Specific deformation behavior of isotactic polypropylene films under a multiaxial stress field.

The specific deformation behavior of crystalline polymer films, namely unoriented crystallized isotactic polypropylene (it PP) films, was investigated under a multiaxial stress field. Changes in the aggregation structure of the films were investigated during the bulge deformation process using in situ small-angle X-ray scattering, wide-angle X-ray diffraction (WAXD) measurements, and polarized high-speed-camera observations. The films had a thickness of approximately 10 µm. The it PP films were fixed at the hole of a plate, then bulge deformation was applied using N2 or He gas pressure, and stress-strain curves were then calculated from the applied pressure and bulge height. Yielding was observed in the stress-strain curves. Below the yield point, in situ WAXD measurements revealed that the crystal lattice expanded isotropically at the center, edge, and bottom of the bulge hole. Above the yield point, a craze started to form slightly near the center, and crazes formed in various directions with a further increase in strain, while the crystal lattice expanded uniaxially along the circumference at the edge and bottom. Crazes oriented in various directions merged and lost birefringence, indicating a change to the isotropic orientation. The different directions of the crazes indicated several directions of stress. In other words, even if multiaxial deformation is applied to a crystalline it PP film, the string-shaped crystalline polymer chain structure produces local anisotropic uniaxial stress.

Heterointerface Created on Au-Cluster-Loaded Unilamellar Hydroxide Electrocatalysts as a Highly Active Site for the Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) is a critical element for all sorts of reactions that use water as a hydrogen source, such as hydrogen evolution and electrochemical CO2 reduction, and novel design principles that provide highly active sites on OER electrocatalysts push the limits of their practical applications. Herein, Au-cluster loading on unilamellar exfoliated layered double hydroxide (ULDH) electrocatalysts for the OER is demonstrated to fabricate a heterointerface between Au clusters and ULDHs as an active site, which is accompanied by the oxidation state modulation of the active site and interfacial direct OO coupling ("interfacial DOOC"). The Au-cluster-loaded ULDHs exhibit excellent activities for the OER with an overpotential of 189 mV at 10 mA cm-2 . X-ray absorption fine structure measurements reveal that charge transfer from the Au clusters to ULDHs modifies the oxidation states of trivalent metal ions, which can be active sites on the ULDHs. The present study, supported by highly sensitive spectroscopy combining reflection absorption infrared spectroscopy and modulation-excitation spectroscopy and density functional theory calculations, indicates that active sites at the interface between the Au clusters and ULDHs promote a novel OER mechanism through interfacial DOOC, thereby achieving outstanding catalytic performance.

Probing the in-plane liquid-like behavior of liquid crystal elastomers.

When isotropic solids are unequally stretched in two orthogonal directions, the true stress (force per actual cross-sectional area) in the larger strain direction is typically higher than that in the smaller one. We show that thiol-acrylate liquid crystal elastomers with polydomain texture exhibit an unusual tendency: The true stresses in the two directions are always identical and governed only by the area change in the loading plane, independently of the combination of imposed strains in the two directions. This feature proves a previously unidentified state of matter that can vary its shape freely with no extra mechanical energy like liquids when deformed in the plane. The theory and simulation that explain the unique behavior are also provided. The in-plane liquid-like behavior opens doors for manifold applications, including wrinkle-free membranes and adaptable materials.

Exploring the Mesoscopic Morphology in Mussel Adhesive Proteins by Soft X-ray Spectromicroscopy.

Marine mussels efficiently adhere under wet conditions by precisely controlling the hierarchical structure of the adhesive plaque through sequential mussel foot protein secretion in the foot-tip cavity. Chemical analysis of the non-uniform mussel plaque morphology has been performed using spectromicroscopy; however, the mesoscopic morphology has not been elucidated yet because of the limited spatial resolution of conventional chemical imaging techniques. We investigated the chemical speciation in the non-uniform mussel plaque morphology employing scanning transmission soft X-ray spectromicroscopy (STXM). The high-spatial-resolution STXM chemical imaging with C 1s near-edge X-ray absorption fine structure yields the distribution of the hydroxy-substituted aromatic residues in the sub-micron scale non-uniform mussel plaque morphology. The matrix consists of a high-protein-density cured product containing a large number of hydroxy-substituted aromatic carbons, including tyrosine and 3,4-dihydroxyphenylalanine (Dopa), whereas the microdomains are poor-protein-density regions with a low aromatic residue relative content. The adhesive interface was covered with the matrix phase to ensure adhesion. The cuticle layer involves a moderate Dopa content, which appears to be optimized for the mechanical performance of the skin.

Direct Evaluation of Local Dynamic Viscoelastic Properties of Isotactic Polypropylene Films Based on a Dynamic µ-Beam X-ray Diffraction Method.

The local mechanical properties of crystalline polymer were evaluated using synchrotron radiation X-ray diffraction with 10 µm lateral resolution. A nonoriented isotactic polypropylene (iPP) film with isolated spherulites in a crystallized matrix was used as a model sample. In situ wide-angle X-ray diffraction (WAXD) measurement was performed on the iPP film using a microbeam synchrotron radiation X-ray under sinusoidal strain. The lattice spacing of the crystal planes increased and decreased in response to the applied sinusoidal strain. Local dynamic viscoelastic functions (dynamic storage and loss moduli (E' and E″)) were calculated at room temperature from the relationship between the calculated applied stress and the response strain obtained by dynamic µ-beam WAXD measurement inside and outside of the spherulites. The E' values inside and outside of spherulite obtained from the change in spacing of the (110) plane were 1.8 and 1.1 GPa, respectively. Furthermore, the E' value inside of spherulite obtained from the change in spacing of the (1̅13) plane was 6.0 GPa. These values can be explained by the deformation of crystallite, which depends on the direction of crystal planes. The results obtained here revealed that synchrotron radiation X-ray diffraction measurement gives not only structural information but also the local mechanical properties of the materials E'.

Organic-Inorganic Hybrid Thin Films Fabricated by Layer-by-Layer Assembly of the Phosphorylated Cellulose Nanocrystal and Imogolite Nanotubes.

Phosphorylated cellulose nanocrystal (P-CNC)/imogolite nanotube (natural aluminosilicate nanotube) hybrid thin films were fabricated by spin-assisted layer-by-layer assembly. Phosphorylation of CNC with diammonium hydrogen phosphate ((NH4)2HPO4) was carried out to introduce phosphate groups on the CNC surface for enhanced interaction with imogolite. Structure of the P-CNC/imogolite thin film was characterized by atomic force microscopy, scanning electron microscopy, X-ray diffraction (XRD), and grazing incidence wide-angle XRD. The film thickness increased linearly with the increment of the P-CNC/imogolite bilayer. Benefitting from the strong affinity between the phosphate group of the P-CNC and the Al-OH group of imogolite, the P-CNC/imogolite thin films were quite stable in water within a wide range of pH values, compared with the deterioration of the CNC/imogolite film under same soaking conditions.

Depth-Resolved Characterization of Perylenediimide Side-Chain Polymer Thin Film Structure Using Grazing-Incidence Wide-Angle X-ray Diffraction with Tender X-rays.

Polymers with a perylenediimide (PDI) side chain (PAc12PDI) consist of two kinds of crystalline structures with various types of orientations in a thin film. Understanding the population of the microcrystalline structure and its orientation along the thickness is strongly desired. Grazing-incidence wide-angle X-ray diffraction (GIWAXD) measurements with hard X-rays, which are generally chosen as λ = 0.1 nm, are a powerful tool to evaluate the molecular aggregation structure in thin films. A depth-resolved analysis for the outermost surface of the polymeric materials using conventional GIWAXD measurements, however, has limitations on depth resolution because the X-ray penetration depth dramatically increases above the critical angle. Meanwhile, tender X-rays (λ = 0.5 nm) have the potential advantage that the penetration depth gradually increases above the critical angle, leading to precise characterization for the population of crystallite distribution along the thickness. The population of the microcrystalline states in the PAc12PDI thin film was precisely characterized utilizing GIWAXD measurements using tender X-rays. The outermost surface of the PAc12PDI thin film is occupied by a monoclinic lattice with a = 2.38 nm, b = 0.74 nm, c = 5.98 nm, and ß = 108.13°, while maintaining the c-axis perpendicular to the substrate surface. Additionally, the presence of solid substrate controls the formation of the crystallite with unidirectional orientation.

Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity.

Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrole-based tetradentate macrocyclic ligands with NNNC coordination cores were synthesized, and their structures were elucidated by spectroscopic means including X-ray crystallographic analysis. On the basis of their distinct planar structures, X-ray absorption/photoelectron spectroscopic features, and temperature-independent diamagnetic nature, these organocopper complexes can be preferably considered as novel organocopper(III) species. The remarkable stability of the high-valent Cu(III) states of the complexes stems from the closed-shell electronic structure derived from the peculiar NNNC coordination of the corrole-modified frameworks, which contrasts with the redox-noninnocent radical nature of regular corrole copper(II) complexes with an NNNN core. The proposed structure was supported by DFT (B3LYP) calculations. Furthermore, a π-laminated dimer architecture linked through the inner carbons was obtained from the one-electron oxidation of CuNCC4. We envisage that the precise manipulation of the molecular orbital energies and redox profiles of these organometallic corrole complexes could eventually lead to the isolation of yet unexplored high-valent metal species and the development of their organometallic reactions.

Preparation of High-Density Polymer Brushes with a Multihelical Structure.

It is well-known that a mixture of isotactic and syndiotactic polymethyl methacrylate (PMMA) forms a stereocomplex consisting of a multihelical structure in which an isotactic chain is surrounded by a syndiotactic chain. Here, we report the basic structure of the stereocomplex formed when the syndiotactic PMMA chains are tethered to a silicon substrate and form a high-density polymer brush. The influence of geometric confinement was investigated by preparing the high-density polymer brushes on a flat and spherical substrate. In both cases, mixing the untethered isotactic PMMA with the grafted syndiotactic PMMA led to the formation of a stereocomplex with a multihelical structure. Static contact angle measurements showed a hindered surface mobility at the outermost surface of the polymer brush, indicating that the stereocomplex forms a crystalline structure. A syndiotactic polymer brush with substituted fluoroalkyl groups was prepared to increase the contrast for grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements. The GIWAXD results verified that the stereocomplex forms a crystalline structure oriented perpendicular to the substrate with a relatively low degree of orientation.

In situ synchrotron radiation X-ray diffraction studies on molecular aggregation structure of nylon 12 films during bulge testing.

It is desirable to establish a method for evaluating mechanical properties, such as modulus and strength, of micrometer and sub-micrometer thick polymer films. Bulge tests, where bulge deformation is imposed on films by the pressure of an inert gas, are suitable for satisfying this demand. However, very few studies on polymer films exist in the literature. In this study, bulge testing equipment for in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurements is designed and used to study the relationship between the molecular aggregation structure and the mechanical properties of a crystalline nylon 12 (Ny12) film during bulge testing. Isothermally crystallized and quenched Ny12 films exhibited stress-strain curves similar to those obtained by conventional uniaxial elongation. In situ WAXD measurements during bulge testing revealed that the lattice extension of the crystallites is clearly dependent on crystallinity. Concretely, crystallites in the isothermally crystallized film show higher elastic properties than those in the quenched one. The results of the molecular aggregation structure, including the crystal structure and the amorphous chain surrounding the crystallites, of the films during bulge deformation firstly obtained in this study must be useful for designing toughened polymer films.

Design of High-Density Helical Polymer Brush on Silica Nanoparticles for the Size Recognition of Fullerene Molecules.

High-density syndiotactic poly(methyl methacrylate) (st-PMMA) brushes form a helical structure and encapsulate fullerene molecules in their helical cavities, leading to a PMMA brush/fullerene inclusion complex. The brushes recognize the size of guest molecules and spontaneously adapt their helical diameter to the guest molecules. Both polymer brush/C60 and polymer brush/C70 inclusion complex on the flat substrate were characterized on the basis of grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements, and it is revealed that the main chains oriented perpendicular to the substrate. Moreover, high-density st-PMMA brushes grafted onto nanoparticles efficiently separate C70 molecules from the mixture of C60 and C70 solution. Even after 5× repeating process, the selectivity for C70 molecules remains at 99%.

Bis-Copper(II)/π-Radical Multi-Heterospin System with Non-innocent Doubly N-Confused Dioxohexaphyrin(1.1.1.1.1.0) Ligand.

A contracted doubly N-confused dioxohexaphyrin(1.1.1.1.1.0) complex consisting of two paramagnetic copper metals and open-shell π-radical ligand was synthesized as a new multi-heterospin motif. X-ray spectroscopy supported the divalent character of the inner copper centers, and electron paramagnetic resonance and magnetometric studies suggested the presence of unpaired d electrons strongly antiferromagnetically coupled with π-radicals delocalized on the macrocycle. The 25 π non-innocent dioxohexaphyrin ligand allowed the facile interconversion between antiaromatic 24 π and aromatic 26 π species, respectively, upon redox reactions.