Overcoming the entropy of polymer chains by making a plane with terminal groups: a thermoplastic PDMS with a long-range 1D structural order.

Due to its unique physical and chemical properties, polydimethylsiloxane (PDMS) is widely used in many applications, in which covalent cross-linking is commonly used to cure the fluidic polymer. The formation of a non-covalent network achieved through the incorporation of terminal groups that exhibit strong intermolecular interactions has also been reported to improve the mechanical properties of PDMS. Through the design of a terminal group capable of two-dimensional (2D) assembly, rather than the generally used multiple hydrogen bonding motifs, we have recently demonstrated an approach for inducing long-range structural ordering of PDMS, resulting in a dramatic change in the polymer from a fluid to a viscous solid. Here we present an even more surprising terminal-group effect: simply replacing a hydrogen with a methoxy group leads to extraordinary enhancement of the mechanical properties, giving rise to a thermoplastic PDMS material without covalent cross-linking. This finding would update the general notion that less polar and smaller terminal groups barely affect polymer properties. Based on a detailed study of the thermal, structural, morphological and rheological properties of the terminal-functionalized PDMS, we revealed that 2D assembly of the terminal groups results in networks of PDMS chains, which are arranged as domains with long-range one-dimensional (1D) periodic order, thereby increasing the storage modulus of the PDMS to exceed its loss modulus. Upon heating, the 1D periodic order is lost at around 120 °C, while the 2D assembly is maintained up to ∼160 °C. The 2D and 1D structures are recovered in sequence upon cooling. Due to the thermally reversible, stepwise structural disruption/formation as well as the lack of covalent cross-linking, the terminal-functionalized PDMS shows thermoplastic behavior and self-healing properties. The terminal group presented herein, which can form a 'plane', might also drive other polymers to assemble into a periodically ordered network structure, thereby allowing for significant modulation of their mechanical properties.

Mechanochromic cyclodextrins.

Mechanochromic cyclodextrins (MCDs) that can generate blue radical species, which are exceptionally stable toward atmospheric oxygen and can thus be quantitatively characterized via electron paramagnetic resonance (EPR) spectroscopy, were synthesized. MCDs have a defined structure that consists of a diarylbibenzofuranone skeleton mechanophore sandwiched between two CDs. Grinding tests and EPR measurements of the MCDs revealed their high mechanoresponsiveness, reflecting the inherent rigidity of the CDs and the formation of a supramolecular structure in the bulk.

Persistent Water Repellency of Syndiotactic Polymethylene with Perfluoroethyl Hexyloxycarbonyl Side Chains.

Polyacrylates bearing long fluoroalkyl (Rf) side chains are known to have ultralow surface energies that are appropriate for functional coating and fabric finishing. However, these long Rf chains cause health concerns because of the risk of toxic and bioaccumulative perfluoroalcanoic acid emission via oxidative degradation. This work demonstrates that incorporating a short Rf chain of perfluoroethylene at the end of the side chains of syndiotactic poly(substituted methylene) (PM) produces hydrophobicity. A contact angle of 105° of PM remains constant for more than 50 s, whereas that of the polyacrylate (PA) with the same side chain rapidly decreases from 85° to 44° over the same period. Such persistent water repellency of the PM is ascribed to a liquid crystal structure comprised the main chains arranged in a 2D hexagonal lattice and side chains that extend perpendicularly from these main chains.

Microstructure Investigation of Polymer Electrolyte Fuel Cell Catalyst Layers Containing Perfluorosulfonated Ionomer.

Perfluorosulfonated ionomers are the most successful ion-exchange membranes at an industrial scale. One recent, cutting-edge application of perfluorosulfonated ionomers is in polymer electrolyte fuel cells (PEFCs). In PEFCs, the ionomers are used as a component of the catalyst layer (CL) in addition to functioning as a proton-exchange membrane. In this study, the microstructures in the CLs of PEFCs were characterized by combined synchrotron X-ray scattering and transmission electron microscopy (TEM) analyses. The CL comprised a catalyst, a support, and an ionomer. Fractal dimensional analysis of the combined ultrasmall- and small-angle X-ray scattering profiles indicated that the carbon-black-supported Pt catalyst (Pt/CB) surface was covered with the ionomer in the CL. Anomalous X-ray scattering revealed that the Pt catalyst nanoparticles on the carbon surfaces were aggregated in the CLs. These findings are consistent with the ionomer/catalyst microstructures and ionomer coverage on the Pt/CB surface obtained from TEM observations.

Changing the structural and physical properties of 3-arm star poly(δ-valerolactone)s by a branch-point design.

The chemical structure of a branch point of star-shaped polymers has been considered to have a small influence on the physical properties of the entire polymer. Contrary to this general notion, here we show that a 3-arm star polymer, composed of three poly(δ-valerolactone) arms extended from one side of a triptycene branch point, exhibits a remarkably high complex viscosity, compared to the analogous star-shaped polymers with a branch point of a triptycene isomer or triphenylethane.

Synthesis of fluorescent polycarbonates with highly twisted N,N-bis(dialkylamino)anthracene AIE luminogens in the main chain.

A synthetic route to embed aggregation-induced-emission-(AIE)-active luminophores in polycarbonates (PCs) in various ratios is reported. The AIE-active monomer is based on the structure of 9,10-bis(piperidyl)anthracene. The obtained PCs display good film-forming properties, similar to those observed in poly(bisphenol A carbonate) (Ba-PC). The fluorescence quantum yield (Φ) of the PC with 5 mol% AIE-active monomer was 0.04 in solution and 0.53 in solid state. Moreover, this PC is also miscible with commercially available Ba-PC at any blending ratio. A combined analysis by scanning electron microscopy and differential scanning calorimetry did not indicate any clear phase separation. These results thus suggest that even engineering plastics like polycarbonates can be functionalized with AIE luminogens without adverse effects on their physical properties.

Terminal Functionalization with a Triptycene Motif That Dramatically Changes the Structural and Physical Properties of an Amorphous Polymer.

A surprising terminal-group effect on the structural and physical properties of an amorphous polymer is reported. We recently demonstrated that triptycene derivatives with substituents at the 1,8,13-positions show specific self-assembly behavior, enabling the formation of a well-defined "2D + 1D" structure based on nested hexagonal packing of the triptycenes. Upon terminal functionalization with a 1,8-substituted triptycene (1,8-Trip), a liquid polymer, polydimethylsiloxane (PDMS, Mn = 18-24 kDa), turned into a highly viscous solid that exhibits birefringence at 25 °C. Small-angle and wide-angle X-ray scattering measurements revealed that the resulting telechelic PDMS assembles into a 2D + 1D structure, where layers of PDMS domains, formed between 2D assemblies of the triptycene termini, stack into a 1D multilayer structure with a layer spacing of 18-20 nm. Because of this structuring, the complex viscosity of the telechelic PDMS was dramatically enhanced, providing a value 4 orders of magnitude greater than that of the original PDMS. Remarkably, the structural and physical properties of PDMS were hardly changed upon terminal functionalization with another regioisomer of triptycene (1,4-Trip), which differs only in the substitution pattern.

Self-Assembly of Hierarchical Structures Using Cyclotriphosphazene-Containing Poly(substituted methylene) Block Copolymers.

The cyclotriphosphazene-substituted diazoacetate homopolymer (polyPNDA') (PNDA' = hexaphenoxy-substituted phosphazene-containing methylene) and a novel poly(substituted methylene) block copolymer, polyPNDA'-block-poly(hexyloxycarbonylmethylene) (polyPNDA'-b-polyHDA'), were synthesized, and the self-assembly behavior of these polymers was studied in detail. A hexagonally packed aggregated structure was observed in the self-assembled structure of polyPNDA', whereas a lamellar structure was observed in the microphase-separated nanoassembly of polyPNDA'-b-polyHDA'. These results indicate that a hierarchical structure composed of highly regular polyPNDA' nanoaggregates and the long-range microphase-separated polyPNDA' and polyHDA' domains had formed.

Two-Dimensional Skyrmion Lattice Formation in a Nematic Liquid Crystal Consisting of Highly Bent Banana Molecules.

We synthesized a novel banana-shaped molecule based on a 1,7-naphthalene central core that exhibits a distinct mesomorphism of the nematic-to-nematic phase transition. Both the X-ray profile and direct imaging of atomic force microscopy (AFM) investigations clearly indicates the formation of an anomalous nematic phase possessing a two-dimensional (2D) tetragonal lattice with a large edge (ca. 59 Å) directed perpendicular to the director in the low-temperature nematic phase. One plausible model is proposed by an analogy of skyrmion lattice in which two types of cylinders formed from left- and right-handed twist-bend helices stack into a 2D tetragonal lattice, diminishing the inversion domain wall.

Alkylated cage silsesquioxane forming a long-range straight ordered hierarchical lamellar nanostructure.

An alkylated cage silsesquioxane (1), targeting for a new class of bottom-up-type fabricating materials, was successfully synthesized, and its self-assembled structure is described and discussed herein. Through this, it was found that the intermolecular interaction of long alkyl chains of 1 could be manipulated by thermal annealing to form a long-range straight ordered hierarchical lamellar structure with a periodicity of around 5 nm. Subsequent transmission electron microscopy (TEM) clearly identified polyhedral oligomeric silsesquioxane (POSS) molecules of 1 arranged in a highly ordered fashion, with a "head-to-head" type bilayered structure. The observation of a sublayer structure measuring approximately 0.4 nm in width was attributed to the highly regular packing of isobutyl groups in POSS molecules identified by TEM analysis. Moreover, the formation of a long-range straight structure with sharp interfacial boundaries, which is difficult to achieve with traditional diblock copolymers, is considered to be of significant importance to developing new practical applications of self-assembled nanostructures.

Bent molecules with a 60° central core angle that form B7 and B2 phases.

Small-angle bent-core liquid-crystalline (LC) molecules based on a 1,2-bis(phenylethynyl)benzene central core have been synthesized that form banana smectic phases with a ferroelectric B7-antiferroelectric B2 phase sequence upon cooling. The formation of polar, switchable ferro-/antiferroelectric banana phases indicates that, despite the low core bend angle of approximately 60°, banana smectic phases are still formed with the bend direction parallel to the layer. This study offers significant evidence that shows bent-core molecules with a 60° bend angle can form the well-known B2 and B7 banana phases. Consequently, it may lead to the preparation of a wide variety of novel bent molecules with low bend angles that spontaneously form an LC phase with both polarization and chirality.

Biaxial and antiferroelectric structure of the orthogonal smectic phase of a bent-shaped molecule and helical structure in a chiral mixture system.

We examined the biaxial and antiferroelectric properties in the Smectic-AP(A) (Sm-AP(A)) phase of bent-shaped DC-S-8. The biaxiality, which results from the existence of a secondary director, was well established from birefringence observations in the homeotropically aligned Sm-AP(A). By entering into Sm-AP(A) phase, the birefringence (Δn, difference between two refractive indices of short axes) continuously increased from 0 to 0.02 with decreasing temperature. The antiferroelectric switching and second harmonic generation (SHG) activity on the field-on state were also observed in the Sm-AP(A) phase, and the evaluated spontaneous polarization (P(S)) value strongly depended on temperature. The temperature dependence of Δn and P(S) resembles each other and follows Haller's approximation, showing that the biaxiality is due to polar packing in which the molecules are preferentially packed with their bent direction arranged in the same direction, and that the phase transition of Sm-AP(A) to Sm-A is second order. The biaxiality was further examined in chiral Sm-AP(A)(*). Doping with chiral components induced the helical twisting of the secondary director in the Sm-AP(A)(*) phase, which was confirmed by observing the reflection of the circular dichroism (CD) bands in the homeotropically aligned cell. The helical pitch of Sm-AP(A)(*) is tunable in the range of 300-700 nm wavelength with a variation in the chiral content of 5 to 10 weight (wt)%.

Thermal diffusivity of hexagonal boron nitride composites based on cross-linked liquid crystalline polyimides.

Hexagonal boron nitride (h-BN) composites with the oriented cross-linked liquid crystalline (LC) polyimide have been developed as high thermally conductive materials. Well-dispersed h-BN composite films were obtained, as observed by scanning electron microscopy. The morphology of the composite films was further investigated in detail by the wide-angle X-ray diffraction. The obtained composite films based on the cross-linked LC polyimide showed that the polymer chains vertically aligned in the direction parallel to the films, while those based on the amorphous polyimide showed an isotropic nature. Moreover, the alignment of the cross-linked LC polyimides was maintained, even after increasing the volume fraction of h-BN. This alignment plays an important role in the effective phonon conduction between h-BN and the matrices. Indeed, the thermal diffusivity in the thickness direction of the composite films based on the LC polyimide measured by a temperature wave analysis method was increased to 0.679 mm(2) s(-1) at a 30 vol % h-BN loading, which was higher than that based on the amorphous polyimide.

Formation of regularly spaced wetting ridges at 1 µm intervals on the surface of a liquid-crystalline polymer.

A liquid-crystalline (LC) polymer melt coating a glass support shows a remarkable wetting ridge pattern resulting from a "stick-and-break" phenomenon when submerged into water at a velocity of 20 cm/s. A series of parallel, regularly spaced wetting ridges of 0.2 µm height are formed perpendicular to the advancing direction of the plate at 1 µm intervals, and the pattern continues over a wide area (1 × 2 cm(2)). The ridges function as a narrow line diffraction grating, similar to a prism that separates white light into the spectrum of colors. This process provides new insight into the controlled nanofabrication of polymers that is low-cost and high-throughput.

Structural and mechanical properties of Laponite-PEG hybrid films.

Inorganic/organic hybrids were obtained by the sol-gel type organic modification reaction of Laponite sidewalls with poly(ethylene glycol) (PEG) bearing alkoxysiloxy terminal functionality. By casting an aqueous dispersion of the hybrid, the flexible and transparent hybrid films were obtained. Regardless of the inorganic/organic component ratio, the hybrid film had the ordered structure of Laponite in-plane flat arrays. The mechanical strength of hybrid films was drastically improved by the presence of cross-linking among alkoxysilyl functionalities of PEG terminals and the absence of PEG crystallines. Hybrid films, especially those that consisted of PEG with short chain, showed good mechanical properties that originate from quasi-homogeneous dispersion of components due to anchoring of PEG terminal to Laponite sidewall and interaction of PEG to Laponite surface.

Flexible, transparent nanocomposite film with a large clay component and ordered structure obtained by a simple solution-casting method.

A flexible, transparent nanocomposite (NC) film with 57 wt % inorganic components was obtained by the simple casting of a solution of Laponite and modified organic molecules through a sol-gel reaction. The NC film has solvent resistance and a disco-nematic liquid-crystalline-like structure of Laponite that originates from the cross linking of Laponite by silanol agents and the large amount of Laponite in the film.

Unusual swelling of HPC in toluene forming a microspherical domain structure that causes Christiansen scattering coloration.

The unusual swelling behavior of hydroxypropyl cellulose (HPC) by toluene is described. At temperatures as high as 100 degrees C, toluene molecules can enter the HPC film up to the weight fraction of 55%; however, they are segregated from the HPC matrix and form microspherical domains. The size of the spherical domain is approximately 4.5 microm in diameter on average. Such an unusual swelling behavior is due to the amphiphilic nature of the HPC; HPC polymers rearrange to contact their hydrophobic group with toluene and confine the toluene molecules in spherical domains. Because of the similarity in refractive indices of the toluene microspherical phase and the HPC continuum phase, the swollen film shows a beautiful scattering color that is called the Christiansen filter effect.

Control over Internal Structure of Liquid Crystal Polymer Nanofibers by Electrospinning.

Liquid crystal polymer nanofibers with a diameter ranging from 0.13 to 4.71 µm were prepared by electrospinning from a main-chain liquid crystalline polyester, BB-5(3-Me). WAXD measurements showed that the formation and orientation of the ordered structure in the electrospun fibers were controlled by the fiber diameter formed during electrospinning. For BB-5(3-Me), the SmA structure with two layer spacings was formed in the fiber during the electrospinning. Under optimal spinning conditions, the SmA structure is highly oriented in the fiber. In addition, annealing transformed the metastable SmA structure in the BB-5(3-Me) fiber into stable SmCA one.

Structural characteristics of the B6 phase for a bent-core molecular system observed through the B1-B6 transition.

A bent-shaped molecule exhibiting the mesophase sequence of B6-B1 was studied to understand the structural characteristics of the B6 phase compared with those of the B1 phase. A well-oriented sample was prepared in a magnetic field and examined by wide-angle x-ray diffraction measurements through the B6-B1 phase transition. The B6 phase has been considered to show only the (002) reflection, but this B6 phase showed broad scattering just inside the (002) reflection. The broad scattering has an intensity maximum at a very similar position to that of the (101) reflection in B1 and evolves into the well-defined (101) reflection on cooling into B1. Thus, B6 has a similar frustrated structure to B1, but the size of the antidomain in B6 may be dynamically distributed while B1 possesses an antidomain of definite size.

Unusual transformation of the mechanically induced monodomain state to the polydomain one in polar nematic liquid crystals of aromatic polyesters.

We present an interesting phenomenon of the mechanically aligned monodomain state of polar nematic liquid crystals transforming into the polydomain one. This unusual transformation may result from mismatching of the dipolar vectors. By stretching or shear-flowing the polar nematic liquid crystal, the perfect orientation can be achieved with respect to the long molecular axis, but the misorientation exists with respect to the polar vector. After the prolonged annealing, then, the free energy of the molecules is minimized by producing new defects which satisfy the continuity of polar orientation, but lead to the loss of macroscopic molecular orientation.