Polarized optical microscopy (POM) images of polymer network liquid crystals (PNLCs) were first analyzed using a pretrained machine learning model for feature extraction and hierarchical clustering. The analyses worked well in predicting and improving the thermoresponsive changes individually in direct luminous and hemispheric solar transmittance, both of which are crucial properties of energy-saving smart windows. The features of a 1280 × 1920-pixel color POM image were extracted by the latest pretrained algorithm, EfficientNet-B7, as a 2560-dimensional vector and then reduced into a two-dimensional space for clustering and visualization using the uniform manifold approximation and projection (UMAP) algorithm while efficiently preserving the global structures of the distance relationship in a high-dimensional space. The feature vectors in the UMAP space were correlated with the thermoresponsive transmittance and classified using hierarchical clustering analysis. The extracted features belonging to some clusters were also correlated with the fabrication parameters. The PNLCs here were produced from various raw materials under different fabrication conditions. These analyses and predictability are extensively applied to different PNLCs for stimuli-responsive optical devices, such as solar- and privacy-control windows.
Background: Gelatinous zooplankton in epipelagic environments often have highly transparent bodies to avoid detection by their visual predators and prey; however, the digestive systems are often exceptionally opaque even in these organisms. In a holoplanktonic gastropod, Pterotrachea coronata, the visceral nucleus is an opaque organ located at the posterior end of its alimentary system, but this organ has a mirrored surface to conceal its internal opaque tissue. Results: Our ultrastructural observation proved that the cortex of the visceral nucleus comprised a stack of thin cellular lamellae forming a Bragg reflector, and the thickness of lamellae (0.16 µm in average) and the spaces between the lamellae (0.1 µm in average) tended to become thinner toward inner lamellae. Based on the measured values, we built virtual models of the multilamellar layer comprising 50 lamellae and spaces, and the light reflection on the models was calculated using rigorous coupled wave analysis to evaluate their properties as reflectors. Our simulation supported the idea that the layer is a reflective tissue, and the thickness of the lamella/space must be chirped to reflect sunlight as white/silver light, mostly independent of the angle of incidence. Conclusions: In P. coronata, the cortex of the visceral nucleus comprised multicellular lamellae that form a chirped Bragg reflector. It is distinct in structure from the intracellular Bragg structures of common iridophores. This novel Bragg reflector demonstrates the diversity and convergent evolution of reflective tissue using reflectin-like proteins in Mollusca.
Gastropoda , Animals , Cell Nucleus , Light , Vision, Ocular
Molecular interactions between liquid crystals (LCs) and reactive mesogens (RMs) at temperatures across the phase transition regions were comprehensively studied during photopolymerization-induced phase separation (PPIPS) beginning with raw mixtures until the formation of polymer network liquid crystals (PNLCs). Then, the molecules were found to be nonuniformly more and less mobile in response to temperature as PPIPS progressed. Optical birefringence and infrared absorption were carefully measured throughout PPIPS, using 4-cyano-4'-hexylbiphenyl (6CB) and 1,4bis-[4-(3-acryloyloxypropyloxy) benzoyloxy]-2-methylbenzene (RM257) as typical LCs and RMs. Microscopic views of thermoresponsive changes in the molecular orientation order of both LCs and RMs were obtained: LCs and RMs in raw mixtures interacted with one another but uniformly transformed their molecular orientation. Such interactions continuously change to become nonuniform with progress in PPIPS. At the incipient stages of PPIPS, RMs, which are polymerized but not completely networked, inhibit LCs from changing their molecular orientation and vice versa. As PPIPS progresses, some LCs become more mobile and some less mobile owing to RM constraints. The domain configuration of the submicrometer phase separation affects the thermoresponsive mobility of LCs and RMs, that is, LCs become more mobile in LC-richer areas. The quantitative knowledge here provides comprehensive insight that LCs and RMs are mutually constrained and that such interactive behavior varies nonuniformly as PPIPS progresses.
This study examined the thermal response of polymer-dispersed liquid crystal (PDLC) diffusers, patterned using a two-lens imaging system. Optical modulation was achieved by modifying the PDLC transmittance using temperature-induced changes to liquid crystal (LC) orientation. PDLCs with controllable scattering properties were obtained by irradiating LC-polymer composites with laser speckle patterns. The variation of the scattering characteristics of the PDLCs with temperature, average speckle size, and LC orientation order was analyzed to determine the most suitable parameters for a diffuser for smart window solar-ray control applications. The findings of these experiments demonstrate that using speckle patterns, a one-time laser exposure process, can provide a simple fabrication method of novel optical devices.
Surface modifications for easy removal of liquids and solids from various metal surfaces are much less established than for silicon (Si) or glass substrates. Trimethylsiloxy-terminated polymethylhydrosiloxane (PMHS) is very promising because it can be directly immobilized covalently to a wide variety of metal surfaces by simply heating neat PMHS liquid, resulting in a film showing excellent dynamic omniphobicity. However, such PMHS films are easily degraded by hydrolytic attack in an aqueous environment. In this study, we have successfully improved the hydrolytic stability of the PMHS-covered ultrasmooth metal (Ti, Al, Cr, Ni, and Cu) surfaces by end-capping of the residual Si-H groups of the PMHS films with vinyl-terminated organosilanes, for example, trimethylvinylsilane (TMVS), through a platinum-catalyzed hydrosilylation reaction. The resulting TMVS-capped PMHS film surfaces showed significantly greater stability even after submersion in water for 6 days, with their excellent dynamic dewetting behavior toward water, toluene, n-hexadecane, and ethanol changing little. In addition, they also showed reasonable anti-icing (icephobic) properties with low ice-adhesion strength of less than 50 kPa even after 20 cycles of testing at -15 °C.
Polymer network liquid crystals (PNLCs) capable of thermoresponsive change in reflective scattering were fabricated using a self-organization technique called photopolymerization-induced phase separation. These PNLCs exhibit nonscattering states at temperatures τ below the nematic-to-isotropic (NI) phase transition temperature τNI but reflective scattering states at τ values above τNI. The magnitude of change of optical clarity is 80% and of solar transmittance is 20% in PNLCs with a thickness of 50 µm. The microscopic structures consist of wavelength- or meso-scale phase separation domains of liquid crystals (LCs) and polymerized reactive mesogens (RMs) in which cyanobiphenyl (CB) groups are thermoresponsively transformed between uniaxially orientation-co-ordered and disordered states. Such thermoresponsive structures were fabricated by employing the CB groups as mesogenic bodies, which were expected to mutually associate due to their physicochemical structures. Cross-linkers stabilized the meso-scale domains and made the PNLCs durable through repeated temperature changes. Polarizing optical microscopy (POM) and scanning electron microscopy showed meso-scale composites that reflectively scatter visible and near-infrared light. POM and Fourier-transform infrared spectroscopy at different temperatures suggest that the orientation order of the CB groups changes in the LC phase in response to temperature but remains ordered in the RM phase. Such a thermoresponsive change in the orientation order produces the switchability in meso-scale nonuniformity and consequently in reflective light scattering. The thermoresponsive PNLCs are not only effective as energy-saving smart windows but also advantageous at stages of manufacture, installation, and operation.
A simple nonuniform irradiation method for photopolymerization-induced phase separation (PPIPS) was developed to produce unconventional mesoscale domain structures composed of liquid crystal (LC) and reactive mesogen (RM) phases. The LC/RM phase formations and their molecular orientation ordering through PPIPS were comprehensively investigated as a function of LC/RM molar ratio, curing temperature, and the use of uniform or nonuniform irradiation. Then, two different optical-anisotropic structures that can cause normal- or reverse-mode thermoresponsive light attenuation were formed by nonuniform irradiation at different curing temperatures at the same molar ratios. These two structures consist of mesoscale domains organized with multiaxially orientation-ordered LCs and orientation-disordered RMs for normal-mode thermoresponse and uniaxially orientation-ordered LCs and RMs for reverse-mode thermoresponse. Phase-separation nuclei were generated by nonuniform irradiation at the incipient stage during the PPIPS process under nonuniform irradiation and subsequently coalesced to form mesoscale polymer networks while maintaining their molecular orientation order. This is a promising method to overcome the restraint of structural controllability due to intrinsic material properties and thus to provide unconventional optical and photonic devices, such as thermoresponsive smart windows and thermometric sheets.
Various metal (Al, Ti, Fe, Ni, and Cu) surfaces with native oxide layers were rendered "omniphobic" by a simple thermal treatment of neat liquid trimethylsiloxy-terminated polymethylhydrosiloxanes (PMHSs) with a range of different molecular weights (MWs). Because of this treatment, the PMHS chains were covalently attached to the oxidized metal surfaces, giving 2-10 nm thick PMHS layers. The resulting surfaces were fairly smooth, liquid-like, and showed excellent dynamic omniphobicity with both low contact angle hysteresis (â²5°) and substrate tilt angles (â²8°) toward small-volume liquid drops (5 µL) with surface tensions ranging from 20.5 to 72.8 mN/m. Droplet mobility was improved overall as a result of heating the substrates to 70 °C. The reaction kinetics and final dynamic dewetting properties were found to be not dependent of the types of metals employed or MWs of PMHS, but mainly dominated by both reaction temperatures and reaction times.
Polyurethane (PU)-based transparent and flexible ionogels, showing unusual thermo-responsive optical properties, were successfully prepared by mixing PU-precursor and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM-TFSI). Although the initial ionogels were transparent at room temperature, significant increases in opacity were observed with increasing temperature up to 120°C, because of macroscopic phase separation of the PU-matrix and hydrophobic EMIM-TFSI. In addition, the optical transition temperature could be arbitrarily controlled simply by varying the mixing ratio of EMIM-TFSI within the PU-matrix. As confirmed by UV-Vis spectra acquired at different temperatures, this thermo-responsive optical behavior was found to be reversible, repeatable and durable even after 30 cycles of a thermal-stress testing between 30 and 100°C.
BACKGROUND: Invisibility in the water column is a crucial strategy for gelatinous zooplanktons in avoiding detection by visual predators, especially for animals distributed in the euphotic zone during the daytime; i.e., surface dwellers that do not undergo diel vertical migration. Salps, a member of the subphylum Tunicata (Urochordata), usually have a transparent body that is entirely covered with a cellulosic matrix, called the tunic. Some non-migrator species are known to exhibit a nano-scale nipple array on the tunic surface. However, the physical properties of the salp tunic has been poorly investigated, except for Thetys vagina, in which the tunic was expected to show low reflectance based on the refractive index of the tunic. Pegea confoederata is a non-vertical migrant salp showing pinkish-brown body. We measured the hardness, water content, absorption spectra, and refractive index of its tunic to evaluate its fragility and visibility. RESULTS: There are nipple-like protuberances about 80 nm high on the surface of the tunic in P. confoederata. The tunic is very soft; the maximum force to pierce the tunic with a steel rod (1 mm diameter) was < 1 N. The water content of the tunic was > 95%. The absorption spectra of the tunic had no prominent peaks in the wavelength range of 280-800 nm, indicating the tunic is nearly transparent. The difference in refractive indices between tunic and seawater was estimated as 0.002-0.015 at 589 nm. Rigorous coupled wave analyses (RCWA) of light reflection based on 3-dimensional models supported an anti-reflective effect of the nipple array on the tunic surface, which was estimated to vary slightly depending on the forms and the arrangement patterns of nipple-like protuberances in an array. CONCLUSIONS: The tunic of P. confoederata is very soft and contains more water than those of sessile tunicates (ascidians). Based on the refractive index of the tunic, light reflection is expected to be very low, making this salp's tunic barely visible in water column. Our results suggest that the nipple array may produce an anti-reflective effect.
BACKGROUND: Tunic is a cellulosic, integumentary matrix found in tunicates (Subphylum Tunicata or Urochordata). The tunics of some ascidian species and pelagic tunicates, such as salps, are nearly transparent, which is useful in predator avoidance. Transparent materials can be detected visually using light reflected from their surfaces, with the different refractive indices between two media, i.e., tunic and seawater, being the measure of reflectance. A larger difference in refractive indices thus provides a larger measure of reflectance. RESULTS: We measured the refractive indices of the transparent tunic of Thetys vagina (salp: Thaliacea) and Rhopalaea sp. (ascidian: Ascidiacea) using an Abbe refractometer and an ellipsometer to estimate the light reflection at the tunic surface and evaluate the anti-reflection effect of the nipple array structure on the tunic surface of T. vagina. At D-line light (λ = 589 nm), the refractive indices of the tunics were 0.002-0.004 greater than seawater in the measurements by Abbe refractometer, and 0.02-0.03 greater than seawater in the measurements by ellipsometer. The refractive indices of tunics were slightly higher than that of seawater. According to the simulation of light reflection based on rigorous coupled wave analysis (RCWA), light at a large angle of incidence will be completely reflected from a surface when its refractive indices are smaller than seawater. Therefore, the refractive index of integument is important for enabling transparent organisms to remain invisible in the water column. CONCLUSION: In order to minimize reflectance, the refractive index should be similar to, but never smaller than, that of the surrounding seawater. The simulation also indicated that the presence or absence of a nipple array does not cause significant difference in reflectance on the surface. The nipple array on the tunic of the diurnal salp may have another function, such as bubble repellence, other than anti-reflection.
We first fabricated holographic polymer-dispersed liquid crystals (HPDLCs) that produce multiple Bragg diffractions with different polarization states for every angle of incidence, through a photopolymerization-induced phase separation by one-time interferential exposure. The polarizations of the Bragg diffractions were well-controlled at individual wavelengths in the fabrication process by the compositional ratio of LCs to monomers. The raw mixtures of extremely low-functionality monomers having very different viscosities were used to reduce the domain size in phase separation and subsequently to form elaborate periodic structures of the LC and polymer phases. A cross-linker (1-vinyl-2-pyrrolidione) and a prepolymer with urethane groups were employed to strengthen the polymer network. Note that the diffractions of our HPDLCs are regarded as not purely but mostly Bragg type, according to the evaluation with the established criteria. The devices, which are monolithic but versatile in diffractive behaviors, have advantages of simple manufacturing and handling.
Optical diffractometry is proposed as a practical method of quantitatively analyzing the microscopic structural origins of a wide range of highly efficient and linearly polarized optical diffraction grating produced from holographic polymer-dispersed liquid crystal. The structure is organized by a spatially periodical distribution of submicrometer-scale liquid crystal (LC) droplets in a polymer matrix. Six independent Bragg diffraction spectra were obtained at two orthogonal polarization states at temperatures below, at, and above the nematic-to-isotropic phase transition point. These spectra were simultaneously analyzed by employing anisotropic diffraction theory under the restraint of a simple and widely useful structural model constructed on the basis of the previously reported microscopic observations. The refractive indices of spatially periodic LC- and polymer-rich phases were analyzed using Cauchy's equation as a function of optical wavelength. The present diffractometry was demonstrated for a variety of holographic structures, and the structural parameters were discussed such as the filling ratio of LC droplets to polymer matrix, the orientational order in the droplets, and the thermo-optic properties in the LC droplets. Furthermore, the higher order Bragg diffractions were measured and discussed. The proposed method was examined in consistency by comparisons with polarizing optical microscopy and scanning electron microscopy.
A microperiodic structure composed of polymer and liquid crystal (LC) phases, called holographic polymer dispersed LC, is fabricated by a photo-induced phase separation technique using LC composites with different physical properties, such as refractive indices and clearing points. Effects of thermal modulation on diffraction properties of LC composite gratings are experimentally investigated in the viewpoints of polarization and temperature dependences. The diffractions based on the change of refractive index induced by the nematic-isotropic transition of LCs with the increase of temperature are applied for a holographic image reconstruction.
Orientation-controlled anisotropic diffraction gratings are realized by interferometric exposure using composite materials of nematic liquid crystals (LCs) and LC diacrylate monomers. The anisotropic diffraction properties in volume gratings, which dominantly diffract p- or s-polarized light, are shown to be controlled by the rubbed directions of the alignment layers under the control of the photopolymerization temperature. Images of the fringe patterns observed by polarization microscopy show the effects of the alignment layers on the LC orientation during grating formation.
The structure and viscoelastic properties of an organic-inorganic hybrid system composed of an organically modified polysiloxane network were examined, and the influence of organic groups on elastic-modulus variation by heat treatment was studied. The increase in the number of phenyl (Ph) groups per silicon decelerates the increase in elastic modulus; the substitution of the Ph group for a methyl (Me) group accelerates it. The system basically consists of R4-mSi[O-]m/2 units, where R is the organic group. The 29Si magic-angle spinning (MAS) NMR and gel permeation chromatography (GPC) measurements classified the structure related with the viscoelastic behavior into two factors: the number of bridging oxygens and the distribution of molecular weight. The elastic modulus was expressed by these structural factors through a simple empirical formula, irrespective of the type and number of the organic groups. The effects of the organic groups on the variation in elastic modulus by heat treatment were found to work mostly only through the molecular-weight change, and such effects can be controlled by the type or the number of organic groups.
The relationships between the viscoelastic and structural properties of glass-forming materials with polysiloxane bonds, which serve as network formers, and phenyl groups, which act as network terminators, are examined based on shear viscoelasticity, (29)Si MAS NMR, and GPC measurements during the early stages of the network-forming process. The viscosities of the present samples do not depend on the frequency at temperatures up to 200 degrees C, suggesting that the origin of the viscous flow does not include intermolecular entanglement. According to the results of the strain dependence of the elastic modulus, the bridging-oxygen number, and molecular weight, the present polysiloxane system has a complex structure, or distribution of various-sized molecules composed of a polysiloxane network with various dimensionalities, and furthermore an elementary process of the viscosity is simple flow of these molecules. The structural factors that determine the viscosity and its temperature dependence are categorized into the molecular size and the intramolecular structure by using a theory based on the free-volume model. The relationship between the viscosity and the structure around the glass transition temperature is quantitatively examined and it is concluded that introducing larger numbers of Ph groups makes the viscosity less sensitive to structural factors.
