Segregation in the MgO–MgAl2O4 system processed from nitrate precursors

The occurrence of segregation and its influence on microstructural and phase evolution have been studied in MgO–MgAl2O4 powders synthesized by thermal decomposition of aqueous nitrate precursors. When the nitrate solutions of Mg and Al were spray-pyrolyzed on a substrate held at 673 or 573 K, homogeneous mixed oxides were produced. Spraying and drying the nitrate solutions at 473 K resulted in the formation of compositionally inhomogeneous, segregated oxide mixtures. It is suggested that segregation in the dried powders was caused by the difference in solubility of the individual nitrate salts in water which caused Mg-rich and Al-rich salts to precipitate during dehydration of the solutions. The occurrence of segregation in the powders sprayed at 473 K and not 573 or 673 K is ascribed to the sluggish rate at which the early stages of decomposition occurred during which the cations segregated. The phase evolution in segregated and segregation-free MgO–MgAl2O4 powders has been compared. The distinguishing feature of the segregated powders was the appearance of stoichiometric periclase grain dimensions in excess of 0.3 μm at temperatures as low as 973 K. By comparison, the segregation-free powders displayed broad diffraction peaks corresponding to fine-grained and nonstoichiometric periclase. The grain size was in the range 5–30 nm at temperatures up to 1173 K. The key to obtaining fine-grained periclase was the ability to synthesize (Mg Al)O solid solutions with the rock salt structure. In the temperature range 973–1173 K, spinel grain size varied from 5 to 40 nm irrespective of its composition and did not appear to be influenced by segregation.

Understanding Self-Segregation of Immiscible Peripheral Segments in Pseudodendritic Hyperbranched Polydithioacetals: Formation of Improved Janus Structures

Peripherally heterofunctionalized hyperbranched polymers (HBPs) undergo immiscibility-driven self-segregation of the outer segments to form Janus molecular entities (Macromolecules 2012, 45, 2348). In HBPs prepared via AB2 type self-condensation, single-step peripheral heterofunctionalization would lead to random distribution of the two types of terminal units, namely, homofunctionalized (homo-T) and heterofunctionalized (hetero-T) termini. Here, we examine the role of such hetero-T units on the self-segregation of heterofunctionalized pseudodendritic hyperbranched polydithioacetals. Three different heterofunctionalized HB dithioacetals bearing roughly 50 mol % each of docsyl (C-22) and MPEG-350 chains at the periphery were prepared: one of them carried a statistical distribution of homo-T and hetero-T units, and the other carried only two types of homo-T (-TR1R1 and -TR2R2) termini, whereas the third carried largely hetero-T (-TR1R2) termini. Careful examination of DSC and SAXS data reveals that the self-segregation is most effective in HBPs devoid of hetero-T units; interestingly, however, it also showed that randomly heterofunctionalized HBPs self-segregated nearly as effectively.

Multi-scale modelling of Suzuki segregation in gamma' precipitates in Ni and Co-base superalloys

The high temperature strength of alloys with (gamma +gamma') microstructure is primarily due to the resistance of the ordered precipitate to cutting by matrix dislocations. Such shearing requires higher stresses since it involves the creation of a planar fault. Planar fault energy is known to be dependent on composition. This implies that the composition on the fault may be different from that in the bulk for energetic reasons. Such segregation (or desegregation) of specific alloying elements to the fault may result in Suzuki strengthening which has not been explored extensively in these systems. In this work, segregation (or desegregation) of alloying elements to planar faults was studied computationally in Ni-3(Al, Ti) and Co-3(W, Al) type gamma' precipitates. The composition dependence of APB energy and heat of mixing were evaluated from first principle electronic structure calculations. A phase field model incorporating the first principles results, was used to simulate the motion of an extended superdislocation under stress concurrently with composition evolution. Results reveal that in both systems, significant (de) segregation occurs on equilibration. On application of stress, solutes were dragged along with the APB in some cases. Additionally, it was also noted the velocity of the superdislocation under an applied stress is strongly dependent on atomic mobility (i. e. diffusivity).

Investigation of Annealing Induced Yttria Segregation in Sputtered Yttria-Stabilized Zirconia Thin Films

8mol% yttria-stabilized zirconia (8YSZ) is an extensively studied solid electrolyte. But there is no consistency in the reported ionic conductivity values of 8YSZ thin films. Interfacial segregation in YSZ thin films can affect its ionic conductivity by locally altering the surface chemistry. This article presents the effects of annealing temperature and film thickness on free surface yttria segregation behavior in 8YSZ thin film by Angle Resolved XPS and its influence on the ionic conductivity of sputtered 8YSZ thin films. Surface yttria concentration of about 32, 20, and 9mol% have been found in 40nm 8YSZ films annealed at 1273, 1173, and 1073K, respectively. Yttria segregation is found to increase with increase in annealing temperature and film thickness. Ionic conductivities of 0.23, 0.16, and 0.08Scm(-1) are observed at 923K for 40nm 8YSZ films annealed at 1073, 1173, and 1273K, respectively. The decrease in conductivity with increase in annealing temperature is attributed to the increased yttria segregation with annealing. Neither segregation nor film thickness is found to affect the activation energy of oxygen ion conduction. Target purity is found to play a key role in determining free surface yttria segregation in 8YSZ thin films.

Microstructural evolution and mechanical characteristics in nanocrystalline nickel with a bimodal grain-size distribution

An attractive microstructural possibility for enhancing the ductility of high-strength nanocrystals is to develop a bimodal grain-size distribution, in which the fine grains provide strength, and the coarser grains enable strain hardening. Annealing of nanocrystalline Ni over a range of temperatures and times led to microstructures with varying volume fractions of coarse grains and a change in texture. Tensile tests revealed a drastic reduction in ductility with increasing volume fraction of coarse grains. The reduction in ductility may be related to the segregation of sulphur to grain boundaries.

XPS and XAES studies of surface segregation and oxidation of Cu-Ge alloy

Surface segregation of Ge is seen in the Cu-5at%Ge alloy with an activation enthalpy equal to 17 kJ/mol. Oxidation of the alloy in the temperature range 400 to 600 K shows the formation of Cu2O and GeO which on further heating in vacuum at 650 K converts to GeO2 with the reduction of Cu2O to Cu.

Surface segregation and oxidation studies of Cu-Sn and Cu-Pd alloys by x-ray photoelectron and auger spectroscopy

X-ray photoelectron and Auger spectroscopic techniques have been employed to study surface segregation and oxidation of Cu-1 at%Sn, Cu-9at%Pd and Cu-25at%Pd alloys. Both Cu-Pd(9%) and Cu-Pd(25%) alloys show segregation of Cu when heated above 500 K. The Pd concentration was reduced by 50% at 750 K compared to the bulk composition; the enthalpy of segregation of Cu is around - 6kJ/mol. Sn segregation is seen from 470 to 650 K in the Cu-Sn(1%) alloy, and a saturation plateau of Sn concentration above 650 K is observed. Surface oxidation of Cu-Sn(1%) and Cu-Pd(9%) alloys at 500 K showed the formation of Cu2O on the surface with total suppression of Sn or Pd on the respective alloy surfaces. On vacuum annealing the oxidised Cu-Sn alloy surface at 550 K, a displacement reaction 2Cu2O+Sn→4Cu+SnO2 was observed. However, under similar annealing of the oxidised Cu-Pd(9%) alloy surface at 500 K, oxide oxygen was totally desorbed leaving the Cu-Pd alloy surface clean. In the case of the Cu-Pd(25%) alloy, only dissociatively chemisorbed oxygen was seen at 500 K which desorbed at the same temperature. Oxygen spill-over from copper to palladium is suggested as the mechanism of oxygen desorption from the oxidised Cu-Pd alloy surfaces.

Diffusion and Creep in Silica-Doped Tetragonal Zirconia

Silica segregation at two grain junctions or in amorphous triple junction pockets can influence creep by altering the grain-boundary diffusion coefficient. Although the addition of silica to superplastic yttria-stabilized tetragonal zirconia enhances ductility, differences in reported creep parameters have limited critical identification of rate controlling mechanisms. The present study on a pure 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) and 3YTZ with 0.39 or 3.9 wt% silica involved a detailed characterization of creep over a wide range of experimental conditions and also tracer diffusion measurements. The data broadly show transitions in creep stress exponents from n∼1 to ∼2 to ∼3 with a decrease in the stress. The data at high stresses are consistent with Coble diffusion creep, and creep at lower stresses is attributed to interface-controlled diffusion creep. Measurements indicated that silica does not have any significant influence on grain boundary or lattice diffusion, and this is consistent with the observation that 3YTZ and 3YTZ with 0.39% or 3.9% silica exhibit essentially identical creep behavior in the Coble creep regime. Silica influences the interface control process so that the transitions in stress exponents are pushed to lower stresses with an increase in silica content.

Induced swelling of kaolinitic soil in alkali solution

Unexpected swelling induced in foundation soils can cause distress to structures founded on them. In this paper, the swelling of kaolinitic soils due to interaction with alkali solution has been reported. The induced swelling is attributed to the formation of new minerals, which has been confirmed by X-ray diffraction patters and SEM studies. To understand the effect of alkali concentration and duration of interaction, two series of consolidation experiments have been carried out. In series 1, the specimen were remoulded with water and inundated with alkali solutions and in series 2, the specimen were remoulded and inundated with same alkali solutions. A steep compression during loading cycle and no abnormal swelling during unloading cycle has been noticed for the specimen remoulded with water and inundated with 1 N NaOH solutions. The steep compression is due to the segregation or break down of clay minerals due to alkali interactions. In case of specimen inundated with 4 N NaOH solutions, abnormal swelling has been observed during unloading cycle of the consolidation test. New minerals are formed on interaction of soil with 4 N solution as confirmed by X-ray diffraction patterns. These minerals are known to have very fine pores and possess high water holding capacity. The differences in the amount of swelling of samples remoulded with water and remoulded with alkali solution are due to variations in the concentration of alkali and duration of interaction.

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu3Ti4O12 (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250K, in addition to the well-investigated dielectric relaxation close to 100K. The effect of sintering and doping (La3+) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La2/3Cu3Ti4O12, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers. (C) 2007 Elsevier Ltd. All rights reserved.

Specific Small-Molecule Activator of Aurora Kinase A Induces Autophosphorylation in a Cell-Free System

Aurora kinases are essential for chromosomal segregation and cell division and thereby important for maintaining the proper genomic integrity. There are three classes of aurora kinases in humans: A, B, and C. Aurora kinase A is frequently overexpressed in various cancers. The link of the overexpression and tumorigenesis is yet to be understood. By employing virtual screening, we have found that anacardic acid, a pentadecane aliphatic chain containing hydroxylcarboxylic acid, from cashew nut shell liquid could be docked in Aurora kinases A and B. Remarkably, we found that anacardic acid could potently activate the Aurora kinase A mediated phosphorylation of histone H3, but at a similar concentration the activity of aurora kinase B remained unaffected in vitro. Mechanistically, anacardic acid induces the structural changes and also the autophosphorylation of the aurora kinase A to enhance the enzyme activity. This data thus indicate anacardic acid as the first small-molecule activator of Aurora kinase, which could be highly useful for probing the function of hyperactive (overexpressed) Aurora kinase A.

The role of polar and facial amphipathic character in determining lipopolysaccharide-binding properties in synthetic cationic peptides

Two series of peptides, designated K and NK were synthesized and tested for lipid A binding and neutralizing properties. K-2, which has an 11-residue amphiphilic core, and a branched N-terminus bearing two branched lysinyl residues does not bind lipid A, while NK2, also with an 11-residue amphiphilic core comprised entirely of non-ionizable residues, and a similarly branched, cationic N-terminus, binds lipid A very weakly. Both peptides do not inhibit lipopolysaccharide (LPS) activity in the Limulus assay, nor do they inhibit LPS-induced TNF-alpha and NO production in 5774 cells. These results are entirely unlike a homologous peptide with an exclusively hydrophobic core whose LPS-binding and neutralizing properties are very similar to that of polymyxin B [David SA, Awasthi SK, Wiese A et al. Characterization of the interactions of a polycationic, amphiphilic, terminally branched oligopeptide with lipid A and lipopolysaccharide from the deep rough mutant of Salmonella minnesota. J Endotoxin Res 1996; 3: 369-379]. These data suggest that a clear segregation of charged and apolar domains is crucial in molecules designed for purposes of LPS sequestration and that head-tail (polar) orientation of the cationic/hydrophobic regions is preferable to molecules with mixed or facial cationic/amphipathic character.

H I deficiency in cluster spiral galaxies - Dependence on galaxy size

From the available H I data on spiral galaxies in three rich Abell clusters and the Virgo Cluster, it is shown that galaxies with medium to large optical sizes tend to be more severely deficient in atomic hydrogen than the small galaxies. This is so both in terms of the fractional number of galaxies that are deficient and the amount of gas lost by a galaxy. The fraction of H I-deficient galaxies increases with size over most of the size range, saturating or dropping only for the largest galaxies. A comparative study is made of various currently accepted gas removal mechanisms, namely those which are a result of galaxy-intracluster medium interactions, e.g., ram pressure stripping, as well as those due to galaxy-galaxy interactions, i.e., collisions and tidal interactions. It is shown that, with the exception of tidal interactions, all of these mechanisms would produce a size dependence in H I deficiency that is the opposite of that observed. That is, the gas in the largest galaxies would be the least affected by these mechanisms. However, if there is significant mass segregation, these processes may give the trends observed in the size dependence of H I deficiency.

Angelman Syndrome Protein UBE3A Interacts with Primary Microcephaly Protein ASPM, Localizes to Centrosomes and Regulates Chromosome Segregation

Many proteins associated with the phenotype microcephaly have been localized to the centrosome or linked to it functionally. All the seven autosomal recessive primary microcephaly (MCPH) proteins localize at the centrosome. Microcephalic osteodysplastic primordial dwarfism type II protein PCNT and Seckel syndrome (also characterized by severe microcephaly) protein ATR are also centrosomal proteins. All of the above findings show the importance of centrosomal proteins as the key players in neurogenesis and brain development. However, the exact mechanism as to how the loss-of-function of these proteins leads to microcephaly remains to be elucidated. To gain insight into the function of the most commonly mutated MCPH gene ASPM, we used the yeast two-hybrid technique to screen a human fetal brain cDNA library with an ASPM bait. The analysis identified Angelman syndrome gene product UBE3A as an ASPM interactor. Like ASPM, UBE3A also localizes to the centrosome. The identification of UBE3A as an ASPM interactor is not surprising as more than 80% of Angelman syndrome patients have microcephaly. However, unlike in MCPH, microcephaly is postnatal in Angelman syndrome patients. Our results show that UBE3A is a cell cycle regulated protein and its level peaks in mitosis. The shRNA knockdown of UBE3A in HEK293 cells led to many mitotic abnormalities including chromosome missegregation, abnormal cytokinesis and apoptosis. Thus our study links Angelman syndrome protein UBE3A to ASPM, centrosome and mitosis for the first time. We suggest that a defective chromosome segregation mechanism is responsible for the development of microcephaly in Angelman syndrome.