No abstract available

[en] Microphase separated structures of block copolymer, polystyrene-b-polyisoprene (PS-b-PI, φ_PS = 14%) including non-volatile selective solvent thin films were investigated using grazing incidence small angle X-ray scattering technique. The diethyl phthalate (DEP) was used as a non-volatile selective solvent which solves PS only. The DEP swelled PS phase selectively and the microphase separated structure transited from the PS spherical domain to the lamellar domain with an increase in DEP content in the bulk state. Similarly, the phase separated structure in the thin film prepared by spin cast on a silicon wafer from the mixture of toluene/DEP and block copolymer changed according to the initial DPE concentration. However, the morphologies developed in the thin film were shifted to the structures at lower DEP concentration than that expected from the initial concentration. Moreover, the cylindrical and lamellar domains were aligned parallel and perpendicularly to the substrate, respectively.

[en] The nanoscopic morphology of soft material thin films such as plastic, elastomer and rubber films has been successfully analyzed by grazing-incidence small-angle X-ray scattering (GISAXS). Recently, advanced GISAXS techniques for analysis for surface-, volume-, and material (element)-sensitive method has been reported. Resonant (anomalous) GISAXS and GISAXS with low X-ray photon energy (tender X-rays and soft X-rays near K-edge of carbon) allows probing a complex nanomorphology with those sensitivity. In this report, principle of GISAXS will be outlined simply and advanced GI-SAXS methods will be picked up to open for discussion on new possibility of structure analysis. (author)

[en] Valvular insufficiency in radiation-induced heart disease is very rare. We described a patient, 53 years old woman, who developed congestive heart failure 2.5 years later following radiotherapy for esophageal carcinoma. The findings on examinations including cardiac catheterization revealed pericarditis with effusion, mitral and tricuspid valve insufficiency and pulmonary infarction. (author)

[en] Small-angle X-ray scattering is a method to measure scattered X-ray interference by the spatial scattering length density fluctuation in the sample. One can investigate, for example, the radius of gyration of polymer in solution, size and shape of a protein in aqueous solution, the structure of micelle (size and shape, its distribution), microphase separated structure (period and morphology), crystal lamella, the network structure of gels, nanoparticles. SAXS is a non-destructive method for observing the nanometer-scale structure and is suited for various in-situ measurements. Here, the principle of small-angle X-ray scattering is introduced, and a few examples of SAXS experiments related to the rubber materials will be given. (author)

[en] The ESR spin-label method has been used for studies on molecular dynamics in polymers. Advanced computer simulation for the dynamics and a novel technique (microwave power saturation method) for determination of T_g by ESR are introduced here. These techniques reveal the polymer dynamics at the specific sites and in specific environments. (author)

[en] Crystalline polymers spontaneously form hierarchical structures, which provide us a potential use as a specialty material. Recently, not only a crystalline homopolymer but also semi-crystalline block copolymers and crystalline polymer blends have been attracting interests for the study of a hierarchical structure. In order to analyze such hierarchical structures in a variety of length scales, a simultaneous measurement of small-(SAXS) and wide-angle (WAXS) X-ray scattering with differential scanning calorimetry (DSC), or with small-angle light scattering (Hv-SALS) are most suitable. In this review, we show some examples of the simultaneous measurements. With DSC, exothermic heat flow can be simultaneously measured with X-ray scattering. On the other hand, with Hv-SALS it is possible to analyze evolution of a spherulitic structure, which is the structure at the highest rank in the hierarchy. For both cases, one can realize that it is impossible to obtain good statistics for SAXS and WAXS measurements without synchrotron radiations. (author)

[en] The microphase separated structure of PS-b-PHS/PEG blend thin film with thickness of 500 ∼ 600 nm was investigated by grazing incidence small angle X-ray scattering. The thin film was obtained by two different solutions; one was THF which was common good solvent for all components of polymers used here. The other is toluene which was selective solvent for PS and poor-solvent for PHS and PEG. The equilibrium morphology of the block copolymer and blend sample was hexagonally packed cylinder in the bulk and thin film. The structure in the thin film obtained by spin cast from toluene solution was non-equilibrium. After THF vopar annealing of the thin film (cast from toluene), the highly ordered and perpendicular oriented cylindrical structure was obtained. Perpendicular orientation was failure when the thin film sample made by spin cast from THF solution and subsequent THF vapor annealing. The perpendicular nano-holes were fabricated after removing PEG oligomer by washing with water.

[en] The morphologies of the microdomain structures in polystyrene-polyisoprene (PS-PI) diblock copolymer and polyisoprene (PI) homopolymer blends were investigated by small-angle X-ray scattering. The PS-PI investigated in the present study has number-average molecular weight $M_n=29400\text{g/mol}$ and volume fraction of PI $f_{\mathrm{P}\mathrm{I}}=0.33$, and PI has $M_n=11400$. The weight fraction of added homopolymer was 0.17. We demonstrated that the existence of ordered-bicontinuous-double-diamond (OBDD) structure was explicitly identified in the PS-PI/PI blend by the scattering method. It was confirmed that OBDD microdomain changed to gyroid (Gyr) when the sample was heated, and the order-order transition between OBDD and Gyr thermo-reversibly occurred. The kinetics of the transformation between OBDD and Gyr was also investigated. In this study, the intermediate structure during the transition between OBDD and Gyr was not observed. A comparison between the rates of transformation revealed that the rate of the OBDD to Gyr transformation is faster than that of the Gyr to OBDD. (letter)

[en] Microphase-separated structures in a polybutadiene-poly( ε -caprolactone) diblock copolymer (PB-PCL)/polybutadiene homopolymer (PB) blend were investigated by small-angle x-ray scattering (SAXS). Non-equilibrium spherical micelles were observed at temperatures ranging between 60 and 100 °C. An SAXS profile with  >60 scattering peaks was recorded at 140 °C. All the peak positions were in good agreement with theoretical Frank–Kasper σ phase peak positions. Thus, these results indicate the formation of a Frank–Kasper σ phase in the PB-PCL/PB blend at 140 °C. (paper)