Influence of processing on stability,microstructure and thermoelectric properties of Ca3Co4 − xO9 + δ

Due to high figure of merit, Ca₃Co_4 ? xO_9 + δ (CCO) has potential as p-type material for high-temperature thermoelectrics. Here, the influence of processing including solid state sintering, spark plasma sintering and post-calcination on stability, microstructure and thermoelectric properties is reported. By a new post-calcination approach, single-phase materials were obtained from precursors to final dense ceramics in one step. The highest zT of 0.11 was recorded at 800 °C for CCO with 98 and 72% relative densities. In situ high-temperature X-ray diffraction in air and oxygen revealed a higher stability of CCO in oxygen (～970 °C) than in air (～930 °C), with formation of Ca₃Co₂O₆ which also showed high stability in oxygen, even at 1125 °C. Since achievement of phase pure high density CCO by post-calcination method in air is challenging, the phase stability of CCO in oxygen is important for understanding and further improvement of the method.     

In Situ X‐Ray Diffraction Studies on Structural Changes of a P2 Layered Material during Electrochemical Desodiation/Sodiation

Sodium layered oxides with mixed transition metals have received significant attention as positive electrode candidates for sodium‐ion batteries because of their high reversible capacity. The phase transformations of layered compounds during electrochemical reactions are a pivotal feature for understanding the relationship between layered structures and electrochemical properties. A combination of in situ diffraction and ex situ X‐ray absorption spectroscopy reveals the phase transition mechanism for the ternary transition metal system (Fe–Mn–Co) with P2 stacking. In situ synchrotron X‐ray diffraction using a capillary‐based microbattery cell shows a structural change from P2 to O2 in P2–Na_0.7Fe_0.4Mn_0.4Co_0.2O₂ at the voltage plateau above 4.1 V on desodiation. The P2 structure is restored upon subsequent sodiation. The lattice parameter c in the O2 structure decreases significantly, resulting in a volumetric contraction of the lattice toward a fully charged state. Observations on the redox behavior of each transition metal in P2–Na_0.7Fe_0.4Mn_0.4Co_0.2O₂ using X‐ray absorption spectroscopy indicate that all transition metals are involved in the reduction/oxidation process.     

Herd-level variables associated with delayed milk ejection in Michigan dairy herds

The objective of this study was to determine which herd-level variables were associated with delayed milk ejection (bimodal milk let-down) in 64 Michigan dairy herds. Median herd size was 294 cows (range 59 to 2,771 cows). For each herd, milking protocols were observed and milk flow dynamics were estimated by use of digital vacuum recorders. Surveys were also administered to the producers to measure mastitis management practices and attitudes. Milk flow dynamics were recorded for a total of 3,824 cow milkings, with a mean of 60 milkings per herd (range of 11 to 154). Backward multivariable analysis was used to determine which of the 47 herd-level milking and management variables were associated with delayed milk ejection (cows with milk let-down periods between milking cluster attachment and the incline phase of milk flow of >30 s). Delayed milk ejection occurred in an average of 25% of the cows in each herd (range 0 to 75%). A multivariable model found that the proportion of cows in a herd with delayed milk ejection was negatively associated with mean total time of tactile stimulation during premilking routines and positively associated with herd size.     

Supplementation of linoleic acid (C18:2n-6) or α-linolenic acid (C18:3n-3) changes microbial agonist-induced oxylipid biosynthesis

Oxylipids are derived from polyunsaturated fatty acids (PUFA) in cellular membranes and the relative abundance or balance may contribute to disease pathogenesis. Previous studies documented unique oxylipid profiles from cows with either coliform or Streptococcus uberis mastitis, suggesting that lipid mediator biosynthesis may be dependent on the type of microbial-derived agonist. Changing the fatty acid content of peripheral blood leukocytes also may be critical to the relative expression of oxylipid profiles and the outcome of bacterial infection. No information is available in dairy cows describing how changing cellular PUFA content will modify oxylipids in the context of a microbial agonist challenge. Therefore, the hypothesis for the current study was that PUFA supplementation would change bovine leukocyte fatty acid content and respective oxylipid profiles from ex vivo microbial agonist-challenged leukocytes. Fatty acid content of leukocytes and plasma was quantified in (1) samples from cows not supplemented with PUFA, (2) cows supplemented with linoleic acid (LnA), and (3) cows supplemented with α-linolenic acid (ALA). Plasma oxylipids were assessed after S. uberis or lipopolysaccharide exposure and was compared with unstimulated oxylipid profiles. Fatty acid supplementation with ALA significantly increased ALA content of blood leukocytes and plasma relative to LnA. Fatty acid supplementation affected several S. uberis-induced oxylipids, but only S. uberis-induced 15-oxoETE was greater with ALA supplementation compared with LnA. Notably, only LPS-induced 5,6 LXA₄ was altered with fatty acid supplementation, but no significant effect of LnA vs. ALA treatment was identified. Future studies are needed to understand how leukocyte activation and membrane PUFA availability collectively contribute to differential oxylipid profiles.     

Evaluation of metastable pitting on titanium by charge integration of current transients

The metastable pitting of titanium has been studied under potentiostatic control in solutions containing chloride ions. An approach based on the charge integration of current transients was proposed for a quantitative determination of metastable pitting. A pit density (d_mpit) was defined as the number of metastable pits per unit area per unit time (cm⁻² h⁻¹) with a typical size, instead of a size distribution. The calculated d_mpit of titanium at 0.5 V_SCE in 0.6 M NaCl was about 1.0 × 10³ cm⁻² h⁻¹ with a typical radius of 0.12 μm. An exponential potential dependence of d_mpit was obtained through the integration approach.     

A liquefied energy chain for transport and utilization of natural gas for power production with CO2 capture and storage – Part 1

A novel transport chain for stranded natural gas utilized for power production with CO₂ capture and storage is developed. It includes an offshore section, a combined gas carrier, and an onshore integrated receiving terminal. Due to utilization of the cold exergy both in the offshore and onshore processes, and combined use of the gas carrier, the transport chain is both energy and cost effective. In this paper, the liquefied energy chain (LEC) is explained, including novel processes for both the offshore field site and onshore market site. In the offshore section, natural gas (NG) is liquefied to LNG by liquid carbon dioxide (LCO₂) and liquid inert nitrogen (LIN), which are used as cold carriers. The LNG is transported in a combined gas carrier to the receiving terminal where it is used as a cooling agent to liquefy CO₂ and nitrogen. The LCO₂ and LIN are transported offshore using the same combined carrier. Pinch and Exergy Analyses are used to determine the optimal offshore and onshore processes and the best transport conditions. The exergy efficiency for a thermodynamically optimized process is 87% and 71% for the offshore and onshore processes, respectively, yielding a total efficiency of 52%. The offshore process is self-supported with power and can operate with few units of rotating equipment and without flammable refrigerants. The loss of natural gas due to power generation for the energy requirements in the LEC processes is roughly one third of the loss in a conventional transport chain for stranded natural gas with CO₂ sequestration. The LEC has several configurations and can be used for small scale (<0.25 MTPA LNG) to large-scale (>5 MTPA LNG) transport. In the example in this paper, the total costs for the simple LEC including transport of natural gas to a 400 MW_net power plant and return of 85% of the corresponding carbon as CO₂ for a total sailing distance of 24 h are 58.1 EUR/tonne LNG excluding or including the cost of power. The total power requirements are 319 kWh/tonne, hence the energy costs are 31.9 EUR/tonne LNG adding up to 90.0 EUR/tonne LNG. The exergy efficiency for this energy chain including power production and CO₂ capture is 46.4% with a total cost of 20.4 EUR/MWh for the produced electricity. The total emissions (in CO₂ equivalents) in the chain are 1–1.5% of the transported CO₂.     

High-Temperature Proton Conductivity in Acceptor-Substituted Rare-Earth Ortho-Tantalates, LnTaO4

The electrical properties of 1 mol% Ca-doped LnTaO₄ (Ln=La, Nd, Gd, Er) have been characterized by AC impedance spectroscopy and by the EMF transport number technique as a function of the oxygen pressure and the water vapor pressure from 300° to 1200°C. Protons, oxide ions, electron holes, and electrons contribute to the total conductivity, depending on the conditions. Ionic conductivity predominates under reducing and weakly reducing conditions, with protons prevailing in wet atmospheres up to temperatures of around 1000°C. p -type electronic conductivity prevails at high temperatures under oxidizing conditions. The conductivity behavior has been interpreted according to a point-defect model where protons and oxygen vacancies charge compensate the acceptor doping. Thermodynamic and transport parameters have been extracted based on the changes in total conductivity upon variations in the conditions. The hydration enthalpy becomes increasingly negative with increasing oxide ion density from LaTaO₄ to ErTaO₄.     

The performance of SAS-super-180 air sampler and settle plates for assessing viable fungal particles in the air of dry-cured meat production facility

Performances of SAS-super-180 air sampler and settle plates were investigated for the assessment of airborne fungal food contamination. Air samples were taken from processing rooms of a dry-cured production facility and outdoors. Fungal colonies and numbers of species were counted and compared. Quantitatively, the air sampler showed higher numbers of species and mean CFU/plate compared to settle plates. Qualitatively, the two methods showed similar dominating fungal genera and species associated with dry-cured meat products. The study showed settle plates could provide important qualitative information for food processing plants where airborne fungi associated with food products are the targets.     

Process design methodology for energy‐efficient processes operating below and across ambient temperature

This article presents a targeting and design methodology that can be implemented for any process where pressure‐based exergy, also known as mechanical exergy, has an important contribution to the total exergy conversion and transfer. However, in this article it is applied to processes that operate at sub‐ambient conditions, or processes where the ambient conditions are crossed. Exergy efficiencies, new Exergetic Composite Curves, Cascades, and Extended Grid Diagrams are tools that had to be implemented, improved, or invented, to develop a methodology with considerable potential for energy‐efficient process design. The appropriate placement (correct integration) of compressors and expanders in heat exchanger networks is also analyzed to minimize the number of units. An example is used to demonstrate the methodology, where several simplifying assumptions are made to facilitate understanding and to explain the design method. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2324–2340, 2016