Spontaneous Chiral Symmetry Breaking and Lane Formation in Ferromagnetic Ferrofluids.

Ferromagnetic ferrofluids are synthetic materials consisting of magnetic nanoplatelets dispersed in an isotropic fluid. Their main characteristics are the formation of stable magnetic domains and the presence of macroscopic magnetization even in the absence of a magnetic field. Here, the authors report on the experimental observation of spontaneous stripe formation in a ferromagnetic ferrofluid in the presence of an oscillating external magnetic field. The striped structure is identified as elongated magnetic domains, which exhibit reorientation upon reversal of the magnetic field. The stripes are oriented perpendicular to the magnetic field and are separated by alternating flow lanes. The velocity profile is measured using a space-time correlation technique that follows the motion of the thermally excited fluctuations in the sample. The highest velocities are found in the depleted regions between individual domains and reach values up to several µm s-1 . The fluid in adjacent lanes moves in the opposite directions despite the applied magnetic field being uniform. The formation of bidirectional flow lanes can be explained by alternating rotation of magnetic nanoparticles in neighboring stripes, which indicates spontaneous breaking of the chiral symmetry in the sample.

Collective and non-collective molecular dynamics in a ferroelectric nematic liquid crystal studied by broadband dielectric spectroscopy.

A great deal of effort has been recently devoted to the study of dielectric relaxation processes in ferroelectric nematic liquid crystals, yet their interpretation remains unclear. In this work, we present the results of broadband dielectric spectroscopy experiments of a prototypical ferroelectric nematogen in the frequency range 10 Hz-110 MHz at different electrode separations and under the application of DC bias fields. The results evidence a complex behavior in all phases due to the magnitude of polar correlations in these systems. The observed modes have been assigned to different relaxation mechanisms based on existing theoretical frameworks.

Miniature magneto-optic angular position sensor.

This Letter describes a miniature Fabry-Perot, contactless, magneto-optic sensor for angular position measurement. The sensor utilizes a magneto-optic fluid comprising barium hexaferrite nanoplatelets that become birefringent in the presence of an external magnetic field and a compact fiber-optic sensor system for tracking the liquid's optical axis direction. An efficient temperature compensation system is provided which allows the use of otherwise highly temperature-sensitive magneto-optic liquids. An unambiguous measurement range of 90° and a resolution of better than 0.05° are demonstrated experimentally.

Ferroelectric-Ferroelastic Phase Transition in a Nematic Liquid Crystal.

Ferroelectric ordering in liquids is a fundamental question of physics. Here, we show that ferroelectric ordering of the molecules causes the formation of recently reported splay nematic liquid-crystalline phase. As shown by dielectric spectroscopy, the transition between the uniaxial and the splay nematic phase has the characteristics of a ferroelectric phase transition, which drives an orientational ferroelastic transition via flexoelectric coupling. The polarity of the splay phase was proven by second harmonic generation imaging, which additionally allowed for determination of the splay modulation period to be of the order of 5-10 microns, also confirmed by polarized optical microscopy. The observations can be quantitatively described by a Landau-de Gennes type of macroscopic theory.

Magnetically controllable random laser in ferromagnetic nematic liquid crystals.

This paper first reports random laser action in dye-doped ferromagnetic nematic liquid crystals, which act as a randomly distributed cavity. The random laser intensity of the ferromagnetic nematic liquid crystals can be controlled by a weak magnetic field (∼1 mT). Moreover, the magnetic switching of random laser is attributed to the direction and polarization dependent emission of light in the ferromagnetic nematic liquid crystals in an external magnetic field.

Optical second harmonic generation in a ferromagnetic liquid crystal.

A comparative experimental investigation of the dependence of second harmonic generation (SHG) on an applied external voltage between a standard nematic liquid crystalline material and an analogue ferromagnetic nematic liquid crystalline material was performed by using a fundamental optical beam at an 800 nm wavelength. For the ferromagnetic material, the dependence of SHG on an applied magnetic field was also examined. Three different polarization combinations of the fundamental and the second harmonic radiation were analysed. The SHG signal observed in the former material is attributed to a combination of electric field-induced SHG (EFISHG) and flexoelectric deformation-induced SHG, while the SHG signal observed in the latter material is attributed solely to flexoelectric deformation-induced SHG. The obtained dependences of the SHG signal on the associated optical retardation show that, in the most favourable polarization combination, the two contributions generate about the same effective nonlinear optical susceptibility.

Evolution of nematic and ferromagnetic ordering in suspensions of magnetic nanoplatelets.

Suspensions of magnetic nanoplatelets in isotropic solvents are very interesting examples of ferrofluids. It has been shown that above a certain concentration ΦNI such suspensions form a ferromagnetic nematic phase, which makes this system a unique example of a dipolar fluid. The formation of a nematic phase is driven by anisotropic electrostatic and long-range dipolar magnetic interactions. Here, we present studies of the evolution of short range positional and orientational magnetic order in suspensions with volume fractions below and above ΦNI, using small angle neutron scattering (SANS). The results show that in the absence of an external magnetic field, short range positional and orientational order already exist at relatively low volume fractions. Polarized SANS revealed that the contribution of ferromagnetic ordering to the formation of the nematic phase is significant. The ferromagnetic correlations can be qualitatively explained by a simple model, which takes into account anisotropic screened electrostatic and dipolar magnetic interactions.

Orientational order in the splay nematic ground state.

Modulated nematic liquid crystal phases, which lack positional order but have some periodic variation in the direction of average orientation present in a classical nematic, have attracted significant interest. In the recently discovered splay nematic (NS) phase the average orientational order is augmented with a periodic splay deformation of orientation perpendicular to the director. We use X-ray scattering experiments to measure the orientational order parameters in the nematic (N) and splay nematic (NS) phases of the liquid crystalline material RM734. The degree of orientational order is somewhat larger in the NS phase than in the preceding nematic and temperature dependent. We reconstruct the orientational distribution function and find it to be nematic-like in the NS phase, indicating the change in orientation between neighbouring molecules due to the splay modulation is very small. A small splay angle implies that the splay modulation period is larger than the few tens of nanometers originally envisaged. The method described herein can be used to assist in unambiguous identification of the splay-nematic phase.

Ferromagnetism in suspensions of magnetic platelets in liquid crystal.

More than four decades ago, Brochard and de Gennes proposed that colloidal suspensions of ferromagnetic particles in nematic (directionally ordered) liquid crystals could form macroscopic ferromagnetic phases at room temperature. The experimental realization of these predicted phases has hitherto proved elusive, with such systems showing enhanced paramagnetism but no spontaneous magnetization in the absence of an external magnetic field. Here we show that nanometre-sized ferromagnetic platelets suspended in a nematic liquid crystal can order ferromagnetically on quenching from the isotropic phase. Cooling in the absence of a magnetic field produces a polydomain sample exhibiting the two opposing states of magnetization, oriented parallel to the direction of nematic ordering. Cooling in the presence of a magnetic field yields a monodomain sample; magnetization can be switched by domain wall movement on reversal of the applied magnetic field. The ferromagnetic properties of this dipolar fluid are due to the interplay of the nematic elastic interaction (which depends critically on the shape of the particles) and the magnetic dipolar interaction. This ferromagnetic phase responds to very small magnetic fields and may find use in magneto-optic devices.

Director reorientation dynamics of ferromagnetic nematic liquid crystals.

Successful realization of ferromagnetic nematic liquid crystals has opened up the possibility to experimentally study a completely new set of fundamental physical phenomena. In this contribution we present a detailed investigation of some aspects of the static response and the complex dynamics of ferromagnetic liquid crystals under the application of an external magnetic field. Experimental results are then compared with a macroscopic model. Dynamics of the director were measured by optical methods and analyzed in terms of a theoretical macroscopic model. A dissipative cross-coupling coefficient describing the dynamic coupling between the two system order parameters, the magnetization and the nematic director, is needed to explain the results. In this contribution we examine the dependency of this coefficient on material parameters and the saturation magnetization and the liquid crystal host. Despite the complexity of the system, the theoretical description allows for a proper interpretation of the results and is connected to several microscopic aspects of the colloidal suspension.

Magnetic-field tuning of whispering gallery mode lasing from ferromagnetic nematic liquid crystal microdroplets.

We report magnetic field tuning of the structure and Whispering Gallery Mode lasing from ferromagnetic nematic liquid crystal micro-droplets. Microlasers were prepared by dispersing a nematic liquid crystal, containing magnetic nanoparticles and fluorescent dye, in a glycerol-lecithin matrix. The droplets exhibit radial director structure, which shows elastic distortion at a very low external magnetic field. The fluorescent dye doped ferromagnetic nematic droplets show Whispering Gallery Mode lasing, which is tunable by the external magnetic field. The tuning of the WGM lasing modes is linear in magnetic field with a wavelength-shift of the order of 1 nm/100 mT. Depending on the lasing geometry, the WGMs are red- or blue-shifted.

Dynamic Magneto-optic Coupling in a Ferromagnetic Nematic Liquid Crystal.

Hydrodynamics of complex fluids with multiple order parameters is governed by a set of dynamic equations with many material constants, of which only some are easily measurable. We present a unique example of a dynamic magneto-optic coupling in a ferromagnetic nematic liquid, in which long-range orientational order of liquid crystalline molecules is accompanied by long-range magnetic order of magnetic nanoplatelets. We investigate the dynamics of the magneto-optic response experimentally and theoretically and find out that it is significantly affected by the dissipative dynamic cross-coupling between the nematic and magnetic order parameters. The cross-coupling coefficient determined by fitting the experimental results with a macroscopic theory is of the same order of magnitude as the dissipative coefficient (rotational viscosity) that governs the reorientation of pure liquid crystals.

Design of a single-chain polypeptide tetrahedron assembled from coiled-coil segments.

Protein structures evolved through a complex interplay of cooperative interactions, and it is still very challenging to design new protein folds de novo. Here we present a strategy to design self-assembling polypeptide nanostructured polyhedra based on modularization using orthogonal dimerizing segments. We designed and experimentally demonstrated the formation of the tetrahedron that self-assembles from a single polypeptide chain comprising 12 concatenated coiled coil-forming segments separated by flexible peptide hinges. The path of the polypeptide chain is guided by a defined order of segments that traverse each of the six edges of the tetrahedron exactly twice, forming coiled-coil dimers with their corresponding partners. The coincidence of the polypeptide termini in the same vertex is demonstrated by reconstituting a split fluorescent protein in the polypeptide with the correct tetrahedral topology. Polypeptides with a deleted or scrambled segment order fail to self-assemble correctly. This design platform provides a foundation for constructing new topological polypeptide folds based on the set of orthogonal interacting polypeptide segments.

Influence of the morphology of ferrite nanoparticles on the directed assembly into magnetically anisotropic hierarchical structures.

The effect of the morphology of ferrite nanoparticles on their assembly in a magnetic field was studied. Thin BaFe12O19 nanoplatelets were compared with isotropic, spherical or octahedral, CoFe2O4 nanoparticles, all of which were synthesized hydrothermally. The nanoplatelets and nanoparticles assembled into a variety of hierarchical structures from stable suspensions during the "drop deposition" and drying in a magnetic field. The alignment of the nanoparticles in the magnetic field was observed in situ with an optical microscope. The morphologies of the nanoparticles and the subsequent assemblies were observed with transmission and scanning electron microscopes, respectively. The magnetic properties of the nanoparticles and the assemblies were measured with a vibrating-sample magnetometer. The BaFe12O19 nanoplatelets aligned in the plane of the substrate and formed several-micrometers-thick, ordered films with a magnetic alignment of approximately 90%. The CoFe2O4 nanoparticles assembled into thick, dense columns with a height of several hundreds of micrometers and showed a magnetic alignment of up to 60%. The differences in the morphologies and the magnetic alignments between the BaFe12O19 and CoFe2O4 hierarchical structures could be explained in terms of the differences in the shape and magnetocrystalline structure of the specific nanoparticles.

Magneto-optic and converse magnetoelectric effects in a ferromagnetic liquid crystal.

We have studied the response of ferromagnetic liquid crystals to external magnetic and electric fields, and compared it to the usual response of nematic liquid crystals (NLCs). We have observed effects, which are not present in a pure NLC and are a consequence of the coupling between the nematic director and the magnetization. The electro-optic effect, which is in the ferromagnetic phase the same as in the pure NLC, is accompanied by a converse magnetoelectric effect. The magneto-optic effect differs completely from the one observed in the pure NLC, where it is a quadratic effect and it only appears when a magnetic field larger than a critical field is applied perpendicular to the director. In the ferromagnetic NLC in addition to the response to the perpendicular field, there is also a qualitatively different response to the parallel field. Contrary to the pure NLC no critical field needs to be exceeded for the system to respond to a perpendicular field, but a critical field needs to be exceeded to observe a response to the field parallel to the director and antiparallel to the magnetization. The critical field is in this case two orders of magnitude smaller than the critical field of the magnetic Frederiks transition in the pure NLC. The experimental observations are well described by a simple macroscopic theory.

Spontaneous symmetry breaking in polar fluids.

Spontaneous symmetry breaking and emergent polar order are each of fundamental importance to a range of scientific disciplines, as well as generating rich phase behaviour in liquid crystals (LCs). Here, we show the union of these phenomena to lead to two previously undiscovered polar liquid states of matter. Both phases have a lamellar structure with an inherent polar ordering of their constituent molecules. The first of these phases is characterised by polar order and a local tilted structure; the tilt direction processes about a helix orthogonal to the layer normal, the period of which is such that we observe selective reflection of light. The second new phase type is anti-ferroelectric, with the constituent molecules aligning orthogonally to the layer normal. This has led us to term the phases the Sm C P H and SmAAF phases, respectively. Further to this, we obtain room temperature ferroelectric nematic (NF) and Sm C P H phases via binary mixture formulation of the novel materials described here with a standard NF compound (DIO), with the resultant materials having melting points (and/or glass transitions) which are significantly below ambient temperature. The new soft matter phase types discovered herein can be considered as electrical analogues of topological structures of magnetic spins in hard matter.

Polarization patterning in ferroelectric nematic liquids via flexoelectric coupling.

The recently discovered ferroelectric nematic liquids incorporate to the functional combination of fluidity, processability and anisotropic optical properties of nematic liquids, an astonishing range of physical properties derived from the phase polarity. Among them, the remarkably large values of second order optical susceptibility encourage to exploit these new materials for non-linear photonic applications. Here we show that photopatterning of the alignment layer can be used to structure polarization patterns. To do so, we take advantage of the flexoelectric effect and design splay structures that geometrically define the polarization direction. We demonstrate the creation of periodic polarization structures and the possibility of guiding polarization by embedding splay structures in uniform backgrounds. The demonstrated capabilities of polarization patterning, open a promising new route for the design of ferroelectric nematic based photonic structures and their exploitation.

Saturation magnetisation as an indicator of the disintegration of barium hexaferrite nanoplatelets during the surface functionalisation.

Barium hexaferrite nanoplatelets (BHF NPLs) are permanent nanomagnets with the magnetic easy axis aligned perpendicular to their basal plane. By combining this specific property with optimised surface chemistry, novel functional materials were developed, e.g., ferromagnetic ferrofluids and porous nanomagnets. We compared the interaction of chemically different phosphonic acids, hydrophobic and hydrophilic with 1-4 phosphonic groups, with BHF NPLs. A decrease in the saturation magnetisation after functionalising the BHF NPLs was correlated with the mass fraction of the nonmagnetic coating, whereas the saturation magnetisation of the NPLs coated with a tetraphosphonic acid at 80 °C was significantly lower than expected. We showed that such a substantial decrease in the saturation magnetisation originates from the disintegration of BHF NPLs, which was observed with atomic-resolution scanning transmission electron microscopy and confirmed by a computational study based on state-of-the-art first-principles calculations. Fe K-edge XANES (X-ray absorption near-edge structure) and EXAFS (Extended X-ray absorption fine structure) combined with Fourier-transformed infrared (FTIR) spectroscopy confirmed the formation of an Fe-phosphonate complex on the partly decomposed NPLs. Comparing our results with other functionalised magnetic nanoparticles confirmed that saturation magnetisation can be exploited to identify the disintegration of magnetic nanoparticles when insoluble disintegration products are formed.

Ferroelectric nematic liquid-crystalline phases.

Recent experimental realization of ferroelectric nematic liquid crystalline phases stimulated material development and numerous experimental studies of these phases, guided by their fundamental and applicative interest. In this Perspective, we give an overview of this emerging field by linking history and theoretical predictions to a general outlook of the development and properties of the materials exhibiting ferroelectric nematic phases. We will highlight the most relevant observations to date, e.g., giant dielectric permittivity values, polarization values an order of magnitude larger than in classical ferroelectric liquid crystals, and nonlinear optical coefficients comparable with several ferroelectric solid materials. Key observations of anchoring and electro-optic behavior will also be examined. The collected contributions lead to a final discussion on open challenges in materials development, theoretical description, experimental explorations, and possible applications of the ferroelectric phases.

New Insights into Amino-Functionalization of Magnetic Nanoplatelets with Silanes and Phosphonates.

Magnetic nanoplatelets (NPLs) based on barium hexaferrite (BaFe12O19) are suitable for many applications because of their uniaxial magneto-crystalline anisotropy. Novel materials, such as ferroic liquids, magneto-optic composites, and contrast agents for medical diagnostics, were developed by specific surface functionalization of the barium hexaferrite NPLs. Our aim was to amino-functionalize the NPLs' surfaces towards new materials and applications. The amino-functionalization of oxide surfaces is challenging and has not yet been reported for barium hexaferrite NPLs. We selected two amine ligands with two different anchoring groups: an amino-silane and an amino-phosphonate. We studied the effect of the anchoring group, backbone structure, and processing conditions on the formation of the respective surface coatings. The core and coated NPLs were examined with transmission electron microscopy, and their room-temperature magnetic properties were measured. The formation of coatings was followed by electrokinetic measurements, infrared and mass spectroscopies, and thermogravimetric analysis. The most efficient amino-functionalization was enabled by (i) amino-silanization of the NPLs precoated with amorphous silica with (3-aminopropyl)triethoxysilane and (ii) slow addition of amino-phosphonate (i.e., sodium alendronate) to the acidified NPL suspension at 80 °C.