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Both AB diblock and ABA triblock copolymers consisting of poly(L-lactide) (PLLA: A) and poly(ethylene glycol) (PEG: B) were deposited on a silicon surface on which poly(D-lactide) (PDLA) had been preimmobilized. The deposit of the diblock copolymer (PLLA-PEG) formed band structures similar to those observed when the same copolymer was directly deposited on the silicon surface. In contrast, the deposit of the triblock copolymer (PLLA-PEG-PLLA) formed many particulates scattering over the surface. When the PLLA-PEG deposit was subjected to water-soaking, the original band morphology was completely replaced by the particulate morphology that was identical to that of the PLLA-PEG-PLLA deposit. Their FT-IR analyses revealed that both copolymers had been bound through the stereocomplex (sc) formation between the preimmobilized PDLA chains and the PLLA blocks of the copolymers. Grazing-incidence small-angle X-ray scattering (GISAXS) also supported these surface morphologies. It was therefore evident that hydrophilic PEG chains can be immobilized on the PDLA-preimmobilized surface by the sc formation.

Analysis of nanostructures is of increasing importance with advances of nanotechnology. Embedded nanostructures in thin films in particular are of recent interest. Grazing incident small angle x-ray scattering (GISAXS) has been recognized to be a powerful method to probe such embedded nanostructures; however, quantitative analysis of scattering pattern is not always trivial due to complex refraction and reflection at surface and interfaces. We prepared nanocellular thin films using block copolymer template with carbon dioxide (CO2); CO2 “bubbles” were formed in the CO2-philic block domains. Such nanocellular structures were analyzed by GISAXS and simulated using distorted wave Born approximation (DWBA). Unlike traditional transmission x-ray scattering, GISAXS requires a careful choice of incident angle to analyze the form factor of scatters embedded in a thin film. Nevertheless, the GISAXS measurements under optimized geometry with quantitative calculations using DWBA revealed that the nanocells are spherical and aligned in a single layer of hexagonal lattice and are surrounded by CO2-philic block domains. [ABSTRACT FROM AUTHOR]

A liquid/liquid interfacial synthesis is employed, for the first time, to synthesize a covalent two-dimensional polymer nanosheet. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) between a three-way terminal alkyne and azide at a water/dichloromethane interface generates a 1,2,3-triazole-linked nanosheet. The resultant nanosheet, with a flat and smooth texture, has a maximum domain size of 20 μm and minimum thickness of 5.3 nm. The starting monomers in the organic phase and the copper catalyst in the aqueous phase can only meet at the liquid/liquid interface as a two-dimensional reaction space; this allows them to form the two-dimensional polymer. The robust triazole linkage generated by irreversible covalent-bond formation allows the nanosheet to resist hydrolysis under both acidic and alkaline conditions, and to endure pyrolysis up to more than 300 °C. The coordination ability of the triazolyl group enables the nanosheet to act as a reservoir for metal ions, with an affinity order of Pd2+>Au3+>Cu2+. [ABSTRACT FROM AUTHOR]

Block copolymers forming glassy spheres in the matrix of rubbery chains can exhibit elastomeric properties. It is well known that the spherical microdomains are arranged in the body-center cubic (bcc) lattice. However, recently, we have found packing in the face-centered cubic (fcc) lattice, which is easily transformed into the bcc lattice upon uniaxial stretching. In the same time, the packing regularity of the spheres in the bcc lattice was found to be enhanced for samples completely recovered from the stretched state. This reminds us that a cycle of stretching-and-releasing plays an important role from analogy of densification of the packing in granules upon shaking. In the current paper, we quantify the enhancement of packing regularity of spherical microdomains in the bcc lattice upon uniaxial stretching of the same elastomeric triblock copolymer as used in our previous work by conducting small-angle X-ray scattering (SAXS) measurements using high brilliant synchrotron radiation. Isotropically circular rings of the lattice peaks observed for the unstretched sample turned into deformed ellipsoidal rings upon the uniaxial stretching, with sharpening of the peaks in the direction parallel to the stretching direction and almost disappearing of the peaks in the perpendicular direction. By quantitatively analyzing the SAXS results, it was found that the packing regularity of the spherical microdomains was enhanced in the parallel direction while it was spoiled in the perpendicular direction under the stretched state. The enhanced regularity of packing was unchanged even if the stretching load was completely removed. [ABSTRACT FROM AUTHOR]

Surface properties of polymeric materials were controlled by fabrication of nano-structure and submicronorder structure of poly(fluoroalkyl acrylate) using the chemical and physical surface modification techniques. The relationship between the ordered structure of fluoroalkyl (Rf) groups and water repellency mechanism was precisely investigated by grazing-incidence X-ray diffraction, water contact angle measurements and X-ray photoelectron spectroscopy. It was revealed that poly{2-(perfluorooctyl)ethyl acrylate} (PFA-C8) was crystallized and formed ordered structure to result in high water repellency. Surface nano-texturing onto PFA-C8 film surface was carried out using an anodic aluminum oxide (AAO) membrane as a mold. The nano-texture of AAO mold with a pore diameter of 200 nm was transformed onto the PFA-C8 film surface to fabricate nano-structure, which revealed high water and oil repellency. On the other hand, various types of monomers were grafted on the solid surface through surface-initiated atom transfer radical polymerization to result in high-density polymer brushes. Hydrophobic PFA-C8 brush surface revealed a low friction coefficient and a good wear resistance. Water lubrication and low friction were observed on the hydrophilic polymer brush. These polymer brushes were successfully introduced on the commercial fluoropolymer, which has inherent radical initiator functional groups. These results indicated that nano-layer immobilization through surface-initiated polymerization and surface texturing are promising methods to control the surface chemistry and surface structure at dimensions in the nano-meter range. [ABSTRACT FROM AUTHOR]

A new system of rapidly-scanning DSC/WAXD/SAXS simultaneous measurements has been successfully developed at the BL40B2 in SPring-8, Japan. The combination of the ultra-bright and highly-directional X-ray beams with the highly-sensitive two-dimensional (2D) detectors such as an imaging plate (IP), a CCD detector and a flat panel (FP) detector has made it possible to perform the rapidly-scanning time-resolved measurements of WAXD and SAXS for the polymeric materials subjected to the various kinds of external field like temperature, tensile force, magnetic field, hydrostatic pressure, and so on. The experimental data about the phase transitions of vinylidene fluoride-trifluoroethylene copolymer with VDF 82 mol % content and poly(vinylidene fluoride) form 1 have been presented as actual examples, where the phase transitions of the polar crystal consisting of planar-zigzag chains to the gauche-type high-temperature phase have been confirmed definitely and the remarkable change in lamellar stacking structure could be detected in the temperature region immediately below the melting point. [ABSTRACT FROM AUTHOR]

The time-resolved small-angle X-ray scattering technique was used to investigate the structural change during uniaxial stretching of dynamically asymmetric polymer blends irradiated by an electron beam. The concentration fluctuations were enhanced by stretching and became large in particular along the direction of deformation. In the early stages of the stretch-induced enhancement of concentration fluctuations, the growth rate of their q-Fourier mode was found to have a maximum at a certain value of q [= (4π/λ)sin(θ/2), where θ and λ are the scattering angle and the wavelength of the X-rays, respectively]. A dominant mode in the enhancement of concentration fluctuations exists in the initial stage, like the early stage of spinodal decomposition for fluid mixtures. The viscoelastic effects of the growth rate were taken into consideration, so that for blends irradiated by an electron beam, elastic effects are found to significantly suppress the growth rate of concentration fluctuations at small wavenumbers. [ABSTRACT FROM AUTHOR]

Abstract: Nucleation mechanism of polymers was studied by means of small angle X-ray scattering (SAXS) by improving our two previous studies. The first one showed first direct SAXS observation of nucleation of polyethylene (PE). The second one reported how “size distribution f(N,t)” of nuclei of nano-meter size (nano-nuclei) evolves with time (t), where N is number of “repeating unit” in a nucleus. Unfortunately the f(N,t) was obtained by incorrect analysis of SAXS intensity (I X), i.e., too simple one-dimensional (1D) nucleus was assumed to analyze the I X. In this paper, we determined simultaneously correct f(N,t) and “two-dimensional (2D) shape” of nano-nucleus. From this it is clarified that nano-nucleus shows significant fluctuation in size and shape and repeats frequent generation and disappearance, which corresponds to the conclusion that the end surface free energy of the nano-nucleus (σ e(nano)) is 1/5 times as large as that of macroscopic crystal (σ e(macro)). f(N,t) decreased with increase of N. f(N,t) increased and saturated with increase of t. [Copyright &y& Elsevier]