New insight into the pit-to-crack transition from finite element analysis of the stress and strain distribution around a corrosion pit

A finite element (FE) analysis has been undertaken to evaluate the stress and strain distribution associated with a single corrosion pit in a cylindrical steel specimen stressed remotely in tension. A key observation was the localisation of plastic strain to the pit walls (just below the surface of the specimen). Simulation of a growing pit in a static stress field indicated corresponding plastic strain rates that were commensurate with values associated with stress corrosion cracking. This observation introduces a wholly new concept in understanding of the evolution of stress corrosion cracks from pits and correlates with recent X-ray tomography measurements.     

Synthesis and structure of [{As(NBu)3}2Li6] containing an [As(NBu)3] trianion

Attempts to prepare the [As(N^tBu)₃]³⁻ trianion by the reaction of As(NMe₂)₃ with [^tBuNHLi]_n (1:3 monomer equiv.) proved unsuccessful. However, if the reaction is carried out with an excess of ^tBuNH₂ (3 equiv.) the target complex [{As(N^tBu)₃}₂Li₆] (1) is obtained. This is the first example of a complex containing an [As(NR)₃]³⁻ trianion.     

Sand corrosion,thermal expansion,and ablation of medium- and high-entropy compositionally complex fluorite oxides

Sand corrosion, thermal expansion, and ablation properties of a new class of medium- and high-entropy compositionally complex fluorite oxides (CCFOs) are examined as potential protective coating materials. Five binary oxides were mixed and sintered into dense, single-phase CCFOs of the general formula: [Hf_(1-2x)/3Zr_(1-2x)/3Ce_(1-2x)/3Y_xYb_x]O_2-δ (x = 0.2, 0.074, and 0.029). These CCFOs exhibit decreased molten sand infiltration and interaction at intermediate temperatures (1200-1300°C) in comparison with a cubic yttria-stabilized zirconia (YSZ) reference; however, at higher temperatures, the trend is reversed due to the increased chemical reactivity. The equimolar high-entropy (Hf_0.2Zr_0.2Ce_0.2Y_0.2Yb_0.2)O_2-δ exhibits no grain boundary penetration by molten sand at all examined temperatures (1200°C-1500°C), although reaction and precipitation are significant. Moreover, these CCFOs exhibit higher intrinsic thermal expansion coefficients (CTE) than the YSZ reference, thereby being more compatible with Ni-based superalloys. The 8YSZ-like (Hf_0.284Zr_0.284Ce_0.284Y_0.074Yb_0.074)O_2-δ exhibits the highest CTE in this series of CCFOs due to oxygen clustering effects. Finally, these CCFOs also exhibit lower emissivities and form unique faceted microstructures in ablative environments.     

Synthesis method comparison of compositionally complex rare earth-based Ruddlesden–Popper n = 1 T′-type cuprates

The multicomponent approach has been successfully expanded to the Ruddlesden–Popper structure with the synthesis of two different high-entropy cuprate compositions: (La_0.2Nd_0.2Gd_0.2Tb_0.2Dy_0.2)₂CuO₄ and (La_0.2Pr_0.2Nd_0.2Sm_0.2Eu_0.2)₂CuO₄. The effect of synthesis method is explored using both solid-state reaction and polymeric steric entrapment (PSE) methods. It is found that PSE leads to more randomly distributed cation species, providing an advantageous method of synthesis for the growing field of high entropy oxides. In situ high-temperature x-ray diffraction tracks the amorphous to crystalline phase transformation in (La_0.2Nd_0.2Gd_0.2Tb_0.2Dy_0.2)₂CuO₄ powder, synthesized using the PSE method. Using the High-Temperature XRD data, a method for gaining information on the kinetic behavior is also applied. Magnetometry of both compositions indicates ferrimagnetic behavior at low temperatures.     

Properties and Stability of Solid Lipid Particle Dispersions Based on Canola Stearin and Poloxamer 188

Solid lipid particles (SLP) are one strategy for encapsulating lipophilic molecules, including for controlled release and enhanced bioavailability applications. SLP based on fully hydrogenated canola stearin (CaSt, 5, 10, 20, and 30 wt%) and the non-ionic surfactant Poloxamer 188 (P188, 0.0, 0.5, 1.0, 2.5, 5.0 and 10.0 wt%) were produced by high pressure melt homogenization using a microfluidizer. Spherical particles in the region of 140 nm were formed, depending on compostion and processing parameters. Surfactant concentration and pressure had a significant influence on particle diameter (P < 0.05), although number of homogenization cycles did not (P > 0.05). A maximum surfactant surface load of approximately 4 mg m⁻² was observed and, at or above 2.5% P188, excess surfactant was present in the continuous phase after production. P188 had the effect of decreasing particle size and facilitating transitions from the α to the β polymorph (P < 0.05) both through surface nucleation and size reduction effects. A stability study of the 10% CaSt SLP with 0.0, 1.0, or 5.0% P188 revealed particle growth for the 0.0 and 1.0% P188 SLP, especially at 20 versus 4 °C, but no changes in the 5.0% P188 SLP, which were exclusively in the β form, at both temperatures for up to 240 days.     

Regulating the geological sequestration of CO2

Governments worldwide should provide incentives for initial large-scale GS projects to help build the knowledge base for a mature, internationally harmonized GS regulatory framework. Health, safety, and environmental risks of these early projects can be managed through modifications of existing regulations in the EU, Australia, Canada, and the U.S. An institutional mechanism, such as the proposed Federal Carbon Sequestration Commission in the U.S., should gather data from these early projects and combine them with factors such as GS industrial organization and climate regime requirements to create an efficient and adaptive regulatory framework suited to large-scale deployment. Mechanisms to structure long-term liability and fund long-term postclosure care must be developed, most likely at the national level, to equitably balance the risks and benefits of this important climate change mitigation technology. We need to do this right. During the initial field experiences, a single major accident, resulting from inadequate regulatory oversight, anywhere in the world, could seriously endanger the future viability of GS. That, in turn, could make it next to impossible to achieve the needed dramatic global reductions in CO2 emissions over the next several decades. We also need to do it quickly. Emissions are going up, the climate is changing, and impacts are growing. The need for safe and effective CO2 capture with deep GS is urgent.     

Dam effects on bedload transport on the upper Santa Ana River,California, and implications for native fish habitat

Dams disrupt the flow of water and sediment and thus have the potential to affect the downstream geomorphic characteristics of a river. Though there are some well‐known and common geomorphic responses to dams, such as bed armouring, the response downstream from any particular dam is dependent on local conditions. Herein, we investigate the response of the upper Santa Ana River in southern California, USA, to the construction of a large dam at the transition from mountains to valley, using calculations of bedload transport capacity on the mainstem below the dam and for major tributaries. Approximate sediment budgets were constructed for downstream reaches to estimate deposition and erosion rates for sand, gravel, and cobble particle sizes. Our results indicate that the classical response of bed armouring and erosion is likely limited to a short reach immediately below the dam. Farther downstream, though transport capacity is reduced by flow regulation by the dam, the channel reaches are likely to remain depositional but with reduced deposition rates. Persistent deposition, as opposed to erosion, is the result of the replenishment of flow and sediment supply by large downstream tributaries. In addition, the calculations indicate that the composition of the bed is unlikely to change substantially in downstream reaches. A Monte Carlo approach was employed to estimate the uncertainty in the sediment budget predictions. The impacts of the dam on the geomorphic character of the river downstream could have implications for native fish that rely on coarse substrate that supports their food base.     

Accuracy of recorded birth and calving dates of dairy cattle in the United States

Frequencies of births that were reported for specific days of the month were documented for US dairy cattle born since 1987 by birth year, herd size, and registry status and compared with calving frequencies for those dates. Because birth dates are expected to be random and uniformly distributed throughout each month, percentages of births on individual dates were expected to be equal (3.3% for d 1 to d 28, 3.2% for d 29, 3.0% for d 30, and 1.9% for d 31). However, percentages of reported birth dates for d 1, 2, 10, 15, and 20 were higher than expected. The percentage of reported births for d 1 was highest (5.3%) of all days of the month regardless of herd size or registry status. The nonuniform distribution of birth dates within month indicated that a substantial number of birth dates were unknown and that estimated birth dates had been reported. About one-third of the birth dates recorded on d 1 appeared to have been estimated, or altered to gain an advantage in cattle shows. The highest frequencies for birth dates on d 1 (5.9 to 7.4%) were found for registered cows during months that initiated age groupings for dairy shows (March, June, September, and December). Birth dates for some registered cows were intentionally misreported as confirmed by comparison of birth dates of individual cows with calving dates of their dams. Reported calving dates appeared to be more accurate than reported births; the inflated frequency of recorded calvings on d 1 was only about 30% as large as the inflated frequency of recorded births. Because cow age is determined by birth date, proper reporting of birth dates is important to ensure the accuracy of standardized yield and fitness records and the genetic evaluations that are based on those records. When animals' recorded birth dates and their dams' calving dates differ, more credence should be given to the latter to improve accuracy.