International Journal of Modern Physics B, Vol. 16, Nos.

17 & 18 (2002) 2576-2582

© World Scientific Publishing Company

EFFECT OF MAGNETIC HYSTERESIS OF THE SOLID PHASE

ON THE RHEOLOGICAL PROPERTIES OF MR FLUIDS

J. DE VICENTE, J. D. G. DURAN, A. V. DELGADO AND F. GONZALEZ-CABALLERO

Departamento de Fisica Aplicada. Facultadde Ciencias. Universidad de Granada, 18071 -
Granada, SPAIN.
E-mail: jvicente@ugr.es

G. BOSSIS
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Laboratoire de Physique de la Matiere Condensee. Universite de Nice-Sophia Antipolis. Pare

Valrose, 06108 - Nice Cedex 2, FRANCE.
by UNIVERSITY OF MICHIGAN on 03/03/15. For personal use only.

E-mail: bossis@unice.fr

An experimental investigation is described concerning the effect of the existence of a remanent

magnetization of the dispersed particles on the Theological properties of magnetorheological fluids
(MRF). Two MRF's were used: (1) solid phase: cobalt ferrite particles + silica gel (1.5 % w/w); liquid
phase: silicone oil (viscosity 20 mPa-s); and (2) solid phase: carbonyl iron -I- silica gel; liquid phase:
silicone oil. The cobalt ferrite particles were synthetized as monodisperse colloidal spheres with an
average diameter of 850 nm. The dependence of the dimensionless shear stress (T*/$) VS. Mason number
(Mn) tails to scale when a "magnetorheological hysteresis procedure" is followed, specially for the
higher volume fractions used (« 7.5 %). The yield stress (xy) is first estimated from successive rheograms
obtained decreasing the external field (H0) values for different §. A more precise determination can be
done by applying a stress ramp in the oscillatory regime. The critical stress amplitude (t c ) needed to
exceed the viscoelastic linear region (VLR) is obtained. It is found that both t y and TC strongly depend on
the magnetic history of the sample. As expected, the previous results were not obtained in a classical
MRF of carbonyl iron particles since they do not present magnetic hysteresis. We conclude that cobalt
ferrite suspensions are an other kind of MRF which works at low fields (0 -17.8 kA/m) with the opposite
effect: decrease of the yield stress with the field. This property can be improved using particles with
stronger remanent magnetization.

1 Introduction
Magnetorheological fluids (MRF) are non-aqueous suspensions of micron-
sized magnetizable particles. They usually consist of a magnetically soft
solid phase material. Iron has been a popular choice since it is the element
with the highest saturation magnetization. Furthermore, it is easily obtained
from iron pentacarbonyl through a relatively inexpensive chemical vapor
deposition (CVD) process. Some properties of the magnetic dispersed
phase have been studied: Felt et al [1] studied the effect of particle size on
the magnetorheological effect. Wu and Conrad [2] studied the role of
surface roughness, and Foister [3] studied the effect of particle size
distribution. Also, other soft magnetic materials have been studied [4].
Due to the increasing use of this kind of systems in many fields [5], it seems
necessary to incorporate novel studies concerning the relation between their
rheological and magnetic properties. The aim of the present work is to
investigate the effect of the existence of a remanent magnetization in the

2576
 Magnetic Hysteresis 2577

solid phase, after the application of an external magnetic field, on the

rheological properties of MRF's. In order to do that, we will not only study
their flow properties but also their dynamic oscillatory behavior.
This paper is organized as follows: Sec. 2 is devoted to the experimental
part. Firstly, we describe the model system including its magnetic
characterization. Then, the steady shear and dynamic oscillatory studies are
described. Finally, in Sec. 3 the results are discussed.

2 Experimental
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Cobalt ferrite particles were prepared following the coprecipitation method

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described elsewhere [6,7]. The method involves the precipitation of iron

(II) and cobalt (II) hydroxides that, upon heating at 90°C in an oxidizing
aqueous medium, yield the ferrite particles with a diameter of 850 ±150
nm. The density of the particles was ascertained by picnometry and resulted
3.6 ± 0.1 g-cm"3. The MRF consisted in a suspension of these cobalt ferrite
particles in silicone oil (47V20) with viscosity 0.02 Pa*s and density 0.95
g-cm'3 (Rhone-Poulenc, France). With the purpose of avoiding the
sedimentation of the particles during the experiments, 1.5 % w/w of fine
spherical particles of silica gel with 7 nm of diameter (Aerosil-300) was
added to the suspensions.
The magnetization of the solids was measured as a function of the applied
magnetic field H 0 in a Manics DSM-8 magneto-susceptometer (France).
The whole magnetic characterization can be found elsewhere [7].
Steady shear and dynamic oscillatory properties were investigated with a
plate-plate (20 mm of diameter) controlled-stress rheometer (Haake
RSI50) at 25°C. The magnetic field was always oriented in perpendicular
direction to the plates. The gap was fixed at 0.1 mm.
Figs, la and lb schematically show the experimental procedures. In all
cases studied, the suspensions were subjected to a steady preshear of 700
Pa during 60 s. The magnetic field was immediately applied at the end of
the preshear, maintained for 480 s and suddenly removed. Seven
experiments were performed for each sample, varing the external magnetic
field according to the next sequence: 0, 29.7, 23.7, 17.8, 11.9, 5.9 and 0
kA/m. In the stress-amplitude sweep experiments the frequency was fixed
to 1 Hz.
Also, frequency sweep experiments were performed in a similar way. For
each magnetic field, the stress amplitude applied (to) followed the
sequence: 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 18, 21,24, 27, 30, 33 and 40 Pa.
The curve corresponding to the maximum stress amplitude still in the
 2578 J. De Vicente et al.

66
viscoelastic linear region" is only considered. The fact that the response to
low enough excitations depends on its value has also been reported in the
literature for ERF [8].

Preshear Measurement
ramp
(a)
\
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t(s)
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HopqA/ii)
29.'
23:

5.9 4
t(s)

3060 180 300 Constant magnetic field

applied

;»;< >;< >;< >j

3060 180 300

Figure 1. Schematics of the experimental routines in steady-shear (a) and dynamic oscillatory (b) experiments. In
(a), the sequence is: preshear, equilibration, shear ramp, preshear, magnetic field on, equilibration, shear ramp, and
so on. In (b) the steady shear ramps are substituted by an oscillatory shear, with increasing amplitude and frequency
1Hz.
 Magnetic Hysteresis 2579

3 Results and discussions

Steady-state measurements performed as described above showed that the

dimensionless shear-stress (x*), defined by

normalized by the particle volume fraction ($), depends linearly on the

Mason number (Mn) in the range Mn = 10"4 - 10"1, for the maximum
magnetic field, and volume fractions between 0.5 and 7.5 %. Recall that
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Mn is given by
8r| t
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^" = -^fer c
W
where r\c and \icr are the apparent viscosity and relative permeability of the
continuous phase (silicone oil) respectively, (5 = —— — is the magnetic

contrast factor and iipr is the relative permeability of the particles. The
results, not shown here for brevity, demonstrate a good agreement with the
predictions of non-interacting chain models, no matter the hydrodynamic
interaction considered [9]: a slope close to -1 is found in all cases when
x*/<|> is plotted vs. Mn in a log-log scale. For Mn below = 10"4, a plateau is
found for x*/<|>, suggesting that the suspensions do not exhibit a pure
Bingham behavior, other researchers found similar results [10].
It is also possible to perform a similar analysis in oscillatory measurements,
by studying the viscoelastic behavior during a frequency sweep experiment
analogous to the one described in Fig. lb. for an amplitude stress sweep. In
terms of the dynamic analogues of x* and Mn, the curves properly scale
and have almost identical slopes (-1 ± 5X10"4) (we do not show the results
here for brevity).
However, the most important finding concerns the rheological behavior
obtained for a high enough volume fraction (= 7.5 %), by varying the
external magnetic field in the sequence described in the Sec. 2. In this case,
the curves (x* vs. Mn), both in stationary and dynamic conditions, no
longer collapse although their separation decreases when the volume
fraction decreases (inset in Fig. 2). Fig. 2 is a typical example of the steady
flow curves in the cobalt ferrite suspensions.
Non-negligible thermodynamic forces are not a good explanation for the
lack of scaling since for high fields the typical size of the aggregates must
increase and hence the effect of brownian motion should be less significant.
 2580 J. De Vicente et al.

We would expect larger viscosities for larger fields contrary to our

experimental findings (Fig. 2).
10 T
H0 (kA/m)
—n- - 5 . 9
10°^
— O - -11.9
— A - -17.8

104 —v--23.7
—O- -29.7
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iow
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Figure 2. Typical flow curves of 2.5 % volume fraction cobalt ferrite suspensions for different external magnetic
fields. Inset: width of the steady-state T* VS. Mn plots for cobalt ferrite suspensions of different volume fractions.

The possibility that we have two magnetic forces, one coming from the
induced magnetization (at high fields), and the other from the permanent
magnetization of the particles (at low fields) could explain the lack of
scaling at low fields and the trend of the curves to collapse for H 0 >« 20
kA/m.
A stronger evidence of this interpretation comes from the analysis of
the dependence of the yield stress (xy) on the external field. xy was
calculated following the usual procedure of extrapolating the stress towards
zero shear rate in a logaritmic scale. The results are shown in Fig. 3a. In
our opinion, a more precise determination can be done by applying a stress
ramp in the oscillatory regime (Fig. lb). From dynamic measurements it is
possible to obtain a similar behavior (Fig. 3b). We will call "critical stress"
(xc) to the one corresponding to the sharp decrease in the curve G' (storage
modulus) vs. To in an oscillatory amplitude sweep.
The increase in xy under the application of the magnetic field is easily
explainable due to the structuration of the MRF. At high fields the model of
multipolar interactions between polarizable particles is enough to predict
the behavior observed. At medium fields, the chains formed by the
 Magnetic Hysteresis 2581

permanent moments could be aligned with the external field. In this

situation the yield stress will be low and the chains will break at low angle.
At low fields, the chains are not oriented by the field but by the strain and
they break at higher angle giving a higher yield stress [11].
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i—•—i—•—i—«—i—•—»—•—i—•—r
0 29.7 23.7 17.8 11.9 5.9 0
H0(kA/m)

Figure 3. a) Yield stress as a function of the external magneticfieldfor different volumefractions,b) Same as a),
but for critical stress.

To check this qualitative explanation we did similar experiences in carbonyl

iron based MRF's. Following the same process as described in Fig la, the
results obtained are coherent with our previous discussion (Fig. 4). The
yield stress monotonically decreases towards its value at zero field, never
surpassing it.
In conclusion, we have shown an other kind of MR fluid which works at
low fields (between 0 and 17.8 kA/m) with the opposite effect: decrease of
the yield stress with the field. This MRF can be improved by using particles
with stronger remanent magnetization.
 2582 J. De Vicente et al.
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i • 1 « 1 * 1 « 1 » 1 • r
0 29.7 23.7 17.8 11.9 5.9 0
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H0(kA/m)
Figure 4. Yield stress of suspensions of carbonyl iron particles at 10 % volumenfraction,as afiinctionof the
applied magnetic field.

Acknowledgements

Financial support through projects MAT98-0940 (CICYT, Spain) and

INTAS99-0510 (EU) is gratefully acknowledged.

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