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.

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.

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.

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 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.

Preparation of Barium-Hexaferrite/Gold Janus Nanoplatelets Using the Pickering Emulsion Method.

Janus particles, which have two surfaces exhibiting different properties, are promising candidates for various applications. For example, magneto-optic Janus particles could be used for in-vivo cancer imaging, drug delivery, and photothermal therapy. The preparation of such materials on a relatively large scale is challenging, especially if the Janus structure consists of a hard magnetic material like barium hexaferrite nanoplatelets. The focus of this study was to adopt the known Pickering emulsion, i.e., Granick's method, for the preparation of barium-hexaferrite/gold Janus nanoplatelets. The wax-in-water Pickering emulsions were stabilized with a combination of cetyltrimethyl ammonium bromide and barium hexaferrite nanoplatelets at 80 °C. Colloidosomes of solidified wax covered with the barium hexaferrite nanoplatelets formed after cooling the Pickering emulsions to room temperature. The formation and microstructure of the colloidosomes were thoroughly studied by optical and scanning electron microscopy. The process was optimized by various processing parameters, such as the composition of the emulsion system and the speed and time of emulsification. The colloidosomes with the highest surface coverage were used to prepare the Janus nanoplatelets by decorating the exposed surfaces of the barium hexaferrite nanoplatelets with gold nanospheres using mercaptan chemistry. Transmission electron microscopy was used to inspect the barium-hexaferrite/gold Janus nanoplatelets that were prepared for the first time.

On the molecular origins of the ferroelectric splay nematic phase.

Nematic liquid crystals have been known for more than a century, but it was not until the 60s-70s that, with the development of room temperature nematics, they became widely used in applications. Polar nematic phases have been long-time predicted, but have only been experimentally realized recently. Synthesis of materials with nematic polar ordering at room temperature is certainly challenging and requires a deep understanding of its formation mechanisms, presently lacking. Here, we compare two materials of similar chemical structure and demonstrate that just a subtle change in the molecular structure enables denser packing of the molecules when they exhibit polar order, which shows that reduction of excluded volume is in the origin of the polar nematic phase. Additionally, we propose that molecular dynamics simulations are potent tools for molecular design in order to predict, identify and design materials showing the polar nematic phase and its precursor nematic phases.

Formation of Fe(III)-phosphonate Coatings on Barium Hexaferrite Nanoplatelets for Porous Nanomagnets.

Amorphous coatings formed with mono-, di-, and tetra-phosphonic acids on barium hexaferrite (BHF) nanoplatelets using various synthesis conditions. The coatings, synthesized in water with di- or tetra-phosphonic acids, were thicker than that could be expected from the ligand size and the surface coverage, as determined by thermogravimetric analysis. Here, we propose a mechanism for coating formation based on direct evidence of the surface dissolution/precipitation of the BHF nanoplatelets. The partial dissolution of the nanoplatelets was observed with atomic-resolution scanning transmission electron microscopy, and the released Fe(III) ions were detected with energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy in amorphous coating. The strong chemical interaction between the surface Fe(III) ions with phosphonic ligands induces the dissolution of BHF nanoplatelets and the consequent precipitation of the Fe(III)-phosphonates that assemble into a porous coating. The so-obtained porous nanomagnets are highly responsive to a very weak magnetic field (in the order of Earth's magnetic field) at room temperature, which is a major advantage over the classic mesoporous nanomaterials and metal-organo-phosphonic frameworks with only a weak magnetic response at a few kelvins. The combination of porosity with the intrinsic magneto-crystalline anisotropy of BHF can be exploited, for example, as sorbents for heavy metals from contaminated water.

Acrylate-Based Hybrid Sol-Gel Coating for Corrosion Protection of AA7075-T6 in Aircraft Applications: The Effect of Copolymerization Time.

Pre-hydrolysed/condensed tetraethyl orthosilicate (TEOS) was added to a solution of methyl methacrylate (MMA) and 3-methacryloxypropyltrimethoxysilane (MAPTMS), and then copolymerised for various times to study the influence of the latter on the structure of hybrid sol-gel coatings as corrosion protection of aluminium alloy 7075-T6. The reactions taking place during preparation were characterised using real-time Fourier transform infrared spectroscopy, dynamic light scattering and gel permeation chromatography. The solution characteristics were evaluated, using viscosimetry, followed by measurements of thermal stability determined by thermogravimetric analysis. The optimal temperature for the condensation reaction was determined with the help of high-pressure differential scanning calorimetry. Once deposited on 7075-T6 substrates, the coatings were evaluated using a field emission scanning electron microscope coupled to an energy dispersive spectrometer to determine surface morphology, topography, composition and coating thickness. Corrosion properties were tested in dilute Harrison's solution (3.5 g/L (NH4)2SO4 and 0.5 g/L NaCl) using electrochemical impedance spectroscopy. The copolymerization of MMA and MAPTMS over 4 h was optimal for obtaining 1.4 µm thick coating with superior barrier protection against corrosion attack (Z10 mHz 1 GΩ cm2) during three months of exposure to the corrosive medium.

Q-tensor model of twist-bend and splay nematic phases.

The twist-bend nematic phase (N_{TB}) is characterized by a conically twisting director and by a dramatic softening of the bend elastic constant before the transition to the N_{TB} phase. In the recently found splay nematic phase (N_{S}) the splay elastic constant tends to zero, resulting in a splay modulation perpendicular to the director. We model both phases with a single Q-tensor free energy including a term that breaks the degeneracy between the splay and bend elastic constant, and a flexoelectric term coupling the divergence of the Q-tensor with polarization. The N_{TB} or N_{S} phase is obtained by a change of sign of one elastic parameter. Measured elastic constants show that the N-N_{TB} transition is mainly driven by the increase of the nematic order, while the N_{S} transition is due to flexoelectric coupling.

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.

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.

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.

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.

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.

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.

Nanocomposites comprised of homogeneously dispersed magnetic iron-oxide nanoparticles and poly(methyl methacrylate).

Nanocomposites with a high, uniform loading of magnetic nanoparticles are very desirable for applications such as electromagnetic shielding and cancer treatment based on magnetically induced hyperthermia. In this study, a simple and scalable route for preparing nanocomposites with a high, uniform loading of magnetic nanoparticles is presented. The magnetic iron-oxide nanoparticles were functionalized with a methacrylate-based monomer that copolymerized in a toluene solution with the methyl methacrylate (MMA) monomer. The resulting suspension of magnetic nanoparticles decorated with poly(methyl methacrylate) (PMMA) chains in toluene were colloidal, even in the presence of a magnetic field gradient. Nanocomposites were precipitated from these suspensions. The transmission electron microscopy investigation of the prepared nanocomposites revealed that the magnetic nanoparticles were homogeneously dispersed in the PMMA matrix, even in amounts up to 53 wt %. The uniform dispersion of the nanoparticles in the PMMA matrix was attributed to the good solvation of the grafted PMMA chains from the magnetic nanoparticles by the PMMA chains of the matrix. The nanocomposites were superparamagnetic and exhibited large values for the saturation magnetization of up to 36 emu/g. Moreover, the nanocomposite with the largest amount of incorporated nanoparticles exhibited relatively large values for the specific power loss when subjected to alternating magnetic fields, giving this material great potential for the magnetically induced hyperthermia-based treatment of cancer.

Magneto-optic dynamics in a ferromagnetic nematic liquid crystal.

We investigate dynamic magneto-optic effects in a ferromagnetic nematic liquid crystal experimentally and theoretically. Experimentally we measure the magnetization and the phase difference of the transmitted light when an external magnetic field is applied. As a model we study the coupled dynamics of the magnetization, M, and the director field, n, associated with the liquid crystalline orientational order. We demonstrate that the experimentally studied macroscopic dynamic behavior reveals the importance of a dynamic cross-coupling between M and n. The experimental data are used to extract the value of the dissipative cross-coupling coefficient. We also make concrete predictions about how reversible cross-coupling terms between the magnetization and the director could be detected experimentally by measurements of the transmitted light intensity as well as by analyzing the azimuthal angle of the magnetization and the director out of the plane spanned by the anchoring axis and the external magnetic field. We derive the eigenmodes of the coupled system and study their relaxation rates. We show that in the usual experimental setup used for measuring the relaxation rates of the splay-bend or twist-bend eigenmodes of a nematic liquid crystal one expects for a ferromagnetic nematic liquid crystal a mixture of at least two eigenmodes.