Pseudonematic order fluctuations of the director in the smectic phase of thermotropic liquid crystals.

PubMed

Acosta, R H; Pusiol, D J

1999-08-01

The NMR spin-lattice proton relaxation dispersion in the smectic mesophase of two liquid crystals, 4cyano-4'-8-alkylbiphenyl and 4,4'-bis-heptyloxyazoxybenzene, are studied over several decades of Larmor frequencies. The results show that the order fluctuation of the local smectic director contribution to T1(nu(L)) undergoes a transition between two power regimes: from T1(nu(L)) proportional, variantnu(1)(L) to nu(1/2)(L) on going from low to high Larmor frequencies. We explain this behavior by assuming, in the smectic mesophases, short coherence length nematiclike cooperative molecular reorientations.

Electron paramagnetic resonance study of alinement induced by magnetic fields in two smectic-A liquid crystals not exhibiting nematic phases

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Gelerinter, E.

1972-01-01

Using vanadyl acetylacetonate (VAAC) as a paramagnetic probe, the molecular ordering in two smectic-A liquid crystals that do not display nematic phases were studied. Reproducible alinement was attained by slow cooling throughout the isotropic smectic-A transition in dc magnetic fields of 1.1 and 2.15 teslas. The degree of order attained is small for a smectic-A liquid crystal. Measurements were made of the variation of the average hyperfine splitting of the alined samples as a function of orientation relative to the dc magnetic field of the spectrometer. This functional dependence is in agreement with the theoretical prediction except where the viscosity of the liquid crystal becomes large enough to slow the tumbling of the VAAC, as indicated by asymmetry in the end lines of the spectrum.

Paraelectric-antiferroelectric phase transition in achiral liquid crystals

NASA Astrophysics Data System (ADS)

Pociecha, Damian; Gorecka, Ewa; Čepič, Mojca; Vaupotič, Nataša; Gomola, Kinga; Mieczkowski, Jozef

2005-12-01

Critical freezing of molecular rotation in an achiral smectic phase, which leads to polar ordering through the second order paraelectric-antiferroelectric (Sm-A→Sm-APA) phase transition is studied theoretically and experimentally. Strong softening of the polar mode in the Sm-A phase and highly intensive dielectric mode in the Sm-APA phase are observed due to weak antiferroelectric interactions in the system. In the Sm-APA phase the dielectric response behaves critically upon biasing by a dc electric field. Such a behavior is found general for the antiferroelectric smectic phase with significant quadrupolar interlayer coupling.

Structure and Dynamics of Freely Suspended Liquid Crystals

NASA Technical Reports Server (NTRS)

Clark, Noel A.

2004-01-01

Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1 D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline or quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enables the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new LC physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and Kosterlitz Thouless phase transition has been observed and 2D XY quasi long range order verified. Smectic films have enabled the precise determination of smectic layer electron density and positional fluctuation profiles and have been used to show that the interlayer interactions in antiferroelectric tilted smectics do not extend significantly beyond nearest neighbors. Freely suspended films played a pivotal role in the recent discovery of macroscopic chiral-polar ordering in fluids of achiral molecules. The interactions which are operative in liquid crystals are generally weak in comparison to those in crystalline phases, leading to the facile manipulation of the order in liquid crystals by external agents such as applied fields and surfaces. Effects arising from weak ordering are significantly enhanced in ultrathin free films and filaments, in which the intermolecular coupling is effectively further reduced by loss of neighbors. Over the past four years this research, which we now detail, has produced a host of exciting new discoveries and unexpected results, maintaining the study of freely suspended liquid crystal structures as one of most exciting and fruitful areas of complex fluid physics. In addition, a class of experiments on the behavior of 1D interfaces in 2D films have been pursued with results that point to potentially quite interesting effects in microgravity.

Molecular organization of the cholesteryl ester droplets in the fatty streaks of human aorta.

PubMed Central

Engelman, D M; Hillman, G M

1976-01-01

X-ray diffraction patterns from human arterial specimens containing atherosclerotic fatty streak lesions exhibited a single sharp reflection, corresponding to a structural spacing of about 35 A. Specimens without lesions did not. When specimens with fatty streaks were heated, an order-to-disorder phase transition was revealed by the disappearance of the sharp reflection. The transition was thermally reversible and its temperature varied from aorta to aorta over a range from 28 degrees to 42 degrees C. Since cholesteryl ester droplets are a major component of fatty streaks, comparison studies were made of the diffraction behavior from pure cholesteryl esters. We found that the diffraction patterns of the fatty streak material could be accounted for by the organization of the cholesteryl esters into a liquid-crystalline smectic phase that melts from the smectic to a less ordered phase upon heating. When combined with the conclusions of others from polarized light microscopy, our study shows that a droplet in the smectic phase has well-defined concentric layers of lipid molecules. In each layer, the long axes of the molecules have a net radial orientation with respect to the droplet, but the side-to-side organization is disordered. We suggest that the accessibility of portions of the lipids for specific binding to enzymes or transport proteins may be restricted when they are in the smectic state, and that exchange of lipids with surrounding membranes or other potential binding sites may likewise be inhibited. The restriction in the smectic phase should be greater than in the less ordered phases that exist at higher temperatures. Images PMID:965500

A novel model for smectic liquid crystals: Elastic anisotropy and response to a steady-state flow.

PubMed

Püschel-Schlotthauer, Sergej; Meiwes Turrión, Victor; Stieger, Tillmann; Grotjahn, Robin; Hall, Carol K; Mazza, Marco G; Schoen, Martin

2016-10-28

By means of a combination of equilibrium Monte Carlo and molecular dynamics simulations and nonequilibrium molecular dynamics we investigate the ordered, uniaxial phases (i.e., nematic and smectic A) of a model liquid crystal. We characterize equilibrium behavior through their diffusive behavior and elastic properties. As one approaches the equilibrium isotropic-nematic phase transition, diffusion becomes anisotropic in that self-diffusion D ⊥ in the direction orthogonal to a molecule's long axis is more hindered than self-diffusion D ∥ in the direction parallel to that axis. Close to nematic-smectic A phase transition the opposite is true, D ∥ < D ⊥ . The Frank elastic constants K 1 , K 2 , and K 3 for the respective splay, twist, and bend deformations of the director field n̂ are no longer equal and exhibit a temperature dependence observed experimentally for cyanobiphenyls. Under nonequilibrium conditions, a pressure gradient applied to the smectic A phase generates Poiseuille-like or plug flow depending on whether the convective velocity is parallel or orthogonal to the plane of smectic layers. We find that in Poiseuille-like flow the viscosity of the smectic A phase is higher than in plug flow. This can be rationalized via the velocity-field component in the direction of the flow. In a sufficiently strong flow these smectic layers are not destroyed but significantly bent.

Heliconical smectic phases formed by achiral molecules

DOE PAGES

Abberley, Jordan P.; Killah, Ross; Walker, Rebecca; ...

2018-01-15

Chiral symmetry breaking in soft matter is a hot topic of current research. Recently, such a phenomenon was found in a fluidic phase showing orientational order of molecules - the nematic phase; although built of achiral molecules, the phase can exhibit structural chirality - average molecular direction follows a short-pitch helix. Here in this paper, we report a series of achiral asymmetric dimers with an odd number of atoms in the spacer, which form twisted structures in nematic as well as in lamellar phases. The tight pitch heliconical nematic (N TB) phase and heliconical tilted smectic C (SmC TB) phasemore » are formed. The formation of a variety of helical structures is accompanied by a gradual freezing of molecular rotation. In the lowest temperature smectic phase, HexI, the twist is expressed through the formation of hierarchical structure: nanoscale helices and mesoscopic helical filaments. The short-pitch helical structure in the smectic phases is confirmed by resonant X-ray measurements.« less

Heliconical smectic phases formed by achiral molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abberley, Jordan P.; Killah, Ross; Walker, Rebecca

Chiral symmetry breaking in soft matter is a hot topic of current research. Recently, such a phenomenon was found in a fluidic phase showing orientational order of molecules - the nematic phase; although built of achiral molecules, the phase can exhibit structural chirality - average molecular direction follows a short-pitch helix. Here in this paper, we report a series of achiral asymmetric dimers with an odd number of atoms in the spacer, which form twisted structures in nematic as well as in lamellar phases. The tight pitch heliconical nematic (N TB) phase and heliconical tilted smectic C (SmC TB) phasemore » are formed. The formation of a variety of helical structures is accompanied by a gradual freezing of molecular rotation. In the lowest temperature smectic phase, HexI, the twist is expressed through the formation of hierarchical structure: nanoscale helices and mesoscopic helical filaments. The short-pitch helical structure in the smectic phases is confirmed by resonant X-ray measurements.« less

Landau-de Gennes theory of surface-enhanced ordering in smectic films.

PubMed

Shalaginov, A N; Sullivan, D E

2001-03-01

A Landau theory for surface-enhanced ordering in smectic-A free-standing films is described, based on a generalization of de Gennes' model for a "presmectic" fluid confined between two walls. According to the theory, smectic ordering in free-standing films heated above the bulk smectic melting temperature is due to an intrinsic surface contribution rather than an external field. The theory yields a persistent finite-size effect, in that the film melting temperatures do not tend to the bulk transition temperature in the limit of infinite film thickness. It also predicts that a continuous transition from (N+1)- to N-layer films is impossible without an external field. The theory closely fits existing experimental data on layer-thinning transitions in compounds which exhibit a bulk smectic-A to nematic phase transition. Possible origins of the intrinsic surface contribution are discussed.

Observation of a pretransitional effect near a virtual smectic-A--smectic-C* transition.

PubMed

Shibahara, S; Takanishi, Y; Yamamoto, J; Ogasawara, T; Ishikawa, K; Yokoyama, H; Takezoe, H

2001-06-01

Unusual softening of the layer compression modulus B has been observed near the phase boundary where the smectic-C* phase vanishes in a naphtalene-based liquid crystal mixture. From the systematic study of x-ray and layer compression measurements, this unusual effect is attributed to the pretransitional softening near a virtual smectic-A-smectic-C* phase transition in the smectic-A phase, which no longer appears on the thermoequilibrium phase diagram. This phenomenon is similar but not equivalent to supercritical behavior.

(13)C NMR Studies, Molecular Order, and Mesophase Properties of Thiophene Mesogens.

PubMed

Veeraprakash, B; Lobo, Nitin P; Narasimhaswamy, T

2015-12-03

Three-ring mesogens with a core comprising thiophene linked to one phenyl ring directly and to the other via flexible ester are synthesized with terminal alkoxy chains to probe the mesophase properties and find the molecular order. The phenyl thiophene link in the core offers a comparison of the mesophase features with the molecular shape of the mesogen. The synthesized mesogens display enantiotropic polymesomorphism and accordingly nematic, smectic A, smectic C and smectic B mesophases are perceived depending upon the terminal chain length. For some of the homologues, monotropic higher order smectic phases such as smectic F and crystal E are also witnessed. The existence of polymesomorphism are originally observed by HOPM and DSC and further confirmed by powder X-ray diffraction studies. For the C8 homologue, high resolution solid state (13)C NMR spectroscopy is employed to find the molecular structure in the liquid crystalline phase and using the 2D SLF technique, the (13)C-(1)H dipolar couplings are extracted to calculate the order parameter. By comparing the ratio of local order of thiophene as well as phenyl rings, we establish the bent-core shape of the mesogen. Importantly, for assigning the carbon chemical shifts of the core unit of aligned C8 mesogen, the (13)C NMR measured in mesophase of the synthetic intermediate is employed. Thus, the proposed approach addresses the key step in the spectral assignment of target mesogens with the use of (13)C NMR data of mesomorphic intermediate.

Chiral smectic-A and smectic-C phases with de Vries characteristics

NASA Astrophysics Data System (ADS)

Yadav, Neelam; Panov, V. P.; Swaminathan, V.; Sreenilayam, S. P.; Vij, J. K.; Perova, T. S.; Dhar, R.; Panov, A.; Rodriguez-Lojo, D.; Stevenson, P. J.

2017-06-01

Infrared and dielectric spectroscopic techniques are used to investigate the characteristics of two chiral smectics, namely, 1,1,3,3,5,5,5-heptamethyltrisiloxane 1-[4'-(undecyl-1-oxy)-4-biphenyl(S,S)-2-chloro-3-methylpentanoate] (MS i3M R11 ) and tricarbosilane-hexyloxy-benzoic acid (S)-4'-(1-methyl-hexyloxy)-3'-nitro-biphenyl-4-yl ester (W599). The orientational features and the field dependencies of the apparent tilt angle and the dichroic ratio for homogeneous planar-aligned samples were calculated from the absorbance profiles obtained at different temperatures especially in the smectic-A* phase of these liquid crystals. The dichroic ratios of the C-C phenyl ring stretching vibrations were considered for the determination of the tilt angle at different temperatures and different voltages. The low values of the order parameter obtained with and without an electric field applied across the cell in the Sm -A* phase for both smectics are consistent with the de Vries concept. The generalized Langevin-Debye model introduced in the literature for explaining the electro-optical response has been applied to the results from infrared spectroscopy. The results show that the dipole moment of the tilt-correlated domain diverges as the transition temperature from Sm -A* to Sm -C* is approached. The Debye-Langevin model is found to be extremely effective in confirming some of the conclusions of the de Vries chiral smectics and gives additional results on the order parameter and the dichroic ratio as a function of the field across the cell. Dielectric spectroscopy finds large dipolar fluctuations in the Sm -A* phase for both compounds and again these confirm their de Vries behavior.

Defect dynamics and coarsening dynamics in smectic-C films

NASA Astrophysics Data System (ADS)

Pargellis, A. N.; Finn, P.; Goodby, J. W.; Panizza, P.; Yurke, B.; Cladis, P. E.

1992-12-01

We study the dynamics of defects generated in free-standing films of liquid crystals following a thermal quench from the smectic-A phase to the smectic-C phase. The defects are type-1 disclinations, and the strain field between defect pairs is confined to 2π walls. We compare our observations with a phenomenological model that includes dipole coupling of the director field to an external ordering field. This model is able to account for both the observed coalescence dynamics and the observed ordering dynamics. In the absence of an ordering field, our model predicts the defect density ρ to scale with time t as ρ lnρ~t-1. When the dipole coupling of the director field to an external ordering field is included, both the model and experiments show the defect coarsening proceeds as ρ~e-αt with the strain field confined to 2π walls. The external ordering field most likely arises from the director's tendency to align with edge dislocations within the liquid-crystal film.

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation.

PubMed

Liang, Ting; van Kuringen, Huub P C; Mulder, Dirk J; Tan, Shuai; Wu, Yong; Borneman, Zandrie; Nijmeijer, Kitty; Schenning, Albertus P H J

2017-10-11

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.

Evidence of monotropic hexatic tilted smectic phase in the phase sequence of ferroelectric liquid crystal

NASA Astrophysics Data System (ADS)

Różycka, Anna; Deptuch, Aleksandra; Jaworska-Gołąb, Teresa; Węgłowska, Dorota; Marzec, Monika

2018-02-01

Physical properties of a new ferroelectric liquid crystal have been studied by complementary methods: differential scanning calorimetry, polarizing optical microscopy, dielectric and X-ray diffraction. It was found that next to enantiotropic ferroelectric smectic C* phase, the monotropic smectic phase appears at cooling. X-ray diffraction measurements allowed to identify this phase as hexatic tilted smectic. Temperature dependence of spontaneous polarization, tilt angle of molecules and switching time were found in both liquid crystalline phases at cooling. Based on the dielectric results, the dielectric processes were identified as Goldstone mode in the smectic C* phase, whereas as the bond-orientation-like phason and the bulk domain mode in the monotropic hexatic tilted smectic phase.

Effects of Shear on the Smectic A Phase of Thermotropic Liquid Crystals

NASA Astrophysics Data System (ADS)

Panizza, Pascal; Archambault, Pascal; Roux, Didier

1995-02-01

The rheological behaviour of the smectic A phase of the thermotropic liquid crystal 4-cyano-4'-octylbiphenyl (8CB) is examined. X-ray scattering studies under shear flow were performed to probe changes of structures. We found that in a certain range of temperatures two states of orientation of lamellae exist. These two steady states of orientation are separated by a first order dynamic transition that becomes continuous at T_c (a temperature different from that of the smectic/nematic transition). At low shear rates, the smectic A phase is non-Newtonian: its viscosity η varies as (T_c-T)^{1/2}.dot{γ}^{-1/2} (where dot{γ} is the shear rate and T the temperature). In this regime, the structure of the system is compatible with multilamellar cylinders oriented along the flow direction. At high shear rates, the system becomes Newtonian, its layers are then oriented perpendicular to the shearing plates (as already noticed by Safinya et al. [1]).

Reassessment of structure of smectic phases: Nano-segregation in smectic E phase in 4-n-alkyl-4'-isothiocyanato-1,1'-biphenyls

NASA Astrophysics Data System (ADS)

Saito, Kazuya; Miyazawa, Takahito; Fujiwara, Akio; Hishida, Mafumi; Saitoh, Hideki; Massalska-Arodź, Maria; Yamamura, Yasuhisa

2013-09-01

Based on new diffraction data from aligned samples of smectic E (SmE) phase of 4-n-alkyl-4'-isothiocyanato-1,1'-biphenyls, systematics against the alkyl chain length n is analyzed. In order to perform the analysis, the molecular form factor approximated by a box-shaped distribution is calculated while taking the rounding of the distribution at corners into account. The analysis clearly shows the nano-segregated layered structure, which does not fit to the traditional structural view of SmE phase but does fit to the model the present authors proposed recently. Some implications of this conclusion are discussed in relation to the importance of the molten state of alkyl chains in most of real mesogens revealed previously through thermodynamic analyses.

Structural Rheology of the Smectic Phase

PubMed Central

Fujii, Shuji; Komura, Shigeyuki; Lu, Chun-Yi David

2014-01-01

In this review article, we discuss the rheological properties of the thermotropic smectic liquid crystal 8CB with focal conic domains (FCDs) from the viewpoint of structural rheology. It is known that the unbinding of the dislocation loops in the smectic phase drives the smectic-nematic transition. Here we discuss how the unbinding of the dislocation loops affects the evolution of the FCD size, linear and nonlinear rheological behaviors of the smectic phase. By studying the FCD formation from the perpendicularly oriented smectic layers, we also argue that dislocations play a key role in the structural development in layered systems. Furthermore, similarities in the rheological behavior between the FCDs in the smectic phase and the onion structures in the lyotropic lamellar phase suggest that these systems share a common physical origin for the elasticity. PMID:28788123

Polymorphism and mesomorphism of oligomeric surfactants: effect of the degree of oligomerization.

PubMed

Jurašin, D; Pustak, A; Habuš, I; Šmit, I; Filipović-Vinceković, N

2011-12-06

A series of cationic oligomeric surfactants (quaternary dodecyldimethylammonium ions with two, three, or four chains connected by an ethylene spacer at the headgroup level, abbreviated as dimer, trimer, and tetramer) were synthesized and characterized. The influence of the degree of oligomerization on their polymorphic and mesomorphic properties was investigated by means of X-ray diffraction, polarizing optical microscopy, thermogravimetry, and differential scanning calorimetry. All compounds display layered arrangements with interdigitated dodecyl chains. The increase in the degree of oligomerization increases the interlayer distance and decreases the ordering in the solid phase; whereas the dimer sample is fully crystalline with well-developed 3D ordering and the trimer and tetramer crystallize as highly ordered crystal smectic phases. The number of thermal phase transitions and sequence of phases are markedly affected by the number of dodecyl chains. Anhydrous samples exhibit polymorphism and thermotropic mesomorphism of the smectic type, with the exception of the tetramer that displays only transitions at higher temperature associated with decomposition and melting. All hydrated compounds form lyotropic mesophases showing reversible phase transitions upon heating and cooling. The sequence of liquid-crystalline phases for the dimer, typical of concentrated ionic surfactant systems, comprises a hexagonal phase at lower temperatures and a smectic phase at higher temperatures. In contrast, the trimer and tetramer reveal textures of the hexagonal phase. © 2011 American Chemical Society

Textures in a chiral smectic liquid-crystal film

NASA Astrophysics Data System (ADS)

Langer, Stephen A.; Sethna, James P.

1986-12-01

Freely suspended liquid-crystal films of the smectic-I phase of HOBACPC [R(-) hexyloxybenzylidene p'-amino-2-chloropropyl cinnamate] display distinctive stripe and droplet textures. We derive these patterns from a Landau expansion of the free energy using a vector order parameter. Strong pinning boundary conditions lead to boojums in the droplets and stable defect lines between the stripes. The boojum is a two-dimensional version of its namesake in superfluid 3A. The surface defect in the boojum is expelled from the smectic-I droplet in order to lower the internal gradient energy, leaving a defect-free texture. The expulsion distance and the width of the stripes are calculated in terms of the elastic constants.

Thermo-optical properties and nonlinear optical response of smectic liquid crystals containing gold nanoparticles.

PubMed

de Melo, P B; Nunes, A M; Omena, L; do Nascimento, S M S; da Silva, M G A; Meneghetti, M R; de Oliveira, I N

2015-10-01

The present work is devoted to the study of the thermo-optical and nonlinear optical properties of smectic samples containing gold nanoparticles with different shapes. By using the time-resolved Z-scan technique, we determine the effects of nanoparticle addition on the critical behavior of the thermal diffusivity and thermo-optical coefficient at the vicinity of the smectic-A-nematic phase transition. Our results reveal that introduction of gold nanoparticles affects the temperature dependence of thermo-optical parameters, due to the local distortions in the orientational order and heat generation provided by guest particles during the laser exposure. Further, we show that a nonlinear optical response may take place at temperatures where the smectic order is well established. We provide a detailed discussion of the effects associated with the introduction gold nanoparticles on the mechanisms behind the thermal transport and optical nonlinearity in liquid-crystal samples.

Self-organisation of semi-flexible rod-like particles

NASA Astrophysics Data System (ADS)

de Braaf, Bart; Oshima Menegon, Mariana; Paquay, Stefan; van der Schoot, Paul

2017-12-01

We report on a comprehensive computer simulation study of the liquid-crystal phase behaviour of purely repulsive, semi-flexible rod-like particles. For the four aspect ratios we consider, the particles form five distinct phases depending on their packing fraction and bending flexibility: the isotropic, nematic, smectic A, smectic B, and crystal phase. Upon increasing the particle bending flexibility, the various phase transitions shift to larger packing fractions. Increasing the aspect ratio achieves the opposite effect. We find two different ways in which the layer thickness of the particles in the smectic A phase may respond to an increase in concentration. The layer thickness may either decrease or increase depending on the aspect ratio and flexibility. For the smectic B and the crystalline phases, increasing the concentration always decreases the layer thickness. Finally, we find that the layer spacing jumps to a larger value on transitioning from the smectic A phase to the smectic B phase.

Symmetry breaking in smectics and surface models of their singularities

PubMed Central

Chen, Bryan Gin-ge; Alexander, Gareth P.; Kamien, Randall D.

2009-01-01

The homotopy theory of topological defects in ordered media fails to completely characterize systems with broken translational symmetry. We argue that the problem can be understood in terms of the lack of rotational Goldstone modes in such systems and provide an alternate approach that correctly accounts for the interaction between translations and rotations. Dislocations are associated, as usual, with branch points in a phase field, whereas disclinations arise as critical points and singularities in the phase field. We introduce a three-dimensional model for two-dimensional smectics that clarifies the topology of disclinations and geometrically captures known results without the need to add compatibility conditions. Our work suggests natural generalizations of the two-dimensional smectic theory to higher dimensions and to crystals. PMID:19717435

Local structural ordering in surface-confined liquid crystals

NASA Astrophysics Data System (ADS)

Śliwa, I.; Jeżewski, W.; Zakharov, A. V.

2017-06-01

The effect of the interplay between attractive nonlocal surface interactions and attractive pair long-range intermolecular couplings on molecular structures of liquid crystals confined in thin cells with flat solid surfaces has been studied. Extending the McMillan mean field theory to include finite systems, it has been shown that confining surfaces can induce complex orientational and translational ordering of molecules. Typically, local smectic A, nematic, and isotropic phases have been shown to coexist in certain temperature ranges, provided that confining cells are sufficiently thick, albeit finite. Due to the nonlocality of surface interactions, the spatial arrangement of these local phases can display, in general, an unexpected complexity along the surface normal direction. In particular, molecules located in the vicinity of surfaces can still be organized in smectic layers, even though nematic and/or isotropic order can simultaneously appear in the interior of cells. The resulting surface freezing of smectic layers has been confirmed to occur even for rather weak surface interactions. The surface interactions cannot, however, prevent smectic layers from melting relatively close to system boundaries, even when molecules are still arranged in layers within the central region of the system. The internal interfaces, separating individual liquid-crystal phases, are demonstrated here to form fronts of local finite-size transitions that move across cells under temperature changes. Although the complex molecular ordering in surface confined liquid-crystal systems can essentially be controlled by temperature variations, specific thermal properties of these systems, especially the nature of the local transitions, are argued to be strongly conditioned to the degree of molecular packing.

Effect of hockey-stick-shaped molecules on the critical behavior at the nematic to isotropic and smectic-A to nematic phase transitions in octylcyanobiphenyl

NASA Astrophysics Data System (ADS)

Chakraborty, Anish; Chakraborty, Susanta; Das, Malay Kumar

2015-03-01

In the field of soft matter research, the characteristic behavior of both nematic-isotropic (N -I ) and smectic-A nematic (Sm -A N ) phase transitions has gained considerable attention due to their several attractive features. In this work, a high-resolution measurement of optical birefringence (Δ n ) has been performed to probe the critical behavior at the N -I and Sm -A N phase transitions in a binary system comprising the rodlike octylcyanobiphenyl and a laterally methyl substituted hockey-stick-shaped mesogen, 4-(3-n -decyloxy-2-methyl-phenyliminomethyl)phenyl 4-n -dodecyloxycinnamate. For the investigated mixtures, the critical exponent β related to the limiting behavior of the nematic order parameter close to the N -I phase transition has come out to be in good conformity with the tricritical hypothesis. Moreover, the yielded effective critical exponents (α', β', γ') characterizing the critical fluctuation near the Sm -A N phase transition have appeared to be nonuniversal in nature. With increasing hockey-stick-shaped dopant concentration, the Sm -A N phase transition demonstrates a strong tendency to be driven towards a first-order nature. Such a behavior has been accounted for by considering a modification of the effective intermolecular interactions and hence the related coupling between the nematic and smectic order parameters, caused by the introduction of the angular mesogenic molecules.

Effect of smectic A temperature width on the soft mode in ferroelectric liquid crystals

NASA Astrophysics Data System (ADS)

Choudhary, A.; Kaur, S.; Prakash, J.; Sreenivas, K.; Bawa, S. S.; Biradar, A. M.

2008-08-01

The behavior of soft mode range with respect to the temperature width of smectic A (Sm A) phase has been studied in four different ferroelectric liquid crystal (FLC) materials in the frequency range 10Hz-10MHz. The studies have been carried out in a planarly well aligned cells at different temperatures and different bias fields in Sm C* and Sm A phases. Dielectric studies of these FLCs near Sm C*-Sm A phase transition show that the temperature range of soft mode relaxation frequency phenomenon varies with the temperature width of Sm A phase. The dependence of tilt angle on temperature shows the nature of the order of transition at Sm C*-Sm A phase. The coupling between order parameters of Sm C* and Sm A phase influences the soft mode and phase transition in Sm C* and Sm A phases.

Third-order nonlinear electro-optic measurements in the smectic-? phase

NASA Astrophysics Data System (ADS)

Nowicka, Kamila; Bielejewska, Natalia

2018-02-01

The chiral smectic subphase with three-layer structure, ?, is now of great interest from the point of view of device technologies such as multistate or symmetric switching. We report that the unique nonlinear electro-optic response can serve as precise mark of the phase transition into three-layer structure. The problem is illustrated with the first and third harmonic electro-optic spectra. Furthermore, the characteristic response of the helical liquid crystal phases correlated with particular collective modes using the Debye-type relaxation method for the well-known prototype liquid crystal material (MHPOBC) are presented.

Study of variation in thermal width of nematic and induced smectic ordering phase of citric acid (CA) and 4-heptyloxybenzoic acid (7OBA) hydrogen bonded liquid crystal complexes

NASA Astrophysics Data System (ADS)

Sundaram, S.; Jayaprakasam, R.; Praveena, R.; Rajasekaran, T. R.; Senthil, T. S.; Vijayakumar, V. N.

2018-01-01

Hydrogen-bonded liquid crystals (HBLCs) have been derived from nonmesogenic citric acid (CA) and mesogenic 4-heptyloxybenzoic acid (7OBA) yielding a highly ordered smectic C (Sm C) phase along with the new smectic X (Sm X) phase which has been identified as fingerprint-type texture. Optical (polarizing optical microscopy), thermal (differential scanning calorimetry) and structural (Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy) properties are studied. A noteworthy observation is that the intermolecular H-bond (between CA and 7OBA) influences on its melting point and clearing temperature of the HBLCs which exhibits lower value than those of the individual compounds. A typical extended mesophase region has been observed in the present complex while varying the mixture ratio (1:1 to 1:3) than those of individual compounds. The change in the ratio of the mesogenic compound in the mixture alters thermal properties such as enthalpy value and thermal span width in nematic (N) region of HBLC complex. Optical tilt angle measurement of CA+7OBA in Sm C phase has been discussed to identify the molecular position in the mesophase.

Elasticity of smectic liquid crystals with in-plane orientational order and dispiration asymmetry

NASA Astrophysics Data System (ADS)

Alageshan, Jaya Kumar; Chakrabarti, Buddhapriya; Hatwalne, Yashodhan

2017-02-01

The Nelson-Peliti formulation of the elasticity theory of isolated fluid membranes with orientational order emphasizes the interplay between geometry, topology, and thermal fluctuations. Fluid layers of lamellar liquid crystals such as smectic-C , hexatic smectics, and smectic-C* are endowed with in-plane orientational order. We extend the Nelson-Peliti formulation so as to bring these smectics within its ambit. Using the elasticity theory of smectics-C*, we show that positive and negative dispirations (topological defects in Smectic-C* liquid crystals) with strengths of equal magnitude have disparate energies—a result that is amenable to experimental tests.

Mesomorphic phase transitions of 3F7HPhF studied by complementary methods

NASA Astrophysics Data System (ADS)

Deptuch, Aleksandra; Jaworska-Gołąb, Teresa; Marzec, Monika; Pociecha, Damian; Fitas, Jakub; Żurowska, Magdalena; Tykarska, Marzena; Hooper, James

2018-02-01

Physical properties and the phase sequence of (S)-4‧-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-2-fluorobenzoate exhibiting the liquid crystalline paraelectric smectic A*, ferroelectric smectic C* and antiferroelectric smectic CA* phases were studied by complementary methods in the temperature range from -125 to 120 °C. Differential scanning calorimetry measurements together with polarizing optical microscopy provided the phase sequence, including the glass transition and a cold crystallization. X-ray diffraction was used to obtain the unit-cell parameters of the crystal phase, as well as the layer thickness and correlation length in the liquid crystalline smectic phases. The tilt angle was found to reach 45°, as determined from the measurements of the layer thickness and molecular modeling. Relaxation processes in the smectic phases and the fragility parameter were studied using frequency-domain dielectric spectroscopy.

Theoretical model for the discrete flexoelectric effect and a description for the sequence of intermediate smectic phases with increasing periodicity.

PubMed

Emelyanenko, A V; Osipov, M A

2003-11-01

A general phenomenological description and a simple molecular model is proposed for the "discrete" flexoelectric effect in tilted smectic liquid crystal phases. This effect defines a polarization in a smectic layer induced by a difference of director orientations in the two smectic layers adjacent to it. It is shown that the "discrete" flexoelectric effect is determined by electrostatic dipole-quadrupole interaction between positionally correlated molecules located in adjacent smectic layers, while the corresponding dipole-dipole interaction is responsible for a coupling between polarization vectors in neighboring layers. It is shown that a simple phenomenological model of a ferrielectric smectic liquid crystal, which has recently been proposed in the literature, can be used to describe the whole sequence of intermediate chiral smectic C* phases with increasing periods, and to determine the nonplanar structure of each phase without additional assumptions. In this sequence the phases with three- and four-layer periodicities have the same structure, as observed in the experiment. The theory predicts also the structure of intermediate phases with longer periods that have not been studied experimentally so far. The structures of intermediate phases with periodicities of up to nine layers are presented together with the phase diagrams, and a relationship between molecular chirality and the three-dimensional structure of intermediate phases is discussed. It is considered also how the coupling between the spontaneous polarization determined by molecular chirality and the induced polarization determined by the discrete flexoelectric effect stabilizes the nonplanar structure of intermediate phases.

Influence of nematic range on birefringence, heat capacity and elastic modulus near a nematic-smectic-A phase transition

NASA Astrophysics Data System (ADS)

Beaubois, F.; Claverie, T.; Marcerou, J. P.; Rouillon, J. C.; Nguyen, H. T.; Garland, C. W.; Haga, H.

1997-11-01

The birefringence Δn, the specific heat Cp, and the layer compressional elastic modulus B are reported for two liquid crystals near the nematic (N) to smectic-A (SmA) phase transition. As predicted long ago by MacMillan and de Gennes [P. G. de Gennes and J. Prost, The Physics of Liquid Crystals (Clarendon, Oxford, 1993)] the coupling of the nematic orientational order parameter to the smectic-A layering order parameter can substantially alter the critical behavior near the N-SmA transition if the nematic range is small and the nematic order parameter susceptibility is large. In this paper, we present a direct experimental comparison of two compounds: 4-octyloxy-4'-cyanobiphenyl (8OCB) with a short nematic range and 4-octyloxybenzoyloxy-4'-cyanotolane (C8tolane) with a very large N range. The temperature variations of the apparent birefringence Δn and the specific heat Cp across the N-SmA phase transition show the definite influence of the proximity of the isotropic phase in the case of 8OCB while the C8tolane behaves as expected for the three-dimensional XY universality class. The elastic modulus B in the SmA phase, measured at several wave vectors by the second-sound resonance technique, was studied with high resolution as a function of temperature on approaching Tc(N-SmA). These elastic data confirm the B leveling off in both cases with an apparent breakdown of hydrodynamics in the case of the C8tolane compound.

Small Angle Neutron Scattering (sans) Studies on "SIDE-END FIXED" and "SIDE-ON FIXED" Liquid Crystal Polymers

NASA Astrophysics Data System (ADS)

Hardouin, F.; Noirez, L.; Keller, P.; Leroux, N.; Cotton, J. P.

The following sections are included: * Introduction * Experimental * Results and discussion * Determination of the backbone conformation in the nematic and smectic A phases of "side-end fixed" L.C. polymethacrylates (PMA) or polyacrylates (PA) * Determination of the global and backbone conformation in the nematic and smectic A phases of "side-end fixed" L.C. polysiloxanes (PMS) * Determination of the backbone conformation in the unique nematic phase (without smectic A phase) or in the reentrant nematic phase (below smectic A phase) of "side-end fixed" L.C. polyacrylates (PA) * Determination of the global conformation in the nematic phase of "side-on fixed" L.C. polysiloxanes (PMS) * Determination of the global conformation in the nematic phase of "diluted side-on fixed" L.C. copolysiloxanes * Determination of the backbone conformation in the nematic phase of "side-on fixed" L.C. polyacrylates * Conclusions * References

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharya, S.; Shen, S.Y.; Ketterson, J.B.

Anisotropy in the velocity and attenuation of longitudinal ultrasound was studied for the first time in a stable smectic-B liquid crystal (..beta..-methyl-butyl-methoxybenzylidene amino cinnamate). Anisotropy in the velocity was found to be consistent with the predictions of the Martin-Parodi-Pershan hydrodynamic theory in both smectic-A and -B phases, but was significantly smaller than when measured in the same material by Brillouin scattering. Furthermore, strong dispersion was observed near the smectic-A--smectic-B phase transition for sound propagating perpendicular to the symmetry direction.

The taming of the screw: Or how I learned to stop worrying and love elliptic functions

NASA Astrophysics Data System (ADS)

Matsumoto, Elisabetta A.

2011-12-01

Nonlinear elastic phenomena appear time and again in the world around us. This work considers two separate soft matter systems, instabilities in an elastic membrane perforated by a lattice of circular holes and defect textures in smectic liquid crystals. By studying the set of singularities characterizing each system, not only do the analytics become tractable, we gain intuition and insight into complex structures. Under hydrostatic compression, the holes decorating an elastic sheet undergo a buckling instability and collapse. By modeling each of the buckled holes as a pair of dislocation singularities, linear elasticity theory accurately captures the interactions between holes and predicts the pattern transformation they undergo. The diamond plate pattern generated by a square lattice of holes achieves long ranged order due to the broken symmetry of the underlying lattice. The limited number of two dimensional lattices restricts the classes of patterns that can be produced by a at sheet. By changing the topology of the membrane to a cylinder the types of accessible patterns vastly increases, from a chiral wrapped cylinder to pairs of holes alternating orientations to even more complex structures. Equally spaced layered smectics introduce a plethora of geometric constraints yielding novel textures based upon topological defects. The frustration due to the incompatibility of molecular chirality and layers drives the formation of both the venerable twist-grain-boundary phase and the newly discovered helical nanofilament (HN) phase. The HN phase is a newly found solution of the chiral Landau-de Gennes free energy. Finally, we consider two limiting cases of the achiral Landau-de Gennes free energy, bending energy dominated allows defects in the layers and compression energy dominated enforces equally spaced layers. In order to minimize bending energy, smectic layers assume the morphology of minimal surfaces. Riemann's minimal surface is composed of a nonlinear sum of two oppositely handed screw dislocations and has the morphology of a pore. Likewise, focal conic domains result from enforcing the equal spacing condition. We develop an approach to the study of focal sets in smectics which exploits a hidden Poincare symmetry revealed only by viewing the smectic layers as projections from one-higher dimension.

Ferroelectric Nematic and Ferrielectric Smectic Mesophases in an Achiral Bent-Core Azo Compound.

PubMed

Kumar, Jitendra; Prasad, Veena

2018-03-22

Here, we report the observation of ferroelectric nematic and ferrielectric smectic mesophases in an achiral bent-core azo compound consisting of nonsymmetrical molecules with a lateral fluoro substitution on one of the wings. These mesophases are enantiotropic in nature with fairly low transition temperatures and wide mesophase ranges. The liquid crystalline properties of this compound are investigated using polarizing optical microscope, differential scanning calorimeter, X-ray diffraction, and electro-optical studies. As revealed by X-ray diffraction measurements, the nematic mesophase is composed of skewed cybotactic clusters and, in the smectic mesophase, the molecules are tilted with respect to the layer normal. The polar order in these mesophases was confirmed by the electro-optical switching and dielectric spectroscopy measurements. The dielectric study in the nematic mesophase shows a single relaxation process at low frequency ( f < 1 kHz) measured in the range 10 Hz to 5 MHz, which is attributed to the collective motion of the molecules within cybotactic clusters. The formation of local polar order in these clusters leads to a ferroelectric-like polar switching in the nematic mesophase. Of particular interest is the fact that the smectic phase exhibits a field induced ferrielectric state, which can be exploited for designing of the potential optical devices due to multistate switching.

Calamitic Smectic A-Polar Smectic APA Transition Observed in Bent Molecules with Large Bent-Angle Central Core of 4,6-Dichlorobenzene and Alkylthio Terminal Tail

NASA Astrophysics Data System (ADS)

Nguyen, Ha; Kang, Sungmin; Tokita, Masatoshi; Watanabe, Junji

2011-07-01

New homologs of bent molecules with a large bent-angle central core of 4,6-dichloro benzene and an alkylthio terminal tail have been synthesized. Although the corresponding alkoxy-tail homologs show only the calamitic phases because of its large bent angles around 160°, the new homologs with an alkylthio tail exhibit the antiferroelectric smectic APA (SmAPA) banana phase that is transformed on cooling from the calamitic smectic A (SmA) phase. The biaxial polar packing of bent molecules in the SmAPA phase is considered to arise from the hindered rotation around the molecular long axis due to the expansion of the mesophase temperatures to a lower temperature region. This study indicates that the bent molecules, even with a large bent angle, have the potential to form a switchable banana phase with a remarkable decrease in its phase temperature range to around 60 °C.

Live Soap: Stability, Order, and Fluctuations in Apolar Active Smectics

NASA Astrophysics Data System (ADS)

Adhyapak, Tapan Chandra; Ramaswamy, Sriram; Toner, John

2013-03-01

We construct a hydrodynamic theory of noisy, apolar active smectics in bulk suspension or on a substrate. Unlike purely orientationally ordered active fluids, active apolar smectics can be dynamically stable in Stokesian bulk suspensions. Smectic order in these systems is quasilong ranged in dimension d=2 and long ranged in d=3. We predict reentrant Kosterlitz-Thouless melting to an active nematic in our simplest model in d=2, a nonzero second-sound speed parallel to the layers in bulk suspensions, and that there are no giant number fluctuations in either case. We also briefly discuss possible instabilities in these systems.

Focal Conic Stacking in Smectic A Liquid Crystals: Smectic Flower and Apollonius Tiling

PubMed Central

Meyer, Claire; Cunff, Loic Le; Belloul, Malika; Foyart, Guillaume

2009-01-01

We investigate two different textures of smectic A liquid crystals. These textures are particularly symmetric when they are observed at crossed polars optical microscopy. For both textures, a model has been made in order to examine the link between the defective macroscopic texture and the microscopic disposition of the layers. We present in particular in the case of some hexagonal tiling of circles (similar to the Apollonius tiling) some numeric simulation in order to visualize the smectic layers. We discuss of the nature of the smectic layers, which permit to assure their continuity from one focal conic domain to another adjacent one.

Calculation of the absolute free energy of a smectic-A phase

NASA Astrophysics Data System (ADS)

Huang, Chien-Cheng; Ramachandran, Sanoop; Ryckaert, Jean-Paul

2014-12-01

In this paper, we provide a scheme to compute the absolute free energy of a smectic-A phase via the "indirect method." The state of interest is connected through a three-step reversible path to a reference state. This state consists of a low-density layer of rods coupled to two external fields maintaining these rods close to the layer's plane and oriented preferably normal to the layer. The low-density free energy of the reference state can be computed on the basis of the relevant second virial coefficients between two rods coupled to the two external fields. We apply this technique to the Gay-Berne potential for calamitics with a parameter set leading to stable isotropic (I), nematic (N), smectic-A (SmA), and crystal (Cr) phases. We locate the I-SmA phase transition at low pressure and the sequence of phase transitions I-N-SmA along higher-pressure isobars and we establish the location of the I-N-SmA triple point. Close to this triple point, we show that the N-SmA transition is clearly first order. Our results are compared to the coexistence lines of the approximate phase diagram elucidated by de Miguel et al. [J. Chem. Phys. 121, 11183 (2004), 10.1063/1.1810472] established through the direct observation of the sequence of phase transitions occurring along isobars under heating or cooling sequences of runs. Finally, we discuss the potential of our technique in studying similar transitions observed on layered phases under confinement.

Organic Glasses with Tunable Liquid-Crystalline Order

NASA Astrophysics Data System (ADS)

Teerakapibal, Rattavut; Huang, Chengbin; Gujral, Ankit; Ediger, Mark D.; Yu, Lian

2018-02-01

Liquid crystals (LCs) are known to undergo rapid ordering transitions with virtually no hysteresis. We report a remarkable counterexample, itraconazole, where the nematic to smectic transition is avoided at a cooling rate exceeding 20 K /s . The smectic order trapped in a glass is the order reached by the equilibrium liquid before the kinetic arrest of the end-over-end molecular rotation. This is attributed to the fact that smectic ordering requires orientational ordering and suggests a general condition for preparing organic glasses with tunable LC order for electronic applications.

Temperature dependence of the nonlinear optical response of smectic liquid crystals containing gold nanorods.

PubMed

Silva, R S; de Melo, P B; Omena, L; Nunes, A M; da Silva, M G A; Meneghetti, M R; de Oliveira, I N

2017-12-01

The present study is devoted to the investigation of the nonlinear optical properties of a smectic liquid crystal doped with gold nanorods. Using the Z-scan technique, we investigate the changes in the optical birefringence of a homeotropic sample upon laser exposure, considering the configurations of normal and oblique incidence. Our results reveal that the birefringence variations may be governed by distinct physical mechanisms, depending on the relative angle between the far-field director and the wave vector of the excitation laser beam. In particular, we observe that the position dependence of the far-field transmittance exhibits different behaviors as the incidence angle is changed, indicating that distortions in the beam wavefront may be associated with the thermal lens phenomenon or an optically induced reorientation of the nematic director. The temperature dependence of the nonlinear refractive and absorptive coefficients is investigated close to the smectic-A-nematic phase transition. A detailed analysis of the interplay between smectic order and plasmon resonance is performed, thus unveiling the capability of plasmonic liquid crystal to be used in optical devices.

Temperature dependence of the nonlinear optical response of smectic liquid crystals containing gold nanorods

NASA Astrophysics Data System (ADS)

Silva, R. S.; de Melo, P. B.; Omena, L.; Nunes, A. M.; da Silva, M. G. A.; Meneghetti, M. R.; de Oliveira, I. N.

2017-12-01

The present study is devoted to the investigation of the nonlinear optical properties of a smectic liquid crystal doped with gold nanorods. Using the Z -scan technique, we investigate the changes in the optical birefringence of a homeotropic sample upon laser exposure, considering the configurations of normal and oblique incidence. Our results reveal that the birefringence variations may be governed by distinct physical mechanisms, depending on the relative angle between the far-field director and the wave vector of the excitation laser beam. In particular, we observe that the position dependence of the far-field transmittance exhibits different behaviors as the incidence angle is changed, indicating that distortions in the beam wavefront may be associated with the thermal lens phenomenon or an optically induced reorientation of the nematic director. The temperature dependence of the nonlinear refractive and absorptive coefficients is investigated close to the smectic-A -nematic phase transition. A detailed analysis of the interplay between smectic order and plasmon resonance is performed, thus unveiling the capability of plasmonic liquid crystal to be used in optical devices.

Nanolayered Features of Collagen-like Peptides

NASA Technical Reports Server (NTRS)

Valluzzi, Regina; Bini, Elisabetta; Haas, Terry; Cebe, Peggy; Kaplan, David L.

2003-01-01

We have been investigating collagen-like model oligopeptides as molecular bases for complex ordered biomimetic materials. The collagen-like molecules incorporate aspects of native collagen sequence and secondary structure. Designed modifications to native primary and secondary structure have been incorporated to control the nanostructure and microstructure of the collagen-like materials produced. We find that the collagen-like molecules form a number of lyotropic rod liquid crystalline phases, which because of their strong temperature dependence in the liquid state can also be viewed as solvent intercalated thermotropic liquid crystals. The liquid crystalline phases formed by the molecules can be captured in the solid state by drying off solvent, resulting in solid nanopatterned (chemically and physically) thermally stable (to greater than 100 C) materials. Designed sequences which stabilize smectic phases have allowed a variety of nanoscale multilayered biopolymeric materials to be developed. Preliminary investigations suggest that chemical patterns running perpendicular to the smectic layer plane can be functionalized and used to localize a variety of organic, inorganic, and organometallic moieties in very simple multilayered nanocomposites. The phase behavior of collagen-like oligopeptide materials is described, emphasizing the correlation between mesophase, molecular orientation, and chemical patterning at the microscale and nanoscale. In many cases, the textures observed for smectic and hexatic phase collagens are remarkably similar to the complex (and not fully understood) helicoids observed in biological collagen-based tissues. Comparisons between biological morphologies and collagen model liquid crystalline (and solidified materials) textures may help us understand the molecular features which impart order and function to the extracellular matrix and to collagen-based mineralized tissues. Initial studies have utilized synthetic collagen-like peptides while future work will also focus on similar sequences generated via genetic engineering methods.

Optical, thermal and dielectric studies in linear hydrogen bonded liquid crystal homologous series

NASA Astrophysics Data System (ADS)

Vijayakumar, V. N.; Madhu Mohan, M. L. N.

2011-08-01

A novel series of hydrogen bonded liquid crystals (HBLC) have been isolated with hydrogen bond forming between fluoro benzoic acid and various alkyloxy benzoic acids respectively. Phase diagram is constructed from the transition temperatures obtained by Differential Scanning Calorimetry (DSC) and Polarizing Optical Microscopic (POM) studies. A new Smectic ordering which is referred as Smectic R is characterized which exhibits a ribbon like phase. Declinations are observed on these ribbons manifesting the presence of the helicoidal structure. Another interesting feature is the observation of optical shuttering action in some of the complexes with the application of external stimulus in the entire thermal range of Nematic phase. Further this phenomenon is reversible in the sense that when the applied stimulus is withdrawn original texture of Nematic is restored. Unwinding of the helix coupled with molecular dipolar reorientation with the application of external field is supposed to be the major reasons for the observed phenomenon.

Unconventional phase transitions in liquid crystals

NASA Astrophysics Data System (ADS)

Kats, E. I.

2017-12-01

According to classical textbooks on thermodynamics or statistical physics, there are only two types of phase transitions: continuous, or second-order, in which the latent heat L is zero, and first-order, in which L ≠ 0. Present-day textbooks and monographs also mention another, stand-alone type—the Berezinskii-Kosterlitz-Thouless transition, which exists only in two dimensions and shares some features with first- and second-order phase transitions. We discuss examples of non-conventional thermodynamic behavior (i.e., which is inconsistent with the theoretical phase transition paradigm now universally accepted). For phase transitions in smectic liquid crystals, mechanisms for nonconventional behavior are proposed and the predictions they imply are examined.

Dislocations and other topological oddities

NASA Astrophysics Data System (ADS)

Pieranski, Pawel

2016-03-01

We will show that the book Dislocations by Jacques Friedel, published half a century ago, can still be recommended, in agreement with the author's intention, as a textbook ;for research students at University and for students at engineering schools as well as for research engineers;. Indeed, today dislocations are known to occur not only in solid crystals but also in many other systems discovered more recently such as colloidal crystals or liquid crystals having periodic structures. Moreover, the concept of dislocations is an excellent starting point for lectures on topological defects occurring in systems equipped with order parameters resulting from broken symmetries: disclinations in nematic or hexatic liquid crystals, dispirations in chiral smectics or disorientations in lyotropic liquid crystals. The discussion of dislocations in Blue Phases will give us an opportunity to call on mind Sir Charles Frank, friend of Jacques Friedel since his Bristol years, who called these ephemeral mesophases ;topological oddities;. Being made of networks of disclinations, Blue Phases are similar to Twist Grain Boundary (TGB) smectic phases, which are made of networks of screw dislocations and whose existence was predicted by de Gennes in 1972 on the basis of the analogy between smectics and superconductors. We will stress that the book by Jacques Friedel contains seeds of this analogy.

Distribution and Dynamic Properties of Xenon Dissolved in the Ionic Smectic Phase of [C16mim][NO3]: MD Simulation and Theoretical Model.

PubMed

Frezzato, Diego; Saielli, Giacomo

2016-03-10

We have investigated the structural and dynamic properties of Xe dissolved in the ionic liquid crystal (ILC) phase of 1-hexadecyl-3-methylimidazolium nitrate using classical molecular dynamics (MD) simulations. Xe is found to be preferentially dissolved within the hydrophobic environment of the alkyl chains rather than in the ionic layers of the smectic phase. The structural parameters and the estimated local diffusion coefficients concerning the short-time motion of Xe are used to parametrize a theoretical model based on the Smoluchowski equation for the macroscopic dynamics across the smectic layers, a feature which cannot be directly obtained from the relatively short MD simulations. This protocol represents an efficient combination of computational and theoretical tools to obtain information on slow processes concerning the permeability and diffusivity of the xenon in smectic ILCs.

Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [C22C1im]+[NTf2].

PubMed

Mars, Julian; Hou, Binyang; Weiss, Henning; Li, Hailong; Konovalov, Oleg; Festersen, Sven; Murphy, Bridget M; Rütt, Uta; Bier, Markus; Mezger, Markus

2017-10-11

Surface induced smectic order was found for the ionic liquid 1-methyl-3-docosylimidazolium bis(trifluoromethlysulfonyl)imide by X-ray reflectivity and grazing incidence scattering experiments. Near the free liquid surface, an ordered structure of alternating layers composed of polar and non-polar moieties is observed. This leads to an oscillatory interfacial profile perpendicular to the liquid surface with a periodicity of 3.7 nm. Small angle X-ray scattering and polarized light microscopy measurements suggest that the observed surface structure is related to fluctuations into a metastable liquid crystalline SmA 2 phase that was found by supercooling the bulk liquid. The observed surface ordering persists up to 157 °C, i.e. more than 88 K above the bulk melting temperature of 68.1 °C. Close to the bulk melting point, we find a thickness of the ordered layer of L = 30 nm. The dependency of L(τ) = Λ ln(τ/τ 1 ) vs. reduced temperature τ follows a logarithmic growth law. In agreement with theory, the pre-factor Λ is governed by the correlation length of the isotropic bulk phase.

Static and dynamic properties of incommensurate smectic-A(IC) liquid crystals

NASA Technical Reports Server (NTRS)

Lubensky, T. C.; Ramaswamy, Sriram; Toner, John

1988-01-01

The elasticity, topological defects, and hydrodynamics of the incommensurate smectic A(IC) phase liquid crystals are studied. The phase is characterized by two colinear mass density waves of incommensurate spatial frequency. The elastic free energy is formulated in terms of a displacement field and a phason field. It is found that the topological defects of the system are dislocations with a nonzero phason field and phason field components. A two-dimensional Burgers lattice for these dislocations is introduced. It is shown that the hydrodynamic modes of the phase include first- and second-sound modes whose direction-dependent velocities are identical to those in ordinary smectics.

Trapping of edge dislocations by a moving smectic-A smectic-B interface

NASA Astrophysics Data System (ADS)

Oswald, P.; Lejcek, L.

1991-09-01

We analyze how the motion of the edge dislocations of the smectic-A liquid crystal allows the system to relax plastically the stresses that are generated during the growth of the smectic-B plastic crystal. These stresses are both due, to the density difference between the two phases, and to the layer thickness variation at the phase transition. In particular, we calculate under which conditions a dislocation can be trapped by the smectic-B phase. Finally, we suggest that this dynamical trapping is responsible for the very large amount of stacking faults observed by X-ray diffraction. Nous analysons comment le mouvement des dislocations coin du cristal liquide smectique A permet de relaxer plastiquement les contraintes induites par la croissance du cristal plastique smectique B. Ces contraintes sont engendrées à la fois par la différence de densité qui existe entre les deux phases et par la variation d'épaisseur des couches à la transition. Nous calculons en particulier dans quelles conditions une dislocation coin peut être piégée par le smectique B. Enfin, nous suggérons que ce piégeage dynamique est à l'origine de la très forte densité de fautes d'empilement qui est couramment observée aux rayons X dans la phase B.

Mechanical model for filament buckling and growth by phase ordering.

PubMed

Rey, Alejandro D; Abukhdeir, Nasser M

2008-02-05

A mechanical model of open filament shape and growth driven by phase ordering is formulated. For a given phase-ordering driving force, the model output is the filament shape evolution and the filament end-point kinematics. The linearized model for the slope of the filament is the Cahn-Hilliard model of spinodal decomposition, where the buckling corresponds to concentration fluctuations. Two modes are predicted: (i) sequential growth and buckling and (ii) simultaneous buckling and growth. The relation among the maximum buckling rate, filament tension, and matrix viscosity is given. These results contribute to ongoing work in smectic A filament buckling.

8OCB and 8CB Liquid Crystals Confined in Nanoporous Alumina: Effect of Confinement on the Structure and Dynamics.

PubMed

Selevou, Aristoula; Papamokos, George; Steinhart, Martin; Floudas, George

2017-08-03

The effect of oxygen substitution is studied in two homologous compounds of n-cyanobiphenyls with n = 8 in the bulk and under confinement within self-ordered nanoporous alumina (AAO). Oxygen substitution in 8OCB increases the dipole moment and stabilizes the crystalline, smectic, and nematic phases to higher temperatures relative to 8CB. Within their smectic- A (SmA) phase both 8CB and 8OCB behave as weak viscoelastic solids with low shear moduli reflecting the underlying supramolecular defect structure. Dielectric spectroscopy assisted by DFT calculations identified strong dipolar associations within the isotropic phases characterized by a Kirkwood-Fröhlich interaction parameter, g ∼ 0.36. Dielectric spectroscopy further identified a slow process (∼ kHz) of low dielectric strength. The proximity of this process to the rheology time scale suggests as common origin a cooperative relaxation of the defect structure. Confinement alters the phase diagram by stabilizing certain crystalline phases and by reducing the N-I transition temperature in agreement with surface tension effects. However, the N-I transition seems to retain its first order character. Surface treatment with n-decyltrichlorosilane results in destabilization of the SmA phase at the expense of the N phase. This is consistent with a picture of surface anchored LC molecules at the pore walls that stabilize the nematic phase.

Smectic phases in hard particle mixtures: Koda's theory

NASA Astrophysics Data System (ADS)

Vesely, Franz J.

Mixtures of parallel linear particles and spheres tend to demix upon compression. The linear species usually concentrates in regular layers, thus forming a smectic phase. With increasing concentration of spheres this 'smectic demixing' transition occurs at ever lower packing densities. For the specific case of hard spherocylinders and spheres Koda et al. [T. Koda, M. Numajiri, S. Ikeda, J. Phys. Jap., 65, 3551 (1996)] have explained the layering effect in terms of a second virial approximation to the free energy. We extend this approach from spherocylinders to other linear particles, namely fused spheres, ellipsoids and sphero-ellipsoids.

Air-water interface-induced smectic bilayer

NASA Astrophysics Data System (ADS)

El Abed, A.; Pouzet, E.; Fauré, M.-C.; Sanière, M.; Abillon, O.

2000-11-01

We show, using surface pressure versus molecular area isotherms measurements and x-ray reflectivity, that the long diblock semifluorinated n-hexaeicosane molecules, F(CF2)8-(CH2)18H, form a stable smectic bilayer phase, noted M1, with a total thickness of 3.3 nm, at an apparent molecular area about 0.3 nm2, though in the bulk the used molecules do not form smectic phases at any temperature. We discuss different molecular packing models according to our experimental data and deduce that molecules are antiparallel with fluorinated chains outwards and interleaved hydrocarbon chains inwards.

Field alignment of bent-core smectic liquid crystals for analog optical phase modulation

NASA Astrophysics Data System (ADS)

Shen, Y.; Goodhew, L.; Shao, R.; Moran, M.; Korblova, E.; Walba, D. M.; Clark, N. A.; Maclennan, J. E.; Rudquist, P.

2015-05-01

A general method for aligning bent-core smectic liquid crystal materials is described. Alternating electric fields between interdigitated electrodes patterned on one cell surface create torques on the liquid crystal that result in uniform "bookshelf" orientation of the smectic layers. The aligned cell can then be driven in the conventional way by applying an electric field between all of the stripe electrodes connected together and a monolithic electrode on the other cell surface. Fast, analog, optical phase-only modulation is demonstrated in a device containing a polar, bent-core SmAPF material aligned using this technique.

Note: Formation of the nematic splay-bend in two-dimensional systems of bow-shaped particles

NASA Astrophysics Data System (ADS)

Karbowniczek, Paweł

2018-04-01

Recently, Tavarone et al. (J. Chem. Phys. 143, 114505 (2015)) discussed phase behavior of zig-zag and bow-shaped particles composed of three needles. The authors presented very interesting results of extensive Monte Carlo simulations with periodic boundary conditions in the constant-NVT and the constant-NPT ensembles. In addition to isotropic, nematic, and smectic phases, they identified a modulated nematic, which is actually the nematic splay-bend phase ($N_{SB}$), long-anticipated for bent-core systems (Europhys. Lett. 56, 247 (2001)). They also described isotropic-nematic and nematic-smectic transitions using Density Functional Theory in mean-field approximation. The authors, however, did not provided a theoretical description of the $N_{SB}$. Here, we present a simple theory of a phase transition to the $N_{SB}$ phase to fill the gap. In our study, we use Onsager-type Density Functional Theory with perfect order approximation and Meyer parametrization of modulated structures. We present results for arbitrary ratios of the length of central and side segments and opening angles of bow-shaped particles.

Myelin structures formed by thermotropic smectic liquid crystals

NASA Astrophysics Data System (ADS)

Peddireddy, Karthik Reddy; Kumar, Pramoda; Thutupalli, Shashi; Herminghaus, Stephan; Bahr, Christian

2014-03-01

We report on transient structures, formed by thermotropic smectic-A liquid crystals, resembling the myelin figures of lyotropic lamellar liquid crystals. The thermotropic myelin structures form during the solubilization of a smectic-A droplet in an aqueous phase containing a cationic surfactant at concentrations above the critical micelle concentration. Similar to the lyotropic myelin figures, the thermotropic myelins appear in an optical microscope as flexible tube-like structures growing at the smectic/aqueous interface. Polarizing microscopy and confocal fluorescence microscopy show that the smectic layers are parallel to the tube surface and form a cylindrically bent arrangement around a central line defect in the tube. We study the growth behavior of this new type of myelins and discuss similarities and differences to the classical lyotropic myelin figures.

Molecular Order and Mesophase Investigation of Thiophene-Based Forked Mesogens.

PubMed

Reddy, K Rajasekhar; Lobo, Nitin P; Narasimhaswamy, T

2016-07-14

Thiophene-based rodlike molecules constructed from a three phenyl ring core and terminal dialkoxy chains recognized as forked mesogens are synthesized, and their mesophase properties as well as the molecular order are investigated. The synthesized forked mesogens would serve as model compounds for tetracatenar or biforked mesogens. On the basis of the position of the thiophene link with the rest of the core, 2-substituted and 3-substituted mesogens are realized in which the length of the terminal alkoxy chains is varied. The mesophase properties are evaluated using a hot-stage polarizing microscope and differential scanning calorimetry. For both homologues, the appearance of either nematic phase alone or in conjunction with smectic C phase is noticed depending on the length of the terminal alkoxy chains. The existence of layer ordering characteristic of the smectic C phase is confirmed for a representative mesogen using variable-temperature powder X-ray diffraction. High-resolution solid-state (13)C NMR measurements of C12 homologues of the two series reveal orientational order parameters of all rings of the core as well as terminal chains in the liquid crystalline phase. For both homologues, because of the asymmetry of ring I, the order parameter value is higher in contrast to ring II, ring III, and the thiophene ring. The chemical shifts and (13)C-(1)H dipolar couplings of OCH2 carbons of the terminal dodecyloxy chains provide contrasting conformations, reflecting the orientational constraints. Furthermore, the investigations also reveal that the mesophase range and the tendency for layer ordering are higher for 3-substituted mesogens compared to 2-substituted homologues.

Power of the Poincaré group: elucidating the hidden symmetries in focal conic domains.

PubMed

Alexander, Gareth P; Chen, Bryan Gin-Ge; Matsumoto, Elisabetta A; Kamien, Randall D

2010-06-25

Focal conic domains are typically the "smoking gun" by which smectic liquid crystalline phases are identified. The geometry of the equally spaced smectic layers is highly generic but, at the same time, difficult to work with. In this Letter we develop an approach to the study of focal sets in smectics which exploits a hidden Poincaré symmetry revealed only by viewing the smectic layers as projections from one-higher dimension. We use this perspective to shed light upon several classic focal conic textures, including the concentric cyclides of Dupin, polygonal textures, and tilt-grain boundaries.

Realization of hydrodynamic experiments on quasi-2D liquid crystal films in microgravity

NASA Astrophysics Data System (ADS)

Clark, Noel A.; Eremin, Alexey; Glaser, Matthew A.; Hall, Nancy; Harth, Kirsten; Klopp, Christoph; Maclennan, Joseph E.; Park, Cheol S.; Stannarius, Ralf; Tin, Padetha; Thurmes, William N.; Trittel, Torsten

2017-08-01

Freely suspended films of smectic liquid crystals are unique examples of quasi two-dimensional fluids. Mechanically stable and with quantized thickness of the order of only a few molecular layers, smectic films are ideal systems for studying fundamental fluid physics, such as collective molecular ordering, defect and fluctuation phenomena, hydrodynamics, and nonequilibrium behavior in two dimensions (2D), including serving as models of complex biological membranes. Smectic films can be drawn across openings in planar supports resulting in thin, meniscus-bounded membranes, and can also be prepared as bubbles, either supported on an inflation tube or floating freely. The quantized layering renders smectic films uniquely useful in 2D fluid physics. The OASIS team has pursued a variety of ground-based and microgravity applications of thin liquid crystal films to fluid structure and hydrodynamic problems in 2D and quasi-2D systems. Parabolic flights and sounding rocket experiments were carried out in order to explore the shape evolution of free floating smectic bubbles, and to probe Marangoni effects in flat films. The dynamics of emulsions of smectic islands (thicker regions on thin background films) and of microdroplet inclusions in spherical films, as well as thermocapillary effects, were studied over extended periods within the OASIS (Observation and Analysis of Smectic Islands in Space) project on the International Space Station. We summarize the technical details of the OASIS hardware and give preliminary examples of key observations.

Submicrosecond electro-optic switching in the liquid-crystal smectic A phase: The soft-mode ferroelectric effect

NASA Astrophysics Data System (ADS)

Andersson, G.; Dahl, I.; Keller, P.; Kuczyński, W.; Lagerwall, S. T.; Skarp, K.; Stebler, B.

1987-08-01

A new liquid-crystal electro-optic modulating device similar to the surface-stabilized ferroelectric liquid-crystal device is described. It uses the same kind of ferroelectric chiral smectics and the same geometry as that device (thin sample in the ``bookshelf '' layer arrangement) but instead of using a tilted smectic phase like the C* phase, it utilizes the above-lying, nonferroelectric A phase, taking advantage of the electroclinic effect. The achievable optical intensity modulation that can be detected through the full range of the A phase is considerably lower than for the surface-stabilized device, but the response is much faster. Furthermore, the response is strictly linear with respect to the applied electric field. The device concept is thus appropriate for modulator rather than for display applications. We describe the underlying physics and present measurements of induced tilt angle, of light modulation depth, and of rise time.

Transition Helmholtz free energy, entropy, and heat capacity of free-standing smectic films in water: A mean-field treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Śliwa, Izabela, E-mail: izasliwa@ifmpan.poznan.pl; Zakharov, A. V., E-mail: alexandre.zakharov@yahoo.ca

Using the extended McMillan's mean field approach with anisotropic forces a study of both the structural and thermodynamic properties of free-standing smectic film (FSSF) in water on heating to the isotropic temperature is carried out numerically. By solving the self-consistent nonlinear equations for the order parameters, we obtained that the smectic-A-isotropic (AI) transition occurs through the series of layer-thinning transitions causing the films to thin in the stepwise manner as the temperature is increased above the bulk smectic-A-isotropic temperature T{sub AI}(bulk). With enhanced pair interactions in the bounding layers, the smectic-isotropic transition corresponds to smectic melting of the central layers.more » The effects of surface “enhanced” pair interactions in the bounding layers and of film thickness on the orientational and translational order parameters, the Helmholtz free energy and entropy, as well as the temperature dependence of the heat capacity of FSSFs, have also been investigated. Reasonable agreement between the theoretically predicted and the experimentally obtained – by means of optical microscopy and ellipsometry techniques – data of the temperature when the thin decylcyanobiphenyl smectic film immersing in water ruptures has been obtained.« less

Induced smectic phase in binary mixtures of twist-bend nematogens.

PubMed

Knežević, Anamarija; Dokli, Irena; Sapunar, Marin; Šegota, Suzana; Baumeister, Ute; Lesac, Andreja

2018-01-01

The investigation of liquid crystal (LC) mixtures is of great interest in tailoring material properties for specific applications. The recent discovery of the twist-bend nematic phase (N TB ) has sparked great interest in the scientific community, not only from a fundamental viewpoint, but also due to its potential for innovative applications. Here we report on the unexpected phase behaviour of a binary mixture of twist-bend nematogens. A binary phase diagram for mixtures of imino-linked cyanobiphenyl (CBI) dimer and imino-linked benzoyloxy-benzylidene (BB) dimer shows two distinct domains. While mixtures containing less than 35 mol % of BB possess a wide temperature range twist-bend nematic phase, the mixtures containing 55-80 mol % of BB exhibit a smectic phase despite that both pure compounds display a Iso-N-N TB -Cr phase sequence. The phase diagram shows that the addition of BB of up to 30 mol % significantly extends the temperature range of the N TB phase, maintaining the temperature range of the nematic phase. The periodicity, obtained by atomic force microscopy (AFM) imaging, is in the range of 6-7 nm. The induction of the smectic phase in the mixtures containing 55-80 mol % of BB was confirmed using polarising optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction. The origin of the intercalated smectic phase was unravelled by combined spectroscopic and computational methods and can be traced to conformational disorder of the terminal chains. These results show the importance of understanding the phase behaviour of binary mixtures, not only in targeting a wide temperature range but also in controlling the self-organizing processes.

Tuning the mesomorphic properties of phenoxy-terminated smectic liquid crystals: the effect of fluoro substitution.

PubMed

Thompson, Matthew; Carkner, Carolyn; Mosey, Nicholas J; Kapernaum, Nadia; Lemieux, Robert P

2015-05-21

The mesomorphic properties of phenoxy-terminated 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals can be tuned in a predictable fashion with fluoro substituents on the phenoxy end-group. We show that an ortho-fluoro substituent promotes the formation of a tilted smectic C (SmC) phase whereas a para-fluoro substituent promotes the formation of an orthogonal smectic A (SmA) phase. The balance between SmA and SmC phases may be understood in terms of the energetic preference of the phenoxy end-groups to self-assemble via arene-arene interactions in a parallel or antiparallel geometry, and how these non-covalent interactions may cause either a suppression or enhancement of out-of-layer fluctuations at the interface of smectic layers. Calculations of changes in the potential energy of association ΔE for non-covalent dimers of fluoro-substituted n-butyloxybenzene molecules in parallel and antiparallel geometries support this hypothesis. We also show how mesomorphic properties can be further tuned by difluoro and perfluoro substitution, including difluoro substitution at the ortho positions, which uniquely promotes the formation of a SmC-nematic phase sequence.

Rheological Properties of Quasi-2D Fluids in Microgravity

NASA Technical Reports Server (NTRS)

Trittel, Torsten; Stannarius, Ralf; Eremin, Alexey; Harth, Kirsten; Clark, Noel A.; Maclennan, Joseph; Glaser, Matthew; Park, Cheol; Hall, Nancy; Tin, Padetha

2016-01-01

Freely suspended smectic films of sub-micrometer thickness and lateral extensions of several millimeters are used to study thermally driven convection and diffusion in the film plane. The experiments were performed during a six minute microgravity phase of a TEXUS suborbital rocket flight (Texus 52, launched April 27, 2015). The project served as a preliminary test for a planned ISS Experiment with liquid crystal films (OASIS), and in addition it provided new experimental data on smectic films exposed to in-plane thermal gradients.We find an attraction of the smectic material towards the cold edge of the film in a temperature gradient, similar to a Soret effect. This process is reversed when this edge is heated up again. Thermal convection driven by two thermocontacts in the film is practically absent, even at temperature gradients up to 10 Kmm, thermally driven convection sets in when the hot post reaches the transition temperature to the nematic phase.An additional experiment was performed under microgravity conditions to test the stability of liquid crystal bridges in different smectic phases.

FAST TRACK COMMUNICATION: Ferroelectricity in low-symmetry biaxial nematic liquid crystals

NASA Astrophysics Data System (ADS)

Osipov, Mikhail A.; Gorkunov, Maxim V.

2010-09-01

Order parameters and phenomenological theory for both high- and low-symmetry biaxial nematic phases are presented and it is predicted that the chiral low-symmetry biaxial phase must be ferroelectric. This conclusion is based on general symmetry arguments and on the results of the Landau-de Gennes theory. The microscopic mechanism of the ferroelectric ordering in this chiral biaxial phase is illustrated using a simple molecular model based on dispersion interactions between biaxial molecules of low symmetry. Similar to the chiral smectic C* phase, the ferroelectricity in the chiral biaxial nematic phase is improper, i.e., polarization is not a primary order parameter and is not determined by dipolar interactions. Ferroelectric ordering in biaxial nematics may be found, in principle, in materials composed of chiral analogues of the tetrapod molecules which are known to exhibit biaxial phases.

Effect of the magnetic field on the supramolecular structure of chiral smectic C phases: (2)H NMR studies.

PubMed

Domenici, Valentina; Marini, Alberto; Veracini, Carlo Alberto; Zhang, Jing; Dong, Ronald Y

2007-12-21

We present a theoretical and experimental (2)H NMR study of the effect of external magnetic fields on the supramolecular organization of chiral smectic liquid-crystalline mesophases, such as SmC* and re-entrant SmC*. Three experimental cases in which the supramolecular helical structure of the smectic C* phase is unwound by a magnetic field (H), parallel to the helical axes of this phase, are discussed in detail. Unwinding of the helical structure is described by using a theoretical model based on the Landau-de Gennes theory, which allows us to explain the transition temperatures among the SmA, SmC*, and uSmC* phases. The energy-density behavior in the vicinity of the transitions and the value of the critical magnetic field H(C) for unwinding the helical structure are discussed by applying this model to three ferroelectric smectogens (MBHB, 11EB1M7, ZLL7/*), which are studied by (2)H NMR spectroscopy at different magnetic fields (from 2.4 to 9.4 Tesla). Furthermore, the tilt angle of the three smectogens in the SmC* phase has been directly evaluated, for the first time, by comparing the quadrupolar splittings at different magnetic fields. In one case, (2)H NMR angular measurements are used to obtain the tilt angle in the re-entrant smectic C phase.

Temperature-gradient-induced

NASA Astrophysics Data System (ADS)

Park, Cheol; Glaser, Matt; Maclennan, Joe; Clark, Noel; Trittel, Torsten; Stannarius, Ralf

Freely-suspended smectic films of sub-micrometer thickness and lateral extensions of several millimeters were used to study thermally driven migration and convection in the film plane. Film experiments were performed during the 6 minute microgravity phase of a TEXUS suborbital rocket flight (Texus 52, launched April 27, 2015). We have found an attraction of the smectic material towards the cold edge of the film in a temperature gradient, similar to the Soret effect. This process is reversed when this edge is heated up again. Thermal convection driven by two thermocontacts in the film is practically absent, even at temperature gradients up to 10 K/mm, with thermally driven convection only setting in when the hot post reaches the transition temperature to the nematic phase. The Observation and Analysis of Smectic Islands in Space (OASIS) flight hardware was launched on SpaceX-6 in April 2015 and experiments on smectic bubbles were carried out on the International Space Station using four different smectic A and C liquid crystal materials in separate sample chambers. We observed that smectic islands on the surface of the bubbles migrated towards the colder part of the bubble in a temperature gradient. This work was supported by NASA Grant No. NNX-13AQ81G, by the Soft Materials Research Center under NSF MRSEC Grants No. DMR-0820579 and No. DMR-1420736, and by DLR Grants 50WM1127 and 50WM1430.

Triazolium based ionic liquid crystals: Effect of asymmetric substitution

DOE PAGES

Stappert, K.; Mudring, A. -V.

2015-01-27

A new series of ten different asymmetrical 1-dodecyl-3-alkyl-triazolium bromides, [C 12C nTr][Br], has been synthesized and their mesomorphic behavior studied by DSC (differential scanning calorimetry), POM (polarizing optical microscopy) and SAXS (small angle X-ray scattering). The influence of the chain length of the triazolium salts is investigated to explore the effect of asymmetric substitution on the phase behaviour of these compounds. For that reason, the length of one alkyl chain was varied from 14 to 1 carbon atoms (n = 14, 12, 10, 8–4, 2, 1) while the other alkyl chain was kept at 12 carbon. Single crystal X-ray structuremore » analysis of compounds [C 12C 12Tr][Br] and [C 12C 5Tr][Br] reveal that the cations adopt a U-shaped conformation with head-to-head arranged triazolium cores. In contrast, for [C 12C 1Tr][Br], a rod like shape of the cation with interdigitated alkyl chains is found. All investigated compounds are thermotropic liquid crystals. Higher ordered smectic phases, smectic C as well as smectic A phases were found depending on the chain length of the cation. Moreover, the clearing point temperature decreases with decreasing chain length with exception for the n-dodecyl-3-alkyltrizoliumbromides with the two shortest alkyl chains, [C 12C 2Tr][Br] and [C 12C 1Tr][Br], which present higher clearing temperatures (86 and 156 °C) and are structurally distinctly different.« less

Flow properties of liquid crystal phases of the Gay-Berne fluid

NASA Astrophysics Data System (ADS)

Sarman, Sten

1998-05-01

We have calculated the viscosities of a variant of the Gay-Berne fluid as a function of the temperature by performing molecular dynamics simulations. We have evaluated the Green-Kubo relations for the various viscosity coefficients. The results have been cross-checked by performing shear flow simulations. At high temperatures there is a nematic phase that is transformed to a smectic A phase as the temperature is decreased. The nematic phase is found to be flow stable. Close to the nematic-smectic transition point the liquid crystal model system becomes flow unstable. This is in agreement with the theoretical predictions by Jähnig and Brochard [F. Jähnig and F. Brochard, J. Phys. 35, 301 (1974)]. In a planar Couette flow one can define the three Miesowicz viscosities or effective viscosities η1, η2, and η3. The coefficient η1 is the viscosity when the director is parallel to the streamlines, η2 is the viscosity when the director is perpendicular to the shear plane, and η3 is the viscosity when the director is perpendicular to the vorticity plane. In the smectic phase η1 is undefined because the strain rate field is incommensurate with the smectic layer structure when the director is parallel to the streamlines. The viscosity η3 is found to be fairly independent of the temperature. The coefficient η2 increases with the temperature. This is unusual because the viscosity of most isotropic liquids decreases with the temperature. This anomaly is due to the smectic layer structure that is present at low temperatures. This lowers the friction because the layers can slide past each other fairly easily.

Computerized Liquid Crystal Phase Identification by Neural Networks Analysis of Polarizing Microscopy Textures

NASA Astrophysics Data System (ADS)

Karaszi, Zoltan; Konya, Andrew; Dragan, Feodor; Jakli, Antal; CPIP/LCI; CS Dept. of Kent State University Collaboration

Polarizing optical microscopy (POM) is traditionally the best-established method of studying liquid crystals, and using POM started already with Otto Lehman in 1890. An expert, who is familiar with the science of optics of anisotropic materials and typical textures of liquid crystals, can identify phases with relatively large confidence. However, for unambiguous identification usually other expensive and time-consuming experiments are needed. Replacement of the subjective and qualitative human eye-based liquid crystal texture analysis with quantitative computerized image analysis technique started only recently and were used to enhance the detection of smooth phase transitions, determine order parameter and birefringence of specific liquid crystal phases. We investigate if the computer can recognize and name the phase where the texture was taken. To judge the potential of reliable image recognition based on this procedure, we used 871 images of liquid crystal textures belonging to five main categories: Nematic, Smectic A, Smectic C, Cholesteric and Crystal, and used a Neural Network Clustering Technique included in the data mining software package in Java ``WEKA''. A neural network trained on a set of 827 LC textures classified the remaining 44 textures with 80% accuracy.

The Power of Poincaré: Elucidating the Hidden Symmetries in Focal Conic Domains

NASA Astrophysics Data System (ADS)

Matsumoto, Elisabetta A.; Alexander, Gareth P.; Chen, Bryan Gin-Ge; Kamien, Randall D.

2011-03-01

Focal conic domains are typically the ``smoking gun'' by which smectic liquid crystalline phases are identified. The geometry of the equally spaced smectic layers is highly generic but, at the same time, difficult to work with. We develop an approach to the study of focal sets in smectics which exploits a hidden Poincaré symmetry revealed only by viewing the smectic layers as projections from one-higher dimension. We use this perspective to shed light upon the concentric cyclides of Dupin and several classic focal conic textures which exhibit a more widespread level of geometric organization as in Friedel's law of corresponding cones, the networks and trellises expounded by Bouligand, or Apollonian packings.

On the calculation of the absolute grand potential of confined smectic-A phases

NASA Astrophysics Data System (ADS)

Huang, Chien-Cheng; Baus, Marc; Ryckaert, Jean-Paul

2015-09-01

We determine the absolute grand potential Λ along a confined smectic-A branch of a calamitic liquid crystal system enclosed in a slit pore of transverse area A and width L, using the rod-rod Gay-Berne potential and a rod-wall potential favouring perpendicular orientation at the walls. For a confined phase with an integer number of smectic layers sandwiched between the opposite walls, we obtain the excess properties (excess grand potential Λexc, solvation force fs and adsorption Γ) with respect to the bulk phase at the same μ (chemical potential) and T (temperature) state point. While usual thermodynamic integration methods are used along the confined smectic branch to estimate the grand potential difference as μ is varied at fixed L, T, the absolute grand potential at one reference state point is obtained via the evaluation of the absolute Helmholtz free energy in the (N, L, A, T) canonical ensemble. It proceeds via a sequence of free energy difference estimations involving successively the cost of localising rods on layers and the switching on of a one-dimensional harmonic field to keep layers integrity coupled to the elimination of inter-layers and wall interactions. The absolute free energy of the resulting set of fully independent layers of interacting rods is finally estimated via the existing procedures. This work opens the way to the computer simulation study of phase transitions implying confined layered phases.

Coarsening Dynamics of Inclusions and Thermocapillary Phenomena in Smectic Liquid Crystal Bubbles

NASA Astrophysics Data System (ADS)

Park, Cheol; Maclennan, Joseph; Glaser, Matthew; Clark, Noel; Trittel, Torsten; Eremin, Alexey; Stannarius, Ralf; Tin, Padetha; Hall, Nancy

The Observation and Analysis of Smectic Islands in Space (OASIS) project comprises a series of experiments that probe interfacial and hydrodynamic behavior of thin spherical-bubbles of smectic liquid crystal in microgravity. Smectic films are the thinnest known stable condensed phase structures, making them ideal for studies of two-dimensional (2D) coarsening dynamics and thermocapillary phenomena in microgravity. The OASIS flight hardware was launched on SpaceX-6 in April 2015 and experiments were carried out on the International Space Station using four different smectic A and C liquid crystal materials in separate sample chambers. We will describe the behavior of collective island dynamics on the bubbles, including temperature gradient-induced themomigration, and the diffusion and coalescence-driven coarsening dynamics of island emulsions in microgravity. This work was supported by NASA Grant No. NNX-13AQ81G, and NSF MRSEC Grants No. DMR-0820579 and DMR-1420736.

Electrorotation of colloidal particles in liquid crystals

NASA Astrophysics Data System (ADS)

Liao, G.; Smalyukh, I. I.; Kelly, J. R.; Lavrentovich, O. D.; Jákli, A.

2005-09-01

We present the first observations of dc electric-field-induced rotational motion of finite particles in liquid crystals. We show that the electrorotation is essentially identical to the well-known Quincke rotation, which in liquid crystals triggers an additional translational motion at higher fields. In the smectic phase the translational motion is confined to the two-dimensional geometry of smectic layers, in contrast to the isotropic and nematic phases, where the particles can move in all three dimensions. We demonstrate that by a proper analysis of the electrorotation, one can determine the in-plane viscosity of smectic liquid crystals. This method needs only a small amount of material, does not require uniform alignment over large areas, and enables probing rheological properties locally.

Biaxiality in Nematic and Smectic Liquid Crystals. Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Satyendra; Li, Quan; Srinivasarao, Mohan

2017-01-24

During the award period, the project team explored several phenomena in a diverse group of soft condensed matter systems. These include understanding of the structure of the newly discovered twist-bend nematic phase, solving the mystery of de Vries smectic phases, probing of interesting associations and defect structures in chromonic liquid crystalline systems, dispersions of ferroelectric nanoparticles in smectic liquid crystals, investigations of newly synthesized light sensitive and energy harvesting materials with highly desirable transport properties. Our findings are summarized in the following report followed by a list of 36 publications and 37 conference presentations. We achieved this with the supportmore » of Basic Sciences Division of the US DOE for which we are thankful.« less

Supercooled smectic nanoparticles: a potential novel carrier system for poorly water soluble drugs.

PubMed

Kuntsche, J; Westesen, K; Drechsler, M; Koch, M H J; Bunjes, H

2004-10-01

The possibility of preparing nanoparticles in the supercooled thermotropic liquid crystalline state from cholesterol esters with saturated acyl chains as well as the incorporation of model drugs into the dispersions was investigated using cholesteryl myristate (CM) as a model cholesterol ester. Nanoparticles were prepared by high-pressure melt homogenization or solvent evaporation using phospholipids, phospholipid/ bile salt, or polyvinyl alcohol as emulsifiers. The physicochemical state and phase behavior of the particles was characterized by particle size measurements (photon correlation spectroscopy, laser diffraction with polarization intensity differential scattering), differential scanning calorimetry, X-ray diffraction, and electron and polarizing light microscopy. The viscosity of the isotropic and liquid crystalline phases of CM in the bulk was investigated in dependence on temperature and shear rate by rotational viscometry. CM nanoparticies can be obtained in the smectic phase and retained in this state for at least 12 months when stored at 230C in optimized systems. The recrystallization tendency of CM in the dispersions strongly depends on the stabilizer system and the particle size. Stable drug-loaded smectic nanoparticles were obtained after incorporation of 10% (related to CM) ibuprofen, miconazole, etomidate, and 1% progesterone. Due to their liquid crystalline state, colloidal smectic nanoparticles offer interesting possibilities as carrier system for lipophilic drugs. CM nanoparticles are suitable model systems for studying the crystallization behavior and investigating the influence of various parameters for the development of smectic nanoparticles resistant against recrystallization upon storage.

Asymmetric Conjugated Molecules Based on [1]Benzothieno[3,2-b][1]benzothiophene for High-Mobility Organic Thin-Film Transistors: Influence of Alkyl Chain Length.

PubMed

He, Keqiang; Li, Weili; Tian, Hongkun; Zhang, Jidong; Yan, Donghang; Geng, Yanhou; Wang, Fosong

2017-10-11

Herein, we report the synthesis and characterization of a series of [1]benzothieno[3,2-b][1]benzothiophene (BTBT)-based asymmetric conjugated molecules, that is, 2-(5-alkylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene (BTBT-Tn, in which T and n represent thiophene and the number of carbons in the alkyl group, respectively). All of the molecules with n ≥ 4 show mesomorphism and display smectic A, smectic B (n = 4), or smectic E (n > 4) phases and then crystalline phases in succession upon cooling from the isotropic state. Alkyl chain length has a noticeable influence on the microstructures of vacuum-deposited films and therefore on the performance of the organic thin-film transistors (OTFTs). All molecules except for 2-(thiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene and 2-(5-ethylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene showed OTFT mobilities above 5 cm 2 V -1 s -1 . 2-(5-Hexylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene and 2-(5-heptylthiophen-2-yl)[1]benzothieno[3,2-b][1]benzothiophene showed the greatest OTFT performance with reliable hole mobilities (μ) up to 10.5 cm 2 V -1 s -1 because they formed highly ordered and homogeneous films with diminished grain boundaries.

Asymmetric flavone-based liquid crystals: synthesis and properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timmons, Daren J.; Jordan, Abraham J.; Kirchon, Angelo A.

2017-02-01

A series of flavones (n-F) substituted at the 4', and 6 positions was prepared, characterised by NMR (1H,13C), HRMS, and studied for liquid crystal properties. The 4'-alkoxy,6-methoxyflavones (4-F–16-F) exhibit varying ranges of nematic and smectic A phases as evidenced by polarised optical microscopy and differential scanning calorimetry (DSC). As the tail length is increased, the smectic phase becomes more prevalent. Smectic phases for (8-F–16-F) were further analysed by powder X-ray diffraction (XRD), and the rate of structural transformations was explored by combined DSC/XRD studies. Flavonol 6-F–OH was also prepared but no mesogenic behaviour was observed. The molecular structures of 6-Fmore » and 6-F–OH were determined by single-crystal XRD and help to explain the differences in material properties. Additionally, fluorescence and electrochemical studies were conducted on solutions of n-F.« less

In-plane only retardation switching by certain type of smectic liquid crystal panels

NASA Astrophysics Data System (ADS)

Mochizuki, Akihiro

2018-02-01

A certain type of smectic C phase liquid crystal material panel shows in-plane only retardation switching during its electric field applied driving. This paper explains some chronological approach how such an interesting phenomenon was found and how the in-plane only retardation switching was verified.

Electroclinic effect in the chiral lamellar α phase of a lyotropic liquid crystal

NASA Astrophysics Data System (ADS)

Harjung, Marc D.; Giesselmann, Frank

2018-03-01

In thermotropic chiral Sm -A* phases, an electric field along the smectic layers breaks the D∞ symmetry of the Sm -A* phase and induces a tilt of the liquid crystal director. This so-called electroclinic effect (ECE) was first reported by Garoff and Meyer in 1977 and attracted substantial scientific and technological interest due to its linear and submicrosecond electro-optic response [S. Garoff and R. B. Meyer, Phys. Rev. A 19, 338 (1979), 10.1103/PhysRevA.19.338]. We now report the observation of an ECE in the pretransitional regime from a lyotropic chiral lamellar Lα* phase into a lyo-Sm -C* phase, the lyotropic analog to the thermotropic Sm -C* phase which was recently discovered by Bruckner et al. [Angew. Chem. Int. Ed. 52, 8934 (2013), 10.1002/anie.201303344]. We further show that the observed ECE has all signatures of its thermotropic counterpart, namely (i) the effect is chiral in nature and vanishes in the racemic Lα phase, (ii) the effect is essentially linear in the sign and magnitude of the electric field, and (iii) the magnitude of the effect diverges hyperbolically as the temperature approaches the critical temperature of the second order tilting transition. Specific deviations between the ECEs in chiral lamellar and chiral smectic phases are related to the internal field screening effect of electric double layers formed by inevitable ionic impurities in lyotropic phases.

Physics of smectic membranes

NASA Astrophysics Data System (ADS)

Pieranski, P.; Beliard, L.; Tournellec, J.-Ph.; Leoncini, X.; Furtlehner, C.; Dumoulin, H.; Riou, E.; Jouvin, B.; Fénerol, J.-P.; Palaric, Ph.; Heuving, J.; Cartier, B.; Kraus, I.

1993-03-01

Due to their layered structure, smectic liquid crystals can form membranes, similar to soap bubbles, that can be spanned on frames. Such smectic membranes have been used extensively as samples in many structural X-ray studies of smectic liquid crystals. In this context they have been considered as very convenient and highly perfect samples but little attention has been paid to the reasons for their existence and to the process of their formation. Our aim here is to address a first list of questions, which are the most urgent to answer. We will also describe experiments and models that have been conceived especially in order to understand the physics of these fascinating systems.

Dielectric Anistropy and Elastic Constants Near the Nematic-Smectic A Transition

NASA Astrophysics Data System (ADS)

Visco, Angelo; Mahmood, Rizwan; Zapien, Donald

The present work examines the behavior of dielectric anisotropy and the elastic constants associated with the deformation of liquid crystal molecules under the influence of an AC electric field and measured by an Automatic Liquid Crystal Tester (ALCT). The systems investigated are of various concentrations of 5CB (4-Cyano-4'-pentylbiphenyl) and 8CB (4-octyl-4'-cyanobiphenyl) liquid crystal as a function of temperature. These studies are important due to the complexity of the coupling between the orientational (nematic) and positional (smectic A) order parameters that can drive this transition to be either continuous or discontinuous. Theoretically, NA transition is weakly first order due to nematic director fluctuations in semctic A phase. This is similar to the transition from normal to superconductor. Thus, there exists a triple point similar to He3/He4 mixtures. Moreover, despite more than four decades of intense work, our understanding of this complex and interesting problem remains unclear. The funding for the project was provided by Slippery Rock University (2015-2016).

Glassy phases and driven response of the phase-field-crystal model with random pinning.

PubMed

Granato, E; Ramos, J A P; Achim, C V; Lehikoinen, J; Ying, S C; Ala-Nissila, T; Elder, K R

2011-09-01

We study the structural correlations and the nonlinear response to a driving force of a two-dimensional phase-field-crystal model with random pinning. The model provides an effective continuous description of lattice systems in the presence of disordered external pinning centers, allowing for both elastic and plastic deformations. We find that the phase-field crystal with disorder assumes an amorphous glassy ground state, with only short-ranged positional and orientational correlations, even in the limit of weak disorder. Under increasing driving force, the pinned amorphous-glass phase evolves into a moving plastic-flow phase and then, finally, a moving smectic phase. The transverse response of the moving smectic phase shows a vanishing transverse critical force for increasing system sizes.

Short range smectic order driving long range nematic order: Example of cuprates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Markiewicz, R. S.; Lorenzana, J.; Seibold, G.

We present a model for describing the combined presence of nematic and ‘smectic’ or stripe-like orders seen in recent scanning tunneling microscopy (STM) experiments on cuprates. The smectic order is treated as an electronic charge density wave with an associated Peierls distortion or a ‘Pomeranchuk wave’. This primary order is restricted to nanoscale domains by disorder effects, while the secondary coupling to strain generates the nematic order with a considerably longer range. Lastly, a variety of experimental results are shown to be consistent with our theoretical predictions.

Short range smectic order driving long range nematic order: Example of cuprates

DOE PAGES

Markiewicz, R. S.; Lorenzana, J.; Seibold, G.; ...

2016-01-27

We present a model for describing the combined presence of nematic and ‘smectic’ or stripe-like orders seen in recent scanning tunneling microscopy (STM) experiments on cuprates. The smectic order is treated as an electronic charge density wave with an associated Peierls distortion or a ‘Pomeranchuk wave’. This primary order is restricted to nanoscale domains by disorder effects, while the secondary coupling to strain generates the nematic order with a considerably longer range. Lastly, a variety of experimental results are shown to be consistent with our theoretical predictions.

Computer simulations of a liquid crystalline dendrimer in liquid crystalline solvents

NASA Astrophysics Data System (ADS)

Wilson, Mark R.; Ilnytskyi, Jaroslav M.; Stimson, Lorna M.

2003-08-01

Molecular dynamics simulations have been carried out to study the structure of a model liquid crystalline dendrimer (LCDr) in solution. A simplified model is used for a third generation carbosilane LCDr in which united atom Lennard-Jones sites are used to represent all heavy atoms in the dendrimer with the exception of the terminal mesogenic groups, which are represented by Gay-Berne potentials. The model dendrimer is immersed in a mesogenic solvent composed of Gay-Berne particles, which can form nematic and smectic-A phases in addition to the isotropic liquid. Markedly different behavior results from simulations in the different phases, with the dendrimer changing shape from spherical to rodlike in moving from isotropic to nematic solvents. In the smectic-A phase the terminal mesogenic units are able to occupy five separate smectic layers. The change in structure of the dendrimer is mediated by conformational changes in the flexible chains, which link the terminal mesogenic moieties to the dendrimer core.

Dual gauge field theory of quantum liquid crystals in two dimensions

NASA Astrophysics Data System (ADS)

Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai; Liu, Ke; Slager, Robert-Jan; Nussinov, Zohar; Cvetkovic, Vladimir; Zaanen, Jan

2017-04-01

We present a self-contained review of the theory of dislocation-mediated quantum melting at zero temperature in two spatial dimensions. The theory describes the liquid-crystalline phases with spatial symmetries in between a quantum crystalline solid and an isotropic superfluid: quantum nematics and smectics. It is based on an Abelian-Higgs-type duality mapping of phonons onto gauge bosons (;stress photons;), which encode for the capacity of the crystal to propagate stresses. Dislocations and disclinations, the topological defects of the crystal, are sources for the gauge fields and the melting of the crystal can be understood as the proliferation (condensation) of these defects, giving rise to the Anderson-Higgs mechanism on the dual side. For the liquid crystal phases, the shear sector of the gauge bosons becomes massive signaling that shear rigidity is lost. After providing the necessary background knowledge, including the order parameter theory of two-dimensional quantum liquid crystals and the dual theory of stress gauge bosons in bosonic crystals, the theory of melting is developed step-by-step via the disorder theory of dislocation-mediated melting. Resting on symmetry principles, we derive the phenomenological imaginary time actions of quantum nematics and smectics and analyze the full spectrum of collective modes. The quantum nematic is a superfluid having a true rotational Goldstone mode due to rotational symmetry breaking, and the origin of this 'deconfined' mode is traced back to the crystalline phase. The two-dimensional quantum smectic turns out to be a dizzyingly anisotropic phase with the collective modes interpolating between the solid and nematic in a non-trivial way. We also consider electrically charged bosonic crystals and liquid crystals, and carefully analyze the electromagnetic response of the quantum liquid crystal phases. In particular, the quantum nematic is a real superconductor and shows the Meissner effect. Their special properties inherited from spatial symmetry breaking show up mostly at finite momentum, and should be accessible by momentum-sensitive spectroscopy.

Dual gauge field theory of quantum liquid crystals in two dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai

We present a self-contained review of the theory of dislocation-mediated quantum melting at zero temperature in two spatial dimensions. The theory describes the liquid-crystalline phases with spatial symmetries in between a quantum crystalline solid and an isotropic superfluid: quantum nematics and smectics. It is based on an Abelian-Higgs-type duality mapping of phonons onto gauge bosons (“stress photons”), which encode for the capacity of the crystal to propagate stresses. Dislocations and disclinations, the topological defects of the crystal, are sources for the gauge fields and the melting of the crystal can be understood as the proliferation (condensation) of these defects, givingmore » rise to the Anderson–Higgs mechanism on the dual side. For the liquid crystal phases, the shear sector of the gauge bosons becomes massive signaling that shear rigidity is lost. After providing the necessary background knowledge, including the order parameter theory of two-dimensional quantum liquid crystals and the dual theory of stress gauge bosons in bosonic crystals, the theory of melting is developed step-by-step via the disorder theory of dislocation-mediated melting. Resting on symmetry principles, we derive the phenomenological imaginary time actions of quantum nematics and smectics and analyze the full spectrum of collective modes. The quantum nematic is a superfluid having a true rotational Goldstone mode due to rotational symmetry breaking, and the origin of this ‘deconfined’ mode is traced back to the crystalline phase. The two-dimensional quantum smectic turns out to be a dizzyingly anisotropic phase with the collective modes interpolating between the solid and nematic in a non-trivial way. We also consider electrically charged bosonic crystals and liquid crystals, and carefully analyze the electromagnetic response of the quantum liquid crystal phases. In particular, the quantum nematic is a real superconductor and shows the Meissner effect. Furthermore, their special properties inherited from spatial symmetry breaking show up mostly at finite momentum, and should be accessible by momentum-sensitive spectroscopy.« less

Dual gauge field theory of quantum liquid crystals in two dimensions

DOE PAGES

Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai; ...

2017-04-18

We present a self-contained review of the theory of dislocation-mediated quantum melting at zero temperature in two spatial dimensions. The theory describes the liquid-crystalline phases with spatial symmetries in between a quantum crystalline solid and an isotropic superfluid: quantum nematics and smectics. It is based on an Abelian-Higgs-type duality mapping of phonons onto gauge bosons (“stress photons”), which encode for the capacity of the crystal to propagate stresses. Dislocations and disclinations, the topological defects of the crystal, are sources for the gauge fields and the melting of the crystal can be understood as the proliferation (condensation) of these defects, givingmore » rise to the Anderson–Higgs mechanism on the dual side. For the liquid crystal phases, the shear sector of the gauge bosons becomes massive signaling that shear rigidity is lost. After providing the necessary background knowledge, including the order parameter theory of two-dimensional quantum liquid crystals and the dual theory of stress gauge bosons in bosonic crystals, the theory of melting is developed step-by-step via the disorder theory of dislocation-mediated melting. Resting on symmetry principles, we derive the phenomenological imaginary time actions of quantum nematics and smectics and analyze the full spectrum of collective modes. The quantum nematic is a superfluid having a true rotational Goldstone mode due to rotational symmetry breaking, and the origin of this ‘deconfined’ mode is traced back to the crystalline phase. The two-dimensional quantum smectic turns out to be a dizzyingly anisotropic phase with the collective modes interpolating between the solid and nematic in a non-trivial way. We also consider electrically charged bosonic crystals and liquid crystals, and carefully analyze the electromagnetic response of the quantum liquid crystal phases. In particular, the quantum nematic is a real superconductor and shows the Meissner effect. Furthermore, their special properties inherited from spatial symmetry breaking show up mostly at finite momentum, and should be accessible by momentum-sensitive spectroscopy.« less

Measuring the equation of state for a 2D colloidal membrane: A microfluidic approach to buffer exchange

NASA Astrophysics Data System (ADS)

Balchunas, Andrew; Cabanas, Rafael; Fraden, Seth; Dogic, Zvonimir

Previous work has shown that monodisperse rod-like colloidal particles, such as a filamentous bacteriophage, self assemble into a 2D monolayer smectic in the presence of a non-adsorbing depleting polymer. These structures have the same functional form of bending rigidity and lateral compressibility as conventional lipid bi-layers, so we name the monolayer smectic a colloidal membrane. We have developed a microfluidic device such that the osmotic pressure acting on a colloidal membrane may be controlled via a full in situ buffer exchange. Rod density within individual colloidal membranes was measured as a function of osmotic pressure and a first order phase transition, from 2D fluid to 2D solid, was observed. kon and koff rates of rod to membrane binding were measured by lowering the osmotic pressure until membrane evaporation occurred.

Molecular aspect ratio and anchoring strength effects in a confined Gay-Berne liquid crystal

NASA Astrophysics Data System (ADS)

Cañeda-Guzmán, E.; Moreno-Razo, J. A.; Díaz-Herrera, E.; Sambriski, E. J.

2014-04-01

Phase diagrams for Gay-Berne (GB) fluids were obtained from molecular dynamics simulations for GB(2, 5, 1, 2) (i.e. short mesogens) and GB(3, 5, 1, 2) (i.e. long mesogens), which yield isotropic, nematic, and smectic-B phases. The long-mesogen fluid also yields the smectic-A phase. Ordered phases of the long-mesogen fluid form at higher temperatures and lower densities when compared to those of the short-mesogen fluid. The effect of confinement under weak and strong substrate couplings in slab geometry was investigated. Compared to the bulk, the isotropic-nematic transition does not shift in temprature significantly for the weakly coupled substrate in either mesogen fluid. However, the strongly coupled substrate shifts the transition to lower temperature. Confinement induces marked stratification in the short-mesogen fluid. This effect diminishes with distance from the substrate, yielding bulk-like behaviour in the slab central region. Fluid stratification is very weak for the long-mesogen fluid, but the strongly coupled substrate induces 'smectisation', an ordering effect that decays with distance. Orientation of the fluid on the substrate depends on the mesogen. There is no preferred orientation in a plane parallel to the substrate for the weakly coupled case. In the strongly coupled case, the mesogen orientation mimics that of adjacent fluid layers. Planar anchoring is observed with a broad distribution of orientations in the weakly coupled case. In the strongly coupled case, the distribution leans toward planar orientations for the short-mesogen fluid, while a marginal preference for tilting persists in the long-mesogen fluid.

Direct reconstruction of the two-dimensional pair distribution function in partially ordered systems with angular correlations.

PubMed

Zaluzhnyy, I A; Kurta, R P; Menushenkov, A P; Ostrovskii, B I; Vartanyants, I A

2016-09-01

An x-ray scattering approach to determine the two-dimensional (2D) pair distribution function (PDF) in partially ordered 2D systems is proposed. We derive relations between the structure factor and PDF that enable quantitative studies of positional and bond-orientational (BO) order in real space. We apply this approach in the x-ray study of a liquid crystal (LC) film undergoing the smectic-A-hexatic-B phase transition, to analyze the interplay between the positional and BO order during the temperature evolution of the LC film. We analyze the positional correlation length in different directions in real space.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radzihovsky, Leo

Motivated by a realization of imbalanced Feshbach-resonant atomic Fermi gases, we formulate a low-energy theory of the Fulde-Ferrell and the Larkin-Ovchinnikov (LO) states and use it to analyze fluctuations, stability, and phase transitions in these enigmatic finite momentum-paired superfluids. Focusing on the unidirectional LO pair-density-wave state, which spontaneously breaks the continuous rotational and translational symmetries, we show that it is characterized by two Goldstone modes, corresponding to a superfluid phase and a smectic phonon. Because of the liquid-crystalline ''softness'' of the latter, at finite temperature the three-dimensional state is characterized by a vanishing LO order parameter, quasi-Bragg peaks in themore » structure and momentum distribution functions, and a ''charge''-4, paired-Cooper-pairs, off-diagonal long-range order, with a superfluid-stiffness anisotropy that diverges near a transition into a nonsuperfluid state. In addition to conventional integer vortices and dislocations, the LO superfluid smectic exhibits composite half-integer vortex-dislocation defects. A proliferation of defects leads to a rich variety of descendant states, such as the charge-4 superfluid and Fermi-liquid nematics and topologically ordered nonsuperfluid states, that generically intervene between the LO state and the conventional superfluid and the polarized Fermi liquid at low and high imbalance, respectively. The fermionic sector of the LO gapless superconductor is also quite unique, exhibiting a Fermi surface of Bogoliubov quasiparticles associated with the Andreev band of states, localized on the array of the LO domain walls.« less

Biaxial and antiferroelectric structure of the orthogonal smectic phase of a bent-shaped molecule and helical structure in a chiral mixture system

NASA Astrophysics Data System (ADS)

Kang, Sungmin; Nguyen, Ha; Nakajima, Shunpei; Tokita, Masatoshi; Watanabe, Junji

2013-05-01

We examined the biaxial and antiferroelectric properties in the Smectic-APA (Sm-APA) phase of bent-shaped DC-S-8. The biaxiality, which results from the existence of a secondary director, was well established from birefringence observations in the homeotropically aligned Sm-APA. By entering into Sm-APA phase, the birefringence (Δn, difference between two refractive indices of short axes) continuously increased from 0 to 0.02 with decreasing temperature. The antiferroelectric switching and second harmonic generation (SHG) activity on the field-on state were also observed in the Sm-APA phase, and the evaluated spontaneous polarization (PS) value strongly depended on temperature. The temperature dependence of Δn and PS resembles each other and follows Haller's approximation, showing that the biaxiality is due to polar packing in which the molecules are preferentially packed with their bent direction arranged in the same direction, and that the phase transition of Sm-APA to Sm-A is second order. The biaxiality was further examined in chiral Sm-APA*. Doping with chiral components induced the helical twisting of the secondary director in the Sm-APA* phase, which was confirmed by observing the reflection of the circular dichroism (CD) bands in the homeotropically aligned cell. The helical pitch of Sm-APA* is tunable in the range of 300-700 nm wavelength with a variation in the chiral content of 5 to 10 weight (wt)%.

Critical behavior in the vicinity of nematic to smectic A (N-SmA) phase transition of two polar-polar binary liquid crystalline systems

NASA Astrophysics Data System (ADS)

Barman, Barnali; Sarkar, Sudipta Kumar; Das, Malay Kumar

2018-01-01

Phase diagram, critical behavior and order of the nematic (N)-smectic A (SmA) phase transition of two polar-polar binary systems (i) 4-n-heptyloxy-4‧-cyanobiphenyl (7OCB) and 4-n-octyloxy-4‧-cyanobiphenyl (8OCB); (ii) 4-n-octyloxy-4‧-cyanobiphenyl (8OCB) and 4-n-nonyloxy-4‧-cyanobiphenyl (9OCB) by means of a high-resolution temperature scanning measurement of birefringence have been reported in this work. A simple power law analysis has been adopted to extract the specific heat critical exponent (α‧) at N-SmA transition from birefringence data. The α‧ for N-SmA transition indicates a uniform crossover behavior and has appeared to be non-universal in nature. With increasing concentration of the higher homologues for both the binary systems, the N-SmA transition reveals a strong tendency to be driven towards the tricritical nature. The 3D-XY limit (i.e. α‧ = -0.007) for N-SmA transition reaches at the concentration x8OCB = 0.28 corresponding to the McMillan ratio 0.914, whereas the tricritical point has been found to appear near x9OCB = 1.0 corresponding to McMillan ratio 0.992.

The thermodynamic parameters of sorption and enantioselectivity of the chiral smectic liquid crystal 2-methylbutyl ester of 4-(4-decyloxybenzylideneamino)-cinnamic acid

NASA Astrophysics Data System (ADS)

Onuchak, L. A.; Stepanova, R. F.; Akopova, O. B.; Glebova, O. V.; Chernova, O. M.

2008-06-01

The thermodynamic characteristics of sorption of n-alkanes, arenes, aldehydes, monoatomic alcohols, and optical isomers of camphene and butanediol-2,3 by a chiral smectic liquid crystal, 2-methylbutyl ester of 4-(4-decyloxybenzylideneamino)-cinnamic acid, from the gas phase were studied over the temperature range including the S*C and S*A mesophases and isotropic phase. The standard and excess thermodynamic functions of sorption were determined for 26 sorbates of the classes of substances specified. The S*C and S*A mesophases exhibited selectivity with respect to the separation of para and meta xylenes (α p/m = 1.06 1.07, 90 108°C) and pronounced enantioselectivity (αR/S = 1.05 1.09, 87 108°C). The helically twisted structure of the smectic liquid crystal was shown to play an important role in the mechanism of the chiral recognition of optical isomers of polar and low-polarity compounds under gas-liquid chromatography conditions.

Strain-induced macroscopic magnetic anisotropy from smectic liquid-crystalline elastomer-maghemite nanoparticle hybrid nanocomposites.

PubMed

Haberl, Johannes M; Sánchez-Ferrer, Antoni; Mihut, Adriana M; Dietsch, Hervé; Hirt, Ann M; Mezzenga, Raffaele

2013-06-21

We combine tensile strength analysis and X-ray scattering experiments to establish a detailed understanding of the microstructural coupling between liquid-crystalline elastomer (LCE) networks and embedded magnetic core-shell ellipsoidal nanoparticles (NPs). We study the structural and magnetic re-organization at different deformations and NP loadings, and the associated shape and magnetic memory features. In the quantitative analysis of a stretching process, the effect of the incorporated NPs on the smectic LCE is found to be prominent during the reorientation of the smectic domains and the softening of the nanocomposite. Under deformation, the soft response of the nanocomposite material allows the organization of the nanoparticles to yield a permanent macroscopically anisotropic magnetic material. Independent of the particle loading, the shape-memory properties and the smectic phase of the LCEs are preserved. Detailed studies on the magnetic properties demonstrate that the collective ensemble of individual particles is responsible for the macroscopic magnetic features of the nanocomposite.

Influence of Hydrogen Bond on Thermal and Phase Transitions of Binary Complex Liquid Crystals

NASA Astrophysics Data System (ADS)

Vijayakumar, V. N.; Rajasekaran, T. R.; Baskar, K.

2017-12-01

A novel supramolecular liquid crystal (LC) is synthesized from the binary complex of 4-decyloxy benzoic acid and cholesteryl acetate. Fourier transform infrared (FTIR) spectroscopic study confirms the formation of intermolecular hydrogen bond between the mesogens. Various mesophases and corresponding textural changes in the complex are observed by comparing with its constituents through polarizing optical microscopic (POM) studies. The thermal stability factor of smectic phase for present complex is calculated. An interesting observation of present work is that investigation of extended thermal span of mesomorphic phases, decreased enthalpy, a nematic phase with a high clearing point and a low melting point. This is due to an arrangement of molecular reorientations and the development of new associations by hydrogen bonding. Optical tilt angle for smectic C phase is determined and the same is fitted to a power law.

Electronic polymers and soft-matter-like broken symmetries in underdoped cuprates.

PubMed

Capati, M; Caprara, S; Di Castro, C; Grilli, M; Seibold, G; Lorenzana, J

2015-07-06

Empirical evidence in heavy fermion, pnictide and other systems suggests that unconventional superconductivity appears associated to some form of real-space electronic order. For the cuprates, despite several proposals, the emergence of order in the phase diagram between the commensurate antiferromagnetic state and the superconducting state is not well understood. Here we show that in this regime doped holes assemble in 'electronic polymers'. Within a Monte Carlo study, we find that in clean systems by lowering the temperature the polymer melt condenses first in a smectic state and then in a Wigner crystal both with the addition of inversion symmetry breaking. Disorder blurs the positional order leaving a robust inversion symmetry breaking and a nematic order, accompanied by vector chiral spin order and with the persistence of a thermodynamic transition. Such electronic phases, whose properties are reminiscent of soft-matter physics, produce charge and spin responses in good accord with experiments.

Temperature tuning of lasing emission from dye-doped liquid crystal at intermediate twisted phase

NASA Astrophysics Data System (ADS)

Liao, Kuan-Cheng; Lin, Ja-Hon; Jian, Li-Hao; Chen, Yao-Hui; Wu, Jin-Jei

2015-07-01

Temperature tuning of lasing emission from dye-doped cholesteric liquid crystal (CLC) at intermediate twisted phase has been demonstrated in this work. With heavily doping of 42.5% chiral molecules into the nematic liquid crystals, the shifts of photonic bandgap versus temperature is obviously as thermal controlling of the sample below the certain value. By the differential scanning calorimetr measuremet, we demonstrate the phase transition from the CLC to the smectic phase when the temperature is lowered to be about 15°C. Between CLC and smectic phase, the liquid crystal mixtures are operated at intermediate twisted phase that can be used the temperature related refractive mirror. After pump by the Q-switched Nd:YAG laser, the lasing emission from this dye doped LC mixtures has been demonstrated whose emission wavelength can be tuned from 566 to 637 nm with 1.4°C variation.

Investigation of thermal and optical properties of some quartet mixed hydrogen-bonded liquid crystals

NASA Astrophysics Data System (ADS)

Okumuş, Mustafa

2017-11-01

In this study, the thermal and optical properties of quartet mixtures formed at different weight ratios (1:1:1:1 and 1.5:1:1:1) from liquid crystals 4-octyloxy-4‧-cyanobiphenyl (8OCB), 4-hexylbenzoic acid, 4-(octyloxy)benzoic acid and 4-(decyloxy)benzoic acid were investigated by differential scanning calorimeter (DSC) and polarized optic microscopy (POM). The phase transition temperatures of the novel quartet mixtures measured in the DSC experiments are in line with the POM experiments. The experimental results clearly show that the novel liquid crystal mixtures have displayed pure liquid crystalline properties. According to the phase diagram drawn from DSC results, the nematic range of the novel mixture at the eutectic point is larger than the nematic ranges of the components. The mesomorphic structures of produced homolog complex mixtures are found to be smectic and nematic phases. But the smectic phase cannot be observed in the novel complex 1.5:1:1:1 mixture during continuous cooling. The nematic range of the novel complex 1.5:1:1:1 mixture is bigger than the nematic range of the novel complex 1:1:1:1 mixture with increasing 8OCB. Also, the nematic-to-isotropic phase transition temperature decreases with increasing the weight ratio of 8OCB in the complex quartet mixture. Another interesting result is that the produced mixtures are to be like a medical cream at room temperatures. Furthermore, order parameter and thermal stability factor of the transitions are also calculated.

Field-Induced Alignment of Polar Bent-Ccore Smectic A Liquid Crystals

NASA Astrophysics Data System (ADS)

Shen, Yongqiang; Goodhew, Lisa; Shao, Renfan; Maclennan, Joseph; Clark, Noel; Rudquist, Per

2014-03-01

The SmAPF phase is a promising phase modulator mode. To use the SmAPF materials for applications, we need to obtain uniform, large-area alignment of the samples. However, bent-core liquid crystals are notoriously difficult to align with conventional surface treatment methods because most of them have no nematic phase. We have developed a powerful, new method using in-plane applied electric fields that allows us to create a perfect bookshelf alignment of orthogonal bent-core smectics. By using an interdigitated, finger-like electrode arrangement on one of the cell surfaces, we can align the materials by applying in-plane electric fields. This stripe geometry, which produces curved field lines, allows for only one smectic layer orientation, normal both to the cell walls and to the finger electrodes. After alignment, the cell can be operated in the conventional way by connecting the finger electrodes together to make one effective electrode, opposing continuous, common electrode on the opposite side of the cell. This alignment method opens up the use of these materials in perfectly aligned cells for both amplitude and phase-only modulation applications. This work was supported by NSF MRSEC Grant No. DMR-0820579, by NSF Grant No. DMR-1008300, and by Swedish Research Council (VR) Grant No. 621-2009-3621.

Charge transport in liquid crystalline smectic and discotic organic semiconductors: New results and experimental methodologies

NASA Astrophysics Data System (ADS)

Paul, Sanjoy

Organic electronics offer the possibility of producing low cost, flexible, and large area electronics. Organic semiconductors (OSCs) (organic polymers and crystals), used in organic electronics, are promising materials for novel optical and electronic devices such as organic light emitting diodes, organic field effect transistors, organic sensors, and organic photovoltaics (OPVs). OSCs are composed of molecules weakly held together via van der Walls forces rather than covalent bonds as in the case of inorganic semiconductors such as Si. The combined effect of small wave function overlap, spatial and energetic disorder in organic semiconducting materials lead to localization of charge carriers and, in many cases, hopping conduction. OSCs also differ from conventional semiconductors in that charges photogeneration (e.g., in OPVs) proceeds via the production, diffusion, and dissociation of excitons. Liquid crystalline OSCs (LCOSCs) are semiconductors with phases intermediate between the highly ordered crystalline and completely disordered liquid phases. These materials offer many advantages including facile alignment and the opportunity to study the effects of differing intermolecular geometries on transfer integrals, disorder-induced trapping, charge mobilities, and photogeneration efficiency. In this dissertation work, we explored the photogeneration and charge transport mechanisms in a few model smectic and discotic LCs to better understand the governing principles of photogeneration and charge transport using conventional and novel methods based on the pulsed laser time-of-flight charge carrier transport technique. Four major interrelated topics were considered in this research. First, a sample of smectic LC was aligned in order to compare the resulting hole mobility to that of an unaligned sample, with the aim of understanding how the intermolecular alignment over large length scales affects the hopping probability. The role of the polarization of the photogenerating light was also explored in the context of these anisotropic systems. Next, the photogeneration and charge transport was investigated as a function of temperature, electric field, the wavelength and intensity of photogenerating light. Different exciton dissociation interfaces between the electrode and the LC to probe the details of the mechanism of excitonic dissociation (e.g., surface mediated generation vs. exciton-exciton fusion) were explored. Next, we have also developed a new method of spatially resolving the photogeneration and transport mechanisms in inhomogeneous OSCs called "scanning time of flight microscopy (STOFm)" which simultaneously obtains 2d images of transport coefficients and polarized transmittance. The STOFm was extensively used to study charge transport in various structured semiconductors: smectics, discotics, as well as in phase separated LC/polymer structures. Finally, this work involves characterization and analysis of transport in a number of new phenyl-naphthalene LC OSCs.

Single molecule translocation in smectics illustrates the challenge for time-mapping in simulations on multiple scales

NASA Astrophysics Data System (ADS)

Mukherjee, Biswaroop; Peter, Christine; Kremer, Kurt

2017-09-01

Understanding the connections between the characteristic dynamical time scales associated with a coarse-grained (CG) and a detailed representation is central to the applicability of the coarse-graining methods to understand molecular processes. The process of coarse graining leads to an accelerated dynamics, owing to the smoothening of the underlying free-energy landscapes. Often a single time-mapping factor is used to relate the time scales associated with the two representations. We critically examine this idea using a model system ideally suited for this purpose. Single molecular transport properties are studied via molecular dynamics simulations of the CG and atomistic representations of a liquid crystalline, azobenzene containing mesogen, simulated in the smectic and the isotropic phases. The out-of-plane dynamics in the smectic phase occurs via molecular hops from one smectic layer to the next. Hopping can occur via two mechanisms, with and without significant reorientation. The out-of-plane transport can be understood as a superposition of two (one associated with each mode of transport) independent continuous time random walks for which a single time-mapping factor would be rather inadequate. A comparison of the free-energy surfaces, relevant to the out-of-plane transport, qualitatively supports the above observations. Thus, this work underlines the need for building CG models that exhibit both structural and dynamical consistency to the underlying atomistic model.

Phase transitions and reentrant phenomena in liquid crystals having both rigid and flexible intramolecular joints

NASA Astrophysics Data System (ADS)

Pyżuk, W.; Górecka, E.; Mieczkowski, J.; Przedmojski, J.

1992-07-01

Two series of liquid-crystalline compounds having three phenyl rings separated by flexible spacer —CH(CH{3})CH{2}—COO— and by rigid azo and azoxy group, were studied by DSC, optical and X-ray methods. For esters of dl-3-(4^{prime}-nitro)-phenylbutyric acid with 4^{prime}-alkoxy-phenylazo-phenol-4 having dodecyloxy or longer terminal chains, as well as for related azoxy compounds, a narrow (even below 5 K) reentrant or inverted nematic phase appearing between partly bilayer and monolayer smectics A was observed. For higher homologues of the azoxy series additional smectic phases appear, leading to the occurrence of new multicritical points, e.g. the critical end point Ad Cd N^re. On each of the lines, which separate nematic from smectic A phases, transitions are of weakly first or second-order and more than one tricritical point can occur. On the A{1} N/A{1} N^re line, a simple N A{1} tricritical point is observed at T_NI/T_AN = 0.834. The presence of further critical points depends on the components of the binary system involved. Four of the azoxy compounds studied undergo a second order phase transition between partly bilayer smectics, Ad and Cd. Such a transition is accompanied by a jumb in the specific heat, varying linearly with the length of the molecular tails. Various temperature dependences of the layer spacing in the Ad phase are observed for subsequent homologues from the azoxy series. Plusieurs cristaux liquides composés de trois groupements phényl séparés par un groupement —CH(CH{3})CH{2}—COO—, ainsi que par des groupements azo et azoxy, ont été examinés par AED, méthodes optiques et par rayons X. Pour des esters de l'acide dl-3-(4^{prime}-nitro)phénylbutyrique et de 4^{prime}-alkoxy-phénylazo-phénol-4 ayant comme terminaison une chaîne dodecyloxy ou bien plus longue, ainsi que pour des composés azoxy relatif, on observe (même au-dessous de 5 K) une étroite phase nématique réentrante ou inverse entre les phases smectiques : monocouche et partiellement bicouche. Pour des homologues plus longs dans la série des composés azoxy, on a constaté l'existence d'autres phases smectiques ce qui implique l'apparition, sur les diagrammes des phases, de nouveau points multicritiques, par exemple le point Ad Cd N^re. Sur chaque ligne séparant les phases smectiques A de la phase nématique les transitions sont faiblement du premier ordre ou du deuxième ordre ce qui mène dans certain cas à plus qu'un point tricritique. Sur la ligne A{1} N/A{1} N^re on observe à T_NI/T_AN = 0,834 un simple point tricritique N A{1} — l'apparition des autres dépend du choix des constituants du système binaire. Dans le cas de quatre composés azoxy on a constaté une transition du deuxième ordre entre les phases smectiques partiellement bicouches, Ad et Cd. La transition est accompagnée d'un brusque changement de la chaleur spécifique qui varie linéairement avec la longueur de la queue de la molécule. Pour des homologues suivants de la série des composés azoxy on observe différentes dépendances en température de la distance entre les couches de la phase Ad.

Density functional theory for hard uniaxial particles: Complex ordering of pear-shaped and spheroidal particles near a substrate

NASA Astrophysics Data System (ADS)

Schönhöfer, Philipp W. A.; Schröder-Turk, Gerd E.; Marechal, Matthieu

2018-03-01

We develop a density functional for hard particles with a smooth uniaxial shape (including non-inversion-symmetric particles) within the framework of fundamental measure theory. By applying it to a system of tapered, aspherical liquid-crystal formers, reminiscent of pears, we analyse their behaviour near a hard substrate. The theory predicts a complex orientational ordering close to the substrate, which can be directly related to the particle shape, in good agreement with our simulation results. Furthermore, the lack of particle inversion-symmetry implies the possibility of alternating orientations in subsequent layers as found in a smectic/lamellar phase of such particles. Both theory and Monte Carlo simulations confirm that such ordering occurs in our system. Our results are relevant for adsorption processes of asymmetric colloidal particles and molecules at hard interfaces and show once again that tapering strongly affects the properties of orientationally ordered phases.

Two-dimensional liquid crystalline growth within a phase-field-crystal model.

PubMed

Tang, Sai; Praetorius, Simon; Backofen, Rainer; Voigt, Axel; Yu, Yan-Mei; Wang, Jincheng

2015-07-01

By using a two-dimensional phase-field-crystal (PFC) model, the liquid crystalline growth of the plastic triangular phase is simulated with emphasis on crystal shape and topological defect formation. The equilibrium shape of a plastic triangular crystal (PTC) grown from an isotropic phase is compared with that grown from a columnar or smectic-A (CSA) phase. While the shape of a PTC nucleus in the isotropic phase is almost identical to that of the classical PFC model, the shape of a PTC nucleus in CSA is affected by the orientation of stripes in the CSA phase, and irregular hexagonal, elliptical, octagonal, and rectangular shapes are obtained. Concerning the dynamics of the growth process, we analyze the topological structure of the nematic order, which starts from nucleation of +1/2 and -1/2 disclination pairs at the PTC growth front and evolves into hexagonal cells consisting of +1 vortices surrounded by six satellite -1/2 disclinations. It is found that the orientational and the positional order do not evolve simultaneously; the orientational order evolves behind the positional order, leading to a large transition zone, which can span over several lattice spacings.

Drag of a Cottrell atmosphere by an edge dislocation in a smectic-A liquid crystal.

PubMed

Oswald, P; Lejček, L

2017-10-01

In a recent letter (P. Oswald et al., EPL 103, 46004 (2013)), we have shown that a smectic-A phase hardens in compression normal to the layers when the liquid crystal is doped with gold nanoparticles. This is due to the formation of Cottrell clouds nearby the core of the edge dislocations and the appearance of an additional drag force that reduces their mobility. We theoretically calculate the shape of the Cottrell cloud and the associated drag force as a function of the climb velocity of the dislocations. The main result is that the drag force depends on velocity and vanishes when the temperature tends to the smectic-A-to-nematic transition temperature. The role of the diffusion anisotropy is also evaluated.

Transient phases during fast crystallization of organic thin films from solution

NASA Astrophysics Data System (ADS)

Wan, Jing; Li, Yang; Ulbrandt, Jeffrey G.; Smilgies, Detlef-M.; Hollin, Jonathan; Whalley, Adam C.; Headrick, Randall L.

2016-01-01

We report an in situ microbeam grazing incidence X-ray scattering study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) organic semiconductor thin film deposition by hollow pen writing. Multiple transient phases are observed during the crystallization for substrate temperatures up to ≈93 °C. The layered smectic liquid-crystalline phase of C8-BTBT initially forms and preceedes inter-layer ordering, followed by a transient crystalline phase for temperature >60 °C, and ultimately the stable phase. Based on these results, we demonstrate a method to produce extremely large grain size and high carrier mobility during high-speed processing. For high writing speed (25 mm/s), mobility up to 3.0 cm2/V-s has been observed.

Calculation of electric field–temperature (E, T) phase diagram of a ferroelectric liquid crystal near the SmA–{SmC}}_{\\alpha }^{* } transition

NASA Astrophysics Data System (ADS)

Trabelsi, F.; Dhaouadi, H.; Riahi, O.; Othman, T.

2018-03-01

In this work we perform a theoretical calculation in order to reconstitute the (E–T) phase diagram of a chiral smectic liquid crystal in the vicinity of the SmA–{SmC}}α * transition. This reconstruction is carried out on the basis of a thermodynamic calculation of the slope of the curve joining the {SmC}}α * domain and the unwound SmC*. An empiric correction of the mean field term of Landau De-Gennes development is necessary to accomplish this reconstruction. Thereafter, an experimental validation is performed to verify our calculations.

Electroclinic effect in a chiral carbosilane-terminated 5-phenylpyrimidine liquid crystal with 'de Vries-like' properties.

PubMed

Schubert, Christopher P J; Müller, Carsten; Wand, Michael D; Giesselmann, Frank; Lemieux, Robert P

2015-08-14

The chiral carbosilane-terminated liquid crystal 2-[(2S,3S)-2,3-difluorohexyloxy]-5-[4-(12,12,14,14,16,16-hexamethyl-12,14,16-trisilaheptadecyloxy)phenyl]pyrimidine () undergoes a smectic A*-smectic C* phase transition with a maximum layer contraction of only 0.2%. It exhibits an electroclinic effect (ECE) comparable to that reported for the 'de Vries-like' liquid crystal and shows no appreciable optical stripe defects due to horizontal chevron formation.

Neutron scattering studies of molecular conformations in liquid crystal polymers

NASA Astrophysics Data System (ADS)

Noirez, L.; Moussa, F.; Cotton, J. P.; Keller, P.; Pépy, G.

1991-03-01

A comblike liquid crystal polymer (LPC) is a polymer on which mesogenic molecules have been grafted. It exhibits a succession of liquid crystal phases. Usually the equilibrium conformation of an ordinary polymeric chain corresponds to a maximum entropy, i.e., to an isotropic spherical coil. How does the backbone of a LCP behave in the nematic and smectic field? Small-angle neutron scattering may answer this question. Such measurements are presented here on four different polymers as a function of temperature. An anisotropy of the backbone conformation is found in all these studied compounds, much more pronounced in the smectic phase than in the nematic phase: the backbone spreads more or less perpendicularly to its hanging cores. A comparison with existing theories and a discussion of these results is outlined.

Infrared Transition Moment Directions in Smectic Liquid Crystals

NASA Astrophysics Data System (ADS)

Park, C. S.; Jang, W. G.; Coleman, D.; Glaser, M. A.; Clark, N. A.

1997-03-01

We have investigated the variation of absorbance with polarization for C=O, O-H, and phenyl stretch modes in aligned smectic liquid crystals, for IR radiation propagating parallel to the smectic layers. For the C=O stretch, maximum absorbance is generally observed for radiation polarized perpendicular to the layer normal in the smectic A phase, consistent with the assumption that the IR transition moment direction is coincident with the C=O bond (oriented at an angle of ~ 60^circ with respect to the molecular long axis). In certain cases, however, maximum absorbance is observed for incident polarization parallel to the layer normal, and in general observed dichroic ratios depend sensitively on the nature of the functional groups surrounding the carbonyl moiety. Similar chemical sensitivity is observed for the phenyl and O-H stretch modes. We have succeeding in interpreting these measurements by calculating IR transition moment directions for the most important vibrational modes of several model compounds using quantum chemical methods, including HF/6-311G SCF and B3LYP/6-311G and B3LYP/6-31G DFT calculations.

Effect of an electric field on the structural and optical properties of fluorinated freely suspended smectic films

NASA Astrophysics Data System (ADS)

Śliwa, I.; Zakharov, A. V.

2017-12-01

Within the framework of the generalized mean-field model that takes into account the anisotropic interactions between the nearest neighbors of molecules forming freely suspended smectic films (FSSFs) and the stabilizing effects of the smectic-A (SmA)-air interface, a numerical study was performed of the structural, thermodynamic, and optical properties of these systems in the process of their layer-by-layer thinning. The results of calculating the disjoining pressure P, the average thickness of the smectic layers L, and the reflectivity index R of a FSSF formed by 5- n-alkyl-2-(4- n-(perfluoroalkyl-methylene oxide)-pentyl) (H10F5MOPP) molecules showed that these values undergo precipitous changes in the process of layer-bylayer thinning of the film. Calculations of R( T) as a function of temperature T exceeding the phase transition temperature of SmA into an isotropic state in the bulk of the liquid crystal material are in good agreement with the experimentally obtained data for the reflectivity of the FSSF formed by H10F5MOPP molecules.

Structure of the Mesophases Formed by a Perfluoroalkyl/Biphenyl Compound. Amphiphilic and Steric Effects

NASA Astrophysics Data System (ADS)

Pensec, Sandrine; Tournilhac, François-Genès; Bassoul, Pierre

1996-11-01

We describe the synthesis and mesomorphic behaviour of 4-(1H,1H-perfluorooctyloxy)- 4'-methoxy biphenyl. Two mesophases of smectic E and smectic A types were observed. X-ray diffraction study of the smectic E phase indicates a herringbone arrangement of the biphenyl cores, the perfluoroalkyl chains being in a molten state. The {S_E to S_A} transition is related to the melting of the biphenyl sublattice. In both phases, the flexibility of perfluoroalkyl chains permits the area matching between the two segregated sublayers. Nous décrivons la synthèse et les propriétés mésomorphes du 4-(1H,1H-perfluorooctyloxy)- 4'-méthoxy biphényle. Ce composé forme deux mésophases de type smectique E et smectique A. L'analyse par diffraction des rayons X révèle, dans le cas de la phase smectique E un arrangement en chevrons des coeurs biphényles, les chaînes perfluoroalkyles se trouvant dans un état désordonné. La transition {S_E to S_A} correspond à la fusion partielle de la sous-couche biphényle. Dans les deux phases smectiques, la flexibilité des chaînes perfluoroalkyles permet l'adéquation des aires moléculaires entre les deux sous-couches ségrégées.

Influence of charge and flexibility on smectic phase formation in filamentous virus suspensions

NASA Astrophysics Data System (ADS)

Purdy, Kirstin R.; Fraden, Seth

2007-07-01

We present experimental measurements of the cholesteric-smectic phase transition of suspensions of charged semiflexible rods as a function of rod flexibility and surface charge. The rod particles consist of the bacteriophage M13 and closely related mutants, which are structurally identical to M13, but vary either in contour length and therefore ratio of persistence length to contour length, or surface charge. Surface charge is altered in two ways; by changing solution pH and by comparing M13 with fd virus, a virus which differs from M13 only by the substitution of a single charged amino acid for a neutral one per viral coat protein. Phase diagrams are measured as a function of particle length, particle charge, and ionic strength. The experimental results are compared with existing theoretical predictions for the phase behavior of flexible rods and charged rods.

Photopyroelectric Calorimetry Investigations of 8CB Liquid Crystal-Microemulsion System

NASA Astrophysics Data System (ADS)

Paoloni, S.; Zammit, U.; Mercuri, F.

2018-02-01

In this work, the photopyroelectric technique has been used to investigate the phase transitions in a liquid crystal microemulsion by combining the simultaneous high temperature resolution thermal diffusivity measurements and optical polarization microscopy observations. It has been found that, during the conversion from the isotropic phase into the nematic one, the micelles are expelled from the nematic domains and remain confined in islands of isotropic material which survive down to the smectic temperature range. A hysteresis in the thermal diffusivity profiles between heating and cooling run over the isotropic-nematic transition temperature range has been observed which has been ascribed to the different micelles distribution into the sample volume during cooling and heating runs. Finally, the almost bulk-like behavior of the thermal diffusivity over the nematic-smectic phase transition confirms that a significant fraction of the micelles are expelled during the nucleation of the nematic phase.

Space-inhomogeneous phase modulation of laser radiation in an electro-optical ferroelectric liquid crystal cell for suppressing speckle noise.

PubMed

Andreev, Alexander L; Andreeva, Tatiana B; Kompanets, Igor N; Zalyapin, Nikolay V

2018-02-20

Spatially inhomogeneous modulation of a phase delay with the depth of the order π or more makes it possible to destroy phase relations in a laser beam passing through an electro-optical cell with the ferroelectric liquid crystal (FLC) and, as a consequence, to suppress speckle noise in images formed by this beam. Such a modulation is a consequence of chaotic changes in the position of the scattering indicatrix of helix-free FLC, when an electro-optical cell is simultaneously supplied with a low-frequency and high-frequency bipolar control voltage. In this work, the phase modulation and effective suppressing of the speckles are realized using a new type of helix-free FLC material with periodic deformations of smectic layers.

Structural transitions and guest/host complexing of liquid crystal helical nanofilaments induced by nanoconfinement.

PubMed

Kim, Hanim; Ryu, Seong Ho; Tuchband, Michael; Shin, Tae Joo; Korblova, Eva; Walba, David M; Clark, Noel A; Yoon, Dong Ki

2017-02-01

A lamellar liquid crystal (LC) phase of certain bent-core mesogenic molecules can be grown in a manner that generates a single chiral helical nanofilament in each of the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. By introducing guest molecules into the resulting composite chiral nanochannels, we explore the structures and functionality of the ordered guest/host LC complex, verifying the smectic-like positional order of the fluidic nematic LC phase, which is obtained by the combination of the LC organization and the nanoporous AAO superstructure. The guest nematic LC 4'- n -pentyl-4-cyanobiphenyl is found to form a distinctive fluid layered ordered LC complex at the nanofilament/guest interface with the host 1,3-phenylene bis[4-(4-nonyloxyphenyliminomethyl)benzoate], where this interface contacts the AAO cylinder wall. Filament growth form is strongly influenced by mixture parameters and pore dimensions.

Structural transitions and guest/host complexing of liquid crystal helical nanofilaments induced by nanoconfinement

PubMed Central

Kim, Hanim; Ryu, Seong Ho; Tuchband, Michael; Shin, Tae Joo; Korblova, Eva; Walba, David M.; Clark, Noel A.; Yoon, Dong Ki

2017-01-01

A lamellar liquid crystal (LC) phase of certain bent-core mesogenic molecules can be grown in a manner that generates a single chiral helical nanofilament in each of the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. By introducing guest molecules into the resulting composite chiral nanochannels, we explore the structures and functionality of the ordered guest/host LC complex, verifying the smectic-like positional order of the fluidic nematic LC phase, which is obtained by the combination of the LC organization and the nanoporous AAO superstructure. The guest nematic LC 4′-n-pentyl-4-cyanobiphenyl is found to form a distinctive fluid layered ordered LC complex at the nanofilament/guest interface with the host 1,3-phenylene bis[4-(4-nonyloxyphenyliminomethyl)benzoate], where this interface contacts the AAO cylinder wall. Filament growth form is strongly influenced by mixture parameters and pore dimensions. PMID:28246642

Computational aspects of the smectization process in liquid crystals: An example study of a perfectly aligned two-dimensional hard-boomerang system

NASA Astrophysics Data System (ADS)

Chrzanowska, Agnieszka

2017-06-01

A replica method for calculation of smectic liquid crystal properties within the Onsager theory has been presented and applied to an exemplary case of two-dimensional perfectly aligned needlelike boomerangs. The method allows one to consider the complete influence of the interaction terms in contrast to the Fourier expansion method which uses mostly first or second order terms of expansion. The program based on the replica algorithm is able to calculate a single representative layer as an equivalent set of layers, depending on the size of the considered width of the sample integration interval. It predicts successfully smectic density distributions, energies, and layer thicknesses for different types of layer arrangement—of the antiferroelectric or of the smectic A order type. Specific features of the algorithm performance and influence of the numerical accuracy on the physical properties are presented. Future applications of the replica method to freely rotating molecules are discussed.

Computational aspects of the smectization process in liquid crystals: An example study of a perfectly aligned two-dimensional hard-boomerang system.

PubMed

Chrzanowska, Agnieszka

2017-06-01

A replica method for calculation of smectic liquid crystal properties within the Onsager theory has been presented and applied to an exemplary case of two-dimensional perfectly aligned needlelike boomerangs. The method allows one to consider the complete influence of the interaction terms in contrast to the Fourier expansion method which uses mostly first or second order terms of expansion. The program based on the replica algorithm is able to calculate a single representative layer as an equivalent set of layers, depending on the size of the considered width of the sample integration interval. It predicts successfully smectic density distributions, energies, and layer thicknesses for different types of layer arrangement-of the antiferroelectric or of the smectic A order type. Specific features of the algorithm performance and influence of the numerical accuracy on the physical properties are presented. Future applications of the replica method to freely rotating molecules are discussed.

Xenon NMR of liquid crystals confined to cylindrical nanocavities: a simulation study.

PubMed

Karjalainen, Jouni; Vaara, Juha; Straka, Michal; Lantto, Perttu

2015-03-21

Applications of liquid crystals (LCs), such as smart windows and the ubiquitous display devices, are based on controlling the orientational and translational order in a small volume of LC medium. Hence, understanding the effects of confinement to the liquid crystal phase behaviour is essential. The NMR shielding of (129)Xe atoms dissolved in LCs constitutes a very sensitive probe to the details of LC environment. Linking the experimental results to microscopic phenomena calls for molecular simulations. In this work, the NMR shielding of atomic (129)Xe dissolved in a uniaxial thermotropic LC confined to nanosized cylindrical cavities is computed from coarse-grained (CG) isobaric Monte Carlo (MC) simulations with a quantum-chemically (QC) pre-parameterised pairwise-additive model for the Xe nuclear shielding tensor. We report the results for the (129)Xe nuclear shielding and its connection to the structure and order of the LC appropriate to two different cavity sizes, as well as a comparison to the results of bulk (non-confined) simulations. We find that the confinement changes the LC phase structure dramatically and gives rise to the coexistence of varying degrees of LC order, which is reflected in the Xe shielding. Furthermore, we qualitatively reproduce the behaviour of the mean (129)Xe chemical shift with respect to temperature for atomic Xe dissolved in LC confined to controlled-pore glass materials. In the small-radius cavity the nematic - paranematic phase transition is revealed only by the anisotropic component of the (129)Xe nuclear shielding. In the larger cavity, the nematic - paranematic - isotropic transition is clearly seen in the Xe shielding. The simulated (129)Xe NMR shielding is insensitive to the smectic-A - nematic transition, since in the smectic-A phase, the Xe atoms largely occupy the imperfect layer structure near the cavity walls. The direct contribution of the cavity wall to (129)Xe nuclear shielding is dependent on the cavity size but independent of temperature. Our results show that the combination of CG simulations and a QC pre-parameterised (129)Xe NMR shielding allows efficient studies of the phase behaviour and structure of complex systems containing thousands of molecules, and brings us closer to the simulation of NMR experiments.

Examination of new chiral smectics with four aromatic rings

NASA Astrophysics Data System (ADS)

Żurowska, Magdalena; Czerwiński, Michał; Dziaduszek, Jerzy; Filipowicz, Marek

2018-05-01

This paper presents the results of the study of four chiral mesogens with the acronym (4X1X2). The investigated compounds might be of interest for use as components of multicomponent mixtures useful in technical devices. The compounds have high chemical stability. Their mesomorphic properties were tested by means of polarizing optical microscopy and differential scanning calorimetry. The helical pitch of the prepared compounds and mixtures was estimated using the selective reflection method. Their phase smectic layer structure and usefulness for formulation of multicomponent antiferroelectric mixtures were then reported.

Inclusions in freely suspended smectic films

NASA Astrophysics Data System (ADS)

Stannarius, Ralf; Harth, Kirsten

Smectic liquid crystal phases have a unique property: Like soap solutions, they can form stable freely suspended films. Their aspect ratios can be larger than one million to one. Such films can serve as models for two-dimensional (2D) uids, with or without in-plane anisotropy. Solid or liquid inclusions trapped in these films by capillary forces can move in the film plane and interact with other inclusions, with film thickness gradients or the film boundaries, and even with the local orientation field. We describe preparation techniques to incorporate particles or droplets in thin smectic films, and optical observation methods. Several aspects make inclusions in freely suspended films interesting research objects: They provide rich information on capillary forces as well as surface and interfacial tensions, they can serve as platforms for hydrodynamic studies in 2D, and they may help to understand coalescence dynamics at the transition from 2D to 3D...

Physical properties of new binary antiferroelectric liquid crystal mixtures

NASA Astrophysics Data System (ADS)

Fitas, Jakub; Jaworska-Gołąb, Teresa; Deptuch, Aleksandra; Tykarska, Marzena; Kurp, Katarzyna; Żurowska, Magdalena; Marzec, Monika

2018-02-01

Three newly prepared binary mixtures exhibiting chiral tilted smectic phases have been studied using differential scanning calorimetry, dielectric spectroscopy and electro-optic method, as well as X-ray diffraction. Broad temperature range of ferroelectric and antiferroelectric phases was detected in these mixtures and temperature dependence of spontaneous polarization, tilt angle and switching time were measured for all of them. It's occurred that all of the studied mixtures are orthoconic antiferroelectric liquid crystals. Based on the X-ray diffraction results, the temperature dependence of layer thickness in the paraelectric, ferroelectric and antiferroelectric phases was found. By using dielectric spectroscopy, Goldstone mode was identified in the ferroelectric phase, while antiphase fluctuations of azimuthal angle have been found in the antiferroelectric phase. Based on the results of the complementary methods, the transition temperatures were found as well as the order of the para-ferroelectric phase transition was determined as non-continuous one with critical parameter β equal to ca. 0.25.

An Avoidance Model for Short-Range Order Induced by Soft Repulsions in Systems of Rigid Rods

NASA Astrophysics Data System (ADS)

Han, Jining; Herzfeld, Judith

1996-03-01

The effects of soft repulsions on hard particle systems are calculated using an avoidance model which improves upon the simple mean field approximation. Avoidance reduces, but does not eliminate, the energy due to soft repulsions. On the other hand, it also reduces the configurational entropy. Under suitable conditions, this simple trade-off yields a free energy that is lower than the mean field value. In these cases, the variationally determined avoidance gives an estimate for the short-range positional order induced by soft repulsions. The results indicate little short-range order for isotropically oriented rods. However, for parallel rods, short-range order increases to significant levels as the particle axial ratio increases. The implications for long- range positional ordering are also discussed. In particular, avoidance may explain the smectic ordering of tobacco mosaic virus at volume fractions lower than those necessary for smectic ordering of hard particles.

Smectic Layer Origami via Preprogrammed Photoalignment.

PubMed

Ma, Ling-Ling; Tang, Ming-Jie; Hu, Wei; Cui, Ze-Qun; Ge, Shi-Jun; Chen, Peng; Chen, Lu-Jian; Qian, Hao; Chi, Li-Feng; Lu, Yan-Qing

2017-04-01

Hierarchical architecture is of vital importance in soft materials. Focal conic domains (FCDs) of smectic liquid crystals, characterized by an ordered lamellar structure, attract intensive attention. Simultaneously tailoring the geometry and clustering characteristics of FCDs remains a challenge. Here, the 3D smectic layer origami via a 2D preprogrammed photoalignment film is accomplished. Full control of hierarchical superstructures is demonstrated, including the domain size, shape, and orientation, and the lattice symmetry of fragmented toric FCDs. The unique symmetry breaking of resultant superstructures combined with the optical anisotropy of the liquid crystals induces an intriguing polarization-dependent diffraction. This work broadens the scientific understanding of self-assembled soft materials and may inspire new opportunities for advanced functional materials and devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quasi-elastic neutron scattering study of a re-entrant side-chain liquid-crystal polyacrylate

NASA Astrophysics Data System (ADS)

Benguigui, L.; Noirez, L.; Kahn, R.; Keller, P.; Lambert, M.; Cohen de Lara, E.

1991-04-01

We present a first investigation of the dynamics of a side chain liquid crystal polyacrylate in the isotropic (I), nematic (N), smectic A (SA), and re-entrant nematic (NRe) phases by means of quasi-elastic neutron scattering. The motion or/and the mobility of the mesogen protons decreases as soon as the temperature decreases after the isotropic-nematic transition. The I-N and SA-NRe transitions corrspond to a jump in the curve of the Elastic Incoherent Structure Factor (ratio: elastic scattering/ total scattering) versus temperature, on the other hand the transition N-SA occurs without any change of slope. We conclude that the local order is very similar in the nematic and the smectic A phases. Nous présentons une première étude dynamique par diffusion quasi-élastique des neutrons, d'un échantillon de polyacrylate mésomorphe en peigne dans chacune des phases : isotrope, nématique, smectique et nématique rentrante. On montre que le mouvement et/ou la mobilité des protons du mésogène se restreint à mesure que la température diminue après la transition isotrope-nématique. Contrairement à la transition N-SA, les transitions I-N et SA-NRe correspondent à une discontinuité dans la courbe du Facteur de Structure Incohérent Elastique (rapport : intensité élastique/intensité totale) en fonction de la température ; l'ordre local semble donc très proche pour les phases nématique et smectique.

Mechanism of smectic arrangement of montmorillonite and bentonite clay platelets incorporated in gels of poly(acrylamide) induced by the interaction with cationic surfactants.

PubMed

Starodoubtsev, S G; Lavrentyeva, E K; Khokhlov, A R; Allegra, G; Famulari, A; Meille, S V

2006-01-03

Structure transitions, induced by the interaction with the cationic surfactant cetylpyridinium chloride in nanocomposite gels of poly(acrylamide) with incorporated suspensions of the two closely related layered clays bentonite and montmorillonite, were studied. Unexpectedly, different behaviors were revealed. X-ray diffraction measurements confirm that, due to the interaction with the surfactant, initially disordered bentonite platelets arrange into highly ordered structures incorporating alternating clay platelets and surfactant bilayers. The formation of these smectic structures also in the cross-linked polymer gels, upon addition of the surfactant, is explained by the existence of preformed, poorly ordered aggregates of the clay platelets in the suspensions before the gel formation. In the case of montmorillonite, smectic ordering of the disordered platelets in the presence of the surfactant is observed only after drying the suspensions and the clay-gel composites. Rheology studies of aqueous suspensions of the two clays, in the absence of both surfactant and gel, evidence a much higher viscosity for bentonite than for montmorillonite, suggesting smaller clay-aggregate size in the latter case. Qualitatively consistent results are obtained from optical micrographs.

Effect of Barium Titanate Particles on Dielectric and Electro-Optical Properties of a Smectic-a Liquid Crystal

NASA Astrophysics Data System (ADS)

Ramazanov, M. A.; Imamaliyev, A. R.; Humbatov, Sh. A.; Agamaliev, Z. A.

2018-02-01

The effect of submicron ferroelectric BaTiO3 particles on the dielectric and electro-optical properties of the smectic-A liquid crystal (LC) with a high negative dielectric anisotropy is investigated. It is shown that the addition of BaTiO3 particles with a weight amount of 1% reduces insignificantly the transverse dielectric permittivity component ɛ ⊥ of, but significantly increases the longitudinal dielectric permittivity component ɛ // of the smectic-A LC. As a result, the anisotropy of the dielectric permittivity Δɛ = ɛ // - ɛ ⊥ of the smectic-A LC decreases. The addition of BaTiO3 particles shifts the dispersion ɛ ⊥ toward lower frequencies. Both components of the electrical conductivity of LC colloid + BaTiO3 are an order of magnitude higher than of the pure LC. The threshold voltage of the homeotropic-planar transition of the colloid is twice smaller, and its velocity is 6 times higher in comparison with the pure LC. A simple model explaining qualitatively all results obtained is presented.

Homomorphic filtering textural analysis technique to reduce multiplicative noise in the 11Oba nano-doped liquid crystalline compounds

NASA Astrophysics Data System (ADS)

Madhav, B. T. P.; Pardhasaradhi, P.; Manepalli, R. K. N. R.; Pisipati, V. G. K. M.

2015-07-01

The compound undecyloxy benzoic acid (11Oba) exhibits nematic and smectic-C phases while a nano-doped undecyloxy benzoic acid with ZnO exhibits the same nematic and smectic-C phases with reduced clearing temperature as expected. The doping is done with 0.5% and 1% ZnO molecules. The clearing temperatures are reduced by approximately 4 ° and 6 °, respectively (differential scanning calorimeter data). While collecting the images from a polarizing microscope connected with hot stage and camera, the illumination and reflectance combined multiplicatively and the image quality was reduced to identify the exact phase in the compound. A novel technique of homomorphic filtering is used in this manuscript through which multiplicative noise components of the image are separated linearly in the frequency domain. This technique provides a frequency domain procedure to improve the appearance of an image by gray level range compression and contrast enhancement.

Crystalline smectic E phase revisited in case of symmetrical dibenzo-18-crown-6-ether azomethine dimers

NASA Astrophysics Data System (ADS)

Cozan, Vasile; Ardeleanu, Rodinel; Airinei, Anton; Timpu, Daniel

2018-03-01

Three symmetric azomethine dimers having dibenzo-18-crown-6-ether as internal moiety and halogens (F, Cl, Br) as terminal functional groups were synthesized and characterized by FTIR and 1H NMR spectroscopy. Their thermal behavior was investigated by polarized optical microscopy (POM) and DSC techniques. Interesting textures have been observed at cooling by POM as being representative for a soft crystalline smectic phase. X-ray diffraction measurements in powder at room temperature exhibited a map of reflections corresponding to crystal E phase. The influence of molecular parameters (interdigitation parameter γ, dipole moment, molecular polarizability, halogen radius) on thermal behavior was discussed. The UV-Vis investigations allowed evaluation of photostability and a bathochromic effect was noticed with the increasing of halogen atom radius. Also the values of optical band gap (Eg) are higher than those corresponding to conjugated Schiff bases.

Reversibility of temperature driven discrete layer-by-layer formation of dioctyl-benzothieno-benzothiophene films.

PubMed

Dohr, M; Ehmann, H M A; Jones, A O F; Salzmann, I; Shen, Q; Teichert, C; Ruzié, C; Schweicher, G; Geerts, Y H; Resel, R; Sferrazza, M; Werzer, O

2017-03-22

Film forming properties of semiconducting organic molecules comprising alkyl-chains combined with an aromatic unit have a decisive impact on possible applications in organic electronics. In particular, knowledge on the film formation process in terms of wetting or dewetting, and the precise control of these processes, is of high importance. In the present work, the subtle effect of temperature on the morphology and structure of dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) films deposited on silica surfaces by spin coating is investigated in situ via X-ray diffraction techniques and atomic force microscopy. Depending on temperature, bulk C8-BTBT exhibits a crystalline, a smectic A and an isotropic phase. Heating of thin C8-BTBT layers at temperatures below the smectic phase transition temperature leads to a strong dewetting of the films. Upon approaching the smectic phase transition, the molecules start to rewet the surface in the form of discrete monolayers with a defined number of monolayers being present at a given temperature. The wetting process and layer formation is well defined and thermally stable at a given temperature. On cooling the reverse effect is observed and dewetting occurs. This demonstrates the full reversibility of the film formation behavior and reveals that the layering process is defined by an equilibrium thermodynamic state, rather than by kinetic effects.

Voltage noise of current-driven vortices in disordered Josephson junction arrays.

PubMed

He, G L; Zhao, Z G; Liu, S; Yang, Y H; Liu, M; Xing, D Y

2006-08-16

Dynamical phenomena of moving vortices and voltage noise spectra are studied in disordered Josephson junction arrays (JJAs). The plastic motion of vortices, smectic flow, and moving Bragg glass phases are separated by two dynamic melting transitions driven by current. From the voltage noise spectra of moving vortices, it is found that the driving current plays an important role in the melting of pinning vortices glass and ordering of moving vortices. The features of noise spectra obtained in the disordered JJA model have been observed recently in the high-temperature superconductor Bi(2)Sr(2)CaCu(2)O(y) near the first-order melting transition, indicating that both of them are related to each other.

The global phase diagram of the Gay-Berne model

NASA Astrophysics Data System (ADS)

de Miguel, Enrique; Vega, Carlos

2002-10-01

The phase diagram of the Gay-Berne model with anisotropy parameters κ=3, κ'=5 has been evaluated by means of computer simulations. For a number of temperatures, NPT simulations were performed for the solid phase leading to the determination of the free energy of the solid at a reference density. Using the equation of state and free energies of the isotropic and nematic phases available in the existing literature the fluid-solid equilibrium was calculated for the temperatures selected. Taking these fluid-solid equilibrium results as the starting points, the fluid-solid equilibrium curve was determined for a wide range of temperatures using Gibbs-Duhem integration. At high temperatures the sequence of phases encountered on compression is isotropic to nematic, and then nematic to solid. For reduced temperatures below T=0.85 the sequence is from the isotropic phase directly to the solid state. In view of this we locate the isotropic-nematic-solid triple point at TINS=0.85. The present results suggest that the high-density phase designated smectic B in previous simulations of the model is in fact a molecular solid and not a smectic liquid crystal. It seems that no thermodynamically stable smectic phase appears for the Gay-Berne model with the choice of parameters used in this work. We locate the vapor-isotropic liquid-solid triple point at a temperature TVIS=0.445. Considering that the critical temperatures is Tc=0.473, the Gay-Berne model used in this work presents vapor-liquid separation over a rather narrow range of temperatures. It is suggested that the strong lateral attractive interactions present in the Gay-Berne model stabilizes the layers found in the solid phase. The large stability of the solid phase, particularly at low temperatures, would explain the unexpectedly small liquid range observed in the vapor-liquid region.

Mesomorphism of Newly Synthesized Mesogens and Surface Morphology of Chalcogenide Glass Thin Films

NASA Astrophysics Data System (ADS)

Sharpnack, Lewis Lee

This dissertation research describes three related projects. The first was an investigation of two de Vries smectic liquid crystal phases that exhibit lower thermal dependence of the smectic layer spacing than the corresponding conventional smectic phases and are well suited for use in electrooptical devices. The second project studied newly synthesized mesogens. This included investigations of several liquid crystalline semiconducting mesogens and a multitude of candidate de Vries smectic mesogens. The third was an investigation of a new non-contact alignment layer of Arsenic Sulfide (As2S 3) to anchor the liquid director and use in electrooptical device. In additional to preliminary characterization methodologies such as polarizing optical microscopy and differential scanning calorimetry, two experimental techniques, X-ray diffraction (XRD) and X-ray reflectivity (XRR), were employed. The X-ray studies were conducted using the in-house spectrometers at Kent State University and the synchrotron X-ray source at the Brookhaven National Laboratory. XRR is used to investigate the structure of potential alignment layers. The results provide important insight into the challenges that need to be overcome to develop this alignment material into a viable commercial product. XRD is used to study the structural properties of several members of two new homologous series of liquid crystal compounds. The study of de Vries materials advances our understanding of the role of various molecular moieties on their phase behavior and, most importantly, their relatively temperature independent layer spacing in the Smectic A (SmA) and Smectic C (SmC) phases. This nearly constant layer spacing is critical for developing new fast ferroelectric and electroclinic effect based displays. The Stevenson research group at Queens University synthesized a multitude of new mesogens incorporating a siloxane tail at one end. This moiety is believed to enhance nano-segregation of the molecules and help form de Vries smectic A and C phases. The results indicate that some of the new mesogens exhibit low layer shrinkage that is indicative of the de Vries behavior. The effects of chain lengths and various moieties on the phase behavior is described in detail. These experiments identified several chiral mesogens as viable candidates for use in ferroelectric displays that are currently the subject of further investigations. Many of the non-chiral molecules studied exhibited de Vries or nearly de Vries layer shrinkage, however, these systems would require the addition of a chiral dopant to be used in ferroelectric applications. Three of the chiral siloxane based mesogens displayed ideal de Vries behavior. The smectic layer spacing changed by 1% or less of the total layer thickness for Si3OK11BPO*, Si3OK11BzPO*, and adpc042. These molecules are presently being investigated for device applications and modified with various terminal groups to enhance the miscibility of nano-particle dopants. Structural studies of novel triphenlyene based organic semiconductors mesogens synthesized by the Twieg group were performed. A desirable trait of organic semiconductors is for the pi-electron orbitals to overlap and requires that carbon rings in adjacent molecules be parallel. Results of X-ray studies of a series of triphenylene molecules showed a hexagonal columnar (ColHex) phase. The diffraction patterns revealed that the lateral intermolecular distance was 3.5 A, consistent with the stacking of the triphenelene rings. The high-temperature ColHex phase of these materials at nearly 200 °C may also prove useful for high temperature applications. Films of As2S3 have recently been shown to align liquid crystals. This alignment technique, when fully developed, will eliminate the need for traditional mechanically buffed polymer films deposited on substrates, currently used in liquid crystal displays. Their surface roughness was determined in the two planar directions using x-ray reflectivity profiles to facilitate a comparison with other alignment layers that generate liquid crystal alignment primarily because of their anisotropic surface morphology. Our results reveal that As2S3 films develop anisotropic features under irradiation with polarized blue light that are consistent with the changes that occur in other alignment layers when they are "treated" either with mechanical buffing of polymer films or exposure to linearly polarized UV light. These studies also reveal the development of an extensive oxide layer and the ablation of the film under ambient conditions owing to the absorption of oxygen and moisture. This represents a significant barrier to their commercial applications.

Assessment by Monte Carlo computer simulations of the phase behavior of hard spherocylinders confined within cylindrical cavities.

PubMed

Viveros-Méndez, Perla X; Gil-Villegas, Alejandro; Aranda Espinoza, Said

2017-12-21

The phase behavior of hard spherocylinders (HSCs) confined in cylindrical cavities is studied using Monte Carlo simulations in the canonical ensemble. Results are presented for different values of the particles' aspect ratio l/σ, where l and σ are the length and diameter of the cylinder and hemispherical caps, respectively. Finite cavities with periodic boundary conditions along the principal axis of the cavities have been considered, where the cavity's principal axis is along the z-direction. We first focus our study in the structure induced by varying the degree of confinement, determining the HSC phase diagram for aspect ratios l/σ = 3, 5, 7, and 9, at a fixed packing fraction η = 0.071. By compressing the cavities along the radial direction, the isotropic phase becomes stable before the nematic phase as the length of the cavities is increased, resulting in a second-order transition. The occurrence of phase transitions has also been determined by varying η for constant values of the cavity's length L. Systems with low aspect ratios, l/σ = 3, 5, 7, and 9, exhibit first-order transitions with chiral, paranematic, and isotropic phases, whereas for larger HSCs, l/σ = 50, 70, and 100, the transitions are second order with paranematic, nematic, and isotropic phases, in contrast with the behavior of non-confined systems, with first-order transitions for isotropic, nematic, smectic-A, and solid phases.

Wigner function and the successive measurement of position and momentum

NASA Astrophysics Data System (ADS)

Beller, Daniel A.; Gharbi, Mohamed A.; Honglawan, Apiradee; Stebe, Kathleen J.; Yang, Shu; Kamien, Randall D.

2013-10-01

Focal conic domains (FCDs) in smectic-A liquid crystals have drawn much attention, both for their exquisitely structured internal form and for their ability to direct the assembly of micromaterials and nanomaterials in a variety of patterns. A key to directing FCD assembly is control over the eccentricity of the domain. Here, we demonstrate a new paradigm for creating spatially varying FCD eccentricity by confining a hybrid-aligned smectic with curved interfaces. In particular, we manipulate interface behavior with colloidal particles in order to experimentally produce two examples of what has recently been dubbed the flower texture [C. Meyer , Focal Conic Stacking in Smectic A Liquid Crystals: Smectic Flower and Apollonius Tiling, Materials 2, 499, 2009MATEG91996-194410.3390/ma2020499], where the focal hyperbolæ diverge radially outward from the center of the texture, rather than inward as in the canonical éventail or fan texture. We explain how this unconventional assembly can arise from appropriately curved interfaces. Finally, we present a model for this system that applies the law of corresponding cones, showing how FCDs may be embedded smoothly within a “background texture” of large FCDs and concentric spherical layers, in a manner consistent with the qualitative features of the smectic flower. Such understanding could potentially lead to disruptive liquid-crystal technologies beyond displays, including patterning, smart surfaces, microlens arrays, sensors, and nanomanufacturing.

Anomalous temperature dependence of layer spacing of de Vries liquid crystals: Compensation model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merkel, K.; Kocot, A.; Vij, J. K., E-mail: jvij@tcd.ie

Smectic liquid crystals that exhibit temperature independent layer thickness offer technological advantages for their use in displays and photonic devices. The dependence of the layer spacing in SmA and SmC phases of de Vries liquid crystals is found to exhibit distinct features. On entering the SmC phase, the layer thickness initially decreases below SmA to SmC (T{sub A–C}) transition temperature but increases anomalously with reducing temperature despite the molecular tilt increasing. This anomalous observation is being explained quantitatively. Results of IR spectroscopy show that layer shrinkage is caused by tilt of the mesogen's rigid core, whereas the expansion is causedmore » by the chains getting more ordered with reducing temperature. This mutual compensation arising from molecular fragments contributing to the layer thickness differs from the previous models. The orientational order parameter of the rigid core of the mesogen provides direct evidence for de Vries cone model in the SmA phase for the two compounds investigated.« less

Smectic layer instabilities in liquid crystals.

PubMed

Dierking, Ingo; Mitov, Michel; Osipov, Mikhail A

2015-02-07

Scientists aspire to understand the underlying physics behind the formation of instabilities in soft matter and how to manipulate them for diverse investigations, while engineers aim to design materials that inhibit or impede the nucleation and growth of these instabilities in critical applications. The present paper reviews the field-induced rotational instabilities which may occur in chiral smectic liquid-crystalline layers when subjected to an asymmetric electric field. Such instabilities destroy the so-named bookshelf geometry (in which the smectic layers are normal to the cell surfaces) and have a detrimental effect on all applications of ferroelectric liquid crystals as optical materials. The transformation of the bookshelf geometry into horizontal chevron structures (in which each layer is in a V-shaped structure), and the reorientation dynamics of these chevrons, are discussed in details with respect to the electric field conditions, the material properties and the boundary conditions. Particular attention is given to the polymer-stabilisation of smectic phases as a way to forbid the occurrence of instabilities and the decline of related electro-optical performances. It is also shown which benefit may be gained from layer instabilities to enhance the alignment of the liquid-crystalline geometry in practical devices, such as optical recording by ferroelectric liquid crystals. Finally, the theoretical background of layer instabilities is given and discussed in relation to the experimental data.

Influence of the strength of the smectic order on the backbone anisotropy of side-chain liquid crystal polymers as revealed by SANS

NASA Astrophysics Data System (ADS)

Noirez, L.; Keller, P.; Cotton, J. P.

1992-06-01

It is proposed that the strength of the smectic order determines the backbone anisotropy of side-chain liquid crystal polymers. Here this strength increases with the length of the alkyl terminal group of the mesogens. Two liquid crystal polymethacrylates differing only by the mesogenic tails —OCH3 and —OC4H9 are considered. The backbone anisotropy of these polymers is measured by small angle neutron scattering (SANS) whereas the smectic order is evaluated from the intensity of the 001 Bragg peak. Il est proposé que la qualité de l'ordre smectique détermine l'anisotropie du squelette de polymères mésomorphes en peigne confinés dans les lamelles. Ici l'ordre smectique est augmenté en allongeant le groupe alkyl terminal des mésogènes. Nous étudions deux polyméthacrylates cristal liquide qui ne différent que par leurs groupes terminaux : —OCH3 et —OC4H9. L'anisotropie du squellete est mesurée par diffusion de neutrons aux petits angles tandis que l'ordre smectique est évalué à l'aide de l'intensité du pic de Bragg 001.

Wholly Aromatic Ether-imides. Potential Materials for n-Type Semiconductors

NASA Technical Reports Server (NTRS)

Dingemans, Theo J.; St.Clair, Terry L.; Samulski, Edward T.; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

We report on the synthesis and characterization of a novel series low-molar-mass ether-imide rod-shaped model compounds. All ether-imides were obtained by terminating the appropriate rigid core dianhydride, i.e. pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 3,3,4,4'-oxydiphthalic dianhydride (ODPA) with three flexible aryl-ether tails of different chain length. The mono-functional aryl-ether amines, i.e. 4-(3-phenoxy-phenoxy)-phenylamine (2) and 4-(3-phenoxy-3-phenoxy-phenoxy)-phenylamine (4), were synthesized using standard fluoro-displacement and Ullmann condensation techniques. The corresponding ether-imide model compounds were obtained in high yields using a one-step solution imidization procedure. Increasing the number of meta-substituted aryl-ether units reduces the melt transition temperatures and at the same time it increases the solubility of the model compounds. Most model compounds are crystalline solids and form isotropic melts upon heating. 2,7-Bis-(-4-phenoxy-phenyl)-benzo[Imn][3,8]phenanthroline1,3,6,8-tetraone (NDA-n0), however, displays a smectic A (SA) when cooled from the isotropic phase, followed by what appears to be either a highly ordered smectic phase or a, columnar phase. This is the first example, known to date, in which a mesophase is detected in a wholly aromatic ether-imide compound. For all compounds we present spectroscopic data and X-ray diffraction data. Cyclic voltammetry was used to determine the redox behavior and pertinent energy levels of the model compounds.

From viscous to elastic sheets: Dynamics of smectic bubbles

NASA Astrophysics Data System (ADS)

Harth, Kirsten; Trittel, Torsten; van der Meer, Devaraj; Stannarius, Ralf

2015-11-01

Oscillations and rupture of bubbles composed of an inner fluid separated from an outer fluid by a membrane, represent an old but still immensely active field of research. Membrane properties apart from surface tension are often neglected for fluids (e.g. soap bubbles), whereas they govern the dynamics in systems with a rigid membrane (e.g. vesicles). Due to their layered phase structure, smectic liquid crystals can form stable, uniform and easy-to-handle fluid films of immense aspect ratios. Only recently, freely floating bubbles detached from a support could be prepared. We analyze their relaxation from strongly non-spherical shapes and the rupture using high-speed video recordings. Peculiar dynamics intermediate between simple viscous fluid films and an elastic response are observed: Fast oscillations, slowed relaxation and even the reversible formation of wrinkles and extrusions. Bubble rupture deviates qualitatively from previously observed behavior of simple Newtonian and other complex fluids. It becomes retarded by at least two orders of magnitude compared to the predictions of Taylor and Culick. A transition between fluid-like and elastic behavior is seen with increasing thickness. We give experimental results, an intuitive explanation and a novel hydrodynamic description.

OASIS Observation and Analysis of Smectic Islands in Space

NASA Technical Reports Server (NTRS)

Tin, Padetha

2014-01-01

The Observation and Analysis of Smectic Islands in Space (OASIS) project comprises a series of experiments that will probe the interfacial and hydrodynamic behavior of freely suspended liquid crystal films in space. These are the thinnest known stable condensed phase structures, making them ideal for studies of fluctuation and interface phenomena. The experiments seek to verify theories of coarsening dynamics, hydrodynamic flow, relaxation of hydrodynamic perturbations, and hydrodynamic interactions of a near two-dimensional structure. The effects of introducing islands or droplets on a very thin bubble will be studied, both as controllable inclusions that modify the flow and as markers of flow.

The finite-size effect in thin liquid crystal systems

NASA Astrophysics Data System (ADS)

Śliwa, I.

2018-05-01

Effects of surface ordering in liquid crystal systems confined between cell plates are of great theoretical and experimental interest. Liquid crystals introduced in thin cells are known to be strongly stabilized and ordered by cell plates. We introduce a new theoretical method for analyzing the effect of surfaces on local molecular ordering in thin liquid crystal systems with planar geometry of the smectic layers. Our results show that, due to the interplay between pair long-range intermolecular forces and nonlocal, relatively short-range, surface interactions, both orientational and translational orders of liquid crystal molecules across confining cells are very complex. In particular, it is demonstrated that the SmA, nematic, and isotropic phases can coexist. The phase transitions from SmA to nematic, as well as from nematic to isotropic phases, occur not simultaneously in the whole volume of the system but begin to appear locally in some regions of the LC sample. Phase transition temperatures are demonstrated to be strongly affected by the thickness of the LC system. The dependence of the corresponding shifts of phase transition temperatures on the layer number is shown to exhibit a power law character. This new type of scaling behavior is concerned with the coexistence of local phases in finite systems. The influence of a specific character of interactions of molecules with surfaces and other molecules on values of the resulting critical exponents is also analyzed.

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

NASA Astrophysics Data System (ADS)

Tomi, Ivan H. R.; Jaffer, Hamed J.; Aldhaif, Yasmeen A.

2018-04-01

A homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IVn), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1-10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.

Structure-property relations in siloxane-based main chain liquid crystalline elastomers and related linear polymers

NASA Astrophysics Data System (ADS)

Ren, Wanting

2007-12-01

Soft materials have attracted much scientific and technical interest in recent years. In this thesis, attention has been placed on the underpinning relations between molecular structure and properties of one type of soft matter---main chain liquid crystalline elastomers (MCLCEs), which may have application as shape memory or as auxetic materials. In this work, a number of siloxane-based MCLCEs and their linear polymer analogues (MCLCEs) with chemical variations were synthesized and examined. Among these chemical variations, rigid p-phenylene transverse rod and flat-shaped anthraquinone (AQ) mesogenic monomers were specifically incorporated. Thermal and X-ray analysis found a smectic C phase in most of our MCLCEs, which was induced by the strong self-segregation of siloxane spacers, hydrocarbon spacers and mesogenic rods. The smectic C mesophase of the parent LCE was not grossly affected by terphenyl transverse rods. Mechanical studies of MCLCEs indicated the typical three-region stress-strain curve and a polydomain-to-monodomain transition. Strain recovery experiments of MCLCEs showed a significant dependence of strain retentions on the initial strains but not on the chemical variations, such as the crosslinker content and the lateral substituents on mesogenic rods. The MCLCE with p-phenylene transverse rod showed a highly ordered smectic A mesophase at room temperature with high stiffness. Mechanical properties of MCLCEs with AQ monomers exhibit a strong dependence on the specific combination of hydrocarbon spacer and siloxane spacer, which also strongly affect the formation of pi-pi stacking between AQ units. Poisson's ratio measurement over a wide strain range found distinct trends of Poisson's ratio as a function of the crosslinker content as well as terphenyl transverse rod loadings in its parent MCLCEs.

From viscous to elastic sheets: Dynamics of smectic freely floating films

NASA Astrophysics Data System (ADS)

Stannarius, Ralf; Harth, Kirsten; May, Kathrin; Trittel, Torsten

The dynamics of droplets and bubbles, particularly on microscopic scales, are of considerable importance in biological, environmental, and technical contexts. Soap bubbles, vesicles and components of biological cells are well known examples where the dynamic behavior is significantly influenced by the properties of thin membranes enclosed by fluids. Two-dimensional membrane motions couple to 3D shape transformations. Smectic liquid crystal mesogens form phases with internal molecular layer order. Free-standing films are easily prepared from this class of materials. They represent simple model systems for membrane dynamics and pattern formation in a quasi two-dimensional fluid. These films are usually spanned over a frame, and they can be inflated to bubbles on a support. Recently, closed microscopic shells of liquid-crystalline materials suspended in an outer fluid without contact to a solid support have been introduced and studied. With a special technique, we prepare millimetre to centimetre sized smectic bubbles in air (similar to soap bubbles). Their distinct feature is the fact that any change of surface area is coupled to a restructuring of the layers in the membrane. High-speed cameras are used to observe the shape transformations of freely floating bubbles from a distorted initial shape to a sphere. Bursting dynamics are recorded and compared to models. Most strikingly, an unpreceded cross-over from inviscid to viscous and elastic behaviour with increasing thickness of the membrane is found: Whereas thin bubbles behave almost like inviscid fluids, the relaxation dynamics slows down considerably for larger film thicknesses. Surface wrinkling and formation of extrusions are observed. We will present a characterization and an expalantion for the above phenomena.

Domains, defects, and de Vries: Electrooptics of smectic liquid crystals

NASA Astrophysics Data System (ADS)

Jones, Christopher D.

Liquid crystal (LC) materials are easily manipulated with the introduction of fields. Surface alignment of LC materials is commonly achieved via a rubbed polymer. Electric fields are then applied across the LC in order to reorient the individual molecules. These two controlling fields are the fundamental basis for the entirety of the liquid crystal display (LCD) industry, which in the 1970s was limited to calculators and digital watches but now LCDs are present by the dozen in the average home! Because these manipulations are so simple, and because the applications are so obvious, it has been useful to exploit the display cell geometry for the study of LCs. Novel compounds are being synthesized by chemistry groups at a high rate, and characterization of new materials must keep up. Therefore a primary technique is to probe the electrooptics of a material in a display cell. However, this geometry has its own impact on the behavior of a material: orientation and pinning at the surfaces tend to dominate the rest of the cell volume. With this information in mind, three interesting results of the display cell geometry and the resultant electrooptic measurements will be shown. First, the nucleation of twisted domains in achiral materials, made possible by the high energies required to overcome the orientation of the surface layers as compared to the bulk will be discussed. Second, the foundations of a large scale texture, made possible by surface pinning, expressing the stress of a material that shows large layer expansion on cooling through the smectic A phase will be solved. Finally, a model for the frequency dependence of the unique electrooptical behavior of the de Vries-type of smectics will be provided.

Phase transitions in nanocomposites of hydrogen-bonded dimeric liquid crystals with mesogenic and non-mesogenic components

NASA Astrophysics Data System (ADS)

Katranchev, Boyko; Petrov, Minko

2016-02-01

Microtextural polarization, phase transitions, and electro-optical effects are studied in a series of nanocomposites, grown by mixing alkyloxybenzoic acids (nOBAs), displaying hydrogen-bonded dimeric liquid crystal (LC) state, with non-mesogens (single-walled carbon nanotubes (SWCNTs), perfluorooctanoic acid) or mesogens (bent-core LC compound D14F3). Each of the studied nanocomposites, in which the nOBA serves as a matrix, forms complexes with bent-shaped dimeric, caused by the interaction between the dopant structural units and the dimer rings. This feature, coordinated with the surface anchoring, bulk and electrical effects, leads to drastic reduction of the LC system symmetry. As a result, transitions from achiral (characteristic for the pristine nOBA) to chiral states (including ferroelectric smectic C with C2 symmetry and ferroelectric smectic CG with the lowest C1 triclinic one) take place. The functionalization of the SWCNTs causes drastic increase of the ferroelectricity.

Templated Native Silk Smectic Gels

NASA Technical Reports Server (NTRS)

Park, Jae-Hyung (Inventor); Valluzzi, Regina (Inventor); Jin, Hyoung-Joon (Inventor)

2013-01-01

One aspect of the present invention relates to a method of preparing a fibrous protein smectic hydrogel by way of a solvent templating process, comprising the steps of pouring an aqueous fibrous protein solution into a container comprising a solvent that is not miscible with water; sealing the container and allowing it to age at about room temperature; and collecting the resulting fibrous protein smectic hydrogel and allowing it to dry. Another aspect of the present invention relates to a method of obtaining predominantly one enantiomer from a racemic mixture, comprising the steps of pouring an aqueous fibrous protein solution into a container comprising a solvent that is not miscible with water; sealing the container and allowing it to age at about room temperature; allowing the enantiomers of racemic mixture to diffuse selectively into the smectic hydrogel in solution; removing the smectic hydrogel from the solution; rinsing predominantly one enantiomer from the surface of the smectic hydrogel; and extracting predominantly one enantiomer from the interior of the smectic hydrogel. The present invention also relates to a smectic hydrogel prepared according to an aforementioned method.

Templated Native Silk Smectic Gels

NASA Technical Reports Server (NTRS)

Park, Jae-Hyung (Inventor); Valluzzi, Regina (Inventor); Jin, Hyoung-Joon (Inventor)

2016-01-01

One aspect of the present invention relates to a method of preparing a fibrous protein smectic hydrogel by way of a solvent templating process, comprising the steps of pouring an aqueous fibrous protein solution into a container comprising a solvent that is not miscible with water; sealing the container and allowing it to age at about room temperature; and collecting the resulting fibrous protein smectic hydrogel and allowing it to dry. Another aspect of the present invention relates to a method of obtaining predominantly one enantiomer from a racemic mixture, comprising the steps of pouring an aqueous fibrous protein solution into a container comprising a solvent that is not miscible with water; sealing the container and allowing it to age at about room temperature; allowing the enantiomers of racemic mixture to diffuse selectively into the smectic hydrogel in solution; removing the smectic hydrogel from the solution; rinsing predominantly one enantiomer from the surface of the smectic hydrogel; and extracting predominantly one enantiomer from the interior of the smectic hydrogel. The present invention also relates to a smectic hydrogel prepared according to an aforementioned method.

Templated native silk smectic gels

NASA Technical Reports Server (NTRS)

Park, Jae-Hyung (Inventor); Valluzzi, Regina (Inventor); Jin, Hyoung-Joon (Inventor)

2009-01-01

One aspect of the present invention relates to a method of preparing a fibrous protein smectic hydrogel by way of a solvent templating process, comprising the steps of pouring an aqueous fibrous protein solution into a container comprising a solvent that is not miscible with water; sealing the container and allowing it to age at about room temperature; and collecting the resulting fibrous protein smectic hydrogel and allowing it to dry. Another aspect of the present invention relates to a method of obtaining predominantly one enantiomer from a racemic mixture, comprising the steps of pouring an aqueous fibrous protein solution into a container comprising a solvent that is not miscible with water; sealing the container and allowing it to age at about room temperature; allowing the enantiomers of racemic mixture to diffuse selectively into the smectic hydrogel in solution; removing the smectic hydrogel from the solution; rinsing predominantly one enantiomer from the surface of the smectic hydrogel; and extracting predominantly one enantiomer from the interior of the smectic hydrogel. The present invention also relates to a smectic hydrogel prepared according to an aforementioned method.

Compression driven 2D nematic phase in a columnar Langmuir monolayer

NASA Astrophysics Data System (ADS)

El Abed, A.; Goldmann, M.

2012-08-01

Langmuir films of pyramidic liquid crystals were studied using surface pressure versus molecular area isotherms and synchrotron grazing incidence X-ray diffraction. The used molecule, named 3BCN/14, consists of a pyramidal central core to which are bound symmetrically six lateral C14 alkyl chains. These molecules spread spontaneously at the air-water interface in a metastable side-on phase which relax rapidly upon compression towards a stable edge-on phase. Our results suggest that the new edge-on phase consists of an in-plane organization of columns which are made of about 11 stacked edge-on molecules. This structure remains stable after several expansion-compression cycles. Comparing these results with those obtained previously on two other pyramidic liquid crystals with shorter and longer lateral alkyl chains, C9 and C15 respectively, we attribute the formation of the obtained 2D nematic phase to a suitable lateral chains length which allow for the establishing of strong short smectic order within of the 3BCN/14 columns.

Molecular dynamics and residual entropy in the soft crystal, SmE phase, of 4-butyl-4'-isothiocyano-1,1'-biphenyl.

PubMed

Ishimaru, Shin'ichi; Saito, Kazuya; Ikeuchi, Satoaki; Massalska-Arodz, Maria; Witko, Waclaw

2005-05-26

Molecular dynamics and resulting disorder in the soft crystal, smectic E (SmE) phase, were studied in detail for the title compound, 4-butyl-4'-isothiocyano-1,1'-biphenyl (4TCB), by (1)H NMR spectroscopy and adiabatic calorimetry. The ordered crystal phase of 4TCB was realized for the first time under ambient pressure after long two-step annealing and used as the reference state in the analysis of the experimental results. Four motional modes were identified in the SmE phase through the analysis of the (1)H NMR T(1). The residual entropy was determined as ca. 6 J K(-1) mol(-1). This magnitude implies that most of the disorder in the SmE phase at high temperatures is removed on cooling except for the head-to-tail disorder of the rod-shaped 4TCB molecule. Standard thermodynamic functions are tabulated below 375 K.

Understanding crumpling lipid vesicles at the gel phase transition

NASA Astrophysics Data System (ADS)

Hirst, Linda; Ossowski, Adam; Fraser, Matthew

2011-03-01

Wrinkling and crumpling transitions in different membrane types have been studied extensively in recent years both theoretically and computationally. There has also been very interesting recent work on defects in liquid crystalline shells. Lipid bilayer vesicles, widely used in biophysical research can be considered as a single layer smectic shell in the liquid crystalline phase. On cooling the lipid vesicle a transition to the gel phase may take place in which the lipid chains tilt and assume a more ordered packing arrangement. We observe large scale morphological changes in vesicles close to this transition point using fluorescence microscopy and investigate the possible mechanisms for this transition. Confocal microscopy is used to map 3D vesicle shape and crumpling length-scales. We also employ the molecular tilt sensitive dye, Laurdan to investigate the role of tilt domain formation on macroscopic structure. Funded by NSF CAREER award (DMR - BMAT #0852791).

Phase behavior of 1-dodecyl-3-methylimidazolium fluorohydrogenate salts (C12MIm(FH)(n)F, n = 1.0-2.3) and their anisotropic ionic conductivity as ionic liquid crystal electrolytes.

PubMed

Xu, Fei; Matsumoto, Kazuhiko; Hagiwara, Rika

2012-08-23

The effects of the HF composition, n, in 1-dodecyl-3-methylimidazolium fluorohydrogenate salts (C(12)MIm(FH)(n)F, n = 1.0-2.3) on their physicochemical and structural properties have been investigated using infrared spectroscopy, thermal analysis, polarized optical microscopy, X-ray diffraction, and anisotropic ionic conductivity measurements. The phase diagram of C(12)MIm(FH)(n)F (n vs transition temperature) suggests that C(12)MIm(FH)(n)F is a mixed crystal system that has a boundary around n = 1.9. For all compositions, a liquid crystalline mesophase with a smectic A interdigitated bilayer structure is observed. The temperature range of the mesophase decreases with increasing n value (from 61.8 °C for C(12)MIm(FH)(1.0)F to 37.0 °C for C(12)MIm(FH)(2.3)F). The layer spacing of the smectic structure decreases with increasing n value or increasing temperature. Two structural types with different layer spacings are observed in the crystalline phase (type I, 1.0 ≤ n ≤ 1.9, and type II, 1.9 ≤ n ≤ 2.3). Ionic conductivities parallel and perpendicular to the smectic layers (σ(||) and σ([perpendicular])) increase with increasing n value, whereas the anisotropy of the ionic conductivities (σ(||)/σ([perpendicular])) is independent of the n value, since the thickness of the insulating sheet formed by the dodecyl group remains nearly unchanged.

Interfacial behavior of confined mesogens at smectic-C*-water boundary.

PubMed

Chandran, Achu; Khanna, P K; Haranath, D; Biradar, Ashok M

2018-02-01

In this paper, we have investigated the behavior of mesogens at smectic-C*-water interface confined in a liquid crystal (LC) cell with interfacial geometry. Polarized optical microscopy was used to probe the appearance of various smectic-C* domain patterns at water interface owing to the reorientation of mesogens. The undulated stripe domains observed at the air interface of smectic-C* meniscus vanished as the water entered into the smectic layers and focal conical domain patterns appeared at smectic-C*-water boundary. A spatially variable electro-optical switching of LC molecules was also observed outside the electrode area of the interfacial cell. The electrode region at the interface, as well as on the water side, was damaged upon application of an electric field of magnitude more than 150 kV/m. The change in dielectric parameters of mesogens was extensively studied at interface after evaporating the water. These studies give fundamental insights into smectic-C*-water interface and also will be helpful in fabricating better LC devices for electro-optical and sensing applications.

Interfacial behavior of confined mesogens at smectic-C*-water boundary

NASA Astrophysics Data System (ADS)

Chandran, Achu; Khanna, P. K.; Haranath, D.; Biradar, Ashok M.

2018-02-01

In this paper, we have investigated the behavior of mesogens at smectic-C*-water interface confined in a liquid crystal (LC) cell with interfacial geometry. Polarized optical microscopy was used to probe the appearance of various smectic-C* domain patterns at water interface owing to the reorientation of mesogens. The undulated stripe domains observed at the air interface of smectic-C* meniscus vanished as the water entered into the smectic layers and focal conical domain patterns appeared at smectic-C*-water boundary. A spatially variable electro-optical switching of LC molecules was also observed outside the electrode area of the interfacial cell. The electrode region at the interface, as well as on the water side, was damaged upon application of an electric field of magnitude more than 150 kV/m. The change in dielectric parameters of mesogens was extensively studied at interface after evaporating the water. These studies give fundamental insights into smectic-C*-water interface and also will be helpful in fabricating better LC devices for electro-optical and sensing applications.

Effects of Monomer Structure on Their Organization and Polymerization in a Smectic Liquid Crystal

PubMed

Guymon; Hoggan; Clark; Rieker; Walba; Bowman

1997-01-03

Photopolymerizable diacrylate monomers dissolved in fluid-layer smectic A and smectic C liquid crystal (LC) hosts exhibited significant spatial segregation and orientation that depend strongly on monomer structure. Small, flexible monomers such as 1,6-hexanediol diacrylate (HDDA) oriented parallel to the smectic layers and intercalated, whereas rod-shaped mesogen-like monomers such as 1,4-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)-2-methylbenzene (C6M) oriented normal to the smectic layers and collected within them. Such spatial segregation caused by the smectic layering dramatically enhanced photopolymerization rates; for HDDA, termination rates were reduced, whereas for C6M, both the termination and propagation rates were increased. These polymerization precursor structures suggest novel materials-design paradigms for gel LCs and nanophase-separated polymer systems.

Enhancing and reducing chirality by opposite circularly-polarized light irradiation on crystalline chiral domains consisting of nonchiral photoresponsive W-shaped liquid crystal molecules.

PubMed

Choi, Suk-Won; Takezoe, Hideo

2016-09-28

We found possible chirality enhancement and reduction in chiral domains formed by photoresponsive W-shaped molecules by irradiation with circularly polarized light (CPL). The W-shaped molecules exhibit a unique smectic phase with spontaneously segregated chiral domains, although the molecules are nonchiral. The chirality control was generated in the crystalline phase, which shows chiral segregation as in the upper smectic phase, and the result appeared to be as follows: for a certain chiral domain, right-CPL stimuli enhanced the chirality, while left-CPL stimuli reduced the chirality, and vice versa for another chiral domain. Interestingly, no domain-size change could be observed after CPL irradiation, suggesting some changes in the causes of chirality. In this way, the present system can recognize the handedness of the applied chiral stimuli. In other words, the present material can be used as a sensitive chiral-stimuli-recognizing material and should find invaluable applications, including in chiroptical switches, sensors, and memories as well as in chiral recognition.

PEGylation of supercooled smectic cholesteryl myristate nanoparticles.

PubMed

Mengersen, Friederike; Bunjes, Heike

2012-06-01

Supercooled smectic cholesterol ester nanoparticles are under investigation as a new carrier system for lipophilic drugs. The smectic thermotropic liquid crystalline state of the matrix lipid is expected to lead to advantages with respect to physicochemical stability and drug loading capacity. Such nanoparticles can be prepared by high-pressure melt homogenization in the presence of emulsifiers. The purpose of this study was to develop PEGylated supercooled smectic cholesteryl myristate nanoparticles for parenteral administration and to provide evidence of the successful PEGylation by detecting the alterations of particle properties due to the insertion of PEGylated phospholipid into the surface layer of the particles. To achieve PEGylation, MPEG(2000)-DSPE was processed together with the phospholipids used as emulsifiers during particle preparation. The influence of the PEGylated phospholipid on the size, zeta potential, phase behavior and recrystallization tendency of the nanoparticles indicated the insertion of MPEG(2000)-DSPE into the surface layer of the particles. Evidence of the PEGylation was also obtained by (1)H NMR measurements, and the steric stabilization was verified by neutralizing the particle surface charge with calcium chloride or adjusting the pH value. As sterility is an important aspect with regard to parenteral administration of the dispersions their stability upon autoclaving was a further point of interest in the present study. The results indicate that PEGylated particles can be sterilized by autoclaving. In conclusion, the PEGylated particles are a promising formulation with respect to small particle size, stability against recrystallization and upon autoclaving. Copyright © 2012 Elsevier B.V. All rights reserved.

Plateau borders of smectic liquid crystalline films

NASA Astrophysics Data System (ADS)

Trittel, Torsten; Aldred, Ruth; Stannarius, Ralf

2011-06-01

We investigate the geometrical properties of Plateau borders in an arrangement of connected smectic A free standing films. The geometry is chosen such that a circular Plateau border surrounds a planar smectic film and connects it with two smectic catenoids. It is demonstrated that, similar to soap films, the smectic film geometry can be described by a negative line tension of the circular contact region. Thus, the equilibrium angle between the films depends upon the liquid content in this region, and with increasing liquid content, deviations from Plateau's rule are observed. The experimental results are qualitatively comparable to soap films. A possible origin of slight quantitative differences is discussed.

Depinning and nonequilibrium dynamic phases of particle assemblies driven over random and ordered substrates: A review

DOE PAGES

Reichhardt, Charles; Olson Reichhardt, Cynthia Jane

2016-12-20

Here, we review the depinning and nonequilibrium phases of collectively interacting particle systems driven over random or periodic substrates. This type of system is relevant to vortices in type-II superconductors, sliding charge density waves, electron crystals, colloids, stripe and pattern forming systems, and skyrmions, and could also have connections to jamming, glassy behaviors, and active matter. These systems are also ideal for exploring the broader issues of characterizing transient and steady state nonequilibrium flow phases as well as nonequilibrium phase transitions between distinct dynamical phases, analogous to phase transitions between different equilibrium states. We discuss the differences between elastic andmore » plastic depinning on random substrates and the different types of nonequilibrium phases which are associated with specific features in the velocity-force curves, fluctuation spectra, scaling relations, and local or global particle ordering. We describe how these quantities can change depending on the dimension, anisotropy, disorder strength, and the presence of hysteresis. Within the moving phase we discuss how there can be a transition from a liquid-like state to dynamically ordered moving crystal, smectic, or nematic states. Systems with periodic or quasiperiodic substrates can have multiple nonequilibrium second or first order transitions in the moving state between chaotic and coherent phases, and can exhibit hysteresis. We also discuss systems with competing repulsive and attractive interactions, which undergo dynamical transitions into stripes and other complex morphologies when driven over random substrates. Throughout this work we highlight open issues and future directions such as absorbing phase transitions, nonequilibrium work relations, inertia, the role of non-dissipative dynamics such as Magnus effects, and how these results could be extended to the broader issues of plasticity in crystals, amorphous solids, and jamming phenomena.« less

Depinning and nonequilibrium dynamic phases of particle assemblies driven over random and ordered substrates: a review

NASA Astrophysics Data System (ADS)

Reichhardt, C.; Olson Reichhardt, C. J.

2017-02-01

We review the depinning and nonequilibrium phases of collectively interacting particle systems driven over random or periodic substrates. This type of system is relevant to vortices in type-II superconductors, sliding charge density waves, electron crystals, colloids, stripe and pattern forming systems, and skyrmions, and could also have connections to jamming, glassy behaviors, and active matter. These systems are also ideal for exploring the broader issues of characterizing transient and steady state nonequilibrium flow phases as well as nonequilibrium phase transitions between distinct dynamical phases, analogous to phase transitions between different equilibrium states. We discuss the differences between elastic and plastic depinning on random substrates and the different types of nonequilibrium phases which are associated with specific features in the velocity-force curves, fluctuation spectra, scaling relations, and local or global particle ordering. We describe how these quantities can change depending on the dimension, anisotropy, disorder strength, and the presence of hysteresis. Within the moving phase we discuss how there can be a transition from a liquid-like state to dynamically ordered moving crystal, smectic, or nematic states. Systems with periodic or quasiperiodic substrates can have multiple nonequilibrium second or first order transitions in the moving state between chaotic and coherent phases, and can exhibit hysteresis. We also discuss systems with competing repulsive and attractive interactions, which undergo dynamical transitions into stripes and other complex morphologies when driven over random substrates. Throughout this work we highlight open issues and future directions such as absorbing phase transitions, nonequilibrium work relations, inertia, the role of non-dissipative dynamics such as Magnus effects, and how these results could be extended to the broader issues of plasticity in crystals, amorphous solids, and jamming phenomena.

Thermotropic liquid crystals from biomacromolecules

PubMed Central

Liu, Kai; Chen, Dong; Marcozzi, Alessio; Zheng, Lifei; Su, Juanjuan; Pesce, Diego; Zajaczkowski, Wojciech; Kolbe, Anke; Pisula, Wojciech; Müllen, Klaus; Clark, Noel A.; Herrmann, Andreas

2014-01-01

Complexation of biomacromolecules (e.g., nucleic acids, proteins, or viruses) with surfactants containing flexible alkyl tails, followed by dehydration, is shown to be a simple generic method for the production of thermotropic liquid crystals. The anhydrous smectic phases that result exhibit biomacromolecular sublayers intercalated between aliphatic hydrocarbon sublayers at or near room temperature. Both this and low transition temperatures to other phases enable the study and application of thermotropic liquid crystal phase behavior without thermal degradation of the biomolecular components. PMID:25512508

Liquid crystalline ordering and charge transport in semiconducting materials.

PubMed

Pisula, Wojciech; Zorn, Matthias; Chang, Ji Young; Müllen, Klaus; Zentel, Rudolf

2009-07-16

Organic semiconducting materials offer the advantage of solution processability into flexible films. In most cases, their drawback is based on their low charge carrier mobility, which is directly related to the packing of the molecules both on local (amorphous versus crystalline) and on macroscopic (grain boundaries) length scales. Liquid crystalline ordering offers the possibility of circumventing this problem. An advanced concept comprises: i) the application of materials with different liquid crystalline phases, ii) the orientation of a low viscosity high temperature phase, and, iii) the transfer of the macroscopic orientation during cooling to a highly ordered (at best, crystalline-like) phase at room temperature. At the same time, the desired orientation for the application (OLED or field-effect transistor) can be obtained. This review presents the use of molecules with discotic, calamitic and sanidic phases and discusses the sensitivity of the phases with regard to defects depending on the dimensionality of the ordered structure (columns: 1D, smectic layers and sanidic phases: 2D). It presents ways to systematically improve charge carrier mobility by proper variation of the electronic and steric (packing) structure of the constituting molecules and to reach charge carrier mobilities that are close to and comparable to amorphous silicon, with values of 0.1 to 0.7 cm(2)  · V(-1)  · s(-1) . In this context, the significance of cross-linking to stabilize the orientation and liquid crystalline behavior of inorganic/organic hybrids is also discussed. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Melting of 2D colloidal crystals

NASA Astrophysics Data System (ADS)

Maret, G.; Eisenmann, C.; Gasser, U.; Vongruenberg, H. H.; Keim, P.; Zahn, K.

2004-11-01

We study melting of 2D crystals of super-paramagnetic colloidal particles confined by gravity to a flat air-water interface. The effective system temperature is given by the strength of the dipolar inter-particle interaction controlled by an external magnetic field B. Particle positions are obtained by video-microscopy. In vertical B-field crystals are hexagonal and we find all features of the 2-step melting scenario predicted by KTHNY-theory. In particular, quantitative agreement is found for the translational and orientational order parameters related to bound and isolated dislocations and disclinations. From particle position fluctuations wave-vector (q) dependent normal-mode spring constants are obtained in agreement with phonon band structure calculations. The elastic constants (q=0 limit) soften near melting in quantitative agreement with KTHNY. By tilting B away from vertical anisotropic 2D crystals are generated; at small tilting angles they melt through a quasi-hexatic phase, while at higher tilts a centered rectangular phase is found which melts into a 2D smectic-like phase through orientation-dependent dislocations.

Electric-field-induced motion of colloid particles in smectic liquid crystals

NASA Astrophysics Data System (ADS)

Jakli, Antal

2005-03-01

We present the first observations of DC electric-field-induced rotational and translational motion of finite particles in liquid crystals. The electro-rotation is basically identical to the well known Quincke rotation, which triggers the translational motion at higher fields. From the electric field dependence of the angular velocity of the rotation we obtain the viscosity of the liquid crystals. The analysis of the translational motion in smectic liquid crystals indicates elastic responses near the threshold for translation. At increasing fields the speed of the particles is increasing and at sufficiently high speeds the flow of the smectic A and smectic C liquid crystal around the beads become purely viscous. Colloid particles in smectic materials maybe considered as model systems for understanding motion of proteins in cell membranes.

Emergent Optical Phononic Modes upon Nanoscale Mesogenic Phase Transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolmatov, Dima; Zhernenkov, Mikhail; Sharpnack, Lewis

The investigation of phononic collective excitations in soft matter systems at the molecular scale has always been challenging due to limitations of experimental techniques in resolving low-energy modes. Recent advances in inelastic X-ray scattering (IXS) enabled the study of such systems with unprecedented spectral contrast at meV excitation energies. In particular, it has become possible to shed light on the low-energy collective motions in materials whose morphology and phase behavior can easily be manipulated, such as mesogenic systems. The understanding of collective mode behavior with a Q-dependence is the key to implement heat management based on the control of amore » sample structure. The latter has great potential for a large number of energy-inspired innovations. As a first step toward this goal, we carried out high contrast IXS measurements on a liquid crystal sample, D7AOB, which exhibits solid-like dynamic features, such as the coexistence of longitudinal and transverse phononic modes. For the first time, we found that these terahertz phononic excitations persist in the crystal, smectic A, and isotropic phases. Furthermore, the intermediate smectic A phase is shown to support a van der Waals-mediated nonhydrodynamic mode with an optical-like phononic behavior. In conclusion, the tunability of the collective excitations at nanometer–terahertz scales via selection of the sample mesogenic phase represents a new opportunity to manipulate optomechanical properties of soft metamaterials.« less

Emergent Optical Phononic Modes upon Nanoscale Mesogenic Phase Transitions

DOE PAGES

Bolmatov, Dima; Zhernenkov, Mikhail; Sharpnack, Lewis; ...

2017-05-26

The investigation of phononic collective excitations in soft matter systems at the molecular scale has always been challenging due to limitations of experimental techniques in resolving low-energy modes. Recent advances in inelastic X-ray scattering (IXS) enabled the study of such systems with unprecedented spectral contrast at meV excitation energies. In particular, it has become possible to shed light on the low-energy collective motions in materials whose morphology and phase behavior can easily be manipulated, such as mesogenic systems. The understanding of collective mode behavior with a Q-dependence is the key to implement heat management based on the control of amore » sample structure. The latter has great potential for a large number of energy-inspired innovations. As a first step toward this goal, we carried out high contrast IXS measurements on a liquid crystal sample, D7AOB, which exhibits solid-like dynamic features, such as the coexistence of longitudinal and transverse phononic modes. For the first time, we found that these terahertz phononic excitations persist in the crystal, smectic A, and isotropic phases. Furthermore, the intermediate smectic A phase is shown to support a van der Waals-mediated nonhydrodynamic mode with an optical-like phononic behavior. In conclusion, the tunability of the collective excitations at nanometer–terahertz scales via selection of the sample mesogenic phase represents a new opportunity to manipulate optomechanical properties of soft metamaterials.« less

Rheological Properties of Quasi-2D Fluids in Microgravity

NASA Technical Reports Server (NTRS)

Stannarius, Ralf; Trittel, Torsten; Eremin, Alexey; Harth, Kirsten; Clark, Noel; Maclennan, Joseph; Glaser, Matthew; Park, Cheol; Hall, Nancy; Tin, Padetha

2015-01-01

In recent years, research on complex fluids and fluids in restricted geometries has attracted much attention in the scientific community. This can be attributed not only to the development of novel materials based on complex fluids but also to a variety of important physical phenomena which have barely been explored. One example is the behavior of membranes and thin fluid films, which can be described by two-dimensional (2D) rheology behavior that is quite different from 3D fluids. In this study, we have investigated the rheological properties of freely suspended films of a thermotropic liquid crystal in microgravity experiments. This model system mimics isotropic and anisotropic quasi 2D fluids [46]. We use inkjet printing technology to dispense small droplets (inclusions) onto the film surface. The motion of these inclusions provides information on the rheological properties of the films and allows the study of a variety of flow instabilities. Flat films have been investigated on a sub-orbital rocket flight and curved films (bubbles) have been studied in the ISS project OASIS. Microgravity is essential when the films are curved in order to avoid sedimentation. The experiments yield the mobility of the droplets in the films as well as the mutual mobility of pairs of particles. Experimental results will be presented for 2D-isotropic (smectic-A) and 2D-nematic (smectic-C) phases.

Parenteral formulation of an antileishmanial drug candidate--tackling poor solubility, chemical instability, and polymorphism.

PubMed

Kupetz, Eva; Preu, Lutz; Kunick, Conrad; Bunjes, Heike

2013-11-01

The paullon chalcone derivative KuRei300 is active against Leishmania donovani, the protozoans causing visceral leishmaniasis. The aim of this study was the development of a parenteral formulation of the virtually water insoluble compound in order to enable future studies in mice. Mixed lecithin/bile salt micelles, liposomes, supercooled smectic cholesterol myristate nanoparticles, cubic phase nanoparticles and a triglyceride emulsion were screened for their solubilizing properties. Due to the limited available amount of KuRei300 a passive loading approach with pre-formulated carriers that were incubated with drug substance deposited onto the walls of glass vials was used. The loading capacities of the nanocarriers, the influence of the solid state properties of the drug and its deposits on the loading results and chemical stability aspects of KuRei300 were investigated. Employed methods included HPLC, UV spectroscopy, (1)H NMR, XRPD, and DSC. All nanocarriers substantially improved the solubility of KuRei300; the mixed micelles exhibited the highest drug load. Related to the lipid matrix, however, the smectic nanoparticles solubilized the significantly highest amount of drug. Loading from physically altered drug deposits improved the obtainable concentration to the threefold compared with untreated drug powder. Formulations with KuRei300 must be stored excluded from light under a nitrogen atmosphere as the substance is susceptible to photoisomerization and decomposition. Copyright © 2013 Elsevier B.V. All rights reserved.

Between soap bubbles and vesicles: The dynamics of freely floating smectic bubbles

NASA Astrophysics Data System (ADS)

Stannarius, Ralf; May, Kathrin; Harth, Kirsten; Trittel, Torsten

2013-03-01

The dynamics of droplets and bubbles, particularly on microscopic scales, are of considerable importance in biological, environmental, and technical contexts. We introduce freely floating bubbles of smectic liquid crystals and report their unique dynamic properties. Smectic bubbles can be used as simple models for dynamic studies of fluid membranes. In equilibrium, they form minimal surfaces like soap films. However, shape transformations of closed smectic membranes that change the surface area involve the formation and motion of molecular layer dislocations. These processes are slow compared to the capillary wave dynamics, therefore the effective surface tension is zero like in vesicles. Freely floating smectic bubbles are prepared from collapsing catenoid films and their dynamics is studied with optical high-speed imaging. Experiments are performed under normal gravity and in microgravity during parabolic flights. Supported by DLR within grant OASIS-Co.

Chromonic liquid crystalline nematic phase exhibited in binary mixture of two liquid crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Govindaiah, T. N., E-mail: tngovi.phy@gmail.com; Sreepad, H. R.; Sridhar, K. N.

2015-06-24

A binary mixture of abietic acid and orthophosphoric acid (H{sub 3}PO{sub 4}) exhibits co-existence of biphasic region of Nematic+Isotropic (N+I), lyotropic Nematic (ND) and Smectic-G (SmG) phases. The mixture exhibits N+I, N and SmG phases at different concentrations and at different temperatures. Mixtures with all concentrations of abietic acid exhibit I→N+I→N→SmG phases sequentially when the specimen is cooled from its isotropic melt. These phases have been characterized by using differential scanning calorimetric, X-ray diffraction, and optical texture studies.

Basic and Applied Research in the Field of Electronics and Communications.

DTIC Science & Technology

1983-11-01

Johnson, and M.S. Neubert , "High Resolution X-Ray Study of Snectic A-Smectic C Phase Transition," Phys. Rev. B. 21, 4149-4153 (1980). * C.R. Safinya, R.J...Simonson, Robert Habashy, Terek Solomon, Lorraine Heiney, Paul Spencer, William Roer, Philip Stathis, James Hulet, Randall Stein, Josephine Jan, Darrell

Dicyanamide Salts that Adopt Smectic, Columnar, or Bicontinuous Cubic Liquid-Crystalline Mesophases.

PubMed

Park, Geonhui; Goossens, Karel; Shin, Tae Joo; Bielawski, Christopher W

2018-04-25

Although dicyanamide (i.e., [N(CN) 2 ] - ) has been commonly used to obtain low-viscosity, halogen-free, room-temperature ionic liquids, liquid-crystalline salts containing such anions have remained virtually unexplored. Here we report a series of amphiphilic dicyanamide salts that, depending on their structures and compositions, adopt smectic, columnar, or bicontinuous cubic thermotropic liquid-crystalline mesophases, even at room temperature in some cases. Their thermal properties were explored by polarized light optical microscopy, differential scanning calorimetry, thermogravimetric analysis (including evolved gas analysis), and variable-temperature synchrotron X-ray diffraction. Comparison of the thermal phase characteristics of these new liquid-crystalline salts featuring "V-shaped" [N(CN) 2 ] - anions with those of structural analogues containing [SCN] - , [BF 4 ] - , [PF 6 ] - , or [CF 3 SO 3 ] - anions indicated that not only the size of the counterion but also its shape should be considered in the development of mesomorphic salts. Collectively, these discoveries may be expected to facilitate the design of thermotropic ionic liquid crystals that form inverted-type bicontinuous cubic and other sophisticated liquid-crystalline phases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of elongation on the phase behavior of the Gay-Berne fluid

NASA Astrophysics Data System (ADS)

Brown, Julian T.; Allen, Michael P.; Martín del Río, Elvira; Miguel, Enrique De

1998-06-01

In this paper we present a computer simulation study of the phase behavior of the Gay-Berne liquid crystal model, concentrating on the effects of varying the molecular elongation κ. We study a range of length-to-width parameters 3<=κ<=4, using a variety of molecular dynamics and Monte Carlo techniques, obtaining a guide to the phase behavior for each shape studied. We observe vapor (V), isotropic liquid (I), nematic (N), smectic-A (SA) and smectic-B (SB) liquid crystal phases. Within the small range of elongation studied, the phase diagram shows significant changes. On increasing κ, the liquid-vapor critical point moves to lower temperature until it falls below the I-SB coexistence line, around κ=3.4, where liquid-vapor coexistence proves hard to establish. The liquid-vapor critical point seems to be completely absent at κ=4.0. Another dramatic effect is the growth of a stable SA ``island'' in the phase diagram at elongations slightly above κ=3.0. The SA range extends to both higher and lower temperatures as κ is increased. Also as κ is increased, the I-N transition is seen to move to lower density (and pressure) at given temperature. The lowest temperature at which the nematic phase is stable does not vary dramatically with κ. On cooling, no SB-crystal transition can be identified in the equation of state for any of these elongations; we suggest that, on the basis of simulation evidence, SB and crystal are really the same phase for these models.

Liquid Crystals for Laser Applications

DTIC Science & Technology

1992-07-01

336. Zei’dovich, B . Ya. and Tabiryan, N. V., Induced light scattering in the mesophase of a nematic liquid crystal (NLC), JETP Lett., 30, 478- 482 ...and devices. ADVANCES IN MATERIALS I Ferroelectric LC’s Ferroelectricity in liquid crystals was first suggested in 1974 by R. B . Meyer2 3 who, by means...most recently, 2 4 the M* phase. These tilted chiral smectic phases are classified according to the nature of the intermolecular I I packing within

Mesophase and size manipulation of itraconazole liquid crystalline nanoparticles produced via quasi nanoemulsion precipitation.

PubMed

Mugheirbi, Naila A; Tajber, Lidia

2015-10-01

The fabrication of drug nanoparticles (NPs) with process-mediated tunable properties and performances continues to grow rapidly during the last decades. This study investigates the synthesis and phase tuning of nanoparticulate itraconazole (ITR) mesophases using quasi nanoemulsion precipitation from acetone/water systems to seek out an alternative pathway to the nucleation-based NP formation. ITR liquid crystalline (LC) phases were formed and nematic-smectic mesomorphism was achieved via controlling solvent:antisolvent temperature difference (ΔTS:AS). The use of ΔTS:AS=49.5°C was associated with a nematic assembly, while intercalated smectic A layering was observed at ΔTS:AS=0°C, with both phases confined in the nanospheres at room temperature. The quasi emulsion system has not been investigated at the nanoscale to date and in contrary to the microscale, quasi nanoemulsion was observed over the solvent:antisolvent viscosity ratios of 1:7-1:1.4. Poly(acrylic acid) in the solvent phase exhibited a concentration dependent interaction when ITR formed NPs. This nanodroplet-based approach enabled the preparation of a stable ITR nanodispersion using Poloxamer 407 at 80°C, which was unachievable before using precipitation via nucleation. Findings of this work lay groundwork in terms of rationalised molecular assembly as a tool in designing pharmaceutical LC NPs with tailored properties. Copyright © 2015 Elsevier B.V. All rights reserved.

de Vries liquid crystals based on a chiral 5-phenylpyrimidine benzoate core with a tri- and tetra-carbosilane backbone

NASA Astrophysics Data System (ADS)

Sreenilayam, S. P.; Rodriguez-Lojo, D.; Agra-Kooijman, D. M.; Vij, J. K.; Panov, V. P.; Panov, A.; Fisch, M. R.; Kumar, Satyendra; Stevenson, P. J.

2018-02-01

New chiral de Vries smectic liquid-crystalline compounds are designed, synthesized, and investigated for perspective applications in defect-free bistable surface-stabilized ferroelectric liquid-crystal displays. In these compounds, a 5-phenyl-pyrimidine benzoate core is terminated on one side by a tri- or tetra-carbosilane group linked through an alkoxy group and an alkyl spacer and on the opposite side terminated by a chiral 2-octanol group. The stereogenic center contains either a methyl or perfluoromethyl functional group. These compounds exhibit Iso-Sm A*-Sm C*-Sm X -Cr phases under cooling from the isotropic state. Measurements of the temperature-dependent smectic layer spacing by x-ray diffraction experiments combined with the measured apparent optical tilt angle and the birefringence reveal that Sm A* phase in these compounds is of the de Vries type. In addition, the chiral compound with a tetra-carbosilane backbone, DR277, exhibits good de Vries properties with the Sm C* phase exhibited over a wide temperature range. By varying the carbosilane end group, the de Vries properties are enhanced, that is, the layer shrinkage of ˜1.9 % for the tri-carbosilane DR276 is reduced to ˜0.9 % for tetra-carbosilane DR277 at 10°C below Sm A* to Sm C* transition temperature, TAC. For DR277, the reduction factor R ≈0.22 for T =(TAC-10 )°C is reasonably low and the apparent optical tilt angle θapp=35.1°, hence this compound is a "good de Vries smectic" LC. Therefore, synthesis of the chiral mesogen with an even higher number of carbosilane groups may lead to a further reduction or even zero-layer shrinkage exhibited at TAC with Sm C* phase extending over a wide temperature range close to the room temperature for perspective suitability in device applications. Our results for 5-phenyl-pyrimidine benzoate core-based compounds support a recently drawn conclusion by Schubert et al. [J. Mater. Chem. C 4, 8483 (2016), 10.1039/C6TC03120J] from a different compound, namely that a carbosilane backbone in chiral mesogens strongly influences the de Vries properties.

Electro-Optical Characterization of Bistable Smectic A Liquid Crystal Displays

NASA Astrophysics Data System (ADS)

Buyuktanir, Ebru Aylin

My dissertation focuses the characterization and optimization of the electro-optical properties of smectic A (SmA) based liquid crystal (LC) displays. I present the development of robust and flexible bistable SmA LC displays utilizing polymer dispersed liquid crystal (PDLC) technology. The SmA PDLC displays produced on plastic substrates present electrically reversible memory, high contrast ratio, paper-like sunlight readability, and wide viewing angle characteristics. In order to optimize the SmA PDLC display, I investigated polymerization conditions, such as polymer concentration effect, polymerization temperature, and UV-light intensity variations. I characterized the electro-optical responses-such as static-response, time-response, threshold characteristics, and contrast ratio values' of the optimized SmA PDLC display and compared them to those of the pure SmA LC. The best electro-optical performance of SmA PDLC formulation was obtained using the combination of low mW/cm 2 and high mW/cm2 UV-light curing intensity. The contrast ratio of the optimum SmA PDLC at a 5o collection angle was 83% of that of the pure SmA material on plastic substrates. I fabricated 2.5 x 2.5 in., 4 x 4 in., and 6 x 6 in. sized monochrome flexible SmA PDLC displays, as well as red, yellow, and fluorescent dyes colored SmA PDLC displays on plastic substrates. The electro-optic performance of the bistable SmA LC display consisting of a patterned field-induced polymer wall infrastructure was also studied and compared to those of pure SmA material. I found that the contrast ratio of the SmA LC encapsulated between polymer walls was much greater than that of the SmA PDLC system, approaching the contrast ratio value of the pure SmA material. I also improved the electro-optical characteristics of bistable SmA LC displays by adding ferroparticles into the system. Finally, I illustrated the unique capabilities of polarized confocal Raman microscopy (CRM) to resolve the orientational order of SmA LCs in three-dimension by investigating the characteristic vibrational bands of LC molecules. CRM provides a precise characterization of the molecular order at different depths of the LC films. I examined the director patterns of focal conic defects of smectic A LC, colloidal smectic A LC systems, and the field-oriented nematic LC in the horizontal and vertical planes.

Functional organic materials based on polymerized liquid-crystal monomers: supramolecular hydrogen-bonded systems.

PubMed

Broer, Dirk J; Bastiaansen, Cees M W; Debije, Michael G; Schenning, Albertus P H J

2012-07-16

Functional organic materials are of great interest for a variety of applications. To obtain precise functional properties, well-defined hierarchically ordered supramolecular materials are crucial. The self-assembly of liquid crystals has proven to be an extremely useful tool in the development of well-defined nanostructured materials. We have chosen the illustrative example of photopolymerizable hydrogen-bonding mesogens to show that a wide variety of functional materials can be made from a relatively simple set of building blocks. Upon mixing these compounds with other reactive mesogens, nematic, chiral nematic, and smectic or columnar liquid-crystalline phases can be formed that can be applied as actuators, sensors and responsive reflectors, and nanoporous membranes, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations.

PubMed

Quevillon, Michael J; Whitmer, Jonathan K

2018-01-02

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure-constant temperature ensemble. These materials exhibit a distinct "smectic" liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications.

Temperature dependence of droplet breakup in 8CB and 5CB liquid crystals.

PubMed

Porter, Daniel; Savage, John R; Cohen, Itai; Spicer, Patrick; Caggioni, Marco

2012-04-01

Droplet breakup of many Newtonian fluids is well described by current experiments, theory, and simulations. Breakup in complex fluids where interactions between mesoscopic structural features can affect the flows remains poorly understood and a burgeoning area of research. Here, we report on our investigations of droplet breakup in thermotropic liquid crystals. We investigate breakup in the smectic, nematic, and isotropic phases of 4-cyano 4-octylbiphenyl (8CB) and the nematic and isotropic phases of 4-cyano 4-pentylbiphenyl (5CB). The experiment consists of varying the ambient temperature to control liquid crystalline phase and imaging breakup using a fast video camera at up to 110000 frames/s. We expand on previous work [John R. Savage et al., Soft Matter 6, 892 (2010)] that shows breakup in the smectic phase is symmetric, producing no satellite droplets, and is well described by a similarity solution for a shear-thinning power-law fluid. We show that in the nematic phase the breakup occurs in two stages. In the first stage, the breakup is symmetric and the power-law exponent for the minimum radius dependence on the time left to breakup is 1.2

Intradomain phase transitions in flexible block copolymers with self-aligning segments.

PubMed

Burke, Christopher J; Grason, Gregory M

2018-05-07

We study a model of flexible block copolymers (BCPs) in which there is an enlthalpic preference for orientational order, or local alignment, among like-block segments. We describe a generalization of the self-consistent field theory of flexible BCPs to include inter-segment orientational interactions via a Landau-de Gennes free energy associated with a polar or nematic order parameter for segments of one component of a diblock copolymer. We study the equilibrium states of this model numerically, using a pseudo-spectral approach to solve for chain conformation statistics in the presence of a self-consistent torque generated by inter-segment alignment forces. Applying this theory to the structure of lamellar domains composed of symmetric diblocks possessing a single block of "self-aligning" polar segments, we show the emergence of spatially complex segment order parameters (segment director fields) within a given lamellar domain. Because BCP phase separation gives rise to spatially inhomogeneous orientation order of segments even in the absence of explicit intra-segment aligning forces, the director fields of BCPs, as well as thermodynamics of lamellar domain formation, exhibit a highly non-linear dependence on both the inter-block segregation (χN) and the enthalpy of alignment (ε). Specifically, we predict the stability of new phases of lamellar order in which distinct regions of alignment coexist within the single mesodomain and spontaneously break the symmetries of the lamella (or smectic) pattern of composition in the melt via in-plane tilt of the director in the centers of the like-composition domains. We further show that, in analogy to Freedericksz transition confined nematics, the elastic costs to reorient segments within the domain, as described by the Frank elasticity of the director, increase the threshold value ε needed to induce this intra-domain phase transition.

Intradomain phase transitions in flexible block copolymers with self-aligning segments

NASA Astrophysics Data System (ADS)

Burke, Christopher J.; Grason, Gregory M.

2018-05-01

We study a model of flexible block copolymers (BCPs) in which there is an enlthalpic preference for orientational order, or local alignment, among like-block segments. We describe a generalization of the self-consistent field theory of flexible BCPs to include inter-segment orientational interactions via a Landau-de Gennes free energy associated with a polar or nematic order parameter for segments of one component of a diblock copolymer. We study the equilibrium states of this model numerically, using a pseudo-spectral approach to solve for chain conformation statistics in the presence of a self-consistent torque generated by inter-segment alignment forces. Applying this theory to the structure of lamellar domains composed of symmetric diblocks possessing a single block of "self-aligning" polar segments, we show the emergence of spatially complex segment order parameters (segment director fields) within a given lamellar domain. Because BCP phase separation gives rise to spatially inhomogeneous orientation order of segments even in the absence of explicit intra-segment aligning forces, the director fields of BCPs, as well as thermodynamics of lamellar domain formation, exhibit a highly non-linear dependence on both the inter-block segregation (χN) and the enthalpy of alignment (ɛ). Specifically, we predict the stability of new phases of lamellar order in which distinct regions of alignment coexist within the single mesodomain and spontaneously break the symmetries of the lamella (or smectic) pattern of composition in the melt via in-plane tilt of the director in the centers of the like-composition domains. We further show that, in analogy to Freedericksz transition confined nematics, the elastic costs to reorient segments within the domain, as described by the Frank elasticity of the director, increase the threshold value ɛ needed to induce this intra-domain phase transition.

Smectic viral capsids and the aneurysm instability

NASA Astrophysics Data System (ADS)

Dharmavaram, S.; Rudnick, J.; Lawrence, C. M.; Bruinsma, R. F.

2018-05-01

The capsids of certain Archaea-infecting viruses undergo large shape changes, while maintaining their integrity against rupture by osmotic pressure. We propose that these capsids are in a smectic liquid crystalline state, with the capsid proteins assembling along spirals. We show that smectic capsids are intrinsically stabilized against the formation of localized bulges with non-zero Gauss curvature while still allowing for large-scale cooperative shape transformation that involves global changes in the Gauss curvature.

X-ray study of mesomorphism of bent-core and chromonic mesogens

NASA Astrophysics Data System (ADS)

Joshi, Leela Pradhan

The discovery of thermotropic biaxial nematic phase in bent-core mesogens, have engendered interest in these systems. Also, it undergoes optical switching about 100 times faster than conventional uniaxial nematic liquid crystal. Azo-substituted bent-core compounds, A131 and A103, were investigated as both offer an opportunity to observe their structures and phase transitions from the uniaxial nematic (Nu) to biaxial nematic (Nb) phase and from Nb to the underlying smectic-C (SmC) phase. Plank-like molecular systems are also expected to form Nb phase. Chromonic liquid crystals formed by aqueous solutions of plank-like dye molecules are interesting for their unique self-assembly and structural evolution. They have applications in optical element, coloring in food and textiles, and etc. Both systems were investigated with synchrotron x-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. Temperature dependence of d-spacing and positional order correlations along the director clearly mark the phase boundaries where Nu-Nb transition was approximately 27° below the clearing point. Positional order correlation length of A131 increased from 1.5 in Nu to 3.3 molecular lengths in Nb phase, before it jumps by a factor of at least 5 in SmC phase. The lack of large discontinuous changes in the structural parameters and the subtle signatures in heat capacity establish the second order nature of Nu-Nb and Nb-SmC phase transitions. The chromonic system investigation results provide quantitative information of structural properties in nematic and columnar mesophases. We studied water solutions of (achiral) sunset yellow dye and (chiral and achiral) dihydrochloride salts of perylenebis-dicarboxydiimide. Positional order correlation lengths measurements, parallel and perpendicular to the aggregate axis, revealed that they increase with concentration and decrease with temperature. Temperature dependence of correlation lengths yielded the scission energy to be 1.8 (+/-0.1) x10-20J and 1.5 (+/-0.08) x10-20J in the nematic and columnar phases. The aggregates' small aspect ratio (2.5) is inconsistent with the Onsager model for the formation of an orientationally ordered phase, which strongly suggests more complicated aggregate-shape than simple cylindrical objects as postulated by Laventovich, et al.

Self-assembly of gelator molecules in liquid crystals studied by ESR

NASA Astrophysics Data System (ADS)

Andreis, Mladen; Carić, Dejana; Vujičić, Nataša Šijaković; Jokić, Milan; Žinić, Mladen; Kveder, Marina

2012-07-01

Thermotropic liquid crystal trans-4-heptylcyclohexanecarboxylic acid (HCCA) doped with 4-oxo-2,2,6,6,-tetramethyl-1-piperidinyloxy spin probe (Tempone) is investigated by electron spin resonance (ESR) spectroscopy in the presence of chiral bisoxalamide gelator 1 during both cooling and heating cycles. In the temperature range 295-383 K, where HCCA displays isotropic, nematic, smectic B and crystalline phases, the impact of 1 self-organization was detected via (non) homogeneous partitioning of the spin probe in the environments varying in the polarity, an effect dependent on the gelator concentration. In particular, the evidence of the onset of the gelator network self-assembly in the nematic phase was detected by ESR at higher temperatures than the ones reported so far by other experimental techniques. Additionally, the spectral analysis points to the switching of the polarity in the vicinity of the spin probe when the transfer of chirality from 1 to HCCA upon cooling of the sample from isotropic to chiral nematic phase appears and when the event of LC gelation results in the achiral nematic phase during chiral gel fibers formation. When the gelation proceeds in the smectic phase, the melting of the gelator network is studied in the nematic phase during the heating cycle. Furthermore, the event of HCCA crystallization is shown to be strongly affected by the presence of 1 as well. The experimental evidence is provided that gelator network confines the HCCA into the domains within the bulk crystalline matrix where the local molecular dynamics are still not frozen. Therefore, we propose that non-homogeneous polarity profile of molecular organization/packing within LC gels could be determinable for the physical properties of various LC gel phases.

Phase diagram of two-dimensional hard rods from fundamental mixed measure density functional theory

NASA Astrophysics Data System (ADS)

Wittmann, René; Sitta, Christoph E.; Smallenburg, Frank; Löwen, Hartmut

2017-10-01

A density functional theory for the bulk phase diagram of two-dimensional orientable hard rods is proposed and tested against Monte Carlo computer simulation data. In detail, an explicit density functional is derived from fundamental mixed measure theory and freely minimized numerically for hard discorectangles. The phase diagram, which involves stable isotropic, nematic, smectic, and crystalline phases, is obtained and shows good agreement with the simulation data. Our functional is valid for a multicomponent mixture of hard particles with arbitrary convex shapes and provides a reliable starting point to explore various inhomogeneous situations of two-dimensional hard rods and their Brownian dynamics.

Thermodynamic Parameters of Cholesteric/Smectic A Transition in Cholesteric Myristate and Its Binary Mixture CM/PCPB

NASA Astrophysics Data System (ADS)

Yurtseven, H.; Dogan, E. Kilit

2018-06-01

Thermodynamic properties of the cholesteryl myristate (CM) and its binary mixture CM/PCPB ( p-pentylphenyl-2-chloro-4( p-pentylbenzoyl)-benzoate) are studied at the concentrations of x PCPB = 0.052 and 0.219 as a function of temperature near the cholosteric/smectic A transition. By analyzing the observed molar volume from the literature, the temperature dependences of the thermal expansion, isothermal compressibility and the difference in the specific heat are calculated and, the Pippard relations are established for those compounds close to the cholesteric/smectic A transition. Predictions of the thermodynamic quantities and the Pippard relations can be examined by the experimental measurements of the CM and its binary mixture of CM/PCPB close to the cholesteric/smectic A transition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andreev, A L; Andreeva, T B; Kompanets, I N

We have studied the method for suppressing speckle noise in patterns produced by a laser based on a fast-response electro-optical cell with a ferroelectric liquid crystal (FLC) in which helicoid is absent, i.e., compensated for. The character of smectic layer deformation in an electric field is considered along with the mechanism of spatially inhomogeneous phase modulation of a laser beam passing through the cell which is accompanied by the destruction of phase relations in the beam. Advantages of a helix-free FLC cell are pointed out as compared to helical crystal cells studied previously. (liquid crystal devices)

Thermotropic phase transition in an adsorbed melissic acid film at the n-hexane-water interface

NASA Astrophysics Data System (ADS)

Tikhonov, A. M.

2017-06-01

A reversible thermotropic phase transition in an adsorption melissic acid film at the interface between n-hexane and an aqueous solution of potassium hydroxide (pH ≈ 10) is investigated by X-ray reflectometry and diffuse scattering using synchrotron radiation. The experimental data indicate that the interface "freezing" transition is accompanied not only by the crystallization of the Gibbs monolayer but also by the formation of a planar smectic structure in the 300-Å-thick adsorption film; this structure is formed by 50-Å-thick layers.

From viscous to elastic sheets: Dynamics of smectic freely floating films

NASA Astrophysics Data System (ADS)

Harth, Kirsten; May, Kathrin; Trittel, Torsten; Stannarius, Ralf

2015-03-01

Oscillations and rupture of bubbles, composed of an inner fluid separated from an outer fluid by a membrane, represent an old but still immensely active field of research. Membrane properties except surface tension are often neglected for simple fluid films (e.g. soap bubbles), whereas they govern the dynamics in systems with more complex membranes (e.g. vesicles). Due to their layered phase structure, smectic liquid crystals can form stable, uniform and easy-to handle fluid films of immense aspect ratios. Recently, freely floating bubbles detached from a support were prepared. We analyze the relaxation from strongly non-spherical shapes and the rupture dynamics of such bubbles using high-speed video recordings. Peculiar dynamics intermediate between those of simple viscous fluid films and an elastic response emerge: Oscillations, slowed relaxation and even the formation of wrinkles and extrusions. We characterize these phenomena and propose explanations. We acknowledge funding by the German Aerospace Center DLR within Project OASIS-CO and German Science Foundation Project STA 425-28.

Homogeneous alignment of liquid crystalline dendrimers confined in a slit-pore. A simulation study.

PubMed

Workineh, Zerihun G; Vanakaras, Alexandros G

2016-03-23

In this work we present results from isobaric-isothermal (NPT) Monte Carlo simulation studies of model liquid crystalline dendrimer (LCDr) systems confined in a slit-pore made of two parallel flat walls. The dendrimers are modelled as a collection of spherical and ellipsoidal particles corresponding to the junction points of the dendritic core and to the mesogenic units respectively. Assuming planar uniform (unidirectional) soft anchoring of the mesogenic units on the substrates we investigate the conformational and alignment properties of the LCDr system at different thermodynamic state points. Tractable coarse grained force fields have been used from our previous work. At low pressures the interior of the pore is almost empty, since almost all LCDrs are anchored to the substrates forming two-dimensional smectic-like structures with the mesogens aligned along the aligning direction of the substrates. As the pressure grows the LCDrs occupy the whole pore. However, even at low temperatures, the smectic organization does not transmit in the interior of the pore and is preserved for distances of 2-3 mesogenic diameters from the walls. For this reason, the global orientational order decreases with increasing pressure (density). In the vicinity (2-3 mesogenic diameters) of the pore walls, mesogenic units preserve the smectic structure whose layers are separated by layers of spherical beads. In this region individual LCDrs possess a rod like shape.

Homogeneous alignment of liquid crystalline dendrimers confined in a slit-pore. A simulation study

NASA Astrophysics Data System (ADS)

Workineh, Zerihun G.; Vanakaras, Alexandros G.

2016-03-01

In this work we present results from isobaric-isothermal (NPT) Monte Carlo simulation studies of model liquid crystalline dendrimer (LCDr) systems confined in a slit-pore made of two parallel flat walls. The dendrimers are modelled as a collection of spherical and ellipsoidal particles corresponding to the junction points of the dendritic core and to the mesogenic units respectively. Assuming planar uniform (unidirectional) soft anchoring of the mesogenic units on the substrates we investigate the conformational and alignment properties of the LCDr system at different thermodynamic state points. Tractable coarse grained force fields have been used from our previous work. At low pressures the interior of the pore is almost empty, since almost all LCDrs are anchored to the substrates forming two-dimensional smectic-like structures with the mesogens aligned along the aligning direction of the substrates. As the pressure grows the LCDrs occupy the whole pore. However, even at low temperatures, the smectic organization does not transmit in the interior of the pore and is preserved for distances of 2-3 mesogenic diameters from the walls. For this reason, the global orientational order decreases with increasing pressure (density). In the vicinity (2-3 mesogenic diameters) of the pore walls, mesogenic units preserve the smectic structure whose layers are separated by layers of spherical beads. In this region individual LCDrs possess a rod like shape.

Effects of molecular chirality on self-assembly and switching in liquid crystals at the cross-over between rod-like and bent shapes.

PubMed

Ocak, Hale; Poppe, Marco; Bilgin-Eran, Belkız; Karanlık, Gürkan; Prehm, Marko; Tschierske, Carsten

2016-09-21

A bent-core compound derived from a 4-cyanoresorcinol core unit with two terephthalate based rod-like wings and carrying chiral 3,7-dimethyloctyloxy side chains has been synthesized in racemic and enantiomerically pure form and characterized by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical investigations to study the influence of molecular chirality on the superstructural chirality and polar order in lamellar liquid crystalline phases. Herein we demonstrate that the coupling of molecular chirality with superstructural layer chirality in SmCsPF domain phases (forming energetically distinct diastereomeric pairs) can fix the tilt direction and thus stabilize synpolar order, leading to bistable ferroelectric switching in the SmC* phases of the (S)-enantiomer, whereas tristable modes determine the switching of the racemate. Moreover, the mechanism of electric field induced molecular reorganization changes from a rotation around the molecular long axis in the racemate to a rotation on the tilt-cone for the (S)-enantiomer. At high temperature the enantiomer behaves like a rod-like molecule with a chirality induced ferroelectric SmC* phase and an electroclinic effect in the SmA'* phase. At reduced temperature sterically induced polarization, due to the bent molecular shape, becomes dominating, leading to much higher polarization values, thus providing access to high polarization ferroelectric materials with weakly bent compounds having only "weakly chiral" stereogenic units. Moreover, the field induced alignment of the SmCsPF(()*()) domains gives rise to a special kind of electroclinic effect appearing even in the absence of molecular chirality. Comparison with related compounds indicates that the strongest effects of chirality appear for weakly bent molecules with a relatively short coherence length of polar order, whereas for smectic phases with long range polar order the effects of the interlayer interfaces can override the chirality effects.

Phase transitions in high magnetic fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arko, A.J.; Beers, C.J.; van Deursen, A.P.J.

1982-08-01

The purpose of this paper is to summarize some of the research activities recently performed at the Laboratorium voor Hoge Magneetvelden at the University of Nijmegen. The scope here and unifying aspect is magnetically induced phase transitions. Here we summarize transitions in the settling velocity of paramagnetic aggregates, suppression of spin fluctuations in UAl/sub 2/, the phase diagram of a ferroelectric chiral smectic liquid crystal near the Lifshitz point and the transition from 3D to 2D conduction in a GaAs FET. In no way does this represent a complete review of transitions, but rather a summary of phase transitions observedmore » at the magnet laboratory during the past year. 6 figures.« less

Field-induced phase transitions in chiral smectic liquid crystals studied by the constant current method

NASA Astrophysics Data System (ADS)

H, Dhaouadi; R, Zgueb; O, Riahi; F, Trabelsi; T, Othman

2016-05-01

In ferroelectric liquid crystals, phase transitions can be induced by an electric field. The current constant method allows these transition to be quickly localized and thus the (E,T) phase diagram of the studied product can be obtained. In this work, we make a slight modification to the measurement principles based on this method. This modification allows the characteristic parameters of ferroelectric liquid crystal to be quantitatively measured. The use of a current square signal highlights a phenomenon of ferroelectric hysteresis with remnant polarization at null field, which points out an effect of memory in this compound.

Ferroelectric Liquid Crystals: Synthesis and Thermal Behavior of Optically Active, Three-Ring Schiff Bases and Salicylaldimines.

PubMed

Veerabhadraswamy, Bhyranalyar N; Rao, Doddamane S Shankar; Yelamaggad, Channabasaveshwar V

2018-04-16

The chiral ferroelectric smectic C (SmC*) phase, characterized by a helical superstructure, has been well exploited in developing high-resolution microdisplays that have been effectively employed in the fabrication of a wide varieties of portable devices. Although, an overwhelming number of optically active (chiral) liquid crystals (LCs) exhibiting a SmC* phase have been designed and synthesized, the search for new systems continues so as to realize mesogens capable of meeting technical necessities and specifications for their end-use. In continuation of our research work in this direction, herein we report the design, synthesis, and thermal behavior of twenty new optically active, three-ring calamitic LCs belonging to four series. The first two series comprise five pairs of enantiomeric Schiff bases whereas the other two series are composed of five pairs of enantiomeric salicylaldimines. In each pair of optical isomers, the configuration of a chiral center in one stereoisomer is opposite to that of the analogous center in the other isomer as they are derived from (3 S)-3,7-dimethyloctyloxy and (3 R)-3,7-dimethyloctyloxy tails. To probe the structure-property correlations in each series, the length of the n-alkoxy tail situated at the other end of the mesogens has been varied from n-octyloxy to n-dodecyloxy. The measurement of optical activity of these chiral mesogens was carried out by recording their specific rotations. As expected, enantiomers rotate plane polarized light in the opposite direction but by the same magnitude. The thermal behavior of the compounds was established by using a combination of optical polarizing microscopy, differential scanning calorimetry, and powder X-ray diffraction. These complementary techniques demonstrate the existence of the expected, thermodynamically stable, chiral smectic C (SmC*) LC phase besides blue phase I/II (BPI or BPII) and chiral nematic (N*) phase. However, as noted in our previous analogous study, the vast majority of the Schiff bases show an additional metastable, unfamiliar smectic (SmX) phase just below the SmC* phase. Notably, the SmC* phase persists over the temperature range ≈80-115 °C. Two mesogens chosen each from Schiff bases and salicylaldimines were investigated for their electrical switching behavior. The study reveals the ferroelectric switching characteristics of the SmC* phase featuring the spontaneous polarization (P S ) in the range 69-96 nC cm -2 . The helical twist sense of the SmC* phase as well as the N* phase formed by a pair of enantiomeric Schiff bases and salicylaldimines has been established with the help of circular dichroism (CD) spectroscopic technique. As expected, the SmC* and the N* phase of a pair of enantiomers showed mirror image CD signals. Most importantly, the reversal of helical handedness from left to right and vice versa has been evidenced during the N* to SmC* phase transition, implying that the screw sense of the helical array of the N* phase and the SmC* phase of an enantiomer is opposite. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electric-field effects in the twist-bend nematic phase

NASA Astrophysics Data System (ADS)

Meyer, Claire; Dozov, Ivan; Davidson, Patrick; Luckhurst, Geoffrey R.; Dokli, Irena; Knezevic, Anamarija; Lesac, Andreja

2018-02-01

In the recently discovered Twist-Bend Nematic (NTB) phase, the nematic director is spontaneously distorted and twisted along a conical helix with an extremely short pitch, 10 nm. We have investigated the behavior of the NTB phase subject to an electric-field. We show that, due to the periodic NTB structure, the electro-optic effects are not nematic-like but are close analogs to those in the smectic and cholesteric phases. In particular, we have studied the fast (sub-microsecond) flexoelectrically-induced rotation of the optic axis, which is similar to the electroclinic effect in the SmA* phase and the flexoelectric response of short-pitch cholesterics. We discuss the possible applications of the fast NTB electro-optic effects.

Hard Pd Nanorods in the Soft Surfactant Mixture of CTAB and Pluronics: Seedless Synthesis and Their Self-Assembly.

PubMed

Song, Hyon-Min; Zink, Jeffrey I

2018-04-10

Seedless synthesis of Pd nanorods and their self-assembly into the layered smectic ordering are described. Aqueous Pluronic triblock copolymers (14.3-35.7%) are used as a soft template along with cetyltrimethylammonium bromide for inducing one-dimensional growth of Pd nanorods. Pluronic triblock copolymers are probably the most used polymer surfactants, and they are composed of poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblocks. Neither pH adjustment nor AgNO 3 and other additives, such as poly(vinyl pyrrolidone) and ethylene glycol, are required to obtain Pd nanorods. Sonochemical synthesis at 43 °C, followed by thermal annealing for 1 h at 65 °C produces Pd nanorods with the aspect ratio from 3.1 (17.9%, Pluronic L-64) to 6.7 (35.7%, Pluronic P-123). Two-dimensional self-assembly of the nanorods is observed, and both nematic ordering between the mesogens and smectic ordering between the layers is identified. Micellar hydrophobic PPO with hydrated PEO coronas are known to self-assemble into many crystalline orders, including cubic, hexagonal, lamellar, and inverse hexagonal mesophases, which extend into cylindrical micelles with increasing temperature. Relatively small size of Pluronic copolymers with regard to general polymers, but rather large size of their micelles and their tendency to organize into crystalline mesophases are thought to contribute to the anisotropic growth of Pd nanorods.

Effect of metallic silver nanoparticles on the alignment and relaxation behaviour of liquid crystalline material in smectic C* phase

NASA Astrophysics Data System (ADS)

Vimal, Tripti; Kumar Gupta, Swadesh; Katiyar, Rohit; Srivastava, Atul; Czerwinski, Michal; Krup, Katarzyna; Kumar, Sandeep; Manohar, Rajiv

2017-09-01

The influence of silver nanoparticles dispersed in a Ferroelectric Liquid Crystal (FLC) on the properties of the resultant composite system has been investigated by thermal, electro-optical, and dielectric methods. We show that the concentration of thiol capped silver nanoparticles is a critical factor in governing the alignment of nanoparticles (NPs) in the host FLC. The orientation of NPs in composite samples affects the ordering of the LC (Liquid Crystal) phase and consequently changes the various phase transition temperatures of the host LC. Formation of self-assembled 2D (two dimensional) arrays of nanoparticles is observed for high concentration of dopant in the LC, oriented perpendicular to the direction of rubbing. We propose that the molecular interaction between the thiol capped NPs and LC molecules is the key factor behind such an arrangement of NPs. Orientation of NPs has affected the relaxation behaviour and various other material parameters, significantly. A noteworthy change in DC conductivity articulates our proposed idea of the formation of 2D array of NPs perpendicular to the direction of rubbing. This comprehensive study endorses the importance of dopant concentration in modifying the properties of the host LC material.

Mapping two-dimensional polar active fluids to two-dimensional soap and one-dimensional sandblasting

NASA Astrophysics Data System (ADS)

Chen, Leiming; Lee, Chiu Fan; Toner, John

2016-07-01

Active fluids and growing interfaces are two well-studied but very different non-equilibrium systems. Each exhibits non-equilibrium behaviour distinct from that of their equilibrium counterparts. Here we demonstrate a surprising connection between these two: the ordered phase of incompressible polar active fluids in two spatial dimensions without momentum conservation, and growing one-dimensional interfaces (that is, the 1+1-dimensional Kardar-Parisi-Zhang equation), in fact belong to the same universality class. This universality class also includes two equilibrium systems: two-dimensional smectic liquid crystals, and a peculiar kind of constrained two-dimensional ferromagnet. We use these connections to show that two-dimensional incompressible flocks are robust against fluctuations, and exhibit universal long-ranged, anisotropic spatio-temporal correlations of those fluctuations. We also thereby determine the exact values of the anisotropy exponent ζ and the roughness exponents χx,y that characterize these correlations.

Mapping two-dimensional polar active fluids to two-dimensional soap and one-dimensional sandblasting.

PubMed

Chen, Leiming; Lee, Chiu Fan; Toner, John

2016-07-25

Active fluids and growing interfaces are two well-studied but very different non-equilibrium systems. Each exhibits non-equilibrium behaviour distinct from that of their equilibrium counterparts. Here we demonstrate a surprising connection between these two: the ordered phase of incompressible polar active fluids in two spatial dimensions without momentum conservation, and growing one-dimensional interfaces (that is, the 1+1-dimensional Kardar-Parisi-Zhang equation), in fact belong to the same universality class. This universality class also includes two equilibrium systems: two-dimensional smectic liquid crystals, and a peculiar kind of constrained two-dimensional ferromagnet. We use these connections to show that two-dimensional incompressible flocks are robust against fluctuations, and exhibit universal long-ranged, anisotropic spatio-temporal correlations of those fluctuations. We also thereby determine the exact values of the anisotropy exponent ζ and the roughness exponents χx,y that characterize these correlations.

Smectic C chevrons in nanocylinders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lefort, R., E-mail: ronan.lefort@univ-rennes1.fr; Morineau, D.; Jean, F.

2014-11-17

The structure of an achiral smectic-C liquid crystal confined in nanocylinders with a planar surface anchoring is studied by small angle neutron scattering. We observe an invariant alignment of the nematic director with the pore axis, that promotes an original chevron structure with revolution symmetry.

Design and Development of the Observation and Analysis of Smectic Islands in Space Experiment

NASA Technical Reports Server (NTRS)

Hall, Nancy Rabel; Tin, Padetha; Sheehan, C. C.; Stannarius, R.; Trittel, T.; Clark, N.; Maclennan, J.; Glaser, M.; Park, C.

2012-01-01

The primary objective of Observation and Analysis of Smectic Islands in Space (OASIS) experiment is to exploit the unique characteristics of freely suspended liquid crystals in a microgravity environment to advance the understanding of fluid state physics

Hamiltonian approach to continuum dynamics

NASA Astrophysics Data System (ADS)

Isaev, A. A.; Kovalevskii, M. Yu.; Peletminskii, S. V.

1995-02-01

A study is made of the problem of obtaining the Poisson-bracket algebra of the dynamical variables of continuous media on the basis of specification of the kinematic part of the Lagrangian in terms of generalized coordinates and momenta. Within this algebra, subalgebras of variables corresponding to the description of elastic media, the hydrodynamics of ordinary liquids, and the dynamics of some phases of liquid crystals are identified. The differential conservation laws associated with the symmetries of the Hamiltonian of the system are studied. The dynamics of nematics is considered, and features of the dynamics of the cholesteric, smectic, and discotic phases are noted.

Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Diama, A.; Matthies, B.; Herwig, K. W.; Hansen, F. Y.; Criswell, L.; Mo, H.; Bai, M.; Taub, H.

2009-08-01

We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C24H50 denoted as C24) and dotriacontane (n-C32H66 denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 Å=√3 ag, where ag=2.46 Å is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by ˜10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation.

PubMed

Diama, A; Matthies, B; Herwig, K W; Hansen, F Y; Criswell, L; Mo, H; Bai, M; Taub, H

2009-08-28

We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

Liquid crystals for organic thin-film transistors

PubMed Central

Iino, Hiroaki; Usui, Takayuki; Hanna, Jun-ichi

2015-01-01

Crystalline thin films of organic semiconductors are a good candidate for field effect transistor (FET) materials in printed electronics. However, there are currently two main problems, which are associated with inhomogeneity and poor thermal durability of these films. Here we report that liquid crystalline materials exhibiting a highly ordered liquid crystal phase of smectic E (SmE) can solve both these problems. We design a SmE liquid crystalline material, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), for FETs and synthesize it. This material provides uniform and molecularly flat polycrystalline thin films reproducibly when SmE precursor thin films are crystallized, and also exhibits high durability of films up to 200 °C. In addition, the mobility of FETs is dramatically enhanced by about one order of magnitude (over 10 cm2 V−1 s−1) after thermal annealing at 120 °C in bottom-gate-bottom-contact FETs. We anticipate the use of SmE liquid crystals in solution-processed FETs may help overcome upcoming difficulties with novel technologies for printed electronics. PMID:25857435

Liquid crystals for organic thin-film transistors.

PubMed

Iino, Hiroaki; Usui, Takayuki; Hanna, Jun-ichi

2015-04-10

Crystalline thin films of organic semiconductors are a good candidate for field effect transistor (FET) materials in printed electronics. However, there are currently two main problems, which are associated with inhomogeneity and poor thermal durability of these films. Here we report that liquid crystalline materials exhibiting a highly ordered liquid crystal phase of smectic E (SmE) can solve both these problems. We design a SmE liquid crystalline material, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), for FETs and synthesize it. This material provides uniform and molecularly flat polycrystalline thin films reproducibly when SmE precursor thin films are crystallized, and also exhibits high durability of films up to 200 °C. In addition, the mobility of FETs is dramatically enhanced by about one order of magnitude (over 10 cm(2) V(-1) s(-1)) after thermal annealing at 120 °C in bottom-gate-bottom-contact FETs. We anticipate the use of SmE liquid crystals in solution-processed FETs may help overcome upcoming difficulties with novel technologies for printed electronics.

Liquid crystals for organic thin-film transistors

NASA Astrophysics Data System (ADS)

Iino, Hiroaki; Usui, Takayuki; Hanna, Jun-Ichi

2015-04-01

Crystalline thin films of organic semiconductors are a good candidate for field effect transistor (FET) materials in printed electronics. However, there are currently two main problems, which are associated with inhomogeneity and poor thermal durability of these films. Here we report that liquid crystalline materials exhibiting a highly ordered liquid crystal phase of smectic E (SmE) can solve both these problems. We design a SmE liquid crystalline material, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), for FETs and synthesize it. This material provides uniform and molecularly flat polycrystalline thin films reproducibly when SmE precursor thin films are crystallized, and also exhibits high durability of films up to 200 °C. In addition, the mobility of FETs is dramatically enhanced by about one order of magnitude (over 10 cm2 V-1 s-1) after thermal annealing at 120 °C in bottom-gate-bottom-contact FETs. We anticipate the use of SmE liquid crystals in solution-processed FETs may help overcome upcoming difficulties with novel technologies for printed electronics.

Liquid crystalline phase behavior in systems of hard-sphere chains

NASA Astrophysics Data System (ADS)

Williamson, Dave C.; Jackson, George

1998-06-01

A study of the liquid crystalline phase transitions in a system of hard-sphere chains is presented. The chains comprise m=7 tangentially bonded hard-sphere segments in a linear conformation (LHSC). The isothermal-isobaric Monte Carlo simulation technique is used to obtain the equation of state of the system both by compressing the isotropic (I) liquid and by expanding the solid (K). As well as the usual isotropic and solid phases, nematic and smectic-A liquid crystalline states are seen. A large degree of hysteresis is found in the neighborhood of the I-N transition. The results for the rigid LHSC system were compared with existing data for the corresponding semiflexible hard-sphere chains (FHSC): the flexibility has a large destabilizing effect on the nematic phase and consequently it postpones the I-N transition. The results of the simulations are also compared with rescaled Onsager theories for the I-N transition. It is rather surprising to find that the Parsons approach, which has been so successful for other hard-core models such as spherocylinders and ellipsoids, gives very poor results. The related approach of Vega and Lago gives a good description of the I-N phase transition. The procedure of Vega and Lago, as with all two-body resummations of the Onsager theory, only gives a qualitative description of the nematic order.

European Scientific Notes. Volume 35. Number 1.

DTIC Science & Technology

1981-01-31

thermotropic polymers, primar- formed smectic phases. She also studied ily with aromatic polyesters. Dr. R.W. the orientation of liquid crystal ...booster synchrotron and Linac are switched studies of crystals where a very good off and the electrons are allowed to approximation to a point source...compounds in the temperature Cr in a MgO host crystal in magnetic range of 1 to 25 K and as a function of fields up to 2*S T at temperatures between

Synthesis of new liquid crystals embedded gold nanoparticles for photoswitching properties.

PubMed

Rahman, Md Lutfor; Biswas, Tapan Kumar; Sarkar, Shaheen M; Yusoff, Mashitah Mohd; Yuvaraj, A R; Kumar, Sandeep

2016-09-15

A new series of liquid crystals decorated gold nanoparticles is synthesized whose molecular architecture has azobenzenes moieties as the peripheral units connected to gold nanoparticles (Au NPs) via alkyl groups. The morphology and mesomorphic properties were investigated by field emission scanning electron microscope, high-resolution transmission electron microscopy, differential scanning calorimetry and polarizing optical microscopy. The thiolated ligand molecules (3a-c) showed enantiotropic smectic A phase, whereas gold nanoparticles (5a-c) exhibit nematic and smectic A phase with monotropic nature. HR-TEM measurement showed that the functionalized Au NPs are of the average size of 2nm and they are well dispersed without any aggregation. The trans-form of azo compounds showed a strong band in the UV region at ∼378nm for the π-π(∗) transition, and a weak band in the visible region at ∼472nm due to the n-π(∗) transition. These molecules exhibit attractive photoisomerization behaviour in which trans-cis transition takes about 15s whereas the cis-trans transition requires about 45min for compound 5c. The extent of reversible isomerization did not decay after 10 cycles, which proved that the photo-responsive properties of 5c were stable and repeatable. Therefore, these materials may be suitably exploited in the field of molecular switches and the optical storage devices. Copyright © 2016 Elsevier Inc. All rights reserved.

1,2,4-oxadiazole-based bent-core liquid crystals with cybotactic nematic phases.

PubMed

Shanker, Govindaswamy; Prehm, Marko; Nagaraj, Mamatha; Vij, Jagdish K; Weyland, Marvin; Eremin, Alexey; Tschierske, Carsten

2014-05-19

Several series of bent-core mesogens derived from 3,5-diphenyl-1,2,4-oxadiazole with or without lateral groups and with different length terminal chains at both ends, and polycatenar molecules with three to six alkoxy chains are synthesized and their mesomorphic behaviour is investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction (XRD), dielectric, electro-optical and second-harmonic generation (SHG) experiments. Most compounds exhibit broad regions of skewed cybotactic nematic (NcybC ) and tilted smectic (SmC) phases with a strong tilt of the aromatic cores (up to 63°), but non-tilted SmA and NcybA phases are also observed for a compound that has only one terminal chain. The XRD patterns of the nematic phases of most of the compounds investigated indicate a 2D periodicity with short correlation length in the magnetically aligned samples. This is of importance for the general interpretation of the small-angle XRD splitting patterns typically observed for aligned samples of bent-core nematic phases. In most nematic phases one current peak is observed in the half period of an applied electric field, though no coherent signal is found in the SHG experiments. Based on additional electro-optical and dielectric results, the nematic phases are considered to be cybotactic nematic phases with local polar order, and show a dielectric reorientation of the polar domains. Only chiral nematic phases (NcybC *), but not blue phases, are obtained for compounds with one or two chiral (3S)-3,7-dimethyloctyloxy tail(s). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flow Velocity Profiles in Actively-Driven 2D Nozzle Experiments using Freely-Suspended Smectic Liquid Crystal Films

NASA Astrophysics Data System (ADS)

Dutch, Evan; Briggs, Corrina; Ferguson, Kyle; Green, Adam; Park, Cheol; Glaser, Matt; Maclennan, Joe; Clark, Noel

Freely-suspended smectic A liquid crystal films have been used to explore a large range of interesting flow phenomena. Passive microrheology experiments have confirmed previously that such films are ideal systems with which to investigate two-dimensional (2D) hydrodynamics. Here we describe an experiment that uses smectic films to study actively-driven 2D flows. Flow excited by blowing air over a film of smectic liquid crystal material containing small inclusions is captured using digital video microscopy. The flow fields are extracted using particle imaging velocimetry. We have measured the velocity field generated by flow through a thin nozzle into a large rectangular reservoir and compared this to a theoretical model based on 2D complex potential flows. The observations confirm that there is parabolic flow in straight channels, and that the theory accurately models the film velocity flow field in the reservoir. This work was supported by NASA Grant No. NNX-13AQ81G, and NSF MRSEC Grants No. DMR-0820579 and DMR-1420736.

Elastic moduli of a smectic membrane: a rod-level scaling analysis

NASA Astrophysics Data System (ADS)

Wensink, H. H.; Morales Anda, L.

2018-02-01

Chiral rodlike colloids exposed to strong depletion attraction may self-assemble into chiral membranes whose twisted director field differs from that of a 3D bulk chiral nematic. We formulate a simple microscopic variational theory to determine the elastic moduli of rods assembled into a bidimensional smectic membrane. The approach is based on a simple Onsager-Straley theory for a non-uniform director field that we apply to describe rod twist within the membrane. A microscopic approach enables a detailed estimate of the individual Frank elastic moduli (splay, twist and bend) as well as the twist penetration depth of the smectic membrane in relation to the rod density and shape. We find that the elastic moduli are distinctly different from those of a bulk nematic fluid, with the splay elasticity being much stronger and the curvature elasticity much weaker than for rods assembled in a three-dimensional nematic fluid. We argue that the use of the simplistic one-constant approximation in which all moduli are assumed to be of equal magnitude is not appropriate for modelling the structure-property relation of smectic membranes.

Smectic C liquid crystal growth through surface orientation by ZnxCd1-xSe thin films

NASA Astrophysics Data System (ADS)

Katranchev, B.; Petrov, M.; Bineva, I.; Levi, Z.; Mineva, M.

2012-12-01

A smectic C liquid crystal (LC) texture, consisting of distinct local single crystals (DLSCs) was grown using predefined orientation of ternary nanocrystalline thin films of ZnxCd1-xSe. The surface morphology and orientation features of the ZnxCd1-xSe films were investigated by AFM measurements and micro-texture polarization analysis. The ZnxCd1-xSe surface causes a substantial enlargement of the smectic C DLSCs and induction of a surface bistable state. The specific character of the morphology of this coating leads to the decrease of the corresponding anchoring energy. Two new chiral states, not typical for this LC were indicated. The physical mechanism providing these new effects is presented.

On a Minimum Problem in Smectic Elastomers

NASA Astrophysics Data System (ADS)

Buonsanti, Michele; Giovine, Pasquale

2008-07-01

Smectic elastomers are layered materials exhibiting a solid-like elastic response along the layer normal and a rubbery one in the plane. Balance equations for smectic elastomers are derived from the general theory of continua with constrained microstructure. In this work we investigate a very simple minimum problem based on multi-well potentials where the microstructure is taken into account. The set of polymeric strains minimizing the elastic energy contains a one-parameter family of simple strain associated with a micro-variation of the degree of freedom. We develop the energy functional through two terms, the first one nematic and the second one considering the tilting phenomenon; after, by developing in the rubber elasticity framework, we minimize over the tilt rotation angle and extract the engineering stress.

Rim instability of bursting thin smectic films

NASA Astrophysics Data System (ADS)

Trittel, Torsten; John, Thomas; Tsuji, Kinko; Stannarius, Ralf

2013-05-01

The rupture of thin smectic bubbles is studied by means of high speed video imaging. Bubbles of centimeter diameter and film thicknesses in the nanometer range are pierced, and the instabilities of the moving rim around the opening hole are described. Scaling laws describe the relation between film thickness and features of the filamentation process of the rim. A flapping motion of the retracting smectic film is assumed as the origin of the observed filamentation instability. A comparison with similar phenomena in soap bubbles is made. The present experiments extend studies on soap films [H. Lhuissier and E. Villermaux, Phys. Rev. Lett. 103, 054501 (2009), 10.1103/PhysRevLett.103.054501] to much thinner, uniform films of thermotropic liquid crystals.

Semiflexible polymers confined in a slit pore with attractive walls: two-dimensional liquid crystalline order versus capillary nematization.

PubMed

Milchev, Andrey; Egorov, Sergei A; Binder, Kurt

2017-03-01

Semiflexible polymers under good solvent conditions interacting with attractive planar surfaces are investigated by Molecular Dynamics (MD) simulations and classical Density Functional Theory (DFT). A bead-spring type potential complemented by a bending potential is used, allowing variation of chain stiffness from completely flexible coils to rod-like polymers whose persistence length by far exceeds their contour length. Solvent is only implicitly included, monomer-monomer interactions being purely repulsive, while two types of attractive wall-monomer interactions are considered: (i) a strongly attractive Mie-type potential, appropriate for a strictly structureless wall, and (ii) a corrugated wall formed by Lennard-Jones particles arranged on a square lattice. It is found that in dilute solutions the former case leads to the formation of a strongly adsorbed surface layer, and the profile of density and orientational order in the z-direction perpendicular to the wall is predicted by DFT in nice agreement with MD. While for very low bulk densities a Kosterlitz-Thouless type transition from the isotropic phase to a phase with power-law decay of nematic correlations is suggested to occur in the strongly adsorbed layer, for larger densities a smectic-C phase in the surface layer is detected. No "capillary nematization" effect at higher bulk densities is found in this system, unlike systems with repulsive walls. This finding is attributed to the reduction of the bulk density (in the center of the slit pore) due to polymer adsorption on the attractive wall, for a system studied in the canonical ensemble. Consequently in a system with two attractive walls nematic order in the slit pore can occur only at a higher density than for a bulk system.

Ordering of anisotropic nanoparticles in diblock copolymer lamellae: Simulations with dissipative particle dynamics and a molecular theory.

PubMed

Berezkin, Anatoly V; Kudryavtsev, Yaroslav V; Gorkunov, Maxim V; Osipov, Mikhail A

2017-04-14

Local distribution and orientation of anisotropic nanoparticles in microphase-separated symmetric diblock copolymers has been simulated using dissipative particle dynamics and analyzed with a molecular theory. It has been demonstrated that nanoparticles are characterized by a non-trivial orientational ordering in the lamellar phase due to their anisotropic interactions with isotropic monomer units. In the simulations, the maximum concentration and degree of ordering are attained for non-selective nanorods near the domain boundary. In this case, the nanorods have a certain tendency to align parallel to the interface in the boundary region and perpendicular to it inside the domains. Similar orientation ordering of nanoparticles located at the lamellar interface is predicted by the molecular theory which takes into account that the nanoparticles interact with monomer units via both isotropic and anisotropic potentials. Computer simulations enable one to study the effects of the nanorod concentration, length, stiffness, and selectivity of their interactions with the copolymer components on the phase stability and orientational order of nanoparticles. If the volume fraction of the nanorods is lower than 0.1, they have no effect on the copolymer transition from the disordered state into a lamellar microstructure. Increasing nanorod concentration or nanorod length results in clustering of the nanorods and eventually leads to a macrophase separation, whereas the copolymer preserves its lamellar morphology. Segregated nanorods of length close to the width of the diblock copolymer domains are stacked side by side into smectic layers that fill the domain space. Thus, spontaneous organization and orientation of nanorods leads to a spatial modulation of anisotropic composite properties which may be important for various applications.

Ordering of anisotropic nanoparticles in diblock copolymer lamellae: Simulations with dissipative particle dynamics and a molecular theory

NASA Astrophysics Data System (ADS)

Berezkin, Anatoly V.; Kudryavtsev, Yaroslav V.; Gorkunov, Maxim V.; Osipov, Mikhail A.

2017-04-01

Local distribution and orientation of anisotropic nanoparticles in microphase-separated symmetric diblock copolymers has been simulated using dissipative particle dynamics and analyzed with a molecular theory. It has been demonstrated that nanoparticles are characterized by a non-trivial orientational ordering in the lamellar phase due to their anisotropic interactions with isotropic monomer units. In the simulations, the maximum concentration and degree of ordering are attained for non-selective nanorods near the domain boundary. In this case, the nanorods have a certain tendency to align parallel to the interface in the boundary region and perpendicular to it inside the domains. Similar orientation ordering of nanoparticles located at the lamellar interface is predicted by the molecular theory which takes into account that the nanoparticles interact with monomer units via both isotropic and anisotropic potentials. Computer simulations enable one to study the effects of the nanorod concentration, length, stiffness, and selectivity of their interactions with the copolymer components on the phase stability and orientational order of nanoparticles. If the volume fraction of the nanorods is lower than 0.1, they have no effect on the copolymer transition from the disordered state into a lamellar microstructure. Increasing nanorod concentration or nanorod length results in clustering of the nanorods and eventually leads to a macrophase separation, whereas the copolymer preserves its lamellar morphology. Segregated nanorods of length close to the width of the diblock copolymer domains are stacked side by side into smectic layers that fill the domain space. Thus, spontaneous organization and orientation of nanorods leads to a spatial modulation of anisotropic composite properties which may be important for various applications.

Molecular Dynamics in a Liquid Crystal with Reentrant Mesophases

NASA Astrophysics Data System (ADS)

Sebastião, P. J.; Ribeiro, A. C.; Nguyen, H. T.; Noack, F.

1995-11-01

It is well known that liquid crystalline compounds with a cyano terminal group can present peculiar polymorphisms in particular different types of smectic A mesophases and a reentrant behaviour for both nematic and smectic A mesophases. In this work we study by proton NMR relaxation the influence of these features on the molecular dynamics of the compound 4-cyanobenzoate-4'-octylbenzoyloxyphenyl (DB8CN Sym) in its nematic (N), partial bilayer smectic A (SAd), reentrant nematic (Nre) and reentrant smectic A (SA1) mesophases. Standard and fast field-cycling techniques were used for our spin-lattice relaxation's study over a broad frequency range of 6 decades (200 Hz up to 300 MHz). It was found that the molecular dynamics in the nematic mesophases is rather different from the molecular dynamics in the smectic A mesophases. However, the reentrant aspect present in both nematic and smectic A states is not associated to a major difference on the molecular dynamics of the nematic and reentrant nematic or smectic and reentrant smectic A mesophases. Order director fluctuations and rotations/reorientations are the most important relaxation mechanisms in the nematic mesophases in the lower and higher frequency limits, respectively, while self-diffusion has a very small contribution to the overall relaxation. As for the smectic A mesophases, self-diffusion and rotations/reorientations are the predominant relaxation mechanisms for frequencies above 20 kHz. The collective motions, which for these mesophases have to be associated with layer undulations with the frequency law T_1sim ν, are only important to the spin-lattice relaxation on the low part of the frequency spectrum (ν<10 kHz). The inclusion in the relaxation study of a contribution from the cross-relaxation between protons and nitrogen nuclei improves the quality of the 1/T_1 data fits in both kinds of mesophases. The combined study of the molecular dynamics in the N, SAd, Nre and SA1 mesophases of DB8CN Sym reveals that it is necessary to consider one more contribution to the relaxation in the analysis of the 1/T_1 data in the SAd and high temperature N mesophases. This contribution is associated with a dynamic process of dissociation and recombination of molecules in groups that could be present in this kind of systems as predicted in the literature to explain the layer thickness detected in the SAd mesophases. The characteristic time for this process was estimated. Les composés cristaux liquides à groupe terminal cyano peuvent présenter de curieux polymorphismes, en particulier différents types de mésophases smectiques A et un compotement réentrant pour les mésophases nématiques et smectiques A. Dans ce travail nous étudions par RMN l'influence de ces caractéristiques sur la dynamique moléculaire du composé 4-cyanobenzoate-4'-octylbenzoyloxyphenyl (DB8CN Sym) dans ces phases nématique (N), smectique partiellement bicouche A (SAd), nématique réentrant (Nre) et réentrant smectique A(SA1). Nous avons utilisé dans notre étude de la relaxation spin-réseau des techniques classiques et de champ cyclique rapide sur un intervalle de fréquence de 6 décales (200 Hz à 300 MHz). Nous avons trouvé que la dynamique moléculaire des mésophases nématiques est particulièrement différente de celle des mésophases smectiques A. Toutefois, l'effet de réentrance présent dans les états nématique et smectique A n'est pas associé à une différence majeure de la dynamique moléculaire des mésophases nématique, nématique réentrante ou smectique et smectique A réentrante. Les mécanismes de relaxation les plus importants dans les mésophases nématiques à basse et haute fréquences sont respectivement les fluctuations du vecteur d'ordre et des rotations/réorientations, alors que l'auto-diffusion apporte une très faible contribution à la relaxation totale. Dans les mésophases smectiques A l'auto-diffusion et les rotations/réorientations sont les mécanismes de relaxation dominants pour des fréquences au dessus de 20 kHz. Les mouvements collectifs (qui doivent dans ce cas être associés à des ondulations de couche avec une loi de dispersion T_1sim ν) ne doivent être pris en compte pour la relaxation spin-réseau que pour les basses fréquences de Larmor (ν<10 kHz). L'inclusion d'une contribution de la relaxation croisée entre protons et noyaux d'azote dans le modèle de relaxation augmente la qualité des fits de 1/T_1 dans les deux sortes de mésophases. L'étude combinée de la dynamique moléculaire dans les mésophases N, SAd, Nre et SA1 du DB8CN Sym montre qu'il faut en fait considérer une contribution supplémentaire pour la relaxation dans l'analyse des données 1/T_1 dans les mésophases SAd et nématique à haute température. Cette contribution est associée à un processus dynamique de dissociation et recombinaison de molécules en groupes qui pourraient être présentes dans ces types de systèmes, ce qui permettrait d'expliquer l'épaisseur observée pour les couches dans les mésophases SAd, comme prévu dans la littérature. Le temps caractéristique de ce processus a été estimé.

Multi-responsible chameleon molecule with chiral naphthyl and azobenzene moieties.

PubMed

Kim, Dae-Yoon; Lee, Sang-A; Park, Minwook; Choi, Yu-Jin; Kang, Shin-Woong; Jeong, Kwang-Un

2015-04-21

A photochromic chiral molecule with azobenzene mesogens and a (R)-configuration naphthyl moiety (abbreviated as NCA2M) was specifically designed and synthesized for the demonstration of chameleon-like color changes responding to multitudinous external stimuli, such as temperature, light and electric field. The basic phase transition behaviors of NCA2M were first studied by the combination of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Based on the structure-sensitive X-ray diffraction results obtained at different temperatures, it was comprehended that the NCA2M molecule exhibited the tilted version of highly ordered smectic crystal phase with 5.45 nm layer thickness. Chiral nematic (N*) liquid crystals (LC) with helical superstructures were formed by doping the NCA2M photochromic chiral molecule in an achiral nematic (N) LC medium. By controlling the helical pitch length of N*-LC with respect to temperature, light and electric field, the wavelength of selectively reflected light from the N* photonic crystal was finely tuned. The light-induced color change of N*-LC film was the most efficient method for covering the whole visible region from blue to green and to red, which allowed us to fabricate remote-controllable photo-responsive devices.

Dielectric spectroscopy of the SmQ* phase

NASA Astrophysics Data System (ADS)

Perkowski, P.; Bubnov, A.; Piecek, W.; Ogrodnik, K.; Hamplová, V.; Kašpar, M.

2011-11-01

Liquid crystal possessing two biphenyl moieties in the molecular core and lateral chlorine substitution far from the chiral chain has been studied by dielectric spectroscopy. On cooling from the isotropic phase, the material possesses the frustrated smectic Q* (SmQ*) and SmCA* phases. It has been confirmed by dielectric spectroscopy that the SmQ* phase can be related to the SmCA* anti-ferroelectric phase. However, only one relaxation process has been observed in the SmQ* phase, while in the SmCA*, two relaxations are clearly detectable. It seems that the mode found in the SmQ* can be connected with high-frequency anti-phase mode observed in the SmCA* phase. Its relaxation frequency is similar to PH relaxation frequency, but is weaker. The same relaxation has been observed even a few degrees above the SmQ*-Iso phase transition. Another explanation for the mode detected in SmQ* and isotropic phases can be molecular motions around short molecular axis.

Focus: Two-dimensional electron-electron double resonance and molecular motions: The challenge of higher frequencies.

PubMed

Franck, John M; Chandrasekaran, Siddarth; Dzikovski, Boris; Dunnam, Curt R; Freed, Jack H

2015-06-07

The development, applications, and current challenges of the pulsed ESR technique of two-dimensional Electron-Electron Double Resonance (2D ELDOR) are described. This is a three-pulse technique akin to 2D Exchange Nuclear Magnetic Resonance, but involving electron spins, usually in the form of spin-probes or spin-labels. As a result, it required the extension to much higher frequencies, i.e., microwaves, and much faster time scales, with π/2 pulses in the 2-3 ns range. It has proven very useful for studying molecular dynamics in complex fluids, and spectral results can be explained by fitting theoretical models (also described) that provide a detailed analysis of the molecular dynamics and structure. We discuss concepts that also appear in other forms of 2D spectroscopy but emphasize the unique advantages and difficulties that are intrinsic to ESR. Advantages include the ability to tune the resonance frequency, in order to probe different motional ranges, while challenges include the high ratio of the detection dead time vs. the relaxation times. We review several important 2D ELDOR studies of molecular dynamics. (1) The results from a spin probe dissolved in a liquid crystal are followed throughout the isotropic → nematic → liquid-like smectic → solid-like smectic → crystalline phases as the temperature is reduced and are interpreted in terms of the slowly relaxing local structure model. Here, the labeled molecule is undergoing overall motion in the macroscopically aligned sample, as well as responding to local site fluctuations. (2) Several examples involving model phospholipid membranes are provided, including the dynamic structural characterization of the boundary lipid that coats a transmembrane peptide dimer. Additionally, subtle differences can be elicited for the phospholipid membrane phases: liquid disordered, liquid ordered, and gel, and the subtle effects upon the membrane, of antigen cross-linking of receptors on the surface of plasma membrane, vesicles can be observed. These 2D ELDOR experiments are performed as a function of mixing time, Tm, i.e., the time between the second and third π/2 pulses, which provides a third dimension. In fact, a fourth dimension may be added by varying the ESR frequency/magnetic field combination. Therefore, (3) it is shown how continuous-wave multifrequency ESR studies enable the decomposition of complex dynamics of, e.g., proteins by virtue of their respective time scales. These studies motivate our current efforts that are directed to extend 2D ELDOR to higher frequencies, 95 GHz in particular (from 9 and 17 GHz), in order to enable multi-frequency 2D ELDOR. This required the development of quasi-optical methods for performing the mm-wave experiments, which are summarized. We demonstrate state-of-the-art 95 GHz 2D ELDOR spectroscopy through its ability to resolve the two signals from a spin probe dissolved in both the lipid phase and the coexisting aqueous phase. As current 95 GHz experiments are restricted by limited spectral coverage of the π/2 pulse, as well as the very short T2 relaxation times of the electron spins, we discuss how these limitations are being addressed.

Focus: Two-dimensional electron-electron double resonance and molecular motions: The challenge of higher frequencies

NASA Astrophysics Data System (ADS)

Franck, John M.; Chandrasekaran, Siddarth; Dzikovski, Boris; Dunnam, Curt R.; Freed, Jack H.

2015-06-01

The development, applications, and current challenges of the pulsed ESR technique of two-dimensional Electron-Electron Double Resonance (2D ELDOR) are described. This is a three-pulse technique akin to 2D Exchange Nuclear Magnetic Resonance, but involving electron spins, usually in the form of spin-probes or spin-labels. As a result, it required the extension to much higher frequencies, i.e., microwaves, and much faster time scales, with π/2 pulses in the 2-3 ns range. It has proven very useful for studying molecular dynamics in complex fluids, and spectral results can be explained by fitting theoretical models (also described) that provide a detailed analysis of the molecular dynamics and structure. We discuss concepts that also appear in other forms of 2D spectroscopy but emphasize the unique advantages and difficulties that are intrinsic to ESR. Advantages include the ability to tune the resonance frequency, in order to probe different motional ranges, while challenges include the high ratio of the detection dead time vs. the relaxation times. We review several important 2D ELDOR studies of molecular dynamics. (1) The results from a spin probe dissolved in a liquid crystal are followed throughout the isotropic → nematic → liquid-like smectic → solid-like smectic → crystalline phases as the temperature is reduced and are interpreted in terms of the slowly relaxing local structure model. Here, the labeled molecule is undergoing overall motion in the macroscopically aligned sample, as well as responding to local site fluctuations. (2) Several examples involving model phospholipid membranes are provided, including the dynamic structural characterization of the boundary lipid that coats a transmembrane peptide dimer. Additionally, subtle differences can be elicited for the phospholipid membrane phases: liquid disordered, liquid ordered, and gel, and the subtle effects upon the membrane, of antigen cross-linking of receptors on the surface of plasma membrane, vesicles can be observed. These 2D ELDOR experiments are performed as a function of mixing time, Tm, i.e., the time between the second and third π/2 pulses, which provides a third dimension. In fact, a fourth dimension may be added by varying the ESR frequency/magnetic field combination. Therefore, (3) it is shown how continuous-wave multifrequency ESR studies enable the decomposition of complex dynamics of, e.g., proteins by virtue of their respective time scales. These studies motivate our current efforts that are directed to extend 2D ELDOR to higher frequencies, 95 GHz in particular (from 9 and 17 GHz), in order to enable multi-frequency 2D ELDOR. This required the development of quasi-optical methods for performing the mm-wave experiments, which are summarized. We demonstrate state-of-the-art 95 GHz 2D ELDOR spectroscopy through its ability to resolve the two signals from a spin probe dissolved in both the lipid phase and the coexisting aqueous phase. As current 95 GHz experiments are restricted by limited spectral coverage of the π/2 pulse, as well as the very short T2 relaxation times of the electron spins, we discuss how these limitations are being addressed.

Structural Characterization and Impedance Spectroscopy of Substituted, Fused-Ring Organic Semiconductors

NASA Astrophysics Data System (ADS)

Shaw, Charles Michael

Organic materials present a number of advantages over silicon that make them ideal candidates for modest performance devices like active matrix backplanes and RFID tags. The work detailed here describes both structural characterization of promising new materials, as well as the adaptation of impedance spectroscopy techniques to the study of organic transistors. Unit cells and solution casting behavior for dioctyl- and didodecyl-pentathienoacene are presented. Dioctyl pentathienoacene has an orthorhombic lattice with parameters a = 1.15 nm, b = 0.43 nm and c = 3.05 nm. Didodecyl pentathienoacene has an monoclinic lattice with parameters gamma = 92.2°, a = 1.10 urn, b = 0.42 nm and c = 3.89 nm. Additionally, thermotropic phase behavior is detailed. Both materials exhibit a "side chain melting" transition---characterized by a dramatic unit cell contraction of more than 20%---and smectic C liquid crystal phases. The side chain melting transition shows similarity to phase transitions elicited by exposing these materials to high energy electron flux. In both cases, disorder in the substitutions results in new phases for these materials. Dioctyl-pentathienoacene also exhibits a unique phase, which is intermediately ordered and shows a threefold increase in critical dose over the as-cast phase. Impedance spectroscopy of triisopropylsilyl pentacene transistors suggests these devices are well fit by a Voigt model equivalent circuit. The gate bias dependent resistor represents the channel conductance and the capacitor represents the drain-gate and source-gate capacitances. This in turn suggests that conduction occurs through delocalized states available in ordered regions, with disordered regions contributing localized, immobile states. Impedance spectroscopy of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) shows similar behavior. The use of variable temperature impedance spectroscopy is also demonstrated. This technique is used to measure the reduction in trap energy---from 200 meV to 140 meV---produced by annealing the material in its liquid crystal phase.

Orientational fluctuations and phase transitions in 8CB confined by cylindrical pores of the PET film

NASA Astrophysics Data System (ADS)

Maksimochkin, G. I.; Shmeliova, D. V.; Pasechnik, S. V.; Dubtsov, A. V.; Semina, O. A.; Kralj, S.

2016-08-01

Results of optical investigations of the isotropic-nematic and nematic-smectic A phase transitions in porous polyethyleneterephthalate (PET) films filled with octyl-cyanobihenyl (8CB) liquid crystal (LC) are reported. Samples of porous films of thickness 23 µm with normally oriented cylindrical pores of a radius R ranging from 10 nm to 1000 nm were prepared using the track-etched membrane technology. The dynamic light scattering method was used to probe the nematic orientational fluctuations of confined LC samples. The corresponding relaxation time τ was measured as a function of R and temperature T at slow enough cooling rates (0.3-0.6 K/h) to locate the phase transition temperatures. Changes in τ(T) dependencies relatively sensitivity fingerprint the LC phase transformations. Experimental results are analysed using the Landau-de Gennes-Ginzburg phenomenological approach.

Effects of Structural Variations on the Cellular Response and Mechanical Properties of Biocompatible, Biodegradable, and Porous Smectic Liquid Crystal Elastomers.

PubMed

Sharma, Anshul; Mori, Taizo; Mahnen, Cory J; Everson, Heather R; Leslie, Michelle T; Nielsen, Alek D; Lussier, Laurent; Zhu, Chenhui; Malcuit, Christopher; Hegmann, Torsten; McDonough, Jennifer A; Freeman, Ernest J; Korley, LaShanda T J; Clements, Robert J; Hegmann, Elda

2017-02-01

The authors report on series of side-chain smectic liquid crystal elastomer (LCE) cell scaffolds based on star block-copolymers featuring 3-arm, 4-arm, and 6-arm central nodes. A particular focus of these studies is placed on the mechanical properties of these LCEs and their impact on cell response. The introduction of diverse central nodes allows to alter and custom-modify the mechanical properties of LCE scaffolds to values on the same order of magnitude of various tissues of interest. In addition, it is continued to vary the position of the LC pendant group. The central node and the position of cholesterol pendants in the backbone of ε-CL blocks (alpha and gamma series) affect the mechanical properties as well as cell proliferation and particularly cell alignment. Cell directionality tests are presented demonstrating that several LCE scaffolds show cell attachment, proliferation, narrow orientational dispersion of cells, and highly anisotropic cell growth on the as-synthesized LCE materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mirror Symmetry Breaking by Chirality Synchronisation in Liquids and Liquid Crystals of Achiral Molecules.

PubMed

Tschierske, Carsten; Ungar, Goran

2016-01-04

Spontaneous mirror symmetry breaking is an efficient way to obtain homogeneously chiral agents, pharmaceutical ingredients and materials. It is also in the focus of the discussion around the emergence of uniform chirality in biological systems. Tremendous progress has been made by symmetry breaking during crystallisation from supercooled melts or supersaturates solutions and by self-assembly on solid surfaces and in other highly ordered structures. However, recent observations of spontaneous mirror symmetry breaking in liquids and liquid crystals indicate that it is not limited to the well-ordered solid state. Herein, progress in the understanding of a new dynamic mode of symmetry breaking, based on chirality synchronisation of transiently chiral molecules in isotropic liquids and in bicontinuous cubic, columnar, smectic and nematic liquid crystalline phases is discussed. This process leads to spontaneous deracemisation in the liquid state under thermodynamic control, giving rise to long-term stable symmetry-broken fluids, even at high temperatures. These fluids form conglomerates that are capable of extraordinary strong chirality amplification, eventually leading to homochirality and providing a new view on the discussion of emergence of uniform chirality in prebiotic systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Instability of a Lamellar Phase under Shear Flow: Formation of Multilamellar Vesicles

NASA Astrophysics Data System (ADS)

Courbin, L.; Delville, J. P.; Rouch, J.; Panizza, P.

2002-09-01

The formation of closed-compact multilamellar vesicles (referred to in the literature as the ``onion texture'') obtained upon shearing lamellar phases is studied using small-angle light scattering and cross-polarized microscopy. By varying the shear rate γ ˙, the gap cell D, and the smectic distance d, we show that: (i)the formation of this structure occurs homogeneously in the cell at a well-defined wave vector qi, via a strain-controlled process, and (ii)the value of qi varies as (dγ ˙/D)1/3. These results strongly suggest that formation of multilamellar vesicles may be monitored by an undulation (buckling) instability of the membranes, as expected from theory.

Chiral organosilica particles and their use as inducers of conformational deracemization of liquid crystal phases

NASA Astrophysics Data System (ADS)

Cohen, Orit; Ferris, Andrew J.; Adkins, Raymond; Lemieux, Robert P.; Avnir, David; Gelman, Dmitri; Rosenblatt, Charles

2018-03-01

Chiral organosilica particles of size ∼200 nm were synthesized from an enantio-pure multi-armed chiral D-maltose organosilane precursor in the absence of co-condensation with an achiral monomer. Two distinct experiments were performed to demonstrate the particles' ability to induce conformational deracemization of a host liquid crystal. The first involves an electric field-induced tilt of the liquid crystal director in the deracemized smectic-A phase. The other involves domain wall curvature separating left- and right-handed liquid crystal helical pitch domains imposed by the cells' substrates. The results demonstrate unequivocally that enantio-pure organosilica nanoparticles can be synthesized and can induce chirality in a host.

Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena

2014-09-24

The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 {angstrom} following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms anmore » L{sub 2} phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L{sub {alpha}}) at room temperature and up to {approx} 40 C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) bicontinuous cubic phases in addition to an L{sub {alpha}} phase.« less

Fixation of chiral smectic liquid crystal (S)-(+)-4-(2-methyl-1-butyloyloxy)phenyl 4-[1-(propenoyloxy) butiloxy] benzoate using UV curing techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Afrizal,, E-mail: rizalunj04@yahoo.com; Nurdelima,; Umeir

2014-03-24

Chiral Smectic Liquid Crystal (S)-(+)-4-(2-methyl-1-butyloyloxy)phenyl 4-[1-(propenoyloxy) butiloxy] benzoate has been synthesized using method of steglich esterification at room temperature. The mesomorphic behavior of chiral smectic at 55°C that showed schlieren texture in POM analysis. Fixation of structure chiral smectic liquid crystal by means of photopolymerization of monomer (S)-(+)-4-(2-methyl-1-butyloyloxy)phenyl 4-[1-(propenoyloxy) butiloxy] benzoate under UV irradiation which called UV curing techniques. The curing process using UV 3 lamps 100 volt at 60°C for an hour. The product of photopolymerization could be seen by analysis of FTIR spectra both monomer and polymer. FTIR spectra of monomer, two peaks for ester carbonyl and C-Cmore » double bond groups appeared at 1729.09 cm-1and 3123.46 cm{sup −1}. After UV curing process, peak for the carbonyl group at 1729.09 cm{sup −1} decreased and a new peak at 1160.21 cm{sup −1} appeared due to the carbonyl group attached to a C-C bond group and then peak at 3123.46 cm{sup −1} for C-C double bond group was disappeared.« less

Studies of Islands on Freely Suspended Bubbles of Smectic Liquid Crystal

NASA Technical Reports Server (NTRS)

Pattanaporkratana, A.; Mavel, B.; Park, C. S.; Maclennan, J. E.; Clark, N. A.

2002-01-01

We have constructed an optical system for observing the internal structure of freely suspended smectic liquid crystal bubbles using a reflected light microscope. Liquid crystal bubbles can have thicker circular regions (islands) which can easily be generated by shrinking the bubble diameter. The diameter of these islands is approximately 10 microns and they are typically up to five times thicker than the surrounding liquid crystal film (500 angstroms). In the Laboratory, the location of the islands is strongly influenced by gravity, which causes the majority of islands to migrate to the bottom half of the bubble. We will describe the size and thickness distributions of islands and their time evolution, and also discuss two-dimensional hydrodynamics and turbulence of smectic bubbles, the shapes of islands and holes affected by bubble vibrations, and the interactions between islands, which we have probed using optical tweezers.

Focus: Two-dimensional electron-electron double resonance and molecular motions: The challenge of higher frequencies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franck, John M.; Chandrasekaran, Siddarth; Dzikovski, Boris

2015-06-07

The development, applications, and current challenges of the pulsed ESR technique of two-dimensional Electron-Electron Double Resonance (2D ELDOR) are described. This is a three-pulse technique akin to 2D Exchange Nuclear Magnetic Resonance, but involving electron spins, usually in the form of spin-probes or spin-labels. As a result, it required the extension to much higher frequencies, i.e., microwaves, and much faster time scales, with π/2 pulses in the 2-3 ns range. It has proven very useful for studying molecular dynamics in complex fluids, and spectral results can be explained by fitting theoretical models (also described) that provide a detailed analysis ofmore » the molecular dynamics and structure. We discuss concepts that also appear in other forms of 2D spectroscopy but emphasize the unique advantages and difficulties that are intrinsic to ESR. Advantages include the ability to tune the resonance frequency, in order to probe different motional ranges, while challenges include the high ratio of the detection dead time vs. the relaxation times. We review several important 2D ELDOR studies of molecular dynamics. (1) The results from a spin probe dissolved in a liquid crystal are followed throughout the isotropic → nematic → liquid-like smectic → solid-like smectic → crystalline phases as the temperature is reduced and are interpreted in terms of the slowly relaxing local structure model. Here, the labeled molecule is undergoing overall motion in the macroscopically aligned sample, as well as responding to local site fluctuations. (2) Several examples involving model phospholipid membranes are provided, including the dynamic structural characterization of the boundary lipid that coats a transmembrane peptide dimer. Additionally, subtle differences can be elicited for the phospholipid membrane phases: liquid disordered, liquid ordered, and gel, and the subtle effects upon the membrane, of antigen cross-linking of receptors on the surface of plasma membrane, vesicles can be observed. These 2D ELDOR experiments are performed as a function of mixing time, T{sub m}, i.e., the time between the second and third π/2 pulses, which provides a third dimension. In fact, a fourth dimension may be added by varying the ESR frequency/magnetic field combination. Therefore, (3) it is shown how continuous-wave multifrequency ESR studies enable the decomposition of complex dynamics of, e.g., proteins by virtue of their respective time scales. These studies motivate our current efforts that are directed to extend 2D ELDOR to higher frequencies, 95 GHz in particular (from 9 and 17 GHz), in order to enable multi-frequency 2D ELDOR. This required the development of quasi-optical methods for performing the mm-wave experiments, which are summarized. We demonstrate state-of-the-art 95 GHz 2D ELDOR spectroscopy through its ability to resolve the two signals from a spin probe dissolved in both the lipid phase and the coexisting aqueous phase. As current 95 GHz experiments are restricted by limited spectral coverage of the π/2 pulse, as well as the very short T{sub 2} relaxation times of the electron spins, we discuss how these limitations are being addressed.« less

Coarsening Dynamics and Marangoni Effects in Thin Liquid Crystal Bubbles in Microgravity

NASA Technical Reports Server (NTRS)

Clark, Noel; Glaser, Matthew; Maclennan, Joseph; Park, Cheol; Tin, Padetha; Hall, Nancy R.; Sheehan, Christopher; Storck, Jennifer

2015-01-01

The Observation and Analysis of Smectic Islands in Space (OASIS) flight hardware was successfully launched on SpaceX-6 on April 15, 2015 and was operated in the Microgravity Science Glovebox (MSG) on board the International Space Station (ISS). The OASIS project comprises a series of experiments that probe the interfacial and hydrodynamic behavior of spherical-bubble freely suspended liquid crystal (FSLC) membranes in space. These are the thinnest known stable condensed phase structures, making them ideal for studies of two-dimensional (2D) coarsening dynamics and thermocapillary phenomena in microgravity. The OASIS experimental investigation was carried out using four different smectic A and C liquid crystal materials in four separate sample chambers housed inside the MSG. In this report, we present the behavior of collective dynamics on 2D bubble surface, including the equilibrium spatial organization and interaction of islands in electric fields and temperature gradients, and the diffusion and coalescence-driven coarsening dynamics of island emulsions in microgravity. We have observed spontaneous bubble thickening behavior caused by gradients between the bubble-blowing needle and ambient air temperatures. A uniform, thicker band forms during coarsening as a result of non-uniform heating by the LED illumination panels. These are proposed to be a result of Marangoni convection on the bubble surface.

Effects of polymers on the rotational viscosities of nematic liquid crystals and dynamics of field alignment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, D.

Many of the important physical phenomena exhibited by the nematic phase, such as its unusual flow properties and its responses to the electric and the magnetic fields, can be discussed regarding it as a continous medium. The Leslie-Erickson dynamic theory has the six dissipative coefficients from continuum model of liquid crystal. Parodi showed that only five of them are independent, when Onsagar`s reciprocal relations are used. One of these, which has no counterpart in the isotropic liquids, is the rotational viscosity co-efficient, {gamma}{sub 1}. The main objective of this project is to study the rotational viscosities of selected micellar nematicmore » systems and the effect of dissolved polymers in micellar and thermotropic liqud crystals. We used rotating magnetic field method which allows one to determine {gamma}{sub 1} and the anisotropic magnetic susceptibility, {chi}{sub a}. For the ionic surfactant liquid crystals of SDS and KL systems used in this study, the rotational viscosity exhibited an extraordinary drop after reaching the highest values {gamma}{sub 1} as the temperature was lowered. This behavior is not observed in normal liquid crystals. But this phenomena can be attributed to the existence of nematic biaxial phase below the rod-like nematic N{sub c} phase. The pretransitional increase in {gamma}{sub 1} near the disk-like nematic to smectic-A phase transition of the pure CsPFO/H{sub 2}O systems are better understood with the help of mean-field models of W.L. McMillan. He predicted a critical exponent {nu} = {1/2} for the divergence of {gamma}{sub 1}. The polymer (PEO, molecular weight = 10{sup 5}) dissolved in CsPFO/H{sub 2}O system (which has 0.6% critical polymer concentration), suppressed the nematic to lamellar smectic phase transition in concentrated polymer solutions (0.75% and higher). In dilute polymer solutions with lower than 0.3% polyethylene-oxide, a linear increase of {gamma}{sub 1} is observed, which agrees with Brochard theory.« less

Controlling orientational order in block copolymers using low-intensity magnetic fields

PubMed Central

Choo, Youngwoo; Kawabata, Kohsuke; Kaufman, Gilad; Feng, Xunda; Di, Xiaojun; Rokhlenko, Yekaterina; Mahajan, Lalit H.; Ndaya, Dennis; Kasi, Rajeswari M.

2017-01-01

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP’s anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (<0.5 T) that are accessible using permanent magnets, in contrast to the high fields (>4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system’s nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles. PMID:29078379

Spontaneous helix formation in non-chiral bent-core liquid crystals with fast linear electro-optic effect

PubMed Central

Sreenilayam, Sithara P.; Panarin, Yuri P.; Vij, Jagdish K.; Panov, Vitaly P.; Lehmann, Anne; Poppe, Marco; Prehm, Marko; Tschierske, Carsten

2016-01-01

Liquid crystals (LCs) represent one of the foundations of modern communication and photonic technologies. Present display technologies are based mainly on nematic LCs, which suffer from limited response time for use in active colour sequential displays and limited image grey scale. Herein we report the first observation of a spontaneously formed helix in a polar tilted smectic LC phase (SmC phase) of achiral bent-core (BC) molecules with the axis of helix lying parallel to the layer normal and a pitch much shorter than the optical wavelength. This new phase shows fast (∼30 μs) grey-scale switching due to the deformation of the helix by the electric field. Even more importantly, defect-free alignment is easily achieved for the first time for a BC mesogen, thus providing potential use in large-scale devices with fast linear and thresholdless electro-optical response. PMID:27156514

Stretchable liquid-crystal blue-phase gels.

PubMed

Castles, F; Morris, S M; Hung, J M C; Qasim, M M; Wright, A D; Nosheen, S; Choi, S S; Outram, B I; Elston, S J; Burgess, C; Hill, L; Wilkinson, T D; Coles, H J

2014-08-01

Liquid-crystalline polymers are materials of considerable scientific interest and technological value. An important subset of these materials exhibit rubber-like elasticity, combining the optical properties of liquid crystals with the mechanical properties of rubber. Moreover, they exhibit behaviour not seen in either type of material independently, and many of their properties depend crucially on the particular mesophase employed. Such stretchable liquid-crystalline polymers have previously been demonstrated in the nematic, chiral-nematic, and smectic mesophases. Here, we report the fabrication of a stretchable gel of blue phase I, which forms a self-assembled, three-dimensional photonic crystal that remains electro-optically switchable under a moderate applied voltage, and whose optical properties can be manipulated by an applied strain. We also find that, unlike its undistorted counterpart, a mechanically deformed blue phase exhibits a Pockels electro-optic effect, which sets out new theoretical challenges and possibilities for low-voltage electro-optic devices.

Spontaneous helix formation in non-chiral bent-core liquid crystals with fast linear electro-optic effect

NASA Astrophysics Data System (ADS)

Sreenilayam, Sithara P.; Panarin, Yuri P.; Vij, Jagdish K.; Panov, Vitaly P.; Lehmann, Anne; Poppe, Marco; Prehm, Marko; Tschierske, Carsten

2016-05-01

Liquid crystals (LCs) represent one of the foundations of modern communication and photonic technologies. Present display technologies are based mainly on nematic LCs, which suffer from limited response time for use in active colour sequential displays and limited image grey scale. Herein we report the first observation of a spontaneously formed helix in a polar tilted smectic LC phase (SmC phase) of achiral bent-core (BC) molecules with the axis of helix lying parallel to the layer normal and a pitch much shorter than the optical wavelength. This new phase shows fast (~30 μs) grey-scale switching due to the deformation of the helix by the electric field. Even more importantly, defect-free alignment is easily achieved for the first time for a BC mesogen, thus providing potential use in large-scale devices with fast linear and thresholdless electro-optical response.

Highly organized smectic-like packing in vapor-deposited glasses of a liquid crystal

DOE PAGES

Gujral, Ankit; Gomez, Jaritza; Jiang, Jing; ...

2016-12-26

Glasses of a model smectic liquid crystal-forming molecule, itraconazole, were prepared by vapor deposition onto substrates with temperatures ranging from T substrate = 0.78T g to 1.02T g, where T g (=330 K) is the glass transition temperature. The films were characterized using X-ray scattering techniques. For T substrate near and below T g, glasses with layered smectic-like structures can be prepared and the layer spacing can be tuned by 16% through the choice of T substrate. Remarkably, glasses prepared with T substrate values above T g exhibit levels of structural organization much higher than that of a thermally annealedmore » film. These results are explained by a mechanism based upon a preferred molecular orientation and enhanced molecular motion at the free surface, indicating that molecular organization in the glass is independent of the anchoring preferred at the substrate. Furthermore, these results suggest new strategies for optimizing molecular packing within active layers of organic electronic and optoelectronic devices.« less

Flow Meter Based on Freely Suspended Smectic Liquid Crystal Films

NASA Astrophysics Data System (ADS)

Green, Adam; Qi, Zhiyuan; Park, Cheol; Glaser, Matthew; Maclennan, Joseph; Clark, Noel

We present the realization of a idealized 2D hydrodynamic system coupled to air-flow, and show that freely suspended films (FSF) of smectic liquid crystals can be used as a novel flow-meter. Freely-suspended films of liquid crystals are one of the closest physical realizations of an idealized 2D fluid. The velocity of air-flow above a film suspended above a channel can be inferred by studying the velocity profile of the smectic film. This velocity profile can be measured using digital video microscopy to track the inclusions present in the moving film. The velocity profile is then fitted to the coupled 2D solutions of an embedded fluid in air, and the velocity of the air can then be extracted. This flow meter serves as a demonstration of a robust test-bed for further exploration of 2D hydrodynamics. This work was supported by NASA Grant No. NNX-13AQ81G, NSF MRSEC Grant No. DMR-0820579, and DMR-1420736.

Measurements of Translational and Rotational Mobilities of Inclusions near a Boundary in TiltedFreely-Suspended Smectic Liquid Crystal Films

NASA Astrophysics Data System (ADS)

Cadenhead, Ian; Green, Adam; Park, Cheol; Glaser, Matt; Maclennan, Joe; Clark, Noel

Freely-suspended liquid crystal films serve as an excellent model system for investigating two-dimensional hydrodynamics, including the study of inclusion mobilities near fixed boundaries. We present experimental measurements using digital video microscopy of the translational and rotational mobilities of smectic islands near the boundary of a rectangular smectic A film a few molecular layers thick. The islands are thicker, circular domains that behave as large particles embedded in the film. Tilting the film causes the islands to drift under gravity. Measuring the diffusion and velocities of these islands allows us to extract the translational and rotational mobilities of the inclusions as a function of distance from the film boundary. The results are compared to Saffman-Delbrück theory using the general approach of Levine and MacKintosh. This work was supported by NASA Grant No. NNX-13AQ81G, and NSF MRSEC Grants No. DMR-0820579 and DMR-1420736.

Flow in Smectic Liquid Crystal Films: Examining the Flow Field of a Smectic Liquid Crystal Film due to Fluid Ejected From a Small Nozzle

NASA Astrophysics Data System (ADS)

Ferguson, Kyle; Qi, Zhiyuan; Park, Cheol; Maclennan, Jospeh; Glaser, Matthew; Clark, Noel

The rheological properties of 2D fluids are well-understood theoretically, but few experiments testing theoretical predictions have been carried out. We have used MX 12805, a smectic C liquid crystal at room temperature, to create quasi-2D films with which to study high-Reynolds number flow. We map the flow field as the fluid is ejected from a thin nozzle into a large reservoir, probing both laminar and turbulent flow. We also attempt to carry out the experiment in a vacuum to study the true 2D-regime; despite encountering experimental difficulties, some useful information can still be gleaned. This work was supported by NASA Grant NNX-13AQ81G, by the Soft Materials Research Center under NSF MRSEC Grants DMR-0820579 and DMR-1420736, by Department of Energy Grant DE-FG02-08ER54995, and by NSF Grant CBET-0854108.

Self-regulation in self-propelled nematic fluids.

PubMed

Baskaran, A; Marchetti, M C

2012-09-01

We consider the hydrodynamic theory of an active fluid of self-propelled particles with nematic aligning interactions. This class of materials has polar symmetry at the microscopic level, but forms macrostates of nematic symmetry. We highlight three key features of the dynamics. First, as in polar active fluids, the control parameter for the order-disorder transition, namely the density, is dynamically convected by the order parameter via active currents. The resulting dynamical self-regulation of the order parameter is a generic property of active fluids and destabilizes the uniform nematic state near the mean-field transition. Secondly, curvature-driven currents render the system unstable deep in the nematic state, as found previously. Finally, and unique to self-propelled nematics, nematic order induces local polar order that in turn leads to the growth of density fluctuations. We propose this as a possible mechanism for the smectic order of polar clusters seen in numerical simulations.

The mechanics of active matter: Broken-symmetry hydrodynamics of motile particles and granular layers

NASA Astrophysics Data System (ADS)

Ramaswamy, Sriram; Simha, R. Aditi

2006-09-01

This articles reviews briefly our recent theoretical results on order, fluctuations and flow in collections of self-driven particles, in suspension or on a solid surface. The theoretical approach we have developed applies not only to collections of organisms such as schools of fish or collectively swimming bacteria, but also to motor-microtubule extracts with ATP and, most surprisingly, to agitated monolayers of orientable granular particles. We contrast the behaviour of these active systems with that of thermal equilibrium systems with the same symmetry. As an illustration of the role of activity we show that active smectics in three dimensions show true long-range order, unlike their thermal equilibrium counterparts.

Controlling the volatility of the written optical state in electrochromic DNA liquid crystals

NASA Astrophysics Data System (ADS)

Liu, Kai; Varghese, Justin; Gerasimov, Jennifer Y.; Polyakov, Alexey O.; Shuai, Min; Su, Juanjuan; Chen, Dong; Zajaczkowski, Wojciech; Marcozzi, Alessio; Pisula, Wojciech; Noheda, Beatriz; Palstra, Thomas T. M.; Clark, Noel A.; Herrmann, Andreas

2016-05-01

Liquid crystals are widely used in displays for portable electronic information display. To broaden their scope for other applications like smart windows and tags, new material properties such as polarizer-free operation and tunable memory of a written state become important. Here, we describe an anhydrous nanoDNA-surfactant thermotropic liquid crystal system, which exhibits distinctive electrically controlled optical absorption, and temperature-dependent memory. In the liquid crystal isotropic phase, electric field-induced colouration and bleaching have a switching time of seconds. Upon transition to the smectic liquid crystal phase, optical memory of the written state is observed for many hours without applied voltage. The reorientation of the DNA-surfactant lamellar layers plays an important role in preventing colour decay. Thereby, the volatility of optoelectronic state can be controlled simply by changing the phase of the material. This research may pave the way for developing a new generation of DNA-based, phase-modulated, photoelectronic devices.

Wavelength and bandwidth tunable photonic stopband of ferroelectric liquid crystals.

PubMed

Ozaki, Ryotaro; Moritake, Hiroshi

2012-03-12

The chiral smectic C phase of ferroelectric liquid crystals (FLCs) has a self-assembling helical structure which is regarded as a one-dimensional pseudo-photonic crystal. It is well known that a stopband of a FLC can be tuned in wavelength domain by changing temperature or electric field. We here have demonstrated an FLC stopband with independently tunable wavelength and bandwidth by controlling temperature and incident angle. At highly oblique incidence, the stopband does not have polarization dependence. Furthermore, the bandwidth at highly oblique incidence is much wider than that at normal incidence. The mechanism of the tunable stopband is clarified by considering the reflection at oblique incidence.

Side-Chain Liquid Crystalline Poly(meth)acrylates with Bent-Core Mesogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen,X.; Tenneti, K.; Li, C.

2007-01-01

We report the design, synthesis, and characterization of side-chain liquid crystalline (LC) poly(meth)acrylates with end-on bent-core liquid crystalline (BCLC) mesogens. Both conventional free radical polymerization and atom transfer radical polymerization have been used to synthesize these liquid crystalline polymers (LCP). The resulting polymers exhibit thermotropic LC behavior. Differential scanning calorimetry, thermopolarized light microscopy, wide-angle X-ray diffraction, and small-angle X-ray scattering were used to characterize the LC structure of both monomers and polymers. The electro-optic (EO) measurement was carried out by applying a triangular wave and measuring the LC EO response. SmCP (Smectic C indicates the LC molecules are tilted withmore » respect to the layer normal; P denotes polar ordering) phases were observed for both monomers and polymers. In LC monomers, typical antiferroelectric switching was observed. In the ground state, SmCP{sub A} (A denotes antiferroelectric) was observed which switched to SmCP{sub F} (F denotes ferroelectric) upon applying an electric field. In the corresponding LCP, a unique bilayer structure was observed, which is different from the reported BCLC bilayer SmCG (G denotes generated) phase. Most of the LCPs did not switch upon applying electric field while weak AF switching was observed in a low molecular weight poly{l_brace}3'-[4-(4-n-dodecyloxybenzoyloxy)benzoyloxy]-4-(12-acryloyloxydodecyloxy)benzoyloxybiphenyl{r_brace} sample.« less

Design and investigation of de Vries liquid crystals based on 5-phenyl-pyrimidine and (R,R)-2,3-epoxyhexoxy backbone

NASA Astrophysics Data System (ADS)

Sreenilayam, S. P.; Rodriguez-Lojo, D.; Panov, V. P.; Swaminathan, V.; Vij, J. K.; Panarin, Yu. P.; Gorecka, E.; Panov, A.; Stevenson, P. J.

2017-10-01

Calamitic liquid crystals based on 5-phenyl-pyrimidine derivatives have been designed, synthesized, and characterized. The 5-phenyl pyrimidine core was functionalized with a chiral (R,R)-2,3-epoxyhexoxy chain on one side and either siloxane or perfluoro terminated chains on the opposite side. The one involving a perfluorinated chain shows Sm A* phase over a wide temperature range of 82 °C, whereas the siloxane analog exhibits both Sm A* and Sm C* phases over a broad range of temperatures, and a weak first-order Sm A*-Sm C* transition is observed. For the siloxane analog, the reduction factor for the layer shrinkage R (relative to its thickness at the Sm A*-Sm C* transition temperature, TAC) is ˜0.373 , and layer shrinkage is 1.7% at a temperature of 13 °C below the TAC. This compound is considered to have "de Vries smectic" characteristics with the de Vries coefficient CdeVries of ˜0.86 on the scale of zero (maximum-layer shrinkage) to 1 (zero-layer shrinkage). A three-parameter mean-field model is introduced for the orientational distribution function (ODF) to reproduce the electro-optic properties. This model explains the experimental results and leads to the ODF, which exhibits a crossover from the sugar-loaf to diffuse-cone ODF some 3 °C above TAC.

Can a droplet break up under flow without elongating? Fragmentation of smectic monodisperse droplets

NASA Astrophysics Data System (ADS)

Courbin, L.; Engl, W.; Panizza, P.

2004-06-01

We study the fragmentation under shear flow of smectic monodisperse droplets at high volume fraction. Using small angle light scattering and optical microscopy, we reveal the existence of a break-up mechanism for which the droplets burst into daughter droplets of the same size. Surprisingly, this fragmentation process, which is strain controlled and occurs homogeneously in the cell, does not require any transient elongation of the droplets. Systematic experiments as a function of the initial droplet size and the applied shear rate show that the rupture is triggered by an instability of the inner droplet structure.

Self-assembly of hard helices: a rich and unconventional polymorphism.

PubMed

Kolli, Hima Bindu; Frezza, Elisa; Cinacchi, Giorgio; Ferrarini, Alberta; Giacometti, Achille; Hudson, Toby S; De Michele, Cristiano; Sciortino, Francesco

2014-11-07

Hard helices can be regarded as a paradigmatic elementary model for a number of natural and synthetic soft matter systems, all featuring the helix as their basic structural unit, from natural polynucleotides and polypeptides to synthetic helical polymers, and from bacterial flagella to colloidal helices. Here we present an extensive investigation of the phase diagram of hard helices using a variety of methods. Isobaric Monte Carlo numerical simulations are used to trace the phase diagram; on going from the low-density isotropic to the high-density compact phases a rich polymorphism is observed, exhibiting a special chiral screw-like nematic phase and a number of chiral and/or polar smectic phases. We present full characterization of the latter, showing that they have unconventional features, ascribable to the helical shape of the constituent particles. Equal area construction is used to locate the isotropic-to-nematic phase transition, and the results are compared with those stemming from an Onsager-like theory. Density functional theory is also used to study the nematic-to-screw-nematic phase transition; within the simplifying assumption of perfectly parallel helices, we compare different levels of approximation, that is second- and third-virial expansions and a Parsons-Lee correction.

Calorimetric Study of Phase Transitions Involving Twist-Grain-Boundary TGB{A} and TGB{C} Phases

NASA Astrophysics Data System (ADS)

Navailles, L.; Garland, C. W.; Nguyen, H. T.

1996-09-01

High-resolution calorimetry has been used to determine the heat capacity and latent heat associated with phase transitions in the homologous series of chiral liquid crystals nF_2BTFO_1M_7 [ 3-fluoro-4(1-methylheptyloxy)4'-(4''-alkoxy-2'', 3''-difluorobenzoyloxy)tolane] . These compounds exhibit smectic-C^* (SmC^*), twist-grain-boundary (TGBA for n=10, TGBC for n=11, 12) and cholesteric (N^*) phases. All the phase transitions are first order with small to moderate latent heats. There is a large rounded excess heat capacity peak in the N^* phase that is consistent with the predicted appearance of short-range TGB order (chiral line liquid character). This is analogous to the development of an Abrikosov flux vortex liquid in type-II superconductors. Both the n=11 and 12 homologs exhibit two closely spaced transitions in the region where a single TGBC - N^* transition was expected. This suggests the existence of two thermodynamically distinct TGBC phases. Des exprériences de calorimétrie haute résolution ont été réalisées pour déterminer les chaleurs spécifiques et les chaleurs latentes associées aux transitions de phase des homologues de la série crystal liquide nF_2BTFO_1M_7: 3-fluoro-4[1-methyl-heptyloxy]4'-(4''-alcoxy-2'', 3''-difluorobenzoyloxy)tolanes. Ces produits présentent la phase smectique C^* (SmC^*), les phases à torsion par joint de grain (TGBA pour n=10 et TGBC pour n=11, 12) et la phase cholestérique (N^*). Toutes les transitions de phase sont du premier ordre. La chaleur latente associée à ces transitions est faibles ou modérée. Nous observons, dans la phase N^*, un grand pic arrondi qui est en accord avec les prédictions de l'apparition d'un ordre TGB à courte distance (liquide de ligne de dislocation). Ce phénomène est l'analogue du liquide de vortex dans les supraconducteurs de type II. Les composés n=11 et 12 présentent, dans la région où nous attendions une transition TGBC - N^* unique, deux transitions sur un très faible domaine de température. Ce résultat suggère l'existence de deux phases TGBC thermodynamiquement distinctes.

Improving the thermal stability and electrical parameters of a liquid crystalline material 4-n-(nonyloxy) benzoic acid by using Li ion beam irradiation

NASA Astrophysics Data System (ADS)

Kumar, Satendra; Verma, Rohit; Dwivedi, Aanchal; Dhar, R.; Tripathi, Ambuj

2018-05-01

Li ion beam irradiation studies on a liquid crystalline material 4-n-(nonyloxy) benzoic acid (NOBA) have been carried out. The material has phase sequence of I-N-SmC-Cr. Thermodynamic studies demonstrate that an irradiation fluence of 1×1013 ions-cm-2 results in the increased thermal stability of the smectic C (SmC) phase of the material. Dielectric measurements illustrate that the transverse component of the dielectric permittivity and hence the dielectric anisotropy of the material in the nematic (N) and SmC phases are increased as compared to those of the pure material due to irradiation. UV-Visible spectrum of the irradiated material shows an additional peak along with the peak of the pure material. The observed change in the thermodynamic and electrical parameters is attributed to the conversion of some of the dimers of NOBA to monomers of NOBA due to irradiation.

Brownian dynamics and dynamic Monte Carlo simulations of isotropic and liquid crystal phases of anisotropic colloidal particles: a comparative study.

PubMed

Patti, Alessandro; Cuetos, Alejandro

2012-07-01

We report on the diffusion of purely repulsive and freely rotating colloidal rods in the isotropic, nematic, and smectic liquid crystal phases to probe the agreement between Brownian and Monte Carlo dynamics under the most general conditions. By properly rescaling the Monte Carlo time step, being related to any elementary move via the corresponding self-diffusion coefficient, with the acceptance rate of simultaneous trial displacements and rotations, we demonstrate the existence of a unique Monte Carlo time scale that allows for a direct comparison between Monte Carlo and Brownian dynamics simulations. To estimate the validity of our theoretical approach, we compare the mean square displacement of rods, their orientational autocorrelation function, and the self-intermediate scattering function, as obtained from Brownian dynamics and Monte Carlo simulations. The agreement between the results of these two approaches, even under the condition of heterogeneous dynamics generally observed in liquid crystalline phases, is excellent.

Lasing in a three-dimensional photonic crystal of the liquid crystal blue phase II.

PubMed

Cao, Wenyi; Muñoz, Antonio; Palffy-Muhoray, Peter; Taheri, Bahman

2002-10-01

Photonic-bandgap materials, with periodicity in one, two or three dimensions, offer control of spontaneous emission and photon localization. Low-threshold lasing has been demonstrated in two-dimensional photonic-bandgap materials, both with distributed feedback and defect modes. Liquid crystals with chiral constituents exhibit mesophases with modulated ground states. Helical cholesterics are one-dimensional, whereas blue phases are three-dimensional self-assembled photonic-bandgap structures. Although mirrorless lasing was predicted and observed in one-dimensional helical cholesteric materials and chiral ferroelectric smectic materials, it is of great interest to probe light confinement in three dimensions. Here, we report the first observations of lasing in three-dimensional photonic crystals, in the cholesteric blue phase II. Our results show that distributed feedback is realized in three dimensions, resulting in almost diffraction-limited lasing with significantly lower thresholds than in one dimension. In addition to mirrorless lasing, these self-assembled soft photonic-bandgap materials may also be useful for waveguiding, switching and sensing applications.

Single crystal, liquid crystal, and hybrid organic semiconductors

NASA Astrophysics Data System (ADS)

Twieg, Robert J.; Getmanenko, Y.; Lu, Z.; Semyonov, A. N.; Huang, S.; He, P.; Seed, A.; Kiryanov, A.; Ellman, B.; Nene, S.

2003-07-01

The synthesis and characterization of organic semiconductors is being pursued in three primary structure formats: single crystal, liquid crystal and organic-inorganic hybrid. The strategy here is to share common structures, synthesis methods and fabrication techniques across these formats and to utilize common characterization tools such as the time of flight technique. The single crystal efforts concentrate on aromatic and heteroaromatic compounds including simple benzene derivatives and derivatives of the acenes. The structure-property relationships due to incorporation of small substituents and heteroatoms are being examined. Crystals are grown by solution, melt or vapor transport techniques. The liquid crystal studies exploit their self-organizing properties and relative ease of sample preparation. Though calamitic systems tha deliver the largest mobilities are higher order smectics, even some unusual twist grain boundary phases are being studied. We are attempting to synthesize discotic acene derivatives with appropriate substitution patterns to render them mesogenic. The last format being examined is the hybrid organic-inorganic class. Here, layered materials of alternating organic and inorganic composition are designed and synthesized. Typical materials are conjugated aromatic compounds, usually functinalized with an amine or a pyridine and reacted with appropriate reactive metal derivatives to incorporate them into metal oxide or sulfide layers.

Hard Competition: Stabilizing the Elusive Biaxial Nematic Phase in Suspensions of Colloidal Particles with Extreme Lengths

NASA Astrophysics Data System (ADS)

Dussi, Simone; Tasios, Nikos; Drwenski, Tara; van Roij, René; Dijkstra, Marjolein

2018-04-01

We use computer simulations to study the existence and stability of a biaxial nematic Nb phase in systems of hard polyhedral cuboids, triangular prisms, and rhombic platelets, characterized by a long (L ), medium (M ), and short (S ) particle axis. For all three shape families, we find stable Nb states provided the shape is not only close to the so-called dual shape with M =√{L S } but also sufficiently anisotropic with L /S >9 ,11 ,14 ,23 for rhombi, (two types of) triangular prisms, and cuboids, respectively, corresponding to anisotropies not considered before. Surprisingly, a direct isotropic-Nb transition does not occur in these systems due to a destabilization of Nb by a smectic (for cuboids and prisms) or a columnar (for platelets) phase at small L /S or by an intervening uniaxial nematic phase at large L /S . Our results are confirmed by a density functional theory provided the third virial coefficient is included and a continuous rather than a discrete (Zwanzig) set of particle orientations is taken into account.

Smectic A Filled Birefringent Elements and Fast Switching Twisted Dual Frequency Nematic Cells Used for Digital Light Deflection

NASA Technical Reports Server (NTRS)

Pishnyak, Oleg; Golovin, Andrii; Kreminskia, Liubov; Pouch, John J.; Miranda, Felix A.; Winker, Bruce K.; Lavrentovich, Oleg D.

2006-01-01

We describe the application of smectic A (SmA) liquid crystals for beam deflection. SmA materials can be used in digital beam deflectors (DBDs) as fillers for passive birefringent prisms. SmA prisms have high birefringence and can be constructed in a variety of shapes, including single prisms and prismatic blazed gratings of different angles and profiles. We address the challenges of uniform alignment of SmA, such as elimination of focal conic domains. Fast rotation of the incident light polarization in DBDs is achieved by an electrically switched 90 twisted nematic (TN) cell.

Course 6: Physics of Composite Cell Membrane and Actin Based Cytoskeleton

NASA Astrophysics Data System (ADS)

Sackmann, E.; Bausch, A. R.; Vonna, L.

1 Architecture of composite cell membranes 1.1 The lipid/protein bilayer is a multicomponent smectic phase with mosaic like architecture 1.2 The spectrin/actin cytoskeleton as hyperelastic cell stabilizer 1.3 The actin cortex: Architecture and function 2 Physics of the actin based cytoskeleton 2.1 Actin is a living semiflexible polymer 2.2 Actin network as viscoelastic body 2.3 Correlation between macroscopic viscoelasticity and molecular 3 Heterogeneous actin gels in cells and biological function 3.1 Manipulation of actin gels 3.2 Control of organization and function of actin cortex by cell signalling 4 Micromechanics and microrheometry of cells 5 Activation of endothelial cells: On the possibility of formation of stress fibers as phase transition of actin-network triggered by cell signalling pathways 6 On cells as adaptive viscoplastic bodies 7 Controll of cellular protrusions controlled by actin/myosin cortex

Nonlinear optical properties of metal alkanoate composites with hybrid core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Rudenko, V.; Tolochko, A.; Zhulai, D.; Klimusheva, G.; Mirnaya, T.; Yaremchuk, G.; Asaula, V.

2018-02-01

New composites with hybrid CdSe/ZnS and Au/CdSe nanoparticles (NPs) were chemically synthesized in the thermotropic liquid crystalline phase (smectic A) of cadmium octanoate. Features of structure and nonlinear optical properties of glassy cadmium octanoate composites with hybrid core/shell NPs were studied using small-angle X-ray scattering method and Z-scan technique. Experimental optical setup (Z-scan) is based on a Nd: YAG laser, generating 9 ns pulses with a repetition rate of 0,5 Hz on a wavelength of 532 nm. The effects of the influence of hybrid NPs on the nonlinear optical properties of nanocomposites are considered in this study.

Bent-core fiber structure: Experimental and theoretical studies of fiber stability

NASA Astrophysics Data System (ADS)

Bailey, C.; Gartland, E.; Jakli, A.

2007-03-01

Recent studies have shown that bent core liquid crystals in the B7 and B2 phases can form stable freestanding fibers with a so called ``jelly-roll'' layer configuration, which means that the smectic layers would be arranged in concentric cylindrical shells. This configuration shows layer curvature is necessary for fiber stability. Classically this effect would destabilize the fiber configuration because of the energy cost of layer distortions and surface tension. We propose a model that can predict fiber stability in the experimentally observed range of a few micrometers, by assuming that layer curvature can be stabilized by including a term dealing with the linear divergence of the polarization direction if the polarization is allowed to have a component normal to the smectic layers. We show that this term can stabilize the fiber configuration if its strength is larger than the surface tension. We also propose an entropic model to explain the strength of this term by considering steric effects. Finally we will take results from this model and apply them to better understand experimental findings of bent-core fibers. Financial support by NSF FRG under contract DMS-0456221. Prof. Daniel Phillips, Particia Bauman and Jie Shen at Purdue Univ., Prof. Maria Carme Calderer at Univ. of Minnesota, and Prof. Jonathan Selinger at Kent State Univ. Liou Qiu and Dr. O.D. Lavrentovich, Characterization Facilities, Liquid Crystal Institute, Kent State Univ. Julie Kim and Dr. Quan Li, Chemical Synthesis Facilities, Liquid Crystal Institute, Kent State Univ.

Observation of paramorphic phenomenon and non-tilted orthogonal smectic phases in hydrogen bonded ferroelectric liquid crystals for photonic applications

NASA Astrophysics Data System (ADS)

Subhasri, P.; Venugopal, D.; Jayaprakasam, R.; Chitravel, T.; Vijayakumar, V. N.

2018-06-01

A new class of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been designed and synthesized by intermolecular hydrogen bonds between mesogenic 4-decyloxybenzoic acid (10OBA) and non-mesogenic (R)-(+)-Methylsuccinic acid (MSA) which have been confirmed through experimental and theoretical studies. Further, Mulliken population analysis clearly reveals that the existence of hydrogen bonds, strength and dynamic properties. Textural observation and its corresponding enthalpy values are analyzed by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) respectively. Paramorphic changes in Sm C* phase due to the change of refractive index, which clearly reveal that the complex could be used for filtering action in photonic devices. The transition from lone pair to π* with large stabilization energy evidently exposes the chiral phases in the present HBFLC complex. Intermolecular interaction is analyzed by using natural bond orbital (NBO) studies. The highest energy in the HOMO-LUMO shows the stable phase in the HBFLC complex. Molecular structure of the HBFLC complex possesses the monoclinic which has been evinced through x-ray analysis. The randomly oriented bunch of homogeneous molecules in Sm A* phase of the HBFLC complex is reported.

Ethyl 7-hydroxycoumarin-3-carboxylate derivatives: Synthesis, characterization and effect of liquid crystal properties

NASA Astrophysics Data System (ADS)

Srinivasa, H. T.; Palakshamurthy, B. S.; Mohammad, AbdulKarim-Talaq

2018-03-01

Two sets of new ethyl 7-hydroxycoumarin-3-carboxylate derivatives were synthesized and characterized to study the liquid crystalline properties. Chemical structures were confirmed by IR, NMR, CHN analysis techniques. Mesomarphic properties were accomplished by DSC, POM and X-ray studies. Density functional theory calculations and photophysical studies also performed. In the first set, smaller homologues of alkoxybenzoic acid derivatives exhibit monotropic smectic A (SmA) and higher homologous exhibit enantiotropic smectic A mesophase. The second set alkyl biphenyl derivatives exhibit stable SmA and nematic (N) mesophases. The well defined focal conic texture for SmA and threaded texture for nematic mesophases have been observed.

Phase behavior and characterization of heptamethyltrisiloxane-based de Vries smectic liquid crystal by electro-optics, x rays, and dielectric spectroscopy.

PubMed

Sreenilayam, S P; Agra-Kooijman, D M; Panov, V P; Swaminathan, V; Vij, J K; Panarin, Yu P; Kocot, A; Panov, A; Rodriguez-Lojo, D; Stevenson, P J; Fisch, Michael R; Kumar, Satyendra

2017-03-01

A heptamethyltrisiloxane liquid crystal (LC) exhibiting I-SmA^{*}-SmC^{*} phases has been characterized by calorimetry, polarizing microscopy, x-ray diffraction, electro-optics, and dielectric spectroscopy. Observations of a large electroclinic effect, a large increase in the birefringence (Δn) with electric field, a low shrinkage in the layer thickness (∼1.75%) at 20 °C below the SmA^{*}-SmC^{*} transition, and low values of the reduction factor (∼0.40) suggest that the SmA^{*} phase in this material is of the de Vries type. The reduction factor is a measure of the layer shrinkage in the SmC^{*} phase and it should be zero for an ideal de Vries. Moreover, a decrease in the magnitude of Δn with decreasing temperature indicates the presence of the temperature-dependent tilt angle in the SmA^{*} phase. The electro-optic behavior is explained by the generalized Langevin-Debye model as given by Shen et al. [Y. Shen et al., Phys. Rev. E 88, 062504 (2013)10.1103/PhysRevE.88.062504]. The soft-mode dielectric relaxation strength shows a critical behavior when the system goes from the SmA^{*} to the SmC^{*} phase.

Label-free protein sensing by employing blue phase liquid crystal.

PubMed

Lee, Mon-Juan; Chang, Chung-Huan; Lee, Wei

2017-03-01

Blue phases (BPs) are mesophases existing between the isotropic and chiral nematic phases of liquid crystals (LCs). In recent years, blue phase LCs (BPLCs) have been extensively studied in the field of LC science and display technology. However, the application of BPLCs in biosensing has not been explored. In this study, a BPLC-based biosensing technology was developed for the detection and quantitation of bovine serum albumin (BSA). The sensing platform was constructed by assembling an empty cell with two glass slides coated with homeotropic alignment layers and with immobilized BSA atop. The LC cells were heated to isotropic phase and then allowed to cool down to and maintained at distinct BP temperatures for spectral measurements and texture observations. At BSA concentrations below 10 -6 g/ml, we observed that the Bragg reflection wavelength blue-shifted with increasing concentration of BSA, suggesting that the BP is a potentially sensitive medium in the detection and quantitation of biomolecules. By using the BPLC at 37 °C and the same polymorphic material in the smectic A phase at 20 °C, two linear correlations were established for logarithmic BSA concentrations ranging from 10 -9 to 10 -6 g/ml and from 10 -6 to 10 -3 g/ml. Our results demonstrate the potential of BPLCs in biosensing and quantitative analysis of biomolecules.

Phase behavior and characterization of heptamethyltrisiloxane-based de Vries smectic liquid crystal by electro-optics, x rays, and dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Sreenilayam, S. P.; Agra-Kooijman, D. M.; Panov, V. P.; Swaminathan, V.; Vij, J. K.; Panarin, Yu. P.; Kocot, A.; Panov, A.; Rodriguez-Lojo, D.; Stevenson, P. J.; Fisch, Michael R.; Kumar, Satyendra

2017-03-01

A heptamethyltrisiloxane liquid crystal (LC) exhibiting I -Sm A*-Sm C* phases has been characterized by calorimetry, polarizing microscopy, x-ray diffraction, electro-optics, and dielectric spectroscopy. Observations of a large electroclinic effect, a large increase in the birefringence (Δ n ) with electric field, a low shrinkage in the layer thickness (˜1.75%) at 20 °C below the Sm A*-Sm C* transition, and low values of the reduction factor (˜0.40) suggest that the Sm A* phase in this material is of the de Vries type. The reduction factor is a measure of the layer shrinkage in the Sm C* phase and it should be zero for an ideal de Vries. Moreover, a decrease in the magnitude of Δ n with decreasing temperature indicates the presence of the temperature-dependent tilt angle in the Sm A* phase. The electro-optic behavior is explained by the generalized Langevin-Debye model as given by Shen et al. [Y. Shen et al., Phys. Rev. E 88, 062504 (2013), 10.1103/PhysRevE.88.062504]. The soft-mode dielectric relaxation strength shows a critical behavior when the system goes from the Sm A* to the Sm C* phase.

Tunable optical metamaterial based on liquid crystal-gold nanosphere composite.

PubMed

Pratibha, R; Park, K; Smalyukh, I I; Park, W

2009-10-26

Effect of the surrounding anisotropic liquid crystal medium on the surface plasmon resonance (SPR) exhibited by concentrated suspensions of gold nanospheres has been investigated experimentally and compared with the Mie scattering theory. The observed polarization-sensitive SPR and the red-shift in the SPR wavelength with increasing concentration of the gold nanospheres in the liquid crystal matrix have been explained using calculations based on the Maxwell Garnet effective medium theory. Agglomeration of the gold nanospheres that could also lead to such a red-shift has been ruled out using Atomic force microscopy study of thin nanoparticle-doped smectic films obtained on solid substrates. Our study demonstrates feasibility of obtaining tunable optical bulk metamaterials based on smectic liquid crystal - nanoparticle composites.

Effect of ferroelectric BaTiO3 particles on the threshold voltage of a smectic A liquid crystal.

PubMed

Imamaliyev, Abbas Rahim; Ramazanov, Mahammadali Ahmad; Humbatov, Shirkhan Arastun

2018-01-01

The influence of small ferroelectric BaTiO 3 particles on the planar-homeotropic transition threshold voltage in smectic A liquid crystals consisting of p -nitrophenyl p -decyloxybenzoate and 4-cyano-4'-pentylbiphenyl were studied by using capacitance-voltage ( C - V ) measurements. It was shown that the BaTiO 3 particles significantly reduce the threshold voltage. The obtained result is explained by two factors: an increase of dielectric anisotropy of the liquid crystals and the formation of a strong electric field near polarized particles of BaTiO 3 . It was shown that the role of the second factor is dominant. The explanations of some features observed in the C - V characteristics are given.

Rod shaped oxovanadium(IV) Schiff base complexes: Synthesis, mesomorphism and influence of flexible alkoxy chain lengths

NASA Astrophysics Data System (ADS)

Gupta, Bishop Dev; Datta, Chitraniva; Das, Gobinda; Bhattacharjee, Chira R.

2014-06-01

A series of oxovanadium(IV) complexes of bidentate [N,O] donor Schiff-base ligands of the type [VO(L)2], [L = N-(4-n-alkoxysalicylaldimine)-4‧-octadecyloxyaniline, n = 8, 10, 12, 14, 16 and 18] have been synthesized. The compounds were characterized by elemental analyses, Fourier transform infrared spectroscopy (FTIR), 1H, 13C nuclear magnetic resonance (NMR), ultraviolet-visible spectroscopy (UV-Vis), and fast atom bombardment (FAB) mass spectrometry. The mesomorphic behavior of the compounds was studied by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The ligands and complexes are all thermally stable exhibiting smectic mesomorphism. The ligands 8-OR to16-OR show SmC phase at ∼113-118 °C and an unidentified SmX phase reminiscent of soft crystal at ∼77-91 °C whereas the complexes all showed SmA phases. Interestingly the complexes with C10 and C12 alkoxy chain length exhibited additionally SmC phases also. The melting points of the ligands linearly increases whereas mesophase to isotropic transition temperature decreases as a function of increasing carbon chain length of alkoxy arm while no trend was apparently noticeable for the complexes.

Dichroic Liquid Crystal Displays

NASA Astrophysics Data System (ADS)

Bahadur, Birendra

The following sections are included: * INTRODUCTION * DICHROIC DYES * Chemical Structure * Chemical and Photochemical Stability * THEORETICAL MODELLING * DEFECTS CAUSED BY PROLONGED LIGHT IRRADIATION * CHEMICAL STRUCTURE AND PHOTOSTABILITY * OTHER PARAMETERS AFFECTING PHOTOSTABILITY * CELL PREPARATION * DICHROIC PARAMETERS AND THEIR MEASUREMENTS * Order Parameter and Dichroic Ratio Of Dyes * Absorbance, Order Parameter and Dichroic Ratio Measurements * IMPACT OF DYE STRUCTURE AND LIQUID CRYSTAL HOST ON PHYSICAL PROPERTIES OF A DICHROIC MIXTURE * Order Parameter and Dichroic Ratio * EFFECT OF LENGTH OF DICHROIC DYES ON THE ORDER PARAMETER * EFFECT OF THE BREADTH OF DYE ON THE ORDER PARAMETER * EFFECT OF THE HOST ON THE ORDER PARAMETER * TEMPERATURE VARIATION OF THE ORDER PARAMETER OF DYES IN A LIQUID CRYSTAL HOST * IMPACT OF DYE CONCENTRATION ON THE ORDER PARAMETER * Temperature Range * Viscosity * Dielectric Constant and Anisotropy * Refractive Indices and Birefringence * solubility43,153-156 * Absorption Wavelength and Auxochromic Groups * Molecular Engineering of Dichroic Dyes * OPTICAL, ELECTRO-OPTICAL AND LIFE PARAMETERS * Colour And CIE Colour space120,160-166 * CIE 1931 COLOUR SPACE * CIE 1976 CHROMATICITY DIAGRAM * CIE UNIFORM COLOUR SPACES & COLOUR DIFFERENCE FORMULAE120,160-166 * Electro-Optical Parameters120 * LUMINANCE * CONTRAST AND CONTRAST RATIO * SWITCHING SPEED * Life Parameters and Failure Modes * DICHROIC MIXTURE FORMULATION * Monochrome Mixture * Black Mixture * ACHROMATIC BLACK MIXTURE FOR HEILMEIER DISPLAYS * Effect of Illuminant on Display Colour * Colour of the Field-On State * Effect of Dye Linewidth * Optimum Centroid Wavelengths * Effect of Dye Concentration * Mixture Formulation Using More Than Three Dyes * ACHROMATIC MIXTURE FOR WHITE-TAYLOR TYPE DISPLAYS * HEILMEIER DISPLAYS * Theoretical Modelling * Threshold Characteristic * Effects of Dye Concentration on Electro-optical Parameters * Effect of Cholesteric Doping * Effect of Alignment * Effect of Thickness * Impact of Order Parameter * Impact of the Host * Impact of Polarizer * Colour Applications * Multiplexing * QUARTER WAVE PLATE DICHROIC DISPLAYS * Operational Principle and Display Configuration11-13 * Electro-Optical Performance * DYE-DOPED TN DISPLAYS * Threshold Characteristic, Contrast Ratio and Switching Speed * PHASE CHANGE EFFECT DICHROIC LCDs * Theoretical Background * Threshold Characteristic and Molecular Orientation * MOLECULAR ORIENTATION DURING FIELD-INDUCED PHASE TRANSITION WITH HOMOGENEOUS WALL ALIGNMENT * MOLECULAR ORIENTATION DURING FIELD-INDUCED PHASE TRANSITION WITH HOMEOTROPIC WALL ALIGNMENT * Contrast Ratio, Transmission, Brightness and Switching Speed3,7,10,198-214 * Memory or Reminiscent Contrast * Electro-optical Performance vs. Temperature * Multiplexing Phase Change Dichroic LCDs * DOUBLE CELL DICHROIC LCDs3,9,14-17,232-234 * Double Cell Nematic Dichroic LCD3,8,9,14,15,233 * Double Cell One Pitch Cholesteric LCD16,17 * Double Cell Phase Change Dichroic LCD214,232 * POSITIVE MODE DICHROIC LCDS3,8,9 * Positive Mode Heilmeier Cells3,8,9,43,77,78,235-238 * USING PLEOCHROIC DYES3,8,9,43,235-238 * USING NEGATIVE DICHROIC DYES3,8,9,63,77,78156 * DUAL FREQUENCY ADDRESSED DICHROIC DISPLAYS75,238 * Positive Mode Dichroic LCDs Using λ/4 Plate * Positive Mode Double Cell Dichroic LCD * Positive Mode Dichroic LCDs Using Special Electrode patterns7,8,239-241 * Positive Mode Phase Change Dichroic LCDs3,8,9,230,243-248 * Dichroic LCDs Using an Admixture of Pleochroic and Negative Dichroic Dyes78,118 * SUPERTWIST DICHROIC EFFECT (SDE) DISPLAYS21-23 * FERROELECTRIC DICHROIC LCDs24-27 * Devices Using A Single Polarizer * Devices Using No Polarizer24-27 * POLYMER DISPERSED DICHROIC LCDs28-30,252-259 * DICHROIC POLYMER LIQUID CRYSTAL DISPLAYS * Heilmeier Type Displays * Guest-Host Cell Using an Admixture Of L.C. Polymer and Low Molecular Weight Liquid Crysta As Host * Polymeric Ferroelectric Dichroic LCDs * SMECTIC A DICHROIC LCDs * Laser Addressed Dichroic SA Displays * Thermally and Electrically Addressed Dichroic SA Displays * FLUORESCENT DICHROIC LCDs * ACKNOWLEDGEMENTS * REFERENCES

Calorimetric study of phase transitions in nanocomposites of quantum dots and a liquid crystal

NASA Astrophysics Data System (ADS)

Kalakonda, P.; Iannacchione, G. S.

2015-06-01

The complex specific heat is measured over a wide temperature range for the liquid crystal (LC) 4-cyano-4-octylbiphenyl (8CB) and cadmium sulfate quantum dots (QDs) composites as a function of QD concentration. The thermal scans were performed under near-equilibrium conditions for all samples having QDs weight percent (φw) from 0 to 3wt% over a wide range of temperature well above and below the two transitions in pure 8CB. Isotropic (I) to nematic (N) and nematic to smectic-A (SmA) phase transitions evolve in character and their transition temperatures offset by (∼2.3 to 2.6 K) lower for all composite samples as compared to that in pure 8CB. The enthalpy change associated with I-N phase transitions shows slightly different behavior on heating and cooling and it also shows crossover behavior at lower and higher QD content. The enthalpy change associated with N-SmA phase transitions is independent of QD loading and thermal treatment. Given the homogeneous and random distribution of QD in these nanocomposites, we interpret that these results as arising that the nematic phase imposes self-assembly on QDs to form one-dimensional arrays leading to QDs and induces net local disordering effect in LC media.

Effect of ferroelectric BaTiO3 particles on the threshold voltage of a smectic A liquid crystal

PubMed Central

Imamaliyev, Abbas Rahim; Ramazanov, Mahammadali Ahmad

2018-01-01

The influence of small ferroelectric BaTiO3 particles on the planar–homeotropic transition threshold voltage in smectic A liquid crystals consisting of p-nitrophenyl p-decyloxybenzoate and 4-cyano-4′-pentylbiphenyl were studied by using capacitance–voltage (C–V) measurements. It was shown that the BaTiO3 particles significantly reduce the threshold voltage. The obtained result is explained by two factors: an increase of dielectric anisotropy of the liquid crystals and the formation of a strong electric field near polarized particles of BaTiO3. It was shown that the role of the second factor is dominant. The explanations of some features observed in the C–V characteristics are given. PMID:29600143

Listening to Chemical Materials: Determination of the Photophysical Parameters by Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Yang, Y. T.; Zhang, S. Y.; Liu, X. J.

2012-11-01

Recently, photoacoustic (PA) spectroscopy has emerged as a valuable tool for the study of various kinds of materials. Herein, we present the results of PA spectral studies of chemical materials. First, the PA study on luminescent materials in condensed states is reported. Combining with the luminescence technique, the energy transfer efficiency and the intrinsic luminescence quantum yield are determined for a europium (III) complex in the glassy state, smectic A phase, and the isotropic liquid. Second, neodymium (III) compounds with l-glycine, l-phenylalanine, and l-tryptophan are synthesized and their PA spectra are reported. The nephelauxetic ratio and Sinha parameter are calculated based on the PA spectra. The environmental effect on the f-f transitions of the neodymium(III) ion is also studied.

Polar order in nanostructured organic materials

NASA Astrophysics Data System (ADS)

Sayar, M.; Olvera de la Cruz, M.; Stupp, S. I.

2003-02-01

Achiral multi-block liquid crystals are not expected to form polar domains. Recently, however, films of nanoaggregates formed by multi-block rodcoil molecules were identified as the first example of achiral single-component materials with macroscopic polar properties. By solving an Ising-like model with dipolar and asymmetric short-range interactions, we show here that polar domains are stable in films composed of aggregates as opposed to isolated molecules. Unlike classical molecular systems, these nanoaggregates have large intralayer spacings (a approx 8 nm), leading to a reduction in the repulsive dipolar interactions which oppose polar order within layers. In finite-thickness films of nanostructures, this effect enables the formation of polar domains. We compute exactly the energies of the possible structures consistent with the experiments as a function of film thickness at zero temperature (T). We also provide Monte Carlo simulations at non-zero T for a disordered hexagonal lattice that resembles the smectic-like packing in these nanofilms.

Synthesis and carbon-13 NMR studies of liquid crystals

NASA Astrophysics Data System (ADS)

Sun, Hong

2000-08-01

The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using 13C NMR. The method of proton encoded local field (PELF) spectroscopy was used in combination with off-magic-angle spinning (OMAS) of the sample. High-resolution 2D spectra were obtained and the order parameters were calculated from the spectra. Linear relationships between the obtained order parameters and anisotropic chemical shifts determined by 1D 13C NMR were established and semi-empirical parameters were obtained. A 1:2 mixture of 7CPB and its chain-perfluorinated analog (7PFCPB) shows interesting phase behavior with changing of temperature. The mixture was studied by the use of 13C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained by the 2D NMR method. Eight series of liquid crystals containing an electron- donating group at one end of a conjugated system and an electron-withdrawing group at the other end have been synthesized. The electron-donating group is 4- n-alkylpiperazinyl group, the electron- withdrawing group is nitro group and the conjugated system is diphenyldiazene with zero, one or two substituents on the phenyl rings. The substituents are -F, -Cl, and -CH3. Two series of compounds with cyano group as electron-withdrawing group were also synthesized. Most of the compounds synthesized are nematogenic and exhibit rather broad liquid crystalline ranges. The effects of the lateral substituents on the optical absorption and phase transition temperatures are correlated with their nature and position of substitution. Birefringence, dielectric anisotropy, elastic constant ratio and rise time of the liquid crystals were carried out using 10 wt% LC mixtures in E7. It has been found that lateral substituents have subtle effects on the properties. The presence of lateral substituents depresses melting points and clearing points of the liquid crystals. All the liquid crystals synthesized in this work have relatively large values of birefiringence, although the dielectric anisotropy values were not as high as desired. The incorporation of a fluorine atom onto the position neighboring the nitro group enhances the conjugation of the push-pull system and liquid crystals with better physical properties were obtained.

The effect of surface alignment on analog control of director rotation in polarization stiffened SmC* devices

NASA Astrophysics Data System (ADS)

Reznikov, Mitya; Lopatina, Lena M.; O'Callaghan, Michael J.; Bos, Philip J.

2011-03-01

The effect of surface alignment on the achievement of analog ("V"-shaped) electric field control of director rotation in SmC* liquid crystal devices is investigated experimentally and through numerical modeling. Ferroelectric SmC* liquid crystals are intrinsically analog and thresholdless, i.e. the director can be rotated freely around the tilt cone. Whether or not a SmC* liquid crystal cell exhibits thresholdless switching depends strongly on the influence of the cell's alignment layers, on the magnitude of the liquid crystal's spontaneous polarization, and on whether smectic layers adopt a bookshelf or chevron configuration. To study the effect of the surface alignment layers, we have exploited a technique for the vertical (bookshelf) alignment of the smectic layers that does not depend on surface anisotropy. The alignment technique allows an experimental study of the influence of surfaces spanning a wide range of pretilt angles, azimuthal and zenithal anchoring energies. This technique is used to study the effect of surfaces on the threshold behavior of director rotation in SmC* materials under the influence of an electric field. The alignment technique also allowed us to use a high-PS liquid crystal material having an I-A-C phase sequence and reduced layer shrinkage thought to be well suited to thresholdless switching. We show that the alignment layer has a strong effect, and that excellent analog response can be achieved for the case of alignment layers which promote homeotropic director orientation. We further model and discuss the potential effect of a thin layer of nematic at the surface and the possibility of gliding of the easy axis during switching.

Magnus-induced dynamics of driven skyrmions on a quasi-one-dimensional periodic substrate

DOE PAGES

Reichhardt, Charles; Reichhardt, Cynthia Jane

2016-09-13

Here we numerically examine driven skyrmions interacting with a periodic quasi-one-dimensional substrate where the driving force is applied either parallel or perpendicular to the substrate periodicity direction. For perpendicular driving, the particles in a purely overdamped system simply slide along the substrate minima; however, for skyrmions where the Magnus force is relevant, we find that a rich variety of dynamics can arise. In the single skyrmion limit, the skyrmion motion is locked along the driving or longitudinal direction for low drives, while at higher drives a transition occurs to a state in which the skyrmion moves both transverse and longitudinalmore » to the driving direction. Within the longitudinally locked phase we find a pronounced speedup effect that occurs when the Magnus force aligns with the external driving force, while at the transition to transverse and longitudinal motion, the skyrmion velocity drops, producing negative differential conductivity. For collectively interacting skyrmion assemblies, the speedup effect is still present and we observe a number of distinct dynamical phases, including a sliding smectic phase, a disordered or moving liquid phase, a moving hexatic phase, and a moving crystal phase. The transitions between the dynamic phases produce distinct features in the structure of the skyrmion lattice and in the velocity-force curves. Lastly, we map these different phases as a function of the ratio of the Magnus term to the dissipative term, the substrate strength, the commensurability ratio, and the magnitude of the driving force.« less

Magnus-induced dynamics of driven skyrmions on a quasi-one-dimensional periodic substrate

NASA Astrophysics Data System (ADS)

Reichhardt, C.; Reichhardt, C. J. Olson

2016-09-01

We numerically examine driven skyrmions interacting with a periodic quasi-one-dimensional substrate where the driving force is applied either parallel or perpendicular to the substrate periodicity direction. For perpendicular driving, the particles in a purely overdamped system simply slide along the substrate minima; however, for skyrmions where the Magnus force is relevant, we find that a rich variety of dynamics can arise. In the single skyrmion limit, the skyrmion motion is locked along the driving or longitudinal direction for low drives, while at higher drives a transition occurs to a state in which the skyrmion moves both transverse and longitudinal to the driving direction. Within the longitudinally locked phase we find a pronounced speedup effect that occurs when the Magnus force aligns with the external driving force, while at the transition to transverse and longitudinal motion, the skyrmion velocity drops, producing negative differential conductivity. For collectively interacting skyrmion assemblies, the speedup effect is still present and we observe a number of distinct dynamical phases, including a sliding smectic phase, a disordered or moving liquid phase, a moving hexatic phase, and a moving crystal phase. The transitions between the dynamic phases produce distinct features in the structure of the skyrmion lattice and in the velocity-force curves. We map these different phases as a function of the ratio of the Magnus term to the dissipative term, the substrate strength, the commensurability ratio, and the magnitude of the driving force.

Elasticity and hydrodynamic properties of ``doped solvent dilute'' lamellar phases

NASA Astrophysics Data System (ADS)

Nallet, Frédéric; Roux, Didier; Quilliet, Catherine; Fabre, Pascale; Milner, Scott T.

1994-09-01

The equilibrium fluctuations and weakly out-of-equilibrium relaxation properties of “doped solvent" dilute lamellar phases are investigated, both theoretically and experimentally, in the low-frequency, long-wavelength limit. The physical system of interest is a three-component smectic A lyotropic liquid crystal where surfactant bilayers infinite in extent are periodically stacked along one direction in space and separated by a colloidal solution. Two experimentally relevant modes are found in the lowest frequency part of the fluctuation spectrum of such multicomponent systems. Both are associated to the relaxation of coupled layer displacement and colloid concentration waves. In the limit of small coupling, one mode is close to the well-known undulation/baroclinic mode of two-component lamellar phases, while the other corresponds to the Brownian diffusive motion of the colloid in an anisotropic medium. Elastic constants of the smectic liquid crystal and diffusion parameters of the colloidal solution may be deduced from a measurement of the anisotropic dispersion relation of these two modes, as illustrated by dynamic light scattering experiments on the ferrosmectic system. Les fluctuations à l'équilibre ainsi que la relaxation des états légèrement en dehors de l'équilibre des phases lamellaires à “solvant dopé” sont étudiées, aussi bien d'un point de vue théorique qu'expérimental, dans la limite de basses fréquences et de grandes longueurs d'onde. Les systèmes décrits sont des cristaux-liquides smectiques A lyotropes formés de trois constituants : un tensioactif en solution dans une suspension colloïdale forme des bicouches de grande extension latérale qui s'empilent de façon périodique le long d'une direction dans l'espace. Avec de tels systèmes anisotropes et à plusieurs constituants deux modes présents dans la partie à basse fréquence du spectre des fluctuations (associés à la relaxation d'ondes, couplées, de concentration colloïdale et de déplacement des couches smectiques) ont une certaine importance expérimentale. Dans la limite d'un couplage faible, l'un des deux modes est similaire au mode barocline des phases lamellaires à deux constituants ; le second s'identifie au mouvement brownien de diffusion d'un colloïde dans un substrat anisotrope. Les constantes élastiques du cristal liquide smectique de même que le coefficient de diffusion du colloïde peuvent en principe être déduits de la mesure des relations anisotropes de dispersion de ces deux modes ; cela est illustré par des expériences de diffusion quasi-élastique de la lumière sur des ferrosmectiques.

Visualization of Thin Liquid Crystal Bubbles in Microgravity

NASA Technical Reports Server (NTRS)

Park, C. S.; Clark, N. A.; Maclennan, J. E.; Glaser, M. A.; Tin, P.; Stannarius, R.; Hall, N.; Storck, J.; Sheehan, C.

2015-01-01

The Observation and Analysis of Smectic Islands in Space (OASIS) experiment exploits the unique characteristics of freely suspended liquid crystals in a microgravity environment to advance the understanding of fluid state physics.

Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

DOE PAGES

Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; ...

2015-07-23

The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds ismore » studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.« less

Induced amphotropic and thermotropic ionic liquid crystallinity in phosphonium halides: "lubrication" by hydroxyl groups.

PubMed

Ma, Kefeng; Somashekhar, B S; Gowda, G A Nagana; Khetrapal, C L; Weiss, Richard G

2008-03-18

The influence of covalently attaching hydroxymethylene to the methyl groups of methyl-tri-n-alkylphosphonium halides (where the alkyl chains are decyl, tetradecyl, or octadecyl and the halide is chloride or bromide) or adding methanol as a solute to the salts on their solid, liquid-crystalline (smectic A2), and isotropic phases has been investigated using a variety of experimental techniques. These structural and compositional changes are found to induce liquid crystallinity in some cases and to enhance the temperature range and lower the onset temperature of the liquid-crystalline phases in some others. The results are interpreted in terms of the lengths of the three n-alkyl chains attached to the phosphorus cation, the nature of the halide anion, the influence of H-bonding interactions at the head group regions of the layered phases, and other solvent-solute interactions. The fact that at least 1 molar equiv of methanol must be added to effect complete (isothermal) conversion of a solid methyl-tri-n-alkylphosphonium salt to a liquid crystal demonstrates a direct and strong association between individual methanol molecules and the phosphonium salts. Possible applications of such systems are suggested.

Applications of Density Functional Theory in Soft Condensed Matter

NASA Astrophysics Data System (ADS)

Löwen, Hartmut

Applications of classical density functional theory (DFT) to soft matter systems like colloids, liquid crystals and polymer solutions are discussed with a focus on the freezing transition and on nonequilibrium Brownian dynamics. First, after a brief reminder of equilibrium density functional theory, DFT is applied to the freezing transition of liquids into crystalline lattices. In particular, spherical particles with radially symmetric pair potentials will be treated (like hard spheres, the classical one-component plasma or Gaussian-core particles). Second, the DFT will be generalized towards Brownian dynamics in order to tackle nonequilibrium problems. After a general introduction to Brownian dynamics using the complementary Smoluchowski and Langevin pictures appropriate for the dynamics of colloidal suspensions, the dynamical density functional theory (DDFT) will be derived from the Smoluchowski equation. This will be done first for spherical particles (e.g. hard spheres or Gaussian-cores) without hydrodynamic interactions. Then we show how to incorporate hydrodynamic interactions between the colloidal particles into the DDFT framework and compare to Brownian dynamics computer simulations. Third orientational degrees of freedom (rod-like particles) will be considered as well. In the latter case, the stability of intermediate liquid crystalline phases (isotropic, nematic, smectic-A, plastic crystals etc) can be predicted. Finally, the corresponding dynamical extension of density functional theory towards orientational degrees of freedom is proposed and the collective behaviour of "active" (self-propelled) Brownian particles is briefly discussed.

Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof.

PubMed

Shao, Hua; Pinnavaia, Thomas J

2010-09-01

The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

DOE PAGES

Li, Yuzhan; Pruitt, Cole; Rios, Orlando; ...

2015-04-10

Here, we describe how a smectic main-chain liquid crystalline elastomer (LCE), with controlled shape memory behavior, is synthesized by polymerizing a biphenyl-based epoxy monomer with an aliphatic carboxylic acid curing agent. Microstructures of the LCEs, including their liquid crystallinity and cross-linking density, are modified by adjusting the stoichiometric ratio of the reactants to tailor the thermomechanical properties and shape memory behavior of the material. Thermal and liquid crystalline properties of the LCEs, characterized using differential scanning calorimetry and dynamic mechanical analysis, and structural analysis, performed using small-angle and wide-angle X-ray scattering, show that liquid crystallinity, cross-linking density, and network rigiditymore » are strongly affected by the stoichiometry of the curing reaction. With appropriate structural modifications it is possible to tune the thermal, dynamic mechanical, and thermomechanical properties as well as the shape memory and thermal degradation behavior of LCEs.« less

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuzhan; Pruitt, Cole; Rios, Orlando

Here, we describe how a smectic main-chain liquid crystalline elastomer (LCE), with controlled shape memory behavior, is synthesized by polymerizing a biphenyl-based epoxy monomer with an aliphatic carboxylic acid curing agent. Microstructures of the LCEs, including their liquid crystallinity and cross-linking density, are modified by adjusting the stoichiometric ratio of the reactants to tailor the thermomechanical properties and shape memory behavior of the material. Thermal and liquid crystalline properties of the LCEs, characterized using differential scanning calorimetry and dynamic mechanical analysis, and structural analysis, performed using small-angle and wide-angle X-ray scattering, show that liquid crystallinity, cross-linking density, and network rigiditymore » are strongly affected by the stoichiometry of the curing reaction. With appropriate structural modifications it is possible to tune the thermal, dynamic mechanical, and thermomechanical properties as well as the shape memory and thermal degradation behavior of LCEs.« less

Formation and stability of twisted ribbons in mixtures of rod-like fd-virus and non-adsorbing polymer

NASA Astrophysics Data System (ADS)

Dogic, Z.; Didonna, B.; Bryning, M.; Lubensky, T. C.; Yodh, A. G.; Janmey, P. A.

2003-03-01

We are investigating the behavior of mixtures of monodisperse fd-virus rods and non-adsorbing polymer. We observe the formation of isolated smectic disks. The single smectic disk is of a monolayer of aligned rods while its thickness equal to the length of a single rod. As disks coalesce they undergo shape transformations from flat structures to elongated twisted ribbons. A theoretical model is formulated wherein the chirality of the molecule favors the formation of the elongated ribbon structure while the line tension favors formation of untwisted disks. To check the validity of the theoretical model line tension and twist constants are experimentally measured. The line tension is deduced from thermal fluctuations of the interface. The twist constant is determined by unwinding the twisted ribbons using optical tweezers. This work is partially supported by NSF grants DMR-0203378, the PENN MRSEC, DMR-0079909, and NASA grant NAG8-2172.

Role of aerosil dispersion on the activated kinetics of the LC1-xSilx system.

PubMed

Sharma, Dipti; MacDonald, John C; Iannacchione, Germano S

2006-12-28

This study explores the role of aerosil dispersion on activated phase transitions of bulk octylcyanobiphenyl (8CB) liquid crystals by performing heating rate-dependent experiments. Differential scanning calorimetry (DSC) was used at various heating ramp rates in order to probe the activated phase dynamics of the system. The system, LC1-xSilx, was prepared by mixing aerosil nanoparticles (7 nm in diameter) in the bulk 8CB by the solvent dispersion method (SDM). LC represents bulk 8CB, and Sil represents aerosil nanoparticles with concentration x in percent. The concentration of the aerosil nanoparticles (x) varied from 0 to 0.2 g/cm3 in the bulk 8CB. Well-defined, endothermic peaks were found on a heating scan at melting and at the smectic-A to nematic (SmA-N) and nematic to isotropic (N-I) transitions. These peaks show a temperature shift and a change in their shapes and sizes in the presence of aerosil nanoparticles. In addition, an exothermic peak also appeared before the melting peak during the heating scan in the presence of aerosil nanoparticles. All transitions shifted significantly with different heating ramp rates, following an Arrhenius behavior, showing activated kinetics. The presence of aerosil nanoparticles caused a significant increase in the enthalpy and a decrease in the activation energy compared to the results found in bulk 8CB. This behavior can be explained by aerosil dispersion in the LC1-xSilx, inducing a disorder in the bulk 8CB. Infrared (IR) spectroscopy shows a shift to higher frequency for the broad peak at 1082 cm-1, corresponding to an Si-O bond as the density of the aerosil increases, and can be explained in terms of surface and molecular interactions between aerosil nanoparticles and 8CB liquid crystal molecules.

iss047e012492

NASA Image and Video Library

2016-03-21

ISS047e012492 (03/21/2016) --- NASA astronaut Tim Kopra stows hardware from the OASIS experiment aboard the International Space Station. OASIS, which stands for Observation and Analysis of Smectic Islands In Space, studies the unique behavior of liquid crystals in microgravity.

TGBA and TGBC phases in some chiral tolan derivatives

NASA Astrophysics Data System (ADS)

Nguyen, H. T.; Bouchta, A.; Navailles, L.; Barois, P.; Isaert, N.; Twieg, R. J.; Maaroufi, A.; Destrade, C.

1992-10-01

Three chiral compounds (n=10, 11, 12) belonging to the optically active series : 3-fluoro-4-[(R) or (S)-1-methylheptyloxy]-4'-(4''-alkoxy-2'', 3''-difluorobenzoyloxy) tolans (nF{2}BTFO{1}M{7}) have been synthesized. The helical SA^{*} phase or TGBA phase is found in the decyloxy derivative. The most interesting compound is obtained with n=11. It displays, for the first time, two TGB phases (TGBA and TGBC phases). The nature of these helical smectic phases is confirmed by different studies : optical observation, DSC, contact method, mixtures, X-ray diffraction and helical pitch measurements. the electrooptical properties of the SC^{*} phase have also been studied. Trois produits (n=10, 11, 12) de la série chirale : 3-fluoro-4-[(R) ou (S)-1-methylheptyloxy]-4'-(4''-alcoxy-2'', 3''-difluorobenzoyloxy) tolanes (nF{2}BTFO{1}M{7}) ont été synthétisés. Les deux premiers produits présentent la phase SA^{*} hélicoïdale ou torse (TGBA). L'existence de la nouvelle phase TGBC, prédite par Renn et Lubensky, a été trouvée dans les deux derniers matériaux et prouvée par plusieurs études : observation microscopique, AED, méthode de contact, mélanges binaires, diffraction de rayons X et mesures du pas d'hélice. Le diagramme de phase réalisé entre ces trois matériaux est similaire à celui prédit par Renn. Les propriétés électrooptiques de la phase SC^{*} ferroélectrique ont aussi été étudiées.

Solution processed nanogap organic diodes based on liquid crystalline materials

NASA Astrophysics Data System (ADS)

Wang, Yi-Fei; Iino, Hiroaki; Hanna, Jun-ichi

2017-09-01

Co-planar nanogap organic diodes were fabricated with smectic liquid crystalline materials of the benzothienobenzothiophene (BTBT) derivative by a spin-coating technique. A high rectification ratio of the order of 106 at ±3 V was achieved when a liquid crystalline material of 2,7-didecyl benzothieno[3,2-b][1]benzothiophene (10-BTBT-10) was used in a device configuration of Al/10-BTBT-10/pentafluorobenzenethiol-treated Au on a glass substrate, which was 4 orders higher than that of the device based on non-liquid crystalline materials of 2,7-dibutyl benzothieno[3,2-b][1]benzothiophene (4-BTBT-4) and BTBT. Similar results were also observed when another liquid crystalline material of ω, ω'-dioctylterthiophene (8-TTP-8) and a non-liquid crystalline material of terthiophene (TTP) were used. These improved rectifications can be ascribed to the self-assembly properties and controllable molecular orientation of liquid crystalline materials, which made uniform perpendicular oriented polycrystalline films favorable for superior charge transport in nano-channels.

Concerted growth and ordering of cobalt nanorod arrays as revealed by tandem in situ SAXS-XAS studies

DOE PAGES

Cormary, Benoit; Li, Tao; Liakakos, Nikos; ...

2016-06-14

The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray Absorption Spectroscopy – Small Angle X-ray Scattering (XAS - SAXS). The super-crystals were obtained by reducing a Co(II) precursor under H 2 in the presence of a long chain amine and a long chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism, and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom by atom anisotropic growth and amore » slower oriented attach-ment process that continues well after cobalt reduction is complete. As a result, smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized super-lattices, which can be regarded as mesocrystals.« less

Dual gauge field theory of quantum liquid crystals in three dimensions

NASA Astrophysics Data System (ADS)

Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai; Zaanen, Jan

2017-10-01

The dislocation-mediated quantum melting of solids into quantum liquid crystals is extended from two to three spatial dimensions, using a generalization of boson-vortex or Abelian-Higgs duality. Dislocations are now Burgers-vector-valued strings that trace out worldsheets in space-time while the phonons of the solid dualize into two-form (Kalb-Ramond) gauge fields. We propose an effective dual Higgs potential that allows for restoring translational symmetry in either one, two, or three directions, leading to the quantum analogues of columnar, smectic, or nematic liquid crystals. In these phases, transverse phonons turn into gapped, propagating modes, while compressional stress remains massless. Rotational Goldstone modes emerge whenever translational symmetry is restored. We also consider the effective electromagnetic response of electrically charged quantum liquid crystals, and find among other things that as a hard principle only two out of the possible three rotational Goldstone modes are observable using propagating electromagnetic fields.

Three-dimensional textures and defects of soft material layering revealed by thermal sublimation.

PubMed

Yoon, Dong Ki; Kim, Yun Ho; Kim, Dae Seok; Oh, Seong Dae; Smalyukh, Ivan I; Clark, Noel A; Jung, Hee-Tae

2013-11-26

Layering is found and exploited in a variety of soft material systems, ranging from complex macromolecular self-assemblies to block copolymer and small-molecule liquid crystals. Because the control of layer structure is required for applications and characterization, and because defects reveal key features of the symmetries of layered phases, a variety of techniques have been developed for the study of soft-layer structure and defects, including X-ray diffraction and visualization using optical transmission and fluorescence confocal polarizing microscopy, atomic force microscopy, and SEM and transmission electron microscopy, including freeze-fracture transmission electron microscopy. Here, it is shown that thermal sublimation can be usefully combined with such techniques to enable visualization of the 3D structure of soft materials. Sequential sublimation removes material in a stepwise fashion, leaving a remnant layer structure largely unchanged and viewable using SEM, as demonstrated here using a lamellar smectic liquid crystal.

GPU-Accelerated Molecular Dynamics Simulation to Study Liquid Crystal Phase Transition Using Coarse-Grained Gay-Berne Anisotropic Potential.

PubMed

Chen, Wenduo; Zhu, Youliang; Cui, Fengchao; Liu, Lunyang; Sun, Zhaoyan; Chen, Jizhong; Li, Yunqi

2016-01-01

Gay-Berne (GB) potential is regarded as an accurate model in the simulation of anisotropic particles, especially for liquid crystal (LC) mesogens. However, its computational complexity leads to an extremely time-consuming process for large systems. Here, we developed a GPU-accelerated molecular dynamics (MD) simulation with coarse-grained GB potential implemented in GALAMOST package to investigate the LC phase transitions for mesogens in small molecules, main-chain or side-chain polymers. For identical mesogens in three different molecules, on cooling from fully isotropic melts, the small molecules form a single-domain smectic-B phase, while the main-chain LC polymers prefer a single-domain nematic phase as a result of connective restraints in neighboring mesogens. The phase transition of side-chain LC polymers undergoes a two-step process: nucleation of nematic islands and formation of multi-domain nematic texture. The particular behavior originates in the fact that the rotational orientation of the mesogenes is hindered by the polymer backbones. Both the global distribution and the local orientation of mesogens are critical for the phase transition of anisotropic particles. Furthermore, compared with the MD simulation in LAMMPS, our GPU-accelerated code is about 4 times faster than the GPU version of LAMMPS and at least 200 times faster than the CPU version of LAMMPS. This study clearly shows that GPU-accelerated MD simulation with GB potential in GALAMOST can efficiently handle systems with anisotropic particles and interactions, and accurately explore phase differences originated from molecular structures.

GPU-Accelerated Molecular Dynamics Simulation to Study Liquid Crystal Phase Transition Using Coarse-Grained Gay-Berne Anisotropic Potential

PubMed Central

Cui, Fengchao; Liu, Lunyang; Sun, Zhaoyan; Chen, Jizhong; Li, Yunqi

2016-01-01

Gay-Berne (GB) potential is regarded as an accurate model in the simulation of anisotropic particles, especially for liquid crystal (LC) mesogens. However, its computational complexity leads to an extremely time-consuming process for large systems. Here, we developed a GPU-accelerated molecular dynamics (MD) simulation with coarse-grained GB potential implemented in GALAMOST package to investigate the LC phase transitions for mesogens in small molecules, main-chain or side-chain polymers. For identical mesogens in three different molecules, on cooling from fully isotropic melts, the small molecules form a single-domain smectic-B phase, while the main-chain LC polymers prefer a single-domain nematic phase as a result of connective restraints in neighboring mesogens. The phase transition of side-chain LC polymers undergoes a two-step process: nucleation of nematic islands and formation of multi-domain nematic texture. The particular behavior originates in the fact that the rotational orientation of the mesogenes is hindered by the polymer backbones. Both the global distribution and the local orientation of mesogens are critical for the phase transition of anisotropic particles. Furthermore, compared with the MD simulation in LAMMPS, our GPU-accelerated code is about 4 times faster than the GPU version of LAMMPS and at least 200 times faster than the CPU version of LAMMPS. This study clearly shows that GPU-accelerated MD simulation with GB potential in GALAMOST can efficiently handle systems with anisotropic particles and interactions, and accurately explore phase differences originated from molecular structures. PMID:26986851

Oxygen transport as a structure probe for heterogeneous polymeric systems

NASA Astrophysics Data System (ADS)

Hu, Yushan

Although permeability of small molecules is often measured as an important performance property, deeper analysis of the transport characteristics provides insight into polymer structure, especially if used in combination with other characterization techniques. Transport of small gas molecules senses the permeable amorphous structure and probes the nature of free volume. This work focuses on oxygen transport, supplemented with other methods of physical analysis, as a probe for: (1) the nature of free volume and crystalline morphology in the crystallized glassy state, (2) the nature of free volume and hierarchical structure in liquid crystalline polymers, and (3) the role of dispersed polyamide phase geometry on oxygen barrier properties of poly(ethylene terephthalate) (PET)/polyamide blends. In the first part, the improvement in oxygen-barrier properties of glassy polyesters by crystallization was examined. Examples included poly(ethylene naphthalate) (PEN), and a copolymer based on PET in which 55 mol% terephthalate was replaced with 4,4'-bibenzoate. Explanation of the unexpectedly high solubility of crystallized PEN required a two-phase transport model consisting of an impermeable crystalline phase of constant density and a permeable amorphous phase of variable density. The resulting relationship between oxygen solubility and amorphous phase density was consistent with free volume concepts of gas sorption. In the second part, oxygen barrier properties of liquid crystalline (LC) polyesters based on poly(diethylene glycol 4,4'-bibenzoate) (PDEGBB) were studied. This study extended the 2-phase transport model for oxygen transport of non-LC crystalline polymers to a smectic LCP. It was possible to systematically vary the solid state structure of (PDEGBB) from LC glass to crystallized LC glass. The results were consistent with a liquid crystalline state intermediate between the permeable amorphous glass and the impermeable 3-dimensional crystal. In this interpretation, LC order naturally led to inherently low gas solubility. In the third part, improvement of gas-barrier properties of poly(ethylene terephthalate) (PET) by blending with an aromatic polyamide, either poly(m-xylylene adipamide) (MXD6) or a copolyamide based on MXD6 in which 12 mol% adipamide was replaced with isophthalamide (MXD6-12I), was studied. Aromatic polyamides provided higher barrier than aliphatic polyamides, and unlike aliphatic polyamides, the aromatic polyamides retained high barrier under conditions of high humidity, making them more suitable for beverage packaging applications. (Abstract shortened by UMI.)

Temperature Dependence of Smectic Liquid Crystals Mixed With Magnetic Nanoparticles

NASA Astrophysics Data System (ADS)

Taylor, Jefferson W.; Kurihara, Lynn K.; Martinez-Miranda, Luz J.

2012-02-01

We investigate the properties of bulk liquid crystal mixed with a magnetic nanoparticle (CoFe) as a function of temperature. We compare our results to those of a heat capacity measurement of Cordoyiannis et al.ootnotetextGeorge Cordoyiannis, Lynn K. Kurihara, Luz J. Martinez-Miranda, Christ Glorieux, and Jan Thoen, Phys. Rev. E 79, 011702 (2009) and compare the way the smectic as a function of temperature the way the nematic behaves. We study how the liquid crystal reorganizes in the presence of the functionalized nanoparticles as a function of temperature and compare it to how it behaves at room temperature.ootnotetextL. J. Mart'inez-Miranda, and Lynn Kurihara, J. Appl. Phys, 105, p. 084305 (2009). The X-rays give rise to three or four peaks whose evolution in temperature varies depending on their origin. In particular the second peak does not seem to vary much with temperature, and can be associated with the first several molecular layers attached to the nanoparticles.

Asymmetric van der Waals Forces Drive Orientation of Compositionally Anisotropic Nanocylinders within Smectic Arrays: Experiment and Simulation

PubMed Central

Smith, Benjamin D.; Fichthorn, Kristen A.; Kirby, David J.; Quimby, Lisa M.; Triplett, Derek A.; González, Pedro; Hernández, Darimar; Keating, Christine D.

2014-01-01

Understanding how micro- and nanoparticles interact is important for achieving bottom-up assembly of desired structures. Here, we examine the self-assembly of two-component, compositionally asymmetric nanocylinders that sediment from solution onto a solid surface. These particles spontaneously formed smectic arrays. Within the rows of an array, nanocylinders tended to assemble such that neighboring particles had the same orientation of their segments. As a probe of interparticle interactions, we classified nanocylinder alignments by measuring the segment orientations of many sets of neighboring particles. Monte Carlo simulations incorporating an exact expression for the van der Waals (vdW) energy indicate that differences in the vdW interactions, even when small, are the key factor in producing observed segment alignment. These results point to asymmetrical vdW interactions as a potentially powerful means of controlling orientation in multicomponent cylinder arrays, and suggest that designing for these interactions could yield new ways to control self-assembly. PMID:24308771

The Stokesian hydrodynamics of flexing, stretching filaments

NASA Astrophysics Data System (ADS)

Shelley, Michael J.; Ueda, Tetsuji

2000-11-01

A central element of many fundamental problems in physics and biology lies in the interaction of a viscous fluid with slender, elastic filaments. Examples arise in the dynamics of biological fibers, the motility of microscopic organisms, and in phase transitions of liquid crystals. When considering the dynamics on the scale of a single filament, the surrounding fluid can often be assumed to be inertialess and hence governed by the Stokes’ equations. A typical simplification then is to assume a local relation, along the filament, between the force per unit length exerted by the filament upon the fluid and the velocity of the filament. While this assumption can be justified through slender-body theory as the leading-order effect, this approximation is only logarithmically separated (in aspect ratio) from the next-order contribution capturing the first effects of non-local interactions mediated by the surrounding fluid; non-local interactions become increasingly important as a filament comes within proximity to itself, or another filament. Motivated by a pattern forming system in isotropic to smectic-A phase transitions, we consider the non-local Stokesian dynamics of a growing elastica immersed in a fluid. The non-local interactions of the filament with itself are included using a modification of the slender-body theory of Keller and Rubinow. This modification is asymptotically equivalent, and removes an instability of their formulation at small, unphysical length-scales. Within this system, the filament lives on a marginal stability boundary, driven by a continual process of growth and buckling. Repeated bucklings result in filament flex, which, coupled to the non-local interactions and mediated by elastic response, leads to the development of space-filling patterns. We develop numerical methods to solve this system accurately and efficiently, even in the presence of temporal stiffness and the close self-approach of the filament. While we have ignored many of the thermodynamic aspects of this system, our simulations show good qualitative agreement with experimental observations. Our results also suggest that non-locality, induced by the surrounding fluid, will be important to understanding the dynamics of related filament systems.

Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

NASA Astrophysics Data System (ADS)

Velayutham, T. S.; Ng, B. K.; Gan, W. C.; Majid, W. H. Abd.; Hashim, R.; Zahid, N. I.; Chaiprapa, Jitrin

2014-08-01

Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10-2-106 Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.

Nanospheres with a smectic hydrophobic core and an amorphous PEG hydrophilic shell: structural changes and implications for drug delivery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murthy, N. Sanjeeva; Zhang, Zheng; Borsadia, Siddharth

The structural changes in nanospheres with a crystalline core and an amorphous diffuse shell were investigated by small-angle neutron scattering (SANS), small-, medium-, and wide-angle X-ray scattering (SAXS, MAXS and WAXS), and differential scanning calorimetry (DSC).

Bias-stress characterization of solution-processed organic field-effect transistor based on highly ordered liquid crystals

NASA Astrophysics Data System (ADS)

Kunii, M.; Iino, H.; Hanna, J.

2017-06-01

Bias-stress effects in solution-processed, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) field effect transistors (FETs) are studied under negative and positive direct current bias. The bottom gate, bottom contact polycrystalline Ph-BTBT-10 FET with a hybrid gate dielectric of polystyrene and SiO2 shows high field effect mobility as well as a steep subthreshold slope when fabricated with a highly ordered smectic E liquid crystalline (SmE) film as a precursor. Negative gate bias-stress causes negative threshold voltage shift (ΔVth) for Ph-BTBT-10 FET in ambient air, but ΔVth rapidly decreases as the gate bias decreases and approaches to near zero when the gate bias goes down to 9 V in amplitude. In contrast, positive gate bias-stress causes negligible ΔVth even with a relatively high bias voltage. These results conclude that Ph-BTBT-10 FET has excellent bias-stress stability in ambient air in the range of low to moderate operating voltages.

Reply to "Comment on 'Origin of tilted-phase generation in systems of ellipsoidal molecules with dipolar interactions' "

NASA Astrophysics Data System (ADS)

Bose, Tushar Kanti; Saha, Jayashree

2014-04-01

In a recent article [T. K. Bose and J. Saha, Phys. Rev. E 86, 050701 (2012), 10.1103/PhysRevE.86.050701], we have presented the results of a Monte Carlo simulation study of the systems of dipolar Gay-Berne ellipsoids where two terminal antiparallel dipoles are placed symmetrically on the long axis of each ellipsoid, and the results revealed the combined contribution of dipolar separation and transverse orientations in controlling the tilt angle in the tilted hexatic smectic phase. The tilt angle changed from zero to a significant value, in the case of transverse dipoles, with a change in the dipolar separation. In the related comment, Madhusudana [preceding Comment, Phys. Rev. E 89, 046501 (2014), 10.1103/PhysRevE.89.046501] has claimed that the physical origin of the molecular tilt in the significantly tilted phases found in the simulations is similar to that proposed by McMillan [Phys. Rev. A 8, 1921 (1973), 10.1103/PhysRevA.8.1921]. Here, we explain that the claim is not correct and make it clear that the two compared pictures are quite different. In the preceding Comment, Madhusudana has also suggested an alternative explanation for tilt generation in the simulations by criticizing the original one proposed by us. We argue here in support of the original explanation and clarify that his explanation does not follow the simulation results.

SANS study of deformation and relaxation of a comb-like liquid crystal polymer in the nematic phase

NASA Astrophysics Data System (ADS)

Brûlet, A.; Boué, F.; Keller, P.; Davidson, P.; Strazielle, C.; Cotton, J. P.

1994-06-01

A comb-like liquid crystal polymer is stretched and quenched after a certain time in the nematic phase. The conformation of the deformed chain is determined using small angle neutron scattering (SANS) as a function of the temperature of stretching, the stretching ratio and the duration of the relaxation. The scattering data are well fitted to junction affine and phantom network models. Some data are even well fitted by a totally affine model that we call “ pseudo affine ” because the only parameter, the stretching ratio, is found to be well below the macroscopic stretching ratio. The latter result, never encountered with amorphous polymers, is attributed to the cooperative effects of the nematic phase. We also note that the form factors of the chain in the underformed sample remain similar in the isotropic, nematic and glassy state ; they correspond to a Gaussian chain. The same samples were studied by wide angle X-ray scattering. On one hand, the orientation of the mesogenic groups is found to be parallel or perpendicular to the stretching direction depending on the stretching temperature. This result is discussed as a function of the presence of smectic fluctuations. On the other hand, longer relaxations at constant elongation ratio do not lead to a disorganization of the mesogenic group orientation whereas the polymer chains are partly relaxed.

Cholesteryl-containing ionic liquid crystals composed of alkylimidazolium cations and different anions

NASA Astrophysics Data System (ADS)

Lan, Xin; Bai, Lu; Li, Xin; Ma, Shuang; He, Xiaozhi; Meng, Fanbao

2014-10-01

Cholesteryl-containing ionic liquid crystals (ILCs) 1-cholesteryloxycarbonylmethyl(propyl)-3-methyl(butyl)imidazolium chlorides ([Ca-Me-Im]Cl, [Ca-Bu-Im]Cl, [Cb-Me-Im]Cl and [Cb-Bu-Im]Cl) and corresponding imidazolium tetrachloroaluminates ([Ca-Me-Im]AlCl4, [Ca-Bu-Im]AlCl4, [Cb-Me-Im]AlCl4 and [Cb-Bu-Im]AlCl4) were synthesized in this work, and the chemical structure, LC behavior and ionic conductivity of all these ILCs were characterized by several technical methods. The imidazolium-based salts with Cl- ions showed chiral smectic A (SA*) phase on both heating and cooling cycles, while the tetrachloroaluminates exhibited chiral nematic (N*) phase. The mesophase was confirmed by characteristic LC textures observed by polarizing optical microscopy and typical diffractogram obtained by X-ray diffraction measurements. The samples with similar cholesteryl-linkage component showed similar phase transition temperature and entropy, indicating the cholesteryl component influence predominately on the phase transition rather than alkyl substituents on the imidazole ring. The imidazolium tetrachloroaluminates display relatively low phase transition temperature compared with the precursor chlorides. The functional difference in LC behavior and ionic conductivity were discussed by investigated the structural difference between the Cl--containing and AlCl4-containing materials. The imidazolium chlorides exhibited layer structure both in crystal and mesophase states, and should be organized with a ‘head-to-tail’ organization to form interdigitated monolayer structures due to the tight ion pairs. But the imidazolium tetrachloroaluminates displayed layer structure only in crystal phase, and should be organized in ‘head-to-head’ arrangements form bilayer structures due to loose combination of ion pairs despite of hydrogen-bond and electrostatic attraction interaction.

Electro-optic response in thin smectic C* film with chevron structures

NASA Astrophysics Data System (ADS)

Kudreyko, Aleksey A.; Migranov, Nail G.; Migranova, Dana N.

2016-12-01

The effects in electrostatic models of chevron surface-stabilized ferroelectric liquid crystals are investigated through numerical modeling. To study smectic C* director distribution within the cell, we consider two nonlinear approaches: the chevron interface does not interplay with the electric field; the electric field interplays with the chevron interface. The obtained results of the director field distribution are compared with the earlier linearized studies. We find that whether or not the electric field interplays with the chevron interface, the electro-optic response requires a generalized approach for its description. The threshold electric field, which is necessary for switching between two stable director states in the chevron cell is evaluated. This study suggests that, in many cases of practical interest, electro-optic response to the electric field and the threshold electric field can be precisely estimated. We argue that, beside being numerically efficient, our approach provides a convenient and a novel standpoint for looking at the electro-optic response problem. Project supported by the Russian Foundation for Basic Research (RFBR) (Grant Nos. 16-32-00043 and 14-02-97026).

Liquid-Crystalline Collapse of Pulmonary Surfactant Monolayers

PubMed Central

Schief, William R.; Antia, Meher; Discher, Bohdana M.; Hall, Stephen B.; Vogel, Viola

2003-01-01

During exhalation, the surfactant film of lipids and proteins that coats the alveoli in the lung is compressed to high surface pressures, and can remain metastable for prolonged periods at pressures approaching 70 mN/m. Monolayers of calf lung surfactant extract (CLSE), however, collapse in vitro, during an initial compression at ∼45 mN/m. To gain information on the source of this discrepancy, we investigated how monolayers of CLSE collapse from the interface. Observations with fluorescence, Brewster angle, and light scattering microscopies show that monolayers containing CLSE, CLSE-cholesterol (20%), or binary mixtures of dipalmitoyl phosphatidylcholine(DPPC)-dihydrocholesterol all form bilayer disks that reside above the monolayer. Upon compression and expansion, lipids flow continuously from the monolayer into the disks, and vice versa. In several respects, the mode of collapse resembles the behavior of other amphiphiles that form smectic liquid-crystal phases. These findings suggest that components of surfactent films must collapse collectively rather than being squeezed out individually. PMID:12770885

Dual gauge field theory of quantum liquid crystals in three dimensions

DOE PAGES

Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai; ...

2017-10-09

The dislocation-mediated quantum melting of solids into quantum liquid crystals is extended from two to three spatial dimensions, using a generalization of boson-vortex or Abelian-Higgs duality. Dislocations are now Burgers-vector-valued strings that trace out worldsheets in space-time while the phonons of the solid dualize into two-form (Kalb-Ramond) gauge fields. We propose an effective dual Higgs potential that allows for restoring translational symmetry in either one, two, or three directions, leading to the quantum analogues of columnar, smectic, or nematic liquid crystals. In these phases, transverse phonons turn into gapped, propagating modes, while compressional stress remains massless. Rotational Goldstone modes emergemore » whenever translational symmetry is restored. Lastly, we also consider the effective electromagnetic response of electrically charged quantum liquid crystals, and find among other things that as a hard principle only two out of the possible three rotational Goldstone modes are observable using propagating electromagnetic fields.« less

Dual gauge field theory of quantum liquid crystals in three dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai

The dislocation-mediated quantum melting of solids into quantum liquid crystals is extended from two to three spatial dimensions, using a generalization of boson-vortex or Abelian-Higgs duality. Dislocations are now Burgers-vector-valued strings that trace out worldsheets in space-time while the phonons of the solid dualize into two-form (Kalb-Ramond) gauge fields. We propose an effective dual Higgs potential that allows for restoring translational symmetry in either one, two, or three directions, leading to the quantum analogues of columnar, smectic, or nematic liquid crystals. In these phases, transverse phonons turn into gapped, propagating modes, while compressional stress remains massless. Rotational Goldstone modes emergemore » whenever translational symmetry is restored. Lastly, we also consider the effective electromagnetic response of electrically charged quantum liquid crystals, and find among other things that as a hard principle only two out of the possible three rotational Goldstone modes are observable using propagating electromagnetic fields.« less

Effect of the C-2 hydroxyl group on the mesomorphism of alkyl glycosides: synthesis and thermotropic behavior of alkyl 2-deoxy-D-arabino-hexopyranosides.

PubMed

Singh, Madan Kumar; Jayaraman, Narayanaswamy; Rao, D S Shankar; Prasad, S Krishna

2008-10-01

A homologous series of alkyl 2-deoxy-alpha-d-arabino-hexopyranosides and alkyl 2-deoxy-beta-d-arabino-hexopyranosides were synthesized, upon glycosylation of 1-alkanols (from C8 to C18 alkanols) with ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-d-arabino-hexopyranoside, followed by a deprotection. The thermotropic behavior of these new types of alkyl glycosides was investigated. It was observed that the beta-anomers of these alkyl glycosides, bearing nonyl to tetradecyl alkyl chain are mesomorphic, exhibiting monotropic smectic A phase. In contrast, the alpha-anomers are all non-mesomorphic. An effort to identify the liquid crystalline behavior of binary mixtures of the alpha- and beta-anomers was undertaken and it was found that mixtures containing equimolar amounts of the anomers exhibited mesomorphic behavior. A fine balance of the hydrophilic and hydrophobic components within the molecule is also found to be important for the alkyl 2-deoxy glycosides to form the mesophase.

Reversible and dissipative macroscopic contributions to the stress tensor: active or passive?

PubMed

Brand, H R; Pleiner, H; Svenšek, D

2014-09-01

The issue of dynamic contributions to the macroscopic stress tensor has been of high interest in the field of bio-inspired active systems over the last few years. Of particular interest is a direct coupling ("active term") of the stress tensor with the order parameter, the latter describing orientational order induced by active processes. Here we analyze more generally possible reversible and irreversible dynamic contributions to the stress tensor for various passive and active macroscopic systems. This includes systems with tetrahedral/octupolar order, polar and non-polar (chiral) nematic and smectic liquid crystals, as well as active fluids with a dynamic preferred (polar or non-polar) direction. We show that it cannot a priori be seen, neither from the symmetry properties of the macroscopic variables involved, nor from the structure of the cross-coupling contributions to the stress tensor, whether the system studied is active or passive. Rather, that depends on whether the variables that give rise to those cross-couplings in the stress tensor are driven or not. We demonstrate that several simplified descriptions of active systems in the literature that neglect the necessary counter term to the active term violate linear irreversible thermodynamics and lead to an unphysical contribution to the entropy production.

Free energy perturbation method for measuring elastic constants of liquid crystals

NASA Astrophysics Data System (ADS)

Joshi, Abhijeet

There is considerable interest in designing liquid crystals capable of yielding specific morphological responses in confined environments, including capillaries and droplets. The morphology of a liquid crystal is largely dictated by the elastic constants, which are difficult to measure and are only available for a handful of substances. In this work, a first-principles based method is proposed to calculate the Frank elastic constants of nematic liquid crystals directly from atomistic models. These include the standard splay, twist and bend deformations, and the often-ignored but important saddle-splay constant. The proposed method is validated using a well-studied Gay-Berne(3,5,2,1) model; we examine the effects of temperature and system size on the elastic constants in the nematic and smectic phases. We find that our measurements of splay, twist, and bend elastic constants are consistent with previous estimates for the nematic phase. We further outline the implementation of our approach for the saddle-splay elastic constant, and find it to have a value at the limits of the Ericksen inequalities. We then proceed to report results for the elastic constants commonly known liquid crystals namely 4-pentyl-4'-cynobiphenyl (5CB) using atomistic model, and show that the values predicted by our approach are consistent with a subset of the available but limited experimental literature.

Hydrodynamic interactions in freely suspended liquid crystal films

NASA Astrophysics Data System (ADS)

Kuriabova, Tatiana; Powers, Thomas R.; Qi, Zhiyuan; Goldfain, Aaron; Park, Cheol Soo; Glaser, Matthew A.; Maclennan, Joseph E.; Clark, Noel A.

2016-11-01

Hydrodynamic interactions play an important role in biological processes in cellular membranes, a large separation of length scales often allowing such membranes to be treated as continuous, two-dimensional (2D) fluids. We study experimentally and theoretically the hydrodynamic interaction of pairs of inclusions in two-dimensional, fluid smectic liquid crystal films suspended in air. Such smectic membranes are ideal systems for performing controlled experiments as they are mechanically stable, of highly uniform structure, and have well-defined, variable thickness, enabling experimental investigation of the crossover from 2D to 3D hydrodynamics. Our theoretical model generalizes the Levine-MacKintosh theory of point-force response functions and uses a boundary-element approach to calculate the mobility matrix for inclusions of finite extent. We describe in detail the theoretical and computational approach previously outlined in Z. Qi et al., Phys. Rev. Lett. 113, 128304 (2014), 10.1103/PhysRevLett.113.128304 and extend the method to study the mutual mobilities of inclusions with asymmetric shapes. The model predicts well the observed mutual mobilities of pairs of circular inclusions in films and the self-mobility of a circular inclusion in the vicinity of a linear boundary.

Topological defects and shapes of triatic liquid crystal vesicles

NASA Astrophysics Data System (ADS)

Serafin, Francesco; Manyuhina, Oksana; Bowick, Mark

Is shape the manifestation of function, or does shape determine function? Since the time of Aristotle, the study of shape has proven to be a fruitful way to understand the behavior of physical systems, from atomic to biological systems scales. Two dimensional soft membranes are a perfect setting to understand the emergence of shape. An interesting possibility is to control and design new self-assemblable supramolecular shapes by coating the surface of soft closed vesicles with liquid crystals (LC) of various symmetries. The microscopic geometry of the liquid crystal molecules, in particular the structure of topological defects, when combined with the topology of the vesicle's surface, ultimately determines the vesicle's shape. Recent work has shown that the minimal energy shapes of smectic and nematic vesicles are faceted polyhedra. A very soft smectic vesicle develops sharp creases and forms a faceted tetrahedron. When the coating LC has the symmetries of the square, the vesicle forms a cube. In this work we extend these results to a 3-fold symmetric LC, proving that the vesicle's ground state is an octahedron. This gives a systematic way of predicting vesicle's shapes as we change the liquid crystal's symmetry. Soft Matter Program of Syracuse University.

Alignment of smectic mesogens over engineered surfaces

NASA Astrophysics Data System (ADS)

Chandran, Achu; Joshi, Tilak; Khanna, P. K.; Mehta, Dalip. S.; Haranath, D.; Biradar, Ashok M.

2017-07-01

The alignment of smectic C* liquid crystals (LCs) has been manipulated over and near different surfaces such as bare glass, indium tin oxide (ITO) coated glass, patterned glass, and near spacers. The LC sample cell is made of one ITO coated glass plate and other having striped ITO with a Mylar spacer maintaining a finite cell gap between them. Laser scribing is used to make striped ITO, while the scribed area results in the formation of the patterned glass surface. The geometry of the cell is such that overlapped ITO lie in the middle and spacers are placed in the two extreme corners of the cell. The alignment of LC is found to be homeotropic over the ITO coated glass, while it is planar near the spacer. Interestingly, a transition from homeotropic to planar is observed while moving away from the middle towards either corner of the cell. The origin of both types of alignment in the same cell has been explained by considering the difference in the surface energy of different surfaces. This work renders new advancement towards the manipulation of LC alignment using different surfaces and interfaces for advanced electro-optical and photonic devices based on LCs.

Extrinsic curvature, geometric optics, and lamellar order on curved substrates

NASA Astrophysics Data System (ADS)

Kamien, Randall D.; Nelson, David R.; Santangelo, Christian D.; Vitelli, Vincenzo

2009-11-01

When thermal energies are weak, two-dimensional lamellar structures confined on a curved substrate display complex patterns arising from the competition between layer bending and compression in the presence of geometric constraints. We present broad design principles to engineer the geometry of the underlying substrate so that a desired lamellar pattern can be obtained by self-assembly. Two distinct physical effects are identified as key factors that contribute to the interaction between the shape of the underlying surface and the resulting lamellar morphology. The first is a local ordering field for the direction of each individual layer, which tends to minimize its curvature with respect to the three-dimensional embedding. The second is a nonlocal effect controlled by the intrinsic geometry of the surface that forces the normals to the (nearly incompressible) layers to lie on geodesics, leading to caustic formation as in optics. As a result, different surface morphologies with predominantly positive or negative Gaussian curvature can act as converging or diverging lenses, respectively. By combining these ingredients, as one would with different optical elements, complex lamellar morphologies can be obtained. This smectic optometry enables the manipulation of lamellar configurations for the design of materials.

Large-scale self-assembled zirconium phosphate smectic layers via a simple spray-coating process

NASA Astrophysics Data System (ADS)

Wong, Minhao; Ishige, Ryohei; White, Kevin L.; Li, Peng; Kim, Daehak; Krishnamoorti, Ramanan; Gunther, Robert; Higuchi, Takeshi; Jinnai, Hiroshi; Takahara, Atsushi; Nishimura, Riichi; Sue, Hung-Jue

2014-04-01

The large-scale assembly of asymmetric colloidal particles is used in creating high-performance fibres. A similar concept is extended to the manufacturing of thin films of self-assembled two-dimensional crystal-type materials with enhanced and tunable properties. Here we present a spray-coating method to manufacture thin, flexible and transparent epoxy films containing zirconium phosphate nanoplatelets self-assembled into a lamellar arrangement aligned parallel to the substrate. The self-assembled mesophase of zirconium phosphate nanoplatelets is stabilized by epoxy pre-polymer and exhibits rheology favourable towards large-scale manufacturing. The thermally cured film forms a mechanically robust coating and shows excellent gas barrier properties at both low- and high humidity levels as a result of the highly aligned and overlapping arrangement of nanoplatelets. This work shows that the large-scale ordering of high aspect ratio nanoplatelets is easier to achieve than previously thought and may have implications in the technological applications for similar materials.

Colloidal membranes: The rich confluence of geometry and liquid crystals

NASA Astrophysics Data System (ADS)

Kaplan, Cihan Nadir

A simple and experimentally realizable model system of chiral symmetry breaking is liquid-crystalline monolayers of aligned, identical hard rods. In these materials, tuning the chirality at the molecular level affects the geometry at systems level, thereby inducing a myriad of morphological transitions. This thesis presents theoretical studies motivated by the rich phenomenology of these colloidal monolayers. High molecular chirality leads to assemblages of rods exhibiting macroscopic handedness. In the first part we consider one such geometry, twisted ribbons, which are minimal surfaces to a double helix. By employing a theoretical approach that combines liquid-crystalline order with the preferred shape, we focus on the phase transition from simple flat monolayers to these twisted structures. In these monolayers, regions of broken chiral symmetry nucleate at the interfaces, as in a chiral smectic A sample. The second part particularly focuses on the detailed structure and thermodynamic stability of two types of observed interfaces, the monolayer edge and domain walls in simple flat monolayers. Both the edge and "twist-walls" are quasi-one-dimensional bands of molecular twist deformations dictated by local chiral interactions and surface energy considerations. We develop a unified theory of these interfaces by utilizing the de Gennes framework accompanied by appropriate surface energy terms. The last part turns to colloidal "cookies", which form in mixtures of rods with opposite handedness. These elegant structures are essentially flat monolayers surrounded by an array of local, three dimensional cusp defects. We reveal the thermodynamic and structural characteristics of cookies. Furthermore, cookies provide us with a simple relation to determine the intrinsic curvature modulus of our model system, an important constant associated with topological properties of membranes. Our results may have impacts on a broader class of soft thin films.

Nematic DNA Thermotropic Liquid Crystals with Photoresponsive Mechanical Properties.

PubMed

Zhang, Lei; Maity, Sourav; Liu, Kai; Liu, Qing; Göstl, Robert; Portale, Giuseppe; Roos, Wouter H; Herrmann, Andreas

2017-09-01

Over the last decades, water-based lyotropic liquid crystals of nucleic acids have been extensively investigated because of their important role in biology. Alongside, solvent-free thermotropic liquid crystals (TLCs) from DNA are gaining great interest, owing to their relevance to DNA-inspired optoelectronic applications. Up to now, however, only the smectic phase of DNA TLCs has been reported. The development of new mesophases including nematic, hexagonal, and cubic structures for DNA TLCs remains a significant challenge, which thus limits their technological applications considerably. In this work, a new type of DNA TLC that is formed by electrostatic complexation of anionic oligonucleotides and cationic surfactants containing an azobenzene (AZO) moiety is demonstrated. DNA-AZO complexes form a stable nematic mesophase over a temperature range from -7 to 110 °C and retain double-stranded DNA structure at ambient temperature. Photoisomerization of the AZO moieties from the E- to the Z-form alters the stiffness of the DNA-AZO hybrid materials opening a pathway toward the development of DNA TLCs as stimuli-responsive biomaterials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Polarized Fluorescent Illumination Using Liquid Crystal Phase.

PubMed

Gim, Min-Jun; Turlapati, Srikanth; Debnath, Somen; Rao, Nandiraju V S; Yoon, Dong Ki

2016-02-10

Liquid crystal (LC) materials are currently the dominant electronic materials in display technology because of the ease of control of molecular orientation using an electric field. However, this technology requires the fabrication of two polarizers to create operational displays, reducing light transmission efficiency below 10%. It is therefore desirable to develop new technologies to enhance the light efficiency while maintaining or improving other properties such as the modulation speed of the molecular orientation. Here we report a uniaxial-oriented B7 smectic liquid crystalline film, using fluorescent bent-core LC molecules, a chemically modified substrate, and an in-plane electric field. A LC droplet under homeotropic boundary conditions of air/LC as well as LC/substrate exhibits large focal conic like optical textures. The in-plane electric field induced uniaxial orientation of the LC molecules, in which molecular polar directors are aligned in the direction of the electric field. This highly oriented LC film exhibits linearly polarized luminescence and microsecond time-scale modulation characteristics. The resultant device is both cheap and easy to fabricate and thus has great potential for electro-optic applications, including LC displays, bioimaging systems, and optical communications.

Dynamic and magneto-optic properties of bent-core liquid crystals

NASA Astrophysics Data System (ADS)

Salili, Seyyed Muhammad

In this work, we describe dynamic behavior of free-standing bent-core liquid crystal filaments under dilative and axial compressive stresses in the B7 phase. We found that such filaments demonstrate very complex structures depending on the filament's temperature relative to the isotropic phase, initial filament thickness, and velocity at which the filament is pulled or compressed. We also present our experimental methods, results and analysis of the rupture and recoil properties of several bent-core liquid crystal filaments, anticipating that they may serve as a model system for complex biological fibers. After that, we systematically describe rheological measurements for dimeric liquid crystal compounds. We studied the shear-induced alignment properties, measured the viscoelastic properties as a function of temperature, shear rate, stress and frequency, and compared the results with the rheological properties of conventional chiral nematic and smectic phases. Then we present results of chiral nematic liquid crystals composed of flexible dimer molecules subject to large DC magnetic fields between 0 and 31T. We observe that these fields lead to selective reflection of light depending on temperature and magnetic field. The band of reflected wavelengths can be tuned from ultraviolet to beyond the IR-C band. A similar effect induced by electric fields has been presented previously, and was explained by a field-induced oblique-heliconical director deformation in accordance with early theoretical predictions. Finally, we report an unprecedented magnetic field-induced shifts of the isotropic-nematic phase transition temperature observed in liquid crystal dimers where two rigid linear mesogens are linked by flexible chains of either even- or odd-numbered hydrocarbon groups. This effect is explained in terms of quenching of the thermal fluctuations and decrease of the average bend angle of molecules in the odd-numbered dimers.

Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates

PubMed Central

Xie, Yujiao; Liu, Xiaofeng; Hu, Zhuang; Hou, Zhipeng; Chen, Zhangpei; Hu, Jianshe; Yang, Liqun

2018-01-01

New amphiphilic liquid crystal (LC) polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR) spectrum, 1H NMR, gel permeation chromatographic (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarizing optical microscope (POM), and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td), glass temperature (Tg), and isotropic temperature (Ti) increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX), together with drug release tracking, were evaluated by dynamic light scattering (DLS), SEM, and UV–vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications. PMID:29584691

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects.

PubMed

Pastor, María Jesús; Cuerva, Cristián; Campo, José A; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-05-12

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO R(n)pyH ]⁺ and BF₄ - , ReO₄ - , NO₃ - , CF₃SO₃ - , CuCl₄ 2- counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO R(12)pyH ][ReO₄] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl₄ 2- salts exhibit the best LC properties followed by the ReO₄ - ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO₄ - , and CuCl₄ 2- families, and for the solid phase in one of the non-mesomorphic Cl - salts. The highest ionic conductivity was found for the smectic mesophase of the ReO₄ - containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.

Magnetically aligned phospholipid bilayers in weak magnetic fields: optimization, mechanism, and advantages for X-band EPR studies.

PubMed

Cardon, Thomas B; Tiburu, Elvis K; Lorigan, Gary A

2003-03-01

Our lab is developing a spin-labeled EPR spectroscopic technique complementary to solid-state NMR studies to study the structure, orientation, and dynamics of uniaxially aligned integral membrane proteins inserted into magnetically aligned discotic phospholipid bilayers, or bicelles. The focus of this study is to optimize and understand the mechanisms involved in the magnetic alignment process of bicelle disks in weak magnetic fields. Developing experimental conditions for optimized magnetic alignment of bicelles in low magnetic fields may prove useful to study the dynamics of membrane proteins and its interactions with lipids, drugs, steroids, signaling events, other proteins, etc. In weak magnetic fields, the magnetic alignment of Tm(3+)-doped bicelle disks was thermodynamically and kinetically very sensitive to experimental conditions. Tm(3+)-doped bicelles were magnetically aligned using the following optimized procedure: the temperature was slowly raised at a rate of 1.9K/min from an initial temperature being between 298 and 307K to a final temperature of 318K in the presence of a static magnetic field of 6300G. The spin probe 3beta-doxyl-5alpha-cholestane (cholestane) was inserted into the bicelle disks and utilized to monitor bicelle alignment by analyzing the anisotropic hyperfine splitting for the corresponding EPR spectra. The phases of the bicelles were determined using solid-state 2H NMR spectroscopy and compared with the corresponding EPR spectra. Macroscopic alignment commenced in the liquid crystalline nematic phase (307K), continued to increase upon slowly raising the temperature, and was well-aligned in the liquid crystalline lamellar smectic phase (318K).

Light Scattering Studies of Defects in Nematic/Twist-Bend Liquid Crystals and Layer Fluctuations in Free-Standing Smectic Membranes

NASA Astrophysics Data System (ADS)

Pardaev, Shokir A.

This research described in this dissertation comprises three experimental topics and includes the development of an appropriate theoretical framework to understand the various observations in each. In the first part, we present results from angle-resolved second-harmonic light scattering measurements on three different classes of thermotropic nematic liquid crystals: polar and non-polar rodlike compounds, and a bent-core compound. We analyze the data in terms of the "flexoelectric" polarization induced by distortions of the nematic director field around topological defects known as inversion walls, which are analogous to Neel walls in magnetic spin systems and which often exhibit a closed loop morphology in nematic systems. The second part of this dissertation explores the possible existence of a helical polarization field in the nematic twist-bend (NTB) phase of dimeric liquid crystals, utilizing a similar nonlinear light scattering approach. The NTB phase is characterized by a heliconical winding of the local molecular long axis (director) with a remarkably short, nanoscale pitch. According to theoretical conjecture, a helical electric polarization field accompanies this director modulation, but, due to the short pitch, presents a significant challenge for experimental detection. Our study focuses on topological defects, classified as parabolic focal conics, in two achiral, NTB-forming liquid crystals. These defects generate distortions of the polarization field on sufficiently long (micron) lengths to enable a confirmation of the existence of polar structure. We analyze our results with a coarse-grained free energy density that combines a Landau-deGennes expansion of the polarization field, the elastic energy of a nematic, and a bilinear coupling between the two. The last part of the dissertation focuses on the layer dynamics of thin, free-standing membranes of a smectic-A liquid crystal, with a particular consideration of the surface (interfacial) parameters that control these dynamics. We utilize photon correlation spectroscopy to probe the contributions of distinct under- and overdamped processes to the membrane motion. According to hydrodynamic theory, the frequency and damping rate of underdamped layer motion should scale with scattering vector in a manner controlled by the relative magnitude of a surface elastic constant, which is associated with gradients in surface tension, as well as by the average surface tension. In addition, the damping in very thin films is predicted to be quite sensitive to the presence of an atmosphere surrounding the film. A distinct, overdamped mode, observable in sufficiently thick films, is also predicted to couple to the layer motion. We present results on these dynamical modes and their dispersion and demonstrate their consistency with the hydrodynamic theory subject to appropriate surface boundary conditions.

Physical vapor deposition as a route to glasses with liquid crystalline order

NASA Astrophysics Data System (ADS)

Gomez, Jaritza

Physical vapor deposition (PVD) is an effective route to prepare glasses with a unique combination of properties. Substrate temperatures near the glass transition (Tg) and slow deposition rates can access enhanced mobility at the surface of the glass allowing molecules at the surface additional time to sample different molecular configurations. The temperature of the substrate can be used to control molecular mobility during deposition and properties in the resulting glasses such as higher density, kinetic stability and preferential molecular orientation. PVD was used to prepare glasses of itraconazole, a smectic A liquid crystal. We characterized molecular orientation using infrared and ellipsometry. Molecular orientation can be controlled by choice of Tsubstrate in a range of temperatures near Tg. Glasses deposited at Tsubstrate = Tg show nearly vertical molecular orientation relative to the substrate; at lower Tsubstrate, molecules are nearly parallel to the substrate. The molecular orientation depends on the temperature of the substrate during preparation and not on the molecular orientation of the underlying layer. This allows preparing samples of layers with differing orientations. We find these glasses are homogeneous solids without evidence of domain boundaries and are molecularly flat. We interpret the combination of properties obtained for vapor-deposited glasses of itraconazole to result from a process where molecular orientation is determined by the structure and dynamics at the free surface of the glass during deposition. We report the thermal and structural properties of glasses prepared using PVD of a rod-like molecule, posaconazole, which does not show equilibrium liquid crystal phases. These glasses show substantial molecular orientation that can be controlled by choice of Tsubstrate during deposition. Ellipsometry and IR indicate that glasses prepared at Tg - 3 K are highly ordered. At these Tsubstrate, molecules show preferential vertical orientation and orientation is similar to that measured in aligned nematic liquid crystal. Our results are consistent with a recently proposed mechanism where molecular orientation in equilibrium liquids can be trapped in PVD glasses and suggest that the orientation at the free surface of posaconazole is nematic-like. In addition, we show posaconazole glasses show high kinetic stability controlled by Tsubstrate.

The Self- and Directed Assembly of Nanowires

NASA Astrophysics Data System (ADS)

Smith, Benjamin David

This thesis explores the self- and directed assembly of nanowires. Specifically, we examine the driving forces behind nanowire self-assembly and the macro-structures that are formed. Particle-dense, oriented nanowire structures show promise in the fields of photonics, energy, sensing, catalysis, and electronics. Arrays of spherical particles have already found uses in electronic inks, sensing arrays, and many other commercial applications; but, it is a challenge to create specific arrays of morphologically and/or compositionally anisotropic particles. The following chapters illuminate the interactions that drive the assembly of anisotropic particles in high density solutions in the absence of applied fields or solution drying. Special emphasis is placed on the structures that are formed. The properties of micro- and nanoparticles and their assembly are introduced in Chapter 1. In particular, the properties of shape and material anisotropic particles are highlighted, while challenges in producing desired arrays are discussed. In this thesis, metallic nanowires of increasing complexity were used to examine the self-assembly behavior of both shape and material anisotropic particles. Nanowires were synthesized through templated electrodeposition. In this process, porous alumina membranes served as a template in which metal salts were reduced to form particles. Upon template dissolution, billions of nominally identical particles were released. We specifically focused on segmented, metallic nanowires 2-13 mum in length and 180 to 350 nm in diameter. Since these particles have strong van der Waals (VDWs) attractions, an electrostatically repulsive coating was necessary to prevent aggregation; we used small molecule, DNA, or amorphous silica coatings. Nanowires and their coatings were characterized by electron microscopy. In order to study self-assembly behavior, particle-dense aqueous suspensions were placed within an assembly chamber defined by a silicone spacer. The nanowires rapidly sedimented due to gravity onto a glass cover slip to concentrate and form a dense film. Particles and assemblies were imaged using inverted optical microscopy. We quantitatively analyzed the images and movies captured in order to track and classify particles and classify the overall arrays formed. We then correlated how particle characteristics, e.g., materials, size, segmentation, etc. changed the ordering and alignment observed. With that knowledge, we hope to be able to form new and interesting structures. We began our studies by examining the assembly of single component nanowires. Chapter 2 describes this work, in which solid Au nanowires measuring 2-7 mum in length and 290 nm in diameter self-assembled into smectic rows. By both experiment and theory, we determined that these rows formed due to a balance of electrostatic repulsions and van der Waals attractions. Final assemblies were stable for at least several days. Monte Carlo methods were used to simulate assemblies and showed structures that mirrored those experimentally observed. Simulations indicated that the smectic phase was preferred over others, i.e., nematic, when an additional small charge was added to the ends of the nanowires. Our particles have rough tips, which might create these additional electrostatic repulsions. To increase the particle and array complexity, two-component, metallic nanowire assembly was explored in Chapter 3. We examined numerous types of nanowires by changing the segment length, ratio, and material, the nanowire length, the surface coating, and the presence of small third segments. These segmented nanowires were generally Au-Ag and also ordered into smectic rows. Segmented wires arranged in rows, however, can be aligned in two possible ways with respect to a neighboring particle. The Au segments on neighboring particles can be oriented in the same direction or opposed to each other. Orientation was quantified in terms of an order parameter that took into account alignment with respect to nearest neighbor particles. All experiments showed order parameters indicating a slight preference for orientational ordering that was relatively insensitive to segment size, nanowire size, and nanowire coating. Monte Carlo simulations pointed towards this alignment as a consequence of small differences in the van der Waals attractions between the segments. Experimentally, ordering might to be limited by the large size of the nanowires, which results in kinetically trapped structures. In an attempt to obtain better ordering within rows, silica coated nanowires with partial Au cores were made. The synthesis involved silica-coating the nanowires and selectively etching a Ag segment. These particles have extremely different VDWs attractions between their segments, as the Au cores are much more attractive than the solvent-filled etched ends. The assembly of these partially etched nanowires (PENs) is detailed in Chapters 4, 5, and 6. When allowed to self-assemble, we observed the formation of either vertically or horizontally oriented arrays depending on PEN composition. The formation of vertically oriented arrays of anisotropic particles is important, since not many methods to produce these structures are currently available for particles of this size. We examined the effects of PEN length, PEN diameter, and the size, number, and location of the core segments. Our findings showed a large etched segment at one end (which resulted in a large offset in the center of mass and concentrated the VDWs attractions to one end of the particle) resulted in the best columnar assemblies. These vertically orientated arrays formed in a two part process. First, after PENs sedimented, they fell flat and oriented parallel to the surface. These PENs then sampled many orientations, including rotating out of the surface plane. When higher surface concentrations of particles built as more PENs fell to the surface of the cover slip, neighboring particles stabilized vertical orientations. Second, particles fell oriented vertically and when the surface concentrations were high, they retained this orientation upon reaching the substrate. Since vertically aligned PENs supported each other, assembly into vertical arrays was highly dependent on the surface concentration. But, oriented arrays could be easily formed on larger or smaller substrates, provided a particle concentration scaled to the substrate were used. The mixing of these particles to form heterogeneous arrays was examined. The overall array structure favored that of particles which sedimented more quickly and/or were present in higher amounts. The semi-automated counting of PENs in images by software is used heavily in Chapters 4 and 5. Appendix A describes the use, development, and validation of macros within Image-Pro. The structure, syntax, and use are specifically examined for three nanowire counting macros. The counting results; including: number of particles in an image, number of horizontally vs. vertically oriented PENs, and PENs in microwells; are compared with manual hand counts. Chapter 7 examines the overall conclusions and future directions for this research. By combining our assembly techniques with known directing forces (e.g., electric or magnetic fields) more specific alignment and/or positioning could be achieved. We have also begun to explore directing assembly through lithographic microwells. Further work needs to explore the integration of arrays into devices and the use of functional materials. Then, high density, oriented arrays could be created for photonic, energy, sensing, catalytic, and electronic applications.

The onset of layer undulations in smectic A liquid crystals due to a strong magnetic field

NASA Astrophysics Data System (ADS)

Contreras, A.; Garcia-Azpeitia, C.; García-Cervera, C. J.; Joo, S.

2016-08-01

We investigate the effect of a strong magnetic field on a three dimensional smectic A liquid crystal. We identify a critical field above which the uniform layered state loses stability; this is associated to the onset of layer undulations. In a previous work García-Cervera and Joo (2012 Arch. Ration. Mech. Anal. 203 1-43), García-Cervera and Joo considered the two dimensional case and analyzed the transition to the undulated state via a simple bifurcation. In dimension n  =  3 the situation is more delicate because the first eigenvalue of the corresponding linearized problem is not simple. We overcome the difficulties inherent to this higher dimensional setting by identifying the irreducible representations for natural actions on the functional that take into account the invariances of the problem thus allowing for reducing the bifurcation analysis to a subspace with symmetries. We are able to describe at least two bifurcation branches, highlighting the richer landscape of energy critical states in the three dimensional setting. Finally, we analyze a reduced two dimensional problem, assuming the magnetic field is very strong, and are able to relate this to a model in micromagnetics studied in Alouges et al (2002 ESAIM Control Optim. Calc. Var. 8 31-68), from where we deduce the periodicity property of minimizers.

Self-assembled microstructures of confined rod-coil diblock copolymers by self-consistent field theory.

PubMed

Yang, Guang; Tang, Ping; Yang, Yuliang; Wang, Qiang

2010-11-25

We employ the self-consistent field theory (SCFT) incorporating Maier-Saupe orientational interactions between rods to investigate the self-assembly of rod-coil diblock copolymers (RC DBC) in bulk and especially confined into two flat surfaces in 2D space. A unit vector defined on a spherical surface for describing the orientation of rigid blocks in 3D Euclidean space is discretized with an icosahedron triangular mesh to numerically integrate over rod orientation, which is confirmed to have numerical accuracy and stability higher than that of the normal Gaussian quadrature. For the hockey puck-shaped phases in bulk, geometrical confinement, i.e., the film thickness, plays an important role in the self-assembled structures' transitions for the neutral walls. However, for the lamellar phase (monolayer smectic-C) in bulk, the perpendicular lamellae are always stable, less dependent on the film thicknesses because they can relax to the bulk spacing with less-paid coil-stretching in thin films. In particular, a very thin rod layer near the surfaces is formed even in a very thin film. When the walls prefer rods, parallel lamellae are obtained, strongly dependent on the competition between the degree of the surface fields and film geometrical confinement, and the effect of surface field on lamellar structure as a function of film thickness is investigated. Our simulation results provide a guide to understanding the self-assembly of the rod-coil films with desirable application prospects in the fabrication of organic light emitting devices.

Effects of alkyl chain length and anion size on thermal and structural properties for 1-alkyl-3-methylimidazolium hexafluorocomplex salts (C(x)MImAF6, x = 14, 16 and 18; A = P, As, Sb, Nb and Ta).

PubMed

Xu, Fei; Matsumoto, Kazuhiko; Hagiwara, Rika

2012-03-28

A series of 1-alkyl-3-methylimidazolium hexafluorocomplex salts (C(x)MImAF(6), x = 14, 16 and 18, A = P, As, Sb, Nb and Ta) have been characterized by thermal analysis, X-ray diffraction and polarized optical microscopy. A liquid crystalline mesophase is observed for all the C(16)MIm and C(18)MIm salts. The C(14)MIm(+) cation gives a liquid crystalline mesophase only with PF(6)(-). The temperature range of the liquid crystalline mesophase increases with an increase in alkyl chain length or with decrease in anion size. Single-crystal X-ray diffraction revealed that all the C(18)MImAF(6) salts (A = P, As, Sb, Nb and Ta) are isostructural with each other in the crystalline phase and have a layered structure. The interdigitated alkyl chain of the cation has a bent shape like a spoon near the imidazolium ring in the crystalline phase at -100 °C and is tilted with respect to the sheets of the imidazolium headgroups and anions. An increase of temperature increases the ratio of an all-trans conformation to the bent conformation in the crystalline phase. X-ray diffraction and polarized optical microscopy suggested that the liquid crystalline mesophase has a smectic A(2) structure. The interlayer distance increases with a decrease in the anion size since the smaller anion has a stronger coulombic interaction with the imidazolium headgroup, resulting in the decrease of the interdigitated part to give a larger layer spacing.

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects

PubMed Central

Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-01-01

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

Dynamics of elastic interactions in soft and biological matter.

PubMed

Yuval, Janni; Safran, Samuel A

2013-04-01

Cells probe their mechanical environment and can change the organization of their cytoskeletons when the elastic and viscous properties of their environment are modified. We use a model in which the forces exerted by small, contractile acto-myosin filaments (e.g., nascent stress fibers in stem cells) on the extracellular matrix are modeled as local force dipoles. In some cases, the strain field caused by these force dipoles propagates quickly enough so that only static elastic interactions need be considered. On the other hand, in the case of significant energy dissipation, strain propagation is slower and may be eliminated completely by the relaxation of the cellular cytoskeleton (e.g., by cross-link dissociation). Here, we consider several dissipative mechanisms that affect the propagation of the strain field in adhered cells and consider these effects on the interaction between force dipoles and their resulting mutual orientations. This is a first step in understanding the development of orientational (nematic) or layering (smectic) order in the cytoskeleton. We use the theory to estimate the propagation time of the strain fields over a cellular distance for different mechanisms and find that in some cases it can be of the order of seconds, thus competing with the cytoskeletal relaxation time. Furthermore, for a simple system of two force dipoles, we predict that in some cases the orientation of force dipoles might change significantly with time, e.g., for short times the dipoles exhibit parallel alignment while for later times they align perpendicularly.

Electrically tunable spatially variable switching in ferroelectric liquid crystal/water system

NASA Astrophysics Data System (ADS)

Choudhary, A.; Coondoo, I.; Prakash, J.; Sreenivas, K.; Biradar, A. M.

2009-04-01

An unusual switching phenomenon in the region outside conducting patterned area in ferroelectric liquid crystal (FLC) containing about 1-2 wt % of water has been observed. The presence of water in the studied heterogeneous system was confirmed by Fourier transform infrared spectroscopy. The observed optical studies have been emphasized on the "spatially variable switching" phenomenon of the molecules in the nonconducting region of the cell. The observed phenomenon is due to diffusion of water between the smectic layers of the FLC and the interaction of the curved electric field lines with the FLC molecules in the nonconducting region.

Influence of ZnO nanostructures in liquid crystal interfaces for bistable switching applications

NASA Astrophysics Data System (ADS)

Pal, Kaushik; Zhan, Bihong; Madhu Mohan, M. L. N.; Schirhagl, Romana; Wang, Guoping

2015-12-01

The controlled fabrication of nanometer-scale objects is without doubt one of the central issues in current science and technology. In this article, we exhibit a simple, one-step bench top synthesis of zinc oxide nano-tetrapods and nano-spheres which were tailored by the facial growth of nano-wires (diameter ≈ 24 nm; length ≈ 118 nm) and nano-cubes (≈395 nm edge) to nano-sphere (diameter ≈ 585 nm) appeaded. The possibilities of inexpensive, simple solvo-chemical synthesis of nanostructures were considered. In this article, a successful attempt has been made that ZnO nano-structures dispersed on well aligned hydrogen bonded liquid crystals (HBLC) comprising azelaic acid (AC) with p-n-alkyloxy benzoic acid (nBAO) by varying the respective alkyloxy carbon number (n = 5). The dispersion of nanomaterials with HBLC is an effective route to enhance the existing functionalities. A series of these composite materials were analyzed by polarizing optical microscope's electro-optical switching. An interesting feature of AC + nBAO is the inducement of tilted smectic G phase with increasing carbon chain length. Phase diagrams of the above hybrid ZnO nanomaterial influenced LC complex and pure LC were constructed and compared. The switching times, the contrast ratio and spontaneous polarization of the nanostructures-HBLC composite film were carried out by systematic investigation. The sample preparation parameters, such as the curing time and curing intensity were optimized. The critical applied voltage to achieve the switching bi-stability of our device is only 4.5 V, which is approximately twice its threshold voltage for Freedericksz transition. This performance puts the hybrid structure at the top level in the state of the art in application oriented research in optics of liquid crystalline composite materials.

Pattern Formation in Complex Fluids

NASA Astrophysics Data System (ADS)

Shelley, Michael

2000-03-01

Classical fluid instabilities -- such as the Saffman-Taylor instability in a Hele-Shaw cell -- are dramatically modified by using complex fluids. For example, polymeric liquids driven in a Hele-Shaw cell yield "dendritic" patterns with an apparent directional anisotropy. The dynamics of complex liquids can also lead to new instabilities and patterns, such as space-filling patterns formed by successive bucklings of growing "elastica" seen in the phase transition of a liquid crystalline material. Understanding such problems requires an interplay between physical modeling, mathematical analysis, and sophisticated nonlinear simulation. For the first problem, I will discuss a non-Newtonian version of Darcy's law for Hele-Shaw flow. This yields a free-boundary problem for the pattern formation, and requires the solution of a nonlinear elliptic equation in a time-dependent domain. This is pushing the development of adaptive grid methods that represent the geometry accurately and efficiently. Our simulations yield insight into how shear-thinning, as is evinced by polymeric liquids, can produce patterns reminiscent of experiment, with "dendritic fingers", side-branching, and reduced tip-splitting. In the second problem, a long filament in a smectic-A phase grows within an isotropic fluid. The splay deformation of the material gives this filament an elastic response. The macroscopic model describes the dynamics of a growing, elastic filament immersed in a Stokesian fluid. The model marries filament elasticity and tensile forces with a numerically tractable nonlocal slender-body theory. Analysis shows that growth of the filament, despite fluid drag, produces a buckling instability. When coupled to a nonlocal hydrodynamic self-interaction, our fully nonlinear simulations show that such instabilities iterate along the filament, and give "space-filling" patterns.

Comparison of the fouling release properties of hydrophobic fluorinated and hydrophilic PEGylated block copolymer surfaces: attachment strength of the diatom Navicula and the green alga Ulva.

PubMed

Krishnan, Sitaraman; Wang, Nick; Ober, Christopher K; Finlay, John A; Callow, Maureen E; Callow, James A; Hexemer, Alexander; Sohn, Karen E; Kramer, Edward J; Fischer, Daniel A

2006-05-01

To understand the role of surface wettability in adhesion of cells, the attachment of two different marine algae was studied on hydrophobic and hydrophilic polymer surfaces. Adhesion of cells of the diatom Navicula and sporelings (young plants) of the green macroalga Ulva to an underwater surface is mainly by interactions between the surface and the adhesive exopolymers, which the cells secrete upon settlement and during subsequent colonization and growth. Two types of block copolymers, one with poly(ethylene glycol) side-chains and the other with liquid crystalline, fluorinated side-chains, were used to prepare the hydrophilic and hydrophobic surfaces, respectively. The formation of a liquid crystalline smectic phase in the latter inhibited molecular reorganization at the surface, which is generally an issue when a highly hydrophobic surface is in contact with water. The adhesion strength was assessed by the fraction of settled cells (Navicula) or biomass (Ulva) that detached from the surface in a water flow channel with a wall shear stress of 53 Pa. The two species exhibited opposite adhesion behavior on the same sets of surfaces. While Navicula cells released more easily from hydrophilic surfaces, Ulva sporelings showed higher removal from hydrophobic surfaces. This highlights the importance of differences in cell-surface interactions in determining the strength of adhesion of cells to substrates.

Structure and interactions in biomaterials based on membrane-biopolymer self-assembly

NASA Astrophysics Data System (ADS)

Koltover, Ilya

Physical and chemical properties of artificial pure lipid membranes have been extensively studied during the last two decades and are relatively well understood. However, most real membrane systems of biological and biotechnological importance incorporate macromolecules either embedded into the membranes or absorbed onto their surfaces. We have investigated three classes of self-assembled membrane-biopolymer biomaterials: (i) Structure, interactions and stability of the two-dimensional crystals of the integral membrane protein bacteriorhodopsin (bR). We have conducted a synchrotron x-ray diffraction study of oriented bR multilayers. The important findings were as follows: (1) the protein 2D lattice exhibited diffraction patterns characteristic of a 2D solid with power-law decay of in-plane positional correlations, which allowed to measure the elastic constants of protein crystal; (2) The crystal melting temperature was a function of the multilayer hydration, reflecting the effect of inter-membrane repulsion on the stability of protein lattice; (3) Preparation of nearly perfect (mosaicity < 0.04° ) multilayers of fused bR membranes permitted, for the first time, application of powerful interface-sensitive x-ray scattering techniques to a membrane-protein system. (ii) Interactions between the particles chemically attached or absorbed onto the surfaces of flexible giant phospholipid vesicles. Using video-enhanced light microscopy we have observed a membrane-distortion induced attraction between the particles with the interaction range of the order of particle diameter. Fluid membranes decorated with many particles exhibited: (i) a finite-sized two-dimensional closed packed aggregates and (ii) a one-dimensional ring-like aggregates. (iii) Structure, stability and interactions in the cationic lipid-DNA complexes. Cationic liposomes complexed with DNA are among the most promising synthetic non-viral carriers of DNA vectors currently used in gene therapy applications. We have established that DNA complexes with cationic lipid (DOTAP) and a neutral lipid (DOPC) have a compact multilayer liquid crystalline structure ( L ca ) with DNA intercalated between the lipid bilayers in a periodic 2D smectic phase. Furthermore, a different 2D columnar phase of complexes was found in mixtures with a transfectionen-hancing lipid DOPE. This structure ( HcII ) derived from synchrotron x-ray diffraction consists of DNA coated by cationic lipid monolayers and arranged on a two-dimensional hexagonal lattice. Optical microscopy revealed that the L ca complexes bind stably to anionic vesicles (models of cellular membranes), whereas the more transfectant HcII complexes are unstable, rapidly fusing and releasing DNA upon adhering to anionic vesicles.

Self assembling bioactive materials for cell adhesion in tissue repair

NASA Astrophysics Data System (ADS)

Hwang, Julia J.

This work involved the study of biodegradable and biocompatible materials that have the potential to modify tissue engineering scaffolds through self assembly, generating multiple layers that deliver bioactivity. Diblock biomaterials containing cholesteryl moieties and oligomers of lactic acid units were found to form single crystals when precipitated from hot ethanol and smectic liquid crystalline phases when cast as a film. Cell culture experiments on these films with 3T3 and 3T6 fibroblasts indicated that these ordered materials form surfaces with specific chemistries that favored cell adhesion, spreading, and proliferation suggesting the potential of mediating human tissue repair. The author believes the cholesteryl moieties found on the surface play a key role in determining cell behavior. Cholesteryl-(L-lactic acid) diblock molecules were then functionalized with moieties including vitamin Bx, cholesterol, and the anti-inflammatory drug indomethacin. An unstable activated ester between indomethacin and the diblock molecule resulted in the release of indomethacin into the culture medium which inhibited the proliferation of 3T3 fibroblasts. Finally, a series of molecules were designed to incorporate dendrons based on amino acids at the termini of the diblock structures. It was determined that lysine, a basic amino acid, covalently coupled to cholesteryl-(L-lactic acid) can promote cell adhesion and spreading while negatively charged and zwitterionic 2nd generation dendrons based on aspartic acid do not. Incorporation of the well known arginine-glycine-aspartic acid (RGD) sequence, which is found in many adhesive proteins, to the dendrons imparted integrin-mediated cell adhesion as evidenced by the formation of stress fibers. We also explored the capacity of integrin receptors to bind to ligands that are not the linear form of RGD, but have R, G, and D spatially positioned to mimic the linear RGD environments. For this purpose, the arms of the 2 nd generation lysine dendrons were functionalized with R, G, and D to yield an 'R,G,D library' of molecules. These materials were found to promote adhesion of 3T3 fibroblasts through integrin receptors. A dendron is multifunctional and allows a large degree of functionality in chemical design.

Characterization of the dynamics of surface stabilized ferroelectric liquid crystal under electric field by full optical snapshot matrix Mueller polarimeter

NASA Astrophysics Data System (ADS)

Silva, Vinicius N. H.; Babilotte, Philippe; Rivet, Sylvain; Dubreuil, Mathieu; Le Jeune, Bernard; Dupont, Laurent

2012-12-01

We investigated the layer dynamics of a conventional surface-stabilized ferroelectric liquid crystal (SSFLC) using a full-optical snapshot Mueller matrix polarimeter (SMMP) based on wavelength polarization coding. Time-resolved polarimetric measurements were performed with different SSFLC samples, and a strong correlation between the polarimetric parameters and the SSFLC under electric field at different exposure times was found. It has been shown that the SMMP polarimeter is able to determine the evolution of the trajectory of the liquid crystal director between the two addressed states, the reversible motion of the smectic layer while switching, as well as the irreversible transition from chevron to bookshelf texture.

Defect interactions in anisotropic two-dimensional fluids

NASA Astrophysics Data System (ADS)

Stannarius, Ralf; Harth, Kirsten

Disclinations in liquid crystals bear striking analogies to defect structures in a wide variety of physical systems, they are excellent models to study fundamental properties of defect interactions. Freely suspended smectic C films behave like quasi 2D polar nematics. An experimental procedure is introduced to capture high-strength disclinations in localized spots. After they are released in a controlled way, the motion of the mutually repelling topological charges is studied. We demonstrate that the classical models, based on elastic one-constant approximation, fail to describe their dynamics correctly. In realistic liquid crystals, the models work only in ideal configurations. In general, additional director walls modify interactions substantially. Funded by DFG within project STA 425/28-1.

Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

DOE PAGES

Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; ...

2015-07-23

Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn) 2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and mmore » = 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12) 2 (1d), Azo(-C1-Im-C12) 2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV-light (320–366 nm) all compounds undergo trans–cis isomerization, which reverses under visible light (440 nm).« less

Multivariate data analysis to characterize gas chromatography columns for dioxin analysis.

PubMed

Do, Lan; Geladi, Paul; Haglund, Peter

2014-06-20

Principal component analysis (PCA) was applied for evaluating the selectivity of 22 GC columns for which complete retention data were available for the 136 tetra- to octa-chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Because the hepta- and octa-homologues are easy to separate the PCA was focused on the 128 tetra- to hexa-CDD/Fs. The analysis showed that 21 of the 22 GC columns could be subdivided into four groups with different selectivity. Group I consists of columns with non-polar thermally stable phases (Restek 5Sil MS and Dioxin 2, SGE BPX-DXN, Supelco Equity-5, and Agilent DB-1, DB-5, DB-5ms, VF-5ms, VF-Xms and DB-XLB). Group II includes ionic liquid columns (Supelco SLB-IL61, SLB-IL111 and SLB-IL76) with very high polarity. Group III includes columns with high-percentage phenyl and cyanopropyl phases (Agilent DB-17 and DB-225, Quadrex CPS-1, Supelco SP-2331, and Agilent CP-Sil 88), and Group IV columns with shape selectivity (Dionex SB-Smectic and Restek LC-50, Supelco βDEXcst, Agilent VF-Xms and DB-XLB). Thus, two columns appeared in both Group I and IV (Agilent VF-Xms and DB-XLB). The selectivity of the other column, Agilent DB-210, differs from those of these four groups. Partial least squares (PLS) regression was used to correlate the retention times of the tetra- to hexa-CDD/Fs on the 22 stationary phases with a set of physicochemical and structural descriptors to identify parameters that significantly influence the solute-stationary phase interactions. The most influential physicochemical parameters for the interaction were associated with molecular size (as reflects in the total energy, electron energy, core-core repulsion and standard entropy), solubility (aqueous solubility and n-octanol/water partition coefficient), charge distribution (molecular polarizability and dipolar moment), and reactivity (relative Gibbs free energy); and the most influential structural descriptors were related to these parameters, in particular, size and dipolar moment. Finally, the PCA and PLS analyses were complemented with linear regression analysis to identify the most orthogonal column combinations, which could be used in comprehensive two-dimensional gas chromatography (GC×GC) to enhance PCDD/F separation and congener profiling. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, liquid crystallinity, and chiroptical properties of sterol-containing polyacetylenes

NASA Astrophysics Data System (ADS)

Lam, Jacky Wing Yip; Lai, Lo Ming; Tang, Ben Zhong

2006-08-01

Poly(phenylacetylene)s and poly(1-alkyne)s containing chiral sterol pendant groups with molecular structures of -[HC=C-C 6H 4-CO II-R] n-, -[HC=C-C 6H 4-O(CH II) 10-CO II-R] n- and -[HC=C(CH II) mCO II-R] n-, (where R = cholesterol, stigmasterol, ergosterol and m = 2, 3, 8} are designed and synthesized. The monomers are prepared by esterifications of acetylenic acids with cholesterol, stigmasterol, and ergosterol and exhibit cholestericity at high temperatures. Polymerizations of the monomers are effected by WCl 6-Ph 4Sn, MoCl 5-Ph 4Sn, and organorhodium catalysts, giving high molecular weight (M w up to 8.0 × 10 5) polymers in high yields (up to 99%). The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, DSC, POM, X-ray, UV, and CD analyses. All the polymers are thermally stable (greater than or equal to 300 °C). Polymers with long flexible alkyl chains form smectic and cholesteric phases at elevated temperatures. With an increase in the spacer length in poly(1-alkyne)s, the packing arrangements of the mesogenic pendants in the mesophases change from bilayer or mixed mono- and bilayer into homogeneous monolayer structures. Few poly(phenylacetylene)s show CD bands in the absorption region of the polyacetylene backbones, revealing that the main chains are helically rotating with a preferred screw sense.

Spontaneous Symmetry Breaking of Domain Walls in Phase-Competing Regions

NASA Astrophysics Data System (ADS)

Ishizuka, Hiroaki; Yamada, Yasusada; Nagaosa, Naoto

2018-05-01

In this study, we investigate the nature of domain walls in an ordered phase in the phase-competing region of two Ising-type order parameters. We consider a two-component ϕ4 theory and show that the domain wall of the ground-state (primary) order parameter shows a second-order phase transition associated with the secondary order parameter of the competing phase; the effective theory of the phase transition is given by the Landau theory of an Ising-type phase transition. We find that the phase boundary of this phase transition is different from the spinodal line of the competing order. The phase transition is detected experimentally by the divergence of the susceptibility corresponding to the secondary order when the temperature is quenched to introduce the domain walls.

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

Phase transitions in a multistate majority-vote model on complex networks

NASA Astrophysics Data System (ADS)

Chen, Hanshuang; Li, Guofeng

2018-06-01

We generalize the original majority-vote (MV) model from two states to arbitrary p states and study the order-disorder phase transitions in such a p -state MV model on complex networks. By extensive Monte Carlo simulations and a mean-field theory, we show that for p ≥3 the order of phase transition is essentially different from a continuous second-order phase transition in the original two-state MV model. Instead, for p ≥3 the model displays a discontinuous first-order phase transition, which is manifested by the appearance of the hysteresis phenomenon near the phase transition. Within the hysteresis loop, the ordered phase and disordered phase are coexisting, and rare flips between the two phases can be observed due to the finite-size fluctuation. Moreover, we investigate the type of phase transition under a slightly modified dynamics [Melo et al., J. Stat. Mech. (2010) P11032, 10.1088/1742-5468/2010/11/P11032]. We find that the order of phase transition in the three-state MV model depends on the degree heterogeneity of networks. For p ≥4 , both dynamics produce the first-order phase transitions.

Wilson loop's phase transition probed by non-local observable

NASA Astrophysics Data System (ADS)

Li, Hui-Ling; Feng, Zhong-Wen; Yang, Shu-Zheng; Zu, Xiao-Tao

2018-04-01

In order to give further insights into the holographic Van der Waals phase transition, it would be of great interest to investigate the behavior of Wilson loop across the holographic phase transition for a higher dimensional hairy black hole. We offer a possibility to proceed with a numerical calculation in order to discussion on the hairy black hole's phase transition, and show that Wilson loop can serve as a probe to detect a phase structure of the black hole. Furthermore, for a first order phase transition, we calculate numerically the Maxwell's equal area construction; and for a second order phase transition, we also study the critical exponent in order to characterize the Wilson loop's phase transition.

Chemotherapy Order Entry by a Clinical Support Pharmacy Technician in an Outpatient Medical Day Unit

PubMed Central

Neville, Heather; Broadfield, Larry; Harding, Claudia; Heukshorst, Shelley; Sweetapple, Jennifer; Rolle, Megan

2016-01-01

Background: Pharmacy technicians are expanding their scope of practice, often in partnership with pharmacists. In oncology, such a shift in responsibilities may lead to workflow efficiencies, but may also cause concerns about patient risk and medication errors. Objectives: The primary objective was to compare the time spent on order entry and order-entry checking before and after training of a clinical support pharmacy technician (CSPT) to perform chemotherapy order entry. The secondary objectives were to document workflow interruptions and to assess medication errors. Methods: This before-and-after observational study investigated chemotherapy order entry for ambulatory oncology patients. Order entry was performed by pharmacists before the process change (phase 1) and by 1 CSPT after the change (phase 2); order-entry checking was performed by a pharmacist during both phases. The tasks were timed by an independent observer using a personal digital assistant. A convenience sample of 125 orders was targeted for each phase. Data were exported to Microsoft Excel software, and timing differences for each task were tested with an unpaired t test. Results: Totals of 143 and 128 individual orders were timed for order entry during phase 1 (pharmacist) and phase 2 (CSPT), respectively. The mean total time to perform order entry was greater during phase 1 (1:37 min versus 1:20 min; p = 0.044). Totals of 144 and 122 individual orders were timed for order-entry checking (by a pharmacist) in phases 1 and 2, respectively, and there was no difference in mean total time for order-entry checking (1:21 min versus 1:20 min; p = 0.69). There were 33 interruptions not related to order entry (totalling 39:38 min) during phase 1 and 25 interruptions (totalling 30:08 min) during phase 2. Three errors were observed during order entry in phase 1 and one error during order-entry checking in phase 2; the errors were rated as having no effect on patient care. Conclusions: Chemotherapy order entry by a trained CSPT appeared to be just as safe and efficient as order entry by a pharmacist. Changes in pharmacy technicians’ scope of practice could increase the amount of time available for pharmacists to provide direct patient care in the oncology setting. PMID:27402999

Chemotherapy Order Entry by a Clinical Support Pharmacy Technician in an Outpatient Medical Day Unit.

PubMed

Neville, Heather; Broadfield, Larry; Harding, Claudia; Heukshorst, Shelley; Sweetapple, Jennifer; Rolle, Megan

2016-01-01

Pharmacy technicians are expanding their scope of practice, often in partnership with pharmacists. In oncology, such a shift in responsibilities may lead to workflow efficiencies, but may also cause concerns about patient risk and medication errors. The primary objective was to compare the time spent on order entry and order-entry checking before and after training of a clinical support pharmacy technician (CSPT) to perform chemotherapy order entry. The secondary objectives were to document workflow interruptions and to assess medication errors. This before-and-after observational study investigated chemotherapy order entry for ambulatory oncology patients. Order entry was performed by pharmacists before the process change (phase 1) and by 1 CSPT after the change (phase 2); order-entry checking was performed by a pharmacist during both phases. The tasks were timed by an independent observer using a personal digital assistant. A convenience sample of 125 orders was targeted for each phase. Data were exported to Microsoft Excel software, and timing differences for each task were tested with an unpaired t test. Totals of 143 and 128 individual orders were timed for order entry during phase 1 (pharmacist) and phase 2 (CSPT), respectively. The mean total time to perform order entry was greater during phase 1 (1:37 min versus 1:20 min; p = 0.044). Totals of 144 and 122 individual orders were timed for order-entry checking (by a pharmacist) in phases 1 and 2, respectively, and there was no difference in mean total time for order-entry checking (1:21 min versus 1:20 min; p = 0.69). There were 33 interruptions not related to order entry (totalling 39:38 min) during phase 1 and 25 interruptions (totalling 30:08 min) during phase 2. Three errors were observed during order entry in phase 1 and one error during order-entry checking in phase 2; the errors were rated as having no effect on patient care. Chemotherapy order entry by a trained CSPT appeared to be just as safe and efficient as order entry by a pharmacist. Changes in pharmacy technicians' scope of practice could increase the amount of time available for pharmacists to provide direct patient care in the oncology setting.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.

Here, we report how the superconducting phase forms in pseudo-single-crystal K xFe 2-ySe 2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition.more » It should be emphasized that the phase separation in pseudo-single-crystal K xFe 2-ySe 2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.« less

Formation mechanism of superconducting phase and its three-dimensional architecture in pseudo-single-crystal K xFe 2-ySe 2

DOE PAGES

Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.; ...

2016-02-11

Here, we report how the superconducting phase forms in pseudo-single-crystal K xFe 2-ySe 2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition.more » It should be emphasized that the phase separation in pseudo-single-crystal K xFe 2-ySe 2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.« less

Kibble-Zurek scaling and string-net coarsening in topologically ordered systems.

PubMed

Chandran, Anushya; Burnell, F J; Khemani, Vedika; Sondhi, S L

2013-10-09

We consider the non-equilibrium dynamics of topologically ordered systems driven across a continuous phase transition into proximate phases with no, or reduced, topological order. This dynamics exhibits scaling in the spirit of Kibble and Zurek but now without the presence of symmetry breaking and a local order parameter. The late stages of the process are seen to exhibit a slow, coarsening dynamics for the string-net that underlies the physics of the topological phase, a potentially interesting signature of topological order. We illustrate these phenomena in the context of particular phase transitions out of the Abelian Z2 topologically ordered phase of the toric code/Z2 gauge theory, and the non-Abelian SU(2)k ordered phases of the relevant Levin-Wen models.

Design of an all-optical fractional-order differentiator with terahertz bandwidth based on a fiber Bragg grating in transmission.

PubMed

Liu, Xin; Shu, Xuewen

2017-08-20

All-optical fractional-order temporal differentiators with bandwidths reaching terahertz (THz) values are demonstrated with transmissive fiber Bragg gratings. Since the designed fractional-order differentiator is a minimum phase function, the reflective phase of the designed function can be chosen arbitrarily. As examples, we first design several 0.5th-order differentiators with bandwidths reaching the THz range for comparison. The reflective phases of the 0.5th-order differentiators are chosen to be linear phase, quadratic phase, cubic phase, and biquadratic phase, respectively. We find that both the maximum coupling coefficient and the spatial resolution of the designed grating increase when the reflective phase varies from quadratic function to cubic function to biquadratic function. Furthermore, when the reflective phase is chosen to be a quadratic function, the obtained grating coupling coefficient and period are more likely to be achieved in practice. Then we design fractional-order differentiators with different orders when the reflective phase is chosen to be a quadratic function. We see that when the designed order of the differentiator increases, the obtained maximum coupling coefficient also increases while the oscillation of the coupling coefficient decreases. Finally, we give the numerical performance of the designed 0.5th-order differentiator by showing its temporal response and calculating its cross-correlation coefficient.

Binocular Combination of Second-Order Stimuli

PubMed Central

Zhou, Jiawei; Liu, Rong; Zhou, Yifeng; Hess, Robert F.

2014-01-01

Phase information is a fundamental aspect of visual stimuli. However, the nature of the binocular combination of stimuli defined by modulations in contrast, so-called second-order stimuli, is presently not clear. To address this issue, we measured binocular combination for first- (luminance modulated) and second-order (contrast modulated) stimuli using a binocular phase combination paradigm in seven normal adults. We found that the binocular perceived phase of second-order gratings depends on the interocular signal ratio as has been previously shown for their first order counterparts; the interocular signal ratios when the two eyes were balanced was close to 1 in both first- and second-order phase combinations. However, second-order combination is more linear than previously found for first-order combination. Furthermore, binocular combination of second-order stimuli was similar regardless of whether the carriers in the two eyes were correlated, anti-correlated, or uncorrelated. This suggests that, in normal adults, the binocular phase combination of second-order stimuli occurs after the monocular extracting of the second-order modulations. The sensory balance associated with this second-order combination can be obtained from binocular phase combination measurements. PMID:24404180

Study of anyon condensation and topological phase transitions from a Z4 topological phase using the projected entangled pair states approach

NASA Astrophysics Data System (ADS)

Iqbal, Mohsin; Duivenvoorden, Kasper; Schuch, Norbert

2018-05-01

We use projected entangled pair states (PEPS) to study topological quantum phase transitions. The local description of topological order in the PEPS formalism allows us to set up order parameters which measure condensation and deconfinement of anyons and serve as substitutes for conventional order parameters. We apply these order parameters, together with anyon-anyon correlation functions and some further probes, to characterize topological phases and phase transitions within a family of models based on a Z4 symmetry, which contains Z4 quantum double, toric code, double semion, and trivial phases. We find a diverse phase diagram which exhibits a variety of different phase transitions of both first and second order which we comprehensively characterize, including direct transitions between the toric code and the double semion phase.

Phase coexistence and electric-field control of toroidal order in oxide superlattices.

PubMed

Damodaran, A R; Clarkson, J D; Hong, Z; Liu, H; Yadav, A K; Nelson, C T; Hsu, S-L; McCarter, M R; Park, K-D; Kravtsov, V; Farhan, A; Dong, Y; Cai, Z; Zhou, H; Aguado-Puente, P; García-Fernández, P; Íñiguez, J; Junquera, J; Scholl, A; Raschke, M B; Chen, L-Q; Fong, D D; Ramesh, R; Martin, L W

2017-10-01

Systems that exhibit phase competition, order parameter coexistence, and emergent order parameter topologies constitute a major part of modern condensed-matter physics. Here, by applying a range of characterization techniques, and simulations, we observe that in PbTiO 3 /SrTiO 3 superlattices all of these effects can be found. By exploring superlattice period-, temperature- and field-dependent evolution of these structures, we observe several new features. First, it is possible to engineer phase coexistence mediated by a first-order phase transition between an emergent, low-temperature vortex phase with electric toroidal order and a high-temperature ferroelectric a 1 /a 2 phase. At room temperature, the coexisting vortex and ferroelectric phases form a mesoscale, fibre-textured hierarchical superstructure. The vortex phase possesses an axial polarization, set by the net polarization of the surrounding ferroelectric domains, such that it possesses a multi-order-parameter state and belongs to a class of gyrotropic electrotoroidal compounds. Finally, application of electric fields to this mixed-phase system permits interconversion between the vortex and the ferroelectric phases concomitant with order-of-magnitude changes in piezoelectric and nonlinear optical responses. Our findings suggest new cross-coupled functionalities.

Phase coexistence and electric-field control of toroidal order in oxide superlattices

NASA Astrophysics Data System (ADS)

Damodaran, A. R.; Clarkson, J. D.; Hong, Z.; Liu, H.; Yadav, A. K.; Nelson, C. T.; Hsu, S.-L.; McCarter, M. R.; Park, K.-D.; Kravtsov, V.; Farhan, A.; Dong, Y.; Cai, Z.; Zhou, H.; Aguado-Puente, P.; García-Fernández, P.; Íñiguez, J.; Junquera, J.; Scholl, A.; Raschke, M. B.; Chen, L.-Q.; Fong, D. D.; Ramesh, R.; Martin, L. W.

2017-10-01

Systems that exhibit phase competition, order parameter coexistence, and emergent order parameter topologies constitute a major part of modern condensed-matter physics. Here, by applying a range of characterization techniques, and simulations, we observe that in PbTiO3/SrTiO3 superlattices all of these effects can be found. By exploring superlattice period-, temperature- and field-dependent evolution of these structures, we observe several new features. First, it is possible to engineer phase coexistence mediated by a first-order phase transition between an emergent, low-temperature vortex phase with electric toroidal order and a high-temperature ferroelectric a1/a2 phase. At room temperature, the coexisting vortex and ferroelectric phases form a mesoscale, fibre-textured hierarchical superstructure. The vortex phase possesses an axial polarization, set by the net polarization of the surrounding ferroelectric domains, such that it possesses a multi-order-parameter state and belongs to a class of gyrotropic electrotoroidal compounds. Finally, application of electric fields to this mixed-phase system permits interconversion between the vortex and the ferroelectric phases concomitant with order-of-magnitude changes in piezoelectric and nonlinear optical responses. Our findings suggest new cross-coupled functionalities.

Phase coexistence and electric-field control of toroidal order in oxide superlattices

DOE PAGES

Damodaran, A. R.; Clarkson, J. D.; Hong, Z.; ...

2017-08-07

Systems that exhibit phase competition, order parameter coexistence, and emergent order parameter topologies constitute a major part of modern condensed-matter physics. Here, by applying a range of characterization techniques, and simulations, we observe that in PbTiO 3/SrTiO 3 superlattices all of these effects can be found. By exploring superlattice period-, temperature- and field-dependent evolution of these structures, we observe several new features. First, it is possible to engineer phase coexistence mediated by a first-order phase transition between an emergent, low-temperature vortex phase with electric toroidal order and a high-temperature ferroelectric a 1/a 2 phase. At room temperature, the coexisting vortexmore » and ferroelectric phases form a mesoscale, fibre-textured hierarchical superstructure. The vortex phase possesses an axial polarization, set by the net polarization of the surrounding ferroelectric domains, such that it possesses a multi-order-parameter state and belongs to a class of gyrotropic electrotoroidal compounds. Finally, application of electric fields to this mixed-phase system permits interconversion between the vortex and the ferroelectric phases concomitant with order-of-magnitude changes in piezoelectric and nonlinear optical responses. Here, our findings suggest new cross-coupled functionalities.« less

Command Surface of Self-Organizing Structures by Radical Polymers with Cooperative Redox Reactivity.

PubMed

Sato, Kan; Mizuma, Takahiro; Nishide, Hiroyuki; Oyaizu, Kenichi

2017-10-04

Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched in response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10 3 ). The switching enabled both a rapid cell response and long charge retention. Such a cooperative command surface of self-assembled structures will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.

Improvement in device performance from a mixture of a liquid crystal and photosensitive acrylic prepolymer with the photoinduced vertical alignment method

PubMed Central

Ho, Czung-Yu; Lin, Fa-Hsin; Tao, Yu-Tai; Lee, Jiunn-Yih

2011-01-01

In a multicomponent nematic liquid crystal (NLC) mixture of a liquid crystal (negative-type NLC) and a photosensitive acrylic prepolymer, photopolymerization upon UV irradiation induces the separation of the LC and photosensitive acrylic prepolymer layers, thereby leading to a vertical arrangement of LC molecules. In this study, we propose a simple vertical alignment method for LC molecules, by adding a chiral smectic A (SmA∗) liquid crystal having homeotropic texture characteristics to an NLC mixture solution. Measurements of electro-optical properties revealed that the addition of the SmA∗ LC not only strengthened the anchoring force of the copolymer alignment film surface, but also significantly enhanced the contrast ratio (∼73%), response time and grayscale switching performance of the device. PMID:27877462

First-order inflation

NASA Technical Reports Server (NTRS)

Kolb, Edward W.

1991-01-01

In the original proposal, inflation occurred in the process of a strongly first-order phase transition. This model was soon demonstrated to be fatally flawed. Subsequent models for inflation involved phase transitions that were second-order, or perhaps weakly first-order; some even involved no phase transition at all. Recently the possibility of inflation during a strongly first-order phase transition has been revived. In this talk I will discuss some models for first-order inflation, and emphasize unique signatures that result if inflation is realized in a first-order transition. Before discussing first-order inflation, I will briefly review some of the history of inflation to demonstrate how first-order inflation differs from other models.

Stepwise positional-orientational order and the multicritical-multistructural global phase diagram of the s=3/2 Ising model from renormalization-group theory.

PubMed

Yunus, Çağın; Renklioğlu, Başak; Keskin, Mustafa; Berker, A Nihat

2016-06-01

The spin-3/2 Ising model, with nearest-neighbor interactions only, is the prototypical system with two different ordering species, with concentrations regulated by a chemical potential. Its global phase diagram, obtained in d=3 by renormalization-group theory in the Migdal-Kadanoff approximation or equivalently as an exact solution of a d=3 hierarchical lattice, with flows subtended by 40 different fixed points, presents a very rich structure containing eight different ordered and disordered phases, with more than 14 different types of phase diagrams in temperature and chemical potential. It exhibits phases with orientational and/or positional order. It also exhibits quintuple phase transition reentrances. Universality of critical exponents is conserved across different renormalization-group flow basins via redundant fixed points. One of the phase diagrams contains a plastic crystal sequence, with positional and orientational ordering encountered consecutively as temperature is lowered. The global phase diagram also contains double critical points, first-order and critical lines between two ordered phases, critical end points, usual and unusual (inverted) bicritical points, tricritical points, multiple tetracritical points, and zero-temperature criticality and bicriticality. The four-state Potts permutation-symmetric subspace is contained in this model.

Size-dependent phase diagrams of metallic alloys: A Monte Carlo simulation study on order–disorder transitions in Pt–Rh nanoparticles

PubMed Central

Stahl, Christian; Albe, Karsten

2012-01-01

Summary Nanoparticles of Pt–Rh were studied by means of lattice-based Monte Carlo simulations with respect to the stability of ordered D022- and 40-phases as a function of particle size and composition. By thermodynamic integration in the semi-grand canonical ensemble, phase diagrams for particles with a diameter of 7.8 nm, 4.3 nm and 3.1 nm were obtained. Size-dependent trends such as the lowering of the critical ordering temperature, the broadening of the compositional stability range of the ordered phases, and the narrowing of the two-phase regions were observed and discussed in the context of complete size-dependent nanoparticle phase diagrams. In addition, an ordered surface phase emerges at low temperatures and low platinum concentration. A decrease of platinum surface segregation with increasing global platinum concentration was observed, when a second, ordered phase is formed inside the core of the particle. The order–disorder transitions were analyzed in terms of the Warren–Cowley short-range order parameters. Concentration-averaged short-range order parameters were used to remove the surface segregation bias of the conventional short-range order parameters. Using this procedure, it was shown that the short-range order in the particles at high temperatures is bulk-like. PMID:22428091

Phase diagram for a two-dimensional, two-temperature, diffusive XY model.

PubMed

Reichl, Matthew D; Del Genio, Charo I; Bassler, Kevin E

2010-10-01

Using Monte Carlo simulations, we determine the phase diagram of a diffusive two-temperature conserved order parameter XY model. When the two temperatures are equal the system becomes the equilibrium XY model with the continuous Kosterlitz-Thouless (KT) vortex-antivortex unbinding phase transition. When the two temperatures are unequal the system is driven by an energy flow from the higher temperature heat-bath to the lower temperature one and reaches a far-from-equilibrium steady state. We show that the nonequilibrium phase diagram contains three phases: A homogenous disordered phase and two phases with long range, spin texture order. Two critical lines, representing continuous phase transitions from a homogenous disordered phase to two phases of long range order, meet at the equilibrium KT point. The shape of the nonequilibrium critical lines as they approach the KT point is described by a crossover exponent φ=2.52±0.05. Finally, we suggest that the transition between the two phases with long-range order is first-order, making the KT-point where all three phases meet a bicritical point.

First-order inflation. [in cosmology

NASA Technical Reports Server (NTRS)

Kolb, Edward W.

1991-01-01

In the original proposal, inflation occurred in the process of a strongly first-order phase transition. This model was soon demonstrated to be fatally flawed. Subsequent models for inflation involved phase transitions that were second-order, or perhaps weakly first-order; some even involved no phase transition at all. Recently the possibility of inflation during a strongly first-order phase transition has been revived. In this paper, some models for first-order inflation are discussed, and unique signatures that result if inflation is realized in a first-order transition are emphasized. Some of the history of inflation is reviewed to demonstrate how first-order inflation differs from other models.

Theory of phase diagrams described by thermodynamic potentials with T d symmetry

NASA Astrophysics Data System (ADS)

Mukovnin, A. A.; Talanov, V. M.

2014-09-01

Phase diagrams of crystals induced by irreducible representations with symmetry group ( T d ) are constructed within the phenomenological theory of second-order phase transitions. A model of the Landau thermodynamic potential is studied, state equations of all symmetry-conditioned phases are obtained, and general conditions for their thermodynamic stability are formulated. Equations for the boundaries of phase areas and lines of phase transitions are obtained for the fourth order of expansion of the potential via components of the order parameter. Some types of the collapse of the multicritical point of the phase diagram for the eighth order of potential expansion are studied using computer calculations. The possible existence of phase diagrams that contain one or more triple points and areas of existence of three and four phases is shown for the first time for the potentials with the above symmetry. Examples are given of crystals that undergo phase transitions in the considered symmetry of the order parameter.

Phase transformations during the growth of paracetamol crystals from the vapor phase

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.

2014-07-01

Phase transformations during the growth of paracetamol crystals from the vapor phase are studied by differential scanning calorimetry. It is found that the vapor-crystal phase transition is actually a superposition of two phase transitions: a first-order phase transition with variable density and a second-order phase transition with variable ordering. The latter, being a diffuse phase transition, results in the formation of a new, "pretransition," phase irreversibly spent in the course of the transition, which ends in the appearance of orthorhombic crystals. X-ray diffraction data and micrograph are presented.

Fringe order correction for the absolute phase recovered by two selected spatial frequency fringe projections in fringe projection profilometry.

PubMed

Ding, Yi; Peng, Kai; Yu, Miao; Lu, Lei; Zhao, Kun

2017-08-01

The performance of the two selected spatial frequency phase unwrapping methods is limited by a phase error bound beyond which errors will occur in the fringe order leading to a significant error in the recovered absolute phase map. In this paper, we propose a method to detect and correct the wrong fringe orders. Two constraints are introduced during the fringe order determination of two selected spatial frequency phase unwrapping methods. A strategy to detect and correct the wrong fringe orders is also described. Compared with the existing methods, we do not need to estimate the threshold associated with absolute phase values to determine the fringe order error, thus making it more reliable and avoiding the procedure of search in detecting and correcting successive fringe order errors. The effectiveness of the proposed method is validated by the experimental results.

75 FR 51988 - Bison Pipeline LLC; Notice of Application

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-24

... (Certificate) in order to construct the Project in two phases; first to meet the service requirements of the... rates for transportation service approved in the Order. During the first phase, Bison would construct... and related appurtenances as authorized in the Order (Phase 1). During the second phase, Bison plans...

Vapor-crystal phase transition in synthesis of paracetamol films by vacuum evaporation and condensation

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.; Zarembo, V. I.

2014-03-01

We report on the structural and technological investigations of the vapor-crystal phase transition during synthesis of paracetamol films of the monoclinic system by vacuum evaporation and condensation in the temperature range 220-320 K. The complex nature of the transformation accompanied by the formation of a gel-like phase is revealed. The results are interpreted using a model according to which the vapor-crystal phase transition is not a simple first-order phase transition, but is a nonlinear superposition of two phase transitions: a first-order transition with a change in density and a second-order phase transition with a change in ordering. Micrographs of the surface of the films are obtained at different phases of formation.

Symmetric Topological Phases and Tensor Network States

NASA Astrophysics Data System (ADS)

Jiang, Shenghan

Classification and simulation of quantum phases are one of main themes in condensed matter physics. Quantum phases can be distinguished by their symmetrical and topological properties. The interplay between symmetry and topology in condensed matter physics often leads to exotic quantum phases and rich phase diagrams. Famous examples include quantum Hall phases, spin liquids and topological insulators. In this thesis, I present our works toward a more systematically understanding of symmetric topological quantum phases in bosonic systems. In the absence of global symmetries, gapped quantum phases are characterized by topological orders. Topological orders in 2+1D are well studied, while a systematically understanding of topological orders in 3+1D is still lacking. By studying a family of exact solvable models, we find at least some topological orders in 3+1D can be distinguished by braiding phases of loop excitations. In the presence of both global symmetries and topological orders, the interplay between them leads to new phases termed as symmetry enriched topological (SET) phases. We develop a framework to classify a large class of SET phases using tensor networks. For each tensor class, we can write down generic variational wavefunctions. We apply our method to study gapped spin liquids on the kagome lattice, which can be viewed as SET phases of on-site symmetries as well as lattice symmetries. In the absence of topological order, symmetry could protect different topological phases, which are often referred to as symmetry protected topological (SPT) phases. We present systematic constructions of tensor network wavefunctions for bosonic symmetry protected topological (SPT) phases respecting both onsite and spatial symmetries.

Phase transitions in a system of hard rectangles on the square lattice

NASA Astrophysics Data System (ADS)

Kundu, Joyjit; Rajesh, R.

2014-05-01

The phase diagram of a system of monodispersed hard rectangles of size m ×mk on a square lattice is numerically determined for m =2,3 and aspect ratio k =1,2,...,7. We show the existence of a disordered phase, a nematic phase with orientational order, a columnar phase with orientational and partial translational order, and a solidlike phase with sublattice order, but no orientational order. The asymptotic behavior of the phase boundaries for large k is determined using a combination of entropic arguments and a Bethe approximation. This allows us to generalize the phase diagram to larger m and k, showing that for k ≥7, the system undergoes three entropy-driven phase transitions with increasing density. The nature of the different phase transitions is established and the critical exponents for the continuous transitions are determined using finite size scaling.

Global phase diagram of the spinless Falicov-Kimball model in d = 3 : renormalization-group theory

NASA Astrophysics Data System (ADS)

Sariyer, Ozan S.; Hinczewski, Michael; Berker, A. Nihat

2011-03-01

The global phase diagram of the spinless Falicov-Kimball model in d = 3 spatial dimensions is obtained by renormalization-group theory. This global phase diagram exhibits five distinct phases. Four of these phases are charge-ordered (CO) phases, in which the system forms two sublattices with different electron densities. The phase boundaries are second order, except for an intermediate interaction regime, where a first-order phase boundary between two CO phases occurs. The first-order phase boundary is delimited by special bicritical points. The cross-sections of the global phase diagram with respect to the chemical potentials of the localized and mobile electrons, at all representative interaction and hopping strengths, are calculated and exhibit three distinct topologies. The phase diagrams with respect to electron densities are also calculated. This research was supported by the Alexander von Humboldt Foundation, the Scientific and Technological Research Council of Turkey (TÜBITAK), and the Academy of Sciences of Turkey.

Magnetic Ordering of Erbium and Uranium NICKEL(2) SILICON(2) by Neutron Scattering

NASA Astrophysics Data System (ADS)

Lin, Hong

The magnetic ordering has been studied in UNi _2Si_2 and erbium single crystals by elastic neutron scattering. Abundant results are given regarding the magnetic structure, magnetic phase transitions, and the effect of a magnetic field on these properties. Three ordered phases are observed in UNi _2Si_2. They have been determined to be an incommensurate longitudinal spin density wave with a magnetic wave vector around q = 0.74c ^* in the high temperature phase, a simple body-centred antiferromagnet in the intermediate temperature phase, and a square wave in the low temperature phase. This square wave can be viewed equivalently as a longitudinal spin density wave with q = 2/3c ^* superimposed on a ferromagnetic component. Hysteresis and sample dependence are observed in the low-temperature phase transition. The two lower temperature phase transitions are both first order. The transition to paramagnetism is second order with a critical exponent beta = 0.35 +/- 0.03. When a magnetic field is applied along the c axis, the intermediate temperature phase is destabilised and disappears above a field of 3.5T. Although there is no new phase induced by the field, there exists a reentrant point where the three ordered phases can coexist. Erbium has three distinct ordered phases: the cone phase at low temperatures, the c-axis modulated (CAM) phase at higher temperatures, and the intermediate phase with moments modulated both along c and perpendicular to c. Within these phases the modulation of the moments may lock in to the lattice. The observed weak harmonics of the wave vector q in the basal plane for the cone phase and the q = 1/4c^* structure in the intermediate phase can be explained by a basal-plane spin slip model. The effect of magnetic field along the c axis on the magnetic structure is to stabilise the cone phase and to destabilise the intermediate phase. A new lock-in structure with q = 1/4c^* in the cone phase is induced by fields above 1.8T. The presence of the field also stabilises the lock-in structure with q = 2/7c^* in both the intermediate and the CAM phases.

Chiral domain formation from the mixture of achiral rod-like liquid crystal and tri boomerang-shaped molecule

NASA Astrophysics Data System (ADS)

Lee, Ji-Hoon; Yoon, Tae-Hoon

2013-08-01

Spontaneous formation of chiral domains such as a helical filament and a bent-broom texture was observed from the mixture of a rod-like liquid crystal octylcyano-biphenyl (8CB) and a tri boomerang-shaped 2,4,6-triphenoxy-1,3,5-triazine (triphenoxy) molecule. Although the constituent molecules were achiral, their mixture showed the chiral domains with the equal fraction of the opposite handedness. No tilt of 8CB molecules in the smectic layer was observed, implying the chirality is not due to the polar packing and tilt of the molecules. In addition, the splay and bend elastic constant of 8CB was decreased after doping triphenoxy. A structural conformation of triphenoxy and an orientational coupling between 8CB and triphenoxy are considered to be related to the chiral domain formation.

Low-voltage tunable color in full visible region using ferroelectric liquid-crystal-doped cholesteric liquid-crystal smart materials

NASA Astrophysics Data System (ADS)

Lin, Jia-De; Lin, Jyun-Wei; Lee, Chia-Rong

2018-02-01

Electrical tuning of photonic bandgap (PBG) of cholesteric liquid crystal (CLC) without deformation within the entire visible region at low voltages is not easy to achieve. This study demonstrates low-voltage-tunable PBG in full visible region with less deformation of the PBG based on smart materials of ferroelectric liquid crystal doped CLC (FLC-CLC) integrating with electrothermal film heaters. Experimental results show that the reflective color of the FLC-CLC can be low-voltage-tuned through entire visible region. The induced temperature change is induced by electrically heating the electrothermal film heaters at low voltages at near the smectic-CLC transition temperature. Coaxial electrospinning can be used to develop smart fibrous devices with FLC/CLC-core and polymer-shell which color is tunable in full visible region at low voltages.

REVIEWS OF TOPICAL PROBLEMS: Order-disorder transformations and phase equilibria in strongly nonstoichiometric compounds

NASA Astrophysics Data System (ADS)

Gusev, Aleksandr I.

2000-01-01

Data on order-disorder phase transformations in strongly nonstoichiometric carbides and nitrides MXy (X=C, N) of Group IV and V transition metals at temperatures below 1300-1400 K are reviewed. The order-parameter functional method as applied to atomic and vacancy ordering in strongly nonstoichiometric MXy compounds and to phase equilibrium calculations for M-X systems is discussed. Phase diagram calculations for the Ti-C, Zr-C, Hf-C, V-C, Nb-C, Ta-C, Ti-N, and Ti-B-C systems (with the inclusion of the ordering of nonstoichiometric carbides and nitrides) and those for pseudobinary carbide M(1)C-M(2)C systems are presented. Heat capacity, electrical resistivity and magnetic susceptibility changes at reversible order-disorder phase transformations in nonstoichiometric carbides are considered.

Magnetic quasi-long-range ordering in nematic systems due to competition between higher-order couplings

NASA Astrophysics Data System (ADS)

Žukovič, Milan; Kalagov, Georgii

2018-05-01

Critical properties of the two-dimensional X Y model involving solely nematic-like terms of the second and third orders are investigated by spin-wave analysis and Monte Carlo simulation. It is found that, even though neither of the nematic-like terms alone can induce magnetic ordering, their coexistence and competition leads to an extended phase of the magnetic quasi-long-range-order phase, wedged between the two nematic-like phases induced by the respective couplings. Thus, except for the multicritical point, at which all the phases meet, for any finite value of the coupling parameters ratio there are two phase transition: one from the paramagnetic phase to one of the two nematic-like phases followed by another one at lower temperatures to the magnetic phase. The finite-size scaling analysis indicates that the phase transitions between the magnetic and nematic-like phases belong to the Ising and three-state Potts universality classes. Inside the competition-induced algebraic magnetic phase, the spin-pair correlation function is found to decay even much more slowly than in the standard X Y model with purely magnetic interactions. Such a magnetic phase is characterized by an extremely low vortex-antivortex pair density attaining a minimum close to the point at which the two couplings are of about equal strength.

Unconventional slowing down of electronic recovery in photoexcited charge-ordered La 1/3Sr 2/3FeO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Yi; Hoffman, Jason; Rowland, Clare E.

Ordered electronic phases are intimately related to emerging phenomena such as high Tc superconductivity and colossal magnetoresistance. The coupling of electronic charge with other degrees of freedom such as lattice and spin are of central interest in correlated systems. Their correlations have been intensively studied from femtosecond to picosecond time scales, while the dynamics of ordered electronic phases beyond nanoseconds are usually assumed to follow a trivia thermally driven recovery. Here, we report an unusual slowing down of electronic phases across a first-order phase transition, far beyond thermal relaxation time. Following optical excitation, the recovery time of both transient opticalmore » reflectivity and x-ray diffraction intensity from a charge-ordered superstructure in a La 1/3Sr 2/3FeO 3 thin film increases by orders of magnitude longer than the independently measured lattice cooling time when the sample temperature approaches the phase transition temperature. The combined experimental and theoretical investigations show that the slowing down of electronic recovery corresponds to the pseudo-critical dynamics that originates from magnetic interactions close to a weakly first-order phase transition. As a result, this extraordinary long electronic recovery time exemplifies an interplay of ordered electronic phases with magnetism beyond thermal processes in correlated systems.« less

Unconventional slowing down of electronic recovery in photoexcited charge-ordered La 1/3Sr 2/3FeO 3

DOE PAGES

Zhu, Yi; Hoffman, Jason; Rowland, Clare E.; ...

2018-05-04

Ordered electronic phases are intimately related to emerging phenomena such as high Tc superconductivity and colossal magnetoresistance. The coupling of electronic charge with other degrees of freedom such as lattice and spin are of central interest in correlated systems. Their correlations have been intensively studied from femtosecond to picosecond time scales, while the dynamics of ordered electronic phases beyond nanoseconds are usually assumed to follow a trivia thermally driven recovery. Here, we report an unusual slowing down of electronic phases across a first-order phase transition, far beyond thermal relaxation time. Following optical excitation, the recovery time of both transient opticalmore » reflectivity and x-ray diffraction intensity from a charge-ordered superstructure in a La 1/3Sr 2/3FeO 3 thin film increases by orders of magnitude longer than the independently measured lattice cooling time when the sample temperature approaches the phase transition temperature. The combined experimental and theoretical investigations show that the slowing down of electronic recovery corresponds to the pseudo-critical dynamics that originates from magnetic interactions close to a weakly first-order phase transition. As a result, this extraordinary long electronic recovery time exemplifies an interplay of ordered electronic phases with magnetism beyond thermal processes in correlated systems.« less

Origin of in-plane anisotropic resistivity in the antiferromagnetic phase of Fe1 +xTe

NASA Astrophysics Data System (ADS)

Kaneshita, Eiji; Tohyama, Takami

2016-07-01

Motivated by a recent experimental report on in-plane anisotropic resistivity in the double-striped antiferromagnetic phase of FeTe, we theoretically calculate in-plane resistivity by applying a memory function approach to the ordered phase. We find that the resistivity is larger along an antiferromagnetically ordered direction than along a ferromagnetically ordered one, consistent with experimental observation. The anisotropic results are mainly contributed from Drude weight, whose behavior is attributed to Fermi surface topology of the ordered phase.

Absolute phase estimation: adaptive local denoising and global unwrapping.

PubMed

Bioucas-Dias, Jose; Katkovnik, Vladimir; Astola, Jaakko; Egiazarian, Karen

2008-10-10

The paper attacks absolute phase estimation with a two-step approach: the first step applies an adaptive local denoising scheme to the modulo-2 pi noisy phase; the second step applies a robust phase unwrapping algorithm to the denoised modulo-2 pi phase obtained in the first step. The adaptive local modulo-2 pi phase denoising is a new algorithm based on local polynomial approximations. The zero-order and the first-order approximations of the phase are calculated in sliding windows of varying size. The zero-order approximation is used for pointwise adaptive window size selection, whereas the first-order approximation is used to filter the phase in the obtained windows. For phase unwrapping, we apply the recently introduced robust (in the sense of discontinuity preserving) PUMA unwrapping algorithm [IEEE Trans. Image Process.16, 698 (2007)] to the denoised wrapped phase. Simulations give evidence that the proposed algorithm yields state-of-the-art performance, enabling strong noise attenuation while preserving image details. (c) 2008 Optical Society of America

Humidity-Induced Phase Transitions in Ion-Containing Block Copolymer Membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Moon Jeong; Nedoma, Alisyn J.; Geissler, Phillip L.

2008-08-21

The phase behavior of ion-containing block copolymer membranes in equilibrium with humidified air is studied as a function of the relative humidity (RH) of the surrounding air, ion content of the copolymer, and temperature. Increasing RH at constant temperature results in both disorder-to-order and order-to-order transitions. In-situ small-angle neutron scattering experiments on the open block copolymer system, when combined with water uptake measurement, indicate that the disorder-to-order transition is driven by an increase in the partial molar entropy of the water molecules in the ordered phase relative to that in the disordered phase. This is in contrast to most systemsmore » wherein increasing entropy results in stabilization of the disordered phase.« less

String order parameters for one-dimensional Floquet symmetry protected topological phases

NASA Astrophysics Data System (ADS)

Kumar, Ajesh; Dumitrescu, Philipp T.; Potter, Andrew C.

2018-06-01

Floquet symmetry protected topological (FSPT) phases are nonequilibrium topological phases enabled by time-periodic driving. FSPT phases of one-dimensional (1D) chains of bosons, spins, or qubits host dynamically protected edge states that can store quantum information without decoherence, making them promising for use as quantum memories. While FSPT order cannot be detected by any local measurement, here we construct nonlocal string order parameters that directly measure general 1D FSPT order. We propose a superconducting-qubit array based realization of the simplest Ising FSPT phase, which can be implemented with existing quantum computing hardware. We devise an interferometric scheme to directly measure the nonlocal string order using only simple one- and two-qubit operations and single-qubit measurements.

Active control on high-order coherence and statistic characterization on random phase fluctuation of two classical point sources.

PubMed

Hong, Peilong; Li, Liming; Liu, Jianji; Zhang, Guoquan

2016-03-29

Young's double-slit or two-beam interference is of fundamental importance to understand various interference effects, in which the stationary phase difference between two beams plays the key role in the first-order coherence. Different from the case of first-order coherence, in the high-order optical coherence the statistic behavior of the optical phase will play the key role. In this article, by employing a fundamental interfering configuration with two classical point sources, we showed that the high- order optical coherence between two classical point sources can be actively designed by controlling the statistic behavior of the relative phase difference between two point sources. Synchronous position Nth-order subwavelength interference with an effective wavelength of λ/M was demonstrated, in which λ is the wavelength of point sources and M is an integer not larger than N. Interestingly, we found that the synchronous position Nth-order interference fringe fingerprints the statistic trace of random phase fluctuation of two classical point sources, therefore, it provides an effective way to characterize the statistic properties of phase fluctuation for incoherent light sources.

Unconventional charge order in a co-doped high-Tc superconductor

PubMed Central

Pelc, D.; Vučković, M.; Grafe, H. -J.; Baek, S. -H.; Požek, M.

2016-01-01

Charge-stripe order has recently been established as an important aspect of cuprate high-Tc superconductors. However, owing to the complex interplay between competing phases and the influence of disorder, it is unclear how it emerges from the parent high-temperature state. Here we report on the discovery of an unconventional ordered phase between charge-stripe order and (pseudogapped) metal in the cuprate La1.8−xEu0.2SrxCuO4. We use three complementary experiments—nuclear quadrupole resonance, nonlinear conductivity and specific heat—to demonstrate that the order appears through a sharp phase transition and exists in a dome-shaped region of the phase diagram. Our results imply that the new phase is a state, which preserves translational symmetry: a charge nematic. We thus resolve the process of charge-stripe development in cuprates, show that this nematic phase is distinct from high-temperature pseudogap and establish a link with other strongly correlated electronic materials with prominent nematic order. PMID:27605152

Non-Abelian Geometric Phases Carried by the Quantum Noise Matrix

NASA Astrophysics Data System (ADS)

Bharath, H. M.; Boguslawski, Matthew; Barrios, Maryrose; Chapman, Michael

2017-04-01

Topological phases of matter are characterized by topological order parameters that are built using Berry's geometric phase. Berry's phase is the geometric information stored in the overall phase of a quantum state. We show that geometric information is also stored in the second and higher order spin moments of a quantum spin system, captured by a non-abelian geometric phase. The quantum state of a spin-S system is uniquely characterized by its spin moments up to order 2S. The first-order spin moment is the spin vector, and the second-order spin moment represents the spin fluctuation tensor, i.e., the quantum noise matrix. When the spin vector is transported along a loop in the Bloch ball, we show that the quantum noise matrix picks up a geometric phase. Considering spin-1 systems, we formulate this geometric phase as an SO(3) operator. Geometric phases are usually interpreted in terms of the solid angle subtended by the loop at the center. However, solid angles are not well defined for loops that pass through the center. Here, we introduce a generalized solid angle which is well defined for all loops inside the Bloch ball, in terms of which, we interpret the SO(3) geometric phase. This geometric phase can be used to characterize topological spin textures in cold atomic clouds.

A new phase correction method in NMR imaging based on autocorrelation and histogram analysis.

PubMed

Ahn, C B; Cho, Z H

1987-01-01

A new statistical approach to phase correction in NMR imaging is proposed. The proposed scheme consists of first-and zero-order phase corrections each by the inverse multiplication of estimated phase error. The first-order error is estimated by the phase of autocorrelation calculated from the complex valued phase distorted image while the zero-order correction factor is extracted from the histogram of phase distribution of the first-order corrected image. Since all the correction procedures are performed on the spatial domain after completion of data acquisition, no prior adjustments or additional measurements are required. The algorithm can be applicable to most of the phase-involved NMR imaging techniques including inversion recovery imaging, quadrature modulated imaging, spectroscopic imaging, and flow imaging, etc. Some experimental results with inversion recovery imaging as well as quadrature spectroscopic imaging are shown to demonstrate the usefulness of the algorithm.

Refusing to Twist: Demonstration of a Line Hexatic Phase in DNA Liquid Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strey, H. H.; NICHD/LPSB, National Institutes of Health, Building 12A/2041, Bethesda, Maryland 20892-5626; Wang, J.

2000-04-03

We report conclusive high resolution small angle x-ray scattering evidence that long DNA fragments form an untwisted line hexatic phase between the cholesteric and the crystalline phases. The line hexatic phase is a liquid-crystalline phase with long-range hexagonal bond-orientational order, long-range nematic order, but liquidlike, i.e., short-range, positional order. So far, it has not been seen in any other three dimensional system. By line-shape analysis of x-ray scattering data we found that positional order decreases when the line hexatic phase is compressed. We suggest that such anomalous behavior is a result of the chiral nature of DNA molecules. (c) 2000more » The American Physical Society.« less

Calibration Method to Eliminate Zeroth Order Effect in Lateral Shearing Interferometry

NASA Astrophysics Data System (ADS)

Fang, Chao; Xiang, Yang; Qi, Keqi; Chen, Dawei

2018-04-01

In this paper, a calibration method is proposed which eliminates the zeroth order effect in lateral shearing interferometry. An analytical expression of the calibration error function is deduced, and the relationship between the phase-restoration error and calibration error is established. The analytical results show that the phase-restoration error introduced by the calibration error is proportional to the phase shifting error and zeroth order effect. The calibration method is verified using simulations and experiments. The simulation results show that the phase-restoration error is approximately proportional to the phase shift error and zeroth order effect, when the phase shifting error is less than 2° and the zeroth order effect is less than 0.2. The experimental result shows that compared with the conventional method with 9-frame interferograms, the calibration method with 5-frame interferograms achieves nearly the same restoration accuracy.

Phenomenological model and phase behavior of saturated and unsaturated lipids and cholesterol.

PubMed

Putzel, G Garbès; Schick, M

2008-11-15

We present a phenomenological theory for the phase behavior of ternary mixtures of cholesterol and saturated and unsaturated lipids, one that describes both liquid and gel phases. It leads to the following description of the mechanism of the phase behavior: In a binary system of the lipids, phase separation occurs when the saturated chains are well ordered, as in the gel phase, simply due to packing effects. In the liquid phase, the saturated ones are not sufficiently well ordered for separation to occur. The addition of cholesterol, however, increases the saturated lipid order to the point that phase separation is once again favorable. Our theory addresses this last mechanism-the means by which cholesterol-mediated ordering of membrane lipids leads to liquid-liquid immiscibility. It produces, for the system above the main chain transition of the saturated lipid, phase diagrams in which there can be liquid-liquid phase separation in the ternary system but not in any of the binary ones, while below that temperature it yields the more common phase diagram in which a gel phase, rich in saturated lipid, appears in addition to the two liquid phases.

Dynamical phase transitions in generalized Kuramoto model with distributed Sakaguchi phase

NASA Astrophysics Data System (ADS)

Banerjee, Amitava

2017-11-01

In this numerical work, we have systematically studied the dynamical phase transitions in the Kuramoto-Sakaguchi model of synchronizing phase oscillators controlled by disorder in the Sakaguchi phases. We derive the numerical steady state phase diagrams for quenched and annealed kinds of disorder in the Sakaguchi parameters, using the conventional order parameter and other such statistical quantities as strength of incoherence and discontinuity measures. We have also considered the correlation profile of the local order parameter fluctuations in the various phases identified. The phase diagrams for quenched disorder are qualitatively much different from those in the global coupling regime. The order of various transitions is confirmed by a study of the distribution of the order parameter and its fourth order Binder’s cumulant across the transition for an ensemble of initial distribution of phases. For the annealed type of disorder, in contrast to the case with quenched disorder, the system is almost insensitive to the amount of disorder. We also elucidate the role of chimeralike states in the synchronizing transition of the system, and study the effect of disorder on these states. Finally, we seek justification of our results from simulations guided by the Ott-Antonsen ansatz.

Phase diagram of the underdoped cuprates at high magnetic field

NASA Astrophysics Data System (ADS)

Chakraborty, Debmalya; Morice, Corentin; Pépin, Catherine

2018-06-01

The experimentally measured phase diagram of cuprate superconductors in the temperature-applied magnetic field plane illuminates key issues in understanding the physics of these materials. At low temperature, the superconducting state gives way to a long-range charge order with increasing magnetic field; both the orders coexist in a small intermediate region. The charge order transition is strikingly insensitive to temperature and quickly reaches a transition temperature close to the zero-field superconducting Tc. We argue that such a transition along with the presence of the coexisting phase is difficult to obtain in a weak coupling competing orders formalism. We demonstrate that for some range of parameters there is an enlarged symmetry of the strongly coupled charge and superconducting orders in the system depending on their relative masses and the coupling strength of the two orders. We establish that this sharp switch from the superconducting phase to the charge order phase can be understood in the framework of a composite SU(2) order parameter comprising the charge and superconducting orders. Finally, we illustrate that there is a possibility of the coexisting phase of the competing charge and superconducting orders only when the SU(2) symmetry between them is weakly broken due to biquadratic terms in the free energy. The relation of this sharp transition to the proximity to the pseudogap quantum critical doping is also discussed.

First-order inflation. [in cosmology

NASA Technical Reports Server (NTRS)

Turner, Michael S.

1992-01-01

I discuss the most recent model of inflation. In first-order inflation the inflationary epoch is associated with a first-order phase transition, with the most likely candidate being GUT symmetry breaking. The transition from the false-vacuum inflationary phase to the true-vacuum radiation-dominated phase proceeds through the nucleation and percolation of true-vacuum bubbles. The first successful and simplest model of first-order inflation, extended inflation, is discussed in some detail: evolution of the cosmic-scale factor, reheating, density perturbations, and the production of gravitational waves both from quantum fluctuations and bubble collisions. Particular attention is paid to the most critical issue in any model of first-order inflation: the requirements on the nucleation rate to ensure a graceful transition from the inflationary phase to the radiation-dominated phase.

Colloquium: Zoo of quantum-topological phases of matter

NASA Astrophysics Data System (ADS)

Wen, Xiao-Gang

2017-10-01

What are topological phases of matter? First, they are phases of matter at zero temperature. Second, they have a nonzero energy gap for the excitations above the ground state. Third, they are disordered liquids that seem to have no feature. But those disordered liquids actually can have rich patterns of many-body entanglement representing new kinds of order. This Colloquium gives a simple introduction and a brief survey of topological phases of matter. First topological phases with topological order (i.e., with long-range entanglement) are discussed. Then topological phases without topological order (i.e., with short-range entanglement) are covered.

Volume moiré tomography based on projection extraction by spatial phase shifting of double crossed gratings

NASA Astrophysics Data System (ADS)

Wang, Jia; Guo, Zhenyan; Song, Yang; Han, Jun

2018-01-01

To realize volume moiré tomography (VMT) for the real three-dimensional (3D) diagnosis of combustion fields, according to 3D filtered back projection (FBP) reconstruction algorithm, the radial derivatives of the projected phase should be measured firstly. In this paper, a simple spatial phase-shifting moiré deflectometry with double cross gratings is presented to measure the radial first-order derivative of the projected phase. Based on scalar diffraction theory, the explicit analytical intensity distributions of moiré patterns on different diffracted orders are derived, and the spatial shifting characteristics are analyzed. The results indicate that the first-order derivatives of the projected phase in two mutually perpendicular directions are involved in moiré patterns, which can be combined to compute the radial first-order derivative. And multiple spatial phase-shifted moiré patterns can be simultaneously obtained; the phase-shifted values are determined by the parameters of the system. A four-step phase-shifting algorithm is proposed for phase extraction, and its accuracy is proved by numerical simulations. Finally, the moiré deflectometry is used to measure the radial first-order derivative of projected phase of a propane flame with plane incident wave, and the 3D temperature distribution is reconstructed.

Order parameter free enhanced sampling of the vapor-liquid transition using the generalized replica exchange method.

PubMed

Lu, Qing; Kim, Jaegil; Straub, John E

2013-03-14

The generalized Replica Exchange Method (gREM) is extended into the isobaric-isothermal ensemble, and applied to simulate a vapor-liquid phase transition in Lennard-Jones fluids. Merging an optimally designed generalized ensemble sampling with replica exchange, gREM is particularly well suited for the effective simulation of first-order phase transitions characterized by "backbending" in the statistical temperature. While the metastable and unstable states in the vicinity of the first-order phase transition are masked by the enthalpy gap in temperature replica exchange method simulations, they are transformed into stable states through the parameterized effective sampling weights in gREM simulations, and join vapor and liquid phases with a succession of unimodal enthalpy distributions. The enhanced sampling across metastable and unstable states is achieved without the need to identify a "good" order parameter for biased sampling. We performed gREM simulations at various pressures below and near the critical pressure to examine the change in behavior of the vapor-liquid phase transition at different pressures. We observed a crossover from the first-order phase transition at low pressure, characterized by the backbending in the statistical temperature and the "kink" in the Gibbs free energy, to a continuous second-order phase transition near the critical pressure. The controlling mechanisms of nucleation and continuous phase transition are evident and the coexistence properties and phase diagram are found in agreement with literature results.

Systematic approaches to layered materials with strong electron correlations

NASA Astrophysics Data System (ADS)

Chung, Chung-Hou

I present systematic large-N approaches to study the ground state magnetic orderings and charge transport of layered materials with strong electron correlations, including the organic material kappa-(BEDT-TTF)2X, and the antiferromagnetic insulators Cs2CuCl4 and SrCu2(BO3) 2. I model the electronic properties of the organic materials kappa-(BEDT-TTF) 2X with a fermionic SU(N) Hubbard-Heisenberg model on an anisotropic triangular lattice. The ground state phase diagram shows a metal-insulator transition and a depression of the density of states in the metallic phase which are consistent with the experiments. The magnetic properties of kappa-(BEDT-TTF) 2X are modeled by a bosonic Sp(N) quantum Heisenberg antiferromagnet on the same lattice. The phase diagram consists of five different phases as a function of the size of the spin and the degree of frustration: the Neel ordered phase, a (pi, pi) short-range-order (SRO) phase, an incommensurate (q, q) long-range-order (LRO) phase, a (q, q) SRO phase, and a decoupled chain phase. I apply the same Sp(N) approach on the same triangular lattice to model the magnetic properties of Cs2CuCl 4 both with and without a magnetic field. At zero field, I find the ground state either exhibits incommensurate spin order, or is in a quantum disordered phase with deconfined spin-1/2 excitations and topological order. The Sp(N) calculation of spin excitation spectrum shows a large upward quantum renormalization consistent with that seen in experiments. For fields perpendicular to the plane of spin rotation, I find that the spins form an incommensurate "cone" of polarization up to a saturation field where all spins are fully polarized. There is a large quantum renormalization of the zero-field incommensuration. The results are in apparent agreement with neutron scattering experiments. Finally, the magnetic properties of the insulator SrCu2(BO 3)2 is modeled by the Sp(N) quantum antiferromagnet on the Shastry-Sutherland lattice. In addition to the familiar Neel and dimer phases, I find a confining phase with plaquette order, and a topologically ordered phase with deconfined S = 1/2 spinons and helical spin correlations. The deconfined phase is contiguous to the dimer phase, and in a regime of couplings close to those appropriate for the material.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Yi, Ming; Tian, Wei

Here, the complex interdigitated phases have greatly frustrated attempts to document the basic features of the superconductivity in the alkali metal intercalated iron chalcogenides. Here, using elastic neutron scattering, energy-dispersive x-ray spectroscopy, and resistivity measurements, we elucidate the relations of these phases in Rb xFe ySe 2-zS z. We find (i) the iron content is crucial in stabilizing the stripe antiferromagnetic (AF) phase with rhombic iron vacancy order (y ≈ 1.5), the block AF phase with root 5 x root 5 iron vacancy order (y ≈ 1.6), and the iron vacancy-free phase (y ≈ 2); and (ii) the iron vacancy-freemore » superconducting phase (z = 0) evolves into an iron vacancy-free metallic phase with sulfur substitution (z > 1.5) due to the progressive decrease of the electronic correlation strength. Both the stripe AF phase and the block AF phase are Mott insulators. The iron-rich compounds (y > 1.6) undergo a first order transition from an iron vacancy disordered phase at high temperatures into the √5 x √5 iron vacancy ordered phase and the iron vacancy-free phase below T s. Our data demonstrate that there are miscibility gaps between these three phases. The existence of the miscibility gaps in the iron content is a key to understanding the relationship between these complicated phases.« less

Ground-state ordering of the J1-J2 model on the simple cubic and body-centered cubic lattices

NASA Astrophysics Data System (ADS)

Farnell, D. J. J.; Götze, O.; Richter, J.

2016-06-01

The J1-J2 Heisenberg model is a "canonical" model in the field of quantum magnetism in order to study the interplay between frustration and quantum fluctuations as well as quantum phase transitions driven by frustration. Here we apply the coupled cluster method (CCM) to study the spin-half J1-J2 model with antiferromagnetic nearest-neighbor bonds J1>0 and next-nearest-neighbor bonds J2>0 for the simple cubic (sc) and body-centered cubic (bcc) lattices. In particular, we wish to study the ground-state ordering of these systems as a function of the frustration parameter p =z2J2/z1J1 , where z1 (z2) is the number of nearest (next-nearest) neighbors. We wish to determine the positions of the phase transitions using the CCM and we aim to resolve the nature of the phase transition points. We consider the ground-state energy, order parameters, spin-spin correlation functions, as well as the spin stiffness in order to determine the ground-state phase diagrams of these models. We find a direct first-order phase transition at a value of p =0.528 from a state of nearest-neighbor Néel order to next-nearest-neighbor Néel order for the bcc lattice. For the sc lattice the situation is more subtle. CCM results for the energy, the order parameter, the spin-spin correlation functions, and the spin stiffness indicate that there is no direct first-order transition between ground-state phases with magnetic long-range order, rather it is more likely that two phases with antiferromagnetic long range are separated by a narrow region of a spin-liquid-like quantum phase around p =0.55 . Thus the strong frustration present in the J1-J2 Heisenberg model on the sc lattice may open a window for an unconventional quantum ground state in this three-dimensional spin model.

Structural-Phase Transformations of CuZn Alloy Under Thermal-Impact Cycling

NASA Astrophysics Data System (ADS)

Potekaev, A. I.; Chaplygina, A. A.; Kulagina, V. V.; Chaplygin, P. A.; Starostenkov, M. D.; Grinkevich, L. S.

2017-02-01

Using the Monte Carlo method, special features of structural - phase transformations in β-brass are investigated during thermal impact using thermal cycling as an example (a number of successive order - disorder and disorder - order phase transitions in the course of several heating - cooling cycles). It is shown that a unique hysteresis is observed after every heating and cooling cycle, whose presence indicates irreversibility of the processes, which suggests a difference in the structural - phase states both in the heating and cooling stages. A conclusion is drawn that the structural - phase transformations in the heating and cooling stages occur within different temperature intervals, where the thermodynamic stimuli of one or the other structural - phase state are low. This is also demonstrated both in the plots of configurational energy, long- and short-range order parameter, atomic structure variations, and structural - phase state distributions. Simultaneously, there coexist ordered and disordered phases and a certain collection of superstructure domains. This implies the presence of low - stability states in the vicinity of the order - disorder phase transition. The results of investigations demonstrate that the structural - phase transitions within two successive heating and cooling cycles at the same temperature are different in both stages. These changes, though not revolutionary, occur in every cycle and decrease with the increasing cycle number. In fact, the system undergoes training with a tendency towards a certain sequence of structural - phase states.

Formation of the molecular crystal structure during the vacuum sublimation of paracetamol

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.

2015-04-01

The results from structural and thermal studies on the formation of molecular crystals during the vacuum sublimation of paracetamol from its vapor phase are given. It is established that the vapor-crystal phase transition proceeds in a complicated way as the superposition of two phase transitions: a first-order phase transition with a change in density, and a second-order phase transition with a change in ordering. It is shown that the latter is a smeared phase transition that proceeds with the formation of a pretransitional phase that is irreversibly dissipated during phase transformation, leading to the formation of crystals of the rhombic syngony. Data from differential scanning calorimetry and X-ray diffraction analysis are presented along with microphotographs.

Discovery of carbon-vacancy ordering in Nb4AlC3–x under the guidance of first-principles calculations

PubMed Central

Zhang, Hui; Hu, Tao; Wang, Xiaohui; Li, Zhaojin; Hu, Minmin; Wu, Erdong; Zhou, Yanchun

2015-01-01

The conventional wisdom to tailor the properties of binary transition metal carbides by order-disorder phase transformation has been inapplicable for the machinable ternary carbides (MTCs) due to the absence of ordered phase in bulk sample. Here, the presence of an ordered phase with structural carbon vacancies in Nb4AlC3–x (x ≈ 0.3) ternary carbide is predicted by first-principles calculations, and experimentally identified for the first time by transmission electron microscopy and micro-Raman spectroscopy. Consistent with the first-principles prediction, the ordered phase, o-Nb4AlC3, crystalizes in P63/mcm with a = 5.423 Å, c = 24.146 Å. Coexistence of ordered (o-Nb4AlC3) and disordered (Nb4AlC3–x) phase brings about abundant domains with irregular shape in the bulk sample. Both heating and electron irradiation can induce the transformation from o-Nb4AlC3 to Nb4AlC3–x. Our findings may offer substantial insights into the roles of carbon vacancies in the structure stability and order-disorder phase transformation in MTCs. PMID:26388153

Phase stability, ordering tendencies, and magnetism in single-phase fcc Au-Fe nanoalloys

DOE PAGES

Zhuravlev, I. A.; Barabash, S. V.; An, J. M.; ...

2017-10-01

Bulk Au-Fe alloys separate into Au-based fcc and Fe-based bcc phases, but L1 0 and L1 2 orderings were reported in single-phase Au-Fe nanoparticles. Motivated by these observations, we study the structural and ordering energetics in this alloy by combining density functional theory (DFT) calculations with effective Hamiltonian techniques: a cluster expansion with structural filters, and the configuration-dependent lattice deformation model. The phase separation tendency in Au-Fe persists even if the fcc-bcc decomposition is suppressed. The relative stability of disordered bcc and fcc phases observed in nanoparticles is reproduced, but the fully ordered L1 0 AuFe, L1 2 Au 3Fe,more » and L1 2 AuFe 3 structures are unstable in DFT. But, a tendency to form concentration waves at the corresponding [001] ordering vector is revealed in nearly-random alloys in a certain range of concentrations. Furthermore, this incipient ordering requires enrichment by Fe relative to the equiatomic composition, which may occur in the core of a nanoparticle due to the segregation of Au to the surface. Effects of magnetism on the chemical ordering are also discussed.« less

Phase stability, ordering tendencies, and magnetism in single-phase fcc Au-Fe nanoalloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhuravlev, I. A.; Barabash, S. V.; An, J. M.

Bulk Au-Fe alloys separate into Au-based fcc and Fe-based bcc phases, but L1 0 and L1 2 orderings were reported in single-phase Au-Fe nanoparticles. Motivated by these observations, we study the structural and ordering energetics in this alloy by combining density functional theory (DFT) calculations with effective Hamiltonian techniques: a cluster expansion with structural filters, and the configuration-dependent lattice deformation model. The phase separation tendency in Au-Fe persists even if the fcc-bcc decomposition is suppressed. The relative stability of disordered bcc and fcc phases observed in nanoparticles is reproduced, but the fully ordered L1 0 AuFe, L1 2 Au 3Fe,more » and L1 2 AuFe 3 structures are unstable in DFT. But, a tendency to form concentration waves at the corresponding [001] ordering vector is revealed in nearly-random alloys in a certain range of concentrations. Furthermore, this incipient ordering requires enrichment by Fe relative to the equiatomic composition, which may occur in the core of a nanoparticle due to the segregation of Au to the surface. Effects of magnetism on the chemical ordering are also discussed.« less

Kibble-Zurek Scaling and String-Net Coarsening in Topologically Ordered Systems

NASA Astrophysics Data System (ADS)

Khemani, Vedika; Chandran, Anushya; Burnell, F. J.; Sondhi, S. L.

2013-03-01

We consider the non-equilibrium dynamics of topologically ordered systems, such as spin liquids, driven across a continuous phase transition into proximate phases with no, or reduced, topological order. This dynamics exhibits scaling in the spirit of Kibble and Zurek but now without the presence of symmetry breaking and a local order parameter. The non-equilibrium dynamics near the critical point is universal in a particular scaling limit. The late stages of the process are seen to exhibit slow, quantum coarsening dynamics for the extended string-nets characterizing the topological phase, a potentially interesting signature of topological order. Certain gapped degrees of freedom that could potentially destroy coarsening are, at worst, dangerously irrelevant in the scaling limit. We also note a time dependent amplification of the energy splitting between topologically degenerate states on closed manifolds. We illustrate these phenomena in the context of particular phase transitions out of the abelian Z2 topologically ordered phase of the toric code, and the non-abelian SU(2)k ordered phases of the relevant Levin-Wen models. This research was supported in part by the National Science Foundation under Grant No. NSF PHY11-25915 and DMR 10-06608.

A time-dependent order parameter for ultrafast photoinduced phase transitions.

PubMed

Beaud, P; Caviezel, A; Mariager, S O; Rettig, L; Ingold, G; Dornes, C; Huang, S-W; Johnson, J A; Radovic, M; Huber, T; Kubacka, T; Ferrer, A; Lemke, H T; Chollet, M; Zhu, D; Glownia, J M; Sikorski, M; Robert, A; Wadati, H; Nakamura, M; Kawasaki, M; Tokura, Y; Johnson, S L; Staub, U

2014-10-01

Strongly correlated electron systems often exhibit very strong interactions between structural and electronic degrees of freedom that lead to complex and interesting phase diagrams. For technological applications of these materials it is important to learn how to drive transitions from one phase to another. A key question here is the ultimate speed of such phase transitions, and to understand how a phase transition evolves in the time domain. Here we apply time-resolved X-ray diffraction to directly measure the changes in long-range order during ultrafast melting of the charge and orbitally ordered phase in a perovskite manganite. We find that although the actual change in crystal symmetry associated with this transition occurs over different timescales characteristic of the many electronic and vibrational coordinates of the system, the dynamics of the phase transformation can be well described using a single time-dependent 'order parameter' that depends exclusively on the electronic excitation.

Topology-driven phase transitions in the classical monomer-dimer-loop model.

PubMed

Li, Sazi; Li, Wei; Chen, Ziyu

2015-06-01

In this work, we investigate the classical loop models doped with monomers and dimers on a square lattice, whose partition function can be expressed as a tensor network (TN). In the thermodynamic limit, we use the boundary matrix product state technique to contract the partition function TN, and determine the thermodynamic properties with high accuracy. In this monomer-dimer-loop model, we find a second-order phase transition between a trivial monomer-condensation and a loop-condensation (LC) phase, which cannot be distinguished by any local order parameter, while nevertheless the two phases have distinct topological properties. In the LC phase, we find two degenerate dominating eigenvalues in the transfer-matrix spectrum, as well as a nonvanishing (nonlocal) string order parameter, both of which identify the topological ergodicity breaking in the LC phase and can serve as the order parameter for detecting the phase transitions.

Mixed-order phase transition in a colloidal crystal.

PubMed

Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

2017-12-05

Mixed-order phase transitions display a discontinuity in the order parameter like first-order transitions yet feature critical behavior like second-order transitions. Such transitions have been predicted for a broad range of equilibrium and nonequilibrium systems, but their experimental observation has remained elusive. Here, we analytically predict and experimentally realize a mixed-order equilibrium phase transition. Specifically, a discontinuous solid-solid transition in a 2D crystal of paramagnetic colloidal particles is induced by a magnetic field [Formula: see text] At the transition field [Formula: see text], the energy landscape of the system becomes completely flat, which causes diverging fluctuations and correlation length [Formula: see text] Mean-field critical exponents are predicted, since the upper critical dimension of the transition is [Formula: see text] Our colloidal system provides an experimental test bed to probe the unconventional properties of mixed-order phase transitions.

Mixed-order phase transition in a colloidal crystal

NASA Astrophysics Data System (ADS)

Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

2017-12-01

Mixed-order phase transitions display a discontinuity in the order parameter like first-order transitions yet feature critical behavior like second-order transitions. Such transitions have been predicted for a broad range of equilibrium and nonequilibrium systems, but their experimental observation has remained elusive. Here, we analytically predict and experimentally realize a mixed-order equilibrium phase transition. Specifically, a discontinuous solid-solid transition in a 2D crystal of paramagnetic colloidal particles is induced by a magnetic field H. At the transition field Hs, the energy landscape of the system becomes completely flat, which causes diverging fluctuations and correlation length ξ∝|H2-Hs2|-1/2. Mean-field critical exponents are predicted, since the upper critical dimension of the transition is du=2. Our colloidal system provides an experimental test bed to probe the unconventional properties of mixed-order phase transitions.

Spontaneous membrane formation and self-encapsulation of active rods in an inhomogeneous motility field

NASA Astrophysics Data System (ADS)

Grauer, Jens; Löwen, Hartmut; Janssen, Liesbeth M. C.

2018-02-01

We study the collective dynamics of self-propelled rods in an inhomogeneous motility field. At the interface between two regions of constant but different motility, a smectic rod layer is spontaneously created through aligning interactions between the active rods, reminiscent of an artificial, semipermeable membrane. This "active membrane" engulfes rods which are locally trapped in low-motility regions and thereby further enhances the trapping efficiency by self-organization, an effect which we call "self-encapsulation." Our results are gained by computer simulations of self-propelled rod models confined on a two-dimensional planar or spherical surface with a stepwise constant motility field, but the phenomenon should be observable in any geometry with sufficiently large spatial inhomogeneity. We also discuss possibilities to verify our predictions of active-membrane formation in experiments of self-propelled colloidal rods and vibrated granular matter.

Self-organization processes and topological defects in nanolayers in a nematic liquid crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuvyrov, A. N.; Girfanova, F. M.; Mal'tsev, I. S.

Atomic force microscopy is used to study the self-organization processes that occur during the formation of topological defects in nanomolecular layers in a nematic liquid crystal with the homeotropic orientation of its molecules with respect to the substrate. In this case, a smectic monolayer with a thickness of one molecule length (about 2.2 nm) forms on the substrate, and a nanomolecular layer of a nematic liquid crystal forms above this monolayer. In such virtually two-dimensional layers, numerous different nanoclusters, namely, hut structures, pyramids, raft structures with symmetry C{sub nm} (where n = 2, 4, 5, 6, 7, ?, {infinity}), cones,more » and nanopools, form [1]. They have a regular shape close to the geometry of solid crystals. Modulated linear structures and topological point defects appear spontaneously in the nanopools and raft structures.« less

Liquid crystals for organic transistors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Hanna, Jun-ichi; Iino, Hiroaki

2016-09-01

Liquid crystals are a new type of organic semiconductors exhibiting molecular orientation in self-organizing manner, and have high potential for device applications. In fact, various device applications have been proposed so far, including photosensors, solar cells, light emitting diodes, field effect transistors, and so on.. However, device performance in those fabricated with liquid crystals is less than those of devices fabricated with conventional materials in spite of unique features of liquid crystals. Here we discuss how we can utilize the liquid crystallinity in organic transistors and how we can overcome conventional non-liquid crystalline organic transistor materials. Then, we demonstrate high performance organic transistors fabricated with a smectic E liquid crystal of Ph-BTBT-10, which show high mobility of over 10cm2/Vs and high thermal durability of over 200oC in OFETs fabricated with its spin-coated polycrystalline thin films.

Flexible daylight memory displays EASL DMD: a new approach toward displays for cockpit and soldier systems

NASA Astrophysics Data System (ADS)

Holter, Borre; Kamfjord, Thor G.; Fossum, Richard; Fagerberg, Ragnar

2000-08-01

The Norwegian based company PolyDisplayR ASA, in collaboration with the Norwegian Army Material Command and SINTEF, has refined, developed and shown with color and black/white technology demonstrators an electrically addressed Smectic A reflective LCD technology featuring: (1) Good contrast, all-round viewing angle and readability under all light conditions (no wash-out in direct sunlight). (2) Infinite memory -- image remains without power -- very low power consumption, no or very low radiation ('silent display') and narrow band updating. (3) Clear, sharp and flicker-free images. (4) Large number of gray tones and colors possible. (5) Simple construction and production -- reduced cost, higher yield, more robust and environmentally friendly. (6) Possibility for lighter, more robust and flexible displays based on plastic substrates. The results and future implementation possibilities for cockpit and soldier-system displays are discussed.

Calculation of gyrotropy coefficients in media with low-pitch helical structures

NASA Astrophysics Data System (ADS)

Dhaouadi, H.; Trabelsi, F.; Riahi, O.; Othman, T.

2018-04-01

Chiral smectic liquid crystals are known for their huge optical activity due to the precession of the anisotropic dielectric tensor around the helicoidal axis. For an oblique direction of the propagating wave, the helix acts as a grating which splits an incident beam in different directions as long as the pitch is not too small with respect to the light wavelength. When the pitch of the helix is smaller than the wavelength, the effect of the helix is a renormalization of the gyrotropic coefficients (g⊥ and g∥) of the resulting uniaxial medium. We report here on a method to compute these coefficients in that limit. Resolution of the Maxwell equations, using a perturbative approach, gives expressions for g⊥ and g∥ as a power development of the ratio (p/λ ) . The various terms of these developments coincide with the approximate expressions of these coefficients known in the literature.

Layering transitions and Schlieren textures in Langmuir films of two organic radicals.

PubMed

Gallani, J-L; Bourgogne, C; Nakatsuji, S

2004-11-09

Two paramagnetic radicals have been investigated in terms of their film-forming properties at the air-water interface. Although the radicals failed to display any mesomorphic behavior in the bulk, they were found prone to built-up multilayer films on the Langmuir trough. The molecules seem to dimerize in the upper layers of the films that exhibit striking Schlieren textures when observed with Brewster angle microscopy. These Schlieren textures, together with the ability to form multilayers, indicate that the molecules came close to displaying smectic mesomorphism. A tentative model of the layers' structure is proposed, and a suggestion for synthesizing new molecules with actual mesomorphism is offered. The presented results show that the study of the behavior of molecules at the air-water interface can shed a new light on their behavior in the bulk and help in the design of new magnetic mesogens.

Defect Interactions in Anisotropic Two-Dimensional Fluids

NASA Astrophysics Data System (ADS)

Stannarius, R.; Harth, K.

2016-10-01

Disclinations in liquid crystals bear striking analogies to defect structures in a wide variety of physical systems, and their straightforward optical observability makes them excellent models to study fundamental properties of defect interactions. We employ freely suspended smectic-C films, which behave as quasi-two-dimensional polar nematics. A procedure to capture high-strength disclinations in localized spots is introduced. These disclinations are released in a controlled way, and the motion of the mutually repelling topological charges with strength +1 is studied quantitatively. We demonstrate that the classical models, which employ elastic one-constant approximation, fail to describe their dynamics correctly. In realistic liquid crystals, even small differences between splay and bend constants lead to the selection of pure splay or pure bend +1 defects. For those, the models work only in very special configurations. In general, additional director walls are involved which reinforce the repulsive interactions substantially.

Two-order parameters theory of the metal-insulator phase transition kinetics in the magnetic field

NASA Astrophysics Data System (ADS)

Dubovskii, L. B.

2018-05-01

The metal-insulator phase transition is considered within the framework of the Ginzburg-Landau approach for the phase transition described with two coupled order parameters. One of the order parameters is the mass density which variation is responsible for the origin of nonzero overlapping of the two different electron bands and the appearance of free electron carriers. This transition is assumed to be a first-order phase one. The free electron carriers are described with the vector-function representing the second-order parameter responsible for the continuous phase transition. This order parameter determines mostly the physical properties of the metal-insulator transition and leads to a singularity of the surface tension at the metal-insulator interface. The magnetic field is involved into the consideration of the system. The magnetic field leads to new singularities of the surface tension at the metal-insulator interface and results in a drastic variation of the phase transition kinetics. A strong singularity in the surface tension results from the Landau diamagnetism and determines anomalous features of the metal-insulator transition kinetics.

On the structure of the disordered Bi 2Te 4O 11 phase

NASA Astrophysics Data System (ADS)

Masson, O.; Thomas, P.; Durand, O.; Hansen, T.; Champarnaud, J. C.; Mercurio, D.

2004-06-01

The structure of the disordered metastable Bi 2Te 4O 11 phase has been investigated using both neutron powder diffraction and reverse Monte Carlo (RMC) modelling. The average structure, of fluorite-type (space group Fm 3¯m ), is characterized by very high Debye-Waller parameters, especially for oxygen. Whereas the cations form a fairly well-defined FCC lattice, the oxygen sublattice is very disordered. It is shown that the local order is similar to that present in the stable monoclinic Bi 2Te 4O 11 phase. Clear differences are observed for the intermediate range order. The present phase is analogous to the "anti-glass" phases reported by Trömel in other tellurium-based mixed oxides. However, whereas Trömel defines anti-glass as having long range order but no short range order, it is shown here that this phase is best described as an intermediate state between the amorphous and crystalline states, i.e. having short and medium range order similar to that of tellurite glasses and a premise of long range order with the cations only.

The scaling of weak field phase-only control in Markovian dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Am-Shallem, Morag; Kosloff, Ronnie

We consider population transfer in open quantum systems, which are described by quantum dynamical semigroups (QDS). Using second order perturbation theory of the Lindblad equation, we show that it depends on a weak external field only through the field's autocorrelation function, which is phase independent. Therefore, for leading order in perturbation, QDS cannot support dependence of the population transfer on the phase properties of weak fields. We examine an example of weak-field phase-dependent population transfer, and show that the phase-dependence comes from the next order in the perturbation.

Local and nonlocal order parameters in the Kitaev chain

NASA Astrophysics Data System (ADS)

Chitov, Gennady Y.

2018-02-01

We have calculated order parameters for the phases of the Kitaev chain with interaction and dimerization at a special symmetric point applying the Jordan-Wigner and other duality transformations. We use string order parameters (SOPs) defined via the correlation functions of the Majorana string operators. The SOPs are mapped onto the local order parameters of some dual Hamiltonians and easily calculated. We have shown that the phase diagram of the interacting dimerized chain comprises the phases with the conventional local order as well as the phases with nonlocal SOPs. From the results for the critical indices, we infer the two-dimensional Ising universality class of criticality at the particular symmetry point where the model is exactly solvable.

Experimental and theoretical methods to study structural phase transition mechanisms in K{sub 3}WO{sub 3}F{sub 3} oxyfluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krylov, A.S., E-mail: shusy@iph.krasn.ru; Sofronova, S.N.; Kolesnikova, E.M.

2014-10-15

The results of structural phase transitions mechanisms study in K{sub 3}WO{sub 3}F{sub 3}oxyfluoride are represented by different experimental and theoretical methods. The structural phase transition anomalies at T{sub 1}=452 K and T{sub 2}=414 K of Raman and IR spectra have been analyzed. Using vibrational spectroscopy methods, the NMR-experiment has been done to clarify the nature of found phase transitions: displacive types or order-disorder types. The model of “disordered” crystal was proposed, and the results of lattice dynamics calculation in frameworks of the generalized Gordon–Kim method of ordered (R3) and “disordered” crystals were compared. The high pressure phases were studied bymore » the Raman technique too. - Graphical abstract: (1) Two possible configuration of octahedra. (2). All phases Raman lines of octahedra. (3) All phases IR lines of octahedra. (4) NMR spectra of all phases. - Highlights: • The results of study oxyfluoride K{sub 3}WO{sub 3}F{sub 3} are represented by Raman, IR, NMR technique. • The high pressure phases were studied by the Raman technique. • The anionic octahedra [WO{sub 3}F{sub 3}]{sup 3−} are not ordered below the both phase transitions. • The ferroelectric phase is realized due to the shift of atoms without F/O ordering. • Both of found phase transitions are close to the second order.« less

Ground-state phases of the spin-1 J1-J2 Heisenberg antiferromagnet on the honeycomb lattice

NASA Astrophysics Data System (ADS)

Li, P. H. Y.; Bishop, R. F.

2016-06-01

We study the zero-temperature quantum phase diagram of a spin-1 Heisenberg antiferromagnet on the honeycomb lattice with both nearest-neighbor exchange coupling J1>0 and frustrating next-nearest-neighbor coupling J2≡κ J1>0 , using the coupled cluster method implemented to high orders of approximation, and based on model states with different forms of classical magnetic order. For each we calculate directly in the bulk thermodynamic limit both ground-state low-energy parameters (including the energy per spin, magnetic order parameter, spin stiffness coefficient, and zero-field uniform transverse magnetic susceptibility) and their generalized susceptibilities to various forms of valence-bond crystalline (VBC) order, as well as the energy gap to the lowest-lying spin-triplet excitation. In the range 0 <κ <1 we find evidence for four distinct phases. Two of these are quasiclassical phases with antiferromagnetic long-range order, one with two-sublattice Néel order for κ <κc1=0.250(5 ) , and another with four-sublattice Néel-II order for κ >κc 2=0.340 (5 ) . Two different paramagnetic phases are found to exist in the intermediate region. Over the range κc1<κ<κci=0.305 (5 ) we find a gapless phase with no discernible magnetic order, which is a strong candidate for being a quantum spin liquid, while over the range κci<κ <κc 2 we find a gapped phase, which is most likely a lattice nematic with staggered dimer VBC order that breaks the lattice rotational symmetry.

Identifying product order with restricted Boltzmann machines

NASA Astrophysics Data System (ADS)

Rao, Wen-Jia; Li, Zhenyu; Zhu, Qiong; Luo, Mingxing; Wan, Xin

2018-03-01

Unsupervised machine learning via a restricted Boltzmann machine is a useful tool in distinguishing an ordered phase from a disordered phase. Here we study its application on the two-dimensional Ashkin-Teller model, which features a partially ordered product phase. We train the neural network with spin configuration data generated by Monte Carlo simulations and show that distinct features of the product phase can be learned from nonergodic samples resulting from symmetry breaking. Careful analysis of the weight matrices inspires us to define a nontrivial machine-learning motivated quantity of the product form, which resembles the conventional product order parameter.

Quantum corrections for the phase diagram of systems with competing order.

PubMed

Silva, N L; Continentino, Mucio A; Barci, Daniel G

2018-06-06

We use the effective potential method of quantum field theory to obtain the quantum corrections to the zero temperature phase diagram of systems with competing order parameters. We are particularly interested in two different scenarios: regions of the phase diagram where there is a bicritical point, at which both phases vanish continuously, and the case where both phases coexist homogeneously. We consider different types of couplings between the order parameters, including a bilinear one. This kind of coupling breaks time-reversal symmetry and it is only allowed if both order parameters transform according to the same irreducible representation. This occurs in many physical systems of actual interest like competing spin density waves, different types of orbital antiferromagnetism, elastic instabilities of crystal lattices, vortices in a multigap SC and also applies to describe the unusual magnetism of the heavy fermion compound URu 2 Si 2 . Our results show that quantum corrections have an important effect on the phase diagram of systems with competing orders.

Quantum corrections for the phase diagram of systems with competing order

NASA Astrophysics Data System (ADS)

Silva, N. L., Jr.; Continentino, Mucio A.; Barci, Daniel G.

2018-06-01

We use the effective potential method of quantum field theory to obtain the quantum corrections to the zero temperature phase diagram of systems with competing order parameters. We are particularly interested in two different scenarios: regions of the phase diagram where there is a bicritical point, at which both phases vanish continuously, and the case where both phases coexist homogeneously. We consider different types of couplings between the order parameters, including a bilinear one. This kind of coupling breaks time-reversal symmetry and it is only allowed if both order parameters transform according to the same irreducible representation. This occurs in many physical systems of actual interest like competing spin density waves, different types of orbital antiferromagnetism, elastic instabilities of crystal lattices, vortices in a multigap SC and also applies to describe the unusual magnetism of the heavy fermion compound URu2Si2. Our results show that quantum corrections have an important effect on the phase diagram of systems with competing orders.

Real-time fringe pattern demodulation with a second-order digital phase-locked loop.

PubMed

Gdeisat, M A; Burton, D R; Lalor, M J

2000-10-10

The use of a second-order digital phase-locked loop (DPLL) to demodulate fringe patterns is presented. The second-order DPLL has better tracking ability and more noise immunity than the first-order loop. Consequently, the second-order DPLL is capable of demodulating a wider range of fringe patterns than the first-order DPLL. A basic analysis of the first- and the second-order loops is given, and a performance comparison between the first- and the second-order DPLL's in analyzing fringe patterns is presented. The implementation of the second-order loop in real time on a commercial parallel image processing system is described. Fringe patterns are grabbed and processed, and the resultant phase maps are displayed concurrently.

Possible higher order phase transition in large-N gauge theory at finite temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishimura, Hiromichi

2017-08-07

We analyze the phase structure of SU(¥) gauge theory at finite temperature using matrix models. Our basic assumption is that the effective potential is dominated by double-trace terms for the Polyakov loops. As a function of the temperature, a background field for the Polyakov loop, and a quartic coupling, it exhibits a universal structure: in the large portion of the parameter space, there is a continuous phase transition analogous to the third-order phase transition of Gross,Witten and Wadia, but the order of phase transition can be higher than third. We show that different confining potentials give rise to drastically differentmore » behavior of the eigenvalue density and the free energy. Therefore lattice simulations at large N could probe the order of phase transition and test our results. Critical« less

Field-induced spin-density wave beyond hidden order in URu2Si2

NASA Astrophysics Data System (ADS)

Knafo, W.; Duc, F.; Bourdarot, F.; Kuwahara, K.; Nojiri, H.; Aoki, D.; Billette, J.; Frings, P.; Tonon, X.; Lelièvre-Berna, E.; Flouquet, J.; Regnault, L.-P.

2016-10-01

URu2Si2 is one of the most enigmatic strongly correlated electron systems and offers a fertile testing ground for new concepts in condensed matter science. In spite of >30 years of intense research, no consensus on the order parameter of its low-temperature hidden-order phase exists. A strong magnetic field transforms the hidden order into magnetically ordered phases, whose order parameter has also been defying experimental observation. Here, thanks to neutron diffraction under pulsed magnetic fields up to 40 T, we identify the field-induced phases of URu2Si2 as a spin-density-wave state. The transition to the spin-density wave represents a unique touchstone for understanding the hidden-order phase. An intimate relationship between this magnetic structure, the magnetic fluctuations and the Fermi surface is emphasized, calling for dedicated band-structure calculations.

Mixed-order phase transition in a colloidal crystal

PubMed Central

Tierno, Pietro; Casademunt, Jaume

2017-01-01

Mixed-order phase transitions display a discontinuity in the order parameter like first-order transitions yet feature critical behavior like second-order transitions. Such transitions have been predicted for a broad range of equilibrium and nonequilibrium systems, but their experimental observation has remained elusive. Here, we analytically predict and experimentally realize a mixed-order equilibrium phase transition. Specifically, a discontinuous solid–solid transition in a 2D crystal of paramagnetic colloidal particles is induced by a magnetic field H. At the transition field Hs, the energy landscape of the system becomes completely flat, which causes diverging fluctuations and correlation length ξ∝|H2−Hs2|−1/2. Mean-field critical exponents are predicted, since the upper critical dimension of the transition is du=2. Our colloidal system provides an experimental test bed to probe the unconventional properties of mixed-order phase transitions. PMID:29158388

Pressure-Induced Phase Transitions in the Cd-Yb Periodic Approximant to a Quasicrystal

NASA Astrophysics Data System (ADS)

Watanuki, Tetsu; Machida, Akihiko; Ikeda, Tomohiro; Aoki, Katsutoshi; Kaneko, Hiroshi; Shobu, Takahisa; Sato, Taku J.; Tsai, An Pang

2006-03-01

The phase study of a Cd-Yb 1/1 approximant crystal over a wide pressure and temperature range is crucial for the comparison study between periodic and quasiperiodic crystals. The Cd4 tetrahedra, the most inner part of the atomic clusters, exhibited various structural ordering in the orientation sensitive to pressure and temperature. Five ordered phases appeared in a P-T span up to 5.2 GPa and down to 10 K. The propagation direction of ordering alternated from [110] to ⟨111⟩ at about 1.0 GPa and again to [110] at 3.5 4.3 GPa. The primarily ordered phases that appeared by cooling to 210 250 K between 1.0 5.2 GPa further transformed to finely ordered ones at 120 155 K. Besides the original short-range type interaction, a long-range type interaction was likely developed under pressure to lead to the primary ordering of Cd4 tetrahedra. Coexistence of these interactions is responsible for the complicated phase behavior.

Field-induced spin density wave and spiral phases in a layered antiferromagnet

DOE PAGES

Stone, Matthew B.; Lumsden, Mark D.; Garlea, Vasile O.; ...

2015-07-28

Here we determine the low-field ordered magnetic phases of the S=1 dimerized antiferromagnet Ba 3Mn 2O 8 using single crystal neutron diffraction. We find that for magnetic fields between μ 0H=8.80 T and 10.56 T applied along themore » $$1\\bar{1}0$$ direction the system exhibits spin density wave order with incommensurate wave vectors of type (η,η,ε). For μ 0H > 10.56 T, the magnetic order changes to a spiral phase with incommensurate wave vectors only along the [hh0] direction. For both field induced ordered phases, the magnetic moments are lying in the plane perpendicular to the field direction. Finally, the nature of these two transitions is fundamentally different: the low-field transition is a second order transition to a spin-density wave ground state, while the one at higher field, toward the spiral phase, is of first order.« less

Device and method for creating Gaussian aberration-corrected electron beams

DOEpatents

McMorran, Benjamin; Linck, Martin

2016-01-19

Electron beam phase gratings have phase profiles that produce a diffracted beam having a Gaussian or other selected intensity profile. Phase profiles can also be selected to correct or compensate electron lens aberrations. Typically, a low diffraction order produces a suitable phase profile, and other orders are discarded.

Unique atom hyper-kagome order in Na4Ir3O8 and in low-symmetry spinel modifications.

PubMed

Talanov, V M; Shirokov, V B; Talanov, M V

2015-05-01

Group-theoretical and thermodynamic methods of the Landau theory of phase transitions are used to investigate the hyper-kagome atomic order in structures of ordered spinels and a spinel-like Na4Ir3O8 crystal. The formation of an atom hyper-kagome sublattice in Na4Ir3O8 is described theoretically on the basis of the archetype (hypothetical parent structure/phase) concept. The archetype structure of Na4Ir3O8 has a spinel-like structure (space group Fd\\bar 3m) and composition [Na1/2Ir3/2](16d)[Na3/2](16c)O(32e)4. The critical order parameter which induces hypothetical phase transition has been stated. It is shown that the derived structure of Na4Ir3O8 is formed as a result of the displacements of Na, Ir and O atoms, and ordering of Na, Ir and O atoms, ordering dxy, dxz, dyz orbitals as well. Ordering of all atoms takes place according to the type 1:3. Ir and Na atoms form an intriguing atom order: a network of corner-shared Ir triangles called a hyper-kagome lattice. The Ir atoms form nanoclusters which are named decagons. The existence of hyper-kagome lattices in six types of ordered spinel structures is predicted theoretically. The structure mechanisms of the formation of the predicted hyper-kagome atom order in some ordered spinel phases are established. For a number of cases typical diagrams of possible crystal phase states are built in the framework of the Landau theory of phase transitions. Thermodynamical conditions of hyper-kagome order formation are discussed by means of these diagrams. The proposed theory is in accordance with experimental data.

Nature and evolution of incommensurate charge order in manganites visualized with cryogenic scanning transmission electron microscopy

PubMed Central

Savitzky, Benjamin H.; Admasu, Alemayehu S.; Kim, Jaewook; Cheong, Sang-Wook; Hovden, Robert; Kourkoutis, Lena F.

2018-01-01

Incommensurate charge order in hole-doped oxides is intertwined with exotic phenomena such as colossal magnetoresistance, high-temperature superconductivity, and electronic nematicity. Here, we map, at atomic resolution, the nature of incommensurate charge–lattice order in a manganite using scanning transmission electron microscopy at room temperature and cryogenic temperature (∼93 K). In diffraction, the ordering wave vector changes upon cooling, a behavior typically associated with incommensurate order. However, using real space measurements, we discover that the ordered state forms lattice-locked regions over a few wavelengths interspersed with phase defects and changing periodicity. The cations undergo picometer-scale (∼6 pm to 11 pm) transverse displacements, suggesting that charge–lattice coupling is strong. We further unearth phase inhomogeneity in the periodic lattice displacements at room temperature, and emergent phase coherence at 93 K. Such local phase variations govern the long-range correlations of the charge-ordered state and locally change the periodicity of the modulations, resulting in wave vector shifts in reciprocal space. These atomically resolved observations underscore the importance of lattice coupling and phase inhomogeneity, and provide a microscopic explanation for putative “incommensurate” order in hole-doped oxides. PMID:29382750

Possible Existence of Two Amorphous Phases of D-Mannitol Related by a First-Order Transition

NASA Astrophysics Data System (ADS)

Zhu, Men; Wang, Jun-Qiang; Perepezko, John; Yu, Lian

We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above Tg (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase (Phase X). The enthalpy of Phase X is roughly halfway between those of the known amorphous and crystalline phases. The amorphous nature of Phase X is suggested by its absence of birefringence, transparency, broad X-ray diffraction, and broad Raman and NIR spectra. Phase X has greater molecular spacing, higher molecular order, fewer intra- and more inter-molecular hydrogen bonds than the normal liquid. On fast heating, Phase X transforms back to SCL near 330 K. Upon temperature cycling, it shows a glass-transition-like change of heat capacity. The presence of D-sorbitol enables a first-order liquid-liquid transition (LLT) from SCL to Phase X. This is the first report of polyamorphism at 1 atm for a pharmaceutical relevant substance. As amorphous solids are explored for many applications, polyamorphism could offer a tool to engineer the properties of materials. (Ref: M. Zhu et al., J. Chem. Phys. 2015, 142, 244504)

Ordering Transformations in High-Entropy Alloys

NASA Astrophysics Data System (ADS)

Singh, Prashant; Johnson, Duane D.

The high-temperature disordered phase of multi-component alloys, including high-entropy alloys (HEA), generally must experience segregation or else passes through partially-ordered phases to reach the low-temperature, fully-ordered phase. Our first-principles KKR-CPA-based atomic short-range ordering (SRO) calculations (analyzed as concentration-waves) reveal the competing partially and fully ordered phases in HEA, and these phases can be then directly assessed from KKR-CPA results in larger unit cells [Phys. Rev. B 91, 224204 (2015)]. For AlxCrFeNiTi0.25, Liu et al. [J Alloys Compd 619, 610 (2015)] experimentally find FCC+BCC coexistence that changes to BCC with increasing Al (x from 0-to-1), which then exhibits a partially-ordered B2 at low temperatures. CALPHAD (Calculation of Phase Diagrams) predicts a region with L21+B2 coexistence. From KKR-CPA calculations, we find crossover versus Al from FCC+BCC coexistence to BCC, as observed, and regions for partially-order B2+L21 coexistence, as suggest by CALPHAD. Our combined first-principles KKR-CPA method provides a powerful approach in predicting SRO and completing long-range order in HEA and other complex alloys. Supported by the U.S. DOE, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. Work was performed at Ames Laboratory, which is operated by Iowa State University for the U.S. DOE under Contract #DE-AC02-07CH11358.

Successive phase transitions and kink solutions in Φ⁸, Φ¹⁰, and Φ¹² field theories

DOE PAGES

Khare, Avinash; Christov, Ivan C.; Saxena, Avadh

2014-08-27

We obtain exact solutions for kinks in Φ⁸, Φ¹⁰, and Φ¹² field theories with degenerate minima, which can describe a second-order phase transition followed by a first-order one, a succession of two first-order phase transitions and a second-order phase transition followed by two first-order phase transitions, respectively. Such phase transitions are known to occur in ferroelastic and ferroelectric crystals and in meson physics. In particular, we find that the higher-order field theories have kink solutions with algebraically-decaying tails and also asymmetric cases with mixed exponential-algebraic tail decay, unlike the lower-order Φ⁴ and Φ⁶ theories. Additionally, we construct distinct kinks withmore » equal energies in all three field theories considered, and we show the co-existence of up to three distinct kinks (for a Φ¹² potential with six degenerate minima). We also summarize phonon dispersion relations for these systems, showing that the higher-order field theories have specific cases in which only nonlinear phonons are allowed. For the Φ¹⁰ field theory, which is a quasi-exactly solvable (QES) model akin to Φ⁶, we are also able to obtain three analytical solutions for the classical free energy as well as the probability distribution function in the thermodynamic limit.« less

Phase behavior and orientational ordering in block copolymers doped with anisotropic nanoparticles

NASA Astrophysics Data System (ADS)

Osipov, M. A.; Gorkunov, M. V.; Berezkin, A. V.; Kudryavtsev, Y. V.

2018-04-01

A molecular field theory and coarse-grained computer simulations with dissipative particle dynamics have been used to study the spontaneous orientational ordering of anisotropic nanoparticles in the lamellar and hexagonal phases of diblock copolymers and the effect of nanoparticles on the phase behavior of these systems. Both the molecular theory and computer simulations indicate that strongly anisotropic nanoparticles are ordered orientationally mainly in the boundary region between the domains and the nematic order parameter possesses opposite signs in adjacent domains. The orientational order is induced by the boundary and by the interaction between nanoparticles and the monomer units in different domains. In simulations, sufficiently long and strongly selective nanoparticles are ordered also inside the domains. The nematic order parameter and local concentration profiles of nanoparticles have been calculated numerically using the model of a nanoparticle with two interaction centers and also determined using the results of computer simulations. A number of phase diagrams have been obtained which illustrate the effect of nanoparticle selectivity and molar fraction of the stability ranges of various phases. Different morphologies have been identified by analyzing the static structure factor and a phase diagram has been constructed in coordinates' nanoparticle concentration-copolymer composition. Orientational ordering of even a small fraction of nanoparticles may result in a significant increase of the dielectric anisotropy of a polymer nanocomposite, which is important for various applications.

Estimation of Phase in Fringe Projection Technique Using High-order Instantaneous Moments Based Method

NASA Astrophysics Data System (ADS)

Gorthi, Sai Siva; Rajshekhar, G.; Rastogi, Pramod

2010-04-01

For three-dimensional (3D) shape measurement using fringe projection techniques, the information about the 3D shape of an object is encoded in the phase of a recorded fringe pattern. The paper proposes a high-order instantaneous moments based method to estimate phase from a single fringe pattern in fringe projection. The proposed method works by approximating the phase as a piece-wise polynomial and subsequently determining the polynomial coefficients using high-order instantaneous moments to construct the polynomial phase. Simulation results are presented to show the method's potential.

Suppressing Transients In Digital Phase-Locked Loops

NASA Technical Reports Server (NTRS)

Thomas, J. B.

1993-01-01

Loop of arbitrary order starts in steady-state lock. Method for initializing variables of digital phase-locked loop reduces or eliminates transients in phase and frequency typically occurring during acquisition of lock on signal or when changes made in values of loop-filter parameters called "loop constants". Enables direct acquisition by third-order loop without prior acquisition by second-order loop of greater bandwidth, and eliminates those perturbations in phase and frequency lock occurring when loop constants changed by arbitrarily large amounts.

On higher order discrete phase-locked loops.

NASA Technical Reports Server (NTRS)

Gill, G. S.; Gupta, S. C.

1972-01-01

An exact mathematical model is developed for a discrete loop of a general order particularly suitable for digital computation. The deterministic response of the loop to the phase step and the frequency step is investigated. The design of the digital filter for the second-order loop is considered. Use is made of the incremental phase plane to study the phase error behavior of the loop. The model of the noisy loop is derived and the optimization of the loop filter for minimum mean-square error is considered.

Phase-field-crystal model for ordered crystals

NASA Astrophysics Data System (ADS)

Alster, Eli; Elder, K. R.; Hoyt, Jeffrey J.; Voorhees, Peter W.

2017-02-01

We describe a general method to model multicomponent ordered crystals using the phase-field-crystal (PFC) formalism. As a test case, a generic B2 compound is investigated. We are able to produce a line of either first-order or second-order order-disorder phase transitions, features that have not been incorporated in existing PFC approaches. Further, it is found that the only elastic constant for B2 that depends on ordering is C11. This B2 model is then used to study antiphase boundaries (APBs). The APBs are shown to reproduce classical mean-field results. Dynamical simulations of ordering across small-angle grain boundaries predict that dislocation cores pin the evolution of APBs.

Spin-flop quasi-first order phase transition and putative tricritical point in Gd3Co

NASA Astrophysics Data System (ADS)

Samatham, S. Shanmukharao; Barua, Soumendu; Suresh, K. G.

2017-12-01

Magnetic nature of Gd3Co is investigated using detailed measurements of temperature and field dependent magnetization. The antiferromagnetic phase is field-instable due to prevailing ferromagnetic exchange correlations above Néel temperature TN ∼ 130K . Below TN , with gradually increasing magnetic fields, the compound undergoes a quasi-first order phase transition from AFM to spin-flop over region and eventually acquires ferromagnetic phase in higher fields. Further the point at which the quasi-first order transition ends and second order transition sets in is the tricritical point, TTCP ∼ 125.6K , HTCP ∼ 4.4kOe .

Magnetic Correlations in URu2Si2 under Chemical and Hydrostatic Pressure

NASA Astrophysics Data System (ADS)

Williams, Travis; Aczel, Adam; Broholm, Collin; Buyers, William; Leao, Juscelino; Luke, Graeme; Rodriguez-Riviera, Jose; Stone, Matthew; Wilson, Murray; Yamani, Zahra

URu2Si2 has been an intense area of study for the last 30 years due to a mysterious hidden order phase that appears below T0 = 17.5 K. The hidden order phase has been shown to be extremely sensitive to perturbations, being destroyed quickly by the application of a magnetic field, hydrostatic or uniaxial pressure, and chemical doping. While attempting to understand the properties of URu2Si2, neutron scattering has found spin correlations that are intimately related to this hidden order phase and which are also suppressed with these perturbations. Here, I will outline some recent neutron scattering work to study these correlations in two exceptional cases where the hidden order phase is enhanced: hydrostatic pressure and chemical pressure using Fe- and Os-doping. In both of these cases, T0 increases before an antiferromagnetic phase emerges. By performing a careful analysis of the neutron data, we show that these two phases are much more related than had been previously appreciated. This implies that the hidden order is likely compatible with an antiferromagnetic ground state, placing constraints on the nature of the missing order parameter.

Third Law of Thermodynamics and The Shape of the Phase Diagram for Systems With a First-Order Quantum Phase Transition.

PubMed

Kirkpatrick, T R; Belitz, D

2015-07-10

The third law of thermodynamics constrains the phase diagram of systems with a first-order quantum phase transition. For a zero conjugate field, the coexistence curve has an infinite slope at T=0. If a tricritical point exists at T>0, then the associated tricritical wings are perpendicular to the T=0 plane, but not to the zero-field plane. These results are based on the third law and basic thermodynamics only, and are completely general. As an explicit example we consider the ferromagnetic quantum phase transition in clean metals, where a first-order quantum phase transition is commonly observed.

High pressure ferroelastic phase transition in SrTiO3

NASA Astrophysics Data System (ADS)

Salje, E. K. H.; Guennou, M.; Bouvier, P.; Carpenter, M. A.; Kreisel, J.

2011-07-01

High pressure measurements of the ferroelastic phase transition of SrTiO3 (Guennou et al 2010 Phys. Rev. B 81 054115) showed a linear pressure dependence of the transition temperature between the cubic and tetragonal phase. Furthermore, the pressure induced transition becomes second order while the temperature dependent transition is near a tricritical point. The phase transition mechanism is characterized by the elongation and tilt of the TiO6 octahedra in the tetragonal phase, which leads to strongly nonlinear couplings between the structural order parameter, the volume strain and the applied pressure. The phase diagram is derived from the Clausius-Clapeyron relationship and is directly related to a pressure dependent Landau potential. The nonlinearities of the pressure dependent strains lead to an increase of the fourth order Landau coefficient with increasing pressure and, hence, to a tricritical-second order crossover. This behaviour is reminiscent of the doping related crossover in isostructural KMnF3.

Quantum phase transition with dissipative frustration

NASA Astrophysics Data System (ADS)

Maile, D.; Andergassen, S.; Belzig, W.; Rastelli, G.

2018-04-01

We study the quantum phase transition of the one-dimensional phase model in the presence of dissipative frustration, provided by an interaction of the system with the environment through two noncommuting operators. Such a model can be realized in Josephson junction chains with shunt resistances and resistances between the chain and the ground. Using a self-consistent harmonic approximation, we determine the phase diagram at zero temperature which exhibits a quantum phase transition between an ordered phase, corresponding to the superconducting state, and a disordered phase, corresponding to the insulating state with localized superconducting charge. Interestingly, we find that the critical line separating the two phases has a nonmonotonic behavior as a function of the dissipative coupling strength. This result is a consequence of the frustration between (i) one dissipative coupling that quenches the quantum phase fluctuations favoring the ordered phase and (ii) one that quenches the quantum momentum (charge) fluctuations leading to a vanishing phase coherence. Moreover, within the self-consistent harmonic approximation, we analyze the dissipation induced crossover between a first and second order phase transition, showing that quantum frustration increases the range in which the phase transition is second order. The nonmonotonic behavior is reflected also in the purity of the system that quantifies the degree of correlation between the system and the environment, and in the logarithmic negativity as an entanglement measure that encodes the internal quantum correlations in the chain.

Electric-field-induced spin disorder-to-order transition near a multiferroic triple phase point

DOE PAGES

Jang, Byung -Kweon; Lee, Jin Hong; Chu, Kanghyun; ...

2016-10-03

Here, the emergence of a triple phase point in a two-dimensional parameter space (such as pressure and temperature) can offer unforeseen opportunities for the coupling of two seemingly independent order parameters. On the basis of this, we demonstrate the electric control of magnetic order by manipulating chemical pressure: lanthanum substitution in the antiferromagnetic ferroelectric BiFeO 3. Our demonstration relies on the finding that a multiferroic triple phase point of a single spin-disordered phase and two spin-ordered phases emerges near room temperature in Bi 0.9La 0.1FeO 3 ferroelectric thin films. By using spatially resolved X-ray absorption spectroscopy, we provide direct evidencemore » that the electric poling of a particular region of the compound near the triple phase point results in an antiferromagnetic phase while adjacent unpoled regions remain magnetically disordered, opening a promising avenue for magnetoelectric applications at room temperature.« less

Selective suppression of high-order harmonics within phase-matched spectral regions.

PubMed

Lerner, Gavriel; Diskin, Tzvi; Neufeld, Ofer; Kfir, Ofer; Cohen, Oren

2017-04-01

Phase matching in high-harmonic generation leads to enhancement of multiple harmonics. It is sometimes desired to control the spectral structure within the phase-matched spectral region. We propose a scheme for selective suppression of high-order harmonics within the phase-matched spectral region while weakly influencing the other harmonics. The method is based on addition of phase-mismatched segments within a phase-matched medium. We demonstrate the method numerically in two examples. First, we show that one phase-mismatched segment can significantly suppress harmonic orders 9, 15, and 21. Second, we show that two phase-mismatched segments can efficiently suppress circularly polarized harmonics with one helicity over the other when driven by a bi-circular field. The new method may be useful for various applications, including the generation of highly helical bright attosecond pulses.

78 FR 76789 - Additional Connect America Fund Phase II Issues

Federal Register 2010, 2011, 2012, 2013, 2014

2013-12-19

... inspection and copying during normal business hours in the FCC Reference Information Center, Portals II, 445... Phase I to Phase II. 2. Timing of Phase II Support Disbursements. In the USF/ICC Transformation Order... language in paragraph 180 of the USF/ICC Transformation Order. We now seek to more fully develop the record...

Spin and topological order in a periodically driven spin chain

NASA Astrophysics Data System (ADS)

Russomanno, Angelo; Friedman, Bat-el; Dalla Torre, Emanuele G.

2017-07-01

The periodically driven quantum Ising chain has recently attracted a large attention in the context of Floquet engineering. In addition to the common paramagnet and ferromagnet, this driven model can give rise to new topological phases. In this work, we systematically explore its quantum phase diagram by examining the properties of its Floquet ground state. We specifically focus on driving protocols with time-reversal invariant points, and demonstrate the existence of an infinite number of distinct phases. These phases are separated by second-order quantum phase transitions, accompanied by continuous changes of local and string order parameters, as well as sudden changes of a topological winding number and of the number of protected edge states. When one of these phase transitions is adiabatically crossed, the correlator associated to the order parameter is nonvanishing over a length scale which shows a Kibble-Zurek scaling. In some phases, the Floquet ground state spontaneously breaks the discrete time-translation symmetry of the Hamiltonian. Our findings provide a better understanding of topological phases in periodically driven clean integrable models.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

NASA Astrophysics Data System (ADS)

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; Kreyssig, Andreas; Ran, S.; Bud'ko, Sergey L.; Canfield, Paul C.; Mompean, Federico J.; García-Hernández, Mar; Munuera, Carmen; Guillamón, Isabel; Suderow, Hermann

2018-01-01

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co-substituted CaFe2As2 . We use atomic force, magnetic force, and scanning tunneling microscopy to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micrometers long and about 30 nm wide; have the same Tc as unstrained samples; and hold vortices in a magnetic field. Thus, biaxial strain produces a phase-separated state, where each phase is equivalent to what is found on either side of the first-order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of the order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first-order quantum phase transitions lead to nanometric-size phase separation under the influence of strain.

Visualization of a stable intermediate phase in photoinduced metal-to-insulator transition in manganites

NASA Astrophysics Data System (ADS)

Lin, Hanxuan; Liu, Hao; Bai, Yu; Miao, Tian; Yu, Yang; Zhu, Yinyan; Chen, Hongyan; Kou, Yunfang; Niu, Jiebin; Wang, Wenbin; Yin, Lifeng; Shen, Jian

First order metal-insulator transition, accounting for various intriguing phenomena, is one of the most important phase transitions in condensed matter systems. Aside from the initial and final states, i.e. the metallic and insulating phases, no stable intermediate phase has been experimentally identified in such first order phase transition, though some transient phases do exist at the ultrafast time scale. Here, using our unique low-temperature, high-field magnetic force microscopy with photoexcitation, we directly observed a stable intermediate phase emerging and mediating the photoinduced first order metal-insulator transition in manganites. This phase is characteristic of low net magnetization and high resistivity. Our observations unveil the microscopic details of the photoinduced metal-insulator transition in manganites, which may be insightful to study first order metal-insulator transition in other condensed matter systems. This work was supported by National Key Research Program of China (2016YFA0300702), National Basic Research Program of China (973 Program) under the Grant No. 2013CB932901 and 2014CB921104; National Natural Science Foundation of China (11274071, 11504053).

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe 2 As 2 close to a first-order phase transition

DOE PAGES

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; ...

2018-01-09

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

Orientational order in bipolar nematic microdroplets close to the phase transition

NASA Astrophysics Data System (ADS)

Vilfan, I.; Vilfan, M.; Žumer, S.

1989-10-01

The ordering in bipolar liquid-crystal droplets close to the nematic-paranematic phase translation is studied. Here, ``paranematic'' refers to the phase above the nematic-isotropic transition temperature. The structure of spherical droplets is obtained after the minimization of the Landau-de Gennes-type free energy assuming a constant value of the surface order parameter and strong anchoring of the molecules parallel to the surface. Disordered defect regions caused by elastic deformations are found close to the poles. The defect regions grow into the droplet as the coexistence temperature between the paranematic and nematic phases is approached from below. The temperature-radius phase diagram shows the first-order coexistence curve terminating in the critical point and a pronounced decrease of the coexistence temperature on approaching the critical radius.

X-cube model on generic lattices: Fracton phases and geometric order

NASA Astrophysics Data System (ADS)

Slagle, Kevin; Kim, Yong Baek

2018-04-01

Fracton order is a new kind of quantum order characterized by topological excitations that exhibit remarkable mobility restrictions and a robust ground-state degeneracy (GSD) which can increase exponentially with system size. In this paper, we present a generic lattice construction (in three dimensions) for a generalized X-cube model of fracton order, where the mobility restrictions of the subdimensional particles inherit the geometry of the lattice. This helps explain a previous result that lattice curvature can produce a robust GSD, even on a manifold with trivial topology. We provide explicit examples to show that the (zero-temperature) phase of matter is sensitive to the lattice geometry. In one example, the lattice geometry confines the dimension-1 particles to small loops, which allows the fractons to be fully mobile charges, and the resulting phase is equivalent to (3+1)-dimensional toric code. However, the phase is sensitive to more than just lattice curvature; different lattices without curvature (e.g., cubic or stacked kagome lattices) also result in different phases of matter, which are separated by phase transitions. Unintuitively, however, according to a previous definition of phase [X. Chen et al., Phys. Rev. B 82, 155138 (2010), 10.1103/PhysRevB.82.155138], even just a rotated or rescaled cubic results in different phases of matter, which motivates us to propose a coarser definition of phase for gapped ground states and fracton order. This equivalence relation between ground states is given by the composition of a local unitary transformation and a quasi-isometry (which can rotate and rescale the lattice); equivalently, ground states are in the same phase if they can be adiabatically connected by varying both the Hamiltonian and the positions of the degrees of freedom (via a quasi-isometry). In light of the importance of geometry, we further propose that fracton orders should be regarded as a geometric order.

Heisenberg spin-1/2 XXZ chain in the presence of electric and magnetic fields

NASA Astrophysics Data System (ADS)

Thakur, Pradeep; Durganandini, P.

2018-02-01

We study the interplay of electric and magnetic order in the one-dimensional Heisenberg spin-1/2 XXZ chain with large Ising anisotropy in the presence of the Dzyaloshinskii-Moriya (DM) interaction and with longitudinal and transverse magnetic fields, interpreting the DM interaction as a coupling between the local electric polarization and an external electric field. We obtain the ground state phase diagram using the density matrix renormalization group method and compute various ground state quantities like the magnetization, staggered magnetization, electric polarization and spin correlation functions, etc. In the presence of both longitudinal and transverse magnetic fields, there are three different phases corresponding to a gapped Néel phase with antiferromagnetic (AF) order, gapped saturated phase, and a critical incommensurate gapless phase. The external electric field modifies the phase boundaries but does not lead to any new phases. Both external magnetic fields and electric fields can be used to tune between the phases. We also show that the transverse magnetic field induces a vector chiral order in the Néel phase (even in the absence of an electric field) which can be interpreted as an electric polarization in a direction parallel to the AF order.

A method searching for optimum fractional order and its application in self-phase modulation induced nonlinear phase noise estimation in coherent optical fiber transmission systems

NASA Astrophysics Data System (ADS)

Huang, Chuan; Guo, Peng; Yang, Aiying; Qiao, Yaojun

2018-07-01

In single channel systems, the nonlinear phase noise only comes from the channel itself through self-phase modulation (SPM). In this paper, a fast-nonlinear effect estimation method is proposed based on fractional Fourier transformation (FrFT). The nonlinear phase noise caused by Self-phase modulation effect is accurately estimated for single model 10Gbaud OOK and RZ-QPSK signals with the fiber length range of 0-200 km and the launch power range of 1-10 mW. The pulse windowing is adopted to search the optimum fractional order for the OOK and RZ-QPSK signals. Since the nonlinear phase shift caused by the SPM effect is very small, the accurate optimum fractional order of the signal cannot be found based on the traditional method. In this paper, a new method magnifying the phase shift is proposed to get the accurate optimum order and thus the nonlinear phase shift is calculated. The simulation results agree with the theoretical analysis and the method is applicable to signals whose pulse type has the similar characteristics with Gaussian pulse.

Probing topological order with Rényi entropy

NASA Astrophysics Data System (ADS)

Halász, Gábor B.; Hamma, Alioscia

2012-12-01

We present an analytical study of the quantum phase transition between the topologically ordered toric-code-model ground state and the disordered spin-polarized state. The phase transition is induced by applying an external magnetic field, and the variation in topological order is detected via two nonlocal quantities: the Wilson loop and the topological Rényi entropy of order 2. By exploiting an equivalence with the transverse-field Ising model and considering two different variants of the problem, we investigate the field dependence of these quantities by means of an exact treatment in the exactly solvable variant and complementary perturbation theories around the limits of zero and infinite fields in both variants. We find strong evidence that the phase transition point between topological order and disorder is marked by a discontinuity in the topological Rényi entropy and that the two phases around the phase transition point are characterized by its different constant values. Our results therefore indicate that the topological Rényi entropy is a proper topological invariant: its allowed values are discrete and can be used to distinguish between different phases of matter.

Appearance of superconductivity at the vacancy order-disorder boundary in KxFe2 -ySe2

NASA Astrophysics Data System (ADS)

Duan, Chunruo; Yang, Junjie; Ren, Yang; Thomas, Sean M.; Louca, Despina

2018-05-01

The role of phase separation and the effect of Fe-vacancy ordering in the emergence of superconductivity in alkali metal doped iron selenides AxFe2 -ySe2 (A = K, Rb, Cs) is explored. High energy x-ray diffraction and Monte Carlo simulation were used to investigate the crystal structure of quenched superconducting (SC) and as-grown nonsuperconducting (NSC) KxFe2 -ySe2 single crystals. The coexistence of superlattice structures with the in-plane √{2 }×√{2 } K-vacancy ordering and the √{5 }×√{5 } Fe-vacancy ordering were observed in both the SC and NSC crystals alongside the I4/mmm Fe-vacancy-free phase. Moreover, in the SC crystals, an Fe-vacancy-disordered phase is additionally proposed to be present. Monte Carlo simulations suggest that it appears at the boundary between the I4/mmm vacancy-free phase and the I4/m vacancy-ordered phases (√{5 }×√{5 } ). The vacancy-disordered phase is nonmagnetic and is most likely the host of superconductivity.

Charge ordered ferromagnetic phase in La_0.5Ca_0.5MnO_3

NASA Astrophysics Data System (ADS)

Mathur, Neil

2003-03-01

Charge order and ferromagnetism should be mutually exclusive in the manganites, because ferromagnetism in these materials is normally promoted by delocalised electrons. Surprisingly, a phase that is both strongly charge ordered and fully ferromagnetic is observed [1] at 90 K in La_0.5Ca_0.5MnO_3, using Fresnel imaging, dark-field TEM and electron holography. This new phase coexists with the two low temperature phases that were already known to coexist in La_0.5Ca_0.5MnO_3. (One of these expected phases is ferromagnetic but not charge-ordered, the other is charge-ordered but not ferromagnetic.) Strain fields could be responsible for the novel microscopic texture presented here - perhaps creating conditions in which nearest neighbour hopping is sufficient to promote ferromagnetism. Similarly, strain fields are believed to cause sub-micron phase separation in the manganites. It therefore seems that the manganites can adapt to their environments over a wide range of length scales [2]. [1] http://xxx.lanl.gov/abs/cond-mat/0209436 [2] Neil Mathur and Peter Littlewood, Physics Today, early 2003.

Mott localization in a pure stripe antiferromagnet Rb 1 - δ Fe 1.5 - σ S 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Yi, Ming; Cao, Huibo

A combination of neutron diffraction and angle-resolved photoemission spectroscopy measurements on a pure antiferromagnetic stripe Rb 1-δFe 1.5-σS 2 is reported. A neutron diffraction experiment on a powder sample shows that a 98% volume fraction of the sample is in the antiferromagnetic stripe phase with rhombic iron vacancy order and a refined composition of Rb 0.66Fe 1.36S 2, and that only 2% of the sample is in the block antiferromagnetic phase with √5×√5 iron vacancy order. Furthermore, a neutron diffraction experiment on a single crystal shows that there is only a single phase with the stripe antiferromagnetic order with themore » refined composition of Rb 0.78Fe 1.35S 2, while the phase with block antiferromagnetic order is absent. Angle-resolved photoemission spectroscopy measurements on the same crystal with the pure stripe phase reveal that the electronic structure is gapped at the Fermi level with a gap larger than 0.325 eV. The data collectively demonstrate that the extra 10% iron vacancies in addition to the rhombic iron vacancy order effectively impede the formation of the block antiferromagnetic phase; the data also suggest that the stripe antiferromagnetic phase with rhombic iron vacancy order is a Mott insulator.« less

Effects of temperature and electric field on order parameters in ferroelectric hexagonal manganites

NASA Astrophysics Data System (ADS)

Zhang, C. X.; Yang, K. L.; Jia, P.; Lin, H. L.; Li, C. F.; Lin, L.; Yan, Z. B.; Liu, J.-M.

2018-03-01

In Landau-Devonshire phase transition theory, the order parameter represents a unique property for a disorder-order transition at the critical temperature. Nevertheless, for a phase transition with more than one order parameter, such behaviors can be quite different and system-dependent in many cases. In this work, we investigate the temperature (T) and electric field (E) dependence of the two order parameters in improper ferroelectric hexagonal manganites, addressing the phase transition from the high-symmetry P63/mmc structure to the polar P63cm structure. It is revealed that the trimerization as the primary order parameter with two components: the trimerization amplitude Q and phase Φ, and the spontaneous polarization P emerging as the secondary order parameter exhibit quite different stability behaviors against various T and E. The critical exponents for the two parameters Q and P are 1/2 and 3/2, respectively. As temperature increases, the window for the electric field E enduring the trimerization state will shrink. An electric field will break the Z2 part of the Z2×Z3 symmetry. The present work may shed light on the complexity of the vortex-antivortex domain structure evolution near the phase transition temperature.

Higher order cumulants in colorless partonic plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherif, S.; Laboratoire de Physique et de Mathématiques Appliquées; Ahmed, M. A. A.

2016-06-10

Any physical system considered to study the QCD deconfinement phase transition certainly has a finite volume, so the finite size effects are inevitably present. This renders the location of the phase transition and the determination of its order as an extremely difficult task, even in the simplest known cases. In order to identify and locate the colorless QCD deconfinement transition point in finite volume T{sub 0}(V), a new approach based on the finite-size cumulant expansion of the order parameter and the ℒ{sub m,n}-Method is used. We have shown that both cumulants of higher order and their ratios, associated to themore » thermodynamical fluctuations of the order parameter, in QCD deconfinement phase transition behave in a particular enough way revealing pronounced oscillations in the transition region. The sign structure and the oscillatory behavior of these in the vicinity of the deconfinement phase transition point might be a sensitive probe and may allow one to elucidate their relation to the QCD phase transition point. In the context of our model, we have shown that the finite volume transition point is always associated to the appearance of a particular point in whole higher order cumulants under consideration.« less

Frequency-doubled microwave waveforms generation using a dual-polarization quadrature phase shift keying modulator driven by a single frequency radio frequency signal

NASA Astrophysics Data System (ADS)

Zhu, Zihang; Zhao, Shanghong; Li, Xuan; Qu, Kun; Lin, Tao

2018-01-01

A photonic approach to generate frequency-doubled microwave waveforms using an integrated dual-polarization quadrature phase shift keying (DP-QPSK) modulator driven by a sinusoidal radio frequency (RF) signal is proposed. By adjusting the dc bias points of the DP-QPSK modulator, the obtained second-order and six-order harmonics are in phase while the fourth-order harmonics are complementary when the orthogonal polarized outputs of the modulator are photodetected. After properly setting the modulation indices of the modulator, the amplitude of the second-order harmonic is 9 times of that of the six-order harmonic, indicating a frequency-doubled triangular waveform is generated. If a broadband 90° microwave phase shifter is attached after the photodetector (PD) to introduce a 90° phase shift, a frequency-doubled square waveform can be obtained after adjusting the amplitude of the second-order harmonic 3 times of that of the six-order harmonic. The proposal is first theoretically analyzed and then validated by simulation. Simulation results show that a 10 GHz triangular and square waveform sequences are successfully generated from a 5 GHz sinusoidal RF drive signal.

Transverse fields to tune an Ising-nematic quantum phase transition

NASA Astrophysics Data System (ADS)

Maharaj, Akash V.; Rosenberg, Elliott W.; Hristov, Alexander T.; Berg, Erez; Fernandes, Rafael M.; Fisher, Ian R.; Kivelson, Steven A.

2017-12-01

The paradigmatic example of a continuous quantum phase transition is the transverse field Ising ferromagnet. In contrast to classical critical systems, whose properties depend only on symmetry and the dimension of space, the nature of a quantum phase transition also depends on the dynamics. In the transverse field Ising model, the order parameter is not conserved, and increasing the transverse field enhances quantum fluctuations until they become strong enough to restore the symmetry of the ground state. Ising pseudospins can represent the order parameter of any system with a twofold degenerate broken-symmetry phase, including electronic nematic order associated with spontaneous point-group symmetry breaking. Here, we show for the representative example of orbital-nematic ordering of a non-Kramers doublet that an orthogonal strain or a perpendicular magnetic field plays the role of the transverse field, thereby providing a practical route for tuning appropriate materials to a quantum critical point. While the transverse fields are conjugate to seemingly unrelated order parameters, their nontrivial commutation relations with the nematic order parameter, which can be represented by a Berry-phase term in an effective field theory, intrinsically intertwine the different order parameters.

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation Behavior of Ordered Phases

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.

2003-01-01

Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si[3], for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.