Journal of Magnetism and Magnetic Materials 416 (2016) 110–116

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Magnetoviscous effect in ferrofluids with different dispersion media

D.Yu Borin a, V.V. Korolev b, A.G. Ramazanova b,n, S. Odenbach a, O.V. Balmasova b,
V.I. Yashkova b, D.V. Korolev c
a
TU Dresden, Institute of Fluid Mechanics, Dresden 01062, Germany
b
G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo, Russia
c
Federal Sate Unitary Enterprise all Russian Scientific Research Institute of Aviation Materials, Russia

art ic l e i nf o a b s t r a c t

Article history: Ferrofluids based on magnetite nanoparticles dispersed in different carrier media (dialkyldiphenyl and
Received 9 February 2016 polyethylsiloxane) have been synthesized using mixed surfactants (oleic acid, stearic acid and alkenyl
Received in revised form succinic anhydride). Magnetic properties of the samples and a change of their shear viscosities in an
15 April 2016
applied magnetic field have been studied in order to evaluate an influence of the carrier medium on a
Accepted 7 May 2016
Available online 11 May 2016
magnetoviscous effect. A significance of the interaction of the carrier medium and surfactant with a
consideration of the magnetic and rheological behavior of ferrofluids was demonstrated.
Keywords: & 2016 Elsevier B.V. All rights reserved.
Ferrofluid
Magnetoviscous effect
Rheology
Alkyldiphenyl
Polyethylsiloxane
Alkenyl succinic anhydride

1. Introduction magnetization and liquidity, ferrofluids are used in divers techni-

Ferrofluids are unique magnetic colloidal systems, whose dis-
perse phase is represented by magnetic nanoparticles. The parti-
cles are usually coated with a mono- or bimolecular layer of the
surfactant and suspended in an organic or non-organic carrier li-
quid. The character of the surfactant, the carrier liquid and the size
of the magnetic particles are determining parameters for the sta-
bility of ferrofluids. A mean size of classical magnetite particles
used in ferrofluids is about 10 nm and they have a nearly spherical
shape [1]. This size provides the gravitational and magnetic sta-
bility of these colloids. Previous researches have shown that
commercial samples of ferrofluids often represent polydisperse
systems which contain particles fractions with much higher sizes
[2,3], which lead to a change of the ferrofluids viscosity in an ex-
ternally applied magnetic field. It is usually referred as the mag-
netoviscous effect for colloids with single domain ferromagnetic
particles and magnetorheological effect for suspension with non-
Brownian particles [2,3]. A change of the particles material, e.g.
cobalt instead of magnetite, will lead to a changed interparticular
interaction and to a modified rheological behavior of the ferrofluid
respectively. The possibility to tune and control the rheology of
ferrofluids is of a high practical importance [3]. Due to a high
n
Corresponding author.
E-mail address: agr@isc-ras.ru (A.G. Ramazanova).
cal applications, e.g. as a liquid sealing in chemical and biochem-
ical reactors and vacuum feedthroughs, as well as a working body
in tilt sensors etc [1,3–5]. Furthermore, ferrofluids based on con-
ventional lubricating oils show improved tribological character-
istics [6,7].
A targeted synthesis of stable magnetic colloids with desired
physical and chemical properties is a challenging scientific task,
which requires exhaustive studies and, particularly, magne-
torheological characterization. A detailed viewpoint on a flow
behavior of ferrofluids can significantly expand an area of their
applications. Many studies are focused on commercial ferrofluid
samples, for which scarcely ever an exact composition or synthesis
procedure is known. Furthermore, a systematical analysis of the
surfactant influence on magnetoviscous effect in ferrofluids is as
well rather poor published. More attention is usually given to the
nanoparticles material and morphology [8–16] as well as to the
fluid stability [17–20]. Recently, a magnetoviscous effect in a pure
biocompatible ferrofluid and a sample diluted with blood has been
experimentally evaluated, while significantly higher effect was
measured in the diluted samples [21]. Theoretical predictions of
the ferrofluid rheology based on the rotational viscosity and
chains/droplets formation approaches are not able to give an ex-
planation of the enhanced magnetoviscous effect [22–24]. As-
sumably, in this case a complex interaction between a carrier
medium and magnetic nanoparticles should be taken into account.
This requires special investigations.

http://dx.doi.org/10.1016/j.jmmm.2016.05.024
0304-8853/& 2016 Elsevier B.V. All rights reserved.
 D.Yu Borin et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 110–116
In this study stable magnetic colloids based on magnetite na-
noparticles suspended in different dispersion media have been
synthesized. A primary goal was to evaluate an influence of the
carrier medium and surfactant on the magnetoviscous effect in
ferrofluids. Synthesized samples in this work contain magnetite
nanoparticles from one batch and are based on dialkyldiphenyl
and polyethylsiloxane, while combinations of the oleic acid, stearic
acid and alkenylsuccinic anhydride are used as a surfactant to
cover the particles. These compositions makes these ferrofluids
very attractive for engineering oriented application, e.g. at low and
high temperatures, under vacuum condition etc. Magnetic beha-
vior and magnetoviscous effect are experimentally studied and an
influence of the synthesis conditions on a rheological behavior of
these colloids is evaluated.
2. Materials
The following commercial grade components from Acros Or-
ganics have been used: iron sulfate ( FeSO4 ·7H2 O , 99%), iron
chloride ( FeCl3·6H2 O, 98%), aqueous ammonia ( NH4 OH, 25%), oleic
acid ( C17H33, 97%), alkenylsuccinic anhydride ( C76 H145 O3, 80%).
2.1. Nanoparticles
Magnetite nanoparticles have been synthesized using an in-
tensive mixing of the iron sulfate salt (II) and iron chloride (III) salt
with an excess amount of the aqua ammonia solution ( NH4 OH) in
a thermostatically controlled vessel at a temperature of 298 K.
Similar methods are reported elsewhere and protected with
patents [25–28].
Obtained suspension has been repeatedly flushed out with
distilled water up to pH ¼7–8. A cleaning grade of the suspension
from sulfate and chloride ions was proved verifying the specific
electrical conductivity of the flush water (1.77 μSm cm  1) as it has
been reported in [29].
To characterize a crystal structure and specific surface of the
nanoparticles an X-Ray analysis of a water suspension of the
synthesized magnetite was conducted using a method presented
in [25]. The X-Ray diffractometer ‘Dron-3’ has been used (diffrac-
tion at small-angels of 2θ = 1 − 30°). Results of the XRD analysis
have shown that most of magnetite crystals have a size of
7.5 ± 3.5 nm .
2.2. Dispersion medium
As dispersion medium dialkyldiphenyl (Alkaren D24S) and
polyethylsiloxane (PES-5tm) were used. Dialkyldiphenyl has a low
viscosity, low vapor pressure, high thermal oxidation stability,
good tribological characteristics and is not affected by the hydro-
lysis. Moreover, it is non toxic and nonreactive. Polyethylsiloxane
is a molecular species, whose molecules consist of interlacing si-
licon and oxygen atoms with cut in hydrocarbonic chemical
groups via unlinked silicon bonds. A polyethylsiloxane liquid used
in this study (PES-5) is known for its low saturated vapor pressure,
low melting point, good dielectric and hydrophobic properties,
low temperature viscosity coefficient and low surface tension.
Additionally, it has a good thermal conductivity and thermal oxi-
dation stability. Such polyethylsiloxane liquid can be used as a
carrier medium of ferrofluids utilized for the liquid sealing and is
especially suitable at low temperatures and vacuum conditions.
Alkaren D24S and PES-5 are considered as Newtonian liquids with
viscosities of 0.046 Pa s and 0.250 Pa s at 20 °C respectively.
111
Fig. 1. Schematic of the molecular structure of alkenylsuccinic anhydride [30].
2.3. Ferrofluid samples
Ferrofluid samples have been produced in two basic stages:
synthesis of magnetic nanoparticles with colloidal sizes and their
stabilization in a liquid medium.
Magnetite was centrifuged and, afterwards, the surface of the
particles was stabilized with a monomolecular absorbing layer of
surfactant followed by a peptizing of the stabilized magnetite in a
disperse medium at T ¼85 °C during 6–10 h under vacuum. The
protective absorbing layer guaranties an aggregation stability of
the ferrofluids. This layer must have a certain thickness in order to
limit an interparticle attraction. Moreover, the coating has to be
sturdy against effects of electrolyte, temperature and mechanical
vibrations. A mixture of oleic acid and alkenylsuccinic anhydride
(Fig. 1) has been used as a surfactant. Alkenylsuccinic anhydride is
intended to enhance a protection of magnetite nanoparticles from
corrosion. It is expected that this mixed surfactant will expand an
applicability of the ferrofluid.
A composition and basic properties of the samples synthesized
within the study are given in Table 1.
3. Experimental
3.1. Magnetic measurements
Magnetic measurements were conducted using a vibrating
sample magnetometer (Lake Shore 7407). An effective applied
magnetic field H was calculated taking into account the geome-
trical demagnetizing factor N
H = Hext − M (H )·N, (1)
where Hext is the strength of an externally applied field, M(H) is the
magnetization of the fluid. The geometrical demagnetizing factor
is N ¼0.44 for the given geometry of the sample holder.
Results of magnetic measurements are presented in Fig. 2 and
Table 2. All samples show for ferrofluids typical super-
paramagnetic behavior without magnetic hysteresis. The satura-
tion magnetization is estimated comparing experimental results
with a spontaneous magnetization of the magnetite (446 kA/m
[1]). The initial magnetic susceptibility is calculated using a linear
approximation of the magnetization curve (H ) in the range of the
low values of an applied field. It is possible to estimate the size of
magnetite cores for monodomain nanoparticles dispersed in a
ferrofluid using the initial susceptibility which is approximated
from the measurements as given by [1]:
π M 2 d3
χi = ϕμ 0 0 ,
18 kT (2)
where χi denotes the initial magnetic susceptibility, μ0 the vacuum
permeability, M0 the spontaneous magnetization of the magnetic
material, d the diameter of the nanoparticles, kB the Boltzmann's
112 D.Yu Borin et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 110–116

Table 1
Composition and basic properties of the synthesized ferrofluid samples (T ¼ 23 °C).

Sample Surfactant Dispersion medium Density, g/cm3 Viscosity, Pa s

1 Alkenyl succinic anhydride Alkaren D24S 1.10 0.35

2 Oleic acid/alkenyl succinic anhydride (2:8) Alkaren D24S 1.23 0.54
3 Oleic acid/stearic acid/ alkenyl succinic anhydride (1:1:8) Alkaren D24S 1.04 0.60
4 Oleic acid/alkenyl succinic anhydride (2:8) PES-5 1.12 0.29
5 Oleic acid/stearic acid/ alkenyl succinic anhydride (1:1:8) PES-5 1.17 0.46

16 be used: since initial parts of the magnetization curves are more or

less coincide, different saturation magnetization is likely reasoned
14
with a various amount of the effectively suspended nanoparticles.
12
A substitution of 10% oleic acid with stearic acid apparently has no
influence on the initial susceptibility of the polyethylsiloxane
10 10 based samples. Noticeable is a difference in a magnetization be-
M, kA/m

8
tween polyethylsiloxane based ferrofluids (samples 4,5) and those
8 based on dialkyldiphenyl (samples 1,2,3). Samples based on poly-
6
ethylsiloxane demonstrate a higher initial magnetic susceptibility.
6
4 This can be caused either by less absorption of the continuous
4 sample 1 2 phase on the magnetite surface or by a variation in magnetic cores
sample 2 sizes. Magnetorheological measurements presented below provide
sample 3 0
2 sample 4 further details on this issue.
0 5 10 15 20
sample 5
0
0 200 400 600 800 1000 1200 3.2. Rheology
H, kA/m
Steady-shear rheological measurements were conducted using
Fig. 2. Magnetization curves of the ferrofluid samples. a rotational rheometer Anton Paar Physica MCR501 occupied with
a magnetorheological device MRD [31]. As measuring geometry a
Table 2 conventional plate–plate arrangement was utilized. The used ex-
Samples properties obtained using magnetometry (T ¼20 °C).
perimental procedure is fairly conventional for magnetically sen-
sample Initial suscept- Saturation mag- Magnetic con- Magnetic sitive liquids: ferrofluids are presheared at same conditions (shear
ibility, χi netization, Ms (kA/ centration (vol%) core size rate γ ̇ ¼ 100 s  1) during 60 s. before the field measurements and
m) (nm) after each application of the magnetic field; temperature of the
samples and measuring geometry is controlled through-out the
1 0.8 15.5 3.5 13.0
2 0.7 12.9 2.9 13.0 whole experiment. Results of the measurements without applied
3 0.8 12.9 2.9 13.6 magnetic field are verified using a cone–plate arrangement, which
4 1.1 15.0 3.4 14.5 provides a constant shear rate through the measuring gap.
5 1.2 16.0 3.6 14.7 Moreover, control experiments using a customized ferrofluid
rheometer were conducted for the fields lower than 40 kA/m. This
constant and T the absolute temperature. rheometer [32] provides a possibility to use a cone–plate ar-
Values of saturation magnetization are equal for two samples rangement in a combination with an applied magnetic field in
only. Magnetite nanoparticles have been dispersed in an identical opposition to the conventional configuration of the MRD device.
weight concentration, therefore, one can expect the same volume However, the range of the field strength which can be applied to a
concentration of the magnetic material for the samples with the sample in the ferrofluid rheometer is limited.
same density of the carrier medium. It is fulfilled for the samples Flow curves measured for the studied ferrofluids without ap-
2 and 3 which are based on dialkyldiphenyl and a combined sur- plied magnetic field can be linearly approximated using the
factant. The sample 1 with a same carrier medium has a higher Newton approach (Fig. 3)
saturation magnetization. For this sample only alkenylsuccinic τ = ηγ ,̇ (3)
anhydride as a surfactant was used and, therefore, higher mag-
netization losses in samples 2 and 3 caused by the absorption of where τ denotes the shear stress, η the viscosity and γ ̇ the shear
the combined surfactant in a surface layer of the magnetite could rate. A comparison of the samples and carrier mediums viscosity is
be assumed [1]. However, initial parts of the magnetization curves provided in Fig. 4. The highest viscosity has the sample 3 and the
for these three samples (samples 1,2 and 3) are approximately lowest viscosity is a feature of the sample 4. Although the viscosity
coincide (see inlet in Fig. 2). The estimated size of magnetic cores of the pure Alkaren 24s (dialkyldiphenyl) is lower than the visc-
using Eq. (2) is equal for the samples 1 and 2, and somewhat larger osity of the pure “PES-5” (polyethylsiloxane), the sample 3 has a
for the sample 3. Hence, from this point of view, it seems to be higher viscosity than the sample 5. According to the magnetization
more realistic, that differences in the saturation magnetization of data, the sample 5 has even a somewhat higher concentration of
these three samples are caused with uncertainties of the magne- the magnetic nanoparticles, thus, one could expect a higher visc-
tite dispergation, i.e. an amount of the effectively suspended na- osity for this sample compared to that of sample 3. However, a
noparticles is higher for the sample 1. A substitution of 10% oleic noteworthy detail is that the hydrodynamic concentration of the
acid with stearic acid leads to a slight change of the initial particles is unknown. Presumably, dialkyldiphenyl interacts with a
magnetization. surfactant, which is absorbed on the magnetite surface. As a result
By comparison of the ferrofluid samples 4 and 5, which are a competent stable structure is formed and, therefore, a viscosity
based on a polyethylsiloxane liquid, the same argumentation can of the ferrofluids based on dialkyldiphenyl becomes significantly
 D.Yu Borin et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 110–116
Fig. 3. Flow curves of the ferrofluid samples without applied magnetic field. Solid
lines represent linear fits of the experimental data.
Fig. 4. Viscosities of pure carrier liquids and ferrofluid samples without applied
magnetic field.
higher. Polyethylsiloxane is rather indifferent relative to the sur-
factant and changes the viscosity of the ferrofluid in a lesser ex-
tent. It is also evident from a comparison of the ferrofluid samples
2 and 4. A substitution of the 10% oleic acid with stearic acid
during stabilization of the magnetite nanoparticles leads to an
increase of the viscosity of ferrofluids based on both kinds of the
carrier medium (samples 2 and 3, and samples 4 and 5).
Application of an external magnetic field significantly changes
the flow behavior of all studied samples. In particular, the shear
viscosity of ferrofluids increases with an increasing magnetic field.
Moreover, a shear thinning is observed at certain strengths of the
applied field. This change of the rheological behavior is associated
with a structure formation forced by the magnetic field and is
usually referred as the magnetoviscous effect [2]. According to the
magnetization data, a mean size of the magnetic cores in all
samples is smaller than ∼14 − 15 nm . However, ferrofluids are in a
varying degree polydisperse suspensions and, as it has been
shown in the past, even a few content of the large magnetic par-
ticles will contribute to significant rheological changes due to
structure formation forced by the magnetic dipole interaction
[2,3]. That is why a key parameter, which provides an evidence of
the structuring, is the amount of the large nanoparticles, regard-
less of a mean size and a total magnetic concentration.
For the samples 1, 2 and 4 a shear thinning is observed at field
strengths equal or higher than 50 kA/m, while the behavior of the
113
Fig. 5. Flow curves of the dialkyldiphenyl based sample with oleic acid and alkenyl
succinic anhydride as a mixed surfactant (sample 2) for various magnetic field
strengths. Solid lines represent fits of the experimental data using the Newtonian
(H¼ 0,10,25 kA/m) and power law models (H ¼50,100 kA/m). Parameters of the
fitting are given in Table 3.
Fig. 6. Flow curves of the polyethylsiloxane based sample with oleic acid, stearic
acid and alkenyl succinic anhydride as a mixed surfactant (sample 5) for various
magnetic field strengths. Solid lines represent fits of the experimental data using
the Newtonian (H¼ 0 kA/m) and power law models (H¼ 10,25,50,100 kA/m).
(Parameters of the fitting are given in Table 3).
samples 3 and 5 is clearly non-Newtonian already at the lowest
applied field H¼ 10 kA/m. As an illustration, flow curves for sam-
ples 2 and 5 are presented in Figs. 5 and 6. The observed non-
Newtonian behavior of all samples can be well described using a
power law approximation:
τ = Kγ ṅ , (4)
where K is the flow consistency index and n is the dimensionless
flow behavior index. Parameters of the fitting are collected in
Table 3.
In Fig. 7 flow curves of the studied samples measured at the
field strength of 100 kA/m are given. A deviation from the New-
tonian behavior is mostly expressed for the sample 5 and corre-
lates with a maximal concentration of the magnetic material and
largest mean magnetic core size obtained from magnetic mea-
surements (Table 2). On the other hand, the sample 3 with the
lowest concentration of magnetic material shows as well a sig-
nificant deviation from the Newtonian behavior, even in a low
magnetic field, while remainder samples have linear flow curves at
the same field. Thus, only deviation of the concentration of the
114 D.Yu Borin et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 110–116

Table 3
Parameters of the fitting of the measured flow curves for various magnetic field
strengths. Asymptotic standard error for all final fit parameters does not exceed
±2% .

Sample H¼ 0 kA/m H¼ 10 kA/m H¼ 25 kA/m H¼50 kA/m H¼100 kA/m

τ = ηγ ̇ τ= K ·γ ṅ
1 η = 0.35 η = 0.37 η = 0.43 K¼0.76 K¼ 1.13
n¼0.91 n¼ 0.85
τ = ηγ ̇ τ = K ·γ ṅ
2 η = 0.54 η = 0.56 η = 0.62 K¼0.84 K¼ 0.93
n¼0.95 n¼ 0.94
τ = ηγ ̇ τ = K ·γ ṅ
3 η = 0.60 K ¼0.83 K¼ 1.03 K¼1.33 K¼ 1.75
n ¼0.95 n ¼0.93 n¼0.90 n¼ 0.86
τ = ηγ ̇ τ = K ·γ ṅ
4 η = 0.29 η = 0.33 η = 0.39 K¼0.70 K¼ 0.93
n¼0.90 n¼ 0.86
τ = ηγ ̇ τ = K ·γ ṅ
5 η = 0.46 K ¼1.13 K¼ 2.62 K¼8.64 K¼ 20.08 Fig. 8. Absolute change of the samples' viscosity (ΔηA ) in an applied magnetic field.
n ¼0.84 n ¼0.73 n¼0.54 n¼ 0.43

5 followed by sample 3. In these samples 10% of oleic acid is

Fig. 7. Flow curves of the ferrofluid samples at H¼ 100 kA/m. Solid lines represent
non-linear fits of the experimental data (parameters of the fitting are given in
Table 3).
magnetic material as well as of the mean size of the magnetic
cores can not provide an explanation of the observed variation in
the ferrofluids behavior. An interaction between carrier medium,
surfactant and magnetic particles can be of importance here.
Furthermore, as it is mentioned above, a distribution of the na-
noparticles' magnetic core sizes must be taken into account.
4. Discussion
Quantitatively the magnetoviscous effect in ferrofluids is
characterized using the absolute ( ΔηA ) and relative ( ΔηR ) change of
the shear viscosity forced by an applied magnetic field H:
ΔηH − Δη0
ΔηA = ΔηH − Δη0, ΔηR = , For further discussion let us consider the magnetic core size
Δη0 (5)
where η0 is the shear viscosity of the fluid in the absence of
magnetic field and ηH is the shear viscosity in the field H. For fluids
with a non-Newtonian behavior a dependence of the viscosity on γ ̇
must be taken into account. In this case the magnetoviscous effect
is estimated for an equivalent range or for a certain value of the
shear rate. Dependencies of ΔηA and ΔηR on the applied magnetic
field strength at γ ̇ = 100 s−1 are shown in Figs. 8 and 9 respectively.
The highest absolute change of viscosity is a feature of the sample
substituted with stearic acid. The lowest effect is a feature of the
samples 2 and 4. These trends are observed at all used field
strengths. In the case of the relative magnetoviscous effect (Fig. 9)
the lowest change is observed for the sample 2 and it is accounted
to the highest initial viscosity.
In order to provide a basis for the clarification of the observed
magnetoviscous effect in the studied samples an information
about the sizes of magnetic nanoparticles is essential. It is well
known and already mentioned above, that the magnetoviscous
effect is associated with a structure formation forced by an applied
magnetic field. The most important parameter for the description
of the field induced structuring is the interaction parameter λ. It
was introduced in [1] as λ = μ0 M02 V2 / 24kB T , where μ0 denotes
( )( )
the vacuum permeability, M0 the spontaneous magnetization of
the magnetic material, V the volume of the magnetic material and
d the mean diameter of the nanoparticles. The formation of
structures is to be expected when λ is significantly larger than
unity. Typically, magnetite nanoparticles to be certainly involved
in the structuring should have diameters larger than 13 nm. Since
the mean size of magnetic cores in all studied samples exceeds this
value (Table 2), it corresponds with the observation of the mag-
netoviscous effect. On the other hand, due to a surfactant coating
the magnetic nanoparticles, they can not be in contact. Therefore,
the magnetic forces must be strong enough to bridge the surfac-
tant layer. To take it into account the parameter should be mod-
ified as given by [33]
μ 0 M02 V 2 ⎛ d ⎞3
λ* = ⎜ ⎟ ,
24kB T ⎝ d + 2s ⎠ (6)
where s denotes the coating thickness. According to Eq. (6), the
thicker a coating layer is, the smaller will be parameter λ* at the
same core diameter. Thereby, the highest effect, observed for the
samples 3 and 5, which have an identically mixed surfactant (oleic
acid, stearic acid and alkenyl succinic anhydride), can be explained
with the thinnest coating layer.
distribution. A very efficient method to perform such analysis for a
ferrofluid is the regularization technique of Tichonov, which al-
lows to determine the distribution of discrete sizes by fitting the
equilibrium magnetization to the measured magnetization curve
[34]. Discrete particle size distribution for the dialkyldiphenyl
based samples is given in Fig. 10 and for the polyethylsiloxane
based samples in Fig. 11. These results are basically in a good
agreement with results of the XRD analysis performed for the
magnetite nanoparticles. On the other hand regularization method
 D.Yu Borin et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 110–116
Fig. 9. Relative change of the samples' viscosity ( ΔηR ) in an applied magnetic field.
Fig. 10. Discrete particle size distribution by regularization method of Tichonov
[34] for the dialkyldiphenyl based samples.
Fig. 11. Discrete particle size distribution by regularization method of Tichonov
[34] for the polyethylsiloxane based samples.
provides quantitative data on magnetic cores size distribution di-
rectly in synthesized ferrofluids. All samples contain fractions of
large particles which are involved in a process of the structure
formation under an applied magnetic field. However, as it can be
115
seen, the highest magnetic concentrations of the samples 1 and
5 are determined mostly with particles smaller than ∼10 nm,
which are not causing a field dependent structure formation. On
the other hand, the sample 5 has the highest amount of particles
with the largest magnetic cores. Hence, additionally to the argu-
ments regarding the surfactant layer thickness, the presence of
particles with large magnetic cores seems to be a reason for the
highest magnetoviscous effect in this ferrofluid sample. The sam-
ple 3 has a lower amount of large particles than the sample 4, but
shows a non-Newton flow behavior already at the smallest field
strength, like the sample 5, and is characterized with a higher
absolute change of the viscosity than the polyethylsiloxane based
sample 4 as well as other samples based on the dialkyldiphenyl.
Moreover, the magnetic field has a higher impact when 10% of
oleic acid was substituted with stearic acid. Thus, a correlation of
such behavior with the surfactant mixed of the oleic acid, stearic
acid and alkenyl succinic anhydride can be specified and inference
should be drawn that a surfactant layer thickness has a major
impact on the observed effects.
Almost identical amounts of large particles for the samples
1 and 2 lead to a comparable structure formation, which is re-
flected in the nearly same absolute magnetoviscous effect (Fig. 8).
Considering relative effects (Fig. 9), one can observe some differ-
ences in the trends discussed above. These differences are simply
reasoned with the different zero field viscosity. However, notice-
able is a not highly pronounced effect for the sample 4, although it
has the lowest zero field viscosity and a little less amount of the
large magnetic nanoparticles than the sample 5. It emphasizes
once more a core role of the surfactant nature in the process of the
structure formation caused by an externally applied magnetic
field.
5. Conclusions
We have experimentally studied ferrofluid samples based on
different dispersive media and mixed surfactants. Samples based
on dialkyldiphenyl and polyethylsiloxane with dispersed magne-
tite particles covered with oleic acid, stearic acid and alke-
nylsuccinic anhydride were under consideration. Since magnetic
nanoparticles from one batch were used for different samples,
obtained results reveal an interaction between magnetic cores,
surfactant and carrier medium resulting in a changed magnetic
and rheological behavior of the ferrofluids. In particular, it has
been shown, that the nature of the surfactant can have a higher
116 D.Yu Borin et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 110–116
impact on the zero field shear viscosity of a ferrofluid than the
viscosity of the pure carrier medium. Furthermore, samples with
similar magnetic behavior can exhibit quite different magneto-
viscous effect, i.e. the magnetic core size distribution is not the
only determining reason of the structure formation in ferrofluids.
The surfactant mixed of oleic acid and alkenylsuccinic anhydride
prevent field induced structurization and an applied magnetic
field has a higher impact on the structuring when 10% of oleic acid
is substituted with stearic acid, while magnetic properties of the
ferrofluid are not changed.
A targeted variation and modification of the mixed surfactant
components provide an efficient possibility to obtain a ferrofluid
with optimized parameters for a certain application and can be as
well used in a development of new devices and technologies based
on magnetic colloids.
Acknowledgment
The work was supported by RFBR grant 12-03-97553.
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