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At least 55 records · Page 3

Should I stay or should I flow? An exploration of phase‐separated metallosupramolecular liquid crystal polymers

Abstract Dynamic liquid crystalline polymers (dLCPs) incorporate both liquid crystalline mesogens and dynamic bonds into a single polymeric material. These dual functionalities impart order‐dependent thermo‐responsive mechano‐optical properties and enhanced reprocessability/programmability enabling their use as soft actuators, adaptive adhesives, and damping materials. While many previous works studying dynamic LCPs utilize dynamic covalent bonds, metallosupramolecular bonds provide a modular platform where a series of materials can be accessed from a single polymeric feedstock through the variation of the metal ion used. A series of dLCPs were prepared by the addition of metal salts to a telechelic 2,6‐bisbenzimidazolylpyridine (Bip) ligand endcapped LCP to form metallosupramolecular liquid crystal polymers (MSLCPs). The resulting MSLCPs were found to phase separate into hard and soft phases which aids in their mechanical robustness. Variations of the metal salts used to access these materials allowed for control of the thermomechanical, viscoelastic, and adhesive properties with relaxations that can be tailored independently of the mesogenic transition. This work demonstrates that by accessing phase separation through the incorporation of metallosupramolecular moieties, highly processable yet robust MSLCP materials can be realized. This class of materials opens the door to LCPs with bulk flow behavior that can also be utilized as multi‐level adhesives.

Chemistry↗

Functional soft materials from blue phase liquid crystals

Blue phase (BP) liquid crystals are chiral fluids wherein millions of molecules self-assemble into cubic lattices that are on the order of hundred nanometers. As the unit cell sizes of BPs are comparable to the wavelength of light, they exhibit selective Bragg reflections in the visible. The exploitation of the photonic properties of BPs for technological applications is made possible through photopolymerization, a process that renders mechanical robustness and thermal stability. We review here the preparation and characterization of stimuli-responsive, polymeric photonic crystals based on BPs. We highlight recent studies that demonstrate the promise that polymerized BP photonic crystals hold for colorimetric sensing and dynamic light control. We review using Landau–de Gennes simulations for predicting the self-assembly of BPs and the potential for using theory to guide experimental design. Finally, opportunities for using BPs to synthesize new soft materials, such as highly structured polymer meshes, are discussed.

36 MATERIALS SCIENCE↗

Ferroelectric liquid crystal display

A ferroelectric liquid crystal display device employs capacitance spoiling layers to minimize unneeded capacitances created by crossovers of X and Y address lines and to accurately define desired capacitances. The spoiler layers comprise low dielectric constant layers which space electrodes from the ferroelectric at crossover points where capacitance is not needed for device operation.

York, Paul K.↗

Liquid crystal point diffraction interferometer

A new instrument, the liquid crystal point diffraction-interferometer (LCPDI), has been developed for the measurement of phase objects. This instrument maintains the compact, robust design of Linnik's point diffraction interferometer (PDI) and adds to it phase stepping capability for quantitative interferogram analysis. The result is a compact, simple to align, environmentally insensitive interferometer capable of accurately measuring optical wavefronts with very high data density and with automated data reduction. This dissertation describes the theory of both the PDI and liquid crystal phase control. The design considerations for the LCPDI are presented, including manufacturing considerations. The operation and performance of the LCPDI are discussed, including sections regarding alignment, calibration, and amplitude modulation effects. The LCPDI is then demonstrated using two phase objects: defocus difference wavefront, and a temperature distribution across a heated chamber filled with silicone oil. The measured results are compared to theoretical or independently measured results and show excellent agreement. A computer simulation of the LCPDI was performed to verify the source of observed periodic phase measurement error. The error stems from intensity variations caused by dye molecules rotating within the liquid crystal layer. Methods are discussed for reducing this error. Algorithms are presented which reduce this error; they are also useful for any phase-stepping interferometer that has unwanted intensity fluctuations, such as those caused by unregulated lasers.

Mercer, Carolyn R.↗

Partially exposed polymer dispersed liquid crystals for boundary layer investigations

A new configuration termed partially exposed polymer dispersed liquid crystal in which the liquid crystal microdroplets dispersed in a rigid polymer matrix are partially entrapped on the free surface of the thin film deposited on a glass substrate is reported. Optical transmission characteristics of the partially exposed polymer dispersed liquid crystal thin film in response to an air flow induced shear stress field reveal its potential as a sensor for gas flow and boundary layer investigations.

Parmar, Devendra S.↗

Novel Microstructures for Polymer-Liquid Crystal Composite Materials

There are a number of interface-dominated composite materials that contain a liquid crystalline (LC) phase in intimate contact with an isotropic phase. For example, polymer- dispersed liquid crystals, used in the fabrication of windows with switchable transparency, consist of micron size LC droplets dispersed in an isotropic polymer matrix. Many other types of liquid crystal composite materials can be envisioned that might have outstanding optical properties that could be exploited in novel chemical sensors, optical switches, and computer displays. This research project was based on the premise that many of these potentially useful LC composite materials can only be fabricated under microgravity conditions where gravity driven flows are absent. In the ground-based research described below, we have focused on a new class of LC composites that we call thermotropic- lyotropic liquid crystal systems (TLLCs). TLLCs consist of nanosize droplets of water dispersed in an LC matrix, with surfactants at the interface that stabilize the structure. By varying the type of surfactant one can access almost an infinite variety of unusual LC composite microstructures. Due to the importance of the interface in these types of systems, we have also developed molecular simulation models for liquid crystals at interfaces, and made some of the first measurements of the interfacial tension between liquid crystals and water.

Magda, Jules J.↗

Enhanced Ion Transport and Molecular Packing Stability in Asymmetric 2D Nanostructured π‐Conjugated Thieno[3,2‐b]Thiophene‐Based Liquid Crystal

Organic semiconductors based on liquid crystal (LC) molecules have attracted increasing interest. Here, in this work, two linear LCs based on 2,5‐bis(thien‐2‐yl)thieno[3,2‐b]thiophene (BTTT) mesogen are designed and synthesized, including BTTT/dEO3 with two symmetrically attached tri(ethylene oxide) groups and BTTT/mEO6 with one asymmetrically attached hexa(ethylene oxide) group. These two molecules have comparable functional‐group compositions but different molecular geometries, leading to their moderately different material performances. Both LCs show smectic mesophases with relatively low transition temperatures as confirmed by differential scanning calorimetry and polarized optical microscopy. A combination of experimental grazing incidence wide‐angle X‐ray scattering and molecular dynamics (MD) simulations reveals a herringbone packing motif of BTTT segments in both LCs while a smaller molecular tilt angle in BTTT/mEO6. Ionic conductivities are measured by doping LCs with different amounts of ionic dopants, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). BTTT/mEO6 shows better smectic phase stability to higher LiTFSI doping ratios. Both LCs exhibit similar ionic conductivities in the smectic phases, but BTTT/mEO6 outperforms BTTT/dEO3 by a factor of three in the amorphous phase at higher temperatures. MD simulations, performed to examine the ion solvation environment, reveal that BTTT/mEO6 is more efficient in coordinating Li‐ions and screening their interactions with TFSI‐ions which further promote ionic transport.

grazing incidence wide-angle X-ray scattering↗

An electrochemical study of a liquid crystal used in information displays

The operational lifetime of liquid crystal displays were investigated. Electrochemical reaction at the electrodes of the display can cause failure after 2000 to 3000 hours of operation. Studies using cyclic voltametry of electrochemical reactions of N (p-methoxybenzilidene p-butylaniline (MBBA), a nematic liquid crystal were made. These studies indicate the presence of a reversible reduction of MBBA at the cathode, and that the reduction product undergoes a further reaction leading to products which are not reversibly oxidized. It is concluded that the degradation of the liquid crystal in displays can be reduced with a suitable frequency of alternating voltage.

Oglesby, D. M.↗

Stereolithography additive manufacturing of magnetically aligned liquid crystal elastomers

A method of forming a three-dimensional structure includes forming a layer of resin comprising liquid crystal oligomers and a photoinitiator, applying a magnetic field to the formed layer in a predefined alignment direction for substantially aligning the liquid crystal oligomers in a first orientation; and exposing the formed layer to radiation for curing a first portion of the layer during application of the magnetic field thereby resulting in the first portion having liquid crystal elastomers substantially aligned in the first orientation. The method includes applying a second magnetic field to the formed layer in a predefined second alignment direction for substantially aligning uncured liquid crystal oligomers in a second orientation, and exposing the layer to radiation for curing a second portion of the layer during application of the second magnetic field thereby resulting in the second portion having liquid crystal elastomers substantially aligned in the second orientation.

Arriaga, Rodrigo Telles↗

Ion Transport in 2D Nanostructured $\pi$-Conjugated Thieno[3,2- b ]thiophene-Based Liquid Crystal

Leveraging the self-assembling behavior of liquid crystals designed for controlling ion transport is of both fundamental and technological significance. Here, we have designed and prepared a liquid crystal that contains (2,5-bis(5-(2,5,8,11-tetraoxatridecan-13-yl)thiophen-2yl)thieno[3,2-b]thiophene (BTTT) as mesogenic core and conjugated segment and symmetric tetra(ethylene oxide) (EO4) as polar side chains for ionic conducting regions. Driven by the crystallization of the BTTT cores, BTTT/dEO4 exhibits well-ordered smectic phases below 71.5 °C as confirmed by differential scanning calorimetry, polarized optical microscope, temperature dependent wide-angle X-ray scattering and grazing incidence wide-angle X-ray scattering (GIWAXS). We adopted a combination of experimental GIWAXS and molecular dynamics (MD) simulations to better understand the molecular packing of BTTT/dEO4 films, particularly when loaded with the ion conducting salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic conduction of BTTT/dEO4 is realized by the addition of LiTFSI, with the material able to maintain smectic phases up to r = [Li + ]/[EO] = 0.1. In this work, The highest ionic conductivity of 8 × 10 -3 S/cm was attained at an intermedium salt concentration of r = 0.05. It was also found that ion conduction in BTTT/dEO4 is enhanced by forming a smectic layered structure with irregular interfaces between the BTTT and EO4 layers and by the lateral film expansion upon salt addition. This can be explained by the enhancement of the misalignment and configurational entropy of the side chains, which increase their local mobility and that of the solvated ions. Our molecular design thus illustrates how, beyond the favorable energetic interactions that drive the assembly and ion solvating domains, modulation of entropic effects can also be favorably harnessed to improve ion conduction.

thin film electrochemical impedance spectroscopy↗

Positron lifetime measurements in chiral nematic liquid crystals

Positron lifetimes in the isotropic phases of chiral nematic liquid crystal formulations and their mixtures up to the racemic level were measured. The lifetime spectra for all liquid crystal systems were analyzed into three components. Although the individual spectra in the left- and right-handed components are identical, their racemic mixtures exhibit much larger orthopositronium lifetimes; these larger lifetimes indicate the presence of larger microvoids. This result is consistent with the reportedly higher thermodynamic stability and color play range in the racemic mixtures of chiral nematic liquid crystals.

Singh, Jag J.↗

Dynamic Time Multiplexing Fabrication of Holographic Polymer Dispersed Liquid Crystals for Increased Wavelength Sensitivity

Described herein is a new holographic polymer dispersed liquid crystal (HPDLC) medium with broadband reflective properties, and a new technique for fabrication of broadband HPDLC mediums. The new technique involves dynamic variation of the holography setup during HPDLC formation, enabling the broadening of the HPDLC medium's wavelength response. Dynamic variation of the holography setup may include the rotation and/or translation of one or more motorized stages, allowing for time and spatial, or angular, multiplexing through variation of the incident angles of one or more laser beams on a pre-polymer mixture during manufacture. An HPDLC medium manufactured using these techniques exhibits improved optical response by reflecting a broadband spectrum of wavelengths. A new broadband holographic polymer dispersed liquid crystal thin film polymeric mirror stack with electrically-switchable beam steering capability is disclosed. XXXX Described herein is a new holographic polymer dispersed liquid crystal (HPDLC) medium with broadband reflective properties, and a new technique for fabrication of broadband 10 HPDLC mediums. The new technique involves dynamic variation of the holography setup during HPDLC formation, enabling the broadening of the HPDLC medium's wavelength response. Dynamic variation of the holography setup may include the rotation and/or translation of one or more 15 motorized stages, allowing for time and spatial, or angular, multiplexing through variation of the incident angles of one or more laser beams on a pre-polymer mixture during manufacture. An HPDLC medium manufactured using these techniques exhibits improved optical response by reflecting 20 a broadband spectrum of wavelengths. A new broadband holographic polymer dispersed liquid crystal thin film polymeric mirror stack with electrically switchable beam steering capability is disclosed.

Fontecchio, Adam K.↗

Observations of Laminar Surface Shear Stress Patterns on the Sidewall of a Rectangular, Mach 3 Quiet Tunnel Using Liquid Crystal Coatings

A shear-stress--sensitive liquid crystal coating (LCC) was used to visualize the surface shear stress distribution on the flat sidewall of the MSU quiet supersonic tunnel as a function of flow stagnation pressure. Under conditions of quiet operation, the LCC color-change response indicated the existence of a nonuniform surface shear stress distribution. This shear pattern was characterized by an elongated, down st ream-point ing triangular region of relatively low shear, with its apex on and its axis coincident with, the sidewall centerline. This low-shear zone was bounded symmetrically by two regions of relatively higher shear; these high-shear zones originated within the concave-curvature portion of the nozzle, in the corners between the flat sidewall and the contoured upper and lower nozzle surfaces. A 3-D Navier-Stokes code was used to compute the pressure and surface shear distributions on the sidewall. Flow-expansion-induced transverse pressure gradients on the nozzle sidewall generated symmetric inflows from the corners towards the sidewall centerline; these inflows caused a thickening of the sidewall boundary layer along the centerline, resulting in lower shear stresses consistent with the liquid crystal results. Peripherally nonuniform laminar boundary layer development, and the associated stability of such complex 3-D flows, must be considered in quiet-tunnel applications using rectangular nozzles. A color video will be shown.

Reda, D.↗

Liquid crystals for high-altitude in-flight boundary layer flow visualization

A novel method for visualization of laminar to turbulent boundary layer transition in flight is presented, in which liquid crystal coatings are used to indicate the transition by a change of color (in response to the changes in the wall shear and the temperature). The liquid crystals applied to the wing surfaces were either cholesteric crystals formulated to be active between temperatures of 30 and 100 F or a sample of chiral nematic liquid crystals formulated to be active between -18 and -22 F. Liquid crystal coatings were shown to provide visualization data at flight altitudes and temperatures at which data could not be obtained previously. Flight evaluations were successfully conducted on a T-34C and a Learjet research aircraft at Mach numbers of up to 0.8 and altitudes of up to 50,000 ft. The time response during oscillating sideslip tests was very rapid. In wind tunnel tests, a hysteresislike behavior was observed in the liquid crystal coatings, possibly because of the lower dynamic pressures in wind tunnels as compared to flight.

Gall, P. D.↗

Investigation of CO2 Sorption Characteristics of Imidazolium Ionic Liquid Crystals

This work is focused on advancing of the understanding the carbon dioxide (CO2) sorption characteristics of imidazolium ionic liquid crystals based on the 1-alkyl-3-methylimidazolium (Cnmim) ionic liquid family. Specifically, the mechanism of sorption across the melting, liquid crystal, and isotropic liquid transitions is investigated for 1-tetradecyl-3-methylimidazolium tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-). A unique reversible CO2 occlusion was observed in 1-tetradecyl-3-methylimidazolium tetrafluoroborate (C14mim BF4) under rapid temperature quench from the liquid phases to the solid phase, while complete desorption occurred upon heating above the melting point (40 degrees C). In situ wide-angle x-ray scattering revealed that the lamellar structure of C14mim BF4 liquid crystal phases provides a high concentration of dynamically accessible anion and cation interaction sites for CO2, facilitating CO2 occlusion upon rapid solidification. The selective occlusion of CO2 in C14mim BF4 suggests a new mechanism for CO2 sorption processes.

08 HYDROGEN↗

Synthetic active liquid crystals powered by acoustic waves.

Active nematic materials combine orientational order with activity at the microscopic level. Current experimental realizations of active nematics include vibrating elongated particles, cell layers, suspensions of elongated bacteria, and a mixture of bio-filaments with molecular motors. The majority of active nematics are of biological origin. The realization of a fully synthetic active liquid crystal comprised of a lyotropic chromonic liquid crystal energized by ultrasonic waves, is reported. This synthetic active liquid crystal is free from biological degradation and variability, exhibits phenomenology associated with active nematics, and enables precise and rapid activity control over a significantly extended range. It is demonstrated that the energy of the acoustic field is converted into microscopic extensile stresses disrupting long-range nematic order and giving rise to an undulation instability and proliferation of topological defects. The emergence of unconventional free-standing persistent vortices in the nematic director field at high activity levels is revealed. The results provide a foundation for the design of externally energized active liquid crystals with stable material properties and tunable topological defect dynamics crucial for the realization of reconfigurable microfluidic systems.

active matter↗