Antonio J. Ramirez

Unveiling the chemical and morphological features of Sb-SnO2 nanocrystals by the combined use of high-resolution transmission electron microscopy and ab initio surface energy calculations.

Modeling of nanocrystals supported by advanced morphological and chemical characterization is a unique tool for the development of reliable nanostructured devices, which depends on the ability to synthesize and characterize materials on the atomic scale. Among the most significant challenges in nanostructural characterization is the evaluation of crystal growth mechanisms and their dependence on the shape of nanoparticles and the distribution of doping elements. This paper presents a new strategy to characterize nanocrystals, applied here to antimony-doped tin oxide (Sb-SnO(2)) (ATO) by the combined use of experimental and simulated high-resolution transmission electron microscopy (HRTEM) images and surface energy ab initio calculations. The results show that the Wulff construction can not only describe the shape of nanocrystals as a function of surface energy distribution but also retrieve quantitative information on dopant distribution by the dimensional analysis of nanoparticle shapes. In addition, a novel three-dimensional evaluation of an oriented attachment growth mechanism is provided in the proposed methodology. This procedure is a useful approach for faceted nanocrystal shape modeling and indirect quantitative evaluation of dopant spatial distribution, which are difficult to evaluate by other techniques.

Secondary austenite and chromium nitride precipitation in simulated heat affected zones of duplex stainless steels

Abstract Primary and secondary intragranular austenite precipitation and its relationship with chromium nitride (Cr2N) were studied in a simulated multipass heat affected zone (HAZ) of five duplex stainless steel alloys (UNS S32304, S32205, S32550, S32750, and S32760). The Gleeble thermal-mechanical simulator was used to perform short duration and high cooling rate ferritisation and reheating heat treatments. TEM and FEG-SEM analysis, coupled with a specially developed electrolytic etching technique, revealed the cooperative growth of secondary austenite and Cr2N precipitation along the ferrite/austenite (α/γ) interfaces. Additionally, the observed close coexistence of intragranular nitride (Cr2N) and intragranular secondary austenite suggests the heterogeneous nucleation of secondary austenite from the nitrides as supported by previously reported low energy nitride/austenite (Cr2N/γ) interfaces for the observed orientation relationship between both phases. Based on these observations, a new mechanism is proposed for intragranular secondary austenite nucleation related to the intragranular nitride precipitates.

Characterization of electroforming-free titanium dioxide memristors

Summary Metal–insulator–metal (MIM) structures based on titanium dioxide have demonstrated reversible and non-volatile resistance-switching behavior and have been identified with the concept of the memristor. Microphysical studies suggest that the development of sub-oxide phases in the material drives the resistance changes. The creation of these phases, however, has a number of negative effects such as requiring an elevated voltage, increasing the device-to-device variability, damaging the electrodes due to oxygen evolution, and ultimately limiting the device lifetime. In this work we show that the deliberate inclusion of a sub-oxide layer in the MIM structure maintains the favorable switching properties of the device, while eliminating many of the negative effects. Electrical and microphysical characterization of the resulting structures was performed, utilizing X-ray and electron spectroscopy and microscopy. In contrast to structures which are not engineered with a sub-oxide layer, we observed dramatically reduced microphysical changes after electrical operation.

Thermal history in UNS S32205 duplex stainless steel friction stir welds

Abstract Consolidated UNS S32205 duplex stainless steel joints welds were performed using a friction stir welding (FSW) process. An experimental set-up was used to record the thermal history of duplex stainless steel FSW joint. For points at equal distance from the weld centreline, temperature measured near the beginning of the weld was lower than that measured in the middle of the welded joint. This was attributed to a non-stationary transfer condition. FSW thermal cycle showed shorter time spent at elevated temperature compared that presented by fusion welding, indicating less propensity to detrimental second phase precipitation. To support temperature measurements with thermocouples, a three-dimensional finite element thermal model of FSW was implemented, which provided a good agreement with experimental data.

Structural and Rate Studies of the Formation of Substituted Benzynes

The key elimination step for the formation of 3-substituted and 3,6-disubstituted benzynes from 2-haloaryllithiums displays a pronounced solvent-dependent regioselectivity. All 2-haloaryllithiums with electron withdrawing groups in the 6 position are shown by 6Li and 13C NMR spectroscopic studies to be monomers in THF. DFT computational studies implicate trisolvates. Rate studies reveal that LiF eliminates via monomer-based pathways requiring THF dissociation whereas LiCl eliminates via nondissociative pathways. Elimination to form 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity that is traced to competing solvent-dissociative and nondissociative dissociative pathways for the elimination of LiCl and LiF, respectively.

Study of microstructural evolution of friction taper plug welded joints of C–Mn steels

Abstract This paper describes the microstructural evolution of friction taper plug welded joints of C–Mn steels. Experimental and numerical analyses included calculations based on Calphad and continuous cooling transformation curves, and characterisation techniques. The studied friction taper plug welded joint contains three macroregions: plug material, thermomechanically affected zone (TMAZ) and base material. The thermomechanical conditions imposed in the studied friction taper plug welded joint precluded the formation of a heat affected zone. However, seven subregions were identified within the TMAZ region and details are discussed. The interface zone is found in the TMAZ region, where the most relevant phase transformations take place. It is suggested that the phase transformations in TMAZ region depend on local conditions, such as chemical composition, deformation rate, thermal history and the previous thermomechanical history of the parent materials.

Weld Solidification Cracking in Solid-Solution Strengthened Ni-Base Filler Metals

The weld solidification cracking susceptibility of several solid-solution strengthened Ni-base filler metals was evaluated using the transverse Varestraint test. The alloys tested included Inconel 617, Inconel 625, Hastelloy X, Hastelloy W, and Haynes 230W.* Susceptibility was quantified by determining the solidification cracking temperature range (SCTR) which is a direct measurement of the range over which cracking occurs. This temperature range was then compared to the equilibrium solidification temperature range derived from Calphad-based ThermoCalc™ calculations, Scheil-Gulliver solidification simulations, and in-situ measurements using the single sensor differential thermal analysis (SS-DTA) technique.

Aspectos metalúrgicos de revestimentos dissimilares com a superliga à base de níquel inconel 625

To extend the life and reliability of pipes and equipment in oil & gas production and processing settings is a continuous demand. These aspects are essentially dependent on corrosion resistant alloys used. In this context, the weld overlay with Ni-based superalloys is a great interesting alternative, since improve the corrosion resistance without increase the cost of manufacture when compared to massive equipment. Thus, the objective of this study was to evaluate the metallurgical aspects of Inconel 625 weld overlays deposited by GTAW cold wire feed process. The welds were performed using a robotic workbench, an electronic power supply and a data acquisition system. The microstructural characterization was carried out using scanning electron microscopy (SEM), transmission electron microscopy (MET), electron dispersive spectroscopy (EDS) and X-ray diffraction. The results shown that the microstructure of overlays was formed by a gamma matrix and secondary phases rich in Nb. These precipitates were identified as Nb-rich Laves phase and a complex TiN/NbC.

Friction stir welding of duplex and superduplex stainless steels and some aspects of microstructural characterization and mechanical performance

Friction stir welding was used to produce butt joints on 6 mm thick plates of UNS S32101 lean duplex stainless steel, S32205 duplex stainless steel, and S32750 and S32760 superduplex stainless steels. Fully consolidated joints were achieved, with full penetration, using heat input of 1.37-1.50 kJ/mm. Specimens submitted to tensile testing performed perpendicular to the welding direction showed failure on the base metal, reflecting better mechanical performance of the welded joints. Furthermore, tensile testing along the joints revealed higher yield and tensile strengths in all cases, as well as increased elongation. Microstructural evaluation showed that there was pronounced grain refinement in the welded joints of all the materials studied, achieving grain sizes as small as 1 µm. The differences in the ferrite and austenite grain sizes in the stir zone, such as the degree of grain refinement, could be explained by the combination of dynamic recrystallization of austenite during the welding process and the recrystallization and growth of the ferrite grains, promoted firstly by the severe deformation and secondly by the high temperature inherent to the FSW process. Superduplex stainless steel FSW joints were more able to maintain a balanced microstructure, compared to conventional and lean duplex stainless steels, due to greater homogeneity of recrystallization in the welded joint.

Kinetic and Mechanistic Insight into the Thermodynamic Degradation of Saxagliptin

The dipeptidyl peptidase-IV inhibitor saxagliptin (Onglyza) can undergo a thermodynamically favored cyclization to form the corresponding cyclic amidine. The kinetics and mechanism of this conversion were examined to develop a commercial synthesis that afforded saxagliptin with only trace levels of this key byproduct. Important findings of this work are the identification of a profound solvent effect and the determination of an autocatalytic pathway. Both of these phenomena result from transition structures involving proton transfer.