The design and investigation of the self-assembly of dimers with two nematic phases

A series of non-symmetric dimers were synthesised containing either cyanobiphenyl or difluoroterphenyl moieties on one side and a range of long, short, bent, polar or apolar mesogens on the other side of the molecules. The dielectric anisotropy of the mesogens was varied systematically. The systems were characterised by differential scanning calorimetry (DSC), optical polarizing microscopy (OPM) and detailed X-ray diffraction (XRD) studies, both in the nematic and the Nx phase. The results are compared and structure properties relationships are discussed. A model for the assembly in the Nx phase is developed discussing Ntb structures, coaxial helices, swiss roll structures and chiral domain formation

On the structure of the Nx phase of symmetric dimers: inferences from NMR

NMR measurements on a selectively deuterated liquid crystal dimer CB-C9-CB, exhibiting two nematic phases, show that the molecules in the lower temperature nematic phase, NX, experience a chiral environment and are ordered about a uniformly oriented director throughout the macroscopic sample. The results are contrasted with previous interpretations that suggested a twist-bend spatial variation of the director. A structural picture is proposed wherein the molecules are packed into highly correlated chiral assemblies

Twist-bend nematic phase in cyanobiphenyls and difluoroterphenyls bimesogens

The paper reviews assignment of the low-temperature nematic phase observed in simple bimesogenic or dimeric systems based on cyanobiphenyls and difluoroterphenyls to the twist-bend nematic phase, NTB, using a range of experimental techniques. These include DSC, X-rays, Polarising Microscopy, electro-optics, birefringence and measurements of the electroclinic effect arising from flexoelectricity. An emphasis is laid on the observations of the chiral domains of opposite handedness at zero field in an otherwise achiral liquid crystalline system in this phase. These observations are a direct consequence of the structure of the twist-bend phase predicted by Ivan Dozov for achiral bent core molecules. The paper reviews the electro-optic phenomena and the observed electroclinic effect and how these observations assign it as the NTB phase. Results of the nanoscale helical pitch measurements using freeze-fracture microscopy are reviewed and discussed briefly. Results of the measurements of elastic constants especially close to the N–NTB transition are also reviewed

Relaxation of a Colloidal Particle into a Nonequilibrium Steady State

We study the relaxation of a single colloidal sphere which is periodically driven between two nonequilibrium steady states. Experimentally, this is achieved by driving the particle along a toroidal trap imposed by scanned optical tweezers. We find that the relaxation time after which the probability distributions have been relaxed is identical to that obtained by a steady state measurement. In quantitative agreement with theoretical calculations the relaxation time strongly increases when driving the system further away from thermal equilibrium

The stabilisation of the Nx phase in mixtures

The phase behaviour of mixtures between two symmetric dimers, CBC9CB and the ether-linked analogue CBOC9OCB was investigated by Polarizing Optical Microscopy (POM), Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD) studies. The dimeric constituents are fully miscible and the construction of a temperature-composition phase diagram reveals a surprising amplification of the stability of the Nx phase in compositions of up to 37 wt% of CBOC9OCB in CBC9CB. The origin for this enhancement of stability is discussed and an explanation based on chiral recognition is developed

Deuteron and proton NMR study of D₂, p-dichlorobenzene and 1,3,5-trichlorobenzene in bimesogenic liquid crystals with two nematic phases

The solutes dideuterium, 1,3,5-trichlorobenzene and p-dichlorobenzene (pdcb) are co-dissolved in a 61/39 wt% mixture of CBC9CB/5CB, a bimesogenic liquid crystal with two nematic phases. NMR spectra are collected for each solute. The local electric field gradient (FZZ) is obtained from the dideuterium spectrum. A double Maier-Saupe potential (MSMS) is used to rationalize the order parameters of pdcb. The liquid-crystal fields G₁ and G₂ are taken to be due to size and shape interactions and interactions between the solute molecular quadrupole and the mean FZZ of the medium. The FZZ’s obtained from D₂ and G₂ (from pdcb) are compared and discussed

Director configuration in the twist-bend nematic phase of CB11CB

The director distribution in the nematic phases exhibited by the 100,1100-bis(4-cyanobiphenyl-40-yl)undecane (CB11CB) liquid crystal has been studied in the bulk with the EPR spin probe technique. EPR spectra confirmed the presence of an higher temperature uniaxial nematic phase and of a lower temperature nematic phase in which the director distribution is not uniform. Spectra recorded in the lower temperature nematic phase were not fully compatible with theoretical EPR spectra calculated according to the recently proposed model for the twist-bend phase in which the local domain director twists around an axis with a fixed tilt angle, θ₀, but were well described by a “distributed-tilt” model in which the director has a relatively narrow distribution, centred at θ₀

Fabrication of salt–hydrogel marbles and hollow-shell microcapsules by an aerosol gelation technique

We designed a new method for preparation of liquid marbles by using hydrophilic particles. Salt–hydrogel marbles were prepared by atomising droplets of hydrogel solution in a cold air column followed by rolling of the collected hydrogel microbeads in a bed of micrometre sized salt particles. Evaporation of the water from the resulting salt marbles with a hydrogel core yielded hollow-shell salt microcapsules. The method is not limited to hydrophilic particles and could potentially be also applied to particles of other materials, such as graphite, carbon black, silica and others. The structure and morphology of the salt–hydrogel marbles were analysed by SEM and their particle size distributions were measured. We also tested the dissolution times of the dried salt marbles and compared them with those of table salt samples under the same conditions. The high accessible surface area of the shell of salt microcrystals allows a faster initial release of salt from the hollow-shell salt capsules upon their dissolution in water than from the same amount of table salt. The results suggest that such hollow-shell particles could find applications as a table salt substitute in dry food products and salt seasoning formulations with reduced salt content without the loss of saltiness

Do the short helices exist in the nematic TB phase?

Dimeric compounds forming twist-bend nematic, Ntb, phase show unusual optical textures related to the formation of arrays of focal conic defects (FCDs). Some of the focal conics exhibit submicron internal structure with 8 nm periodicity, which is very close to that found in the crystalline phase of the material, that might suggest surface freezing