Stress mapping reveals extrinsic toughening of brittle carbon fiber in polymer matrix.

We conducted an in situ study on CFRP fracturing process using atomic-force-microscopy-based stress-sensitive indentation. Tensile stress distribution during fracture initiation and propagation was directly observed quantitatively. It led to a discovery that previously believed catastrophic fracture of individual carbon fiber develops in a controllable manner in the polymer matrix, exhibiting 10 times increase of fracture toughness. Plastic deformation in crack-bridging polymer matrix was accounted for the toughening mechanism. The model was applied to explain low temperature strength weakening of CFRP bulk material when matrix plasticity was intentionally 'shut down' by cryogenic cooling.

Stress dependence of indentation modulus for carbon fiber in polymer composite.

Elastic modulus measured through atomic force microscopy (AFM)-based indentation on single carbon fiber (CF) is found with dependence on lateral applied stress. An in situ indentation experiment inside a high-resolution transmission electron microscope was performed to quantitatively understand this phenomenon by observing microstructure change in the indented area. Change of graphitic basal plane misalignment angle during indentation was linked to a continuous change of modulus with the help of finite element simulation. The established relationship between modulus and indentation force was further used to calculate residual stress distribution in CF imbedded in a CF reinforced polymer composite using the AFM indentation technique. The stress-induced formation of nanoscale defects in the CF and their transformation into fracture were directly characterized.

Rewriting the phase diagram of a diamagnetic liquid crystal by a magnetic field.

Magnetic fields have been considered to only interact with organic materials non-destructively, leaving their fundamental structures unaffected, even when a strong magnetic field generated from a superconducting magnet is applied. Here we report an unprecedented observation that a liquid-crystalline mesophase of a diamagnetic molecular assembly with an orthorhombic or a cubic structure is formed selectively in the absence or presence of a strong magnetic field. The constituent molecule is a triphenylene derivative carrying six imidazolium bromide-terminated alkyl side chains and exhibits a cubic, orthorhombic, or hexagonal columnar mesophase when complexed with an appropriate amount of lanthanum(III) bromide. Thermal processing of the La3+-containing liquid-crystalline assembly in the presence of a 10-tesla magnetic field resulted in a phase diagram, in which the orthorhombic phase is completely replaced with the cubic phase. The discovery of this magneto-induced phase-selection offers an insight into the interactions between magnetic fields and organic material.

Time of flight-secondary ion mass spectrometry analysis of protein adsorption on a polyvinylidene difluoride surface modified by ion irradiation.

We investigated the effects of nanoscopic surface modification of polyvinylidene difluoride (PVDF) and low-density polyethylene (LDPE) by plasma-based ion implantation on protein adsorption with time of flight-secondary ion mass spectrometry (ToF-SIMS) analysis. The chemical composition of the LDPE and PVDF surfaces was changed by ion irradiation. In particular, irradiation substantially decreased the number of CH and CF bonds on the PVDF surface, but only slightly decreased that of CH bonds for LDPE. These decreases may reflect a higher hydrogen recombination rate of the LDPE than the PVDF surface. An increase in oxygen was observed on both the LDPE and PVDF surfaces following ion irradiation, but was saturated after irradiation of 1×1015cm-2 on the PVDF surface. The hydrophilicity of the ion-irradiated LDPE surface was promoted with an increase of the total ion fluence. Ion irradiation also changed the surface properties of PVDF to become more hydrophilic, but the variation did not correlate with the total ion fluence presumably due to the presence of fluorine atoms and the saturation of oxidation. Both bovine serum albumin (BSA) and collagen adsorption were suppressed on the LDPE surface by ion irradiation, which may have resulted from a decrease of the hydrophobic interaction. By contrast, ion irradiation increased protein adsorption on the PVDF surface, and BSA was adsorbed more than collagen, whereas there was no difference in the adsorption between BSA and collagen on the ion-irradiated LDPE surface. Moreover, the adsorption of BSA decreased on the oxygen- and fluorine-rich PVDF surface. These results indicate that the nanoscopic composition changes on the PVDF surface affect the adsorption behavior of BSA. Specifically, ferroelectric property on the PVDF surface was changed by ion irradiation and the nanoscopic change in polarity presumably affected the protein adsorption. Our findings suggest that selective adsorption control of protein can be achieved by ion irradiation to PVDF surface.

Anisotropic magnetic properties and magnetic structure of YbPdSi.

YbPdSi with orthorhombic crystal structure (space group Pmmn) exhibits a magnetic transition at [Formula: see text] K, below which a ferromagnetic moment develops with an enhanced electronic specific-heat coefficient [Formula: see text] mJ K(-2) mol(-1). We have investigated the magnetization, electrical resistivity, and specific heat of YbPdSi using single crystalline samples as functions of temperature and magnetic field. It has been found that the ferromagnetic moment points to the c-direction, although the magnetic moments have an Ising-like anisotropy along the b-direction above the magnetic-transition temperature. Field dependence of the magnetization and electrical resistivity shows a metamagnetic-like transition at [Formula: see text] T when field is applied along the b-axis below T = 3 K, suggesting the existence of an antiferromagnetic component along this direction. The magnetic structure has been investigated by neutron diffraction using powder samples. The magnetic unit cell is identical to the crystal unit cell. The Rietveld fitting has revealed that Yb at the 2a and 2b positions exhibit a collinear ferromagnetic order along the c-axis, whereas Yb at the 4e position undergoes a non-collinear order, involving the ferromagnetic moment along the c-axis and an antiferromagnetic component along the b-axis. The ferromagnetic moments determined by the neutron diffraction are 0.26, 1.3, and 0.15 [Formula: see text] for Yb at the 4e, 2b, and 2a sites, respectively. The reduced moments for the 4e and the 2a sites suggest that the Kondo screening effect is important in YbPdSi.

Magnetic structure of the ferromagnetic Kondo-lattice compounds YbPtGe and YbPdGe.

YbPtGe and YbPdGe exhibit ferromagnetic ordering below Tc = 5.4 and 11.4 K with enhanced electronic specific heat coefficients of γ = 209 and 150 mJ K(-2) mol, respectively. In order to shed light on the origin of the coexistence of a ferromagnetic state and heavy-fermion behavior, we studied the powder neutron diffraction of YbPtGe and YbPdGe at low temperatures. Weak reflections due to magnetic ordering have been resolved. The data were analyzed using the Rietveld method together with group theory analysis. It has been found that YbPtGe exhibits a non-collinear ferromagnetic structure, with a spontaneous moment along the c-axis and a weak antiferromagnetic component along the a-axis. The presence of this antiferromagnetic component explains the origin of the observed metamagnetic-like behavior. In the case of YbPdGe, magnetization measurements confirmed the ferromagnetic moment along the b-axis and revealed a metamagnetic transition at 0.2 T for a field parallel to the c-axis. The neutron diffraction results indicate that the magnetic structure of YbPdGe is also of a non-collinear type, with ferromagnetic moments parallel to the b-axis and weak antiferromagnetic components along the c-axis, which is consistent with the magnetization data. A comparison of the results for YbPtGe and YbPdGe has been made. It is suggested that both the Kondo screening effect of ferromagnetic moments and the fluctuation of antiferromagnetic components can contribute to the enhanced mass in the ferromagnetic state.

Speciation of radioactive soil particles in the Fukushima contaminated area by IP autoradiography and microanalyses.

Radioactive soil particles several tens of micrometers in size were collected from litter soil in the radiation contaminated area by the Fukushima nuclear plant accident and characterized using electron and X-ray microanalyses. The radioactive particles were discriminated by autoradiography using imaging plates (IP) on which microgrids were formed by laser ablation in order to find the particles under microscopy. Fifty radioactive particles were identified and classified into three types from their morphology and chemical composition, namely: (1) aggregates of clay minerals, (2) organic matter containing clay mineral particulates, and (3) weathered biotite originating from local granite. With respect to the second type, dissolution of the organic matter did not reduce the radiation, suggesting that the radionuclides were also fixed by the clay minerals. The weathered biotite grains have a plate-like shape with well-developed cleavages inside the grains, and kaolin group minerals and goethite filling the cleavage spaces. The reduction of the radiation intensity was measured before and after the trimming of the plate edges using a focused ion beam (FIB), to examine whether radioactive cesium primarily sorbed at frayed edges. The radiation was attenuated in proportion to the volume decrease by the edge trimming, implying that radioactive cesium was sorbed uniformly in the porous weathered biotite.

Spiral-spin-driven ferroelectricity in a multiferroic delafossite AgFeO2.

We have performed dielectric measurements and neutron diffraction experiments on the delafossite AgFeO2. A ferroelectric polarization P is approximately equal to 300 µC/m2 was observed in a powder sample, below 9 K. The neutron diffraction experiment demonstrated successive magnetostructural phase transitions at T(N1)=15 K and T(N2)=9 K. The magnetic structure for 9 K≤T≤15 K is a spin-density wave with a temperature dependent incommensurate modulation k=(-1, q, 1/2), q is approximately equal to 0.384. Below 9 K, the magnetic structure turns into elliptical cycloid with the incommensurate propagation vector k=(-1/2,q,1/2), q is approximately equal to 0.2026 Based on the deduced magnetic point-group symmetry m1' of the low-temperature polar phase, we conclude that the ferroelectric polarization in AgFeO2 is perpendicular to the monoclinic b axis and is driven by the inverse Dzyaloshinskii-Moriya effect with two orthogonal components p1 is proportional to r(ij)×(S(i)×S(j)) and p2 is proportional to S(i)×S(j).

Structural analysis of anodic porous alumina used for resistive random access memory.

Anodic porous alumina with duplex layers exhibits a voltage-induced switching effect and is a promising candidate for resistive random access memory. The nanostructural analysis of porous alumina is important for understanding the switching effect. We investigated the difference between the two layers of an anodic porous alumina film using transmission electron microscopy and electron energy-loss spectroscopy. Diffraction patterns showed that both layers are amorphous, and the electron energy-loss spectroscopy indicated that the inner layer contains less oxygen than the outer layer. We speculate that the conduction paths are mostly located in the oxygen-depleted area.

Calibration of an evaporative light-scattering detector as a mass detector for supercritical fluid chromatography by using uniform Poly(ethylene glycol) oligomers.

The quantitativeness of an evaporative light-scattering detector (ELSD) for supercritical fluid chromatography (SFC) was evaluated by using an equimass mixture of uniform poly(ethylene glycol) (PEG) oligomers. Uniform oligomers, in which all molecules have an identical molecular mass, are useful for the accurate calibration of detectors. We calibrated the SFC-ELSD system for various concentrations and molecular masses by using an equimass mixture of PEG oligomers. ELSD not only showed a good linear response to the injected concentration over a wide concentration range, from 10(-4) to 10(-1)g/mL, but also showed a strong dependence on the molecular mass of the solute. By using chromatograms of the equimass mixture of uniform oligomers to calibrate SFC-ELSD, it was possible to determine exact values of not only the average mass but also the molecular-mass distribution for a PEG 1540 sample. The average molecular mass was shifted to a higher value by several percentage points after calibration of the ELSD.

Formaldehyde uptake by Methylobacterium sp. MF1 and Acidomonas methanolica MB 58 with the different formaldehyde assimilation pathways.

Methylobacterium sp. MF1 (an obligate methylotrophic bacterium isolated newly by the authors) and Acidomonas methanolica MB58 (a facultative methylotrophic bacterium) uptake formaldehyde similarly. It was found that the former assimilated formaldehyde via the serine pathway whereas the latter did so via the ribulose-monophosphate pathway from the measurement of the key enzyme activities in each assimilation pathway. That is, hydroxy pyruvate reductase was detected in only the above-mentioned MF1 strain, but hexulose phosphate synthase (HPS) was not. The efficiencies of formaldehyde consumption by both strains under a continuous chemostat cultivation in the steady state were almost the same in spite of their different assimilation pathways. That is, the consumption efficiencies of the MF strain and the MB58 strain were ca. 1.2 g/L/d and ca. 1.8 g/L/d, respectively, under the experimental conditions. In the future, optimal continuous operating conditions will be investigated.

Formaldehyde-limited cultivation of a newly isolated methylotrophic bacterium, Methylobacterium sp. MF1: enzymatic analysis related to C1 metabolism.

Formaldehyde is a highly toxic compound to most living organisms. We have isolated a bacterial strain that is able to efficiently degrade formaldehyde and use it as a sole carbon source. The isolated strain was identified as Methylobacterium sp. MF1, which could grow on formaldehyde and methanol. Methylobacterium sp. MF1 was grown in batch culture using 1.2 g/l formaldehyde as a sole carbon source, which was all consumed within 200 h. In order to decompose formaldehyde more efficiently, formaldehyde-limited chemostat cultivation of Methylobacterium sp. MF1 was investigated. Formaldehyde was consumed at 1.7 g/l/d when the dilution rate was 0.012 h(-1). Under these conditions, the cell turbidity (OD610) reached 2.0. Furthermore, when the initial turbidity was adjusted to 3.0 using methanol-grown cells, continuous cultivation could be started at an initial dilution rate of 0.008 h(-1). Using these conditions, consumption of formaldehyde could be continued for at least 600 h. The enzyme activities of cells growing as a chemostat culture, using methanol or formaldehyde as a sole carbon source, were compared to that of C1 metabolism. No difference was detected in the enzyme activities for the oxidation and assimilation of C1 compounds between the two cell-free extracts. Furthermore, methanol dehydrogenase activity was detected at the same level when formaldehyde was used as a sole carbon source. These results suggest that the resistance to the toxic effects of formaldehyde exhibited by Methylobacterium sp. MF1 is related to factors other than C1 metabolism.