DIRECT CORRELATION FUNCTIONS FOR ARGON 521

here only over a limited range their integral check is
only indicative of the behavior of the space integral
for large r. Continued hand calculation of the direct
correlation function for r> 20 A was not considered
practical because of the inaccuracies involved. It is
believed, however, that the calculations for the range
of r presented here are trustworthy. It might be pointed
out that the shape of the 126.7°K experimental scatter-
ing intensity curve appeared somewhat anomalous,
considering the curves corresponding to temperatures
above and below 126.7°K. This might explain the
somewhat singularly oscillatory behavior of the
corresponding correlation function in the range of r
from 1 to 3 A.
Considering the fact that at the present time no
analysis other than that based on x-ray scattering data
has been presented for obtaining the direct correlation
function, one can assert with reasonable assurance that
the correlation function so derived is a reasonable
approximation to its unknown analytical form.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 26, NUMBER 3 MARCH, 1957

Experiments on the Polarization and Decay of Electrets*

G. G. WISEMAN AND G. R. FEASTERt
Department of Physics and Astronomy, University of Kansas, Lawrence, Kansas
(Received June 13, 1956)

Experiments have been performed to test implications of a two-charge theory of electrets. It was found
that the persistent volume polarization of a number of dielectrics can be expressed by analytical functions
which are linear in the applied field and exponential in time. The linear superposition of the effects of homo-
charge and heterocharge is demonstrated for some dielectrics and is shown to be violated for another,
Lucite. The heterocharge and homocharge are demonstrated to be different but interacting entities, their
interaction being given by the static field equations for a three-layer capacitor. A major cause of electret
decay is shown to be the self-depolarization of the electret by its own electric field.

INTRODUCTION dielectric, is assumed to be homogeneous and isotropic.

N extensive study of electrets has been undertaken
A to define the electrical processes contributing to
their formation and decay. Early in the study it be-
came apparent that of the various processes which
have been proposed to explain electret phenomena,
only the two-charge theory advanced by B. GrossI is
eminently successful. The results which follow will be
recognized to constitute a confirmation and extension
of the Gross theory.
A two-charge theory of electrets can be formulated
on the basis that the net apparent surface charge density
of an electret is the combined effect of two charges: one,
the homocharge, is a real charge lying in the surface of
the dielectric; the other, the heterocharge, is a volume
polarization. These charges do not necessarily combine,
but they do interact during both the formation and
decay of the electret according to the static field equa-
tions appropriate to the electret and its electrodes,
which constitute a three-layer capacitor. Such a capaci-
tor together with an idealized guard ring is depicted in
Fig. 1. Regions 1 and 3 are the dielectric-electrode gaps
frequently present, region 1 being adjacent to the
induction (charge-measuring) electrode. Region 2, the
* Supported in part by the Squier Signal Laboratory, U. S.
Army Signal Corps (Contracts DA-36-039, SC-5467 and DA-36-
039, SC-63111).
t Present address: Electronic Tube Division, Westinghouse
Electric Corporation, Elmira, New York.
1 B. Gross, J. Chern. Phys. 17, 866 (1949).
The positive sense of the vectors is that shown. The polar-
ization of region 2 is strongly time dependent for elec-
tret-forming substances. For the present purpose it is con-
veniently though not rigorously resolved into two parts:
one part which responds practically instantaneously
to changes in applied field and is characterized by the
dielectric constant K 2and another partP8 which responds
slowly to changes in the applied field and gives rise
to a quasi-static or persistent polarization which is
responsible for the electret's heterocharge. The electric
fields in the three regions are (in rationalized mks units)
v - (d 2/K2) (u r - P ~o
8 )/
EI (1)
d I+ (K l ddK 2) + (K Ida/Ka),
V +[(d i / K I)+ (da/Ka)] (u r - p.)/ ~o
E 2= (2)
(K 2d I/ K 1) +d2+ (K 2da/ K a)
and
Ea=KIEI/Ka. (3)
These static field equations when combined with the
proper analytical expression for the total volume
polarization in region 2 as a function of field and time,
together with a proper expression for the real surface
charge, yield expressions predicting electret behavior
during formation and decay. This paper describes an
experimental investigation of some of these predictions
regarding the formation, measurement. and decay of

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 522 G. G. WISEMAN AND G. R. FEASTER
- p
FIG. 1. The elec-
tret as a polarized
dielectric with equiv-
alent surface charges
+v ±<T_ and forming
a three-layer capaci-
-
DI - D)
tor. Regions 1 and 3
are ordinarily air or
vacuum. It is often
convenient to apply
the high voltage to
the unguarded elec-
trode.
electrets. Concomitantly, analytical expressions were
fitted to the experimentally determined field and time
dependence of the volume polarization of typical
electret substances.
ELECTRET MEASUREMENT
The net apparent surface charge density of an
electret is determined by measuring the charge Q
induced on an electrode of known area A adjacent to the
electret's surface by means of a dissectible capacitor or
other arrangement. l - 5 The principal features of the
dissectible capacitors used in the present studies are
described in these references. Several such capacitors
were used which were solenoid-operated and enclosed in
sealed chambers and/or ovens to permit control of
temperature, humidity and pressure. A clock-controlled
programing and automatic charge-recording system
was used. 6
Equations (1), (2), and (3) suggest advantages
of the dissectible capacitor method of measurement.
In using the dissectible capacitor, the gaps dl and d s can
usually be made negligible by appropriate procedures
such as molding the dielectric to the lower electrode,
evaporating a thick metallic film onto the sample, or
carefully machining the dielectric and electrode surfaces.
(We have observed that the contact between the in-
duction electrode and the dielectric must not be too
good-as with liquid mercury-or large molding charges
occur on separation.)
Small gaps increase the accuracy of charge measure-
ment. Customarily the value u= -Q/ A is observed,
whereas the electret's net charge density is [from
Eq. (I)J
(u r - P.)= EoV(K 2/d 2)
-Q/ A [(K 2d s/Kad2) + (K211t/K l d 2) +1]. (4)
Only if V = 0 and the effective gap distances d l / K 1 and
2 M. Eguchi, Phil. Mag. 49,178 (1925).
3 F. Gutmann, Revs. Modern Phys. 20, 457 (1948).
4 L. A. Freedman and L. A. RosenthaJl, Rev. Sci. Instr. 21, 896
(1950).
6 S. Kojima and K. Kato, J. Phys. Soc. Japan 7, 650 (1952).
• Feaster, Prosser, and Wiseman, Rev. Sci. Instr. 23,763 (1952).
Downloaded 22 Jan 2011 to 139.179.64.2. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
ds/Ks are small compared to ddK2 can the quantity
-Q/A be taken as the electret's net charge density.
For an electret stored between well-fitted and short-
circuited plates (i.e., shielded), Eq. (4) reduces to
(ur-P.)=-Q/A. If V is not zero, the measured value
- Q/A contains an additional term EO V (K 2/ d2) arising
from the nonpersistent polarization of the dielectric.
During electret formation, a potential difference V is
applied to the capacitor terminals. For most quantita-
tive work it is desirable to maintain the electret at a
single temperature during both formation and decay.
Examination of Eq. (1) reveals that unless the gaps are
much smaller than the electret thickness d2, the fields
El and E2 which according to the theory are responsible
for the formation of the homocharge and heterocharge,
respectively, are dependent upon the gaps dl and da
and, perhaps more important, upon the transient value
of the electret's charge. Thus, unless the gaps are small
the results are difficult to interpret. Interposing insula-
tors other than air or vacuum in the gaps for some
purpose such as to arrest homocharge formation adds to
the number of gaps and can add the complication of the
insulator's polarization which changes at an unknown
rate with time.
The gaps play another important role in limiting the
maximum measurable charge density. This matter is
discussed in the following section.
HOMOCHARGE
According to the theory, the homocharge is deposited
in the dielectric surface during electret formation partly
as a consequence of the time dependence of p.: as
region 2 becomes polarized under the influence of the
applied field, the interfacial fields increase according to
Eqs. (1) and (3) until dielectric breakdown occurs,
depositing surface charges ±uT (homocharges) in the
dielectric surface until El is lowered below the break-
down field. Interfacial breakdown has been investigated
by Gross 7 for an essentially nonabsorptive dielectric,
polystyrene, and his results have been verified in these
laboratories for polystyrene and another nearly non-
absorptive dielectric, paraffin wax. Figure 2 illustrates
this process for an absorptive electret-forming sub-
stance, carnauba wax, and similar results were obtained
with two other absorptive materials, Plexiglas and
Gelva V-7 (polyvinyl acetate).8
A homocharge deposited in the manner postulated
would be expected to have a discontinuous distribution.
Such discontinuities were revealed by dusting the
dielectric surfaces in question with charged powders or
charcoal dust. Even a carnauba wax electret that had
been stored shielded for five years revealed a discon-
tinuous charge pattern.
A common observation of electret behavior is that the
maximum observable charge density is about 3X10-l0
couljcm2 for an electret in room atmosphere. This limit
7 B. Gross, Brit. J. Appl. Phys. 1,259 (1950).
8 F. Prosser, thesis, University of Kansas, 1953 (unpublished).
 ELECTRETS 523
is imposed by interfacial discharges which occur during
storage or measurement whenever the field in region 1
exceeds the dielectric breakdown strength of that
region. Breakdown is likely to occur during measure-
ment because as d1 is increased the breakdown strength
of region 1 decreases. Of course El also decreases with
increasing gap distance as shown by Eq. (1), but
unfortunately the rate of decrease of the breakdown FIG. 3. Comparison of computed and measured values of the
intrinsic polarization function of polystyrene.
field with increasing gap distance is ordinarily greater
than the rate of decrease in E 1• The situation is even 3 59
more unfavorable to high measured values of surface wax and plastic electrets. • • Evidently the pulses ob-
charge if V is allowed to increase appreciably during served with BaTiO s electrets arise from sporadic break-
the measurement. This is easily prevented by a shunting down "of the gaps as the volume polarization of the
capacitor. Maximum obtainable surface charge densities specimen decays.
were computed by Gross.7 Equation (1) shows that El HETEROCHARGE
can be kept small by decreasing the effective electrical
thickness d 2/K2 of the electret. Accordingly, BaTiOs According to Gross's theory, the polarization which is
samples were polarized and, because of their high responsible}or the heterocharge is given by
dielectric constant, homocharges as large as 13X 10- 9
P(t)='L, EiII(t-ti) (5)
couI/cm2 were obtained on electrets in room atmosphere. i
According to Eq. (1) the applied potential difference where the subscripts denoting region 2 are omitted and
V required to cause breakdown in the gaps should be where II, called the intrinsic polarization function, is the
much smaller for a substance like BaTiOs which has a polarization which results from the application of a unit
high dielectric constant. Experiments showed this to be step function of electric field. Ei is a change of field in
the case j for example, only 45 v applied to a 6-mm thick region 2, a reduction being indicated by a negative
sample of ceramic BaTiO s for 20 hr at 26. 7°C yielded an sign on E i .
electret with a homocharge of 1 X 10-9 couI/ cm2 •
The stronger BaTiO s electrets were found to change 1. Measurement of IT (t)
their charge discontinuously. These discontinuities or Several methods for measuring the polarization
noise pulses were investigated with an oscilloscope and response of a dielectric are known. lO- lS We used the
counting apparatus and it was found that the total dissectible capacitor method. 7 High voltage was applied
number of pulses occurring during an electret's decay to the lower electrode. The upper (guarded) electrode
increases with the period, temperature, and field of was grounded except when lifted for a few seconds to
polarization. The pulse rate, but not the total number of make charge measurements. Although this method has
pulses, was dependent upon the electret's temperature inherent advantages, three likely sources of error exist.
during the decay period. Pulses were not obtained when' First, charges are often generated upon contact between
the specimens were coated with silver or aluminum, the induction electrode and the dielectric. Fortunately,
a result distinctly different from the pulses observed in such charges are often negligible or under certain condi-
tions can be measured and subtracted out. Second,
charge is transferred across the gap at high values of
4'10- 9 CoullCm2
polarization [see Eq. (1)]. This charge transfer can be
(0) 3 practically eliminated in many cases by using smooth
surfaces and enclosing the dissectible capacitor in a good
vacuum. In the case of some gassy dielectrics, evacua-
tion of the interfacial region has evidently been un-
14 kv
successful. Third, errors previously discussed arise from
the finite gaps between the electrodes and the dielectric.
For substances having an ac dielectric constant of
-2
ordinary magnitude, this error can be made negligible
by using well-fitted surfaces and thick specimens. Care
must be taken to minimize the exposure time when the
induction electrode is lifted for a charge measurement.
FIG. 2. Deposit and removal of homocharges on a machined
carnauba wax disk 0.388 cm thick at 24°C. Measuring cycle: V 9 N. P. Baumann and G. G. Wiseman, J. App!. Phys. 25, 1391
applied for 2 min, V =0 for 15 sec, <T measured (about 5 sec), next (1954).
V applied. Point (a), initiation of interfacial breakdown; point 10 K. S. Cole and R. H. Cole, J. Chern. Phys. 10,98 (1942).
(b), initiation of breakdown in opposite direction. Downward 11 R. Moon, thesis, University of Kansas, 1952 (unpublished).
curvature of initial values and scattering of points are due to 12 W. Kauzmann, Revs. Modern Phys. 14, 12 (1942).
dielectric absorption and random character of interfacial 13 D. J. Mead and R. M. Fuoss, J. Am. Chern. Soc. 63, 2832
discharges. (1941).

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 524 G. G. WISEMAN AND G.
16X10" • The effect of a field pulse of duration T can be ob-
":I 12
..
]I
..::::,
Z
:>
8
o
o dicts that the decay curve is in general not the inverse
c: 4 ° E -1.10 kvl.552 em
.. E= L80kvl.552 em
o 4 8 12 16 20 24 28 32
Time in Hours
FIG. 4. Intrinsic volume polarization of carnauba wax for field
strengths of 1.99 kv/cm and 3.26 kv/cm. Sample was prime
yellow carnauba wax, melted and frozen in a glass dish and turned
flat on a lathe. Measurements were taken at 10- 5 mm of Hg pres-
sure and 40°C. A small initial charge has been subtracted from
all readings.
The first lI(t) measurements were made on poly-
styrene because it is nearly nonabsorptive; its II (t)
curve should be a simple step whose ordinate is simply
related to the dielectric constant K by the relation
1I(t) to(K -1). Figure 3 shows the agreement between
computed and measured values.
Polarization response curves were obtained for a
number of electret materials. Figure 4 shows the agree-
ment of the lI(t) values for carnauba wax at widely
differing fields. The relatively small discrepancies
between the lI(t) values for high and low fields are
attributed to experimental errors. The assumption of
linearity is not violated in this case, a result which is
consistent with recent measurements of Gerson and
Rohrbaugh14 who found that a dc field of 8.1 kv/cm
produced no effect on the complex dielectric constant
of polarized carnauba wax below SO°c. The solid curve
in Fig. 4 is a plot of the expression
II (t) = [6.60+3.26(1- e- t /1. 48 )
+5.97(1-e-t/12.5)]Xl0-1l,
where the time is measured in hours. Because data
cannot be taken at very short times, the value of II(O)
or 6.60X 10-11 does not correspond to the ac dielectric
constant.
The polarization response of carnauba wax at 30°C
was found to be smaller and slower:
II(t) = [2.70+ 1.82 (1_e- t / 13 .2 )
+4.93(1-e-t/120)]XIO-ll.
Polarization response curves were obtained for a number
of other substances: plastics, waxes, and inorganic
materials.
14 R. Gerson and J. H. Rohrbaugh, J. Chern. Phys. 23, 2381
(1955). These authors found, however, that both the real and
imaginary parts of the dielectric constant are increased markedJy
by the dc field between 50°C and the softening temperature.
Moreover, such increase is greater at the lowest frequencies
observed, 50 cps.
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R. FEASTER
2. Growth and Decay of Heterocharge
tained by applying Eq. (5) with Eb= -Eaand tb=ta+T
where the subscripts a and b refer to two step fields.
The function II must be known either graphically or
analytically. Note that the superposition principle pre-
of the growth curve, an observed fact of electret
behavior.
Using Eq. (6), the polarization predicted from a field
step of 3.26 kv/cm applied for 6 hr was computed and
is represented by the solid curve of Fig. 5 along with the
measured values. Agreement between measured and
computed values is considered good in view of the in-
herent errors of procedure". Apparently (and deliber-
ately) little or no homo charge was transferred across
the gap. Thus the validity of the superposition principle
has been demonstrated for the growth and decay of
the heterocharge.
ELECTRET BEHAVIOR
1. Electret Formation
If a dielectric possessing a heterocharge is shielded,
the presence of a surface charge (homocharge) should
merely displace the net charge values in the homocharge
direction by a constant amount. To test this idea, a
carnauba wax sample was polarized just as in the pre-
vious experiment except that a homocharge was de-
posited by the expedient of temporarily admitting air
to the experimental chamber and raising the induction
electrode. The amount of homocharge (Jr so deposited
cannot be measured directly but it can be inferred from
the displacement of the charge vs time curve. Figure 6
shows the results of the experiment. The solid curve
shows the behavior computed from the 1I(t) function
with an amount of homo charge added (at t= 5 hr)
sufficient to make the experimental and computed
(6)
Time In Hours
0r-__~4__~8r-__,12~~1:6::::20~==2t4===528~
2
° 0 Meosurecl Values
(7)
- - Compulecl From TT(t)
f---
Field ......... - •• __ ._
Off •• --- •• ------___________ .
HeIt!;i,
6 •
·'69 L.-__-'--__......._ - - "_ _' - - _ - ' - -__- ' - _..............J
FIG. 5. Test of the superposition principle for the heterocharge.
The applied field was 3.26 kv/cm and the temperature was 40°C.
The broken line represents the computed polarization due to the
initial field step.

values agree at 8 hr. This was done because the electret
was unshielded for several minutes during the collection
of homocharge, which renders the immediately succeed-
ing charge measurements too low. The agreement
between computed and measured values is regarded as
sufficiently good to demonstrate the linear superposing
of the effects of heterocharge and of homocharge. In
this case the heterocharge and the homocharge did not
combine appreciably.
The charge behavior depicted in Fig. 6 is seen to be
that of a typical electret. Heating the dielectric during
polarization is seen to be unnecessary, an effect that
was discovered previously.l,a In fact, if the results are to
be interpreted quantitatively, the specimen should be
kept at constant temperature because the polarization
response is very sensitive to temperature.
It is well known that the persistent volume polariza-
tion of many materials is not reversible. An example of
this is that the polarization of Lucite at 66°e in a field
of 2.05 kv/cm as measured by the dissectible capacitor
method appeared to increase linearly with time after
about 160 hr rather than reaching a saturation value.
To extend the measurements to long times, a "cumula-
tive" method was employed in which charge measure-
ments proceed normally until the charge density attains
a value which is large but comfortably below the gap-
breakdown value whereupon the specimen is deliber-
ately exposed to an ion cloud generated by alpha
particles. The net surface charge is thereby drastically
reduced, the amount of reduction being determined by
surface charge measurements taken immediately before
and after exposure. This known reduction is then added
to subsequent readings and the process is repeated. In
the case of Lucite, a smooth increase in the cumulative
polarization was obtained which showed no breaks
where ion accumulation occurred. The apparent polari-
zation rate was constant from 160 to 900 hr, the rate
corresponding to a volume resistivity of 3.S2X 1017
ohm-cm. Shielding the electrodes at 900 hr resulted in
a typical decay curve but its shape did not correspond
-9
4'10
Homo
t 3 Field
Off
2
~ ensuing slow charge decrease from 20 to 40 hr is at-
N I
.3 0
T tributed primarily to ion collection, the heterocharge
.... 4 )~ 12 16 20
Homl Time in Hours
:> A~~
o
o 2
.!:
~ ...... -
b 3 ° 0 Measured Values
- Coml>uted Values
4
Hetero ........ -- ... _---- -----
l 5
6·16 9
FIG. 6. Test of the superposition principle in the presence of a
homocharge. Specimen and conditions are the same as those
described in Figs. 5 and 6. The upper dashed line represents the
computed charge density that would have been obtained without
the addition of the homocharge u r •
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525
5·10-9;:-_...-_-.-_--.._ _r-_-r-_-,-_--,_--, 50·
~ ~-·~-----··--·1
-;00 r / . . ' 0
U ....... Electret Shielded ' .. .. ~ .. -.. ------- ______________ _
.5
b ~ Electret Exposed
5'10-90
---- T emp.raturl
10
20 30
AQ' in Hour.
FIG. 7. Demonstration that an electret's decay can be caused
primarily by self-induced volume polarization. Net charge is
plotted above the zero line if it is homocharge in sign, below zero
if it is heterocharge. Temperature is in °C.
to the rise curve and only a very small homocharge was
obtained upon reversal.
Apparently a large part of the net charge density of
this specimen arose from a pileup of ohmically-con-
ducted charge at the dielectric-electrode gaps. This
charge then combines with nearly all of the externally-
deposited surface charge-a result distinctly different
from that observed with carnauba wax.
2. Electret Decay
The charge decay of an unshielded electret is often
attributed primarily to its collection of stray ions. How-
ever, the theory predicts that an unshielded electret
has an internal field E2 [see Eq. (2)J strong enough to
induce rapid polarization of its own volume. Externally,
this effect is indistinguishable from a decay of the
electret's homocharge except that changes in the
homocharge are not reversible. To test this idea, a
well-shielded Gelva V-7 electret was permitted to
undergo a normal charge reversal at room temperature
and pressure as shown in the first twenty hours of Fig. 7,
such reversal being due to the thermal decay of the
heterocharge. The electret was then cooled to about
- 20 0 e after which the induction electrode was lifted
8 cm. (Subsequent charge readings were made by
~ 0 temporarily lowering the induction electrode.) The
24 26
being nearly frozen in. At 40 hr the electret (still un-
shielded) was warmed and volume self-polarization
occurred. Recooling at 53 hr tended to preserve the
static conditions although a slight increase in net
charge (decay of heterocharge) is observable after the
----------- electret was reshielded at S5 hr. Warming the shielded
electret at 66 hr permits thermal decay of the hetero-
charge to occur, which appears as a recovery of the
electret's original charge. In this instance as in many
others, the principal cause of the decay of an unshielded
electret is self-depolarization rather than ion collection.
 526 c. C. WISEMAN AND G. R. FEASTER
...-
~ Eo
LL.
Time
~
..
a.
a.
« Eb
L...--
I--Q~-·'t"-I'b .,. c-----
FIG. 8. The application of two polarizing fields is regarde~ as t.he
successive application of 3 superposed field steps of mfimte
duration.
Similar experiments were performed which show
(1) that the original electret reversal can be delayed for
an arbitrary period by cooling, (2) that an electret
charge reversal can be attained even with the electret
unshielded but that the reversal is retarded, (3) that
an unshielded decaying electret will show a rapid
recovery when shielded.
A disk of Gelva V-7 was prepared in such a way that
it had never acquired a surface charge and had never
been exposed to an electric field. It was then given a
surface charge by rubbing and immediately shielded.
It was kept well shielded for scores of hours and its net
charge remained nearly constant, but when the shield
was removed it lost about half its charge in 24 hr. This
decrease is attributed primarily to self-induced volume
polarization rather than to ion collection and ohmic
leakage because when the specimen was reshielded it
regained 90% of its former charge in 48 hr. Restoring
the shield had reduced the internal field to a low value
and permitted the thermal decay of the self-induced
volume polarization.
The results of all these experiments on electret decay
are consistent with the macroscopic, two-charge theory
of electrets.
. 3. Electrets Undergoing Two Charge Reversals
The polarization of some electret-forming materials
is a linear, but time dependent, function of the applied
field. For some materials, notably carnauba wax, the
polarization response to a step field E can be fairly well
represented for periods of hours or days by the
expression
p= [Bo+BI(I-e-All)+B2(1-e--A21)]E,
where t is the time measured from the instant E is
applied. The B's and the A's are constants. Such a
dielectric obeys the principle of superposition; it
"remembers" each application of the field to which it is
subjected. To test this idea further, an electret was
formed by the application of two rectangular polarizing
field pulses rather than the usual one. This process is
conveniently regarded as the successive application of
three step fields, Ea, E b, and Ec, each of infinite duration
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and applied at the times shown in Fig. 8. The last step
Ec is chosen so as to bring the final field to zero (electret
shielded). The times a and b are the duration of the
two rectangular field pulses and are variable paramet~rs
for the experiment. The time c is regarded as a runnmg
time variable indicating the elapsed time after the
applied field is brought to zero. Letting E a, E b, and Ec
represent the magnitudes of the three field steps and
writing R in place of E b/ E a , we have
q= {Ble-Alc[(I-e-Al(aH»)- R(I-e- A1b )]
+ B2e-A2c[(I-e-A2(aH»)-R(I-e-A2b)]}Ea (9)
for the net charge density after the electret is shielded
Thus, the dielectric's charge density after being
shielded may be considered to result from two expo-
nential .decays, one fast and one slow. By a suitable
choice of R and the times a and b, these two parts may
be given values of opposite sign. However, in no case
will there be a reversal in the sign of charge density
subsequent to the time c=O. But if a constant value of
charge (say a surface charge) having the proper sign
and magnitude is superimposed on the system, a double
charge reversal can be obtained.
In view of the above argument, specimens of car-
nauba wax and Saran!5 were subjected to two rectan-
gular polarizing field pulses and given a surface charge.
The Saran was polarized at 35°C in a dry atmosphere by
applying + 250 v to the lower electrode for 5 hr,
exposing its surface to ionization produced by alpha
particles for 15 sec out of each minute for 30 min, con-
tinuing the application of the +250 v for 16! hr, apply-
ing -1000 v to the lower electrode for 40 min, and then
shielding the specimen. Surface charge readings were
then made and recorded automatically about once per
minute with the results shown in Fig. 9. Similar results
were obtained with the carnauba wax specimen. The
5 ·1 OI°r--r-r...,.,.TTI"'-""-'-'T'"rTT"[--.--.--r,-1"TT"IJ
4
Homo
3
Ne 2
u
......
~ 0~~~~~~-L-~~~~-\-L~~4
u
c
."
b 2 .'
(8) 3
Hetero
4 rr at c. 0
-10 ~--
5'10 I
10 100 1000
Time ·c· In Minutes
FIG. 9. Charge density of a Saran electre.t polarized so_as to yield
two spontaneous charge reyersals. PolarIzmg fiel~s: E.= -O.~7
kv/cm applied for 21, hr, Eb= +1.49 kv/cm appIJed for 40 mm,
T=35°C.
16 Saran (vinylidene chloride) samples t in. thick were furnished
by Dow Chemical Company, Midland, Michigan.
 ELECTRETS
general features of the charge behavior predicted,
notably the double reversal in sign, are thereby demon-
strated. Attempts to make the experiment quantitative
failed because the electret was unshielded and exposed
to room atmosphere during the ion-accumulation
period. However, these results are consistent with the
two-charge theory. The piezoelectric and pyroelectric
theories of electret formation can hardly be extended to
explain such a double charge reversal, especially when
the entire experiment was performed at constant tem-
perature with a plastic dielectric.
4. Classification of Electret Substances
In the past it has been customary to classify sub-
stances according to whether they acquire homo-
charges, heterocharges, or exhibit no electret behavior.
According to the present theory all electrically absorp-
tive insulators could be made to exhibit typical electret
behavior: acquisition of either heterocharge or homo-
charge, spontaneous charge reversal, and/or increasing
homocharge when shielded. We have observed that
such diverse substances as for example para-methoxy
diphenyl, sugar, glass, and sulfur as well as the sub-
stances discussed elsewhere show the electret effect.
On the other hand rosin, which is an electrically absorp-
tive dielectric of high resistivity, has been classified as
a substance which yields heterocharges only.3 This
discrepancy was investigated.
We first measured the molding charge acquired by
rosin and found that when aluminum foil is stripped
from rosin after being in contact with it during solidi-
fication, the rosin is left with a positive molding charge
of about lXIQ-9 coul/cm2• This is as large as the
typical electret charge on rosin. Consequently electrets
were made with the upper polarizing electrode at a
positive potential to enhance the homocharge with the·
result that electrets were obtained which had a net
homocharge that decayed slowly. These specimens
were formed by melting commercial rosin at 120°C and
applying 11 kv (about 18 kv/cm) while the specimens
cooled to room temperature. Cooling required 13 hr.
Although it should be possible to do so, we did not find
a combination of time, temperature, and field which
wou~d produce electrets undergoing a spontaneous
charge reversal. However, by raising the field at the
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S27
proper time during the polarizing period, rosin electrets
were made which gave fairly consistent charge reversals.
Best results were obtained by raising the field after the
electret had cooled to room temperature. Incidentally,
an extremely large amount of plastic flow occurs in
rosin at about 44°C which is apparently not correlated
with a corresponding change in electrical polarization.
Other examples can be cited of apparently "non-
electret" substances exhibiting the electret effect under
proper circumstances. For example, Cerese AAA Wax
has a very long relaxation time at room temperature
and will not undergo an electret reversal (in a reasonable
time at least) unless warmed to about 30°C. In the
other extreme, typical electret behavior cannot be
readily observed in a paraffin-ethanol mixture unless
the mixture is cooled to about -13SoC, where typical
electret charge reversals occur slowly enough to be
easily observed by the usual techniques. 16
Other substances show remarkable changes in their
ability to acquire static volume polarization with
changes in absorbed water or other vapor, the presence
of the vapor usually increasing the rate and amount of
polarization. These effects are the subject of another
paper.
These experiments show the futility of classifying
insulators according to their electret-forming properties.
This is to be expected because implicit in the present
theory is the idea that the electret effect is not confined
to a few special substances but that all solids capable
of acquiring a surface charge and a volume polarization,
i.e., all solid insulators, exhibit the electret effect, albeit
oftentimes too fast or too slow to measure with conven-
tional apparatus.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the help of their
colleagues in this work, especially Dr. F. Prosser for his
help with the measuring apparatus, Mr. Ralph Moon
for his measurements of complex dielectric constants,
and Dr. N. P. Baumann and Mr. John W. Cooper for
their measurements of noise pulses. We have been
aided by helpful discussions with Mr. E. G. Linden of
the Squier Signal Laboratories, Dr. B. Gross, and
Professor J. D. Stranathan.
16 J. S. Fisher, thesis, University of Kansas, 1954 (unpUblished).