Liquid Crystalline Polymer Films Research Articles

Phase Behaviors and Photoresponsive Thin Films of Syndiotactic Side-Chain Liquid Crystalline Polymers with High Densely Substituted Azobenzene Mesogens.

Azobenzene-containing polymers (azopolymers) are a kind of fascinating stimuli-responsive materials with broad and versatile applications. In this work, a series of syndiotactic C1 type azopolymers of Pm-Azo-Cn with side-chain azobenzene mesogens of varied length alkoxy tails (n = 1, 4, 8, 10) and different length alkyl spacers (m = 6, 10) have been prepared via Rh-catalyzed carbene polymerization. The thermal properties and ordered assembly structures of thus synthesized side chain liquid crystalline polymers (SCLCPs) have been systematically investigated with differential scanning calorimetry (DSC), polarized optical microscopy (POM) and variable-temperature small/wide-angle X-ray scattering (SAXS/WAXS) analyses. P10-Azo-C1 and P10-Azo-C4 with shorter alkoxy tails exhibited hierarchical structures SmB/Colob and transformed into SmA/Colob at a higher temperature, while P10-Azo-C8 and P10-Azo-C10 with longer alkoxy tails only displayed side group dominated layered SmB phase and transformed into SmA phase at higher temperatures. For P6-Azo-C4 with a shorter spacer only showed a less ordered SmA phase owing to interference by partly coupling between the side chain azobenzene mesogens and the helical backbone. More importantly, the series high densely substituted syndiotactic C1 azopolymer thin films, exhibited evidently and smoothly reversible photoresponsive properties, which demonstrated promising photoresponsive device applications.

Effect of polymer concentration on molecular alignment behavior during scanning wave photopolymerization

AbstractMolecularly aligned liquid-crystalline (LC) polymer films hold great promise for next-generation high-performance photonics, electronics, robotics, and medical devices. Photoalignment methods capable of achieving precise molecular alignment in a noncontact manner have been actively studied. Recently, we proposed the concept of using spatiotemporal photopolymerization to induce molecular diffusion and the resulting alignment, termed scanning wave photopolymerization (SWaP). The spatial gradient of the polymer concentration is the dominant factor in inducing the molecular diffusion and alignment of LCs. However, the effect of polymer concentration on molecular alignment behavior remains unclear. In this study, we performed SWaP at different exposure energies to modulate the polymer concentration during polymerization. We found that a certain polymer concentration was required to initiate the alignment. Furthermore, the phase diagram of the polymer/monomer mixtures and real-time observations during SWaP revealed that phase emergence and unidirectional molecular alignment occurred simultaneously when the polymer concentration exceeded 50%. Since SWaP achieves molecular alignment coincident with photopolymerization, it has the potential to revolutionize material fabrication by consolidating the multiple-step processes required to create functional materials in a single step.

Time‐Dependent Information Encryption in Liquid Crystalline Polymer with Programmable Glass Transition Temperature

AbstractTime‐dependent dynamic information encryption technology is a promising approach to enhancing the security and complexity of information transmission. Herein, a time‐dependent information encryption model from a liquid crystalline polymer (LCP) film with a programmable glass transition temperature (Tg) and gradually adjustable fluorescence is demonstrated. The programmable Tg is achieved by adjusting the degree of order of the LC molecules via a configuration interconversion of spiropyran‐based materials (SPBMs), which can convert between a V‐shaped colorless spiro (SP) and a rodlike dark‐colored merocyanine (MC) form. An LCP film obtained by visible light polymerization exhibits a lower Tg than UV light, because the SPBM molecules keep different configurations in the two films. By adjusting the ratio of two isomerization forms of SPBM molecules during the polymerization process, the Tg values of LCP films can change from 11.6 °C to 31.1 °C. Based on the isomerization rate of SPBM in the LCP films with different Tg, time‐dependent information encryption is successfully achieved.

Flexible films of main-chain luminescent liquid crystalline polymers containing renewable biobased bifuran moieties

Luminescent liquid crystalline polymers (LLCPs) have attracted great attention due to their potential applications in liquid crystal display, optical memory storage, organic light-emitting diode, and other fields. However, the fluorescence signals of LLCPs bearing conventional luminophores showing aggregation-caused quenching behavior are strikingly diminished or even vanish in the aggregated state. Herein, we have synthesized three main-chain LLCPs with α-cyanostilbene (CS) and bifuran units connected by different flexible spacer lengths via melt polycondensation. On the one hand, the CS unit acts as a rigid rod-like mesogen with aggregation-induced emission (AIE) characteristics. On the other hand, the renewable biobased bifuran moiety has been chosen because of two main reasons. One is it is a perfect alternative to the rigid fossil-based biphenyl group. The other reason is the addition of bifuran moiety is beneficial for the polycondensation and the extension of the chain length, leading to the enhancement of the toughness of LLCPs. Upon 365 nm UV light irradiation, these polymers undergo an irreversible Z/E isomerization in solution, while the [2 + 2] cycloaddition of CS chromophores occurs in the solid film. Importantly, the polymers display a good film-forming ability, so that the flexible thin films can be achieved by ordinary compression molding. Moreover, the fluorescent patterns can be directly printed on the flexible films on the basis of the [2 + 2] cycloaddition behavior, which shows their promising applications ranging from information storage to high-tech anti-counterfeiting.

The directed self-assembly of reflective liquid crystalline polymer films to form polarization-independent diffractive optical elements

The directed self-assembly of liquid crystal polymers enables significantly enhanced optical properties compared to conventional isotropic optical materials. The transmissive properties of these thin polymeric films have been extensively studied, but the exploration of reflective liquid crystalline polymeric materials films has received little attention due to challenges in producing large, high-quality self-assembled films. We explore here for the first time stacked polymer cholesteric liquid crystal thin films as a pathway to generate reflective diffractive optics that act on both hands of circularly polarized light independently. We present 3 unique exemplar cases with increasing design complexity to communicate the widespread potential of these unique thin polymer films.

Non-volatile optical memory based on cooperative orientation switching: improvement of recording speed and contrast by utilizing out-of-plane orientation mode.

Herein, we report a novel strategy toward non-volatile optical memory with high-contrast, high-speed recording, and non-destructive readout capability based on the cooperative out-of-plane orientation of a fluorescent dye doped into azobenzene liquid crystalline polymer film. By employing the out-of-plane orientation switching upon irradiation with UV light and thermal heating, high-contrast turn-on fluorescence switching was successfully achieved and the optical recording was demonstrated with non-destructive fluorescence readout capability. Furthermore, the recording speed and the fluorescence on/off contrast in the present system were dramatically improved compared to the previous in-plane orientation mode.

Nanostructured liquid-crystalline polymer films for ionic actuators: self-assembly of photopolymerizable ionic itaconate with an ionic liquid

The development of nanostructured polymers that create organized ion-transport pathways represents a promising approach for achieving efficient electrochemical conversion. A fascinating actuator was obtained from a polymer based on layered itaconate.

The Effect of a Topcoat with Amorphous Polymer Layers on the Mesogen Orientation and Photoalignment Behavior of Side Chain Liquid Crystalline Polymer Films

The mesogen orientations of liquid crystals are sensitive to the nature of the contacting surface. For side chain liquid crystalline polymer (SCLCP) films, most investigations have been conducted for thin films formed on a solid substrate surface such as glass, quartz and metal oxides, and little knowledge has been accumulated for SCLCP films whose top surface is covered by amorphous polymers. This work presents the effect of a topcoat with amorphous polymers placed on SCLCP films on the mesogen orientation and photoalignment behavior. When an SCLCP film that adopts a homeotropic mesogen orientation is covered with a glass plate or polymer layer, the mesogens turns to a random planar orientation. This planar orientation is favorable for efficient in-plane photoalignment by irradiation with linear polarized light. An in-plane order parameter exceeding 0.5 is readily obtained. Unexpectedly, a significant stabilization of the liquid crystal phase by over 10 °C is observed above the isotropization temperature of the SCLCP. These fundamental sets of knowledge should be significant in the fabrication of various polymer LC devices.

Bending Behaviors in Photoresponsive Liquid Crystalline Polymer Films Derived from a Hockey Stick-Shaped Reactive Mesogen

Bending Behaviors in Photoresponsive Liquid Crystalline Polymer Films Derived from a Hockey Stick-Shaped Reactive Mesogen

Reprogrammable Humidity-Driven Liquid Crystalline Polymer Actuator Enabled by Dynamic Ionic Bonds.

Liquid crystalline polymer (LCP) is a promising candidate in the design and fabrication of intelligent soft materials due to the combination of programmable anisotropy and elasticity. Here, a novel strategy to fabricate reprogrammable humidity-responsive LCP materials enabled by dynamic ionic cross-links were put forward. The prepared LCP film deforms reversibly with the change of relative humidity (RH). However, the humidity responsivity loses after soaking the film into CaCl2 solution because of the lock of hygroscopic groups by the formed ionic bonds. By selectively cross-linking specific regions of the LCP film, distinctive humidity-driven motions of the film could be realized. More interestingly, by the EDTA-2K solution treatment, ionic cross-links can be interrupted, leading the LCP film responsive to humidity again. Thanks to feasibly removable ionic cross-links, the humidity-directed soft actuator was totally reprogrammable. The behavior of the novel actuator could be manipulated by either the mesogens alignment or the spatially ionic treatment, providing a feasible but robust strategy to fabricate complex humidity-driven soft robots.

Photoindeuced bending behavior of uniaxial aligned crosslinked NBA liquid crystalline polymer films

Crosslinked liquid crystal polymers (CLCPs) have recently attracted much attention because they exhibit unique properties in stimuli responsiveness. We have recently focused on the photoinduced deformation behavior of CLCP containing N-benzylideneaniline (NBA) as a photoresponsive moiety. We prepared two types uniaxially aligned NBA-containing crosslinked liquid crystalline polymer film, homogeneous and homeotropic, and evaluated its photomechanical properties. The initial alignment of photoactive mesogens significantly affects the bending behavior of the CLCP films: the homogeneous films bent toward the irradiation direction of the actinic UV light, while the homeotropic films bent away from the light source.

Photo-triggered surface relief formation of polystyrene films based on the Marangoni flow driven by a surface photoresponsive skin layer

Surface relief gratings (SRGs) are widely investigated in azobenzene-containing polymer films. We have recently demonstrated that a photoresponsive azobenzene layer existing only at the surface of a non-photoresponsive liquid crystalline polymer film can induce mass migration by patterned UV light irradiation, resulting in the SRG structure. This process is explained by the Marangoni flow triggered by the photoinduced surface tension change of the surface layer. In this work, we newly propose that the same strategy is applicable to an amorphous polymer material of polystyrene. The results obtained here indicate that photoinduced SRG formation is expanded for general amorphous polymers.

Hydrogen Bond Enhances Photomechanical Swing of Liquid-Crystalline Polymer Bilayer Films.

Mechanical swing is common in nature, such as sound waves, wingbeat of birds, and heartbeat, which is important to convert input energy into continuous motion. Here, we report a photodriven swing actuator composed of commercially available polyimide (Kapton) and azobenzene-containing liquid-crystalline polymers. The liquid-crystalline polymers act as the photoactive layer, which were synthesized by copolymerization of one benzenecarboxylic acid-containing monomer (M6BCOOH) and one azobenzene-containing monomer (M6ABOC2) with different molar ratios. The Kapton layer with a high elastic modulus is photoinert and functions as the substrate layer. After thermal annealing, the film displays chaotic swing under continuous irradiation of actinic light. Interestingly, the swing amplitude is greatly enhanced by the existence of supramolecular hydrogen bonding in liquid-crystalline polymer films. It is the introduction of M6BCOOH to the copolymer that accelerates the trans-cis photoisomerization rate of azobenzenes. Also, it forms a hydrogen bond as physical crosslinking sites, enabling the polymer film to work as a whole. Thus, it enhances the driving force for photomechanical deformation. Moreover, it improves the elastic modulus of the photoactive layer and modulates the swing behavior of the bilayer strip. More importantly, the formation of a hydrogen bond in the form of acidic dimers has a spatial confinement effect, extending the timescale of photodriven swing. The photomechanical self-vibration of the bilayer film can be ascribed to the combination of the photoisomerization process of azobenzenes with the local photosoftening effect of liquid-crystalline polymers.

Photo-Luminescence Characteristics of Aligned Organic Fluorescent Dye in Liquid Crystalline Polymer Films for Photosynthesis Promotion

Photo-Luminescence Characteristics of Aligned Organic Fluorescent Dye in Liquid Crystalline Polymer Films for Photosynthesis Promotion

Photo-triggered large mass transport driven only by a photoresponsive surface skin layer

Since the discovery 25 years ago, many investigations have reported light-induced macroscopic mass migration of azobenzene-containing polymer films. Various mechanisms have been proposed to account for these motions. This study explores light-inert side chain liquid crystalline polymer (SCLCP) films with a photoresponsive polymer only at the free surface and reports the key effects of the topmost surface to generate surface relief gratings (SRGs) for SCLCP films. The top-coating with an azobenzene-containing SCLCP is achieved by the Langmuir–Schaefer (LS) method or surface segregation. A negligible amount of the photoresponsive skin layer can induce large SRGs upon patterned UV light irradiation. Conversely, the motion of the SRG-forming azobenzene SCLCP is impeded by the existence of a LS monolayer of the octadecyl side chain polymer on the top. These results are well understood by considering the Marangoni flow driven by the surface tension instability. This approach should pave the way toward in-situ inscription of the surface topography for light-inert materials and eliminate the strong light absorption of azobenzene, which is a drawback in optical device applications.

Temperature-Dependent Gas Transport Behavior in Cross-Linked Liquid Crystalline Polyacrylate Membranes

Stable, cross-linked, liquid crystalline polymer (LCP) films for membrane separation applications have been fabricated from the mesogenic monomer 11-(4-cyanobiphenyl-4′-yloxy) undecyl methacrylate (CNBPh), non-mesogenic monomer 2-ethylhexyl acrylate (2-EHA), and cross-linker ethylene glycol dimethacrylate (EGDMA) using an in-situ free radical polymerization technique with UV initiation. The phase behavior of the LCP membranes was characterized using differential scanning calorimetry (DSC) and X-ray scattering, and indicated the formation of a nematic liquid crystalline (LC) phase above the glass transition temperature. The single gas transport behavior of CO2, CH4, propane, and propylene in the cross-linked LCP membranes was investigated for a range of temperatures in the LC mesophase and the isotropic phase. Solubility of the gases was dependent not only on the condensability in the LC mesophase, but also on favorable molecular interactions of penetrant gas molecules exhibiting a charge separation, such as CO2 and propylene, with the ordered polar mesogenic side chains of the LCP. Selectivities for various gas pairs generally decreased with increasing temperature and were discontinuous across the nematic–sotropic transition. Sorption behavior of CO2 and propylene exhibited a significant change due to a decrease in favorable intermolecular interactions in the disordered isotropic phase. Higher cross-link densities in the membrane generally led to decreased selectivity at low temperatures when the main chain motion was limited by the lack of mesogen mobility in the ordered nematic phase. However, at higher temperatures, increasing the cross-link density increased selectivity as the cross-links acted to limit chain mobility. Mixed gas permeation measurements for propylene and propane showed close agreement with the results of the single gas permeation experiments.

Photoinitiated Marangoni flow morphing in a liquid crystalline polymer film directed by super-inkjet printing patterns

Slight contaminations existing in a material lead to substantial defects in applied paint. Herein, we propose a strategy to convert this nuisance to a technologically useful process by using an azobenzene-containing side chain liquid crystalline (SCLCP) polymer. This method allows for a developer-free phototriggered surface fabrication. The mass migration is initiated by UV-light irradiation and directed by super-inkjet printed patterns using another polymer on the SCLCP film surface. UV irradiation results in a liquid crystal-to-isotropic phase transition, and this phase change immediately initiates a mass migration to form crater or trench structures due to the surface tension instability known as Marangoni flow. The transferred volume of the film reaches approximately 440-fold that of the polymer ink, and therefore, the printed ink pattern acts as a latent image towards the amplification of surface morphing. This printing-aided photoprocess for surface inscription is expected to provide a new platform of polymer microfabrication.

Travelling waves on photo-switchable patterned liquid crystal polymer films directed by rotating polarized light.

Nature employs travelling waves to generate propulsion of fluids, cells and organisms. This has inspired the development of responsive material systems based on different external triggers. Especially light-actuation is suitable because of its remote control and scalability, but often complex, moving light sources are required. Here, we developed a method that only requires flood exposure by rotating the linear polarization of light to generate propagating surface waves on azobenzene-modified liquid crystalline polymer films. We built a photomechanical computational model that accounts for the attenuation of polarized light and trans-to-cis isomerization of azobenzene. A non-uniform in-plane distribution of the liquid crystal molecules allows for the generation of travelling surface waves whose amplitude, speed and direction can be controlled through the intensity, rotation direction and rotation speed of the linear polarization of a light source. Our method opens new avenues for motion control based on light-responsive topographical transformations for application in microfluidic lab-on-chip systems and soft robotics.

Photoinduced deformation and isomerization of azobenzene liquid-crystalline polymer films at cryogenic temperature

We prepared 2 types of crosslinked liquid-crystalline polymers (CLCPs) (polyacrylates) with the same side-chain length but a different position of an azobenzene moiety in the side chain. We evaluated photoinduced deformation behavior of the CLCP films and photoisomerization behavior of azobenzene in the films at cryogenic temperature. Azobenzene moieties in both CLCP films showed no trans-cis isomerization and neither film exhibited bending behavior upon irradiation with UV light in liquid nitrogen [77 K]. On the other hand, when the film included azobenzene with a long spacer and a short tail, cis-trans isomerization of azobenzene and photoinduced deformation were observed in liquid nitrogen.

Self-organized wrinkling of liquid crystalline polymer with plasma treatment

Abstract