material of known surface resistivity and
used to compare the values for a set of similar specimens. It can be
very useful because the technique is quite simple to apply. Conse-
quently the principle has b e e n adopted in a n u m b e r of standard test
procedures 9 and in several types of commercial instrument.

6. CONCLUSIONS

F r o m the foregoing considerations we m a y draw the following gen-

eral conclusions about resistivity m e a s u r e m e n t s :
1. For low-resistivity materials, contact resistance is of m a j o r
importance so that m e a s u r e m e n t reliability generally d e m a n d s
a four-terminal m e t h o d . The effect of contact resistance is
exaggerated even m o r e with point probes. H e n c e two-point
probes tend to give very unrealiable results, although again a
four-point version solves the problem and m a y be used with
confidence.
 Electrical resistivity measurements of polymer materials 209

2. For high-resistivity materials, contact resistance is of only

minor significance and current leakage, especially over sur-
faces, b e c o m e s the m o r e serious problem. For this reason,
three-terminal methods using a guard electrode are c o m m o n l y
used. Point p r o b e m e t h o d s are usually impractical on account
of the small currents they incur, requiring insruments that
combine high sensitivity with high input impedance.
3. D e d u c t i o n of absolute surface resistivity values from observa-
tions of charge decay rates is very complex. Nevertheless this
kind of observation affords a convenient technique for com-
parative studies, especially for antistatic films and sheets.

REFERENCES

1. Blythe, A. R. (1979). Electrical Properties of Polymers, Cambridge, Cam-

bridge University Press.
2. BS 2050 (1978). Electrical Resistance of Conducting and Antistatic Pro-
ducts made from Flexible Polymeric Material.
3. Moon, P. and Spencer, D. E. (1961). Field Theory for Engineers, New
York, van Nostrand Co.
4. Peek, F. W. (1929). Dielectric Phenomena in High Voltage Engineering,
Chapter 2, New York, McGraw-Hill Book Co.
5. Valdes, L. B. (1954). Proc. Inst. Radio Engrs., 42, 420.
6. Uhlir, A. (1955). Bell Systems Tech. J., 105.
7. van der Pauw,' L. J. (1961). Phillips Res. Repts., 16, 187.
8. Henry, P. S. H., Livesey, R. G. and Wood, A. M. (1967). J. Textile Inst.,
58, 55.
9. BS 2782:Part 2:Method 250A (1976). Antistatic Behaviour of Film.
Charge Decay Method.