Proceedings of the SEM Annual Conference June 1-4, 2009 Albuquerque New Mexico USA 2009 Society for

Experimental Mechanics Inc.

Structural Behavior of a Mixture of Ferromagnetic Nanoparticles and Nematic Liquid Crystals

M. Krasna1, M. Ambroi2, Samo Kralj1,2
1

Faculty of Natural Sciences and Mathematics, University of Maribor, Koroska 160, 2000 Maribor, Slovenia e-mail: marjan.krasna@uni-mb.si
2

Jozef Stefan Institute, Jamova Street 39, 1000 Ljubljana, Slovenia e-mail: milan.ambrozic@ijs.si e-mail: samo.kralj@ijs.si

Abstract: We study structural ordering of a homogeneous mixture of ferromagnetic nanoparticles (NPs) and liquid crystal (LC) molecules in the nematic phase. Cylindrical symmetry of NPs and LC mesogens is assumed at the mesoscopic level. A modified Lebwohl-Lasher type lattice model is used where configuration is obtained via minimization of the relevant thermodynamic potential. We show that with increasing concentration of NPs the degree of nematic and NP ordering is decreasing and increasing, respectively. Such mixtures are potential candidates for type-II magnetoelectrics providing that LC molecules are a source of ferroelectric order, 1. Introduction Studies of magnetoelectric [1,2] properties represent one of the current research hot topics. These materials exhibit simultaneously ferromagnetic and ferroelectric properties and are promising to revolutionize computers. For example, in nowadays computers writing uses magnetic component and for computation purposes one uses an electric component. In magnetoelectrics both operations could be realized by a single magnetoelectric component. One could address magnetic memory electrically without currents. These materials offer the basis for making a 4-state logic state: (+P,+M), (+P,-M), (-P,+M), and (-P,-M). Here P an M stand for the electric polarization and magnetization, respectively. Furthermore, they could be used as magnetoelectric sensors. However, ferromagnetic and ferroelectric properties are in most cases exclusive at an atomic level [3]. Consequently it is difficult to produce such pure materials, the so called type-I multiferroics. There are rare examples of these materials and they exhibit a relatively weak coupling between P and M. For this reason recently type-II multiferroics are of greater interest [2]. These are composite material in which one component exhibits ferroelectric behavior and the other one ferromagnetic. For such a system we propose a mixture of ferroelectric liquid crystals (LC) [4] and ferromagnetic nanoparticles (NP). In this contribution we study structural ordering of a mixture of nematic liquid crystals and magnetic nanoparticles. Such systems represent a first step towards understanding of LC based multiferroics. As a next step the electric polarization should be included which is the focus of our future research. We perform preliminary simulations in which phase and structural properties of such a system are analyzed. We use a simple Lebwohl-Lasher model [5]. An external electric and magnetic field can be switched on or off. The plan of the paper is as follows. In Sec. 2 the model is presented. Results are presented and discussed in Sec. 3 and in the last Section we make conclusions. 2. Model The three-dimensional (3D) spin model simultaneously describes the nematic director field of nematic LC (shortly nematic spins) and the dimensionless magnetization of the magnetic component (magnetic spins). It is represented by a rectangular simulation cell which is a lattice of M N L sites. Each site is enumerated by a set of indices (i, j, k), where 1 i M, 1 j N and 1 k L, and is occupied either by nematic or magnetic spin S(i, j, k) Sijk, which may point in any direction. The neighboring alike spins tend to align in parallel directions, while

the nematic and magnetic spins tend to be perpendicular to each other. The probability for the specific site to contain the magnetic component (instead of LC) is p giving on average pMNL magnetic spins in the cell. The nematic/and magnetic spins are randomly mixed in the cell. Two uniform ordering fields (electric and magnetic) in arbitrary directions can also be applied to the cell; the electric filed is assumed to act only on nematic spins and the magnetic field on magnetic spins. The free energy functional is modeled by the sum of the terms of all spin sites:

F = f ijk ,
ijk

(1a)

where the energy term fijk consists of two parts:

f ijk =

v v v v 1 J (S ijk S n.n. ) a C (S ijk eC ) b . 2 n. n .

(1b)

The first term includes the spin interactions between the nearest neighbors (denotation n.n.): the spin S(i, j, k) interacts with S(i+1, j, k), S(i1, j, k), S(i, j+1, k), S(i, j1, k), S(i, j, k+1) and S(i, j, k1), respectively. The factor is included because each neighboring spin pair is counted twice in the double sum. The coupling constant J can have two values: it is normalized to 1 for alike neighboring spins (nematic-nematic or magnetic-magnetic), while it has the negative value Jint for the interaction between nematic and magnetic spins. The exponent a is equal to 1 for magnetic-magnetic coupling while for nematic-nematic or nematic-magnetic coupling it has the value 2. The second term describes the interaction of homogeneous external field of magnitude C and direction eC with all spins. For the nematic spin C = E2 and b = 2, and for magnetic spin C = B and b = 1 (E and B are the dimensionless electric and magnetic field strengths, respectively). The different exponents a and b for different kinds of spins are due to their different symmetry properties. For instance, nematic spins correspond to the nematic director field which is insensitive to inversion operation: S S, in contrast to magnetic dipole moments which are real vectors. Similarly, the non-negative interaction energy term for nematic-magnetic coupling (negative Jint, square of the scalar product of both spins) tells, that the minimum coupling energy is zero, i.e., when the nematic and magnetic spins are perpendicular to each other. The equilibrium spin configuration is obtained by minimizing the total free energy with respect to all the spins. In order to satisfy the normalization of the spin vectors, Sijk2 = 1, the operational total free energy must be rewritten as:

F * = f ijk *
ijk

(2a)

where:

f ijk * = ijk ( S ijk 1) + f ijk

2

(2b)

with additional multiplication constants ijk, which also have to be found in order to solve the system. The details of minimizing the system (2) and numerical solving the corresponding equations have been given elsewhere for the nematic system with impurities [6]. After the spins are calculated, various macroscopic quantities can be obtained. One of them is the equilibrium total energy which is conveniently normalized to one spin site:

< f >=
and is the average energy term per spin.

F MNL .

(3)

The orientational ordering of the spin system can be characterized by the traceless symmetric order parameter tensor with 33 components [4]:

Qmn =

3 1 < S ijk ,m S ijk ,n > I 2 2 ,

(4a)

where Sijk,m is the m-th component of the spin Sijk. The brackets <...> denote the statistical average of the quantity through the simulation cell. I is the identity matrix. The eigenvalues of Qmn satisfy the equation: 1 + 2 + 3 = 0, and the scalar order parameter S is defined as the largest eigenvalue which is non-negative. The eigenvalues are limited to the interval (1/2, 1). It can be easily shown that the following equation holds for the eigenvalues of Qmn:

n =

1 3 v v 2 < (S ijk e n ) > , 2 2

(4b)

where en is the unit eigenvector belonging to the eigenvalue n. In this view, the unit eigenvectors can be seen as the three unit vectors, with respect to which the quantity:

(e ) =

1 3 v v 2 < (S ijk e ) > 2 2

(4c)

has extremal values. Indeed, by setting to zero the derivatives of the function (e) with respect to the components of e one automatically arrives at the eigenvalue problem for tensor (6a). The values of S and the remaining eigenvalues indicate the system long-range order (the eigenvalues are arranged so that 1 2 3): 1) 1 = 2 = 3 = 0: isotropic system, no long range order. 2) 1 = 2 = , 3 = 1: maximum order, all spins aligned in one direction 3) <1 = 2 < 0, 0 < 3 = 21 < 1: uniaxial partial order 4) 1 < 0, 2 = 0, 3 = 1: maximum biaxiality 5) 1 = , 2 = 3 = : spin directions confined to a single plane, complete disorder within the plane this is again a uniaxial case when observed in 3D space, but different from the case in point 3) 6) < 1 < 0, 0 < 2 = 3 < : uniaxial partial order with spin directions near a single plane, but their projections on that plane are completely disordered. This procedure of obtaining scalar parameter S from the tensor (4a) was performed only for nematic component. Magnetization (SNP) of magnetic component was obtained more simply: magnetic spin vectors were averaged through the lattice and then the magnitude of the mean magnetic spin was calculated. We further define the degree of biaxiality 2 as [7,8]

=1

6 TrQ 3

(TrQ

2 3

) )

(5)

the value of which is confined to the interval [0,1]. The value 2 = 0 and 2 = 1 reflects an uniaxial state and a state exhibiting maximal biaxiality, respectively. We further measure range of ordering within the system. For this purpose se define the correlation function

g (r ) =

3 v v 1 < (S ijk S mnl ) 2 > , 2 2

(6)

where <...> is the average of the squares of the scalar products of only those spin pairs which are separated by distance r. In order to obtain structural details from a calculated g (r ) dependence we fit it with the ansatz (7) where the , m, and s are adjustable parameters. In simulations distances are scaled with respect to a0 (the nearest neighbour distance of the lattice spins). The quantity estimates the average domain length (the coherence length) of the system. Over this length the nematic spins are relatively well correlated. The distribution width of values is measured by m. Dominance of a single coherence length in the system is signalled by m ~ 1 . A magnitude and system size dependence of s reveals the degree of ordering within the system. The case s = 0 indicates the short range order (SRO). A finite value of s reveals either the long range order (LRO) or quasi long range order (QLRO). To distinguish between these two cases a finite size analysis s ( N 0 ) must be carried out, where N0 = N = M = L. If s (N 0 ) saturates at a finite value the system exhibits LRO. If s ( N 0 ) dependence exhibits algebraic dependence on N 0 the system possesses QLRO. 3. Results We study numerically the mutual influence of NPs and LC molecules. Note that there are two sources of coupling between a NP and its nematic surrounding: the magnetic and elastic coupling [9]. Typically the latter is prevailing, so we will neglect the magnetic coupling. Most studies on magnetic NP+LC mixtures report that long axes of NP and LC molecules tend to be oriented perpendicular [10]. We take this into account in our simulation by negative Jint. In Fig.1 we plot average ordering of NP and LC as a function of concentration of NPs in the absence of external fields. We assume that initially long axes of magnetic and LC molecules are randomly oriented. Experimentally such a condition would correspond to quenching the system from the high temperature isotropic phase to the nematic phase. We see that the degree of nematic ordering SLC decreases with the concentration p. Therefore, presence of NPs introduces effectively a static disorder into the system. On the other hand the degree of magnetic order increases with p. This indicates, that the prevailing nematic component acts as an effectively ordering field. Note that the degree of biaxiality in the nematic ordering is very high. This indicates that nematic ordering is strongly frustrated by presence of NPs. In absence of NPs the configurations with 2 = 0 are preferred.

g (r ) = (1 s )e (r / ) + s,
m

1,0

0,8

0,6

order

0,4

0,2

SLC SNP

0,0 0,00

0,02

0,04

0,06

0,08

0,10

p
Figure 1 Degree of orientational order of the nematic component (SLC) and NPs (SNP) in LC+NP mixtures as a function of concentration p of NPs. For the neamtic component we also plot the degree of biaxiality , which measures departures from uniaxial ordering. Dotted lines are guides for the eye. The nematic-nematic, magnetic-magnetic, nematic-magnetic interaction is set to J = 1, J = 1, Jint = -5, respectively. M = N = L = 80 and E = B = 0.
2

The observed behavior can be explained as follows. On quenching the LC molecules from the initial isotropic configuration the domain pattern forms [11,12,13]. This is due to continuous symmetry breaking character of the nematic phase and causality (i.e., finite speed with which information spreads). Namely, all direction in space are equivalent and the only tendency of LC molecules is to orient locally parallel. Therefore, after the quench at different regions LC molecules in general align in different directions because the sites at causally disconnected. At intersections of domains topological defects are formed. Among them line defects are prevailing. With time, larger domains grow on the expense of smaller ones, because the former have a lower free energy. This process is enabled by annihilation of defects of different topological signs. Consequently, the average linear size of domains grows with time t. The domain growth follows the scaling law t , where represents the scaling coefficient. Therefore, if the nematic pattern is rescaled by a distance (t ) , the patterns look the same from a statistical point of view. For nematic LC it holds 0.5, because SLC is nonconserved order parameter [13,14]. In bulk LC system in equilibrium parallel alignment of nematic spins is obtained which reflects in . However, for a finite concentration p of NPs nematic domains could get pinned by NPs when becomes comparable to the average separation between NPs. This is illustrated in Fig.2 where we plot the time evolution of the average domain size as a function of p. We calculated using Eq.(8). The domain sizes become saturated at a constant value of p , where the subscript p denotes the concentration p. The resulting nematic structure is metastable. Reaching equilibrium would require reorientation of large domains which is energetically too costly. Therefore, presence of NPs introduces into the system a kind of disorder [15] and its degree is increasing on increasing p.

35

30

p = 0.1
25

/a

20

p = 0.2

15

10

p = 0.3
5

2000

4000

6000

8000

t /t

Figure 2 The average nematic domain length for different concentrations p of NPs. The nematic domains become pinned by the NPs into a metastable structure. The nematic-nematic, magnetic-magnetic, nematic-magnetic interaction is set to J = 1, J = 1, Jint = -5, respectively. M = N = L = 80 and E = B = 0. t corresponds to the one sweep (in it the complete spin configuration is updated).

4. Conclusions We study theoretically a mixture of ferromagnetic NPs and LC molecules in the nematic phase. We use a modified Lebwohl-Lasher [5] type pairwise interaction potential, where the neighboring spins interact via coupling strengths Jint. In such systems the elastic origin of interactions plays a dominant role. For this reason we limit the range of couplings to the first neighbors. For the nematic-nematic, magnetic-magnetic and magnetic-nematic coupling we set J = 1, J = 1 and Jint = -0.5, respectively. These interaction values are chosen based on previous works on similar systems [9,10]. We consider relatively low concentrations of NPs. For higher concentrations phase separation is expected [16]. Initial configurations of NPs and LC molecules are randomly distributed where all space directions are equivalent. Quasi static configurations are afterwards calculated. Experimentally such conditions could be realized either by temperature or pressure quenches from the isotropic to the nematic LC phase [14]. We find that with increasing concentration of NPs the degree of nematic ordering decreases. This indicates increasing degree of disorder which is due to the pinning of nematic domains by NPs. On the contrary the LC matrix on average orders NPs. Such a system represents a potential candidate for type-II magnetoelectrics [2] which spontaneously exhibit ferromagnetic and ferroelectric ordering. For this purpose one needs chiral LC molecules in a smectic C phase [4]. In this phase the LC molecules form a layered structure. On average LC molecules are tilted with respect to the layers and consequently an electric polarization is induced due to symmetry reasons. Therefore, one could reorient magnetic NPs indirectly via LC molecules. The latter can be readily controlled by an external electric field. This problem is the topic of our future study. References [1] I. E. Dzyaloshinskii, Sov. Phys. JETP 10, 628 (1959).

[2] J.F. Scott, Science 315, 954 (2007). [3] N.A. Hill, J. Phys.Chem. B 104, 6694 (2000). [4] P. G. de Gennes and J. Prost, The Physics of Liquid Crystals, Oxford University Press, Oxford (1993). [5] Lebwohl P A and Lasher G 1972 Phys. Rev. A 6 426 [6] M. Cvetko, M. Ambrozic, S. Kralj, Liquid Crystals 36, 33 (2009). [7] P. Kaiser and W. Wiese and S. Hess, J. Non-Equilib. Thermodyn. 17, pp 153, (1992) [8] M. Ambrozic and F. Bisi and E.G. Virga", Contin. Mech. Thermodyn. 20, pp 193 (2008) [9] F. Brochard and P. G. de Gennes, J. Phys. (Paris) 31, 691 (1970). [10] S. V. Burylov and Yu. L. Raikher, Phys. Rev. E 50, 358 (1994). [11] Kibble T W B 1976 J. Phys A 9 1387 [12] Bray A J 1994 Adv. Phys 43 357 [13] Zurek W H 1985 Nature 317 505 [14] Z. Brada, S. Kralj, S. umer, Molecular dynamics study of isotropic-nematic quench, Phys.Rev.E 65, 021705-10 (2002). [15] S. Kralj and V. Popa-Nita, Random anisotropy nematic model: connection with experimental systems, Eur. Phys. J E 14, 115-125 (2004). [16] V. Popa-Nita and S. Kralj, Random anisotropy nematic model: nematic--non-nematic mixture, Phys. Rev. E 73, 041705 (2006).