Search

Poly(p-dioxanone) (PPDO) is crystallized with amorphous poly(p-vinyl phenol) (PVPh) and tannic acid (TA) as co-diluents to regulate and induce dendritic-ringed PPDO spherulites, with spoke- or sector-bands, aiming for convenience of analyses on interior lamellar assembly. Morphologies and interior lamellar arrangement leading to the peculiar rings on individual dendrites are evaluated by using polarized-light microscopy (PLM) and scanning electron microscope (SEM). Combinatory microbeam small-/wide-angle X-ray scattering (SAXS/WAXS) analyses further confirm the unique assembly patterns in periodic cycles. Alternate gratings are packed with periodic ridges composed of feather-like branches and the valley is featured with some embossed textures. The periodic gratings in the ringed spokes resemble those in nature's structured coloration and are proven to display light-interference iridescence. [ABSTRACT FROM AUTHOR]

Poly(p-dioxanone) (PPDO) is crystallized with amorphous poly(p-vinyl phenol) (PVPh) and tannic acid (TA) as co-diluents to regulate and induce dendritic-ringed PPDO spherulites, with spoke- or sector-bands, aiming for convenience of analyses on interior lamellar assembly. Morphologies and interior lamellar arrangement leading to the peculiar rings on individual dendrites are evaluated by using polarized-light microscopy (PLM) and scanning electron microscope (SEM). Combinatory microbeam small-/wide-angle X-ray scattering (SAXS/WAXS) analyses further confirm the unique assembly patterns in periodic cycles. Alternate gratings are packed with periodic ridges composed of feather-like branches and the valley is featured with some embossed textures. The periodic gratings in the ringed spokes resemble those in nature’s structured coloration and are proven to display light-interference iridescence.

The objective of this study is to clarify the effect of restoring the lowered masticatory muscle functional pressure and correcting bilateral differences in masticatory muscle functional pressure on jawbone growth during growth and development with a quantitative evaluation of the changes in the micro/nanostructural characteristics of entheses. Male Wistar rats aged 4 weeks were divided into an experimental group injected with a botulinum toxin serotype A (BoNT/A) formulation to reduce muscle function (BTX group) and a control group (CTRL group). They were euthanised after 6, 8, 10, 12, and 16 weeks after measuring the difference between the midline of the upper and lower incisors. The mandibles were harvested for histological examination, second harmonic generation imaging, and the quantitative evaluation of biological apatite (BAp) crystal alignment. The midline difference decreased with age in weeks. In rats from 6 weeks after BoNT/A administration to 12 weeks after administration, the collagen fibre bundle diameter was significantly smaller in the BTX group; the difference between the two groups decreased with increasing age. BAp crystal alignment was significantly different on the x-axis and the y-axis on the BTX group from 6 weeks after BoNT/A administration to 10 weeks after administration. Asymmetry of mandibular bone formation caused by load imbalance during growth could be corrected by the adjustment of the function of the masseter muscle on either side. [ABSTRACT FROM AUTHOR]

The objective of this study is to clarify the effect of restoring the lowered masticatory muscle functional pressure and correcting bilateral differences in masticatory muscle functional pressure on jawbone growth during growth and development with a quantitative evaluation of the changes in the micro/nanostructural characteristics of entheses. Male Wistar rats aged 4 weeks were divided into an experimental group injected with a botulinum toxin serotype A (BoNT/A) formulation to reduce muscle function (BTX group) and a control group (CTRL group). They were euthanised after 6, 8, 10, 12, and 16 weeks after measuring the difference between the midline of the upper and lower incisors. The mandibles were harvested for histological examination, second harmonic generation imaging, and the quantitative evaluation of biological apatite (BAp) crystal alignment. The midline difference decreased with age in weeks. In rats from 6 weeks after BoNT/A administration to 12 weeks after administration, the collagen fibre bundle diameter was significantly smaller in the BTX group; the difference between the two groups decreased with increasing age. BAp crystal alignment was significantly different on the x-axis and the y-axis on the BTX group from 6 weeks after BoNT/A administration to 10 weeks after administration. Asymmetry of mandibular bone formation caused by load imbalance during growth could be corrected by the adjustment of the function of the masseter muscle on either side.

The correlation between water molecules and polylactide was clarified. The crystallinity in stereocomplex (SC) crystal spherulites was investigated using microbeam wide-angle X-ray diffraction. The crystallinity was higher in the central region, and edge-on lamellae grew in a twisted manner. The hydrogen bonding in SC-crystal spherulites was evaluated via microbeam FT-IR spectroscopy in a humidity-controlled cell. The water-derived bands corresponding to OH vibration and HOH bending increased with increasing humidity. Microbeam FT-IR spectroscopy was used to evaluate the water absorption behavior of crystalline films depending on their position. Coarse-grained molecular dynamics simulations indicated that the number of adsorbed water molecules increased with decreasing crystallinity. In SC-crystal spherulites, water molecules are absorbed in both amorphous and crystalline regions but with greater difficulty in the crystalline regions. These insights into water molecule absorption on SC-crystal spherulite can facilitate the development of polylactide materials with controlled biodegradability for advanced medical and optical applications. [Display omitted] • Water absorption on PLLA/PDLA blended films was investigated. • Interactions between water molecules and Sc-crystal spherulites were clarified. • The crystallinity of the spherulites was investigated using microbeam XRD. • Hydrogen bonding in spherulites was assessed by microbeam FT-IR spectroscopy. [ABSTRACT FROM AUTHOR]

The importance of considering bone quality during oral implant treatment is increasingly being recognized. Assessment of bone quality in response to changes in the jaw bone is extremely important when planning treatment. The present study analyzed biological apatite (BAp) crystallites, a bone quality factor, in order to investigate crystallographic anisotropy in dentate and edentulous human mandibles. Using mandibular samples from Japanese adult cadavers, a region of interest was established comprising cortical bone in the central incisors. Samples were classified into five morphological categories based on the extent of bone resorption. Bone mineral density (BMD) was measured and diffraction intensity ratios were calculated using a microbeam X‐ray diffraction system. While no differences were observed in BMD, differences were observed in BAp crystallite alignment between the measurement points. In the alveolar region, samples with residual alveolar bone showed strong alignment in the occlusal direction, while samples with marked alveolar bone resorption had preferential alignment in the mesiodistal direction. The present findings suggest that tooth loss and the extent of alveolar bone resorption affects bone quality in the mandible. © 2018 Wiley Periodicals, Inc. J. Biomed. Mater. Res. Part B: 2018. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 838–846, 2019. [ABSTRACT FROM AUTHOR]

For the development of next-generation batteries it is important to understand the structural changes in electrodes under realistic non-equilibrium conditions. With microbeam X-ray diffraction it is possible to probe many individual electrode grains concurrently under non-equilibrium conditions in realistic battery systems. This makes it possible to capture phase transformation behavior that is difficult or even impossible with powder diffraction. By decreasing the X-ray beam size, the diffraction powder rings fall apart in the (hkl) reflections belonging to individual electrode crystallites. Monitoring these reflections during (dis)charging provides direct insight in the transformation mechanism and kinetics of individual crystallite grains. Here operando microbeam diffraction is applied on two different cathode materials, LiFePO4 (LFP) displaying a first-order phase transformation and LiNi1/3Co1/3Mn1/3O2 (NCM) displaying a solid solution transformation. For LFP four different phase transformation mechanisms are distinguished within a single crystallite: (1) A first-order phase transformation without phase coexistence, (2) with phase coexistence, (3) a homogeneous solid solution phase transformation and (4) an inhomogeneous solid solution crystal transformation, whereas for NCM only type (3) is observed. From the phase transformation times of individual crystallites, the local current density is determined as well as the active particle fractions during (dis)charge. For LFP the active particle fraction increases with higher cycling rates. At low cycling rates the active particle fraction in NCM is much larger compared to LFP which appears to be related to the nature of the phase transition. In particular for LFP the grains are observed to rotate during (dis)charging, which can be quantified by microbeam diffraction. It brings forward the mechanical working of the electrodes due to the volumetric changes of the electrode material possibly affecting electronic contacts to the carbon black conducting matrix. These results demonstrate the structural information that can be obtained under realistic non-equilibrium conditions, combining local information on single electrode crystallites, as well as global information through the observation in many crystallites concurrently. This provides new and complementary possibilities in operando battery research, which can contribute to fundamental understanding as well as the development of electrodes and electrode materials.

When controlling electronic properties of bulk materials, we usually assume that the basic crystal structure is fixed. However, in two-dimensional (2D) materials, atomic structure or polymorph is attracting growing interest as a controlling parameter to functionalize their properties. Various polymorphs can exist in transition metal dichalcogenides (TMDCs) from which 2D materials are generated, and polymorphism has drastic impacts on the electronic states. Here we report the discovery of an unprecedented polymorph of a TMDC 2D material. By mechanical exfoliation, we made thin flakes from a single crystal of 2Ha-type tantalum disulfide (TaS2), a metallic TMDC with a charge-density-wave (CDW) phase. Microbeam X-ray diffraction measurements and electrical transport measurements indicate that thin flakes possess a polymorph different from any one known in TaS2 bulk crystals. Moreover, the flakes with the unique polymorph displayed the dramatically enhanced CDW ordering temperature. The present results suggest the potential existence of diverse structural and electronic phases accessible only in 2D materials. [ABSTRACT FROM AUTHOR]

Microbeam wide-angle X-ray diffraction (WAXD) experiments were carried out at different structural knot positions of SIOC and M4 fibers of ultra-high molecular weight polyethylene (UHMWPE). The optical microscope images revealed that SIOC fiber had bamboo-like structural knots, and M4 fiber had chaotic distribution of structural knots. WAXD patterns showed the monoclinic unit cell in the whole M4 fiber, but different lamellar orientations in the bamboo joint of SIOC fiber. In addition, small-angle X-ray scattering (SAXS) patterns confirmed that the SIOC fiber contained uniform distribution of shish structures, and differential scanning calorimetry (DSC) measurements showed that its less branched and short chains benefited the orthorhombic-hexagonal phase transformation. [ABSTRACT FROM AUTHOR]

Microbeam X-ray diffraction experiments were conducted at beam line 34-ID of the Advanced Photon Source (APS) on fission fragment energy Xe heavy ion irradiated single crystal Molybdenum (Mo). Lattice strain measurements were obtained with a depth resolution of 0.7 μm, which is critical in resolving the peculiar heterogeneity of irradiation damage associated with heavy ion irradiation. Q-space diffraction peak shift measurements were correlated with lattice strain induced by the ion irradiations. Transmission electron microscopy (TEM) characterizations were performed on the as-irradiated materials as well. Nanometer sized Xe bubble microstructures were observed via TEM. Molecular Dynamics (MD) simulations were performed to help interpret the lattice strain measurement results from the experiment. This study showed that the irradiation effects by fission fragment energy Xe ion irradiations can be collaboratively understood with the depth resolved X-ray diffraction and TEM measurements under the assistance of MD simulations. [ABSTRACT FROM AUTHOR]

Bone tissue has a specific anisotropic morphology derived from collagen fiber alignment and the related apatite crystal orientation as a bone quality index. However, the precise mechanism of cellular regulation of the crystallographic orientation of apatite has not been clarified. In this study, anisotropic construction of cell-produced mineralized matrix in vitro was established by initiating organized cellular alignment and subsequent oriented bone-like matrix (collagen/apatite) production. The oriented collagen substrates with three anisotropic levels were prepared by a hydrodynamic method. Primary osteoblasts were cultured on the fabricated substrates until mineralized matrix formation is confirmed. Osteoblast alignment was successfully regulated by the level of substrate collagen orientation, with preferential alignment along the direction of the collagen fibers. Notably, both fibrous orientation of newly synthesized collagen matrix and c-axis of produced apatite crystals showed preferential orientation along the cell direction. Because the degree of anisotropy of the deposited apatite crystals showed dependency on the directional distribution of osteoblasts cultured on the oriented collagen substrates, the cell orientation determines the crystallographic anisotropy of produced apatite crystals. To the best of our knowledge, this is the first report demonstrating that bone tissue anisotropy, even the alignment of apatite crystals, is controllable by varying the degree of osteoblast alignment via regulating the level of substrate orientation. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 489-499, 2015. [ABSTRACT FROM AUTHOR]

Morphological and directional alteration of cells is essential for structurally appropriate construction of tissues and organs. In particular, osteoblast alignment is crucial for the realization of anisotropic bone tissue microstructure. In this article, the orientation of a collagen/apatite extracellular matrix (ECM) was established by controlling osteoblast alignment using a surface geometry with nanometer-sized periodicity induced by laser ablation. Laser irradiation induced self-organized periodic structures (laser-induced periodic surface structures; LIPSS) with a spatial period equal to the wavelength of the incident laser on the surface of biomedical alloys of Ti–6Al–4V and Co–Cr–Mo. Osteoblast orientation was successfully induced parallel to the grating structure. Notably, both the fibrous orientation of the secreted collagen matrix and the c -axis of the produced apatite crystals were orientated orthogonal to the cell direction. To the best of our knowledge, this is the first report demonstrating that bone tissue anisotropy is controllable, including the characteristic organization of a collagen/apatite composite orthogonal to the osteoblast orientation, by controlling the cell alignment using periodic surface geometry. [ABSTRACT FROM AUTHOR]

X-ray diffraction techniques are used in imaging mode in order to characterize micrometre-sized objects. The samples used as models are metal-oxide tunnel junctions made by optical lithography, with lateral sizes ranging from 150 µm down to 10 µm and various shapes: discs, squares and rectangles. Two approaches are described and compared, both using diffraction contrast: full-field imaging (topography) and raster imaging (scanning probe) using a micrometre-sized focused X-ray beam. It is shown that the full-field image gives access to macroscopic distortions ( e.g. sample bending), while the local distortions, at the micrometre scale ( e.g. tilts of the crystalline planes in the vicinity of the junction edges), can be accurately characterized only using focused X-ray beams. These local defects are dependent on the junction shape and larger by one order of magnitude than the macroscopic curvature of the sample. [ABSTRACT FROM AUTHOR]

Abstract: The effects of flow-altering inserts and mold cavity geometry on the mechanical properties of an injection molded liquid crystalline polymer were studied to produce parts with properties approaching macroscopically isotropic state. By inserting fine metal mesh barriers to the gates of the mold cavities, a large number of highly oriented microstreams are produced. After their creation these highly oriented streams of differing flow vectors intertwine and this texture remains reasonably intact even after substantial shearing and extension history imparted on them during ensuing flow into the cavity. This method is effective in the interior away from the skin regions formed under the shearing flow during injection. The local molecular orientation was determined using a matrixing microbeam WAXS technique that allows precision movement of the sample in the microbeam X-ray. Samples produced with the 1.0mm2 mesh showed large variations in the local symmetry axis with respect to the machine as measured by microbeam X-ray diffraction incrementally from the edge to the core of the parts. In comparison, samples with no mesh insert showed only gradual changes in the tilt angle (angle between local symmetry axis and flow direction). The modulus and tensile strengths of all samples with the 1.0mm2 mesh inserts were found to approach virtual global mechanical isotropy. [Copyright &y& Elsevier]

Combinatorial approach for discovering novel functional materials in the huge diversity of chemical composition and processing conditions has become more important for breakthrough in thin film electronic and energy-conversion devices. The efficiency of combinatorial method depends on the preparation of a reliable high-density composition thin-film library. The physico-chemical properties of each sample on the library should be similar to those of the corresponding samples prepared by one-by-one conventional methods. We successfully developed the combinatorial liquid source misted chemical deposition (LSMCD) method and demonstrated its validity in screening the chemical composition of Bi3.75LaxCe0.25-xTi3O12 (BLCT) for high remanent polarization (Pr). LSMCD is a cheap promising combinatorial screening tool, It can control the composition up to ppm level and produce homogeneous multicomponent library. LSMCD method allows us to prepare BLCT thin-film library at the variation of 0.4 mol% of La. Maximum 2Pr is 35 µC/cm-2 at x = 0.21. The intensity of (117) XRD peak is quantitatively related to 2Pr. Newly developed scanning piezoelectric deformation measurement for nano-sized samples using scanning probe microscope (SPM) is also found out to be reliable for determining the relative ranking of Pr value rapidly. [ABSTRACT FROM AUTHOR]

Microbeam wide-angle X-ray scattering (WAXS) experiments have been carried out at different locations of a single-fiber PE homocomposite. The diffraction patterns reveal an oriented crystalline structure within a layer of 9 μm away from the fiber surface. This layer is associated with the occurrence of a transcrystalline interphase. The crystal structure appearing at the different locations of the composite material is predominantly orthorhombic. However, a small amount of a monoclinic phase was found to appear at the fiber skin and within the transcrystalline layer. The azimuthal scans of the two-dimensional (2D) WAXS patterns obtained at different sites of the transcrystalline phase were studied to estimate the crystal unit cell directions at each diffracted point. Finally, an analysis of the integral breadth of the (110) and (200) orthorhombic reflections in the matrix, in the transcrystalline interphase, and in the fiber is reported. *Dedicated to Prof. Francisco J. Baltá Calleja on the occasion of his 65th birthday. [ABSTRACT FROM AUTHOR]

• Structural studies of SOFC materials by microbeam X-ray diffraction technique. • Refinement of the lattice parameters of SOFC materials in the cell cross section. • Clarification of the changes in the crystal structure at micrometer intervals inside the SOFC. Microbeam X-ray diffraction (µ-XRD) using synchrotron radiation at BL33XU (Toyota beamline) in SPring-8 produces a small beam size (1 µm × 1 µm) that allows detecting changes in the lattice parameter and crystal phase of samples. This feature renders this technique suitable for the structural investigation of solid oxide fuel cells (SOFC) having a layered structure of various components in a micrometer order. In this study, using the µ-XRD technique, the refinement of the lattice parameters of SOFC materials and the assignment of secondary phases (e.g., a solid solution of CeO 2 –ZrO 2 and SrZrO 3) formed by interdiffusion between layers at the interface with micrometer intervals are achieved in the cell cross section, which had not been accomplished using conventional XRD methods. [ABSTRACT FROM AUTHOR]

The radial crystallization difference of polypropylene (PP) fiber along spinning line was investigated via synchrotron radiation microbeam X‐ray diffraction (μ‐XRD) analysis for the first time. Running fibers were collected at different spinning line positions to study its radial crystallization difference. The distribution of crystallinity, crystal form, and crystal size of PP fiber were obtained based on peak deconvolution. The relation between radial crystallization difference and processing condition was also investigated. The results indicate that the crystallinity of PP in the center region is found higher than the surface due to the radial temperature gradient during melt spinning, and the structure of fiber is highly sensitive to the radial temperature gradient. The crystallinity increased along spinning line and reaches a steady rate after 50 cm of spinning line position. The crystallite size increased before 50 cm of spinning line position and has a slight decrease after 50 cm due to the growth and splitting of crystal. These results display a 2D view of crystallization development of fiber during the melt spinning and give us a basic knowledge about the relation between structure evolution and processing conditions both in axis and radial directions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47175. [ABSTRACT FROM AUTHOR]

When controlling electronic properties of bulk materials, we usually assume that the basic crystal structure is fixed. However, in two-dimensional (2D) materials, atomic structure or polymorph is attracting growing interest as a controlling parameter to functionalize their properties. Various polymorphs can exist in transition metal dichalcogenides (TMDCs) from which 2D materials are generated, and polymorphism has drastic impacts on the electronic states. Here we report the discovery of an unprecedented polymorph of a TMDC 2D material. By mechanical exfoliation, we made thin flakes from a single crystal of 2Ha-type tantalum disulfide (TaS 2 ), a metallic TMDC with a charge-density-wave (CDW) phase. Microbeam X-ray diffraction measurements and electrical transport measurements indicate that thin flakes possess a polymorph different from any one known in TaS 2 bulk crystals. Moreover, the flakes with the unique polymorph displayed the dramatically enhanced CDW ordering temperature. The present results suggest the potential existence of diverse structural and electronic phases accessible only in 2D materials.