Twist Distortion Research Articles

Nematic liquid crystals on sinusoidal channels: the zigzag instability

Substrates which are chemically or topographically patterned induce a variety of liquid crystal textures. The response of the liquid crystal to competing surface orientations, typical of patterned substrates, is determined by the anisotropy of the elastic constants and the interplay of the relevant lengths scales, such as the correlation length and the surface geometrical parameters. Transitions between different textures, usually with different symmetries, may occur under a wide range of conditions. We use the Landau–de Gennes free energy to investigate the texture of nematics in sinusoidal channels with parallel anchoring bounded by nematic-air interfaces that favour perpendicular (hometropic) anchoring. In micron size channels 5CB was observed to exhibit a non-trivial texture characterized by a disclination line, within the channel, which is broken into a zigzag pattern. Our calculations reveal that when the elastic anisotropy of the nematic does not favour twist distortions the defect is a straight disclination line that runs along the channel, which breaks into a zigzag pattern with a characteristic period, when the twist elastic constant becomes sufficiently small when compared to the splay and bend constants. The transition occurs through a twist instability that drives the defect line to rotate from its original position. The interplay between the energetically favourable twist distortions that induce the defect rotation and the liquid crystal anchoring at the surfaces leads to the zigzag pattern. We investigate in detail the dependence of the periodicity of the zigzag pattern on the geometrical parameters of the sinusoidal channels, which in line with the experimental results is found to be non-linear.

THE OPTIMIZATION OF CLAMPING METHOD IN REDUCING WELDING DISTORTION OF LOW CARBON STEEL

This study aimed to reduce levels of distortion welding through Clamping method so that the parameters of the most optimal Clamping against distortion and cracking resistance would be recognized. The method was applied to the workpiece Clamping before welding by 5 methods that include: without Clamping, 2 points Clamping, 4 points Clamping, 6 points Clamping and 4 points + fulcrum campling. The tests carried out on the workpiece welding include: distortions test (angles, curves and twisting) and shrinkage tests (transverse and longitudinal) and bending test for crack resistance. The results show that Clamping method is capable on reducing the level of distortion due to the welding process. Four Clamping method is considered the most optimal point in reducing the level of distortion with 2.2 angular distortion, 3.2 mm bending distortion, and without twist distortion. Bending testing shows that Clamping method does not degrade the quality of welded joints based on the acceptance of all bending test specimen

Cobalt(II)-Based Single-Ion Magnets with Distorted Pseudotetrahedral [N2O2] Coordination: Experimental and Theoretical Investigations.

The synthesis and magnetic properties of cobalt(II) complexes with sterically demanding Schiff-base ligands are reported. The compounds [Co(L(Br))2] (1) and [Co(L(Ph))2]·CH2Cl2 (2·CH2Cl2) are obtained by the reaction of cobalt(II) acetate with the ligands HL(Br) and HL(Ph) in a dichloromethane/methanol mixture. 1 and 2 crystallize in the space groups P21212 and P1̅, respectively. X-ray diffraction studies revealed mononuclear constitution of both complexes. For 1, relatively short intermolecular Co-Co distances of 569 pm are observed. In compound 2, a hydrogen-bonded dichloromethane molecule is present, leading to a solvent aggregate with remarkable thermal stability for which desolvation is taking place between 150 and 210 °C. Magnetic measurements were performed to determine the zero-field-splitting (ZFS) parameter D for both complexes. Frequency-dependent susceptibility measurements revealed slow magnetic relaxation behavior with spin-reversal barriers of 36 cm(-1) for 1 and 43 cm(-1) for 2 at an applied external field of 400 Oe. This observation is related to an increasing distortion of the pseudotetrahedral coordination geometry for complex 2. These distortions can be decomposed in two major contributions. One is the elongation effect described by the parameter ϵT, which is the ratio of the averaged obtuse and acute bond angles. The other effect is related to a twisting distortion of the chelate coordination planes at the cobalt center. A comparison with literature examples reveals that the elongation effect seems to govern the overall magnetic behavior in pseudotetrahedral complexes with two bidentate chelate ligands. Ab initio calculations for complexes 1 and 2 using the CASPT2 method show strong splitting of the excited (4)T2 term, which explains the observed strong ZFS. Spin-orbit calculations with the RASSI-SO method confirm the single-molecule-magnet behavior because only small transversal elements are found for the lowest Kramers doublet for both complexes.

The pressure induced twisted distortion in the flexible oxide Tc2O7

The pressure induced twisted distortion of the diagonal-double tetrahedrons (DDTs) in Tc2O7 and the corresponding anomalous lattice variation under pressure were unraveled based on van der Waals (vdW) corrected density functional theory calculations. We show that the optPBE functional precisely represents the crystal structure of Tc2O7 with less than 0.5% volume overestimation. The flexibility of the Tc2O7 cell originating from the weak vdW interactions between the Tc2O7 DDTs is confirmed. On the contrary, we have found that the strong ionic bonding in the Tc2O7 DDT leads to the rigidity of the Tc2O7 DDT. According to the analysis of chemical bonding characterization, the pressure induced distortion of the Tc2O7 DDT leads to inhomogeneous Tc–O bonding distributions.

Volume phase transitions of cholesteric liquid crystalline gels.

We present a mean field theory to describe anisotropic deformations of a cholesteric elastomer without solvent molecules and a cholesteric liquid crystalline gel immersed in isotropic solvents at a thermal equilibrium state. Based on the neoclassical rubber theory of nematic elastomers, we derive an elastic energy and a twist distortion energy, which are important to determine the shape of a cholesteric elastomer (or gel). We demonstrate that when the elastic energy dominates in the free energy, the cholesteric elastomer causes a spontaneous compression in the pitch axis and elongates along the director on the plane perpendicular to the pitch axis. Our theory can qualitatively describe the experimental results of a cholesteric elastomer. We also predict the first-order volume phase transitions and anisotropic deformations of a gel at the cholesteric-isotropic phase transition temperature. Depending on a chirality of a gel, we find a prolate or oblate shape of cholesteric gels.

Chiral structures from achiral liquid crystals in cylindrical capillaries

We study chiral symmetry-broken configurations of nematic liquid crystals (LCs) confined to cylindrical capillaries with homeotropic anchoring on the cylinder walls (i.e., perpendicular surface alignment). Interestingly, achiral nematic LCs with comparatively small twist elastic moduli relieve bend and splay deformations by introducing twist deformations. In the resulting twisted and escaped radial (TER) configuration, LC directors are parallel to the cylindrical axis near the center, but to attain radial orientation near the capillary wall, they escape along the radius through bend and twist distortions. Chiral symmetry-breaking experiments in polymer-coated capillaries are carried out using Sunset Yellow FCF, a lyotropic chromonic LC with a small twist elastic constant. Its director configurations are investigated by polarized optical microscopy and explained theoretically with numerical calculations. A rich phenomenology of defects also arises from the degenerate bend/twist deformations of the TER configuration, including a nonsingular domain wall separating domains of opposite twist handedness but the same escape direction and singular point defects (hedgehogs) separating domains of opposite escape direction. We show the energetic preference for singular defects separating domains of opposite twist handedness compared with those of the same handedness, and we report remarkable chiral configurations with a double helix of disclination lines along the cylindrical axis. These findings show archetypally how simple boundary conditions and elastic anisotropy of confined materials lead to multiple symmetry breaking and how these broken symmetries combine to create a variety of defects.

Chiral symmetry breaking and surface faceting in chromonic liquid crystal droplets with giant elastic anisotropy

Confined liquid crystals (LC) provide a unique platform for technological applications and for the study of LC properties, such as bulk elasticity, surface anchoring, and topological defects. In this work, lyotropic chromonic liquid crystals (LCLCs) are confined in spherical droplets, and their director configurations are investigated as a function of mesogen concentration using bright-field and polarized optical microscopy. Because of the unusually small twist elastic modulus of the nematic phase of LCLCs, droplets of this phase exhibit a twisted bipolar configuration with remarkably large chiral symmetry breaking. Further, the hexagonal ordering of columns and the resultant strong suppression of twist and splay but not bend deformation in the columnar phase, cause droplets of this phase to adopt a concentric director configuration around a central bend disclination line and, at sufficiently high mesogen concentration, to exhibit surface faceting. Observations of director configurations are consistent with Jones matrix calculations and are understood theoretically to be a result of the giant elastic anisotropy of LCLCs.

反射型動的光散乱測定による SmC*相のツイスト弾性測定

反射型動的光散乱測定による SmC*相のツイスト弾性測定

PB10 ツイスト配向弾性測定用の反射型動的光散乱測定(ソフトマター,ポスター発表,2013年日本液晶学会討論会)

PB10 ツイスト配向弾性測定用の反射型動的光散乱測定(ソフトマター,ポスター発表,2013年日本液晶学会討論会)

The synthesis and characterisation of LaCa2Fe2GaO8

The synthesis and characterisation of LaCa2Fe2GaO8 is described. Neutron powder diffraction data reveal LaCa2Fe2GaO8 adopts an anion-vacancy ordered, ‘triple layer’ structure consisting of an OOTLOOTR stacking sequence of layers of (Fe/Ga)O6 octahedra (O) and (Fe/Ga)O4 tetrahedra (T), related to that of the 4-layer brownmillerite structures (a=5.4784(1)Å, b=22.6780(4)Å, c=5.6007(1)Å, space group Pbma). The apex-linked chains of tetrahedra within structure of LaCa2Fe2GaO8 exhibit a cooperative twisting distortion which alternates in direction between adjacent layers of tetrahedra, the first time such an arrangement has been seen in a triple-layer phase. Magnetisation and neutron diffraction data reveal that LaCa2Fe2GaO8 exhibits two magnetic ordering transitions. On cooling below 550K the phase adopts a state with short range antiferromagnetic coupling within each double layer of (Fe/Ga)O6 octahedra, but only weak coupling between layers. On cooling below 470K full three-dimensional, G-type antiferromagnetic order is observed.

Investigation on twisting distortion of thin plate stiffened structure under welding

The welding distortion of thin plate was selected as research subject, which causes loss of dimensional control, structural integrity and increases fabrication costs for straightening. To study the characteristic of the welding distortion on thin plate structures, experiments were conducted. The test model was a thin plate stiffened structure and a large twisting distortion was observed. The welding distortion of the same structure was analyzed as a large deformation problem using a thermal elastic plastic FEM and an elastic FEM based on the concept of inherent deformation. The computed results by both methods showed the twisting distortion which is a typical buckling type deformation and the magnitude of this distortion agreed well with the experimental measurement.

Three-dimensional galvanic distortion of three-dimensional regional conductivity structures: Comment on “Three-dimensional joint inversion for magnetotelluric resistivity and static shift distributions in complex media” by Yutaka Sasaki and Max A. Meju

[1] Distortion of natural time variations of the electric and magnetic fields induced by external magnetic sources by local, near-surface inhomogeneities has been the bane of the magnetotelluric method (MT). These distortions are caused by galvanic charges on conductivity gradients at the boundaries of near-surface inhomogeneities that are below the resolution of the MT experiment. They often dominate over the inductive response of deeper structures, leading to erroneous interpretations if not appropriately considered. Indeed, one can argue that MT has become a generally robust and useful geological mapping tool only with the advent of distortion recognition, appraisal and removal methods. On land, these distortions are usually low in regions of laterally uniform surficial layers, such as sedimentary basin environments, and extreme in highly heterogeneous resistive environments, such as on Precambrian regions. On the seafloor they are usually extreme. They are always present and affect the MT responses derived from the observed fields to a greater or lesser extent, and must be considered in any analyses and subsequent interpretations. [2] Distortion methods for MT data responding to onedimensional (1-D) and two-dimensional (2-D) structures (reviewed below) have been advanced and are usually quite effective, except in the situations of very severe distortion. For data from three-dimensional (3-D) structures however, the problems caused by these galvanic charges becomes far more complex and require innovative analysis and treatment. [3] In their paper, Sasaki and Meju [2006] describe their approach to 3-D inversion of MT data for 3-D structure taking galvanic distortion, which they characterize and simplify as static shifts, into account. Their paper is an update on prior work by Sasaki [2004] with the same approach. The assumption made by the authors is that the magnitudes of the observed off-diagonal elements of the impedance tensor can be described as geometrically shifted versions of their true values, namely in their terms

Macroscopic Torsional Strain and Induced Molecular Conformational Deracemization

A macroscopic helical twist is imposed on an achiral nematic liquid crystal by controlling the azimuthal alignment directions at the two substrates. On application of an electric field the director rotates in the substrate plane. This electroclinic effect, which requires the presence of chirality, is strongest at the two substrates and increases with increasing imposed twist distortion. We present a simple model involving a trade-off among bulk elastic energy, surface anchoring energy, and deracemization entropy that suggests the large equilibrium director rotation induces a deracemization of chiral conformations in the molecules-effectively "top-down" chiral induction-quantitatively consistent with experiment.

Elastic lateral buckling of cantilever Litesteel Beams under transverse loading

The LiteSteel Beam (LSB) is a new hollow flange channel section developed by OneSteel Australian Tube Mills using its patented dual electric resistance welding and automated continuous roll-forming technologies. The LSB has a unique geometry consisting of torsionally rigid rectangular hollow flanges and a relatively slender web. Its flexural strength for intermediate spans is governed by lateral distortional buckling characterised by simultaneous lateral deflection, twist and web distortion. Recent research on LSBs has mainly focussed on their lateral distortional buckling behaviour under uniform moment conditions. However, in practice, LSB flexural members are subjected to non-uniform moment distributions and load height effects as they are often under transverse loads applied above or below their shear centre. These loading conditions are known to have significant effects on the lateral buckling strength of beams. Many steel design codes have adopted equivalent uniform moment distribution and load height factors based on data for conventional hot-rolled, doubly symmetric I-beams subject to lateral torsional buckling. The non-uniform moment distribution and load height effects of transverse loading on cantilever LSBs, and the suitability of the current design modification factors to include such effects are not known. This paper presents a numerical study based on finite element analyses of the elastic lateral buckling strength of cantilever LSBs subject to transverse loading, and the results. The applicability of the design modification factors from various steel design codes was reviewed, and suitable recommendations are presented for cantilever LSBs subject to transverse loading.

Twist distortion in rod/liquid crystal mixtures

A simple model is introduced to describe the twist distortion in mixtures of a rigid rod-like molecule (rod) and a liquid crystal (LC) molecule. We take into account the coupling between rods and LCs and calculate the equilibrium reorientation angles of rods and LCs when an external field applies. We find that the dependence of the critical threshold on the rod concentration is changed due to the ratio of the twist elastic constant K 22,2 to the dielectric or magnetic anisotropy χ2 of the rod. The theory can qualitatively describe the observed properties of carbon nanotube/LC mixtures. We also discuss the reorientation dynamics.

Orientation and Stereodynamic Paths of Planar Monodentate Ligands in Square Planar Nickel N2S Complexes

The well-established presence of histidine donors in binding sites of Ni-containing biomolecules prompts the study of orientational preference and stereodynamic nature of flat monodentate ligands (L = imidazoles, pyridine and an N-heterocyclic carbene) bound to planar N(2)SNi moieties. Square planar [N(2)SNiL](n+) complexes are accessed through bridge-splitting reactions of dimeric, thiolate-S bridged [N(2)SNi](2) complexes. The solid state molecular structures of three mononuclear products, and three monothiolate bridged dinickel complexes, reveal that the plane of the added monodentate ligand orients largely orthogonal to the N(2)SNiL square plane. Variable temperature (1)H NMR characterization of dynamic processes and ground state isomer ratios of imidazole complexes in their stopped exchange limiting spectra, readily correlate with density functional theory (DFT)-guided interpretation of Ni-L rotational activation barriers. Full DFT characterization finds Ni-L bond lengthening as well as a tetrahedral twist distortion in the transition state, reaching a maximum in the NHC complex, and relating mainly to the steric hindrance derived both from the ligand and the binding pocket. In the case of the imidazole ligands a minor electronic contribution derives from intramolecular electrostatic interactions (imidazole C-2 C-H(delta+)- - S(delta-) interaction). Computational studies find this donor-acceptor interaction is magnified in O-analogues, predicting coplanar arrangements in the ground state of N(2)ON(imid)Ni complexes.

Large-amplitude vibrations of an N–H⋯π hydrogen bonded cis-amide–benzene complex

The ground-state N-H...pi interaction of 2-pyridone.benzene (2PY.Bz) has been studied by infrared-UV depletion spectroscopy of the supersonic-jet cooled complex [P. Ottiger et al., J. Phys. Chem. B (2009) 113, 2937]. Here, we investigate the large-amplitude vibrations of 2PY.Bz and its d(1)-2PY and benzene-d(6) isotopologues in the S(1) state, using two-color resonant two-photon ionization and UV-holeburning spectroscopies, complemented by RI-CC2 and SCS-RI-CC2 calculations of the S(1) state. The latter predict a tilted T-shaped structure with an N-H...pi hydrogen bond to the benzene ring, similar to the S(0) state. The binding energy is predicted to increase by 1.5 kJ mol(-1) upon S(1)<--S(0) excitation, in close agreement with the experimental value of 1.2 kJ mol(-1). The vibronic band structure up to 60 cm(-1) above the 0 band is dominated by large-amplitude delta tilting excitations, reflecting a change in the tilt angle of the T-shaped complex. The S(0) and S(1) state delta potentials were fitted to experiment, yielding a single minimum in the S(0) state and a double-minimum S(1) potential with delta(min) = +/-13 degrees. The second large-amplitude vibration is the theta twisting or benzene internal-rotation mode. Due to the C(6) symmetry of the benzene moiety the S(0) and S(1) state theta potentials are sixfold symmetric. Analysis of the theta band structure reveals that the S(0) and S(1)theta potentials are mutually aligned and that the internal rotation barriers are V(6)(S(0)) < 0.2 kJ mol(-1) and V(6)(S(1)) = 0.10(1) kJ mol(-1), in close agreement with the calculations. Weaker excitations of the totally symmetric intermolecular vibrations chi (shear), omega (bend) and sigma (stretch) vibrations are also observed. The 2PY intramolecular nu(1) overtone, corresponding to an 2PY amide out-of-plane twist distortion, lies approximately 30% higher than in bare 2PY, reflecting the hindrance of this motion by the strong N-H...pi interaction.

N‐Arylated 3,5‐Dihydro‐4H‐dinaphtho[2,1‐c:1′,2′‐e]azepines: Axially Chiral Donors with High Helical Twisting Powers for Nonplanar Push–Pull Chromophores

Axially chiral, N-arylated 3,5-dihydro-4H-dinaphtho[2,1-c:1',2'-e]azepines have been prepared by short synthetic protocols from enantiopure 1,1'-bi(2,2'-naphthol) (BINOL) and anilines. Alkynes substituted with two N-phenyldinaphthazepine donors readily undergo a formal [2+2] cycloaddition, followed by retro-electrocyclization, with tetracyanoethene (TCNE) to yield donor-substituted 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) featuring intense intramolecular charge-transfer (CT) interactions. A dicyanovinyl derivative substituted with one N-phenyldinaphthazepine donor was obtained by a "one-pot" oxidation/Knoevenagel condensation from the corresponding propargylic alcohol. Comparative electrochemical, X-ray crystallographic, and UV/Vis studies show that the electron-donor qualities of N-phenyldinaphthazepine are similar to those of N,N-dimethylanilino residues. The circular dichroism (CD) spectrum of a push-pull chromophore incorporating the chiral donor moiety features Cotton effects of exceptional intensity. With their elongated shape and the rigidity of the chiral N-aryldinaphthazepine donors, these chromophores are effective inducers of twist distortion in nematic liquid crystals (LCs). Thus, a series of the dinaphthazepine derivatives was used as dopants in the nematic LC E7 (Merck) and high helical twisting powers (beta) of the order of hundreds of microm(-1) were measured. Theoretical calculations were employed to elucidate the relation between the structure of the dopants and their helical twisting power. For the derivatives with two dinaphthazepine moieties, a strong dependence of the beta-values on the structure and conformation of the linker between them was found.

Lateral Buckling Strength of Simply Supported LiteSteel Beams Subject to Moment Gradient Effects

The flexural capacity of a new cold-formed hollow flange channel section known as LiteSteel beam (LSB) is limited by lateral distortional buckling for intermediate spans, which is characterized by simultaneous lateral deflection, twist, and web distortion. Recent research has developed suitable design rules for the member capacity of LSBs. However, they are limited to a uniform moment distribution that rarely exists in practice. Many steel design codes have adopted equivalent uniform moment distribution factors to accommodate the effect of nonuniform moment distributions in design. But they were derived mostly based on the data for conventional hot-rolled doubly symmetric I-beams subject to lateral torsional buckling. The effect of moment distribution for LSBs and the suitability of the current steel design code rules to include this effect for LSBs are not yet known. This paper presents the details of a research study based on finite-element analyses (FEAs) of the lateral buckling strength of simply supported LSBs subject to moment gradient effects. It also presents the details of a number of LSB lateral buckling experiments undertaken to validate the results of FEAs. Finally, it discusses the suitability of the current design methods and provides design recommendations for simply supported LSBs subject to moment gradient effects.

Elastic lateral buckling of simply supported LiteSteel beams subject to transverse loading

The buckling strength of a new cold-formed hollow flange channel section known as LiteSteel beam (LSB) is governed by lateral distortional buckling characterised by simultaneous lateral deflection, twist and web distortion for its intermediate spans. Recent research has developed a modified elastic lateral buckling moment equation to allow for lateral distortional buckling effects. However, it is limited to a uniform moment-distribution condition that rarely exists in practice. Transverse loading introduces a non-uniform bending moment distribution, which is also often applied above or below the shear centre (load height). These loading conditions are known to have significant effects on the lateral buckling strength of beams. Many steel design codes have adopted equivalent uniform moment-distribution and load-height factors to allow for these effects. But they were derived mostly based on data for conventional hot-rolled, doubly symmetric I-beams subject to lateral torsional buckling. The moment-distribution and load-height effects of transverse loading for LSBs, and the suitability of the current design modification factors to accommodate these effects for LSBs are not known. This paper presents the details of a research study based on finite element analyses on the elastic lateral buckling strength of simply supported LSBs subject to transverse loading. It discusses the suitability of the current steel design code modification factors, and provides suitable recommendations for simply supported LSBs subject to transverse loading.