The smectic ZA phase: Antiferroelectric smectic order as a prelude to the ferroelectric nematic.

We have structurally characterized the liquid crystal (LC) phase that can appear as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-y-old void in the taxonomy of smectic LCs and which we term the "smectic ZA," is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole-dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-SmZA-ferroelectric nematic phase sequence.

Observation of a uniaxial ferroelectric smectic A phase.

We report the observation of the smectic AF, a liquid crystal phase of the ferroelectric nematic realm. The smectic AF is a phase of small polar, rod-shaped molecules that form two-dimensional fluid layers spaced by approximately the mean molecular length. The phase is uniaxial, with the molecular director, the local average long-axis orientation, normal to the layer planes, and ferroelectric, with a spontaneous electric polarization parallel to the director. Polarization measurements indicate almost complete polar ordering of the ∼10 Debye longitudinal molecular dipoles, and hysteretic polarization reversal with a coercive field ∼2 × 105 V/m is observed. The SmAF phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic (N)-smectic ZA (SmZA)-ferroelectric nematic (NF)-SmAF phase sequence, and 7N/DIO, exhibiting an N-SmZA-SmAF phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers.

New examples of ferroelectric nematic materials showing evidence for the antiferroelectric smectic-Z phase.

We present a new ferroelectric nematic material, 4-((4'-((trans)-5-ethyloxan-2-yl)-2',3,5,6'-tetrafluoro-[1,1'-biphenyl]-4-yl)difluoromethoxy)-2,6-difluorobenzonitrile (AUUQU-2-N) and its higher homologues, the molecular structures of which include fluorinated building blocks, an oxane ring, and a terminal cyano group, all contributing to a large molecular dipole moment of about 12.5 D. We observed that AUUQU-2-N has three distinct liquid crystal phases, two of which were found to be polar phases with a spontaneous electric polarization Ps of up to 6 µC cm-2. The highest temperature phase is a common enantiotropic nematic (N) exhibiting only field-induced polarization. The lowest-temperature, monotropic phase proved to be a new example of the ferroelectric nematic phase (NF), evidenced by a single-peak polarization reversal current response, a giant imaginary dielectric permittivity on the order of 103, and the absence of any smectic layer X-ray diffraction peaks. The ordinary nematic phase N and the ferroelectric nematic phase NF are separated by an antiferroelectric liquid crystal phase which has low permittivity and a polarization reversal current exhibiting a characteristic double-peak response. In the polarizing light microscope, this antiferroelectric phase shows characteristic zig-zag defects, evidence of a layered structure. These observations suggest that this is another example of the recently discovered smectic ZA (SmZA) phase, having smectic layers with the molecular director parallel to the layer planes. The diffraction peaks from the smectic layering have not been observed to date but detailed 2D X-ray studies indicate the presence of additional short-range structures including smectic C-type correlations in all three phases-N, SmZA and NF-which may shed new light on the understanding of polar and antipolar order in these phases.

Validation of thermophysical data for scientific and engineering applications.

High quality thermophysical property data are essential to many scientific and engineering applications. These data are produced at a high rate and are affected by a range of experimental and reporting error sources that often exceed stated uncertainties. As a result, critical evaluation is required to establish the limits of reliability in a quantified way. The present work describes reporting recommendations and property data validation methods developed and applied at the Thermodynamics Research Center at NIST through the use of the ThermoData Engine (TDE; SRD 103a/b) software. Examples are provided with an emphasis on various consistency checks, which may include the use of equations of state (EOS).