Sillimanite‐mullite transformation observed in synchrotron X‐ray diffraction experiments

High‐resolution synchrotron powder X‐ray diffraction (XRD) experiments were conducted to clarify the transformation of sillimanite to mullite (mullitization) and determine the mullitization temperature (T_c). We were able to distinguish sillimanite and mullite in the XRD patterns, despite their very similar crystallographic parameters, and to detect the appearance of small mullite peaks among sillimanite peaks. Analysis of the Johnson‐Mehl‐Avrami (JMA) equation for mullitization ratio (ζ) revealed that at temperatures T≥1240°C the mullitization had the same kinetics. The activation energy E at T≥1240°C obtained from the Arrhenius plot was 679.8 kJ mol^?1. In analysis using a time‐temperature‐transformation diagram for mullitization, a mullitization curve of ζ=1% can be described as where t is time, n is a reaction‐mechanism‐dependent parameter determined as 0.324 by JMA‐analysis, k₀ is the frequency factor, E_A is the activation energy for atomic diffusion, and represents the activation energy for nucleation. The results of fitting the data to this equation were T_c=1199°C, A=3.9×10⁶ kJ mol^?1 K^?2, E_A=605 kJ mol^?1, and k₀=3.65×10¹⁵. We conclude that the boundary between sillimanite and mullite+SiO₂ in the phase diagram is ~1200°C.     

Investigation of laser consolidation process for metal powder by two-color pyrometer and high-speed video camera

This paper deals with the measurement of surface temperature on metal powder during the laser consolidation process with two-color pyrometer. Additionally, the aspect of selective laser sintering (SLS) and selective laser melting (SLM) of metal powder is visualized with high speed video camera. As a result, the surface temperature during the laser irradiation was ranged 1520–1810 °C and the consolidation phenomena was classified according to the melting point of metal powder. The metal powder at the heating process cohered intermittently to the melt pool although the laser beam was continuously irradiated to the powder surface.     

Internal-external transition for the oxidation of Fe-Cr-Ni austenitic stainless steels in steam

Several Fe-Cr-Ni austenitic stainless steels (Cr wt.%: 13–25, Ni wt.%: 15) were oxidized in steam for 1000 hr at 500–900°C. The oxide scales were examined and categorized with respect to the chromium concentration and the grain size of the base metal. Experiments showed three conditions for the critical bulk Cr concentration and the oxidation temperature at which the oxidation behavior changed drastically. Metallographic examination showed that two of these three conditions resulted from the internal-external transition of Cr₂O₃ either on the metal surface or along the grain boundaries of the base metal. Attempts were made to interpret these conditions from the available oxidation theories. Atkinson's treatment was employed with some modification to incorporate the grain-boundary diffusion of Cr in the base metal. The calculation basically explained the internal-external transition for the oxidation of these steels.     

Syntheses of group 4 transition metal complexes bearing 2-pyridinethiolate ligands and their catalytic activities for ethylene polymerization

Titanium bis(2-pyridinethiolate) complexes, Ti(6-R-SPy)₂(NMe₂)₂ (6-R-SPy = 6-R-2-pyridinethiolate, 3a: R = H; 3b: R = Me; 3c: R = Ph; 3d: R = C₆H₄-4-Me; 3e: R = C₆H₄-4-t-Bu; 3f: R = C₆H₃-3,5-Me₂), and the titanium bis(2-pyridinolate) complexes, Ti(6-Ph-OPy)₂(NMe₂)₂ (6-Ph-OPy = 6-phenyl-2-pyridinolate, 8) were prepared by treating Ti(NMe₂)₄ with 2 equiv. of 6-R-2-pyridinethiol or 6-Ph-2-pyridinol. The cis-configuration of the diamido moieties in the pseudo octahedral geometry was elucidated by X-ray crystallography for 3a. Reaction of M(NMe₂)₄ (M = Ti, Zr) with 4 equiv. of 2-pyridinethiol cleanly gave tetrakis(pyridinethiolate) complexes, M(6-H-SPy)₄·THF (6: M = Ti; 7: M = Zr). The triangular dodecahedral geometries of 6 and 7 were also revealed by X-ray crystallography. These complexes catalyzed ethylene polymerization upon activation with MAO (methylaluminoxane) or MMAO (modified MAO). The catalytic activities of titanium bis(6-aryl-pyridinethiolate) systems were found to be remarkably higher than that of titanium bis(6-methyl-pyridinethiolate) system. Among the complexes synthesized in this study, Ti[6-(C₆H₃-3,5-Me₂)-SPy]₂(NMe₂)₂ (3f)/MMAO showed the highest activity (1200 kg/Ti-mol h atm) for ethylene polymerization at 60 °C under atmospheric pressure. In contrast, the activity of the corresponding 6-aryl-pyridinolate system 8/MMAO was rather low (9.3 kg/Ti-mol h atm). Both the N-S chelating structure and the bulky aryl substituents are essential for the high activities of the 6-aryl-pyridinethiolate complexes.     

Hierarchical polymer nanocomposite coating material for 316L SS implants: Surface and electrochemical aspects of PPy/f-CNTs coatings

Biocompatible nanocomposite coatings can be synthesized to offer improved surface properties for biomaterials and biomedical implants. Nanocomposite coatings containing polypyrrole (PPy) matrix reinforced with functionalized multi-wall carbon nanotubes (f-CNTs) were deposited on 316L SS substrates using electrochemical route. FT-IR, XRD, SEM, and TEM were employed to characterize the nanocomposite microstructure. High resolution imaging showed relatively uniform dispersion of the CNTs in the nanocomposite with a typical tubular structure. Micro-indentation tests revealed improvement in the hardness of the PPy/CNTs coatings. Measurement of the contact angle indicated enhanced surface wettability of the nanocomposite coatings. The corrosion behavior of 316L SS samples coated with PPy/CNTs was studied in SBF medium. The corrosion potential and the breakdown potential of coated 316L SS substrates shifted to more noble values as compared to uncoated 316L SS samples. The results suggest that incorporating CNTs as reinforcements in PPy coatings can provide enhanced properties in terms of surface hardness, biocompatibility, and corrosion resistance.     

上海源水中DOM的分子质量及去除特性

采用分子质量排除高性能液相色谱仪 (SE—HPLC)对长江和黄浦江原水及经常规处理出水中溶解性有机物 (DOM)的分子质量分布进行了测定 ,原水中DOM分子质量分别为 80 0～ 44 0 0u和 80 0～ 1130 0u。长江原水经常规处理后的DOM分子质量分布基本不变 ,对不同分子质量的物质均有不同程度的去除 ,且分子质量越低 ,常规处理对UV2 60 的去除率也越小 ;而黄浦江原水经常规处理后有机物的分子质量分布向低分子侧推移 ,表明对大分子的去除率优于小分子 ,特别是对分子质量 <30 0 0u有机物的去除率极低。     

Fluorescent in situ hybridization analysis of open lactic acid fermentation of kitchen refuse using rRNA-targeted oligonucleotide probes

Reproducible amounts of lactic acid accumulate in minced kitchen refuse under open conditions with intermittent pH neutralization [Sakai et al., Food Sci. Technol. Res., 6, 140 (2000)]. Here, we showed that such pH-controlled open fermentation of kitchen refuse reproducibly resulted a selective proliferation of a major lactic acid bacterial (LAB) species. In one experiment, the predominant microorganisms isolated during the early phase (6 h) were Gammaproteobacteria. In contrast, those that predominated during the late phase (48 h) were always Lactobacillus plantarum in three independent experiments. To further quantify the microbial community within open lactic acid fermentation, we performed fluorescent in situ hybridization (FISH) analysis targeting 16S (23S) rRNA. We designed two new group-specific DNA probes: LAC722(L) was active for most LAB including the genera Lactobacillus, Pediococcus, Leuconostoc and Weisella, whereas Lplan477 was specific for L. plantarum and its related species. We then optimized sample preparation using lysozyme and hybridization conditions including temperature, as well as the formamide concentration and the salt concentration in the washing buffer. We succeeded in quantification of microorganisms in semi-solid, complex biological materials such as minced kitchen refuse by taking color microphotographs in modified RGB balance on pre-coated slides. FISH analysis of the fermentation of kitchen refuse indicated that control of the pH swing leads to domination by the LAB population in minced kitchen refuse under open conditions. We also confirmed that L. plantarum, which generates lactic acid in high quantities but with low optical activity, became the dominant microorganism in kitchen refuse during the late phase of open fermentation.     

Negative staining--carbon replica method, a new procedure to reveal ultrastructure of freeze-fractured membrane.

The present study was undertaken to report a new method which reveals the ultrastructure of freeze-fractured membrane faces. The method consists of initial replication of fractured surfaces of frozen specimens with evaporated carbon and treatment of the replicas with a negative staining solution after dissolution of specimens. This negative staining-carbon replica method reveals clear distribution, ultrastructures and precise size of intramembrane particles on the fractured membrane faces by means of density difference of negative staining solution which is deposited on the surfaces of carbon replicas.     

Neuromelanin in Parkinson’s Disease: Tyrosine Hydroxylase and Tyrosinase

Parkinson’s disease (PD) is an aging-related disease and the second most common neurodegenerative disease after Alzheimer’s disease. The main symptoms of PD are movement disorders accompanied with deficiency of neurotransmitter dopamine (DA) in the striatum due to cell death of the nigrostriatal DA neurons. Two main histopathological hallmarks exist in PD: cytosolic inclusion bodies termed Lewy bodies that mainly consist of α-synuclein protein, the oligomers of which produced by misfolding are regarded to be neurotoxic, causing DA cell death; and black pigments termed neuromelanin (NM) that are contained in DA neurons and markedly decrease in PD. The synthesis of human NM is regarded to be similar to that of melanin in melanocytes; melanin synthesis in skin is via DOPAquinone (DQ) by tyrosinase, whereas NM synthesis in DA neurons is via DAquinone (DAQ) by tyrosine hydroxylase (TH) and aromatic L-amino acid decarboxylase (AADC). DA in cytoplasm is highly reactive and is assumed to be oxidized spontaneously or by an unidentified tyrosinase to DAQ and then, synthesized to NM. Intracellular NM accumulation above a specific threshold has been reported to be associated with DA neuron death and PD phenotypes. This review reports recent progress in the biosynthesis and pathophysiology of NM in PD.