Irreversible Rate Research Articles

Durability Testing of Polymer Electrolyte Fuel Cells Under Stationary and Automotive Conditions

Our presentation focuses on durability testing and degradation of fuel cells. A major motivation of our work is the lack of common description procedures and determination approaches of voltage losses in durability tests of fuel cell for both stationary and automotive applications; this issue leads to severe difficulties in the comparison of results obtained by different institutions or within different projects, especially if only a single value for the degradation rate is reported. In this context, special attention is devoted to the discrimination between so called reversible and irreversible voltage losses. The first are permanent and determine the maximum lifetime of a fuel cell. The latter strongly depend on the chosen operation conditions and can be recovered by specific procedures. In order so systematically address voltage losses we have performed single cell durability measurements of several hundreds of hours in 25 cm2 lab-scale cells using different test protocols containing regular refresh procedures (soak time) allowing to distinguish between reversible and irreversible losses. Furthermore, operation strategies to minimize reversible degradation without using the time consuming refresh procedures are provided. To test the refresh procedures and analyze their effect on cell performance, parameters such as duration of the soak time steps have been varied. Between these refresh steps the cells were typically operated for 50 to 150 h. As samples conventional 5-layer membrane electrode assemblies were used with PFSA membranes, Pt-based catalysts and hydrophobized carbon fiber substrates with micro porous layers as GDLs. For in-situ diagnosis of the operated cells polarization curves, electrochemical impedance spectra, and cyclic voltammograms were recorded in order to determine the impact of the operation conditions and the refresh procedures on degradation. The interpretation of the degradation of the measured membrane electrode assemblies is supported by post-mortem analysis using physical characterization techniques. Additionally, we provide possible approaches to quantitatively determine irreversible voltage decay rates. For instance, voltage values before or after voltage recovery steps can be used to calculate the irreversible loss rate. The advantages and drawbacks of different approaches are discussed. One clear conclusion is that short time tests in the range of 100 hour are not conclusive since this time is too short to make a reliable discrimination between reversible and irreversible losses; also, the decay rate of reversible loss observed after each refresh step increases substantially upon long time operation independent on the type of the refresh procedure. In summary, in our presentation strategies for determination of fuel cell voltages loss rates are compared, evaluated and assessed according to their suitability to distinguish between reversible and irreversible degradation rates; a description of voltage loss rates is proposed. Moreover, operation strategies to minimize reversible degradation are provided. The research leading to these results has received funding from the European Union's Seventh Framework Programme (FP7/2007-2013) for Fuel Cell and Hydrogen Joint Technology Initiative under Grant No. 621216 (SecondAct) and No. 303452 (Impact).

Investigation of SEI Growth on Carbon-Coated ZnFe2O4 Li-Ion Battery Anode Material By I n Situ Raman Microscopy

Lithium-ion batteries (LIBs) are electrochemical devices for energy storage used in portable electronics due to their high energy density, lightweight and flexible design. However, improvements in safety, cost and energy and power density to meet the requirements of automotive industry and large scale storage technology for the wide application of LIBs on these fields.[1, 2] The battery performance is affected by surface layers formed on the electrodes. In particular, the solid electrolyte interphase (SEI) is a protecting surface film formed on the negative electrode in organic-based electrolytes. It consists of inorganic and organic species resulting from electrolyte decomposition.[3, 4] This electron insulating layer allows the transport of lithium ions and it has an impact on the irreversible charge loss, rate capability, cyclability and safety.[3] Therefore, it is essential to understand the processes that occur at the electrode/electrolyte interfaces and the nature of the surface film to improve the efficiency and develop longer-life LIBs. ZnFe2O4 (ZFO) is a non-toxic and cheap material of great interest as anode for LIBs with a high specific theoretical capacity ca. 1000 mAhg-1 due to a conversion-alloying reaction that involves the intake of 9 Li+.[5] An environmental friendly method to encapsulate ZFO nanoparticles within a carbon matrix has been described to avoid the aggregation of particles and loss of electronic conductivity that leads to capacity fading.[5] This work presents in situ Raman measurements of carbon-coated ZnFe2O4(ZFO-C) material during the first discharge/charge cycle.[6] The Raman spectrum of ZFO-C electrode at the open-circuit potential (OCP) only shows the D and G bands characteristic of carbon materials. These peaks weaken during the discharge step suggesting that the lithiation also occurs in the carbon coating. The signal of the D and G bands is recovered at the end of the charge step. The absence of peaks related to ZFO material indicates that the carbon coating remains mechanically intact after the first discharge/charge cycle. New Raman bands are observed within a potential region that coincides with SEI layer formation. These bands have been assigned to poly(ethylene)oxide species and organic lithium alkyl carbonates from electrolyte side reactions. The detection of SEI compounds by conventional Raman microscopy may be the result of “temporary surface enhancement Raman effect” from Zn nanoparticles formed during the conversion reaction of ZnFe2O4 in a similar potential region as SEI formation. The observation of these polymeric species formed on the carbon coating is comparable to shell isolated nanoparticle Raman spectroscopy (SHINERS) reported by Tian and co-workers.[7]

How affordable are the costs compared to benefits brought by the euro to the Kosovo’s economy

Since January 1, 2002, pursuant to UNMIK Regulation[1] no. 1999/4, the EURO (‘’EUR’’) was adopted as the legal currency in Kosovo, and was made the factual currency of the country. All client accounts held by the Central Bank of the Republic of Kosovo (CBK) and commercial banks were converted from DEM into EURO, on an irreversible currency ex-change rate of DEM 1,95583 per 1 EURO. As a result, in practice, while the Euro is legal and while accounts are held in this currency, almost all transactions made in Kosovo are titled and made in Euro. The use of a sustainable currency was important to maintaining a macro-economic stability and played a decisive role in rebuilding the people’s trust on the financial sector. On the other hand, the CBK does not emit currency, and as such, it does not perform any monetary and exchange policies. The currency regime adopted by Kosovo may be rather challenging, given the absence of traditional monetary instruments and the exchange rates. Therefore, the main concern remains whether fair policies (both fiscal and regulations related to the financial sector) will support this regime. The purpose of this paper is to demonstrate costs and benefit brought upon the Kosovar economy by the use of Euro as a main currency in circula-tion, and how affordable are the costs in comparison to benefits brought by the Europeanization of the Kosovo’s economy.[1] UNMIK - United Nations Mission Interim in Kosovo.

The impact of effective stress and gas slippage on coal permeability under cyclic loading

The determination of the effective stress coefficient of porous media (such as coal) remains a controversial issue. The purpose of this paper is to determine the effective stress coefficient of coal during gas penetration and to investigate the impact of effective stress and gas slippage on coal permeability under cyclic loading conditions. Analyzing the evolution law of coal anisotropic permeability with effective stress allows the deformation characteristics of the coal's internal structure, such as cleat or bedding, to be studied. The effective stress coefficient of long flame coal is obtained through modified permeability models based on experimental data. Test results show that the slippage effect significantly influences the permeability of coal samples, specifically in the range of low pore gas pressure, and that the effect of gas slippage is larger than that of effective stress. Permeability decreases gradually when effective stress increases, but it increases during unloading, and ascending and descending curves show significant irreversibility of permeability. Moreover, PLR (permeability loss rate) and IPLR (irreversible permeability loss rate) results indicate that the influence of effective stress on permeability perpendicular to bedding is greater than that of permeability parallel to bedding and that the ability of the cleat to resist deformation induced by effective stress is weaker than that of bedding. Under identical pressure conditions, the cleat shows more vulnerability and produces larger plastic deformation.

Effectiveness of Reversible Contraception in Dog Population Management

Background: Dog fertility depends on human-influenced factors such as sterilization. Uncontrolled fertility can result in unwanted births and overpopulation, which causes problems of public health and animal welfare. Surgical sterilization has been the traditional means of reproduction control but its cost and time can be prohibitive for mass sterilization programs. Non-surgical sterilization alternatives exist, but most of them are reversible and their effectiveness as a population management tool is unknown. To better understand the consequences of reversible contraception, the fertility dynamics was modeled in a hypothetical dog population in a steady-state condition.Materials, Methods & Results: The effect of reversible contraception was simulated using a coupled system of ordinary differential equations. A hypothetical steady-state population of 1000 animals was considered. It was formed by two compartments, one of fertile dogs and the other of infertile dogs. Natality compensated for a fraction of mortality, and the immigration rate compensated for the remaining fraction. The group of immigrant dogs was composed of fertile and infgertile dogs. The dog flow between compartments was given by both the contraception and fertility recovery rate. It was assumed that fertility reversibility in animals of the immigrant group was equal to that of animals already present in the population. Global sensitivities were calculated to assess the uncertainties of fertility dynamics associated with estimation of parameters. In addition, the local sensitivities were calculated to assess the influence of each parameter on fertility dynamics. The treatment effectiveness were expressed in terms of the total number of dogs treated for 20 years by taking a given irreversible contraception rate divided by the total number of dogs treated during the same period, and using the corresponding reversible contraception rate. The global sensitivity analysis consistently indicated a reduction in the number of fertile dogs. The local sensitivity analysis indicated that contraception rate was the most influential parameter, followed by the fertility recovery rate. The fraction of mortality compensated by natality was more influential than the fraction of infertile immigrants. Simulated scenarios indicated that the higher the contraception rate, the greater the difference between the effects of different fertility recovery rates. Variations in the proportion of infertile immigrants minimally changed the number of fertile dogs and the accumulated number of treated dogs. The increase in the fertility recovery rate caused effectiveness to decrease, especially when contraception rates were higher.Discussion: In certain scenarios, reversible contraception can be a viable option for reproduction control. Evaluation of effectiveness of the reversible contraception showed both the importance of duration of the contraceptive effect and the interaction between the contraception and fertility recovery rates. Although the contraception rate is the main determinant of population fertility dynamics, the fertility recovery rate modulates the effect of contraception and determines its viability. Reversible contraception is a viable alternative when loss in effectiveness is compensated by a reduction in costs and ease of application of contraceptive treatments. The lower the contraception rate, the higher the similarity between the effects of reversible and irreversible contraception.

Detailed study of heat generation in porous LiCoO2 electrodes

In this work the heat generation in porous LiCoO2 based electrodes for lithium ion batteries is studied in detail. Irreversible heat generation rates due to ohmic resistance, charge transfer and mass transport limitations as well as the reversible heat of the electrode reaction are determined from electrochemical measurements as a function of the C-rate, the temperature and the lithium concentration in the active material. The results show that all the individual heat sources contribute significantly to the total heat generation in the electrode. The heat sources are functions of the C-rate and the temperature as well as the lithium concentration in the active material. The reversible heat contribution was found to be most significant at higher temperatures und lower C-rates, which tend to reduce kinetic limitations and irreversible heats, respectively. The heat generation rate due to mass transport limitations is most influential among the irreversible heats, whereas the ohmic contribution shows a minor impact. The total heat generation was found to increase with increasing C-rate and decreasing temperature. Furthermore, the heat generation is significantly reduced for charging compared to discharging due to the intrinsic asymmetry of the reversible heat and larger kinetic limitations for lithiation compared to delithiation of LiCoO2.

Dietary Amino Acid Deficiency Reduces the Utilization of Amino Acids for Growth in Growing Pigs after a Period of Poor Health

Background: During immune system activation, partitioning of amino acids (AAs) changes between protein gain and use by the immune system.Objective: We determined the effects of health status and dietary AA deficiency on nitrogen retention and AA utilization in pigs.Methods: Barrows (55 d of age) were obtained from good health (GH, n = 14) or poor health (PH, n = 14) status farms and allocated to a diet either adequate in essential amino acids (Adq) or 25% deficient in Met + Cys, Thr, and Trp (Def). Nitrogen balance was measured and AA irreversible loss rates (ILRs) were measured after an intravenous bolus of U-13C–labeled L-AAs.Results: On arrival at the experimental facilities, the PH pigs had 14% lower serum albumin and 50% greater serum haptoglobin and blood leukocyte counts than the GH pigs (P < 0.01), but the PH pigs showed signs of recovery during the trial. Total tract nitrogen digestibility was 3 percentage points lower in the PH pigs (P < 0.01). The PH-Adq pigs had compensatory body weight gain after arrival, coinciding with 7% greater nitrogen retention (P < 0.01) in the PH pigs than in the GH pigs. The PH pigs had a 24% greater ILR for Lys. Health status × diet interactions for Lys (P = 0.07), Val (P = 0.03), and Leu (P = 0.10) pool sizes and a greater urea pool size in the PH pigs (P = 0.01) support the observation that the increase in the ILR of Lys in the PH pigs was related to oxidation when feeding the Def diet, but to synthesis when feeding the Adq diet. Feeding Def diets increased monocyte counts by 30% (P < 0.01).Conclusions: This study illustrates how the competition for AAs between protein synthesis associated with immune system activation and body protein deposition is greater when the dietary supply of Met + Cys, Thr, and Trp is limited in pigs during and after a period of poor health.

Optimization and kinetic modeling of esterification of the oil obtained from waste plum stones as a pretreatment step in biodiesel production

This study reports on the use of oil obtained from waste plum stones as a low-cost feedstock for biodiesel production. Because of high free fatty acid (FFA) level (15.8%), the oil was processed through the two-step process including esterification of FFA and methanolysis of the esterified oil catalyzed by H2SO4 and CaO, respectively. Esterification was optimized by response surface methodology combined with a central composite design. The second-order polynomial equation predicted the lowest acid value of 0.53mgKOH/g under the following optimal reaction conditions: the methanol:oil molar ratio of 8.5:1, the catalyst amount of 2% and the reaction temperature of 45°C. The predicted acid value agreed with the experimental acid value (0.47mgKOH/g). The kinetics of FFA esterification was described by the irreversible pseudo first-order reaction rate law. The apparent kinetic constant was correlated with the initial methanol and catalyst concentrations and reaction temperature. The activation energy of the esterification reaction slightly decreased from 13.23 to 11.55kJ/mol with increasing the catalyst concentration from 0.049 to 0.172mol/dm3. In the second step, the esterified oil reacted with methanol (methanol:oil molar ratio of 9:1) in the presence of CaO (5% to the oil mass) at 60°C. The properties of the obtained biodiesel were within the EN 14214 standard limits. Hence, waste plum stones might be valuable raw material for obtaining fatty oil for the use as alternative feedstock in biodiesel production.

Responses in whole-body amino acid kinetics to an acute, sub-clinical endotoxin challenge in lambs.

Some effects of parasitism, endotoxaemia or sepsis can be mitigated by provision of extra protein. Supplemented protein may encompass a metabolic requirement for specific amino acids (AA). The current study investigates a method to identify and quantify the amounts of AA required during inflammation induced by an endotoxin challenge. One of each pair of six twin sheep was infused in the jugular vein for 20 h with either saline (control) or lipopolysaccharide (LPS, 2 ng/kg body weight per min) from Escherichia coli. Between 12 and 20 h a mixture of stable isotope-labelled AA was infused to measure irreversible loss rates. From 16 to 20 h all sheep were supplemented with a mixture of unlabelled AA infused intravenously. Blood samples were taken before the start of infusions, and then continuously over intervals between 14 and 20 h. At 20 h the sheep were euthanised, and liver and kidney samples were taken for measurement of serine-threonine dehydratase (SDH) activity. LPS infusion decreased plasma concentrations of most AA (P<0·05; P<0·10 for leucine and tryptophan), except for phenylalanine (which increased P=0·022) and tyrosine. On the basis of the incremental response to the supplemental AA, arginine, aspartate, cysteine, glutamate, lysine (tendency only), glycine, methionine, proline, serine and threonine were important in the metabolic response to the endotoxaemia. The AA infusion between 16 and 20 h restored the plasma concentrations in the LPS-treated sheep for the majority of AA, except for glutamine, isoleucine, methionine, serine and valine. LPS treatment increased (P<0·02) SDH activity in both liver and kidney. The approach allows quantification of key AA required during challenge situations.

Abstract C118: Choline kinase inhibition with the novel pharmacological inhibitor ICL-CCIC-0019 reprograms cellular metabolism and inhibits cancer cell growth

Abstract The glycerophospholipid phosphatidylcholine (PC) is the most abundant phospholipid species of eukaryotic membranes and essential for structural integrity and signaling function of cell membranes required for cancer cell growth. PC is synthesized via the CDP-choline pathway, whereby choline kinase alpha (CHKA) denotes the first committed step in this sequence of enzymatic reactions. CHKA phosphorylates choline to form phosphocholine and its overexpression in many solid tumors is linked to progression of normal cells to malignancy. We developed the highly selective, choline-competitive small-molecule ICL-CCIC-0019 (IC50 of 0.27±0.06 μM). Across a panel of 131 human kinases, the inhibitor showed minimal off-target effects (only 5 kinases were inhibited more than 20% at a concentration of 10 μM). ICL-CCIC-0019 potently inhibited growth of a panel of 60 cancer cell lines with median GI50 of 1.12 μM. Importantly, proliferation of normal cells was only minimally affected (MCF-10A and ST-T1b: GI50 30-120 μM). ICL-CCIC-0019 decreased phosphocholine levels and the fraction of labeled choline in lipids, and induced G1 arrest, endoplasmic reticulum stress and apoptosis. Changes in phosphocholine cellular levels following treatment could be detected non-invasively in tumor xenografts by 18F-fluoromethyl-[1,2-2H4]-choline positron emission tomography. Pharmacokinetic modeling revealed that the macro parameter Ki denoting the net irreversible uptake rate was significantly decreased in tumor after 48 hours (Ki (1/min): control, 0.0054±0.00060; ICL-CCIC-0019, 0.0032±0.00064), confirming in vivo target inhibition. This resulted in potent antitumor activity in HCT116 xenografts. We further reveal a previously unappreciated effect of choline metabolism on mitochondria function. Comparative metabolomics demonstrated that phosphatidylcholine pathway inhibition leads to a metabolically stressed phenotype analogous to mitochondria toxin treatment but without reactive oxygen species activation. Drug treatment decreased TCA cycle activity, oxygen consumption rate and elevated extracellular acidification rate. This was associated with a reduction of citrate synthase expression and AMP kinase activation. Glucose and acetate uptake were increased in an attempt to overcome the metabolic stress. This study indicates that choline pathway pharmacological inhibition is a valid therapeutic strategy and critically affects the metabolic function of the cell beyond reduced synthesis of phospholipids. This work was supported in part by Cancer Research UK-Engineering and Physical Sciences Research Council Grant C2536/A10337. Citation Format: Sebastian Trousil, Maciej Kalisczcak, Zachary Schug, Quang-De Nguyen, Giampaolo Tomasi, Rosy Favicchio, Diana Brickute, Robin Fortt, Frazer J. Twyman, Laurence Carroll, Andrew Kalusa, Naveenan Navaratnam, Thomas Adejumo, David Carling, Eyal Gottlieb, Eric O. Aboagye. Choline kinase inhibition with the novel pharmacological inhibitor ICL-CCIC-0019 reprograms cellular metabolism and inhibits cancer cell growth. [abstract]. In: Proceedings of the AACR-NCI-EORTC International Conference: Molecular Targets and Cancer Therapeutics; 2015 Nov 5-9; Boston, MA. Philadelphia (PA): AACR; Mol Cancer Ther 2015;14(12 Suppl 2):Abstract nr C118.

Evaluation of a 2.5 kWel automotive low temperature PEM fuel cell stack with extended operating temperature range up to 120 °C

Nowadays, the operating temperature of polymer electrolyte membrane fuel cell stacks is typically limited to 80 °C due to water management issues of membrane materials. In the present work, short-term operation at elevated temperatures up to 120 °C and long-term steady-state operation under automotive relevant conditions at 80 °C are examined using a 30-cell stack developed at DLR. The high temperature behavior is investigated by using temperature cycles between 90 and 120 °C without adjustment of the gases dew points, to simulate a short-period temperature increase, possibly caused by an extended power demand and/or limited heat removal. This galvanostatic test demonstrates a fully reversible performance decrease of 21 ± 1% during each thermal cycle. The irreversible degradation rate is about a factor of 6 higher compared to the one determined by the long-term test. The 1200-h test at 80 °C demonstrates linear stack voltage decay with acceptable degradation rate, apart from a malfunction of the air compressor, which results in increased catalyst degradation effects on individual cells. This interpretation is based on an end-of-life characterization, aimed to investigate catalyst, electrode and membrane degradation, by determining hydrogen crossover rates, high frequency resistances, electrochemically active surface areas and catalyst particle sizes.

Coagulation optimization for DOC removal: pilot-scale analysis of UF fouling and disinfection byproduct formation potential

A pilot-scale study was performed to evaluate a coagulant dose which had been optimized for biopolymer (i.e., foulant) removal on subsequent ultrafiltration (UF) fouling, as well as disinfection by-product (DBP) precursor removal. Polyaluminum chloride (PACl) dosages were selected based on a point of diminishing returns for biopolymer removal (0.5 mg/L) and directly compared to that applied at full-scale (6 mg/L). Membrane fouling (reversible and irreversible) was measured as resistance increase over a 48 hour filtration period. DBP formation potential (total trihalomethanes (TTHMs), haloacetic acids (HAA9) and total adsorbable organic halides (AOX)) were measured in both raw and treated waters. Results of the study indicate that application of a PACl dose optimized for biopolymer reduction (0.5 mg/L) resulted in 65% less irreversible UF fouling when compared to 6 mg/L. The addition of PACl prior to the membrane resulted in up to a 14% reduction in DBP precursors relative to the UF membrane alone. A similar level of DBP precursor reduction was achieved for both 0.5 and 6 mg/L dosages. The results have implications for cost savings, which may be realized due to decreased chemical use, as well as increased membrane life associated with lower irreversible fouling rates.

Thermodynamic and fibril formation studies of full length immunoglobulin light chain AL-09 and its germline protein using scan rate dependent thermal unfolding

Light chain (AL) amyloidosis is a fatal disease where monoclonal immunoglobulin light chains deposit as insoluble amyloid fibrils. For many years it has been considered that AL amyloid deposits are formed primarily by the variable domain, while its constant domain has been considered not to be amyloidogenic. However recent studies identify full length (FL) light chains as part of the amyloid deposits. In this report, we compare the stabilities and amyloidogenic properties of two light chains, an amyloid-associated protein AL-09 FL, and its germline protein κ I O18/O8 FL (IGKV 1–33). We demonstrate that the thermal unfolding for both proteins is irreversible and scan rate dependent, with similar stability parameters compared to their VL counterparts. In addition, the constant domain seems to modulate their amyloidogenic properties and affect the morphology of the amyloid fibrils. These results allow us to understand the role of the kappa constant domain in AL amyloidosis.

Time‐scale analysis of atomic layer deposition processes: Predicting the transition from mass‐transfer to kinetically limited regimes

AbstractThe relative rates of adsorption and irreversible reaction are modeled for a prototypical atomic layer deposition (ALD) system. Surface species balance modeling equations are processed through a reaction factorization procedure to eliminate redundant dynamic modes. The resulting singular perturbation problem then is used to develop a criterion that distinguishes between mass‐transfer and kinetically‐limited deposition regimes for this dynamic process. Detailed simulations of a TMA/water alumina ALD process are used to evaluate our analysis approach and to demonstrate the dominance of mass‐transfer limitations for this system during both precursor exposure periods. Our analysis shows the increasing likelihood of encountering mass‐transfer limitations at reduced temperatures, a finding opposite of what might be expected. We find that the ALD dynamics evolve on a manifold defined by the balancing of adsorption and irreversible reaction rates, further reducing the dynamic dimension of the deposition dynamics. (© 2015 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Exploring Nanostructured Tin Oxides (SnOx) As Anodes for Sodium Ion Batteries

Lithium-ion batteries have dominated the field of rechargeable secondary batteries over the past decade. However, in the recent years, the focus has shifted to sodium ion batteries owing to their large energy density, abundance of availability in the earth’s crust, and the low toxicity and relatively better safety prospects of sodium metal in comparison to lithium which makes them an alternative system to pursue for large scale production. Tin / tin oxide in particular, forms a very attractive anode for both lithium and sodium ion battereries with a theoretical capacity of 847 mAh/g for Sn and 1378 mAh/g for SnO2 corresponding to the formation of Na15Sn4 phase [1-3]. However, SnO2 when used as anode for sodium shows a first cycle irreversible (FIR) loss of 52% (giving a stable theoretical capacity of 667 mAh/g) corresponding to the reduction of SnO2 to Sn leading to the formation of sodium oxide matrix embedded with the Sn particles, similar to the phenomenon observed in Li – SnO2 system. However, similar to the Li-analog, Sn/SnO2as an anode undergoes colossal volumetric expansion (~430%) during the sodiation/de-sodiation process hence, leading to the mechanical disintegration and pulverization of the electrode when used in Na ion battery. It has previously been shown that nanostructures help minimize the stresses in the Li – Si system thus improving the stability and electrochemical performance of the anode material. In the present work, SnO2 nanotubes have been synthesized using a sacrificial inorganic nanowire (INW) template. These INWs were dispersed in a solution of suitable tin precursors hence forming hollow SnO2 nanotubes (SONTs). The excess or remnant elements from the INW in the SONTs were removed by dispersing them in suitable liquid medium. In another method, tin(II) precursors were dissolved in suitable solvents and the pH of the solution accordingly adjusted to form nanoparticles of SnO. Slurry based electrodes of these hollow SnO2 nanostructures and SnO nanoparticles mixed with binder and conductive additives were tested in a half cell configuration against sodium metal, between the voltage range 0.01V – 1.2V vs. Na/Na+ in 1M NaClO4 (dissolved in EC:DEC =50:50) as electrolyte. The same electrodes were also tested against lithium metal in 1M LiPF6(dissolved in EC:DEC:FEC=45:45:10) electrolyte to give a comparison of the material performance in both the systems. The SEM (Fig. 1) image shows nanotubes of SnO2 formed by the precipitation of SnO2 from the stannate precursors and the simultaneous etching process of the inorganic wire template due to the release of respective counter ions. The EDS analysis shows the presence of Sn and oxygen without any signature from the elements in the INW template thus, confirming the dissolution of the template. The SEM image (Figure 2) of the synthesized SnO shows agglomerates of the spherical nanoparticles of SnO. The SnO2system when tested for lithium system shows a first cycle capacity of 1420 mAh/g (at 25mA/g), initial first cycle irreversible loss of 60% and a capacity of 632 mAh/g in the subsequent cycles. Furthermore, the cycling data for the testing of these SONTs and SnO nanoparticles in sodium ion battery shall be presented with an analysis on the charge – discharge capacity, the first cycle irreversible loss, rate capability and long term stability of these nanostructures. Acknowledgement: The authors gratefully acknowledge the financial support of NSF grant (CBET-0933141). The authors also acknowledge the Edward R. Weidlein Chair Professorship funds and the Center for Complex Engineered Multifunctional Materials for partial support of this research.

The effect of fine bubble aeration intensity on membrane bioreactor sludge characteristics and fouling

While most membrane bioreactor (MBR) research focuses on improving membrane filtration through air scour, backwashing and chemical cleaning to physically counteract fouling, relatively few studies have dealt with fouling prevention, e.g. minimizing the impact of operational settings that negatively impact sludge filterability. To evaluate the importance of those settings, the effects of bioreactor aeration intensity variations on membrane fouling have been studied in a lab-scale MBR setup while simultaneously monitoring a unique set of key sludge parameters. In particular, this paper focuses on the impact of shear dynamics resulting from fine air bubbles on the activated sludge quality and flocculation state, impacting membrane fouling. When augmenting the fine bubble aeration intensity both the total and irreversible fouling rate increased. Major indications for sludge filterability deterioration were found to be a shift in the particle size distribution (PSD) in the 3–300 μm range towards smaller sludge flocs, and increasing concentrations of submicron particles (10–1000 nm), soluble microbial products and biopolymers. When lowering the aeration intensity, both the sludge characteristics and fouling either went back to background values or stabilized, respectively indicating a temporary or more permanent effect, with or without time delay. The shift in PSD to smaller flocs and fragments likely increased the total fouling through the formation of a less permeable cake layer, while high concentrations of submicron particles were likely causing increased irreversible fouling through pore blocking. The insights from the performed fouling experiments can be used to optimize system operation with respect to influent dynamics.

A priori and a posteriori investigations for developing large eddy simulations of multi-species turbulent mixing under high-pressure conditions

A Direct Numerical Simulation (DNS) database was created representing mixing of species under high-pressure conditions. The configuration considered is that of a temporally evolving mixing layer. The database was examined and analyzed for the purpose of modeling some of the unclosed terms that appear in the Large Eddy Simulation (LES) equations. Several metrics are used to understand the LES modeling requirements. First, a statistical analysis of the DNS-database large-scale flow structures was performed to provide a metric for probing the accuracy of the proposed LES models as the flow fields obtained from accurate LESs should contain structures of morphology statistically similar to those observed in the filtered-and-coarsened DNS (FC-DNS) fields. To characterize the morphology of the large-scales structures, the Minkowski functionals of the iso-surfaces were evaluated for two different fields: the second-invariant of the rate of deformation tensor and the irreversible entropy production rate. To remove the presence of the small flow scales, both of these fields were computed using the FC-DNS solutions. It was found that the large-scale structures of the irreversible entropy production rate exhibit higher morphological complexity than those of the second invariant of the rate of deformation tensor, indicating that the burden of modeling will be on recovering the thermodynamic fields. Second, to evaluate the physical effects which must be modeled at the subfilter scale, an a priori analysis was conducted. This a priori analysis, conducted in the coarse-grid LES regime, revealed that standard closures for the filtered pressure, the filtered heat flux, and the filtered species mass fluxes, in which a filtered function of a variable is equal to the function of the filtered variable, may no longer be valid for the high-pressure flows considered in this study. The terms requiring modeling are the filtered pressure, the filtered heat flux, the filtered pressure work, and the filtered species mass fluxes. Improved models were developed based on a scale-similarity approach and were found to perform considerably better than the classical ones. These improved models were also assessed in an a posteriori study. Different combinations of the standard models and the improved ones were tested. At the relatively small Reynolds numbers achievable in DNS and at the relatively small filter widths used here, the standard models for the filtered pressure, the filtered heat flux, and the filtered species fluxes were found to yield accurate results for the morphology of the large-scale structures present in the flow. Analysis of the temporal evolution of several volume-averaged quantities representative of the mixing layer growth, and of the cross-stream variation of homogeneous-plane averages and second-order correlations, as well as of visualizations, indicated that the models performed equivalently for the conditions of the simulations. The expectation is that at the much larger Reynolds numbers and much larger filter widths used in practical applications, the improved models will have much more accurate performance than the standard one.

Tracking molecular dynamics without tracking: image correlation of photo-activation microscopy

Measuring protein dynamics in the plasma membrane can provide insights into the mechanisms of receptor signaling and other cellular functions. To quantify protein dynamics on the single molecule level over the entire cell surface, sophisticated approaches such as single particle tracking (SPT), photo-activation localization microscopy (PALM) and fluctuation-based analysis have been developed. However, analyzing molecular dynamics of fluorescent particles with intermittent excitation and low signal-to-noise ratio present at high densities has remained a challenge. We overcame this problem by applying spatio-temporal image correlation spectroscopy (STICS) analysis to photo-activated (PA) microscopy time series. In order to determine under which imaging conditions this approach is valid, we simulated PA images of diffusing particles in a homogeneous environment and varied photo-activation, reversible blinking and irreversible photo-bleaching rates. Further, we simulated data with high particle densities that populated mobile objects (such as adhesions and vesicles) that often interfere with STICS and fluctuation-based analysis. We demonstrated in experimental measurements that the diffusion coefficient of the epidermal growth factor receptor (EGFR) fused to PAGFP in live COS-7 cells can be determined in the plasma membrane and revealed differences in the time-dependent diffusion maps between wild-type and mutant Lck in activated T cells. In summary, we have developed a new analysis approach for live cell photo-activation microscopy data based on image correlation spectroscopy to quantify the spatio-temporal dynamics of single proteins.

Induced lung inflammation and dietary protein supply affect nitrogen retention and amino acid metabolism in growing pigs.

It is hypothesised that during immune system activation, there is a competition for amino acids (AA) between body protein deposition and immune system functioning. The aim of the present study was to quantify the effect of immune system activation on N retention and AA metabolism in growing pigs, depending on dietary protein supply. A total of sixteen barrows received an adequate (Ad) or restricted (Res) amount of dietary protein, and were challenged at day 0 with intravenous complete Freund's adjuvant (CFA). At days -5, 3 and 8, an irreversible loss rate (ILR) of eight AA was determined. CFA successfully activated the immune system, as indicated by a 2- to 4-fold increase in serum concentrations of acute-phase proteins (APP). Pre-challenge C-reactive protein concentrations were lower (P<0·05) and pre- and post-challenge albumin tended to be lower in Res-pigs. These findings indicate that a restricted protein supply can limit the acute-phase response. CFA increased urinary N losses (P=0·04) and tended to reduce N retention in Ad-pigs, but not in Res-pigs (P=0·07). The ILR for Val was lower (P=0·05) at day 8 than at day 3 in the post-challenge period. The ILR of most AA, except for Trp, were strongly affected by dietary protein supply and positively correlated with N retention. The correlations between the ILR and APP indices were absent or negative, indicating that changes in AA utilisation for APP synthesis were either not substantial or more likely outweighed by a decrease in muscle protein synthesis during immune system activation in growing pigs.

Recent Advances in Continuum Modeling of Interfacial and Transport Phenomena in Electric Double Layer Capacitors

This paper reviews recent advances in physical modeling of interfacial and transport phenomena in electric double layer capacitors (EDLCs) under both equilibrium and dynamic cycling. The models are based on continuum theory and account for (i) the Stern layer at the electrode/electrolyte interface, (ii) finite ion sizes, (iii) steric repulsions, (iv) asymmetric electrolytes featuring ions with different valencies, effective diameters, or diffusion coefficients, (v) electric-field-dependent dielectric permittivity of the electrolyte, and/or (vi) porous three-dimensional morphology of the electrodes. Typical characterization methods such as electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic cycling were reproduced numerically to identify the dominant physical phenomena and to gain insight into experimental observations. In addition, recent thermal models derived from first principles for EDLCs under constant-current cycling accounting for irreversible Joule heating and reversible heat generation rates due to ion diffusion, steric effects, and changes in entropy are discussed. Scaling analyses of both equilibrium and dynamic models are also presented as a way to identify self-similar and asymptotic behaviors as well as to develop design rules for electrodes and electrolytes of next generation EDLCs. Throughout the document, special effort has been made to compare model predictions with experimental observations and reported data.