Transparent wood (TW)-based composites are of significant interest for smart window applications. In this research, we demonstrate a facile dual-stimuli-responsive chromic TW where optical properties are reversibly controlled in response to changes in temperature and UV-radiation. For this functionality, bleached wood was impregnated with solvent-free thiol and ene monomers containing chromic components, consisting of a mixture of thermo-and photoresponsive chromophores, and was then UV-polymerized. Independent optical properties of individual chromic components were retained in the compositional mixture. This allowed to enhance the absolute optical transmission to 4 times above the phase change temperature. At the same time, the transmission at 550 nm could be reduced 11−77%, on exposure to UV by changing the concentration of chromic components. Chromic components were localized inside the lumen of the wood structure, and durable reversible optical properties were demonstrated by multiple cycling testing. In addition, the chromic TW composites showed reversible energy absorption capabilities for heat storage applications and demonstrated an enhancement of 64% in the tensile modulus as compared to a native thiol−ene polymer. This study elucidates the polymerization process and effect of chromic components distribution and composition on the material's performance and perspectives toward the development of smart photoresponsive windows with energy storage capabilities.

We have studied the confined crystallization behaviour of poly(ethylene oxide) (PEO) in the electrospun nanofibers of the phase-separated blends of polystyrene (PS) and PEO, where PS was present as the major component. The size and shape of PEO domains in the nanofibers were considerably different from those in the cast films, presumably because of the nano-dimensions of the nanofibers and the extensional forces experienced by the polymer solution during electrospinning. The phase-separated morphology in turn influenced the crystallization behaviour of PEO in the blend nanofibers. At a PEO weight fraction of ≥0.3, crystallization occurred through a heterogeneous nucleation mechanism similar to that in cast blend films. However, as the PEO weight fraction in the blend nanofibers was reduced from 0.3 to 0.2, an abrupt transformation of the nucleation mechanism from the heterogeneous to predominantly homogenous type was observed. The change in the nucleation mechanism implied a drastic reduction of the spatial continuity of PEO domains in the nanofibers, which was not encountered in the cast film. The melting temperature and crystallinity of the PEO crystallites developed in the nanofibers were also significantly lower than those in the corresponding cast films. The phenomena observed were reconciled by the morphological observation, which revealed that the phase separation under the radial constraint of the nanofibers led to the formation of small-sized fibrillar PEO domains with limited spatial connectivity. The thermal treatment of the PS/PEO blend nanofibers above the glass transition temperature of PS induced an even stronger confinement effect on PEO crystallization.

We have studied the crystallization behavior of crystalline/crystalline blends of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL) in electrospun nanofibers fabricated from ternary blends of polystyrene (PS), PEO, and PCL, where PS was present as the majority component. It was demonstrated previously that PEO in PS/PEO binary blend nanofibers with a low PEO weight fraction (≦0.2) crystallized predominantly through homogenous nucleation due to the small PEO domain size which excluded the presence of heterogeneities (Soft Matter, 2016, 12, 5110). Here, it was found that PCL in PS/PCL binary blend nanofibers exhibited similar behavior, but at a much lower weight fraction of PCL (≦0.1) due to the presence of an inherently higher concentration of heterogeneities in the PCL homopolymer. In the PS/PEO/PCL ternary blend nanofibers, where the combined weight fraction of PEO and PCL was kept at 0.2 or less, the crystallization of the two components took place separately through both heterogeneous and homogenous nucleation mechanisms. The phase segregated crystallization behavior was further confirmed by the melting behavior of the blend nanofibers and wide angle X-ray diffraction (WAXD) measurements. Most significantly, the homogenous nucleation of both PEO and PCL was suppressed whereas the heterogeneous nucleation was enhanced in the ternary blend nanofibers even at very low weight fraction of PEO or PCL. This was plausibly attributed to the coupling between the crystallization and the liquid-liquid phase separation (LLPS) of the PEO/PCL mixture dispersed in the PS matrix during non-isothermal cooling of the blend nanofibers. Furthermore, it was observed that thermal treatment of the PS/PEO/PCL blend nanofibers above the glass transition temperature of PS further promoted the heterogeneous nucleation-initiated crystallization of PEO because of a complex interplay between Plateau-Rayleigh instability-induced domain breakup and its further coalescence and demixing within the PEO/PCL domains embedded in the PS matrix.

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We investigate the self-assembly of a cylinder-forming polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) mixed with trioctylphosphine oxide (TOPO) capped cadmium selenide (CdSe) quantum dots (QDs). The QDs were found to be enthalpically compatible with the P4VP chains via ligand displacement of TOPO from the QD surface. However, the QDs were found to localize preferentially at the PS/P4VP interphase plausibly to gain translational entropy in order to further lower the energetics of the self-assembled structure. Interestingly, the morphological transformation observed with increasing weight fraction of the QDs in the BCP/QD composite was driven by the migration of the displaced TOPO from the QD surface to the PS phase, effectively increasing its total volume fraction. Hence, the PS-b-P4VP BCP with PS as the minority block displayed lamellar morphology in its composite with QDs. Furthermore, the preferred localization of the QDs at the PS/P4VP interface led to the formation of a trilayer lamellar morphology which was deduced from the suppression of the primary scattering peak, relative to higher order peaks in the SAXS data. The morphological transformation was accompanied by a significant increase in the domain spacing due to excessive stretching of the longer P4VP chains of the asymmetric block copolymer. However, in the PS-b-P4VP/CdSe composites with P4VP as the minority block, cylindrical morphology was retained and the domain spacing decreased due to dominance of the co-surfactant effect as well as interfacial localization of CdSe QDs. We also demonstrate that these PS-b-P4VP/CdSe self-assembled hybrid materials could further be used to obtain isolated core-shell nanoobjects, such as nanofibers and nanosheets, containing CdSe QDs. The nanoobjects so obtained exhibited photoluminescence properties typical of CdSe quantum dots. These photoluminescent polymer nanoobjects could have potential applications in biological targeting and fluorescence labeling.

The preparation of wood substrates modified by charged inorganic nanoparticles (NPs) diffusing into the internal cell wall structure is investigated for generating functional properties. The flammability problem of wood biocomposites is addressed. NPs applied from colloidal sols carry charge to stabilize them against aggregation. The influence of charge on particle diffusion and adsorption should play a role for their spatial distribution and localization in the wood substrate biocomposite. It is hypothesized that improved dispersion, infiltration, and stability of NPs into the wood structure can be achieved by charge control diffusion, also restricting NP agglomeration and limiting distribution to the wood cell wall. Cationic and anionic silica NPs of ≈30 nm are therefore allowed to diffuse into bleached wood. The influence of charge on distribution in wood is investigated as a function of initial sol concentration. Transparent wood is fabricated by in situ polymerization of a thiol‐ene in the wood pore space. These biocomposites demonstrate excellent flame retardancy with self‐extinguishing characteristics. The approach has potential for commercial fabrication of flame retardant transparent composites for glazing and other building applications.

Electrospinning of polymers typically requires high solution concentrations necessitated by the requirement of sufficient chain overlaps to achieve the required viscoelastic properties. Here, we report on a novel supramolecular approach, involving polymer/surfactant complexes, which allows for a significant reduction in the solution concentration of polymer for electrospinning. The approach involved supramolecular complexation of poly(4-vinylpyridine) (P4VP) with a surfactant, dodecylbenzenesulfonic acid (DBSA), via ionic interactions. The supramolecular complexation of P4VP with DBSA led to a significant increase in the solution viscosity even at a DBSA/4VP molar ratio as low as 0.05. Furthermore, the solution viscosity of the P4VP/DBSA complex increased significantly with the DBSA/4VP molar ratio. The increase in the viscosity for the P4VP/DBSA complexes was plausibly due to the formation of physical cross-links between P4VP chains driven by hydrophobic interactions between the surfactant tails. The formation of such physical cross-links led to a significant decrease in the solution concentration needed for the onset of semidilute entangled regime. Thus, the P4VP/DBSA complexes could be electrospun at a much lower concentration. The critical solution concentration to obtain bead-free uniform nanofibers of P4VP/DBSA complexes in dimethylformamide was reduced to 12% (w/v), which was not possible for neat P4VP solution even up to approximately 35% (w/v). Furthermore, small-angle X-ray scattering and polarized optical microscopy results revealed that the electrospun nanofibers of P4VP/DBSA complexes self-assembled in lamellar mesomorphic structures similar to that observed in bulk. However, the electrospun nanofibers exhibited significantly improved lamellar order, which was plausibly facilitated by the preferred orientation of P4VP chains along the fiber axis.