The Role of Microstructure on High-Temperature Oxidation Behavior of Hafnium Carbide

Microstructure development of the products formed upon oxidation of hafnium carbide (HfCx, x = 0.65, 0.81, or 0.94) at 1300°C and 0.8 mbar oxygen pressure was investigated using Raman spectroscopy, X-ray diffraction, electron microscopy, and electron energy-loss spectroscopy. For all specimens a multilayered oxide scale was observed featuring an outermost porous hafnia layer and an interlayer adjacent to the parent carbide containing hafnia interspersed with carbon. The outermost hafnia features coarse pores presumably formed during initial stages of oxidation to allow rapidly evolving gaseous products to escape from the oxidation front. As the oxidation scale thickens, diffusional resistance results in slower oxidation rates and smaller quantities of gaseous products that are removed via networks of increasingly fine pores until the local oxygen partial pressure is sufficiently low to selectively oxidize the parent carbide. Electron microscopy studies suggest that the oxidation sequence at this stage begins with the transformation of parent carbide to an amorphous material having empirical formula HfO2Cx that subsequently phase separates into hafnia and carbon domains. Hafnia polymorphs in the phase-separated region vary from cubic to monoclinic as grains coarsen from ca. 2–20 nm, respectively. Immediately adjacent to the phase-separated region is carbon-free mesoporous hafnia whose pore morphology is inherited from that of prior carbon domains. The average pore size and pore volume fraction observed in mesoporous hafnia are consistent with predictions from kinetic models that ascribe gaseous diffusion through a pore network as the rate determining step in oxidation behavior of hafnium carbide. These observations imply that high-temperature oxidation behavior of hafnium carbide under the employed test conditions is linked to microstructure development via phase separation and coarsening behaviors of an initially formed amorphous HfO2Cx product

Shape Memory Alloys Via Halide-Activated Pack Equilibration

Fabrication of shape memory alloy (SMA) components based on NiTi is challenging due to the precision with which elemental composition and microstructure must be controlled during processing to achieve desired shape memory behavior. Herein, a method to control chemistry in an NiTi SMA via halide-activated pack equilibration (SHAPE) against a constant chemical potential reservoir is described. To demonstrate the efficacy of the SHAPE process, an initially titanium-deficient specimen (pure nickel foam) has been equilibrated against an excess of an intimately mixed two-phase pack (NiTi + Ti2Ni) in the presence of a vapor phase transport agent (iodine). The two-phase pack regulates chemical potentials in this two-component system in accordance with Gibbs\u27 phase rule. Ti-rich NiTi foams thus produced exhibit reproducible and well-defined phase transformation behaviors. The SHAPE process is advantageous for the fabrication of shape memory components of varying areal dimension, shape, and/or complexity owing to independence of the equilibrium state of the system from either the initial state of the specimen or the details of the process kinetics. Current limitations and prospects for the application of this method to improve the quality of SMA components are briefly discussed

Intragranular Nanocomposite Powders As Building Blocks For Ceramic Nanocomposites

A powder-based bottom-up processing scheme is introduced for the production of ceramic nanocomposites. Internal displacement reactions between solid solution powders and metallic reactants proceeding via gaseous intermediates are utilized to generate nanostructured building blocks for the synthesis of ceramic nanocomposites. Subsequent rapid sintering results in ceramic nanocomposites, whose microstructures are inherited from the building blocks. This processing scheme is demonstrated for the production of titanium carbide nanocomposites featuring up to 28 wt.% intragranular tungsten inclusions derived from titanium-tungsten mixed carbide powders. Heat treatment of mixed carbide powders in evacuated ampoules containing titanium sponge and iodine at 1000°C for 24 h resulted in nanocomposite powders featuring tungsten precipitates within titanium carbide grains that were subsequently consolidated via spark plasma sintering at 1300°C for 10 min to produce titanium carbide/metallic tungsten nanocomposites. Transformation of mixed titanium–tungsten carbide powders to titanium carbide/metallic tungsten nanocomposite powders was analyzed via X-ray diffraction. Electron microscopy observations of microstructures pre- and post- sintering showed that the intragranular character of nanocomposite powders can be retained in sintered ceramic nanocomposites. The building block approach demonstrated in this work represents an improved method to make ceramic nanocomposites with majority intragranular character

Synthesis and investigation of the spectral-luminescence characteristics of powder based on zinc oxide

ZnO and ZnAlO composites were synthesized by thermal decomposition of a precursor salt, dried at 200 °C and annealed at 400 and 600 °C, respectively. It was shown that pH and temperature of synthesis has great influence on the spectral-luminescence properties of samples

A Hyperbaric Aerodynamic Levitator For Containerless Materials Research

A hyperbaric aerodynamic levitator has been developed for containerless materials research at specimen temperatures exceeding 2000 °C and pressures up to 10.3 MPa (1500 psi). This report describes the prototype instrument design and observations of the influence of specimen size, density, pressure, and flow rate on levitation behavior. The effect of pressure on heat transfer was also assessed by studying the heating and cooling behavior of levitated Al2O3 liquids. A threefold increase in the convective heat transfer coefficient was estimated as pressure increased to 10.3 MPa. The results demonstrate that hyperbaric aerodynamic levitation is a promising technique for containerless materials research at high gas pressures

The β-1,3-glucanosyltransferases (Gels) affect the structure of the rice blast fungal cell wall during appressorium-mediated plant infection

The fungal wall is pivotal for cell shape and function, and in interfacial protection during host infection and environmental challenge. Here, we provide the first description of the carbohydrate composition and structure of the cell wall of the rice blast fungus Magnaporthe oryzae. We focus on the family of glucan elongation proteins (Gels) and characterize five putative β‐1,3‐glucan glucanosyltransferases that each carry the Glycoside Hydrolase 72 signature. We generated targeted deletion mutants of all Gel isoforms, that is, the GH72+, which carry a putative carbohydrate‐binding module, and the GH72− Gels, without this motif. We reveal that M. oryzae GH72+ GELs are expressed in spores and during both infective and vegetative growth, but each individual Gel enzymes are dispensable for pathogenicity. Further, we demonstrated that a Δgel1Δgel3Δgel4 null mutant has a modified cell wall in which 1,3‐glucans have a higher degree of polymerization and are less branched than the wild‐type strain. The mutant showed significant differences in global patterns of gene expression, a hyper‐branching phenotype and no sporulation, and thus was unable to cause rice blast lesions (except via wounded tissues). We conclude that Gel proteins play significant roles in structural modification of the fungal cell wall during appressorium‐mediated plant infection

Size-Matched Radical Multivalency

Persistent π-radicals such as MV^+• (MV refers to methyl viologen, i.e., N,Nꞌ-dimethyl-4,4ꞌ-bipyridinum) engage in weak radical-radical interactions. This phenomenon has been utilized recently in supramolecular chemistry with the discovery that MV+• and [cyclobis(paraquat-p-phenylene)]2(+•) (CBPQT2(+•)) form a strong 1:1 host-guest complex [CBPQT⊂MV]3(+•). In this full paper, we describe the extension of radical-pairing-based molecular recognition to a larger, square-shaped diradical host, [cyclobis(paraquat-4,4ꞌ-biphenylene)]2(+•) (MS2(+•)). This molecular square was assessed for its ability to bind an isomeric series of possible diradical cyclophane guests, which consist of two radical viologen units that are linked by two ortho-, meta-, or para-xylylene bridges to provide different spacings between the planar radicals. UV-Vis-NIR measurements reveal that only the m-xylylene-linked isomer (m-CBPQT2(+•)) binds strongly inside of MS2(+•), resulting in the formation of a tetra-radical complex [MS⊂m-CBPQT]4(+•). Titration experiments and variable temperature UV-Vis-NIR and EPR spectroscopic data indicate that, relative to the smaller tris-radical complex [CBPQT⊂MV]3(+•), the new host-guest complex forms with a more favorable enthalpy change that is offset by a greater entropic penalty. As a result, the association constant (Ka = (1.12+/- 0.08) x 10^5 M^(-1)) for [MS⊂m-CBPQT]4(+•) is similar to that previously determined for [CBPQT⊂MV]3(+•). The (super)structures of MS2(+•), m-CBPQT2(+•), and [MS⊂m-CBPQT]4(+•) were examined by single-crystal X-ray diffraction measurements and DFT calculations. The solid-state and computational structural analyses reveal that m-CBPQT2(+•) is ideally sized to bind inside of MS2(+•). The solid-state superstructures also indicate that localized radical-radical interactions in m-CBPQT2(+•) and [MS⊂m-CBPQT]4(+•) disrupt the extended radical-pairing interactions that are common in crystals of other viologen radical cations. Lastly, the formation of [MS⊂m-CBPQT]4(+•) was probed by cyclic voltammetry, demonstrating that the radical states of the cyclophanes are stabilized by the radical-pairing interactions

Consensus molecular subtype differences linking colon adenocarcinoma and obesity revealed by a cohort transcriptomic analysis

Colorectal cancer (CRC) is the third-leading cause of cancer-related deaths in the United States and worldwide. Obesity—a worldwide public health concern—is a known risk factor for cancer including CRC. However, the mechanisms underlying the link between CRC and obesity have yet to be fully elucidated in part because of the molecular heterogeneity of CRC. We hypothesized that obesity modulates CRC in a consensus molecular subtype (CMS)-dependent manner. RNA-seq data and associated tumor and patient characteristics including body weight and height data for 232 patients were obtained from The Cancer Genomic Atlas–Colon Adenocarcinoma (TCGA-COAD) database. Tumor samples were classified into the four CMSs with the CMScaller R package; body mass index (BMI) was calculated and categorized as normal, overweight, and obese. We observed a significant difference in CMS categorization between BMI categories. Differentially expressed genes (DEGs) between obese and overweight samples and normal samples differed across the CMSs, and associated prognostic analyses indicated that the DEGs had differing associations on survival. Using Gene Set Enrichment Analysis, we found differences in Hallmark gene set enrichment between obese and overweight samples and normal samples across the CMSs. We constructed Protein-Protein Interaction networks and observed differences in obesity-regulated hub genes for each CMS. Finally, we analyzed and found differences in predicted drug sensitivity between obese and overweight samples and normal samples across the CMSs. Our findings support that obesity impacts the CRC tumor transcriptome in a CMS-specific manner. The possible associations reported here are preliminary and will require validation using in vitro and animal models to examine the CMS-dependence of the genes and pathways. Once validated the obesity-linked genes and pathways may represent new therapeutic targets to treat colon cancer in a CMS-dependent manner

Complete fuzzy scheduling and fuzzy earned value management in construction projects

Complete fuzzy scheduling and fuzzy earned value management in construction projects Por: Luis Ponz-Tienda, Jose; Pellicer, Eugenio; Yepes, Victor JOURNAL OF ZHEJIANG UNIVERSITY-SCIENCE A Volumen: 13 Número: 1 Páginas: 56-68 Fecha de publicación: JAN 2012 Search For Full Text Cerrar abstractCerrar abstract This paper aims to present a comprehensive proposal for project scheduling and control by applying fuzzy earned value. It goes a step further than the existing literature: in the formulation of the fuzzy earned value we consider not only its duration, but also cost and production, and alternatives in the scheduling between the earliest and latest times. The mathematical model is implemented in a prototypical construction project with all the estimated values taken as fuzzy numbers. Our findings suggest that different possible schedules and the fuzzy arithmetic provide more objective results in uncertain environments than the traditional methodology. The proposed model allows for controlling the vagueness of the environment through the adjustment of the alpha-cut, adapting it to the specific circumstances of the project. © Zhejiang University and Springer-Verlag Berlin Heidelberg 2012.The authors want to thank Ms. Doria GIL-SENABRE, Universitat Politecnica de Valencia, Spain, for the support provided.Ponz Tienda, JL.; Pellicer Armiñana, E.; Yepes Piqueras, V. (2012). Complete fuzzy scheduling and fuzzy earned value management in construction projects. Journal of Zhejiang University Science A. 13(1):56-68. https://doi.org/10.1631/jzus.A1100160S566813