Phase transformations and metastable phase equilibria in Al-Ge alloy

In this paper the results of a detailed investigation on the metastable phase relations in undercooled as well as rapidly solidified Al---Ge alloys containing 2–50 at.% Ge are reported. Data obtained on the structure and morphology of phases enable us to arrive at the phase relations and transformation processes occurring in undercooled and rapidly quenched melts of this system. These results are explained with the help of a metastable phase diagram consisting of a peritectic and eutectic reaction involving metastable phases.

Spin-state equilibria in the LCoO3 system from 59Co NMR

Spin-state equilibria in the whole set of LCoO3 (where L stands for a rare-earth metal or Y) have been investigated with the use of 59Co NMR as a probe for the polycrystalline samples (except Ce) in the temperature interval 110-550 K and frequency range 3- 11.6 MHz. Besides confirming the coexistence of the high-spin—low-spin state in this temperature range, a quadrupolar interaction of ∼0.1 -0.5 MHz has been detected for the first time from 59Co NMR. The NMR line shape is found to depend strongly on the relative magnitude of the magnetic and quadrupolar interactions present. Analysis of the powder pattern reveals two basically different types of transferred hyperfine interaction between the lighter and heavier members of the rare-earth series. The first three members of the lighter rare-earth metals La, Pr (rhombohedral), and Nd (tetragonal), exhibit second-order quadrupolar interaction with a zero-asymmetry parameter at lower temperatures. Above a critical temperature TS (dependent on the size of the rare-earth ion), the quadrupolar interaction becomes temperature dependent and eventually gives rise to a first-order interaction thus indicating a possible second-order phase change. Sm and Eu (orthorhombic) exhibit also a second-order quadrupolar interaction with a nonzero asymmetry parameter ((η∼0.47)) at 300 K, while the orthorhombic second-half members (Dy,..., Lu and Y) exhibit first-order quadrupolar interaction at all temperatures. Normal paramagnetic behavior, i.e., a linear variation of Kiso with T-1, has been observed in the heavier rare-earth cobaltites (Er,..., Lu and Y), whereas an anomalous variation has been observed in (La,..., Nd)CoO3. Thus, Kiso increases with increasing temperature in PrCoO3 and NdCoO3. These observations corroborate the model of the spin-state equilibria in LCoO3 originally proposed by Raccah and Goodenough. A high-spin—low-spin ratio, r=1, can be stabilized in the perovskite structure by a cooperative displacement of the oxygen atoms from the high-spin towards the low-spin cation. Where this ordering into high- and low-spin sublattices occurs at r=1, one can anticipate equivalent displacement of all near-neighbor oxygen atoms towards a low-spin cobalt ion. Thus the heavier LCoO3 exhibits a small temperature-independent first-order quadrupolar interaction. Where r<1, the high- and low-spin states are disordered, giving rise to a temperature-dependent second-order quadrupolar interaction with an anomalous Kiso for the lighter LCoO3.

59Co NMR studies of the spin-state equilibria in rare-earth cobaltites

Hyperfine interaction parameters reveal differences in the nature of spin-state equilibria in the lighter and heavier rare-earth cobaltites; the crystal-field parameter is lower in the lighter cobaltites. Temperature variation of the quadrupolar coupling constant is also more marked in the lighter rare-earth cobaltites, with NdCoO3 showing evidence for a structural phase transition.

Achilles tendon loading patterns during barefoot walking and slow running on a treadmill: An ultrasonic propagation study

Measurement of tendon loading patterns during gait is important for understanding the pathogenesis of tendon "overuse" injury. Given that the speed of propagation of ultrasound in tendon is proportional to the applied load, this study used a noninvasive ultrasonic transmission technique to measure axial ultrasonic velocity in the right Achilles tendon of 27 healthy adults (11 females and 16 males; age, 26 ± 9 years; height, 1.73 ± 0.07 m; weight, 70.6 ± 21.2 kg), walking at self-selected speed (1.1 ± 0.1 m/s), and running at fixed slow speed (2 m/s) on a treadmill. Synchronous measures of ankle kinematics, spatiotemporal gait parameters, and vertical ground reaction forces were simultaneously measured. Slow running was associated with significantly higher cadence, shorter step length, but greater range of ankle movement, higher magnitude and rate of vertical ground reaction force, and higher ultrasonic velocity in the tendon than walking (P < 0.05). Ultrasonic velocity in the Achilles tendon was highly reproducible during walking and slow running (mean within-subject coefficient of variation < 2%). Ultrasonic maxima (P1, P2) and minima (M1, M2) were significantly higher and occurred earlier in the gait cycle (P1, M1, and M2) during running than walking (P < 0.05). Slow running was associated with higher and earlier peaks in loading of the Achilles tendon than walking.

Classical and Cosserat plasticity and viscoplasticity models for slow granular flow

We consider models for the rheology of dense, slowly deforming granular materials based of classical and Cosserat plasticity, and their viscoplastic extensions that account for small but finite particle inertia. We determine the scale for the viscosity by expanding the stress in a dimensionless parameter that is a measure of the particle inertia. We write the constitutive relations for classical and Cosserat plasticity in stress-explicit form. The viscoplastic extensions are made by adding a rate-dependent viscous stress to the plasticity stress. We apply the models to plane Couette flow, and show that the classical plasticity and viscoplasticity models have features that depart from experimental observations; the prediction of the Cosserat viscoplasticity model is qualitatively similar to that of Cosserat plasticity, but the viscosities modulate the thickness of the shear layer.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems : I. The lighter lanthanides

Phase diagrams for Nd2O3-H2O-CO2 and Gd2O3-H2O-CO2 systems at 1500 atm are given along with the results of selected runs in La, Sm and Eu systems. The stable phases in systems of La and Nd, are Ln(OH)CO3-B, Ln2O2CO3-II and LnOOH, in addition to the Ln(OH)3 phase at extremely low partial pressures of CO2 in the system. The systems become more and more complex with decreasing ionic radi and the number of stable carbonate phases increases. Ln2(CO3)3 · 3H2O orthorhombic (tengerate-like phase) is stable from Sm to Gd in addition to the other phases. The Gd(OH)CO3-A (ancylite-like phase) is hydrothermally stable at XCO2 greater-or-equal, slanted 0.5 while its hexagonal polymorph, Gd(OH)CO3-B is stable at low partial pressures of CO2 in the system.

Spinel-Corundum Phase Equilibria in the Systems Mn-Cr-Al-O and Co-Cr-Al-O at 1373 K

The tie lines delineating ion-exchange equilibria between MCr2O4-MAl2O4 spinel solid solution, where M is either Mn or Co, and Cr2O3-Al2O3 solid solution with the corundum structure were determined at 1373 K by electron microprobe and E0AX point count analysis of the oxide phases equilibrated with metallic Co and Au-5% Mn. The component activities in the spinel solid solutions are derived from the tie lines and the thernodynamic data for Cr2O3-Al2O3 soiid solutions available hi the literature. The Gibbs free energies of mixing calculated from the experimental data are discussed in relation to the values derived from the cation distribution a.odel based on the site preference energies and assuming random mixing on both tetrahedral and octahedral sites. Positive deviations from ideality observed in this study suggest a miscibility gap for both series of spinel solid solutions at low temperatures in the absence of oxidation.

Hydrothermal phase equilibria studies in Ln2O3---H2O systems and synthesis of cubic lanthanide oxides

Phase diagrams for the systems Ln2O3---H2O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and Y) studied at 5000 to 10,000 psi and temperature range of 200–900°C, show that Ln(OH)3 hexagonal and LnOOH monoclinic are the only stable phases from Nd to Ho. The cubic oxide phase (C---Ln2O3) is stable for systems of Er, Tm, Yb and Lu, with no evidence of its equilibrium in the systems of lighter lanthanides. Using strong acids, HNO3 and HCOOH, as mineralisers the cubic oxides could be stabilised from Eu down to Lu. Solid solution phases of CeO2---Y2O3 and Eu2O3---Y2O3 have also been synthesised with HNO3 as mineraliser, since these compounds have promising use as solid electrolyte and phosphor materials respectively.

Evidence of episodic brittle faulting in the cratonic part of the Peninsular India and its implications for seismic hazard in slow deforming regions

The region around Waclakkancheri, in the province of Kerala, India, which lies in the vicinity of Palghat-Cauvery ;hear zone (within the Precambrian crystalline terrain), has been a site of microseismic activity since 1989. Earlier studies had identified a prominent WNW-ESE structure overprinting on the E-W trending lineaments associated with Palghat-Cauvery shear zone. We have mapped this structure, located in a chamockite quarry near Desamangalam, Waclakkancheri, which we identify as a ca. 30 km-long south dipping reverse fault. This article presents the characteristics of this fault zone exposed on the exhumed crystalline basement and discusses its significance in understanding the earthquake potential of the region. This brittle deformation zone consists of fracture sets with small-scale displacement and slip planes with embedded fault gouges. The macroscopic as well as the microscopic studies of this fault zone indicate that it evolved through different episodes of faulting in the presence of fluids. The distinct zones within consolidated gouge and the cross cutting relationship of fractures indicate episodic fault activity. At least four faulting episodes can be recognized based on the sequential development of different structural elements in the fault rocks. The repeated ruptures are evident along this shear zone and the cyclic behavior of this fault consists of co-seismic ruptures alternating with inter-seismic periods, which is characterized by the sealed fractures and consolidated gouge. The fault zone shows a minimum accumulated dip/oblique slip of 2.1 m in the reverse direction with a possible characteristic slip of 52 cm (for each event). The ESR dating of fault gouge indicates that the deformation zone records a major event in the Middle Quaternary. The empirical relationships between fault length and slip show that this fault may generate events M >= 6. The above factors suggest that this fault may be characterized as potentially active. Our study offers some new pointers that can be used in other slow deforming cratonic hinterlands in exploring the discrete active faults.

AILaNb2O7:A new series of layered perovskites exhibiting ion exchange and intercalation behaviour

A new series of layered perovskite oxides, AILaNb2O7 (A = Li, Na, K, Rb, Cs, NH4) constituting n = 2 members of the family A A′n−1BnO3n+1, has been prepared. Their structure consists of double perovskite slabs interleaved by A atoms. Hydrated HLaNb2O7 is formed by topotactic proton exchange of the A atoms in ALaNb2O7 (A = K, Rb, Cs). The hydrate readily loses water to give anhydrous HLaNb2O7 which is isostructural with RbLaNb2O7. HLaNb2O7 exhibits Bronsted acidity forming intercalation compounds with bases such as n-octylamine and pyridine.

Thermodynamic properties of Pb2PtO4 and PbPt2O4 and phase equilibria in the system Pb–Pt–O

The compounds Pb2PtO4 and PbPt2O4 were synthesized from an intimate mixture of yellow PbO and Pt metal powders by heating under pure oxygen gas at 973 K for periods up to 600 ks with intermediate grinding and recompacting. Both compounds were found to decompose on heating in pure oxygen to PbO and Pt, apparently in conflict with the requirements for equilibrium phase relations in the ternary system Pb–Pt–O. The oxygen chemical potential corresponding to the three-phase mixtures, Pb2PtO4 + PbO + Pt and PbPt2O4 + PbO + Pt were measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas at 0.1 MPa pressure as the reference electrode. The standard Gibbs free energies of formation of the ternary oxides were derived from the measurements. Analysis of the results indicated that the equilibrium involving three condensed phases Pb2PtO4 + PbO + Pt is metastable. Under equilibrium conditions, Pb2PtO4 should have decomposed to a mixture of PbO and PbPt2O4. Measurement of the oxygen potential corresponding to this equilibrium decomposition as a function of temperature indicated that decomposition temperature in pure oxygen is 1014(±2) K. This was further confirmed by direct determination of phase relations in the ternary Pb–Pt–O by equilibrating several compositions at 1023 K for periods up to 850 ks and phase identification of quenched samples using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Only one ternary oxide PbPt2O4 was stable at 1023 K under equilibrium conditions. Alloys and intermetallic compounds along the Pb–Pt binary were in equilibrium with PbO.

Look-alike, sound-alike medication errors: A novel case concerning a Slow-Na, Slow-K prescribing error

A 59-year-old man was mistakenly prescribed Slow-Na instead of Slow-K due to incorrect selection from a drop-down list in the prescribing software. This error was identified by a pharmacist during a home medicine review (HMR) before the patient began taking the supplement. The reported error emphasizes the need for vigilance due to the emergence of novel look-alike, sound-alike (LASA) drug pairings. This case highlights the important role of pharmacists in medication safety.

Outbreak of angular leaf spot, caused by Xanthomonas fragariae, in a Queensland strawberry germplasm collection.

Strawberry (Fragaria (x) ananassa) plants exhibiting leaf lesions consistent with angular leaf spot (ALS, caused by Xanthomonas fragariae Kennedy and King 1962) were identified in the Queensland strawberry germplasm at Bundeberg in May 2010. Water suspensions of bacterial ooze tested positive using a previously described primer set. However, the slow growth rate of X. fragariae and the presence of a fast-growing, non-pathogenic, undescribed Xanthomonas species presented problems that were overcome by dilution plating and DNA sequence analysis. Sequencing of the gyrB locus of putative colonies of X. fragariae indicated 100% sequence similarity to other X. fragariae isolates. A new set of diagnostic primers for X. fragariae based on the gyrB locus is presented.

Quasi-2D XY Magnetic Properties and Slow Relaxation in a Body Centered Metal Organic Network of [Co-4] Clusters

Octahedral Co2+ centers have been connected by mu(3)-OH and mu(2)-OH2 units forming [Co-4] clusters which are linked by pyrazine forming a two-dimensional network. The two-dimensional layers are bridged by oxybisbenzoate (OBA) ligands giving rise to a three-dimensional structure. The [Co-4] clusters bond with the pyrazine and the OBA results in a body-centered arrangement of the clusters, which has been observed for the first time. Magnetic studies reveal a noncollinear frustrated spin structure of the bitriangular cluster, resulting in a net magnetic moment of 1.4 mu B per cluster. For T > 32 K, the correlation length of the cluster moments shows a stretched-exponential temperature dependence typical of a Berezinskii-Kosterlitz-Thouless model, which points to a quasi-2D XY behavior. At lower temperature and down to 14 K, the compound behaves as a soft ferromagnet and a slow relaxation is observed, with an energy barrier of ca. 500 K. Then, on further cooling, a hysteretic behavior takes place with a coercive field that reaches 5 Tat 4 K. The slow relaxation is assigned to the creation/annihilation of vortex-antivortex pairs, which are the elementary excitations of a 2D XY spin system.