Ductile‐to‐brittle transition behavior of low molecular weight polycarbonate under carbon dioxide

We investigated the stress–strain behavior of low molecular weight polycarbonate for optical disc grade (OD‐PC) under carbon dioxide (CO₂) at various pressures, and compared the results with that under ambient pressure at various temperatures. Elongation at break decreased sharply with increased CO₂ pressure at around 2 MPa, while the elastic modulus decreased gradually up to 6 MPa. These results indicate that the tensile property changed from ductile to brittle with increased CO₂ pressure, although the molecular motion is accelerated due to the plasticization effect of CO₂. Such ductile‐to‐brittle transition is similar to that observed under elevated temperatures caused by chain disentanglement due to accelerated molecular motion. Although the changes of tensile properties were similar, the craze structure obtained by the brittle behavior was different, i.e., a filamented‐craze structure was obtained under high‐pressure CO₂, while a lace‐like one was obtained under elevated temperatures. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Molecular simulation and experimental studies of the miscibility of polylactic acid/polyethylene glycol blends

Computer simulation and experiments were performed to investigate the miscibility of PLA/PEG blends with different PEG concentrations. Flory-Huggins interaction (χ) parameter used to predict the miscibility for the blends was estimated by molecular dynamic simulation of fully atomistic model. The calculated χ parameter and radial distribution function suggest that the PLA and PEG blends are likely miscible at low PEG concentrations (10–30 wt%), but they become apparently immiscible at higher PEG content (>50 wt%). This result is consistent with density distribution of PLA and PEG beads calculated from dissipative particle dynamics simulation of coarse-grained model. To support the computational results, experiments based on differential scanning calorimetry (DSC) and rheometry were also performed. The DSC thermograms of 90:10, 80:20, and 70:30 (wt/wt) of PLA/PEG blends showed a single glass transition and PLA melting peak, indicating PLA/PEG is miscible over this composition. In rheometry, frequency (ω) dependence of storage moduli (G′) at low frequencies for 75:25 and 70:30 blends indicate that these samples are near the phase separation point.     

Prediction of brittle fracture initiating at ends of CJP groove welded joints with defects: study into applicability of failure assessment diagram approach

A series of tests, which reproduced brittle fracture starting from the region around the terminations of complete joint penetration groove welded joints, was conducted. The joint models under study represented a portion of welded beam flange-to-through diaphragm joints in beam-to-column connections. Various artificial weld defects were installed in the welded joints prior to testing. Test results were evaluated based on the failure assessment diagram approach specified in BS 7910. The conventional failure assessment diagrams predicted occurrences of brittle fracture erring on the very conservative side as expected, especially when applied to surface defects. The failure assessment diagram approach was modified by considering the effect of enhanced apparent toughness of material due to the loss of crack tip constraint. The modified failure assessment approach was found to predict the test results well.     

Spring bloom in a hypereutrophic lake, lake Kasumigaura, Japan—II Succession of phytoplankton species

Numerous phytoplankton species in Lake Kasumigaura were shown to comprise the Spring bloom in 1980. The predominant phytoplankton species that appeared during the Spring bloom belonged to 28 genera. A few species among them increased at any time to form a phytoplankton pulse, but the few species of phytoplankters that comprised a phytoplankton pulse did not exclude completely other phytoplankters. During the Spring bloom, one pulse was replaced by another pulse composed of a new grouping of different species. Throughout these replacements by natural selection in the bloom were numerous other species by phytoplankters at levels of abundance somewhat less than those which formed phytoplankton pulse.     

A case-control study of the association between urinary cadmium concentration and endometriosis in infertile Japanese women

Cadmium may act like an estrogen and be a potential risk factor for estrogen-related diseases such as breast cancer and endometriosis. Here, we tested the hypothesis that higher cadmium exposure is associated with endometriosis among infertile Japanese women in a hospital-based case-control study. We recruited consecutive female patients aged 20-45 years who had complained of infertility and presented to a university hospital in Tokyo. The subjects were interviewed and provided a urine sample prior to a laparoscopic diagnosis of endometriosis between January 2000 and December 2001. The severity of endometriosis was then dichotomized into controls (stage 0 and I) and cases (stage II-IV). We finally measured urinary total cadmium concentration in 54 cases and 74 controls as a biomarker of long-term cumulative exposure. Odds ratios were adjusted for average menstrual cycle length, body-mass index and smoking status using unconditional logistic regression. Results showed no association between endometriosis and urinary cadmium concentration. Medians (interquartile ranges) of urinary cadmium concentration in cases and controls were 0.53 (0.40-0.73) and 0.54 (0.34-0.76) microg/g creatinine, respectively (P for difference=0.88). Adjusted odds ratio (95% confidence interval) for the highest versus lowest tertile of urinary creatinine-adjusted cadmium concentration was 0.86 (0.30 to 2.49, P for trend=0.79). Our results do not support the hypothesis that higher urinary cadmium concentration is associated with the risk of endometriosis.     

Nanosurface-confined anisotropic growth and magnetism of ellipsoidal alpha-Fe nanogranules

We have investigated the nanosurface-confined anisotropic growth of ordered-ellipsoidal Fe nanogranules when an Fe plume was deposited at a slanting angle onto an anodized aluminum oxide (AAO) film. Layer-by-layer growth was also investigated. This growth is driven by two critical factors: (1) a new rhombic AAO cell and (2) the slanting deposition of the Fe plume. During slanting deposition, the rhombic AAO cell induces strong restrictions in the nucleation site, growth direction, and granular size; therefore, the degree of freedom during growth is restricted. The magnetic dipoles of the ordered Fe nanogranules are placed along the long axis of the ellipsoid at an angle of 180 degrees (antiparallel) due to the demagnetizing field, shape anisotropy, and magnetic dipole-to-dipole interactions.     

Probing the unfolding and refolding processes of carbonic anhydrase 2 using electrospray ionization mass spectrometry combined with pH jump

A novel method for proving the time course of the unfolding and refolding processes of metalloprotein bovine carbonic anhydrase 2 (CA2) is demonstrated using electrospray ionization mass spectrometry (ESI MS) combined with pH jumps between 3.6 and 4.4. The shift in mass accompanied by the release or coordination of a zinc ion and the change in the charge state distribution were measured to evaluate the folding process. The time course of the ESI mass spectra revealed the existence of four types of ions in the experimental system, i.e., lower charged apo-CA2 and holo-CA2 ions and higher charged apo-CA2 and holo-CA2 ions. The deconvolution spectrum of the ion peak ensemble for each type of ion was processed and time course plots of the relative intensities of the four ions were prepared in order to analyze the folding processes. These analyses revealed the coexistence of two folding states of the lower and higher charged apo-CA2 under the condition of pH 3.6. The lower and higher charged apoproteins spontaneously refolded to the lower charged holoprotein by a pH jump from 3.6 to 4.4 without the addition of an extra zinc ion. The higher charged holoprotein observed during both the unfolding and refolding processes was considered to be an intermediate of the change in folding. The present study indicates that ESI MS combined with pH jump would be a powerful method to probe the unfolding and refolding of proteins. This method simultaneously measures mass spectra and analyzes the folding processes as a function of time using deconvolution spectra constructed by selecting a suitable m/z range for the analysis from the peaks of charge state distributions.     

Determination of surface selection rule of surface plasmon resonance near-infrared spectroscopy by using a Langmuir-Blodgett film

Near-infrared (NIR) absorption spectra of a cadmium arachidate Langmuir-Blodgett (LB) film were measured by surface plasmon resonance near-infrared spectroscopy (SPR-NIRS) based on the Kretschmann configuration with a 18.8-nm gold film. An NIR spectrum enhanced severalfold was obtained as a top ridge of the SPR-NIR spectra measured at different incident angles by using the principle of absorption-sensitive SPR. In order to determine the surface selection rule of SPR-NIRS, the enhanced NIR absorption spectrum of the LB film was compared to an unenhanced one without the gold film and to a normal incidence transmission spectrum. Moreover, a pair of out-of-plane (OP) and in-plane (IP) spectra were obtained by multiangle infrared spectroscopy analysis from a series of oblique incidence transmission measurements in the NIR region. It became obvious that the salient feature of the enhanced NIR absorption spectrum, i.e., the top ridge of the SPR-NIR spectra is almost equivalent to that of the OP spectrum. On the other hand, the unenhanced spectrum showed IP modes. These experimental results were well explained by calculation of the mean-square electric field based on the Fresnel formula.     

Electromechanical coupling coefficient k15 of polycrystalline ZnO films with the c-axes lie in the substrate plane

The (1120) textured polycrystalline ZnO films with a high shear mode electromechanical coupling coefficient k15 are obtained by sputter deposition. An over-moded resonator, a layered structure of metal electrode film/(1120) textured ZnO piezoelectric film/metal electrode film/silica glass substrate was used to characterize k15 by a resonant spectrum method. The (1120) textured ZnO piezoelectric films with excellent crystallite c-axis alignment showed an electromechanical coupling coefficient k15 of 0.24. This value was 92% of k15 value in single-crystal (k15 = 0.26).