MAGNETOHYDRODYNAMIGS Vol. 48 (2012), No. 3, pp.

493-501
MAGNETIC ORDERING IN COLLOIDAL SYSTEMS
OF SINGLE-DOMAIN PARTICLES
Yu.I. Dikansky, D.V. Gladkikh, S.A. Kunikin, A.A. Zolotukhin
Stavropol State University, 355009 Stavropol, Russia
e-Mail: Dikansky@mail.ru
Results are reported, which confirm the possibility of magnetic ordering emergence in
magnetic colloids. Conditions providing the emergence of magnetized structural aggre-
gations in the above-mentioned systems have been analyzed; results of investigations
of original samples (fluids), in which they can be produced, as well as colloids with a
well-developed system of magnetized aggregates are discussed,
1. Introduction. The possibility of long-range magnetic ordering emergence
in a system of colloidal single-domain particles has been considered previously [1-
10], however, so far the problem remains unclear. With reference to theoretical
conclusions [11], the implementation of such an order is not feasible in an ensemble
of particles experiencing only magnetic dipole interactions. On the contrary, ac-
cording to the results of numerical modelling of dipole systems in [3,4], the dipole
interactions might result in the formation of "ferromagnetic" phase in the form
of a domain with non-uniform magnetization. Similar results have been obtained
analytically in [5,6], and in [7] it is reported on "ferromagnetic fluctuations" in a
magnetic colloid with iron nitride particles. Referring to the analysis of the already
known and newly obtained results of magnetic measurements of different types of
ferrocolloids [8, 9], it has been concluded that the assumption on the possibility of
spontaneous transition to the state of magnetic ordering in such systems has not
been verified. It should be emphasized, however, that the magnetic colloids, un-
like an idealized system of dipole particles, are a much more complicated system
with polydisperse particles, which, when exposed to a field or other factors re-
lated to their colloidal structure, are capable to form complex magnetostructural
bonds, which have a significant impact on the magnetization processes of such
systems. This allows to presume that the magnetization, occurring due to the
interaction of particles or due to the action of external fields, can be preserved in
structural aggregations composed of colloidal particles. Previously it was reported
in [10] that a well-developed system of magnetized aggregates had been found in a
kerosene-based magnetic fluid (MF) at its long storage. The method is discussed
and conditions of aggregates production are determined in [12]. The current paper
discusses some results of the study of magnetic fluids with such aggregates as well
as original (source) magnetic fluids, in which they originate.
2. Method and procedure of experimental investigations. The struc-
tural aggregations were studied using an optical microscope equipped with Helm-
holtz coils to induce a magnetic field. The obtained images were further processed
by a computer. Magnetization was investigated by a Foner vibration sample mag-
netometer described in detail in [13]. The initial fragment of the magnetization
curves was plotted by a ballistic method using the field "switch on/off", with a MF
sample in the measurement loop. For this purpose, the measuring cell was placed
493
Yu.I. Dikansky, D.V. Gladkikh, S.A. Kunikin, A.A. Zolotukhin
Fig. 1. Schematic presentation of the magnetizing system to study the initial fragment
of the magnetization curve.
into a magnetizing system (Fig. 1), which generates a uniform magnetic field. The
magnetic system is a cubic coil with a five-sectioned winding [14], with the winding
ratio being 19:4:10:4:19. The field non-uniformity at the place of location of the
measuring cell windings does not exceed 0.3%.
The measurement cell was composed of two coils, inserted one into another,
with windings connected opposite to each other. The length of the coils was 7 cm;
the winding of the first coil of larger diameter had 1177 turns and the second
one had 8030 turns of copper wire of 0.2 mm in diameter. The following ratio
was kept SiUi = S2n-2, where ^i , Ui, S2, 7^2 are the cross-section and the num-
ber of turns in the first and second coils, respectively. The coils were coaxially
put on a quartz tube with taps for pumping water for thermostatting. A vessel
(length 40 mm, inner diameter 0.69 cm) with a magnetic fiuid sample under study
was placed coaxially into the quartz tube. The temperature was controlled by a
copper-constantan thermocouple. The setup allowed investigations within a tem-
perature range of 273 to 365 K and in fields of 10 A/m to lOkA/m intensity. The
magnetizing coils were power supplied from a DC power source GPR-7550D. The
magnetizing system was placed along the earth meridian in order to compensate
the earth magnetic field by passing the direct current, which induced a magnetic
fiux, being equal and opposite in direction to the earth one, through the magnetiz-
ing system. Variations of the magnetic fiux through the windings of the measuring
coils, when the field was switched off, were measured by a F199 micro-vibrometer
(the error for the most sensitive limit did not exceed 2.5%).
The magnetization for the described method was defined from the formula
where A$ is the variation of the magnetic fiux through the measuring coils, when
494
Magnetic ordering in colloidal systems of single-domain particles
the field is switched off; So is the cross-section area of a MF sample in the vessel;
An = 712 Ui.
The dynamic magnetic susceptibility was measured by the bridge method [15].
3. Results and discussion.
The conditions of aggregation in magnetic colloids are determined by the ratio
of forces of repulsion and attraction of colloidal particles. The most widespread
kerosene-based colloids are stabilized by the repulsion of sorption-solvate shells
formed by long-chained molecules of oleic acid. The attraction of the particles is
determined by magnetodipole forces and van der Waals forces. If the latter are of
isotropic nature, the efi'ectiveness of the magnetodipole interaction depends on the
mutual location of the particle moments. Herewith, the location is characterized
as by the forces directly as by their rotary moments. The direction of the dipole
moment of a single-domain particle can be changed due to thermal fiuctuations of
the magnetic moment direction inside the particle or by particle rotation due to
rotational diffusion.
Obviously, the domination of one or the other of the above situations must
aflect the processes of structure formation, however, with theoretical justification
for the aggregation processes in magnetic colloids, it is usually ignored. Real
magnetic colloids are polydisperse, but they might contain as small particles, which
are characterized by the Neel mechanism of relaxation, as larger particles, the
magnetic moment of which can be assumed to be rigidly connected to the solid
matrix at room temperatures.
Presently, with the intention to produce stable magnetic colloids, technologies
have been developed providing synthesis of such systems with particles of a limiting
small size (less than 8-9 nm), in which the magnetic moment direction changes due
to thermal fluctuations. Most of the colloids with larger particles (of the mean
diameter more than 10 nm) may be rigid magnetic dipoles. With reference to the
results of our studies, aggregates, which maintain the magnetic moment, can arise
in such colloids under certain conditions. Such aggregates, as a rule, exhibit a
well-pronounced shape anisotropy, respond quickly enough to the switch on of an
() (b)
Fig. 2. Magnetized aggregates emerged in a magnetic colloid at its long-term storage
(a) without the magnetic field and (b) with the field.
495
Yu.I. Dikansky, D.V. Gladkikh, S.A. Kunikin, A.A. Zolotukhin
I ' \ Vv
- \ . \
Fig. 3. Aggregates with the magnetic moment different from zero produced by diluting
a paste-like kerosene-based magnetic fluid.
external magnetic field and, in its absence, are aligned along the force lines of the
earth magnetic field. In some case, these aggregates demonstrate a filament shape,
and, in the absence of magnetic field, the minimum of magnetic energy is obtained
by branching and weaving of the aggregates.
The emergence of magnetized aggregates is possible at long-term (up to several
dozen years) storage of magnetic colloids with a relatively large mean particle size,
when the Brownian mechanism of magnetic relaxation is expected. Furthermore,
such aggregates can be produced by artificial violation of the aggregative stability
of such, originally homogeneous, colloids, when coagulators, for example, an excess
of oleic acid, are added.
Fig. 2 shows magnetized aggregates, which emerged in the magnetic colloid
at its long-term storage without the magnetic field and with the field. Fig. 3
illustrates similar aggregates produced by adding a 7% solution of oleic acid in
kerosene into an initially homogeneous paste-like magnetic fluid, the average size
of disperse particles of which was 14 nm.
Note that a typical feature of the magnetized aggregates is that, being ex-
posed to the external magnetic field, they trigger the formation of long enough
filamentary structures. In some cases, they may be flexible that leads to inter-
esting features of their motion when the direction of the field changes. As an
example. Fig. 4 illustrates the behaviour (motion) of a worm-like magnetized ag-
gregate caused by the change of the external magnetic field direction: (a) the field
is directed from right to left along the figure plane; ()-(e) the position of the
aggregate in equal time intervals (about 1 s) after the field changes its direction to
opposite.
As one can see from the figure, when the direction of the magnetic field
changes, such aggregate behaves like a liquid magnetized object. The behaviour
of the flexible ferromagnetic aggregate at field reversal quite similar to that is
considered in [16].
The investigation results on the magnetic properties of the samples used to
produce magnetized aggregates allow to conclude that the single-domain disperse
particles, which the aggregates are composed of, are magnetically rigid. Their
transformation into a paste due to the increase of the concentration or by intro-
ducing polymerizing additives, results in emergence of a hysteresis loop on their
magnetization curves (Fig. 5).
496
Magnetic ordering in colloidal systems of single-domain particles
(a)
(c)
id)
Fig. 4- 360 rotation of the magnetized aggregate when the external magnetic field
changes its direction to opposite.
20
15
10
-100 100 200 300 400 500 600
H, kA/m
Fig. 5. Magnetization curve of the original sample (in which the magnetized aggregates
have been then produced) and the scaled image of the initial fragment of the curve.
497
Yu.I. Dikansky, D.V. Gladkikh, S.A. Kunikin, A.A. Zolotukhin
100 200 300 400 500 600
H,kA/m
Fig. 6. Magnetization curve of a sample with magnetized aggregates and the scaled
image of the initial fragment of the curve.
The curves of sample magnetization with a well-developed system of magne-
tized aggregates may also exhibit the hysteretic character (see Fig. 6),
It has been found that the initial fragment of the magnetization curves of
the samples with magnetized aggregates has a bend in the zone of small values
of field strength (Fig. 7, curve ), which has never been registered previously for
homogeneous magnetic fluids (without aggregates). This bend has a sharper slope
than the initial fragment of the MF magnetization curve with the same amount of
the magnetic phase, but it is homogeneous in content (curve 2). The existence of
the bend on the magnetization curve evidences that the dependence of the mean
magnetic susceptibility (defined as x = M/H) on the magnetic field intensity has
its maximum in the zone of the bend.
As show the measurements in alternating fields under additional action by a
steady fleld, the field dependence of the real part of the magnetic susceptibility,
which can be identified as a differential susceptibility, also demonstrates the same
character. Fig. 8 illustrates dependences of the differential (curve 1) and the mean
(curve 2) magnetic susceptibility on the steady magnetic field intensity. As one
can see from the figure, there is a match of intensity values maxima, moreover, as
expected, it is more pronounced for the differential magnetic susceptibility. The
study of the dependence of the differential susceptibility on the steady field inten-
sity, with different values of the measuring field frequency, has shown independence
of the steady field intensity on the measuring field frequency corresponding to the
susceptibility maximum.
Apparently, the bend of the magnetization curve and, as a consequence, the
existence of maxima of the susceptibility field dependences are determined by
the contribution of orientational rotation of the magnetized aggregates into the
total magnetization of the fluids under investigation. Indeed, as mentioned above,
under the influence of the field, the aggregates align along the field direction even
at small field intensity values and unite in filamentary structures at the further
498
Magnetic ordering in colloidal systems of single-domain particles
0.12
0.10
0.08
0.06
0.04
0.02
/
J
/ '
A*
r
i
i
o
300 50 100 150 200 250
H, A/m
Fig. 7. Initial fragment of the magnetization curve ( J - MF with magnetized aggregates,
2 - kerosene-based MF with the same volume concentration).
0.70
0.60
0.50
0.40 -
0.30
0.20
0.527
0.526
0.525
0.524
0.523
0.522
0.521
600
0.520
0 100 200 300 400 500
H, A/m
Fig. 8. The difl^erential (curve 1) and the mean (curve Z) magnetic susceptibility versus
the steady magnetic fleld intensity.
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Yu.I. Dikansky, D.V. Gladkikh, S.A. Kunikin, A.A. Zolotukhin
field increase. These processes lead to the initial increase of magnetic suscepti-
bility. With strong enough fields, when all aligned aggregates are lined up along
the field, the increase of the system magnetization is achieved by orientation of
disperse particles, composing the aggregates and remaining in the poorly concen-
trated phase, which washes the aggregates over. Due to the started magnetization
saturation of the system, the magnetic susceptibility decreases in the given range of
field intensity. From the above explanation of the reasons for the x{H) dependence
maxima, it is assumed that the aggregates under investigation have not been mag-
netized up to saturation. This fact has been confirmed by measuring the magnetic
moments of the magnetized aggregates with further determination of the magne-
tization inside the aggregate. It has turned out that the aggregate magnetization
defined from its magnetic moment is lower that the saturation magnetization of
the original magnetic fiuid. Obviously, this explains the relatively small residual
magnetization of the magnetic fiuid containing such aggregates (Fig. 6).
4. Conclusion. With the said above, we can conclude that the formation of
aggregates with the magnetic moment different from zero is possible in magnetic
colloids, which are polydisperse systems of stabilized dipole colloidal particles. The
emergence of such aggregates in a magnetic fluid can be explained by the theory
of slow coagulation, at which short-range fixation of disperse particles takes place
at distances assuring the efi'ective correlation of their magnetic moments. Appar-
ently, this happens when the particles are brought closer together at a distance
corresponding to the first minimum of the interaction energy. As the calculations
show, the process of approaching accompanied by overlapping of the solvate layers
can last for a long time sufficient to correlate the particle moments, i.e. it is com-
mensurate with the characteristic time of a revolution of a dipole particle in the
magnetic field of another particle. As a result, the process of slow coagulation with
the formation of short-chain structures composed of more or less tightly bonded
dipole particles develops in the magnetic fiuid. Further, such chain structures form
larger aggregates, which were observed in experiment. It can be testified that the
necessary condition for the formation of such aggregates (with the magnetic mo-
ment different from zero) is the tight bond of the magnetic moment of a disperse
particle with its matrix, in favour of which stands the fact that the formation of
such aggregates is observed in magnetic fiuids with a relatively large particle size.
With the high enough concentration of the magnetized aggregates, they signifi-
cantly affect the magnetic properties of colloids. Note also that the large value of
the magnetic susceptibility of colloids, containing large dispersive particles, is pos-
sibly determined not only by their size [9], but also by the formation of magnetized
aggregations in them.
It is found that the magnetic fiuids containing magnetized aggregations can
successfully serve as magnetically sensitive environments for visualizing magnetic
records, fields of magnetic heads, and for defectoscopy [17]. For example, using
the magnetic fiuid it is possible to visualize records on magnetic discs, so making
it possible to evaluate their quality by subsequent observations in a microscope or
by studying the diffractive image appearing when a laser beam reflects from the
disc surface.
Acknowledgments. This work was supported by The Ministry of Education
and Science of the Russian Federation.
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Magnetic ordering in colloidal systems of single-domain particles
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Received 21.03.2012
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