Experimental and Modelling Studies of the Thermodynamics and Kinetics of Phase and Structural Transformations in a Gamma TiAl-based Alloy

This work combines microscopy, synchrotron radiation X-ray diffraction, differential scanning calorimetry and thermodynamic calculations in the characterisation of phase transformation behaviour of a Ti–46Al–1.9Cr–3Nb alloy upon continuous heating at constant rates. It has been found that the Ti–46Al–1.9Cr–3Nb alloy after being forged at 1200 °C without further treatment has a duplex microstructure consisting of fine equiaxed and lamellar ? grains with a small amount of a2 plates and particles and about 1 wt.% B2 phase. Differential scanning calorimetry revealed reproducibly several thermal effects upon heating of the as-forged alloy. These thermal effects are related to the equilibration and homogenisation of the sample, change of phase ratios between a2, ? and B2 phases in particular the increase of B2 in respect to a2 and ?, and the following five phase transformations: a2 + ? + B2 a + ? + B2, a + ? + B2 a + ?, ? + a a, a a + ß, a + ß a + ß + L. The observation of these transformations by differential scanning calorimetry is largely in agreement with literature phase diagrams and thermodynamic calculations, though care is needed to consider the different alloy compositions. Kinetics of the ? + a a phase transformation in the Ti–46Al–1.9Cr–3Nb alloy has been quantitatively derived from the calorimetry data, giving phase compositions at any point during the transformation upon continuous heating.

Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also

X-ray diffraction, optical microscopy, and microhardness studies of gas nitrided titanium alloys and titanium aluminide

Thermochemical surface gas nitriding of ß21s, Timetal 205 and a Ti–Al alloy was conducted using differential scanning calorimeter equipment, in nominally pure nitrogen at 850 °C and 950 °C (ß21s), 730 °C and 830 °C (Timetal 205), and 950 °C and 1050 °C (Ti–Al) for 1 h, 3 h and 5 h. X-ray diffraction analyses showed new phases formed in the nitrided layer, depending on the alloy and the time and the temperature of nitriding. Microstructures were analyzed using optical microscopy. Cross-sectional microhardness profiles of cross-sectional samples after nitriding were obtained using a Knoop indenter.

Nonmarket Capabilities and the Prosecution of Trade Remedy Cases in the United States

The study investigates the prosecution of US trade remedy cases as examples of administrative government agency investigations and seeks to identify key capabilities for effective corporate political strategy targeting these institutions. Trade remedy cases are important policy tools, designed to protect domestic firms from ‘unfair’ import competition. The research contributes to the growing literature on corporate political activity and its links with superior outcomes in the marketplace. Three capabilities are identified: the capability to collect market/non-market intelligence, the capability to build and shape the administrative record, and the capability to align business practice with the US trade remedy institutions.

Structural and kinetic studies of spin crossover in an Iron(II) complex with a novel tripodal ligand

Configurational and ligand conformational influences on the kinetics of (1)A(1) reversible arrow T-5(2) spin crossover in the Fe(II) complex with the novel tripodal ligand, 1,1,1-tris((N-(2-pyridylmethyl)-N-methylamino)methyl)ethane (tptMetame), have been explored. Despite having six chelate rings and three chiral nitrogen atoms, only one enantiomeric pair of isomers, Delta, SSS, and Lambda, RRR, of the complex ion is observed. The conformation of the three rings forming the upper ''cap'' of the complex structure can be assigned delta or lambda with respect to the 3-fold molecular axis. X-ray data at 300 and 153 K, above and below the critical temperature for the spin transition, show that the conformation of the ligand ''cap'' is the same as the absolute configuration of the complex, with the same Lambda lambda(CAP)(or Delta delta(CAP)) combination prevailing for both the LS ((1)A(1)) and HS (T-5(2)) isomers. Molecular mechanics calculations further show that the ligand energy remains lowest for this Lambda lambda(CAP) (or Delta delta(CAP)) combination at all Fe-N distances over the range spanning the LS and HS isomers. Measurements of the spin crossover relaxation time have been carried out in solution over the temperature range 293-170 K. The observed monophasic relaxation traces are also consistent with the absolute configuration of the complex remaining unaltered during the spin crossover.

Phase Behaviour, Interactions, and Structural Studies of (Amines+Ionic Liquids) Binary Mixtures

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [Cnmim] [NTf2] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory–Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C2mim] [NTf2]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C2mim][NTf2]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents.

Theoretical and photoemission studies of the band structure of CdI

The band structure of CdI has been calculated using a modified semi-empirical tight-binding method and the results obtained have been compared with both angularly averaged and angularly resolved photoemission spectra. The theoretically computed density of states distribution is in excellent agreement with angularly averaged results and all the main features observed experimentally are reproduced in the theory. Angularly resolved spectra have been used to draw up energy band dispersion curves directly and agreement with calculated bands in both the Gamma M and Gamma K directions of the Brillouin zone is good.