Structural evolution of Ag-Cu nano-alloys confined between AlN nano-layers upon fast heating.

The structural evolution of a Ag-Cu/AlN nano-multilayer (NML), as prepared by magnetron-sputtering on a α-Al2O3 substrate, was monitored during fast heating by real-time in situ XRD analysis (at the synchrotron), as well as by ex situ microstructural analysis using SEM, XPS and in-house XRD. The as-deposited NML is constituted of alternating nano-layers (thickness ≈ 10 nm) of a chemically inert AlN barrier and a eutectic Ag-Cu(40at%) nano-alloy. The nano-alloy in the as-deposited state is composed of a fcc matrix of Ag nano-grains (≈6 nm), which are supersaturated by Cu, and some smaller embedded Cu rich nano-grains (≈4 nm). Heating up to 265 °C activates segregation of Cu out of the supersaturated Ag nano-grains phase, thus initiating phase separation. At T > 265 °C, the phase-separated Cu metal partially migrates to the top NML surface, thereby relaxing thermally-accumulated compressive stresses in the confined alloy nano-layers and facilitating grain coarsening of (still confined) phase-separated nano-crystallites. Further heating and annealing up to 420 °C results in complete phase separation, forming extended Ag and Cu domains with well-defined coherent Ag/AlN interfaces. The observed outflow of Cu well below the eutectic melting point of the bulk Ag-Cu alloy might provide new pathways for designing low-temperature nano-structured brazing materials.

Retrospective and statistical analysis of breeding management on the Italian Heavy Draught Horse breed.

This study investigated some aspects of breeding management in the Italian Heavy Draught Horse breed, aiming at improving its efficiency at stud farm level. A first aim was to evaluate the risk of unsuccessful reproduction in mares after an early (3 years) or normal (4 years) age at first foaling, in interaction with different stud rearing systems. A second objective was the examination of the mean time length in which young 2-year-old stallions maintain a genetic superiority on older proven stallions, identifying a 'genetic lifespan' in which young stallions can be safely used for reducing the cost of services. Reproductive performance at first and second foaling of 1513 mares were used. Mares had a normal first foal at 3 (n = 745) or 4 years of age (n = 768) in stud farms on the basis of stable (n = 488), feral (n = 345) or semi-feral (n = 680) rearing systems. Logistic regression analysis was performed by modeling the risk of unsuccessful reproduction in the subsequent season (i.e., results at second foaling), as affected by the interaction of age at first foaling × rearing system (six classes). Genetic lifespan of young stallions was estimated by regressing the least square means from a mixed model analysis for repeated measures of individual differences in 'total merit' estimated breeding values (EBVs) between young stallions (mean no. of 45/year) and the mean EBV of all proven stallions in a given year of genetic evaluation (mean no. of 483/year). Young stallions born between 1999 and 2005 were used, following each generation (i.e., birth year) from 2 to 7 subsequent yearly genetic evaluations. In comparison with the best reproductive success of second foaling at 4 years in stable systems, the greatest risk of unsuccessful reproduction was at 3 years in feral (+167%) and 3 years in semi-feral conditions (+91%). Young stallions showed a 0.50 s.d. greater EBV at the first evaluation than proven stallions, with a mean annual decrease in EBV of 0.07 s.d./year on proven stallions. Optimal breeding management could be obtained in stud farms by limiting foaling at 3 years, particularly in feral and semi-feral rearing systems, and using young stallions for 3 to 4 years to maintain a perceptible selection differential with older proven stallions and to reduce cost of services. Later, the selection differential with proven stallions become less consistent and genetic improvement could be slowed down.

The measurement of internal strain in core-shell Ni3Si(Al)-SiOx nanoparticles.

Internal defects and strain in nanoparticles can influence their properties and therefore measuring these values is relevant. Powder diffraction techniques (neutron and synchrotron) are successfully used to characterize internal strain in the core-shell Ni(3)Si(Al)-SiO(x) nanoparticles having mean diameters of approximately 80 nm. The nanoparticles, which are strain-free after extraction from the bulk alloys, develop internal strain on heating. Both micro- and macro-strains can be measured from the analysis of Bragg peak shift and broadening. It is identified that differences in thermal expansion coefficient of the metallic core and the amorphous shell of the nanoparticles, as well as partial disordering of the L1(2) ordered core phase, are the main causes of strain evolution. Synchrotron measurements also detected partial crystallization of the amorphous silica shell.

Ni(3)Si(Al)/a-SiO(x) core-shell nanoparticles: characterization, shell formation, and stability.

We have used an electrochemical selective phase dissolution method to extract nanoprecipitates of the Ni(3)Si-type intermetallic phase from two-phase Ni-Si and Ni-Si-Al alloys by dissolving the matrix phase. The extracted nanoparticles are characterized by transmission electron microscopy, energy-dispersive x-ray spectrometry, x-ray powder diffraction, and electron powder diffraction. It is found that the Ni(3)Si-type nanoparticles have a core-shell structure. The core maintains the size, the shape, and the crystal structure of the precipitates that existed in the bulk alloys, while the shell is an amorphous phase, containing only Si and O (SiO(x)). The shell forms around the precipitates during the extraction process. After annealing the nanoparticles in nitrogen at 700 °C, the tridymite phase recrystallizes within the shell, which remains partially amorphous. In contrast, on annealing in air at 1000 °C, no changes in the composition or the structure of the nanoparticles occur. It is suggested that the shell forms after dealloying of the matrix phase, where Si atoms, the main constituents of the shell, migrate to the surface of the precipitates.

Nano-structured materials produced from simple metallic alloys by phase separation.

A method which is able to produce different types of nano-structured materials, namely nano-particles, nano-structured surfaces and nano-porous membranes, from two-phase metallic alloys is reviewed. The new process first establishes nano-structures in the bulk alloy and then separates them by selective phase dissolution. Variation in processing makes it possible to produce different types of nano-structure even from the same alloy. The process can be applied to many different alloy systems. An overview is presented emphasizing the versatility of the process with examples of different nano-structure types that can be produced. Further, the new method is discussed in relation to similar processes (specifically, electrochemical processes) which have been used for nano-structure synthesis.

Effect of chronic ursocholic acid administration on bile lipid composition and bile acid pool size in gallstone patients.

We assessed the effect of chronic (4-6 weeks) administration of ursocholic acid (UCA) (15 mg/kg/day), a natural bile acid with poor detergent capacity, on biliary lipid composition of gallbladder bile (n = 26) and bile acid pool size (n = 5) in gallstone patients. During treatment the biliary molar percentage UCA increased from trace values to 28% (p less than 0.001). This effect was accompanied by an increase in molar percentage deoxycholic acid from 16% to 33% (p less than 0.001). Total bile acid pool size remained unchanged during UCA administration; cholic acid and chenodeoxycholic acid pool sizes decreased from 1.0 to 0.6 mmol (p less than 0.05) and from 1.6 to 0.9 mmol (p less than 0.05), respectively. The molar percentage cholesterol of gallbladder bile decreased from 9.8% to 7.0% (p less than 0.001) during UCA, but bile remained supersaturated with cholesterol in 21 patients. The weak effect on biliary lipid composition and the increase of potentially toxic deoxycholic acid in bile suggest that UCA is unlikely to replace ursodeoxycholic and chenodeoxycholic acid for medical treatment of gallstones.