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Rewritable paper, as an environment-friendly approach of information transmission, has potential possibility to conserve energy and promote a sustainable development of our society. Recently, photonic crystals (PCs) have become a research hotspot in the development of rewritable paper. However, there are still many shortcomings that limit the further application of PC paper, such as slow response sensitivity, short-cycle lifetime, poor storage stability, and so on. Herein, we constructed an optically rewritable azobenzene inverse opals (AZOIOs) with a thin film (ca. 1 μm) plated on an inverse opal structure based on the UV/vis switchable structure color of the sample. The top thin film acts as a protective layer to avoid the large deformation of the pore structure and the bottom inverse opal structure with refractive index/pore structure change that provides reversible structure color. Large, reversible, and rapid bandgap shift (ca. 60 nm, 2 s) of AZOIOs can be repeated more than 100 times under alternating UV/vis irradiation based on isomerization of high content of the azobenzene group. On-demand long-time preservation pattern can be obtained by the appearance of azobenzene's intrinsic color. The proof of concept for rewritable PC paper is demonstrated herein. Such inkless rewritable colorful paper paves a way for developing novel display technology.

Photonic shape memory (SM) polymers based on liquid crystalline blue phase (BP) films have been fabricated by self-assembly and subsequent photopolymerization of liquid-crystal mixtures. These freestanding BP films exhibit narrow photonic band gaps and high reflectivity in the visible wavelength range. Multiple blue-shift colors are achieved by SM programming process at different mechanical pressures. The blue-shift colors can be attributed to a decrease of effective BP pitch along the viewing direction caused by the compressed deformation of the BP films, which are confirmed by a three-dimensional interometric profile. The deformed BP films can recover to their original shapes and reflecting colors by heating the polymer films to temperatures above the glass-transition temperature. Quantitative relationships between the shape change and optical response are established for understanding this SM effect. What is more, the temporary photonic patterns can be reversibly written and erased for dozens of cycles without apparent degradation, making these freestanding BP films appealing as rewritable photonic papers and optical sensors.

Fabrication of liquid-crystalline polymer networks with periodic nanoscale features is highly desired for photonic applications. Here, a printable photonic polymer coating has been fabricated from a monodomain liquid crystalline blue phase (BP) network. The BP polymer coating with high reflectivity is covalently linked to the glass substrate, which can be patterned by using an LC-ink to swell the network. The degree of swelling depends on the printed amount of LC-ink which can be controlled through adjusting the voltages of the inkjet printer. Arbitrary multicolour patterns covering the visible spectrum from 451 to 618 nm can be printed and erased multiple times, making these BP polymer coatings promising as rewritable photonic papers and responsive photonic materials.

We prepared crosslinked azobenzene main-chain liquid-crystalline polymers (MCLCPs), in which the exchange of crosslinks can be brought about by transesterification reactions. The exchangeab...

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...

Poly(4-vinylpyridine) (P4VP) brushes were grafted onto a substrate via Cu(0)-mediated atom transfer radical polymerization and 1-pyrenebutyric acid (PBA) was incorporated into the brushes t...

Janus/gradient actuating materials have become promising candidates for actuating devices. The fabrication of functional Janus gradient actuators remains a challenge. This paper presents a facile fabrication of a hydrophilic/hydrophobic Janus inverse opal actuator via gradient infiltration. The Janus characteristics of the fabricated actuator were attributed to gradient infiltration along the thickness of the film caused by the gradient light intensity and the distinct polymerization behavior of ionic liquids and methyl methacrylate in the methanol system. The Janus film demonstrated directional bending upon water vapor adsorption, with a bending angle approaching 1440° in 4 s, accompanied by structure color/optic signal alteration. The actuating behaviors were effectively modulated by changing the composition of the film and the solvent system. Promising applications of this Janus solvent actuator were demonstrated in two sets of tests: driving an engine and lifting cargo. This work provides insight into the design and fabrication of multifunctional humidity-actuating materials.

The change in shape inducible in some photo-reversible molecules using light can effect powerful changes to a variety of properties of a host material. The most ubiquitous natural molecule for reversible shape change is the rhodopsin–retinal protein system that enables vision, and this is perhaps the quintessential reversible photo-switch. Perhaps the best artificial mimic of this strong photo-switching effect however, for reversibility, speed, and simplicity of incorporation, is azobenzene. This review focuses on the study and application of reversible changes in shape that can be achieved with various systems incorporating azobenzene. This photo-mechanical effect can be defined as the reversible change in shape inducible in some molecules by the adsorption of light, which results in a significant macroscopic mechanical deformation of the host material. Thus, it does not include simple thermal expansion effects, nor does it include reversible but non-mechanical photo-switching or photo-chemistry, nor any of the wide range of optical and electro-optical switching effects for which good reviews exist elsewhere.

Crosslinked liquid-crystalline polymers (CLCPs) containing photochromic moieties show macroscopic deformation upon irradiation with light. This conversion of light energy into mechanical work is attributed to photosynergetic amplification of changes at multiscale: from nano to macro. This chapter focuses on recent progress of photomobile polymer materials to achieve versatile design as soft actuators. Three approaches are detailed: incorporation of amorphous polymers into CLCPs to control mechanical and photoresponsive properties, reshaping of CLCPs into various three-dimensional architectures through the rearrangement of network structures, and application of two-photon absorption processes to enhance the spatial selectivity of photoactuation.

Composite systems of liquid crystals (LCs) and polymers have been extensively studied in various forms such as polymer-dispersed LCs and polymer-stabilised LCs. Blending LCs and polymers is an effective approach to design functional materials with stimuli responsiveness and durability. Here, we show the development of a novel composite material with crosslinked azobenzene LC polymer (PAzo) and poly(dimethylsiloxane) (PDMS) aiming at the improvement of photomobile polymer materials in mechanical properties. The composite films were prepared by photopolymerisation of azobenzene monomers in PDMS elastomers. By forming phase separated structure, in which PAzo chains were dispersed in PDMS matrix, fracture strain of photomobile polymer materials was significantly enhanced. The composite film showed macroscopic bending upon irradiation with UV light. This result implies that PAzo domains in polymer matrix can work as microactuators to afford macroscopic deformation of the whole film. The further improve...

We developed a novel block copolymer composed of poly(ethylene oxide) (PEO) and polymethacrylate functionalized with liquid–cryst-alline oligothiophene by using the atom transfer radical polymeriza...

Crosslinked liquid-crystalline polymers (CLCPs) containing azobenzene moieties show reversible macroscopic deformation upon irradiation with light. The deformation of CLCPs strongly depends on alig...

We prepared crosslinked azotolane liquid-crystalline polymer (LCP) films doped with a stilbene derivative (two-photon chromophore) utilizing an interpenetrating polymer network (IPN) structure. The IPN films bend toward the light source upon irradiation with femtosecond laser pulses at 600 nm, which can excite the stilbene derivative by two-photon absorption. The bending speed of the IPN films increases with the square of the laser pulse intensity, which is compelling evidence for the two-photon processes.

The chemical functionalization of nano-carbon materials such as single-walled carbon nanotubes (SWNTs) and graphene by metal complexes has attracted much attention due to the multitude of potential applications in efficient energy-conversion and -storage devices. The solubilization and single-chirality separation of SWNTs by surface modifications is a useful approach to manipulate SWNTs in the liquid phase. In this study, several Ru and Fe complexes containing two terminal quadruple hydrogen-bonded (H-bonded) ureidopyrimidinedione (UPy) groups were synthesized (Ru-1, Ru-UPy, and Fe-UPy) to form H-bonded supramolecular polymers by self-association. In order to control the solubility of these complexes in nonpolar solvents, Ru-UPy and Fe-UPy were endowed with long alkyl side chain groups in the coordinated 2,6-bis(benzimidazol-2-yl)pyridine ligand, while Ru-1 and Ru-2 do not contain such long alkyl chain groups. AFM measurements revealed that Ru-1, Ru-UPy, and Fe-UPy form a fiber-like network morphology on HOPG surfaces, arising from the H-bonded aggregation. However, only Ru-UPy and Fe-UPy are able to solubilize SWNTs effectively upon simple sonication in chlorobenzene. After the solubilization of a CoMoCAT® SWNT in chlorobenzene using Ru-UPy or Fe-UPy, UV-Vis-NIR spectra showed sharp peaks at 996 and 1150 nm, which were attributed to (6, 5) and (7, 6)-SWNTs. The Raman spectra of the solubilized SWNTs revealed peaks that were attributed to the radial breathing mode (RBM), which suggests an enrichment of semiconducting SWNTs, i.e., Ru-UPy and Fe-UPy are able to selectively solubilize semiconducting SWNTs. Cyclic voltammograms of films of SWNTs covered with Ru-UPy or Fe-UPy on ITO electrodes showed a well-defined adsorbed Ru(ii/iii) or Fe(ii/iii) wave. Upon addition of acid, the redox response from the adsorbed H-bonded Ru-UPy and Fe-UPy disappeared and only SWNTs were left on the ITO electrode. Moreover, the Ru-UPy/SWNT and Fe-UPy/SWNT hybrids exhibited non-linear I-V characteristics.

A reversible solvent-sensitive actuator with a continuous bending/debending process is fabricated by over-infiltration of liquid crystal monomers into a colloidal template and subsequent photopolymerization. The fabricated actuator exhibits a maximum bending angle of 1080° in 1.58 s in dichloromethane, accompanied with successive debending in 0.32 s. The behavior of the actuator can be modulated by changing the solvent type, film thickness/length and molar ratio of A6OCB/C6M. This study will provide an important experimental and theoretical basis for the development of novel actuators.

We developed photomobile polymer materials with interpenetrating polymer network (IPN) structures composed of crosslinked liquid-crystalline azobenzene polymer (PAzo) and poly(dimethylsiloxane) (PDMS). By introducing PDMS into a PAzo template network, IPN was formed without disturbing the alignment of mesogens in the PAzo network. The films showed macroscopic bending behavior upon irradiation with UV and visible light. Although the IPN film showed a phase separated structure, the bending speed was significantly enhanced compared with the pristine film of PAzo, thanks to the soft nature of PDMS. The present method of preparing IPNs can be a promising approach to combine PAzo with various polymers and enhance the mechanical and photoresponsive properties.

We prepared a block copolymer composed of polythiophene (PT) with cinnamate groups and poly(ethylene oxide) (PEO), which are connected through a cleavable acetal bond, aiming at constructing donor/acceptor heterostructures through post deposition of acceptor molecules into donor template networks. The block copolymer films showed phase-separated structures with domain sizes of 10–100 nm. Irradiation with UV light afforded crosslinked films through [2+2] cyclodimerization of cinnamate groups. Then, PEO was removed by acidic cleavage of the acetal bond, yielding PT template networks. Taking advantage of the insoluble networks, a fullerene derivative was deposited into the PT templates through a spin-coating process to form donor/acceptor heterostructures. The introduction of the fullerene derivative was confirmed by UV-Vis absorption and fluorescence spectroscopy. This strategy of depositing acceptor molecules into donor template networks, instead of spin-coating from donor/acceptor blend solutions, could be applied to improve the phase-separated structures and power conversion efficiencies of polymer solar cells.

This paper presents a unique lyophilic but nonwettable property of organosilane-polymerized carbon dots inverse opals photonic crystals (SiCDPCs) with closed-cell structure. Little stopband shift was observed for the SiCDPCs when being immersed into the solvents such as isopropanol, olive oil, DMSO, hexane, silicone oil, ethanediol, etc. but keeping lyophilic property. This could be attributed to the combined effect of closed-cell structure and the unique chemical composition of SiCDPCs. Furthermore, more than 30 kinds of organic solvents had been investigated, it was found that there were two kinds of factors that affected the stopband shift upon solvent's immersing; one was the polarity of solvent, and the other one was the viscosity of solvent. That is, mainly nonpolar or high viscosity solvents showed lyophilic but nonwettable property. The distinct solvent-responsive behaviors of the SiCDPCs toward polar/nonpolar solvents had been utilized for the fabrication of 2D/3D pattern. Additionally, the as-prepared SiCDPCs showed improved optical limiting property, excellent low-temperature resistance, and abrasion tolerant property. It is of great importance for the development of multifunctional novel coating materials and creation of novel optical devices.

We have synthesized a photo-crosslinkable polythiophene copolymer functionalized with a cinnamate moiety to improve the stability of organic photovoltaic (OPV) cells. The active layer of OPV cells is generally bulk heterojunction (BHJ) that consists of two or more organic semiconductors. When BHJ forms a micro-phase-separated structure with a blend of two organic materials, its structure inclines to change into a macro-phase-separated one after some time. To stabilize the BHJ morphology, we used a crosslinkable polymer containing a cinnamate moiety. The copolymer film became insoluble after UV irradiation because of [2+2] dimerization of the cinnamate groups.

We synthesized polymers containing a liquid-crystalline (LC) oligothiophene moiety in the side chain. This oligothiophene shows LC behavior between 101°C and 194°C in its original form, while when incorporated into the side chains of a polymer, the resultant polymer showed a nematic phase in a much wider temperature range. Thin films of these polymers showed nano-phase-separated structures with domain sizes of 15–40 nm upon annealing.

Crosslinked liquid-crystalline polymers (CLCPs) show unique behavior of deforming macroscopically when stimulated with heat, electricity and light. However, they cannot be remolded and reshaped once prepared. Here, we designed crosslinked polysiloxane with side chain mesogens that contain exchangeable crosslinking points based on transesterification between phenyl benzoates and hydroxy groups. After the formation of a polymer network, a base catalyst was introduced into the CLCP. When heated at 80°C, a piece of the CLCP was reshaped into a film and separate pieces of the CLCP were fused together, indicating that the CLCP is remoldable.

We developed interpenetrating polymer networks (IPNs) composed of a crosslinked azobenzene liquid-crystalline polymer (PAzo) and poly(alkyl methacrylate)s (PAMAs). When irradiated with UV and visible light, the IPN films showed reversible bending. The photoresponsive and mechanical properties of PAzo films were significantly enhanced by incorporation of the PAMA components.

We prepared photomobile polymer materials composed of crosslinked azobenzene liquid-crystalline polymers (LCPs) and methacrylates with interpenetrating polymer network (IPN) structures, and explored their photoresponsive behavior. The IPN films exhibited reversible bending upon photoirradiation. In addition, the durability of the IPN films was much higher than that of the pristine crosslinked azobenzene LCP films.

Various fabrication methods of photomobile polymer materials containing photochromic moieties have been developed to improve their photoresponsive and mechanical properties. Here, we newly prepared photomobile polymer materials with interpenetrating polymer network (IPN) structures. The IPN films, which are composed of azobenzene liquid crystalline polymer (LCP) and polymethacrylates, showed reversible bending behavior upon exposure to UV and visible light. Bending speed of the IPN films became higher with decreasing glass-transition temperature of polymethacrylate components. The IPN film containing poly(dodecyl methacrylate) showed faster bending than the pristine azobenzene LCP film.

The synthesis and characterization of organic nanoparticles composed of a polymer network of azobenzene moieties and capable of reproducible, photoinduced mechanical actuation are reported. The molecules within the nanoparticles undergo co-ordinated, reversible isomerization between cis- and trans- conformations in response to ultraviolet and visible electromagnetic radiation, resulting in a reversible 20% height contraction of nanoparticles adsorbed on a substrate. The kinetics of the actuation response as a function of light intensity and duration are reported and closely match the molecular kinetics of azobenzene photoisomerization. The results support the proposed mechanism of co-ordinated molecular conformational changes resulting in observable nanoscale actuation.

Incorporation of dynamic covalent bonds into photomobile liquid-crystalline elastomers with a polysiloxane backbone enables the alignment of mesogens and macroscopic shapes to be controlled through the rearrangement of the network topology, even after the formation of chemically crosslinked networks. The reshaped samples show various sophisticated 3D motions upon irradiation with UV and visible light, depending on their initial shapes.

Organic light-emitting diodes (OLEDs) based on conjugated polymers exhibiting polarized emission have attracted much attention because of their potential as backlights for conventional liquid crystal (LC) displays and 3-D displays. We have reported a new series of LC polymers based on donor-acceptor architecture containing an oxadiazole (OXD) and several amine moieties in the same side chain, which exhibit bipolar character with a wide energy band gap. In this study, to develop phosphorescent OLEDs with polarized emission, we synthesized a platinum complex, Pt(4-decyloxy)salen, with emitting property, and fabricated the device consisting of Pt complex as a guest and LC polymers as a host material. The Pt complex exhibited high thermal stability, good solubility and an emission peak at 530 nm in dichloromethane. To obtain electroluminescense from the Pt complex, we fabricated ITO/rubbed PEDOT:PSS/Pt(4-decyloxy)salen:host polymer/MgAg devices. The devices emitted a yellowish green light, which was dominated...

Organic light-emitting diodes (OLEDs) based on chromophore-containing liquid crystals (LCs) can emit polarized light due to self-assembly of mesogenic chromophores. The stability of LC phases in LC polymers with a mesogenic group in the main chain is higher than that in the polymers containing a mesogenic group in the side chain. In this study, a novel family of polyesters containing a carbazole moiety as a hole-transporting unit and an oxadiazole (OXD) moiety as an electron-transporting unit in the main chain, P10-DOXDCz and P16-DOXDCz, were designed and synthesized. These polyesters were prepared by transesterification of N-hexyl-3,6-di[2-([1,3,4]oxadiazol-5-yl)-4-methylbenzoate]carbazole and 1,10-decanediol or 1,16-hexadecanediol at 220 °C for 20 h. They showed a nematic phase. Both P10-DOXDCz and P16-DOXDCz emitted intense blue fluorescence with a maximum at 439 nm and 450 nm in thin films, respectively, and their fluorescence quantum yields were 0.74 and 0.81 in solution, respectively. Both compounds...

We present a simple way to control the photoinduced bending direction of azobenzene-containing cross-linked liquid-crystalline polymers. By changing the location of the photoactive azobenzene moieties from cross-links to side-chains, the bending direction of the sample is reversed under identical irradiation conditions. In addition to providing a versatile route toward directionality control of the photoinduced macroscopic motions, this observation highlights the complicated nature of the photomechanical response of azobenzene-containing cross-linked liquid-crystalline polymers, showing that the photomobile behavior can be determined by seemingly small details on the materials design.

A new class of polymer materials has been developed that can convert light energy directly into mechanical work, and show a variety of three-dimensional movements simply from exposure to light. These polymer materials can be fabricated into any shape and size using photolithographic methods and it is expected they will be developed for various applications. In this paper recent progress of this interesting class of polymer material is reviewed.

We have investigated the photoresponsive behavior of homogeneously aligned low-azobenzene-concentration crosslinked liquid-crystalline polymers. We compared the thermal contraction and photocontraction of the films, and show that upon UV irradiation, they bend efficiently towards the actinic light source. The photoinduced bending is studied both under continuous-wave irradiation and irradiation with nanosecond pulses. Pulsed irradiation revealed that the photomechanical response can take place within sub-millisecond time scale, and that even a single laser pulse can cause the sample to bend.

Crosslinked azobenzene liquid-crystalline polymer films have been prepared by in-situ photopolymerization, and their photoinduced changes in birefringence and stress on macroscopic motion were investigated. Upon exposure to UV light, the film bent toward an actinic light source along the rubbing direction, and the bent film also reverted to the initial flat state after exposure to visible light at room temperature. Moreover, the birefringence simultaneously decreased and the stress was generated upon UV irradiation. These results indicate that the molecular alignment in the film becomes disordered by trans-cis photoisomerization of the azobenzene moieties and the resultant contraction of the film generates the stress.

We prepared crosslinked azobenzene liquid-crystalline polymer brushes on flexible polymer films by surface-initiated atom transfer radical polymerization and a subsequent crosslinking reaction. Reversible isomerization of azobenzene moieties was observed in the crosslinked films upon irradiation with UV and visible light. Upon exposure to linearly polarized UV light, the films bent slightly along the polarization direction of light toward an actinic light source. After turning off the UV light, the films maintained the bent shape, and then reverted to the initial form by irradiation with visible light. We have successfully developed a novel photomobile material with crosslinked azobenzene liquid-crystalline polymer brushes.

Uniaxially aligned azobenzene liquid-crystalline polymers crosslinked by hydrogen bonding can deform in response to actinic light. The polymers can be precisely shaped due to high processability of hydrogen-bonded polymers. The mechanical properties of the polymer fibers were improved by introducing single-walled carbon nanotubes as a filler material. Because of weak hydrogen bonding, starting materials can be recovered, reused and recycled, which is very useful in view of chemical resource utilization.

We proposed a new approach to fabricate bilayer films with a crosslinked azobenzene liquid-crystalline (LC) polymer. The polyethylene (PE) substrates were coated with linear azobenzene LC polymers, and then the azobenzene layers were crosslinked by irradiation with electron beams (EBs). In the EB-irradiated films with ordered azobenzene moieties, exposure to UV light caused trans-cis isomerization and the change in alignment of azobenzene moieties. Bending of the bilayer films could be induced toward an actinic light source when they were irradiated from the side of the azobenzene layer, while they bent away from the actinic light source upon UV irradiation from the side of the PE layer. In both cases, the bent films reverted to the initial flat state by turning off the light, which could be repeated at room temperature.

Crosslinked liquid-crystalline polymer films with a different content of an azobenzene moiety were prepared by in-situ photopolymerization, and their photoresponsive behavior was investigated. Observation of the films by polarized absorption spectroscopy and polarizing optical microscopy has revealed that the azobenzene moieties are aligned along the rubbing direction in the films. Upon irradiation with UV light, a film with 5 mol% of the azobenzene bent toward an actinic light source along the rubbing direction. The bent film reverted completely to the initial state upon irradiation with visible light. On the other hand, films with 3 and 1 mol% of the azobenzene showed no obvious bending by continuous irradiation with UV light. The bent film also reverted to the flat state upon continuous irradiation with UV light.

A telechelic poly(N-isopropylacrylamide) (PNIPAM) with azobenzene end-groups (telechelic Az-PNIPAM) was prepared by reversible addition-fragmentation chain transfer (RAFT) free radical polymerization of NIPAM. This polymer self-assembles in cold water forming nanoparticles with a hydrodynamic radius (R H) of 8 nm and an aggregation number of 29 chains. The thermoresponsive behavior of Az-PNIPAM in water was investigated by turbidimetry and light scattering. In addition, the photoresponsive behavior of aqueous Az-PNIPAM was investigated by monitoring the changes with temperature of the solution and transmittance at 650 nm before and after irradiation at 366 nm.

We studied the effects of concentration and location of azobenzene chromophores on the photoinduced deformation of crosslinked liquid-crystalline polymers (CLCPs). The concentration of azobenzene chromophores in CLCP affects the degree of isomerization of azobenzene moieties and the macroscopic deformation behaviour of the films while the location of azobenzene moieties determines the contraction force and length.

Blue-emitting polymers based on a donor-acceptor architecture composed of oxadiazole and carbazole moieties containing various substituted groups in the same side chain were used as a host polymer in phosphorescent polymer light-emitting diodes (PhPLEDs). The polymer containing N-methylcarbazole showed a liquid-crystalline (LC) phase above its glass transition temperature but the other polymer containing N-ethylhexylcarbazole exhibited an amorphous phase. The single-layer PLEDs using these polymers exhibited blue emission with peaks from 430 to 440 nm. To examine the LC polymer (LCP) and the amorphous polymer as host materials, we fabricated simple devices using Ir(ppy)3 and (btp)2lr(acac) as phosphorescent dopants at various doping concentrations. The device composed of lTO/PEDOT-PSS/2 wt% of (btp)2Ir(acac) doped into LCP/MgAg showed intense red light (0.67, 0.32) with the luminance efficiency of 4.7 cd/A. The luminance efficiency of the PhPLEDs using the LCP was higher than that of the PhPLEDs using the...

Two azobenzene-containing block copolymers with an oxyethylene (P1) or an alkyl (P2) spacer in the side chain were prepared by atom transfer radical polymerization (ATRP). Neither of the block copolymers with a low azobenzene content showed a liquid-crystalline phase. However, their glass transition temperatures (T gs) were lowered by introducing flexible spacers. In particular, T g was lowered by about 30°C in P1. Their photoalignment and holographic behavior was investigated at various temperatures in thin films. Rapid changes in refractive index were induced in the P1 films upon irradiation at a temperature below T g. But the photoinduced birefringence in the P1 film was lower than that in the P2 films. Similar results were obtained in holographic recording. The azobenzene-containing block copolymer with the oxyethylene spacer (P1) used in this study has potential application for dynamic hologram.

We prepared homogeneously aligned azobenzene liquid-crystalline elastomer (LCE) films with low T g and explored their photomechanical properties. Upon irradiation with UV light, the films bent toward a light source at room temperature. The mechanical force generated upon exposure to UV light was evaluated by thermomechanical analysis. It was found that the mechanical force generated by photo-irradiation increased with an increase in the cross-linking density. In particular, an LCE film containing 80 mol% azobenzene cross-linker produced a force of over 1 MPa by photo-irradiation, which enabled the film to lift an object 20 times heavier than itself. The degree of contraction by photo-irradiation increased with an increase in temperature and light intensity. Bending could be brought about by more than 5000 times with periodic irradiation. Furthermore, it was found that the LCE films exhibited bending and unbending behaviour by irradiation with sunlight.

Laminated films composed of a flexible plastic sheet and a crosslinked azobenzene liquid-crystalline polymer (CLCP) layer with different initial alignment of azobenzene mesogens were prepared by thermal compression bonding of a CLCP film and an unstretched low-density polyethylene (PE) film with an adhesion layer. In both laminated films with a homogeneous alignment of mesogens and a homeotropic one, large movements could be induced by irradiation with UV light at room temperature. A partly laminated film with homogeneous CLCP bent from both ends of the whole film, while one with homeotropic CLCP bent up from the center of the film toward the light source. These results indicate that we enable plastic films with no photoresponsive property to move flexibly upon photoirradiation just by laminating the CLCP layers partly, and the photoinduced motions of the laminated films are completely dependent on the alignment direction of the mesogens in the CLCP layers. In addition, it was found that the maximum stres...

A block copolymer containing an azobenzene (Az) moiety in the side chain was prepared by atom transfer radical polymerization (ATRP). For comparison, a random copolymer with a similar Az content was also designed. Their photoresponsive and holographic behavior was investigated in thin films. The block copolymer film showed microphase separation with cylinder microdomains after annealing, which was then irradiated at 366 nm. It was found that trans-cis photoisomerization in the block copolymer film was slower than that in the random copolymer film. This may be due to the restricted motion of the Az moieties in the Az blocks. The photoinduced birefringence (Δn) of the block copolymer film was higher than that of the random copolymer film upon irradiation with a linearly polarized beam. In holographic recording, similar results were obtained. A block copolymer with 22-mol% Az showed a liquid-crystalline (LC) phase, while a random copolymer with 24-mol% Az exhibited no LC phase. The block copolymer showed an ...

A series of liquid-crystalline (LC) diblock copolymers with an azobenzene moiety in the side chain were prepared by atom transfer radical polymerization (ATRP). Using a bromo-terminated poly(methyl methacrylate) as a macroinitiator, the obtained diblock copolymers showed well-defined structures and narrow molecular-weight distributions. Microphase-separated nanostructures with mesogenic blocks in either continuous or separated phases were observed. Owing to varied content of mesogens in the block copolymers, they showed different behavior of photoinduced alignment and holographic recording. Block copolymers with azobenzenes in the majority phases exhibited a similar performance of photoinduced alignment and refractive-index modulation to the azobenzene-containing homopolymer, but their photoinduced mass transportation was partly suppressed by the microphase separation, leading to a lower surface relief than that of the homopolymer. The photoinduced mass transfer was greatly prohibited in the block copolym...

Plastic films coated with crosslinked liquid-crystalline polymer (CLCP) layers containing azobenzene moieties (plastic/CLCP bilayer films) were prepared by thermal polymerization of mixtures of an azobenzene monomer and a crosslinker placed between a plastic film and a glass substrate. When the glass substrate was untreated, the obtained bilayer film bent slightly away from the UV light source when irradiated on the CLCP layer side. This bending direction was the same as that of a hybridly aligned CLCP film. When the glass substrate was coated with a rubbed polyimide to strengthen the homogeneous alignment of the azobenzene moieties of the CLCP surface layer, the obtained bilayer film bent toward the irradiation direction of the incident UV light. It was the same as a homogeneously aligned CLCP film and the degree of bending was larger than that of the untreated sample. This means that the photoinduced bending behavior of the plastic/CLCP bilayer films strongly depends on the alignment of the azobenzene m...