Polymerisation of twist-bend nematic textures for electro-optical applications.

Polymer-stabilised liquid crystals (PSLCs) have recently been used to maintain the focal conic domains (FCDs) typical of the smectic A phase in the nematic phase for smart window applications. The newly discovered twist-bend nematic phase of bent-shaped dimers also exhibits FCDs due to its pseudo-layered structure. The variety of topological defects in the NTB phase is arguably even greater than in the smectic A phase, but the NTB phase is often metastable and usually crystallises at room temperature, which hinders its use in electro-optical applications. Here we show how different textures (FCDs, rope-like texture, double helices) of the NTB phase can be polymerised and then maintained in the nematic phase, at room temperature. This allows us to combine in PSLCs the optical properties of these defects, the thermal stability of the nematic phase and its reversible response to an electric field. We also show that the polymerised FCDs of the NTB phase could be used in smart glass applications and that the polymerised rope-like texture could be of interest for optical modulators and beam steering. In addition, the polymerisation of double helices could help to better understand their formation and structure in the NTB phase. More fundamentally, our work shows that despite the lack of density modulation, the textures of the NTB phase, thanks to its periodic character, can be exploited in the same way as those of the smectic A phase.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 µm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.

Biaxiality-driven twist-bend to splay-bend nematic phase transition induced by an electric field.

Although the existence of the twist-bend (NTB) and splay-bend (NSB) nematic phases was predicted long ago, only the former has as yet been observed experimentally, whereas the latter remains elusive. This is especially disappointing because the NSB nematic is promising for applications in electro-optic devices. By applying an electric field to a planar cell filled with the compound CB7CB, we have found an NTB-NSB phase transition using birefringence measurements. This field-induced transition to the biaxial NSB occurred, although the field was applied along the symmetry axis of the macroscopically uniaxial NTB Therefore, this transition is a counterintuitive example of breaking of the macroscopic uniaxial symmetry. We show by theoretical modeling that the transition cannot be explained without considering explicitly the biaxiality of both phases at the microscopic scale. This strongly suggests that molecular biaxiality should be a key factor favoring the stability of the NSB phase.

Probing permanent dipoles in CdSe nanoplatelets with transient electric birefringence.

Zinc-blende CdSe semiconducting nanoplatelets (NPL) show outstanding quantum confinement properties thanks to their small, atomically-controlled, thickness. For example, they display extremely sharp absorption peaks and ultra-fast recombination rates that make them very interesting objects for optoelectronic applications. However, the presence of a ground-state electric dipole for these nanoparticles has not yet been investigated. We therefore used transient electric birefringence (TEB) to probe the electric dipole of 5-monolayer thick zinc blende CdSe NPL with a parallelepipedic shape. We studied a dilute dispersion of isolated NPL coated with branched ligands and we measured, as a function of time, the birefringence induced by DC and AC field pulses. The electro-optic behavior proves the presence of a large dipolar moment (>245 D) oriented along the length of the platelets. We then induced the slow face-to-face stacking of the NPL by adding oleic acid. In these stacks, the in-plane dipole components of consecutive NPL cancel whereas their normal components add. Moreover, interestingly, the excess polarizability tensor of the NPL stacks gives rise to an electro-optic contribution opposite to that of the electric dipole. By monitoring the TEB signal of the slowly-growing stacks over up to a year, we extracted the evolution of their average length with time and we showed that their electro-optic response can be explained by the presence of a 80 D dipolar component parallel to their normal. In spite of the 4[combining macron]3m space group of bulk zinc blende CdSe, these NPL thus bear an important ground-state dipole whose magnitude per unit volume is twice that found for wurtzite CdSe nanorods. We discuss the possible origin of this electric dipole, its consequences for the optical properties of these nanoparticles, and how it could explain their strong stacking propensity that severely hampers their colloidal stability.

Liquid-Crystalline Suspensions of Photosensitive Paramagnetic CeF3 Nanodiscs.

The design of high-performance energy-converting materials is an essential step for the development of sensors, but the production of the bulk materials currently used remains costly and difficult. Therefore, a different approach based on the self-assembly of nanoparticles has been explored. We report on the preparation by solvothermal synthesis of highly crystalline CeF3 nanodiscs. Their surface modification by bisphosphonate ligands led to stable, highly concentrated, colloidal suspensions in water. Despite the low aspect ratio of the nanodiscs (∼6), a liquid-crystalline nematic phase spontaneously appeared in these colloidal suspensions. Thanks to the paramagnetic character of the nanodiscs, the nematic phase was easily aligned by a weak (0.5 T) magnetic field, which provides a simple and convenient way of orienting all of the nanodiscs in suspension in the same direction. Moreover, the more dilute, isotropic, suspensions displayed strong (electric and magnetic) field-induced orientation of the nanodiscs (Kerr and Cotton-Mouton effects), with fast enough response times to make them suitable for use in electro-optic devices. Furthermore, an emission study showed a direct relation between the luminescence intensity and magnetic-field-induced orientation of the colloids. Finally, with their fast radiative recombination decay rates, the nanodiscs show luminescence properties that compare quite favorably with those of bulk CeF3. Therefore, these CeF3 nanodiscs are very promising building blocks for the development and processing of photosensitive materials for sensor applications.

Dispersions of Goethite Nanorods in Aprotic Polar Solvents.

Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation). For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH) nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles.

Electric-field-induced shape transition of nematic tactoids.

The occurrence of new textures of liquid crystals is an important factor in tuning their optical and photonics properties. Here, we show, both experimentally and by numerical computation, that under an electric field chitin tactoids (i.e., nematic droplets) can stretch to aspect ratios of more than 15, leading to a transition from a spindlelike to a cigarlike shape. We argue that the large extensions occur because the elastic contribution to the free energy is dominated by the anchoring. We demonstrate that the elongation involves hydrodynamic flow and is reversible: the tactoids return to their original shapes upon removing the field.

A liquid-crystalline hexagonal columnar phase in highly-dilute suspensions of imogolite nanotubes.

Liquid crystals have found wide applications in many fields ranging from detergents to information displays and they are also increasingly being used in the 'bottom-up' self-assembly approach of material nano-structuration. Moreover, liquid-crystalline organizations are frequently observed by biologists. Here we show that one of the four major lyotropic liquid-crystal phases, the columnar one, is much more stable on dilution than reported so far in literature. Indeed, aqueous suspensions of imogolite nanotubes, at low ionic strength, display the columnar liquid-crystal phase at volume fractions as low as ∼ 0.2%. Consequently, due to its low visco-elasticity, this columnar phase is easily aligned in an alternating current electric field, in contrast with usual columnar liquid-crystal phases. These findings should have important implications for the statistical physics of the suspensions of charged rods and could also be exploited in materials science to prepare ordered nanocomposites and in biophysics to better understand solutions of rod-like biopolymers.

Hybrid nanocomposites with tunable alignment of the magnetic nanorod filler.

For many important applications, the performance of polymer-anisotropic particle nanocomposite materials strongly depends on the orientation of the nanoparticles. Using the very peculiar magnetic properties of goethite (α-FeOOH) nanorods, we produced goethite-poly(hydroxyethyl methacrylate) nanocomposites in which the alignment direction and the level of orientation of the nanorods could easily be tuned by simply adjusting the intensity of a magnetic field applied during polymerization. Because the particle volume fraction was kept low (1-5.5 vol %), we used the orientational order induced by the field in the isotropic phase rather than the spontaneous orientational order of the nematic phase. At the strongest field values (up to 1.5 T), the particles exhibit almost perfect antinematic alignment, as measured by optical birefringence and small-angle X-ray scattering. The results of these two techniques are in remarkably good agreement, validating the use of birefringence measurements for quantifying the degree of orientational order. We also demonstrate that the ordering induced by the field in the isotropic suspension is preserved in the final material after field removal. This work illustrates the interest, for such problems, of considering the field-induced alignment of anisotropic nanoparticles in the isotropic phase, an approach that is effective at low filler content, that avoids the need of controlling the nematic texture, and that allows tuning of the orientation level of the particles at will simply by adjusting the field intensity.

Electric-field alignment of chitin nanorod-siloxane oligomer reactive suspensions.

Uniaxially anisotropic chitin-silica nanocomposite solids have been obtained thanks to the electric field-induced macroscopic alignment of liquid-crystalline reactive cosuspensions. We demonstrate how chitin nanorods (260 nm long, 23 nm thick) can be aligned upon the application of an alternating current (ac) electric field, and within water-ethanol suspensions containing reactive siloxane oligomers (D(h) ∼ 3 nm). The alignment at the millimeter length scale is monitored by in situ small-angle X-ray scattering (SAXS) and polarized light optical microscopy. The composition and state (isotropic, chiral nematic) of the cosuspensions are proven to be determining factors. For nematic phases, the alignment is preserved when the electric field is switched off. Further solvent evaporation induces sol-gel transition, and uniaxially anisotropic chitin-silica nanocomposites are formed after complete drying of the aligned nematic suspensions. Here, the collective response of colloidal mesophases to external electric fields and the subsequent formation of ordered nanocomposite solids would represent a new opportunity for materials design.

In-situ SAXS study of aqueous clay suspensions submitted to alternating current electric fields.

Aqueous colloidal suspensions of clay platelets display a sol/gel transition that is not yet understood. Depending on the nature of the clay, liquid-crystalline behavior may also be observed. For example, the suspensions of beidellite display a nematic phase whereas those of montmorillonite do not. Both beidellite and montmorillonite have a "TOT" structure but the structural electric charge is located in the tetrahedral layer for the former and in the octahedral layer for the latter. We built a setup to perform SAXS experiments on complex fluids submitted to an electric field in situ. We found that the fluid nematic phase of beidellite suspensions readily aligns in the field. However, the field had no influence on the gels, showing that the orientational degrees of freedom of the platelets are effectively frozen. Moreover, strong platelet alignment was induced by the field in the isotropic phase of both clays, in a similar way, regardless of their ability to form a nematic phase. This surprising result would suggest that the orientational degrees of freedom are not directly involved in the sol/gel transition. The ability to induce orientational order in the isotropic phase of clay suspensions can be exploited to prepare materials of controlled anisotropy.

Tailoring highly oriented and micropatterned clay/polymer nanocomposites by applying an a.c. electric field.

Clay/polymer nanocomposites have recently raised much interest because of their widespread industrial applications. Nevertheless, controlling both clay platelet exfoliation and orientation during polymerization still remains challenging. Herein, we report the elaboration of clay/polymer nanocomposite hydrogels from aqueous suspensions of natural swelling clays submitted to high-frequency a.c. electric fields. X-ray scattering experiments have confirmed the complete exfoliation of the clay sheets in the polymer matrix, even after polymerization. Moreover, polarized light microscopy shows that the clay platelets were perfectly oriented by the electric field and that this field-induced alignment was frozen in by in situ photopolymerization. This procedure allowed us to not only produce uniformly aligned samples but also pattern platelet orientation, at length scales down to 20 µm. This straightforward and cheap nanocomposite patterning technique can be easily extended to a wide range of natural or synthetic inorganic anisotropic particles.

The complex phase behaviour of suspensions of goethite (alpha-FeOOH) nanorods in a magnetic field.

In 1902, Majorana reported the magneto-optical properties of aqueous colloidal suspensions of mixed iron oxides. Oddly enough, the magnetic-field induced birefringence displayed a non-monotonic dependence upon field intensity. This behaviour was later interpreted as due to the existence in these sols of at least two different chemical species. During the course of our studies of mineral liquid crystals, we have revisited this problem by examining aqueous suspensions of pure goethite (alpha-FeOOH) nanorods. Although they are comprised of a single chemical species, these suspensions show the same odd behaviour reported by Majorana. Moreover, we show that, as the volume fraction increases, the suspensions have an isotropic liquid/nematic/rectangular columnar phase sequence, with first-order transitions between these phases. The non-monotonic dependence of the field-induced birefringence can be explained by the existence of a remanent magnetic moment of the nanorods and the negative anisotropy of their magnetic susceptibility. Therefore, the nanorods align parallel to a weak field but realign perpendicular to the field beyond Bc approximately 375 mT. In addition, other interesting phenomena appear upon application of a magnetic field: the disordered (i.e. isotropic in zero-field) phase becomes highly anisotropic and difficult to distinguish from the nematic phase. Both phases then acquire not only quadrupolar order but also dipolar order. The rectangular columnar phase is strongly stabilised versus the nematic one. Our experimental observations raise new theoretical questions about the phase diagram of these suspensions with respect to volume fraction and magnetic field intensity.

Zenithal gliding of the easy axis of a nematic liquid crystal.

We present experimental evidence of zenithal gliding of the nematic easy axis on a polyimide surface. The reorientation dynamics of the easy axis under external torque, and its relaxation, are extremely slow processes which cannot be described by a single exponential time. They show similarities with aging phenomena previously encountered in glassy systems. At last, the adsorption-desorption-readsorption process which empirically justifies the azimuthal easy axis gliding may also explain our observations.