New ring-opening polymerization via a π-allylpalladium complex

Summary A binary system of a palladium complex as catalyst and zinc alkoxide as initiator conducted a novel ring-opening polymerization of cyclic carbonate, i. e., 5,5-dimethyl-4-ethenyl-1,3-dioxan-2-one. The polymerization proceeded along with releasing carbon dioxide to produce the corresponding polyether. The -allylpalladium complex generated from the monomer with the catalyst is the key intermediate for this new polymerization. The propagating end is zinc alkoxide, which nucleophilically attacks the monomer activated as the -allylpalladium complex in the propagation.     

Monte Carlo simulation of stress corrosion cracking on a smooth surface of sensitized stainless steel type 304

Stress corrosion cracking (SCC) on a smooth surface of structural metal materials occurs by initiation and coalescence of micro cracks, subcritical crack propagation and multiple large crack formation or final failure under combination of material, stress and corrosive environment. In this paper, a Monte Carlo simulation of the SCC process is proposed based on stochastic properties for micro crack initiation and concepts in fracture mechanics for crack coalescence and propagation. The procedure is as follows: The possible number of grain-sized micro cracks which can be initiated is set for a given space and initiation times for all cracks are assigned by random numbers based on exponential distribution. Sites and sizes of cracks are assigned by uniform random numbers and normal random numbers, respectively. Coalescence and propagation of cracks are determined based on fracture mechanics. The emphasis in the model is put on the influence of semi-elliptical surface cracks. Numerical simulations are carried out based on the results of creviced-bent-beam tests for sensitized stainless steel type 304 under high-temperature and high-purity water containing dissolved oxygen and the influence of micro crack initiation rate and coalescence condition on the simulation results is discussed.     

Measurement of the coating thickness on the back side of double-sided coated structures by means of acoustic resonant spectroscopy

This paper describes a technique for measuring the thickness of the back side coating of a double-sided coated structure using acoustic resonance. The technique is used to observe the resonant frequency of high frequency ultrasound for a steel/coating/air structure. The resonant frequency of the transmitted ultrasound occurs when a quarter wavelength corresponds to the thickness of the back side coating, and the reflection coefficient has a minimum value. The top surfaces of the samples are covered with a coating about 30 μm thick and the thickness of the back side coating is in the range of 10.3-17.5 μm. The resonant frequencies for the examined samples are observed in the frequency range of 46.8-75.6 MHz, and the thickness of the back side coating can be accurately determined from the measured resonant frequency. Note that the coating on the top surface of the structure does not affect the thickness measurement accuracy of the back side coating.     

A mechanism governing oxidation-assisted low-cycle fatigue of superalloys

A model capable of characterizing oxidation-assisted low-cycle fatigue is described. It involves the following steps. After a few strain cycles, because of creep, a tensile stress develops during the de-straining phase of the cycle. This stress opens cracks present in the material and exposes the surfaces to the atmosphere, causing thermally grown oxide (TGO) growth. Dilatation takes place upon converting the alloy to oxide, with an associated strain rate that induces a compressive growth stress. Thereafter, during the re-straining phase of the cycle, transverse extension of the substrate induces in-plane tension in the TGO, which “pushes” the TGO into the substrate along the crack front. Finite element simulations of this process have been presented that predict crack growth per cycle, da/dN, comparable with experimental measurements. Trends in da/dN with the TGO dilatation rate and the creep strength of the superalloy have been elucidated.     

Characteristic scales of two‐dimensional turbulence in polymer solutions

An experimental study has been performed to investigate the relationship between the extensional viscosity of polymers and the turbulent drag reduction. Self‐standing flowing soap film was used to generate two‐dimensional (2‐D) turbulent flow to eliminate shear stress. Two types of polymers having different flexibilities were added to the 2‐D turbulence. The effects of these polymers were visualized by the interference pattern of flowing soap films. The vortex deformation by adding polymers was analyzed by Fourier transformation and wavelet transformation. The scaling exponents of the power spectrum of interference patterns indicate that the mechanism of turbulence laminarization due to the extensional viscosity is anisotropic. A wavelet analysis reveals the high and low fluctuations of the polymer‐added flow. Results from wavelet analysis indicate disappearing of original vortices, and appearing of new structures in low frequency in 2‐D flow. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1854–1862, 2014     

Impact of Serum Chemerin Levels on Liver Functional Reserves and Platelet Counts in Patients with Hepatocellular Carcinoma

Obesity-related metabolic abnormalities, including adipokine imbalance and chronic inflammation, are involved in liver carcinogenesis. Chemerin, a novel adipokine, plays a critical role in adipogenesis, energy metabolism, and inflammation. We evaluated the impact of serum chemerin levels on liver functional reserves in hepatocellular carcinoma (HCC) patients and on the recurrence and prognosis of HCC. This study included 44 patients with any stage of HCC who underwent curative treatment at Gifu Municipal Hospital (Gifu, Japan) between 2006 and 2007. Recurrence-free survival and overall survival were estimated using the Kaplan-Meier method. Serum albumin levels (Pearson’s correlation coefficient; r = 0.3110, p = 0.0399), platelet counts (r = 0.4159, p = 0.0050), and prothrombin times (r = 0.3775, p = 0.0115) were significantly correlated with serum chemerin levels in patients with HCC, and they were inversely correlated with Child-Pugh scores (r = −0.3732, p = 0.0126), serum alanine aminotransferase levels (r = −0.3864, p = 0.0105), and total bilirubin levels (r = −0.4023, p = 0.0068). Among these variables, a multiple comparison test identified that platelet counts and total bilirubin levels were associated with serum chemerin levels (p < 0.0083). No significant correlation was found between serum chemerin levels and recurrence-free survival (p = 0.3691) or overall survival (p = 0.7916). In HCC patients, serum chemerin concentrations were correlated with liver functional reserves and platelet counts, but not with recurrence or prognosis.     

Molecular dynamics of DNA and nucleosomes in solution studied by fast-scanning atomic force microscopy

Nucleosome is a fundamental structural unit of chromatin, and the exposure from or occlusion into chromatin of genomic DNA is closely related to the regulation of gene expression. In this study, we analyzed the molecular dynamics of poly-nucleosomal arrays in solution by fast-scanning atomic force microscopy (AFM) to obtain a visual glimpse of nucleosome dynamics on chromatin fiber at single molecule level. The influence of the high-speed scanning probe on nucleosome dynamics can be neglected since bending elastic energy of DNA molecule showed similar probability distributions at different scan rates. In the sequential images of poly-nucleosomal arrays, the sliding of the nucleosome core particle and the dissociation of histone particle were visualized. The sliding showed limited fluctuation within ∼50 nm along the DNA strand. The histone dissociation occurs by at least two distinct ways: a dissociation of histone octamer or sequential dissociations of tetramers. These observations help us to develop the molecular mechanisms of nucleosome dynamics and also demonstrate the ability of fast-scanning AFM for the analysis of dynamic protein–DNA interaction in sub-seconds time scale.     

Quantitative structural analysis of twin boundary in alpha-Zn7Sb2O12 using HAADF STEM method

The structure and composition of the 1/4{110} twin boundary in alpha-Zn7Sb2O12 have been determined by using quantitative high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) analysis. The noise in the experimental HAADF STEM images is reduced by using the maximum entropy method and average processing, and the parameters used in dynamical simulations are experimentally determined. From the analysis, it has been found that octahedral sites in the twin boundary slightly shift parallel to the [110] direction, and a reduction of the Sb concentration at the octahedral sites on the plane adjacent to the twin boundary was detected. The reduction was measured from three regions in the same twin boundary, and the Sb concentrations were 4 +/- 3, 8 +/- 3 and 19 +/-2 at% from 33 at%.     

The Sliding Friction of Hybrid Composite Journal Bearing Under Various Test Conditions

The friction and wear behaviour of SiC, Si₃N₄ and SiC/Si₃N₄ composite ceramics were investigated with oscillating sliding (gross slip fretting) at room temperature. The influence of counter body material and the humidity of the surrounding air was studied with a ball-on-disc configuration with different ball materials (1000Cr6, Al₂O₃ SiC and Si₃N₄). The effect of RH on friction is marginal with exception of SiC (low friction) as counter body material. The wear behaviour, however, is strongly affected by humidity, showing inverse trends for different counter body materials. Consequently, the wear behaviour of a tribo couple can be improved by selecting an adequate mating material. The results reveal the necessity to control RH in tribological tests. For estimation of the performance of tribo couples under varying environmental conditions, a variation of RH is required. In tribo couples with single phase SiC, either as ball or disc, the tribological behaviour of the system is dominated by SiC. The friction behaviour of the composite material is in between the behaviour of the two single phase materials, Si₃N₄ and SiC, whereas the wear behaviour is very similar to that of single phase Si₃N₄.