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1988 J. Phys. D: Appl. Phys. 21 1661

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J. Phys. D: Appl. Phys. 21 (1988) 1661-1677. Printed in the UK

H Block and J P Kelly

Centre for Molecular Electronics, School of Industrial Science, Cranfield Institute of
Technology, Cranfield, Bedfordshire MK43 OAL, UK

Abstract. Electro-rheology is the phenomenon in which the rheology of fluids is

modified by the imposition of electric fields. In this Review the nature of the fluids
active in this role are presented and the influence of important variables such as
shear rate, field strength, field frequency, temperature and fluid composition are
described. Also discussed are the dielectric behaviour of dispersions in flow since
this is of direct bearing on the phenomenon of electro-rheology. Various models for
electro-rheology are presented and assessed. We also describe how recent
developments in new classes of electro-rheological fluids have resulted from a
clearer understanding of the probable electrodynamic origins of the effect. The
Review concludes with an overview of the practical applications that electro-
rheology has and may have in the future.

1. Introduction another curve such asD is often followed leading to an

apparent static yield stress lower than 5,). T h e T,, value
The phenomenon of electro-rheology (ER) described in is subsequently attained after a short period of time.
this Review was first reported by WM Winslow in 1947 Suchcomplex.irreversibleandoftenirreproducible
[ l ] and occasionally bears his name. It related to changes behaviour only occurs in regions of low 9. For most
in rheology of dispersions which are consequent upon reports of E R thephenomenonhasnotevenbeen
theapplication of electricfields(E)and.depending observedbecausemeasurementsatsufficientlylow ;;
upon the nature of the fluids and the conditionsof flow havenotbeenmade.However, it is generalfor T,,
and field. manifests itself in an increase of resistance to measured as a yield value to exceed the excess yield
flow and in some cases. the conversion of fluid to solid stressT(E) - ~ ( 0 )underflow. As developedin 0 5 ,
behaviour. Indeed the tl’pesof possible response to the there are possible theoretical grounds for believing that
imposition of electric fields is quite complex for many T ( E )- s(0) might decrease at high 9 (curve E) but such
E R fluids even when. as is often the case, the fluid is an effect has not been observed. Indeed. the general
NeLvtonian in the absence of an electric field. Figure 1 experience is that T(E) - ~ ( 0 tends ) to remain constant
illustrates the nature of the changes that can occur. As with ;; once the low flow regime has been exceeded.
is implied by thisfigure.someform of field-induced The differential viscosity defined as d r(E)/d;i is not
Ringhnm behaviour is common. Thus on applying elec- markedly E-dependent.
tric fields to such fluids the dependence of shear stress Whatshouldalsobeappreciatedfromfigure 1 is
( T ) on shear rate (;;) shows that both a field-induced that ill defined uses of theterm ‘viscosity’ canlead
increase in T and often the development of a more or to confusion and false conclusions. For example. the
less well defined static yield stress (T,, in curve B). When parameter T(E),/;;. often termed the apparent electro-
the latter is the case, it can be said that the fluids become viscosity.hasbeenused by anumber of workersto
solids. although it is not at present known Lvhether they describetheeffect of E R . andstatementshavebeen
undergo slow creep or are elastic when stressed Tat < S[, madethatthisviscosityundera field droppeddra-
o r Lvhether some form of work hardening occurs under matically with y from very high values to the no-field
these conditions. The onset of flow occursat T = T,, value. Although strictly this is true, it is quite wrong to
andebentuallytherefollows a flow regimeinwhich implythatinconsequencethe E R phenomenon has
T(E) > ~ ( 0at) fixed .;’ I t has been the authors’ exper- disappearedathigh ;. All that has happened is that
iencethattheflowbehaviourimmediatelyafterthe from an infinite value j ;; = 0 andfinite
of 7 , ] ( E ) / ; at
onset o f flow can show behaviourof the type illustrated T[,(E). T(E)/;;- T(O)/’;; when ?-+ x since then
by curve C rather than cur1.e B. with a rapid drop of ~ ( 09) T(E) - ~ ( 0 ) however.
; the conclusion that there-
T(E) at low T but without dropping to ~ ( 0 ) In . contrast. fore T ( E )- r(0) = 0 is invalid. More serious than state-
when approaching the no-flow state from one of flow ments such as theseis the fact that much published data

0022-3727%3,121661t 17 $02.50 0 1988 IOP Publishing Ltd 1661

H Block and J P Kelly

fields [3], which do not form part of this Review. These

phenomena are both different in kindfromthetype
described here and relate to rather minor changes in
viscosity. All the ER fluids that are the subject of this
article comprise dispersions of solid particulates within
an insulating oil. It is in the physics and chemistry of
the particulates and the naturesof the phase boundaries
that the phenomenon of E R originates. Thus. as far as
the authors are aware, simple no isotropic liquid exhibits
field-induced
Bingham behavioureven
orlarge
increases of viscosity. For obvious reasons of electrical
insulation the dispersions have to have non-conducting,
organicliquidsastheirdispersing medium,butfre-
quently water and, on occasion, other polar fluids such
as ethanol or diethylamine are required to enhance or
evenprovidean ER effect.Thisrequirementforthe
traditional ER fluids to be moist was an important obser-
vation first made by Winslow [ l , 41 and it has proved
tobeaseriousrestrictiononsome of thepotential
Figure 1. Some alternative flow situations in ER. Curve A:
the shear stress (t)plotted against shear rate (f) applications of the phenomenon, although recentlya
dependence in the absence of field ( E ) for an ER fluid class of dry ER fluids has been developed [5-7]. It is also
assumed for simplicity to be Newtonian. Curve B: a worth recalling that there is a magnetic analogue to the
simple and often quoted case of €-induced Bingham ER phenomenonwhose active substratesareferro-
behaviour with static yield stress to.Curve C: the situation magnetic dispersions; namely the ferrofluids.
showing a fluid with a rapid drop in t(E) following the onset
of flow but still with an excess shear stress. Curve D: the Exceptfor
these
general characteristics, many
return from a flow situation leading to a temporary static described fluid formulations are not well characterised
yield stress less than the final value achievedon standing chemically, and indeed in their composition ER fluids
(to). Curve E: the possibility, not so far reported, of a exhibit a very extensive diversity as illustrated in table
reversion of t(€) towards 40)at high f. Arrows indicate 1. There are, however, a numberof common attributes
direction of changing f for curves C and D.
belongingtothematerials which formthe basis of
ER fluids. They all comprisedispersedpolarisableor
conducting materials and it is commonly agreed that the
phenomenon of ER has its origin in some formof induced
on ER quotes apparent viscosities rather than actual t polarisation
originating
within around
or the
values. Theproblemthen is that it can be difficult particulates. Thereis less agreement about what occurs
to reverse such calculations using numerical data that subsequently toinducethe rheologicaleffects; we
frequently have to be estimated from published graphs, discuss the various hypotheses for the mechanism for
which are ofteninsufficiently accurate to detect possible ER in D 5 , but before doing so the chemical nature and
changes in enhanced shear stress, particularly at high physical properties, both rheological and dielectric, will
3.Fortunately, reported changes in apparent viscosity bedescribed. Since the ER phenomenon involvesat
reflect <E) changes when measured at constant 3 so least the twin disciplines of rheology and dielectrics, an
thattheinfluence of othervariables in <E) canbe interdisciplinaryapproach is required.Forthesame
established in such cases. reasons, the variables influencing the phenomenon are
The phenomenon of ER is notonly of academic multitudinous, involving variation of t with electricfield
interest, but also has considerable applicability in engin- frequency f, temperature T , composition in terms of
eering technology. This is because with modern fluid volume fraction of particles p, water or other additive
formulationsconsiderable yield stresses,bothstatic concentration, dielectric constants andviscosities of the
(greater than 10 kPa) and dynamic (about 5 kPA), can dispersingoils,as well as E and .j. This multiplicity
betransmittedfor fields of theorder of kVmm". of parameters reflectsa needfor extensiveexperi-
Further, these loads can rapidly be switched withquoted mentation, only some of which appears to have been
timescales under a flow of about lop2S . Thus it is that undertaken. Those influences that are known at present
ER is of considerable practical importance as well as are presented in the following sections.
providing a most interesting scientific phenomenon for
study. In 0 6, we shall discuss these various applications
of ER, but before doingso the effect, its causes and how 2. ER fluids and the ER phenomenon
these can berelatedtothenature of ER fluids are
discussed. Winslow [4] first reported quantitative data on ER for
There area number of other phenomena such as the an ER fluid based on dispersed, moist silica gel. He
visco-electriceffect in emulsions [2] andchanges of observedanapproximatedependence of enhanced
viscosity of homogeneousconducting liquids under shear stress ( t ( E )- ~ ( 0 ) on
) the square of the voltage.

1662
 Electro-rheology

Table 1. The composition of ER-active fluid dispersions.

Dispersed
phase Dispersant Additive Reference

Alginic acid Polychlorinated biphenyls, poly(tri-fluorovinyl Water

Aluminium dihydrogen
tripoly-phosphate
Aluminium oxide (as coating on
aluminium)
Calcium titanate
Carbon
(coal)
Carboxymethyl dextran
Cellulose
Clays”diatomite, kaolinite,
montmorillonite, vermiculite,
polygorskite
Copper phthalo-cyanine
Gelatine
Gypsum
Ion exchange resins-strong
and weak, acid and base, but
otherwise unspecified
Iron(l1) oxide
Iron(ll1) oxide
Lime
Pentaerythritol
Phenol-formaldehyde type ion
exchange resins based on
resorcinol or a-resorcylic acid or
1,5-dihydroxy naphthalene or
2,2‘,4,4‘-tetrahydroxy
benzophenone-as lithium,
sodium, potassium or
guanidinium salts
Phthalocyanine
Piezo-ceramic powder
(unspecified)
Poly(acene-quinone radicals)
based on anthracene or
naphthalene or terphenyl or
ferrocene or pyrene or
phenanthrene
Poly(acry1ic acid) cross linked
with divinyl benzene-as lithium
salt
Poly(methacry1ic acid)
as lithium salt
Poly(methacry1ic acid) cross-
linked with divinyl benzen-
lithium or guanidium or mixed
lithiumichromium salt
Poly(viny1 alcohol)
chloride), o-dichlorobenzene,
p-chlorotoluene, xylene, plus mixtures of
above
Mineral oil Water
Spindle oil or water
Naphthenic oil Non-ionic surfactant
Transformer oil, olive oil or mineral oil
‘Heavy’ oil Water and surfactant
Polychlorinated biphenyls or Water and sorbitan
poly(trifluoroviny1chloride), mono-oleate or sorbitan
o-dichlorobenzene or xylene or mixtures mono-sesquioleate
of the above
Chlorinated insulator oil Water
Liquid paraffin or hydraulic oil or dibutyl Aqueous ammonium
sebacate or oleic acid or chlorotoluene or chloride and other
silicone oil electrolytes
Kerosene, plus 1Yo poly(isobutene) Water
Vaseline oil Water
Hydrocarbons Water
Transformer oil Diethylamine
Lubricating oil Water
Paraffin grease or silicon oil None
Transformer oil or olive oil or mineral oil
Transformer oil or olive oil or mineral oil
Di-n-butylphthalate or di-n-octylphthalate or Water
di-n-decylphthalate or di-isodecylphthalate
or tri-n-octyl trimellitate or tri-2-ethylhexyl
trimellitate or tri-isodecyl trimellitate or
tri-cresyl phosphate
Petroleum fractions or dibutyl sebacate or Water and surfactant
di-2-ethylhexyl adipate
Petroleum fractions or dibutyl sebacate or Water and surfactant
di-2-ethylhexyl adipate
Transformer oil or olive oil or mineral oil
Mineral oil or p-xylene or Water and glycerol
poly( p-phenylmethyl siloxane) oleates
Brominated diphenyl methanes Water
Silicone oil None
Mineral oil or p-xylene Water and glycerol
oleates
Chlorinated hydrocarbons or liquid paraffin/ None
paraffin grease or silicone oils
Chlorinated hydrocarbons or fluorolube FS-5 Water
Chlorinated hydrocarbons or fluorolube FS-5 Water
Dipolar halogenated aromatics or Water
penta-chlorophenyl phenyl ether
Chlorinated hydrocarbons or fluorolube FS-5 Water
Hydrocarbons Water

1663
H Block and J P Kelly

Table 1. Continued.

Dispersed
phase Dispersant Additive Reference

Silica Kerosene or dibutyl sebacate Water and soaps,

sorbitol or fatty acid
esters
Naphthenic oils Non-ionic surfactant
Kerosene plus 1% poly(is0 butene) Water
Hydrocarbons Water
Cetane Diethylamine
Mineral oil or xylene or silicone oil Water and glycerol
oleates
Petroleum distillate or transformer oil or Water or wateriglycerol
silicone oil and surfactant
Sodium carboxymethyl cellulose Paraffin or silicone oils Water
Sodium carboxymethyl dextran Polychlorinated biphenyls or Water and sorbitan
poly(tri-fluorovinylchloride) or mono-oleate or sorbitan
o-dichlorobenzene or p-chlorotoluene or mono-sesquioleate
xylene or mixtures of the above
Starch (flour) Mineral or transformer oil or olive oil
Petroleum spirit or transformer oil Water and sorbitan
oleate or laureate
Hydrocarbons Water
Vaseline oil Water
Stone Transformer oil or olive oil or mineral oil
Sulphopropyl dextran Polychlorinated biphenyls or Water and sorbitan
poly(tri-fluorovinyl chloride) or mono-oleate or sorbitan
o-dicholorobenzene or xylene or mixtures mono-sesquioleate
of the above
Tin(ll) oxide Petroleum fractions or dibutyl sebacate or Water and a surfactant
di-2-ethylhexyl adipate
Titanium dioxide White spirit-Vaseline mixture Glycerol oleate plus a
‘low molecular weight
polyamide’ or
triethanol-amine
Mineral oils or p-xylene or Water and glycerol
poly-(phenylmethylsiloxane) oleate
White spirit-alkyd resin mixture

However, his measurements were madeat a fixed y and

it was not until 1967 that Klass and Martinek in two
classical papers [11,28] on ER reported on the <E)-+
interdependence. Althoughthey briefly mention theuse
of,calcium titanate dispersed in a ‘napthenic’ solvent,
most of their data relates tosilica dispersed in the same
solventandstabilised with an unspecified surfactant.
They studied the effect of E , f, Q, and T on z or more
extensively on the apparent viscosity <E)/Y over the
shear range 0 to 3000 S - ’ . By using a variety of gaps
over which the voltage was applied, they showed that
the phenomenon is field rather than voltage dependent
[ll].In the second paper information is also presented
on the bulkconductance (B) of the fluid asa whole l l l
and the consequent power demand of these typical ER 0 1000 2000 3000
systems under use. The characterisationof the effect in y Is”)
terms of changes in apparent viscosity, which was the
format mostly used in these papers and subsequently Figure 2. The shear stress (t)plotted against shear rate
(p) dependence of a silica dispersion under a field ( E ) as
adopted by many other workers, is,as explained above, observed by Klass and Martinek [l l].(0)E = 1.18 kV
unfortunate, but one example of thedependence of mm” at 60 Hz; (0)E = 0; the volume fraction of silica is
z(E) with i was shown and is reproduced in figure 2. 0.20 ahd the temperature 38 “C.

1664

The 0.20 volume fraction silica dispersion providing the
data for figure 2 was Newtonian in the absence of field
and became a Bingham body underE = 1.18kV mm"
with a static yield stress t o= 40 Pa. Further, the field
enhanced component of shear stress does not appear
to be ?-dependent after the onset of flow. Thus the
behaviour follows the type given by curve B in figure 1
and there is noindication of any reduction in
t ( E ) - t(0) at high 3.
Klass and Martinek and many other workers with
apparently similar data do comment on very a dramatic
drop in therelative viscosity defined as theratio of
apparent viscosities withandwithoutfield,butas
explainedearlierthisonly highlights theinappro-
priateness of this form of viscosity for a Bingham body.
It does not, as is implied, indicate a disappearance of
ER at high shear,andindeedthedata of Klass and
Martinek [ 1l] show nosign of a loss of the field enhance-
ment of shear stress with ?.
From the scant data on the j-dependence of z of ER
fluids, with and without fields,it would appear thatmost
of them behave similarly to the silica system studied so
extensively by Klass and Martinek. The dispersion at
the concentration used for ER (generally ~1 =S 0.4) are
mostly Newtonianin the absenceof fields. An exception
is a report [39] of a fluid composed of titanium dioxide
(v = 0.35) in a dispersant based on a white spirit solu-
tion of analkydresin.This systemshoweddilatant
behaviour in the absence of a field, then became New-
tonianunder field and finally becamepseudo-plastic
with a further field increase.
Fieldsenhance t andfrequentlyinduce Bingham
behaviour. At fixed ? including 3 = 0 the enhanced
shear stress or enhanced apparent viscosity becomes for
most fluids either parabolic [ l l , 231 or sigmoidal [21],
although there are reports of a small threshold field for
onset in some systems [4,25]. Whether there is truly a
lower limit in E for the effect to become manifest, and
if there is, how it relates to particulate concentration,
is not known. Certainly at a field less than or equal to
200V mm" the effects are small even with the most
active fluids,and generally fields in excess of 1 kV mm"
areapplied with fluids operating practically at much
larger fields than this [40]. Dielectric breakdown places
an upper limit on E but even at field levels below this
there is oftensaturation in $ E ) . This may bethe
consequence of higher levels of conductancemaking
the estimated field, in terms of appliedvoltage, less
than the actual field seen by the particles. Alternative
saturation of polarisation at high fields may be thecause
of the high field tail-off exhibited by many fluids.
Electric field frequencyf, can have a great influence,
notwithstanding the original assertion by Winslow that
'alternating currents of any frequency' suffice [l].It is
true that for sufficiently low f,t ( E ) does not vary with
f,so DC fields or fields at frequencies such as50 or 60 Hz
cause much the same effect, but ER responses rapidly
decline with frequencies in the region of 10' to IO4Hz.
The exact decay in effectiveness has been studied by
severalworkers using fluids based on dispersionsof
Electro-rheology
silica [ l1, 281, ion exchange resins [21], titanium dioxide
[23] or cellulose[13], and all theseshowadrop in
apparent electro-viscosity or <E) with f at high
frequencies.
Theobservations of Klass andMartinek [l11 are
reproduced in figure 3 and show, as well as the rather
gentledecline of apparent viscosity with f , which is
mirrored by manysystems,a sharp discontinuity at
about 200 Hz. A possible origin of this effect will be
discussed further in § S .
The influence of temperature on ER is complex and
the various observations contradictory. Klass and Mar-
tinek report thatincreasing the temperature from25 to
65 "C results in an approximately fourfold increase in
the apparent electro-viscosityrelative to the no-field
value for dispersed silica when measured at f = 60 Hz.
However, different levels of enhancement were
observed [ l l , 281 atother f. Similar resultswere
reported by Uejima for
dispersed cellulose
[13].
However, Deynega and co-workers[27] noted thatwith
thissystem,as well as with dispersions of poly-
(vinyl alcohol) or starch, the enhancement of viscosity
resulting from an applied field first increased and then
decreased with temperature over the range 0 to 45 "C,
with maxima lying somewhere between 20 and 30 "C.
As Uejima [l31 and Deynega et a1 [27] comment, the
situation is complexbecause theresponsetotem-
perature is in part areflection of the changesin dielectric
properties which have a strong influence on the effect
and which are critically involved in the mechanism for
the phenomenon. However, another factor involving
temperature is the requirement thatmany fluids require
wet dispersions in which the moisture plays an active
andcritical role. Ice or more preciselyanice-lattice
structure for adsorbed moisture is not an effective pro-
moterof ER andhencethe ER effectdramatically
decreasesat low temperatures(about -20 "C). Loss
ofmoisture by evaporation substantiallyreduces ER
1 l
102 5 103 5 104
f (Hz1
Figure 3. The effect of electrical field frequency ( f ) on the
apparent viscosity of a silica-based ER fluid after Klass and
Martinek [l l]. Measurements were made with a 0.46
volume fraction dispersion at a field of 0.79 kV mm-', a
constant shear rate of 753 S" and a temperature of 38 "C.
1665
H Block and J P Kelly
effectiveness so fluids canfailfor this reasonwhen
operating for protracted periods, even at temperatures
of about 70°C.
The response of E R fluids totheapplicationofa
field is strongly dependent upon the concentration of
dispersedphase.Volumefractions below 0.1 do not
produce fluids thatshow very greator significant
changes in z(E) or electro-viscosity, and dilute systems
below this level have not been much investigated. An
exception is theworkreported by Sasadaandco-
workers [lo] on aluminium hydroxide in oil and in water
suspensionsatapparently low concentration (in the
region of 1 gdm-3).Ratherunexpectedly,andpar-
ticularly so in the aqueous system, these workers report
up to 70-fold increases in viscosities at fields of about
kV mm-]. Most investigators find that 0.1 S q S 0.4 is
the optimum range for a practical balance between a parameter.
useful enhanced t ( E ) or t,(E) (inexcess of kPa),
achievable at several kV mm", and a suitable fluidity
in theabsence of field.Very high particulatecon-
centrations can obviously present problems of loss of
fluidity, but additionally this state often negates the very
effect required sincecontactbetweentheconducting
particles becomes so extensive asto short the electrodes.
The onset of the saturation of the ER effect alluded
to above and the tendency for runaway conductance at
high E through the fluids aremuchmorenoticeable
with fluids with a high solids content. There have been
some reports [ l ,29,411 on the influence of ER effec-
tiveness which confirm that electrically enhanced shear
stresses are strongly dependent on q . However, there
are scant data on the exact form this dependence takes
since the objective of most of the studies appears to
befinding theoptimumconcentration inrelationto
applicationparameters,such as a sufficient level of
fluidity in the absence of fields and the requirement of
minimising operational power demand. Since it is the
particulates that causeER, their concentration and more
particularly the particle-particle separations which
depend upon it, must be a critical parameter. Klass and
Martinek [ 1l], using silica dispersions, investigated the
influence of concentration on ER at q = 0.20 and 0.36.
Assuming close packing of spheres and a consequent
interparticledistance
proportionalto 6 = (0.9045
q"'3 - 1) they observed that their data could be nor-
malised in terms of E',@' and state that such a square
dependence is confirmation of their suggested double-
layer polarisation mechanism (see § 5).
The influence of q on the conductance of a poly-
(lithium methacrylate)-based fluid has been investigated
by Brooks and co-workers[41] and is discussed by them
in terms of knowntheories of the conductivities of
suspensions [42].
There appear to be no reports of any studies using
activeparticulates of well defined,evenspherical,
shape,althoughthetechnologyforpreparing active
substrates of well defined shape andsize is to hand [43].
Hopefully in the future such studies will be undertaken
even if they are restricted on financial grounds to inves-
tigation rather than application. Currently all powders
1666
used in ER fluids comprise quite irregular particles, but
with no hydrodynamicallydominant longdimension.
Such particles behave in combination with entrapped
solvent as if they were roughly spherical.
Mostparticulatesareused in theformof finely
ground powders, and optimum size ranges within the
bounds0.04
to 50 ,pm are frequently specified
[g, 10, 14, 22,25.32-36]. Neither limit is clearly defined
although thereis obviously an uppersize limit in relation
to the electrode gap usually considered to be one-tenth
of thisspacing[25].Particlessmaller thanthe lower
limit are hard to obtain in practice, but some lower limit
must exist, since at some level Brownian motion will
presumably overcome the interactions that give rise to
ER. Notwithstanding these considerations, size, within
a verywide range.does not appearto be a critical
Althoughshapeand size of theparticles do not
greatly influence the ER response of active fluids, the
chemical nature of the particles is critically important
to the effect. Table1 appears to demonstrate that very a
diverse group of materials are effective E R agents when
dispersed in suitable insulating oils. However, the con-
clusion should not be drawn that any particular disper-
sion within an insulating oil would be effective. This is
not the case. since the dispersed phase has an active
roleinitsability to polarise.Negativeresultsare of
coursenotoftenpublished,but we havefoundthat
cross-linked poly(styrene)micro beads dispersedin hep-
tanearecompletely ineffectiveas ER fluids. so also
are stericallystabilisedmicroparticles of poly(methy1
methacrylate)whenfree of moistureandsurfactant.
Sasadaandco-workers havereported very small
increases of viscosity with a polymer colloid based on
styrene when dispersed in benzene [lo]. Most ER for-
mulations require the presence of waterandforthis
class of additive-promoted ER effect, complete drying
destroys the ER effects [13-17, 25, 37, 381. With systems
where additives are necessary, wateris not unique since
alcohols [14], ethylene glycol [22] dimethylamine [18],
and
formamide [14] have all been proposed as
alternatives. Additions of salts or surfactants I381 also
stimulate ER effectiveness as well as, in the latter case.
often being present in their traditional role. The com-
mon factor among all these activated systems is ionic
conductance,and suchactivatedmaterialscomprise
either poly(e1ectrolytes).poly(ampho1ytes) or porous
supportsforthe inclusion of aqueousorothercon-
ductive liquids. Thus there is prima facie evidence that
such ER particulates are required for the system to be
capable of supporting ionic conductance and that the
additivesmediateionisationor elsedirectlyprovide
theirsource.Referencetotable 1 showsthatnot all
systems are or appear to be of this type. Firstly. some
materialsaremorecommonly identified as potential
ferroelectrics: for examplecalcium titanate [ll],barium
titanate [33] and an unspecified piezo-ceramic powder
[23]. However, it is not clear from the reports of these
investigations whether ionisable additives were present.
There is'also no evidence that they had at any previous

0 0
0 Q
c materials. This is developed further in § 5.
0 0
U U
E extensivelyassessed[13,15-17,371.
Fe 0 content also leads to failure. Clay minerals progressively
0 0
Figure 4. Structure of the repeat unit for some
semi-conducting acene-quinone radical polymers
which show ER activity and do so in anhydrous systems.
Polymers with conductivities in S m-’ quoted in
parenthesis are: A = pyrene quinone radical polymer
(lo-*), B = phthenanthrene quinone radical
polymer (1 0-3), C = anthracene quinone radical
polymer D = napthalene quinone radical
polymer E = ferrocene quinone radical polymer
(lo“) and F = p-terphenyl quinone radical polymer
(5 X 10-9).
stage undergone poling, thus it is possible that they act
by an ionic mechanism via surfactants or moisture, or
indeed electronically as does the other class of active
materials. These comprise the recently discoveredtruly
dry systems which are semiconducting. One such type
are the acene-quinone radical polymers which have the
structures shown in figure 4. Copper(I1) phthalocyanine
Electro-rheology
and its metal-free form are also active in an anhydrous
environment [5-71. However, notall conducting systems
are effective. Dispersed metals alone are eitherinactive
or show very small andmechanistically different effects
[6, lo].Howeverwhenmetalpowdersareaddedto
ER fluids they do influence the phenomenon [20,34],
probably by increasing the local field strengths over the
inter-particle gaps. Other semiconductors such as Ge,
Fe304, Fe203, ZnS, SnO, pyrolised poly(viny1 chloride)
and a N-vinyl carbazolinium cation radical polymer are
ineffective when dry [5,6,22]. The position of carbon
is unclear, with some workersfinding activity and others
not [ 5 ] ,whilst powdered coal requires water to be effec-
tive [12]. Much of this diverse and at times apparently
contradictorybehaviourcanberationalised by con-
sidering the nature of the polarisation response of the
There have been a number of studies reported that
quantify certain aspectsof the influence of water [8, 13-
17,21.37]. The majority of these investigations show
that there is anoptimumwaterconcentration in the
solid phase and that exceeding such a level leads to a
drop in t ( E )with a concomitant increasein conductance
pluschangesindielectricproperties.Theamount of
water required to optimise the effect appears to range
between 5 and 10% by weight. Clay minerals and cellu-
lose derivatives have had the influence of water most
Notonly do dry
ionic systems not work as ER fluids, but high moisture
fail at water contents in excess of 10 to 20% by weight
[15-171, whilst the level for starch is higher at 35% by
weight [37].
There is some evidence that the addition of salts to
moist
systems
further
promotes ER response
[14,21,25,36].Thenature of thecounterion in
poly(electro1yte)-basedsytemshasamajorinfluence
on ER. Sugimoto has investigated a number of anion
exchange resins in which univalent and divalent anions
of weak and strong acids are the counter ions [21]. For
a resin stored for some time under vacuum to remove
excess moisture, the order observed was
but, as Sugimoto points out, the tenacity of moisture
retention and the ability for the resins to absorb will
themselves be affected by the nature of the counter
ion. The observed order appears consistent with the
tendency for these anions to be solvated, but it is prob-
able that other factors also play a role. The free ionic
carrier concentration in such a resin is not only water
content dependent, but alsowill be reflected by the pK,
of the conjugate acid of the counter ion, if weak, and
to the charge density on the ion. Thus ineffectiveness
the
of Cr0:- C20’,-, OH- and even SO’,- could in part
~
be the result of such factors. Further, if ionic mobility
is an important factor in ER, as is suggested in some of
1667
H Block and J P Kelly
the models for the effect (see S: 5), then this also varies
with the nature of the ionic carrier, although the order
of effectiveness found by Sugimoto does not of itself
show any strong dominance by carrier mobility.
If thepublishedinformation available on the im-
portant properties of the disperse phaseis meagre, then
the knowledge about the dispersing oils is sparse indeed.
It has been observed that theviscosity of the dispersing
oil appearstohave littleinfluence on theachievable
t o ( E )at any selected E . Various hydrocarbons or sili-
cone oils of greatly differing viscosity but similar dielec-
tric constants were used in these studies [6,32].
The practicalpreference given to liquids of low
dielectricconstant in ER applicationsstemsfromthe
ability of such liquids to withstand high electric fields
without breakdown, to have low electrical conductivities
and not to become readily conductive when there are
extraneous impurities. In contrast, liquids of high dielec-
tric constantarenotoriousforrequiring rigid puri-
fication when used in high field applications. However,
this is not to say that a high dielectricconstant may
not be desirable for ER. There are indications that an
increased dielectric constant can cause an increase in
observed ER but, for example, a report [8] that nitro-
benzene suspensions of moist carbohydrates show no
level of ER probably reflects an inability to maintain a
high field in such systems. The influence of the polarity
of base liquids is by no means clear, although listings of
many polar fluids have been covered within the patent
literature,without,however, providingmuchdetail
about their relative effectiveness [8,26,32].
3. The electric properties of ER fluids
The electricalresponse of ER fluids to electric fields
has a strong bearing on both the understanding of the
physics invoved in ER and its practical application. In
relation to the former it is becoming clear that polar-
isation is of theessence in theeffect. As adisperse
system a number of polarisation mechanisms are poss-
ible, all of which cases are reflected in their intensity
and response time in the complex permittivity and its
f-dependence. Suchpolarisation of materials is con-
ventionallystudied by measuringtherelativeper-
mittivity ( E ’ ) and dielectric loss (E”) as a function of f ,
but in the case of ER fluids there are obvious grounds
formakingsuchmeasurementsunderconditions in
which the fluids are in flow orhave high E applied
to them, as well asvaryingsuch other parameters as
moisture content, T . etc. However, most of the inves-
tigations reviewed below have been doneon still disper-
sions;a few havebeenundertakenundershear(a
techniquetermed flow modifiedpermittivity (FMP))
or under high E .
The other electrical property which is of particular
relevance to the use of ER in devices is their current
demand under field and flow. Since high voltages are
required and large electrode areas are ofteninvolved in
order to obtain resistance to flow under large forces,
1668
current densities (1)approaching mA cm-’ can vitiate
many applications on power demand alone. One of the
prime limitationsin the use of ER fluid can lie in this high
power demand. These problems are further discussed in
D 6, but the levels of currents generated in terms of
various fluid formulations. field. temperatures etc, are
discussed within this section and the possible origins of
such electric current are discussed in Q S.
A number of workers have reportedon the variation
of E ’ with f of still ER fluids involving the following
dispersions: cellulose [13], sodium carboxymethyl cellu-
lose [6], various clay minerals [17]. starch [27]. poly-
(vinyl alcohol) [27], silica [27,28,44], ferrites [45] and
poly(acene-quinones) [6]. As wellas these reportswhich
have relevance toER systems thereis extensive literature
on the dielectric properties and polarisation mechanisms
of dispersed systems. This topic has been reviewed on
anumber of occasions [46-49] so the dielectrics of
dispersions are not comprehensively coveredwithin this
review unless theyhave known ER properties or provide
information germane to the ER phenomenon.
For multi-phase materials in which there are inter-
faces,interfacialpolarisationcanarisewhenmobile
charge carriers are present. These interfacial processes
can
lead
to
polarisation in such inhomogeneous
materialsas well asthevarious processes involving
molecular polarisations. Since ER fluids are dispersions
in which thereareboundariesbetweenthenon-con-
ducting oil phase and the particulate solid phase any
carriers whose migration in a field is restricted by such
boundariescancauseparticlepolarisationunderan
electricfield.Interfacialpolarisationfrequentlypro-
duces a very high E ’ at low f. The permittivity relaxes
out with thedevelopment of a loss peakcentredat
some critical frequency ( f c ) reflecting a commensurate
relaxation time or times. Dispersions that are ER active
do have high E ’ , well above the values for the organic
dispersant phases. Relaxations occur generally within
the range 10 to lo5 Hz in which most of this excess E ‘
relaxes out. The mechanisms responsible for this high
level of low-frequency polarisation of ER fluids are in
most cases and, probably in all, consequent upon some
form of chargemigrationratherthandipolarorien-
tation; that is, in a rather broad sense, theymaybe
classified as interfacial although the precise regions for
charge migrating: bulk, surface or within a double layer
mayvary from system tosystem.It is.however,a
requirementforinterfacialpolarisationthat mobile
charges be present and. as exemplified earlier. most, if
not all.ER-active dispersions do contain sources for such
carriers. be they ions, electrons or even holes.
Interfacial polarisation ceases to contribute to the
total polarisation of a material at sufficiently high fre-
quencies of applied field and this frequency region of
relaxation is recognisedto be controlled. in solid
materials at least,by the mobility of the charge carriers.
In the case of some mechanisms such as a Maxwell-
Wagner-Sillars process the f , is determined by the con-
ductivities (a) of thedifferentphases. I n a still fluid
dispersion. rotary Brownian motion of the particulates

could in theory cause a relaxationof any induced dipole
within theparticles,even if themechanismforthat
polarisationwere
conductive in origin.
However,
because of the viscosity of base fluids and size of par-
ticulates used in E R , it is more likely that the observed
low-frequency dielectric relaxations reflect the change
in ability of the motion of charge carriers to polarise the
medium rather than the much slower particle rotation
rate. Thisis not tosay that in the presence of sufficiently
high shear rate the polarisation is not modified by flow-
induced rotations. As describedbelow FMP clearly show
thatthere is an influence of flow on the dielectric
response of ER active particulate dispersions.
In the absence of high field and flow, the E ' at low
f of E R fluids is considerably higher than that of the
base liquid, implying a considerable contribution by the
particulates to the polarisation [6. 13,281. Many systems
also show higher-f dielectric processes with a further
drop in E ' at higher-f relaxations [6,13, 16.17,441.
Although the low-floss peaks are present in many cases,
there are some systems where no visible loss peak is
seen but where a general decline in E" occurs withf. In
such cases the dielectricloss peak probably exists at low
f(1ess than lo2Hz), but in situations whereit is masked
by a largebulkconductancecontribution.Evidence
from FMP (discussed below) tends to confirm this view.
When visible, loss peaks appear within the range lo2-
lo6 Hz and their position for water-promoted systems is
influenced strongly by the water content. Thus for wet
cellulose in a chlorinated hydrocarbon f, changes from
lo2 to lo4 Hz as the weight fraction of water within the
celluloseparticlesrises from 0.05 to 0.08 [13].Very
similar results were observed for a number of moist
clays in hydrocarbon oils where again the shift was over
the same region forvery similar water contents [16, 171.
Eventheanhydroussystems which are effective ER
fluidsshowlosseswithinthisregion[6]. Thus a time
dependence of the polarisation is implicated in the
effect.IndeedUejima[l31hasshownastrongpar-
allelism in the f-dependence of the ER and dielectric
responses of moist cellulose dispersions. The f-depen-
dence of E ' and apparent viscosities mirror each other
in terms of the fc appropriate to either and they change
in a similar manner as the water content is altered.
The dielectric response of most significance to ER is
that exhibited by E R fluids when subjected to flow and
high fields. Little is known about the influence of high
fields on the permittivitiesand loss of ER fluids. A
study by Deynega and co-workers [27] on hydrocarbon
suspensions of moist starch, poly(viny1 alcohol) or silica
gel shows the complex behaviour of E ' in terms of E
from 4 to 40 kV cm". The measurements were made
by varying T at a fixed f of 50 Hz. The most notable
result was that E ' is not independent of field strength.
Similar conclusions can be drawn from the work of Klass
and Martinek [28], although here the measurements are
further complicated by being performed in the presence
of a shear field. The dependence on E implies a non-
linear E-dependence of polarisation.Suchconditions
where the E ' is enhanced rather than diminished under
Electro-rheology
large E suggest that further polarisable entities such as
carriers are being generated. However, neither Klass
and Martinek nor Deynega andhis co-workers find that
E ' is always enhanced with E . Deynega and co-workers
[27] observed maxima in the loci of the temperature
dependence of E ' which were E-dependent. For moist
starch E ' initially rose with E but then tended to level
off;for silica gel thereverse was observed;andfor
poly(viny1 alcohol) the direction of change depended
upon T . Klass and Martinek noted that for silica the
trends depended on q so thatata low 9 of 0.1, E '
increased with E, whilst the reverse was true at a high
~1 of 0.46. These experiments were carried out at 65"C,
60 Hz and under a 1' of 23.6 S-'.
The question of the influence of ? on polarisation
must be addressed in any discussion of the influence of
dielectric factors upon E R . The E ' of a dispersion can,
in certain circumstances. be strongly affected by shear
fields.This is because in rotationalflow,particlesor
interacting clusters of particles spin and the principal
axis forpolarisationwithin the particlemaythereby
change their inclination relative to the field direction.
Because of the rate of spinning there is a ?-variation of
E ' as well as af-dependence. As well as particles which
are
anisometric
permanently
or polarised being
effected, interacting groups of particles including spheri-
cal ones and even isolated spherical particlesmay show
FMP. The last, which is an important case for ER,occurs
becausepolarisationrates are finite. Thusthepolar-
isation vector in spinning bodies may significantly lag
behind the field vector even with spherical particles.
Okagawa and co-workers [50] have considered how
the relative permittivity of a streaming suspension of
spheroidsmaydependuponand E . Thistheoretical
investigation is one of a number of studies, both theor-
etical and experimental, undertaken by Mason and co-
workers [51-561, into the inter-related aspects of particle
motion in the presence of electrical and shearfields and
its effect upon viscosity and permittivity. Demetriades
[57] hasalso contributedto thisfield. Thesestudies
show that for spheroidal particles with axial ratios not
equal to 1 and composed of af-invariant dielectric, such
combined fields cause complex precessive motions and
lead to FMP effects and field-enhanced viscosities. The
latteroccursbecausethere is anextratorque, elec-
trostatic in origin, against which an isometric particle
has tomove.However, all thesemodels, which are
based upon a dielectric particle whose polarisation is
time-invarient,predictthecompleteabsence of any
FMP or ER forspheres in dilutesolution.Athigher
concentrations of spheres, mutual dielectric interaction
can cause capture, precessive motion of the resulting
dumb-bells or more extended chain-like collection of
spheres withconcomitant ER effects [54,55,58,59].
Although not considered by these workers, either per-
manentpolarisationorcertainforms of frequency
dependence of the particle polarisation can cause FMP
and ER in particles, evenif the particles are spherical and
so dilute as to prevent significant pair-wise interactions.
The FMP effectsrelating topermanentlypolarised
1669
H Block and J P Kelly
particles
have
been
examined theoretically [60]
andobservedexperimentally with macromolecules
[61,62].
Whether any of the suspensions involved in ER sys-
tems relate to any form of permanent polarisation is not
clear, even though potential ferroelectric materials can
be theparticulatephase [ l l ,23,331. In all these
reportedferroelectric-and ER-active materials,addi-
tives capable of providing conductance were present.
When the material of which particles are composed
has a time-dependent polarisation, spinning particles,
even if spherical, do involve further effects on the bulk
permittivities in flow. This is because when such par-
ticles are subjected to flow, the polarisation and field
vectors can be out of alignment. Indeed, a condition in
which the direction of polarisation always matches the
field direction can be achieved when the angular fre-
quencies of rotation and field alternation match, and
this results in resonances in E ’ . This type of behaviour
has been theoretically predicted[63] and experimentally
observed with sterically
stabilised poly(methy1-
methacrylate) particles dispersed in heptane [64]. The
resonances that can occurin flow only do so when there
are dielectric relaxation processes associated with the
particles and they are only observable under conditions
in which f > fc for the polarisationof the particle. In the
case of spheres sufficiently large to render thermalnoise
due to Brownian motion insignificant, the condition is
f L fC/3’l2. With spheres and f P fc these resonances
show up asmaxima in thedependence of E ’ with
which occur at a ymgiven by the relation Pm = 4nf. This
resonance phenomenon is useful ‘in reverse’ since the
occurrence of a resonance indicates the presence of a
loss process at a fc less than the applied f.Variation of
the latter in FMP measurements can thus pinpoint not
only the presence of resonances but also their upper
bounds in f, a result not always achievable by direct
dielectric measurements on still liquids where bulk con-
ductance can screen the relaxation peaks. The method
succeedsbecausebulkconductance per se doesnot
cause variation in E ’ or E’’ with y . It is of relevance to
ER, firstly because itindicatesaprocesswhichinits
energetic role provides a mechanism for viscous change
(see 9 5 ) and secondly, because a number of ER fluids
recently tested show the resonances even in caseswhere
the causative loss process is completely hidden by con-
ductance [65]. An earlierobservation by Bondiand
Penther [44] on silica suspended ina hydrocarbon
showed similar resonances in E ‘ asafunction of P,
although these authors did not recognise the cause for
the peaks they observed.
As well as the polarisation of ER fluids under E , ER
systems all show someconductance.Atourpresent
level of understanding of the ER phenomenon the con-
ductivities of such fluids under flow and E are of most
significance in limiting the practical application of ER
fluids. This is not to imply that causative processes for
current demand are unimportant, rather thatwe do not
quantitatively or even qualitatively properly understand
the origins of the currents involved. Our ignorance in
1670
this respect is probably a major limitation in the design
and development of improved fluids.
Before discussing in detailwhat is known about
individual E R systems in this regard, it is instructive to
highlight in terms of orders of magnitude thesignificance
of typical fluid conductances. Many E R fluids have DC
conductivities of about lo” S m”atambienttem-
perature and operate at3 kV mm-’ toprovide an excess
stress of about 3 kPa. This implies a current demand of
100 A N” or a power demand of 0.3 W N” if the force
is applied over a 1 mm gap. For small forces of tens to
hundreds of N this is not a great power demand but for
some heavier engineering application involving larger
loads or torque transmissionswith forces of tens of kN.
this power demand lies in the kW range. At the latter
level the cost in providing the power at the necessary
high voltages together with the need to dissipate the
heat generated can become a seriouspractical problem
in the use of ER.
The values of excess stress and conductivity given
abovearemeantto beaguide [66] tothesort of
demands involvedbut it shouldbeappreciatedthat
individual
systems
can vary quite widely
[4,11,21,28,67]. Indeed it is an unfortunate fact that
many publications on the subject only quote observed
currentsdrawnthroughwhatever device or test rig
is involved, all too frequently without stipulating the
electrodedimensionsorgap, so thattheimportant
property of powerdemandforaset level of force
transmission cannot be estimated.
With fluids baseduponmoistparticulatesystems
there is always some level of waterdissolved in the
organic dispersing phase no matter how hydrophobic
that liquidis.Thisshouldlead to some level of bulk
ionic conductance but it appears that in most practical
cases this is not the dominant sourceof loss. Thus there
are no reportedobservations of theelectrochemical
decomposition products forming at the electrodes nor
do systems appeareitherto loseeffectiveness orto
decrease their current demand with extended times of
operation,as would beexpected if the electrolysis
proceeded for a sufficient time to significantly remove
water. This is not to say that the level of moisture has
no effect on J . Increased moisture results initially in a
slightincrease in currentbutthen, with evenmore
water, there is a dramatic increase in the current drawn
andeventually sufficient water canbeintroducedto
cause dielectric breakdown [16, 17, 371. The conditions
forlargecurrentincreasescorrespondtosituations
where s(E) declines. It is likely thatat this stage,
when the fluid ceases to be of practical interest, bulk
conductance through a rather wet dispersing liquid is
the cause for both the high current level and low t ( E ) .
The latter can be understood in terms of a decrease in
effective E due to conduction through the medium.
Increased temperature also has the effect of raising
the conductivity [9,27]. It has been stated [66] that a
5 K rise in temperature cancausethecurrentcon-
sumption to double and indeed some aqueous based
systemsshowanevengreatertemperaturevariation

[27]. The electronically conducting dry systems also pass
currents under E and indeed with these systems J is at
present higher than it is with some of the best water-
containingformulationsoperatingatambienttem-
perature [6].
4. Structure formation in ER fluids
Winslow in his originalpublications [ l , 41 and,sub-
sequently, other workers [lo, 21,68,69] have observed
thattheparticles within an ER fluid fibrilate on the
application of E . Such fibrils have been considered [29]
to be of paramount importance in the ER phenomenon
in that they are presumed to provide the mechanical
linkswhich leadto t o ( E ) . However,thecomplete
spatial linking of electrodes which seems to occur when
ER fluids not subject to flow are poled, cannot on its
own explain the excess$ E ) in flow. This is not to imply
that thereis no interaction or aggregationin flow,rather
that it is difficult to see how any such structures could
bridge the gap duringflow. Microscopic observations of
fibrilationhave, of necessity,beenundertaken using
electroded microscope slides and involve rather narrow
gaps and dilute fluids. In the more realistic situation of
gaps of about 1 mm appertaining to flow cells, direct
observation of any such aggregation is still lacking since
ER fluids arerathertooturbidforbirefringenceor
other optical measurements. Aggregation in quiescent
situations is to be expectedin ER fluid systems since the
active particulate ingredientis polarised in E and would
form chains under such circumstances, as do otherelec-
tric systems[70] and their magnetic analogues[71]. How
important this is to the phenomenon of ER isstilla
question requiring resolution and thiswill be discussed
further in the next section.
5. Theories of electro-rheology
Manyresearchers in the field of ER haveproposed
scenarios for the development of ER effects of the type
described above and in some cases they have tried to
place quantitative frameworks upon such models. To
date these attempts have not been notablysuccessful in
producing any viable quantitative theory nor even in
providing an agreed view as to the mechanism of the
effect. The physical situation is indeed complex involv-
ing as it does the interactions of electric and flow fields
in concentrated particulate systems. Modelling of the
behaviour of concentrated dispersions under flow or E
alone presents serious theoretical problemsof rheology
or dielectrics; it is not surprising that in combination
the situation is at present so intractable.
It is generallyagreedthatthe initial step in the
development of ER involvespolarisationunderthe
influence of E . This then introduces some form of inter-
action between particles or between the particles and
Electro-rheology
the impressed electric or shear fields which results in
the rheological manifestations of the effect.
Winslow [l,41 initially and other
workers
[lo, 16.29,68,72] subsequentlyascribedthedevel-
opment of ER to the fibrillation of particles that can
occur on the application of electric fields. This is a well
known consequence of the polarisation of particles and
theirsubsequentchaining if theyarefreetomove.
Undoubtedly a role is played by interactions between
particlesbut it is difficult to acceptthatthe level of
structureformationthatmaybeestablished in con-
ditions of no flow can be maintained in flow.
Criticism of a simple fibrillationtheory hasalso been
made on the grounds that the effect is much too rapid
forsuchextensivestructureformationtooccur [ll].
However, although there may well be cogent grounds
forrejectinglarge-scale fibrillation in flow, including
the time element alluded to by Klass and Martinek, the
reason cited by them that ER is retained even with fields
of considerable frequency (in excess of several kHz in
the casequoted) is nota sufficient reason.This is
becauseinteractions involvingpolarisationcouldbe
maintained once the structure had been formed even
under AC fields provided that f did not greatly exceed
the fc of polarisation. As will be developed more fully
later, this dichotomyof timescale between thatof polar-
isation and one relating toflow has not beensufficiently
appreciated.Nevertheless, it is probablethatthe
response of the effect is too rapid for fully fledged chain
formation to occur. Recently Brooks et nl [41] have
optically observed a timescale for fibrillation of approxi-
mately 20 S , which is vastly in excess of the timescale
fortherheologicalresponse of ER fluids. Thus, in a
study of shear-wave propagation at 1200 rad S" and
under E they deduced that the rheological relaxation
time was €-dependent being extended by increasing E .
It has also been stated on a number of occasions that
the response of the ER effect occurs within the order of
ms. Indeed it would be difficult to envisage a phenom-
enon requiring about 20 S which would be effective in a
high-flow situation. Nevertheless the concept of chain
structure across the flow being disrupted or extended
against interactive forces has been used as a framework
for modelling the ER phenomenon [29,72].
Conceptually more attractive are coulombic inter-
actions between polarised particles leading to clusters
that act more or less as entities within flow but do not
extend throughout the bulk, except in static situations.
There have been a number of studies. both theoretical
and experimental, into the motion duringflow of inter-
acting doublets [41,54,58,59] or short chains [ 5 5 , 731
of polarised particles. Brooks and co-workers[41] have
applied a statistical mechanical approach to the moduli
of fluids in which structure is made up of an inner shell
of associated spherical particles as nearest neighbours
to a reference sphere. When applied to dispersedpoly-
(lithium methacrylate) their theory gives a best fit to
experimental data if the number of nearest neighbours
ranges from 3 to 4 when 0.09 S qc S 0.23 and where
electric fields rangingfrom 200 to 400 kV mm" are
1671
H Block and J P Kelly
involved. The theory is also consistent with the obser-
vation made by Brooks and co-workers that the storage
moduli and loss initially increase, reach a maximum and
subsequently decrease with E .
Most theories and models assume in the main that
the forces causing association are electrostatic in origin
and are consequent upon polarisation alone. They do
not in any very specificmanner ascribe a role to moisture
or other additives. unless it is to provide a vehicle for
inducing double layers, or as a means of enhancing the
possibility of ionic migration
causing
interfacial
polarisation. However. one view of the mechanism of
ER, does give moisture a very specific role, namely as a
binder by surface tension forces of chains or clusters of
particles [69]. Such effects are known to cause agglom-
eration of moist glass beads in liquid poly(butadiene)
[74], but in the case of ER the bridging by water must
be induced in some way by E since the Bingham behav-
iour is initiated by E . Stangroom [69J suggests the
sequence of eventsasa possiblemechanism:ionic
migration, subsequent electro-osmosis of moistureto
one pole of the particle (presumably the cationic region)
and in consequence, a surface supply of water sufficient
for bridging. H e also states that a high porosity for the
particulates is a necessary prerequisite for this type of
ER effect. The moisture bridge mechanism is a possible
contender as a source of ER but it does imply that, if it
alone is the processwhich occurs, then wateris essential
to ER.
Until recently the materials used seemed to require
activation by polar additives andin particular (and most
commonly) water. The advent of anhydrous ER fluids
means that water-bridgingis not an essential mechanism
and may indeednot be operative at all.Since one of the
original reasons advanced against simple polarisation
mechanisms being operative was the selectivity of the
dispersedpowders and in particulartheapparent
absence of ER with other conductivity particles such as
metal powders, another cause must be found for any
selectivity in materials. The common factor relating to
the effectiveness of moist or other promoted systems
and the class of anhydrous fluids now known may be
that, not only is polarisation extensive in both, but also
occurs at commensurate rates in all these systems. It is
implied that the relaxation time for polarisation should
be a critical feature in the mechanism of ER [16,62, 751.
To explain this contentionit is relevant to consider how
phenomena basic to FMP can influence the mechanics of
flowing dispersions. It has already been shown that an
important consequence of the rotational natureof most
flow fields is that the polarisation and field vectors can
be non-parallel. This canoccurbecausetheparticles
are non-spherical or because the rate of polarisation is
slow enough for the direction of polarisation to lag the
E direction. Under either condition a consequence of
flowingsuchdispersions is that work is done against
the restoring torque P X E and thereby the viscosity is
enhanced. This type of effect takes no cognisance of
any particle-particle interactions and therefore predicts
anenhanced viscosity even in dilutesolution.There
1672
should thus be an enhancement of the relative viscosity
number
[ q J = lim
(v - ’70)
( - 0 c
with field. In this expression q,, is the viscosity of the
dispersingliquid and c the mass concentration of
particulates. To date no such field enhanced [ q ] have
been reported, nor apparently have experiments been
performed at sufficiently high dilutions to obtain the
necessary data.
It is also a predictable consequence of particle spin
that [v] might drop to the no-field value at sufficiently
high 9. This is because for a particle undergoing such
rotation the E direction is constantly changing and, if
that change exceeds the natural rate of particle polar-
isation, then polarisation does not occur, consequently
there is no extra torque.If in more concentrated disper-
sions polarisation together with particle-particle inter-
actions play thekey role in ER. then the same relaxation
of effect athigh may occur if the clusters or aggregates
-
are in rotation. On this basis it may be expected that
at sufficiently high y , t ( E ) z(0) andthetype
behaviour depicted in figure 1 would occur.
‘E’
Another characteristic of the FMP of particulates is
the development of resonances in E ’ . It is noteworthy
thatwhatappearsto be a similar phenomenon has
been observed [l11in thefvariation of electro-viscosity
measured at a constantV. Figure 3 reproduces this data
of Klass and Martinek and it will be seen that there is
a sharp troughin electro-viscosity at about200 Hz. This
approximates to the condition y,,, = xf which, with a
match between a rotation rateof y/2 and a cross torque
situation at 4 2 , may indicate an inverted peak occuring
when the polarisation is perpendicular toE and the field
pushes energy into the spin, thereby reducingviscosity.
Although suggestive, further studies are needed to con-
firm such a view. Klass and Martinek offer no expla-
nation nor comment on thesharpdiscontinuity they
observed.
Such simple and individual particle interactions with
E become inappropriate at higher concentrations,
although both particle shape and polarisation time must
continueto be of influenceathigherconcentrations
when inter-particle,coulombic forces will become
increasingly important. It can be envisaged that a rapid
relaxation of polarisationwouldmakeanystructural
reorganisation of interacting clusters. whether in contact
or long range, much easier than would be the case for
aslowerprocess. Attheotherextreme,too slow a
polarisation time would imply an inability forsuccessful
polarisation in rotational flow, whether or not the ER-
effective structures were isolated particles, short-range
aggregates or longer-range interaction
groups of
particles. The statistical details of the groups involved
are not known noraretheretheories based on such
quantifiable factors as shape or polarisation rate. It is
our view, based upon some correlation betweendielec-
tric relaxation time and the effectiveness of particulate
materials,thatthelatter is particularlyimportant

[19,62,63,75]. As examples. the most effective acene-
quinone radical polymers for ER substrates are those,
such as the napthalene and anthracene derivatives, that
have intermediate conductivities (see figure 4) and, in
consequence, dielectric relaxations caused by inerfacial
polarisations which in a chlorinated paraffinoccurat
6.3 and 2.5 kHz respectively [6]. This region is similar
to that of many moisture containing dispersions which
are E R effective. as is mentioned in 8 3. Other examples
of theacene-quinonepolymerseriesthathavecon-
ductivitieseithergreater or less than the napthalene
oranthraceneanaloguesproduce fluidswhose t o at
selectedand E arelower [6].
Little evidence is available on the influence of par-
ticle shapeon ER. Mostsystems arebasedonquite
irregular,groundpowders;a few onparticles which
approach spherical shapes fairly closely. In both cases
the hydrodynamic situation would match very closely
that of perfectspheresbecauseanyirregularitiesare
smoothed out by occlusion of base fluid. Dielectrically
also, anisometry has to be rather extreme to be signifi-
cant [60, 61, 631.
The magnitude of the polarisation also has a signifi-
cantinfluence onthe E R effectiveness of oil-based
dispersions. The E ’ of suchsystems is high and this
appears to be a not unexpected requirement for large
ER effects. Itis our opinion that the mechanism by which
polarisation is achieved is not a controlling factorin ER.
Thus it has been the tendency to ascribe this polarisationactivated will bediscussed.It
to field distortion of double layers [8, 10, 12, 21,23,28,
46-49, 76-84] and this is likely to be correct in many
cases. However, there maybe fluidswhich are excep-
tions tothatrule, particularlytheanhydrous,semi-
conducting systems
described
earlier.
Double-layer
effects are alikely causative process in certain aqueous
systems and in particular those where surfactants are
present.
However, double-layer
polarisation, when it
involves ionic migration within the double layer rather
than the alignment of any dipoles therein, is just one
example of various charge migratory mechanismsinolv-
ing interfacialregions.Suchpolarisations,generally
classified as interfacial or Maxwell-Wagner can involve
migration through the bulk of the particles or along the
surface of the particles as well as within a double-layer
region. The lattertwo might be considered conceptually
differentsincedouble-layerprocesses imply charges
residing within the oilregionboundingtheparticles.
There is atthis stageno definitiveevidencethat ER seem to have been theoretically considered. Perhaps it
involves aparticularform of polarisation within this
wider class of interfacial processes. It has already been
indicated that highly charged double layers arepossible
in some of themoistsystems,particularlywhensur-
factants are present. On the other hand, although the
dispersed semiconductors, in common with all disper-
sions, will have some charge separation at the interface. reasons why E R fluids have finite conductances. Those
it is unlikely that these would lead to large polarisations. fluids which are based on moist particles obviously can
Here a classical Maxwell-Wagnerpolarisation of the support some level of bulk conductance if the water
electronic conductor-insulator kind is probably taking
place [65.75].
Electro-rheology
The development of significant ER by dipole orien-
tation or other forms of polarisation such as atomic or
electronic within the confines of a molecule are probably
ruled out in that their magnitudes are not generally large
and. in the latter cases,the timescales are completely
wrong.
Most researchers when considering polarisation in
relation to ER assume that the resulting dipole-dipole
forces cause coulombic interactions which are then at
the root of the ER effect, even if some form of inter-
particle contact is assumed to occur subsequently. Klass
and Martinek [l11 provide a rather different picture to
this in that they suggest that field-induced double-layer
distortions lead to extra repulsion between regions of
high-charge density. Thisis a formof electrical enhance-
ment of theknownchargerepulsion which provides
thestabilityformanycolloids.However. anycharge
distortionleading to regions of expanded ionatmos-
phere at one poleof a particle mustin consequence lead
to a diminution of that charge at the other pole. It is
then a consequence that at that end, the particle will be
deficient in screening charge and have an excess of the
oppositecharge.This is only another way of saying
that a dipole has been induced: Klass and Martinek’s
scenario is thus only one-half (therepulsion component)
of a coulombic-type dipole-dipole interactive system.
To conclude this section, consideration of the poss-
iblecauses of thecurrentdrawnwhen ER fluids are
is doubtfulwhether in
their entirety, these currents are due to the basic ER
phenomenon. Indeed previous researchers in the field
ascribesuchcurrentsentirelytoextraneouscauses
related to the nature of the fluid materials rather than
thephenomenon itself. It is ourcontentionthat in
certain circumstances at least, a basic loss process lead-
ing toa loss currentoccurs,notwithstandingother
causesforadirectcurrent flow.Thisprocessstems
from the combination of polarisationandparticulate
reorientation in flow which, even with DC fields leads to
an oscillatorypolarisation. Although differentin source,
this is identical in effect to the fvariationof polarisation
under AC fields which canleadtoanout-of-phase,
loss component of permittivity and manifests itself as a
virtual loss current. In practical E R fluids. a current is
still passed even when is zero. that is when the stress
applied is less than t o ( E ) .Whether there is an inherent
phenomenologicalcauseforpartoreven all of this
current is not known and to our knowledge does not
maytentativelybesuggestedthat the fluid in these
circumstances is reduced in entropy because of struc-
tural ordering, and that a work penalty is required to
achieve this state.
Notwithstandingwhetherthesefundamentalpro-
cesses are present or not, there are many other likely
dampens the oil phase [13, 14, 27,37,85].Inter-particle
contactand in particularanyparticlechainingfrom
1673
H Block and J P Kelly

electrodeto
electrode can
providepathways for others, influence device design and whether potential
conductance.Dielectricbreakdownand localelectric applicationsare well suitedornottoan ER system,
discharge may also be contributers to current demand, the types of application will be listed. Possible devices
particularly as high voltages are involved and the local include E R clutches [ l .4, 86-89], brakes [86], hydraulic
E between particles is greater than an apparentE based valves [l, 4, 22, 40, 86. 871, active damper systems
on voltage and electrode gap[20, 21, 371. Irregular par- [88-91, 931, wide-band-high-powervibrators [86,90],
ticles with surface regions of high curvature are more chucks [33] and robotic control systems of various sorts
prone toinduce such a breakdown than smooth, spheri- [22,87]. It has been reported that slurries can be pro-
cal particles and there are some observations on the tected against sedimentation using the ER effect[12].
fibrilar structures which support such a hypothesis [21]. As well as a requirement for ER activity many of these
In the case of the non-aqueous systems the current is applicationsalsohaveotherdemandsforthe fluids.
still present and partof it may well be caused by charge Table 2 gives a list of these requirements and indicates
tunnelling across inter-particulate gaps since the carriers below these comments relating the way in which they
are electronic and have large penetration lengths; break- have influence.
down is again a possibility. The formation of chains in Mention has already been madein Q 5 of the power
similar systems finds application as non-linear colloidal penalty when fluids are required to withstand large z;
resistorsin which electronicconductancesproceeds obviously applications requiring lower t ( E ) are easier
through chaincontacts which haveafield-dependent to achieve at the present time. The voltages required
contact resistance [70]. Finally, in many types of par- are also high sincefield strengths of several kVmm" are
ticulate dispersions within an insulator there exists the needed and these have to be achieved over appropriate
possibility that the particles themselves are the charge electrodegaps.What is anappropriategap is often
carriers.Certain ER fluid suspensionsareknownto determined by the flow requirements of the device
consist of particles with a non-zero zeta potentialwhich (valve, damper, clutch etc) in its non-activated state.
undergoes electrophoresis [41]. It is well known that Viscosity considerations also come in here as high flow
dispersions of insulating particles
readily
pick-up rates are favouredby low viscosities (both of base fluid
charges from electrodes and then translate as such to and dispersion) whilst high t(E) at lesser E imply higher
the opposite electrode. Oscillatory motion of particles with the implication of larger viscosities in the 'off'
which may be causedby charge pick-up has been stated as well as 'on' state. Both r p and E also affect current
to occur in activatedER fluids [ S ] , so that suchprocesses and hence power demand. It is easy to appreciate that
may well contribute least
at something the
to fluids providing higher t ( E ) at lower voltages and cur-
conductance. rent is one of themajor aimsfor thefuture.Some
Whatever process or processes are inovolved in caus- applicationssuchastheelectro-mechanicaldamper
ing conductance, its origins and in particular a knowl- require muchless fluid flow in the off state and therefore
edge as to what extent and under what circumstances narrower inter-electrode spacings become possible.
such currents are inevitable as part of the ER phenom- Fluidstability
against
sedimentation is another
enon,are vital information in anyquest tofurther importantrequirementandone which hasparticular
optimise ER fluids. This is because the power demand significance in ER clutchessincecentrifugationcom-
of current ER fluids is limiting their application. Thus a pounds the problem. Indeed the ER clutch is probably
better understanding and modelling of the ER pheno- the most technologically difficult device to achieve. For
mena in both itsrheologicalresponseanditspower the engineer, long-termusage and the absenceof sludg-
demands is paramount to advances within this field. ing is another consideration and the possibility of steri-
cally stabilising [42] E R fluids needsinvestigation.
However, there exists the possibility that the very prin-
6. The technological application of ER ciple involvedin sterically stabilising against aggregation
and sedimentationwill damage or eventotally eliminate
As well as its intrinsic scientific interest, the phenom- theinducedBingham-typebehaviour of E R . This is
enon of ER has potential in a variety of light and heavy possible if averycloseparticle-particle approach is
machines and devices. Thus a fluid which can readily involved in the ER phenomenon. Density matching also
and rapidly be converted between afluid and a solid on has an important role in the stability of dispersions and
the application or removal of a voltage and so replace in this respect organic particulates are often superior to
moremechanicalmechanismscould, if certainother inorganic ones andhigher density dispersing liquids
limitations are overcome,be a very effective vehicle for more appropriate.High-viscosity fluids also have advan-
all sorts of device applications. This aspect of ER was tages in that sedimentaion is slower. Other factors such
recognised from its initial discovery by Winslow in his as environmentalstability.non-corrosiveorabrasive
earlypatents [l,221 andpublishedwork[4].Atthe nature of fluids,absence of toxicity, areself-evident
present stage of development of ER fluids, the caveat but limit choice as indeed does the cost.
about 'other limitations'is very significant since in many Having outlined these factors it should not be con-
respects the idealfluid does not exist nor is it likely that cludedthatthephenomenon's applicability is fatally
a universally applicable fluid will easily be found. compromised.Theoppositeappearsto be the case
Before consideringhow fluid properties, bothE R and since, after a period of quiescence, there appears to be

1674
 Electro-rheology

Table 2, Some important requirements of ER fluids.

Requirements Comments

l , High T at low E The level at which this is met determines the load sustained by the fluid and also
involves voltage, electrode area and gap.
2. Low conductance Determines with 1 (above) the power consumption and heat dissipation of the device;
the possible need for cooling (see 3 below). Use with device 'off' more than 'On' may
reduce power problems.
3. As wide as possible a temperature Limited in water activated systems to circa -20 "C to +70 "C. At low temperatures
range of operation $4 decreases dramatically; at high temperatures water loss reduces effect and can
cause pressure build up in non-vented systems. Also current rise with temperature
can result in a runaway situation.
4. Stability of dispersion to Influences the long term stability of fluids in systems or storage (sludging). Clutches
sedimentation are particularly susceptible as centrifugal forces operate. Continuous pumping can be
beneficial. There are also indications that a low permanent level of field stabilises fluid
against sedimentation. Fluid design requires as far as possible the density matching
of particulates with the base fluid. The desirability or otherwise of steric stabilisation
is still to be established.
5 . Viscosity of fluids The general requirement is for these to be low in the absence of E and large under
E. They are most important in hydraulic or robotic systems where the fluid transfer
rate determines rate of action, but they are also important in clutches. Implication of
low viscosity is a low q but this implies a higher field requirement. Dilute systems
( q < 10%) are not very effective.
6. General base fluid properties A desirable fluid should be non-toxic, non-flammable, of low volatility and have a low
viscosity (see 5 5). A high E' improves t(E)provided that conductance remains low.
Fluid should be non-corrosive to device construction materials and seals. Factors
negating these are that density match (see 4 above) may best be'achieved with
halogenated fluids which have toxicity and possible corrosion problems. Silicones
cause difficult sealing problems. Hydrocarbons in high voltage situations could be a
fire hazard if arcing occurs. Wet systems may cause corrosion particularly in relation
to ferrous metals. Low conductance with high E' is difficult to achieve and may require
high fluid purity.
7.General particulate properties As well as the required electrical properties to make it active (see previous sections)
the particulate material should be easily powdered and dispersed and mechanically
soft enough so as not to cause wear and abrasion. Density matching with densities
greater than 1.5 x 1O3 kg mW3 is very diff icult, thus steric stabilisation may be important.
Such stabilisation is very specific to individual systems and requires separate for-
mulation for any selected particulate-base fluid combination.

't a recent resurgence of interest into ER [66, 69, 86, 87,

88, 89, 90, 94-97]. Applications in hydraulics, robotics
and damping seem to be the front runners. ER-valve

1
design has been extensively studied and is likely to be
Plston employed in the form of a 'Wheatstone net' of valves
(figure 5) foractuationpurposes in hydraulics or
robotics. The application of AC signals to this system or
the Boeing valve design [90] could well form the basis of
high power, wide-band and frequency tunable vibrators.
Robotic applications need not be limited to hydraulic
controlbutcan involve the on/offlocking of an ER
fluid to control mechanical motion. An example is an
automatictest system formonitoring circuit boards
Figure 5. The arrangement of a 'Wheatstone net' of ER
involving the positioning and ER-locking of test probes
valves for actuating purposes.
as contacts for checking circuit parameters [87]. Engine
Valves closed Movement mounts and vehicle dampers with ER-controlled dash-
pots are currently being developed by the automobile
1+ 4 UP industry
and
the
commercialprospects
appear
2+3 down
1 +2or3+4 locked promising. It is likely that other applications of the ER
effect will be developed in the near future.

1675
H Block and J P Kelly
Acknowledgments
The authors wish toacknowledgethesupport of the
Electro Rheology Research Syndicate plc, andof GEC-
Marconi Avionics plc and the SERC in providing finan-
cial andgeneralsupporttoourwork in thearea of
electro-rheology.
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