Physica E 79 (2016) 3843

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Physica E
journal homepage: www.elsevier.com/locate/physe

Ferromagnetic nanoparticles suspensions in twisted nematic

Cristina Ci^rtoaje a, Emil Petrescu a,n, Cristina Stan a, Dorina Creang b
a
b

University Politehnica of Bucharest, Department of Physics, Splaiul Independenei 313, 060042 Bucharest, Romania
Faculty of Physics, Alexandru Ioan Cuza University of Iai, Carol I Blvd. 11, 700506 Iai, Romania

H I G H L I G H T S

A study of magnetic nanoparticles insertion in planar and twisted nematic cell was performed.

A decrease of the Freedericksz transition threshold was observed in twisted cells.

A theoretical model to explain decrease of Freedericksz transition threshold was developed.

art ic l e i nf o

a b s t r a c t

Article history:
Received 11 November 2015
Received in revised form
2 December 2015
Accepted 10 December 2015
Available online 12 December 2015

Ferromagnetic nanoparticles insertions in nematic liquid crystals (NLC) in twisted conguration are
studied and a theoretical model is proposed to explain the results. Experimental observation revealed
that nanoparticles tend to overcrowd in long strings parallel to the rubbing direction of the alignment
substrate of the LC cell. Their behavior under external eld was studied and their interaction with their
nematic host is described using elastic continuum theory.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
Ferromagnetic nanoparticles
Twisted nematic
Freedericksz transition

1. Introduction
Nematic liquid crystals (NLC) represent an ideal medium for
nanoparticle's study, due to their molecular order and their ability
to connect to the surface. Thus, the particles are dispersed in an
elastic and organized environment and their physical properties
can be analyzed from the interaction forces with the NLC molecules. In addition, new nematic mixtures are obtained with controllable parameters based on nanoparticles concentration.
The original idea of yielding ferronematics belongs to Brochard
and De Gennes [1] who proposed the doping of liquid crystals with
small amount of ne magnetic nanoparticles (MNP-s) to enhance
the sensitivity to magnetic elds since pure LC, because of their
diamagnetic susceptibility small anisotropy, are characterized by
relatively large range of structural transition threshold.
Ferrites are known as low cost materials provided with remarkable physical properties as well as chemical stability, thus
being suitable for many application elds. When prepared as nanosized systems, they may have superparamagnetic features [2],
gas sensing capability and catalytic activity [3] that recommend
n

Corresponding author.
E-mail address: emilpd@yahoo.com (E. Petrescu).

http://dx.doi.org/10.1016/j.physe.2015.12.006
1386-9477/& 2015 Elsevier B.V. All rights reserved.

MNPs for magnetic data storage, sensors, transducers and actuators [4] and also for biomedical purposes (magnetic imaging, drug
delivery, cancer hyperthermia) [5]. Further development of magnetic nanocomposites became one of the most attractive research
areas in advanced materials [6].
Since they act completely different from macroscopic granules
made of the same substance, there are many papers reporting new
materials and devices based on such microparticles or nanoparticles [713]. In isotropic phase, nematic liquid crystals with
ferromagnetic platelets act like a common ferrouid [14] but in
crystalline phase, a completely different behavior is observed due
to the anchoring angle of the molecules on the particles surface
and also to the interaction energy between the components of the
system (moleculemolecule, moleculenanoparticle or nanoparticlenanoparticle). Using these mixtures, new phenomena
were discovered and new methods were developed in order to
obtain the best dispersion [1517]. When subjected to an external
magnetic eld, nematic molecules tend to align themselves to the
eld direction if the intensity is higher than a critical value. This is
called the magnetic Freedericksz transition and the threshold value (Bc) can be experimentally measured. Nanoparticles insertion
in the nematic matrix has a signicant inuence on the critical
eld, depending not only on the nature of the liquid crystal but
also on its orientation. An estimation of this eld can be obtained

C. Ci^rtoaje et al. / Physica E 79 (2016) 3843

39

from the experimental plot of the laser intensity versus the eld
induction but an exact value can be obtained using a theoretical
method based on the continuum elastic medium similar to the one
presented in [18].

2. Experimental set-up and measurements

Glass plates previously prepared for planar alignment were
used for the LC cells. In order to obtain the planar alignment, a
layer of 0.1% polyvinyl alcohol solution was spread by spin coating
on the glass surface, then baked at 120 C for 60 min, cooled at
room temperature and rubbed with a smooth cloth to obtain the
desired ditches direction. In order to obtain a low critical value we
prepared thick cells by using thin glass slides (180 m) as spacers.
For the homogenous (planar) cell the ditches on the two plates are
parallel to each other, while for the twisted one they are perpendicular to each other. Co-precipitation adapted method was applied to yield cobalt ferrite nanosized particles from iron chloride
and cobalt sulfate at molar ratio 2:1, in alkali reaction medium
(2 M NaOH) as described in detail in [19]. All reagents were pure
Merck chemicals used without further purication while deionized water was provided by Barnstead EASYPureII ultrapure
water system (18.2 M/cm). After precipitated particle separation
from the reaction medium they were repeatedly washed with
deionized water to remove any other chemical traces; then perchloric acid aqueous solution (25%) was added to coat particle
surface with perchlorate ions in order to ensure a uniform colloidal suspension by balancing magnetic attraction forces by
means of electrostatic repulsion [20]. The witness cell was lled
with 5CB nematic from Aldrich, while the test one was lled with
a mixture of 5CB and 0.1% (volumetric fraction) of CoFe3O4 powder
obtained by evaporation from a water based ferrouid. Each
sample was placed between the two hollowed poles of an electromagnet and a couple of crossed polarizers. The evolution of the
emergent beam versus the eld intensity was recorded and plotted on a computer (Fig. 1).
When the critical value for the magnetic Freedericksz transition
is reached, the molecules tend to align themselves by the eld
direction. This leads to a decrease of the laser intensity which can
be easily observed from the experimental plot. The molecular reorientation does not appear at once but after a time depending on
elastic constants of the liquid crystalline mixtures and magnetic
eld. This is the reason why for each value of the applied eld we
waited for few minutes before the laser beam intensity was
measured.

3. Results and discussions

In accordance with the theoretical model described in [21] the
insertion of ferromagnetic nanoparticles in planar nematic LC cell
leads to an increase of the critical threshold for the Freedericksz
transition as it can be observed from the light intensity versus
magnetic eld plot presented in Fig. 2. Using the same substances
in twisted cells, we notice that the critical threshold does not
change for the 5CB sample (about 0.04 T) but in the case of the

Fig. 1. Set up for experimental evaluation of critical eld for magnetic Freedericksz
transition.

Fig. 2. Magnetic Freedericksz transition for planar cells. Square dots represent the
plot for 5CB and disc circular dots represent the plot for 5CB ferromagnetic
particles mixture.

Fig. 3. Magnetic Freedericksz transition for twisted cells. Square dots represent the
plot for 5CB and disc circular dots represent the plot for 5CB ferromagnetic
particles mixture.

5CB1% CoFe3O4 lled cell it decreases down beyond 0.03 T,

suggesting that the molecules align themselves easier with the
eld (Fig. 3). Nanoparticles size as given by SEM measurements is
40 nm, but after lling the aligned cells with the mixture we observed that the particles were gathering together in long chains
just as presented in [22]. Length evaluation, made after the system
stabilized itself, gave an average value of 2 m (Fig. 4b, d). The
clusters seem to be less agglomerated in the twisted cell due to the
rotation of the distortion angle in consecutive layers. In contrast to
planar aligned cell where parallel strings in the transparent layers
give us the impression of very tight strings (Fig. 4b), in twisted cell
we see a lattice made of strings in different planes (Fig. 4d). Besides, when the magnetic eld is applied, a faster reorientation is
observed. Experimental studies performed on other mixtures of
liquid crystals and microparticles or nanoparticles indicate specic
ordered structures [23,24] especially for long particles (chains,
nanotubes) which align themselves parallel to nematic director
[25,26]. Thus a twisted structure was designed in Fig. 5 for theoretical analysis. Similar structures were also observed in cholesteric liquid crystals [27] conrming our assumption and results.

40

C. Ci^rtoaje et al. / Physica E 79 (2016) 3843

Fig. 4. Images obtained with polarized optical microscope. (a) 5CB planar cell, (b) 5CB 1% CoFe3O4 planar cell, (c) 5CB twisted cell, (d) 5CB 1% CoFe3O4 twisted cell.

term between the molecules and the micro-strings.

Using the graphical description given in Fig. 6, they can be
written as:

4. Theoretical analysis
4.1. Planar aligned cell
Assuming a string like agglomeration of the nanoparticles the
system can be analyzed by using the elastic continuum theory for
liquid crystals and interaction process based on the theory presented in [18,28,29] for rod like microparticles so we can write the
free energy density of the system as:

f = felastic + fmagnetic + finteraction

(1)

where felastic represents the nematic free energy density due to

elastic deformations of the molecular director, fmagnetic represents
the contribution of the NLC interaction with the magnetic eld to
the system total energy density and finteraction is the interaction

felastic =

2 1
2
1
K1 cos2 + 2 K3 sin2
z
z
2

fmagnetic = 2 p 01a2 B2 sin2 2 p 01F B2 sin2

(2)

(3)

where K1 and K3 are the elastic constant of the nematic, a and F

are the magnetic anisotropies of the nematic and the ferroparticles
respectively, p is the ferroparticles concentration in the mixture
(volumetric fraction), B is the magnetic eld intensity, 0 is the
magnetic permeability of vacuum.
In order to evaluate the interaction energy we consider that

Fig. 5. Schematic representation of the cluster reorientation in nematic matrix: (a) planar sample, (b) twisted sample.

C. Ci^rtoaje et al. / Physica E 79 (2016) 3843

fint =

Fint
wp

[1 3 cos2 ]( u n )2
p=
Vu
R

41

(6)

or, in a simplied form,

(
fint = pw
u n )2

(7)

where

=
w

wp
[1 3 cos2 ]
R

(8)

R is the chain radius, l is its length, u is the direction of the string

n is the nematic director and n0 is the undisturbed nematic director (Fig. 8). Thus, the interaction energy can be written as:
Fig. 6. Nematic molecules and microstrings orientation according to the glass
substrate in planar cells.

cos2 ( )
fint = w

(9)

The system stability is assured by the minimization of the free

energy given by Euler Lagrange equations. For angle these
equations lead to:

cos ( ) sin ( ) = 0
B2F 01p sin cos + 2w

(10)

which, in small angle approximation, gives us

2w

+ 01pF B2
2w

(11)

For , inthe same equation in small angle approximation, we

obtain:

F
2wp

01a B2
a
2
= 0
1 +
+
2
1

K1
z
0 pF B + 2w

(12)

From the boundary conditions 0 for z 0 and for z d it results:

F
2wp
2
01a B2
a
=
1 +
1
2

K1
0 pF B + 2w d

Fig. 7. Nematic molecule anchoring on magnetic string surface.

(13)

:
So, we can evaluate w

K
01pF B2 1 1
1
2

d
0 a B

=
w
F 2
K
1
1 + p + 1
a d 0 a B2

(14)

4.2. Twisted cell

Fig. 8. Molecular orientation in a twisted nematic cell.

magnetic particles are gathering in long strings similar to carbon

nanotubes thus the interaction energy may be written as a function of the anchoring angle and the anchoring energy w (Fig. 7)
[28]:

Fint =

w
2

sin 2 dS.

(4)

The chains are very long compared to their diameter so we can

take into account the interaction with lateral surface only [29]:

Fint = Rlw [1 3 cos2 ]( u n )2 .

The energy density becomes:

(5)

When a twisted nematic cell is used, there are some signicant

differences in the free energy of the system given by the specic
orientation of the nematic molecules but also by the gravity affecting the ferromagnetic strings inside the cell. As it can be noticed from Figs. 2 and 3, there are no major differences of the
critical eld between the planar and twisted pure nematic cells so
we expect no signicant differences on the ferromagnetic particle
- nematic cell either. Experimental results contradict this expectation revealing that the critical eld is strongly decreased. This
can be explained by the effect of the gravitational force on oblique
oriented ferromagnetic strings (Fig. 9b). These strings are denitively heavier than LC molecules so the gravitational contribution
to the total free energy can no longer be neglected. When planar
cell is used and all alignment lines are horizontal, the magnetic
eld gives a rotation movement in the xOz plane which is not
affected by the gravity (Fig. 9a).
In twisted cells (Fig. 9b) there is a uniform distribution of the
ferromagnetic particles' strings on the yOz plane so the gravity

42

C. Ci^rtoaje et al. / Physica E 79 (2016) 3843

Fig. 9. Gravitational force acting on ferromagnetic particlenematic LC mixtures:

(a) planar cell, (b) twisted cell.

acting on them will give a rotational movement in the same direction with the magnetic force which apparently increases the
magnetic eld effect and decreases the threshold value of Freedericksz transition. As consequence we might face some variations
in rotational viscosity as shown in [30] which would inuence the
relaxation time. Since our measurements were made on large time
intervals (to avoid relaxation effects) we will only take into account time indpendent parameters. Using these assumptions, the
system's free energy can now be written as:

f = felastic + fmagnetic + finteraction + fgravitational

(15)

where

felastic =

2
2
1
1

K1 cos2 + K2 cos4
z
z
2
2
2
2
1

+ K3 sin 2 + sin2 cos2
z
z
2

(16)

and

fgravitational =

/2

pmgl0 cos cos d

glp
cos
=
2VF
2

(17)

where l is the string length, g is the gravitational acceleration, is

the density of the ferromagnetic particles and VF is the string's
volume. The magnetic eld and interaction terms remain unchanged. By applying the EulerLagrange equation as a function of
angle we obtain:

2w
=

pgl
2

+ 01pF B2
2w

pgl
2

(18)

From the boundary conditions ( = 0 for z 0 and = /2 for

z = d/2) we get

=
z
2d

and

2
=0
z2

(19)

From Eqs. (18), (19) and the boundary conditions 0 for z 0 and
for z d it results:

02 a F pB 4
2

pgl 1
(2K K ) 1p + 2w

2
3 0
F

2d
2 0 a
+

2K1
+ 2w
01pF 01pF

d2
+

B2

2
pgl
pgl 2K1
(2K K ) 2w

2w
=0
2
3
2d

2
2 d2

(20)

Both Eqs. (13) and (20) were obtained using small angles approximation, so the magnetic eld involved in these equations is

the one giving small deviations of the nematic director i.e. the
critical Freedericksz transition eld. If we use Eq. (14) to evaluate
, for the experimental critical eld B 0.06 T as it can be obw
served in Fig. 2, and replace this value in Eq. (20), when solving it
as a function of B, we should obtain a value between B 0.02 T and
B 0.03 T if our assumptions are correct. Calculations performed
= 1.36 105 N m in Eq. (14) and by
on this specic cell gave w
replacing it in Eq. (20) we obtained a critical eld of 0.028 T, which
is in good agreement with experimental results and other results
presented in [3037]. Physical parameters for the cell and substances used in this experiment are:
K1 = 6.21012 N,
K2 = 3.91012 N, K3 = 8.21012 N , a = 1.43106 [8], 0 = 4 107
N A  2, F = 2105 [38], = 5300 kg /m3 , d = 200106 m and
l = 100106 m . The average length of the chains was estimated
from microscopic images to 2 m.

5. Conclusion
A theoretical model is proposed to describe the interaction
between the nematic molecules and ferromagnetic particles in
twisted nematic cells, in good agreement with experimental results, is proposed. Experimental results indicate that ferromagnetic particles insertion in nematic matrix increases the stability of
the system (in both alignment types there are no intensity variation of the emergent laser beam observed in the mixture sample).
Besides, in the twisted sample, a considerable decrease of the
critical eld is noticed indicating a better response time of the
system to external eld with possible application in LCD industry.

Acknowledgments
The work has been funded by the Sectorial Operational Program Human Resources Development 20072013 of the Ministry
of European Funds through the Financial Agreement POSDRU/159/
1.5/S/132397.

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