Fast-charging aluminium-chalcogen batteries resistant to dendritic shorting.

Although batteries fitted with a metal negative electrode are attractive for their higher energy density and lower complexity, the latter making them more easily recyclable, the threat of cell shorting by dendrites has stalled deployment of the technology1,2. Here we disclose a bidirectional, rapidly charging aluminium-chalcogen battery operating with a molten-salt electrolyte composed of NaCl-KCl-AlCl3. Formulated with high levels of AlCl3, these chloroaluminate melts contain catenated AlnCl3n+1- species, for example, Al2Cl7-, Al3Cl10- and Al4Cl13-, which with their Al-Cl-Al linkages confer facile Al3+ desolvation kinetics resulting in high faradaic exchange currents, to form the foundation for high-rate charging of the battery. This chemistry is distinguished from other aluminium batteries in the choice of a positive elemental-chalcogen electrode as opposed to various low-capacity compound formulations3-6, and in the choice of a molten-salt electrolyte as opposed to room-temperature ionic liquids that induce high polarization7-12. We show that the multi-step conversion pathway between aluminium and chalcogen allows rapid charging at up to 200C, and the battery endures hundreds of cycles at very high charging rates without aluminium dendrite formation. Importantly for scalability, the cell-level cost of the aluminium-sulfur battery is projected to be less than one-sixth that of current lithium-ion technologies. Composed of earth-abundant elements that can be ethically sourced and operated at moderately elevated temperatures just above the boiling point of water, this chemistry has all the requisites of a low-cost, rechargeable, fire-resistant, recyclable battery.

Synthesis and Morphological Control of VO2 Nanostructures via a One-Step Hydrothermal Method.

The morphology of nanostructures is a vital parameter to consider in components comprised of materials exhibiting specific functionalities. The number of process steps and the need for high temperatures can often be a limiting factor when targeting a specific morphology. Here, we demonstrate a repeatable synthesis of different morphologies of a highly crystalline monoclinic phase of vanadium dioxide (VO2(M)) using a one-step hydrothermal method. By adjusting the synthesis parameters, such as pH, temperature, and reducing agent concentration in the precursor, VO2 nanostructures with high uniformity and crystallinity are achieved. Some of these morphologies were obtained via the choice of the reducing agent that allowed us to skip the annealing step. Our results indicate that the morphologies of the nanostructures are very sensitive to the hydrazine hydrate (N2H4.H2O) concentration. Another reducing agent, dodecylamine, was used to achieve well-organized and high-quality VO2(M) nanotubes. Differential scanning calorimetry (DSC) experiments revealed that all samples display the monoclinic-to-tetragonal structural transition (MTST) regardless of the morphology, albeit at different temperatures that can be interpreted as the variations in overheating and undercooling limits. VO2(M) structures with a higher surface to volume ratio exhibit a higher overheating limit than those with low ratios.

Micro and nanostructural analysis of a human tooth using correlated focused ion beam (FIB) and transmission Electron microscopy (TEM) investigations.

In this study, natural molar human tooth specimens were investigated for determining their micro- and nanoscale structural morphology, chemistry and crystallinity. The differences were tracked comparatively for both enamel and dentin layers and at their interfaces. Although dental material structures are hard and tough and the cross-sectioning of these materials using mechanical methods is challenging, FIB-SEM dual-beam instruments serve for preparing ultra-thin homogenous lamella sections. In this work, both FIB-SEM and TEM based advanced characterization methods were applied to reveal different morphological characteristics of dental tissue via complementary imaging and diffraction analysis. In addition, SEM-EDS and Raman spectroscopy techniques provided additional information about the elemental distribution and the chemical composition differences of the dental tissues. According to electron microscopy examinations at the intersection between the enamel and the dentin layers, it was shown that the enamel was denser and polycrystalline, while the dentin layer was porous, fibrillar and of negligible long-range order, due to its tubular structure and organic components. In particular, EDS mapping and linescan analyses showed almost no differences in the elemental distribution. Raman results confirmed that both tissues had similar chemical composition except dentin showed spectral background effects in the spectrum due to its tubular structure and organic components.

Effect of polymeric substrate on sludge settleability.

The study aims to evaluate the role of a polymeric substrate (starch) on sludge settleability. Despite being an important COD component of the wastewater, the relationship between polymeric substrates and bulking sludge has been hardly studied. The polymers are hydrolysed at a rate smaller than the consumption rate of monomers. This means that the soluble substrate resulting from hydrolysis is likely to be present at growth rate limiting concentrations. According to the kinetic selection theory this leads to bulking sludge. However, a recently postulated theory suggests that, strong diffusion limited micro-gradients of substrate concentration inside flocs lead to bulking sludge, and not a low substrate concentration as such. If the polymeric COD is first incorporated in the sludge floc and afterwards hydrolysed in the sludge floc then there is essentially no substrate gradient inside the biological flocs. The experiments showed that conditions leading to bulking sludge with monomers (glucose) did not lead to bulking when starch was used. A bulking sludge event was even cured just by substituting the monomer with starch. These results are clearly in line with a diffusion gradient--based theory for bulking sludge. Nevertheless, flocs growing on starch are more open, fluffy and porous than flocs formed on maltose or glucose, most likely because the starch needs to be hydrolysed at the surface of the micro-colonies forming the flocculated sludge. Some additional observations on occurrence of filamentous bacteria in oxygen diffusion limited systems are also discussed in this manuscript.

Modelling biodegradation of nonylphenol ethoxylate in acclimated and non-acclimated microbial cultures.

The biodegradation and inhibition kinetics of a commercial nonylphenol ethoxylate formulation were modelled for an activated sludge system fed with a synthetic substrate and nonylphenol ethoxylate mixture. Kinetic and stoichiometric coefficients of the proposed activated sludge model were obtained by employing on-line respirometry. Experimental as well as model results confirmed that nonylphenol ethoxylate exhibited non-competitive inhibition on the hydrolysis process with a coefficient of 150mg/L on the basis of COD and negatively influenced biomass growth through a competitive inhibition mechanism with a coefficient of 500mg/L on the basis of COD, when the biomass was not acclimated. Upon acclimation of the activated sludge system, the inhibition concentration for non-competitive inhibition on hydrolysis was increased to 5000mg/L, practically showing no inhibition, and the coefficient of competitive inhibition increased to 450mg/L, corresponding to a significant decrease in the inhibitory effects of NPEO on growth.

Fate of 2,6-dihydroxybenzoic acid and its inhibitory impact on the biodegradation of peptone under aerobic conditions.

This study investigated the fate of 2,6-dihydroxybenzoic acid in a mixed microbial culture acclimated to peptone under aerobic conditions. A laboratory-scale sequencing batch reactor receiving a pulse feeding of peptone at the start of each daily cycle was used for this purpose. Experimental evaluations interpreted changes induced by continuous benzoic acid additions on the oxygen uptake rate profiles associated with peptone biodegradation. At first exposure, 2,6-dihydroxybenzoic acid reduced the activity of the mixed culture and impaired peptone biodegradation. Around one-third of peptone removed could be utilized for microbial metabolism. With continuous feeding the mixture culture became acclimated and simultaneously removed peptone and 2,6-dihydroxybenzoic acid. After 30 days, oxygen uptake rate tests performed separately on peptone, 2,6-dihydroxybenzoic acid and the substrate mixture supported the existence of a dual biomass restructured with the selective growth of another group of microorganisms capable of utilizing 2,6-dihydroxybenzoic acid as an organic carbon source.

Inhibition effect of linear alkylbenzene sulphonates on the biodegradation mechanisms of activated sludge.

The study presents a conceptual approach for the identification of the inhibition mechanisms of biodegradable inhibitors. Synthetic sewage was selected as the model degradable substrate to simulate domestic wastewaters. LAS, known to be a biodegradable but inhibitory compound, was selected as a model substrate for the determination of the inhibition mechanisms. Biodegradation of synthetic sewage and LAS were monitored through oxygen uptake rate (OUR) tests conducted to observe the dynamic response of the system when fed with synthetic sewage and synthetic sewage-LAS mixtures. The approach uses respirometry to calibrate the kinetic and stoichiometric coefficients of the proposed biochemical model. Model simulation results confirmed that presence of LAS has inhibitory effects on the biodegradation mechanisms of synthetic sewage. LAS imposed non-competitive inhibition on the hydrolysis process with an inhibition coefficient of 500 mg COD/L and effected heterotrophic growth through a competitive inhibition mechanism with an inhibition coefficient of 150 mg COD/L.

Biodegradability and denitrification potential of settleable chemical oxygen demand in domestic wastewater.

The effect of settling on mass balance and biodegradation characteristics of domestic wastewater and on denitrification potential was studied primarily using model calibration and evaluation of oxygen uptake rate profiles. Raw domestic wastewater was settled for a period of 30 minutes and a period of 2 hours to assess the effect of primary settling on wastewater characterization and composition. Mass balances in the system were made to evaluate the effect of primary settling on major parameters. Primary settling of the selected raw wastewater for 2 hours resulted in the removal of 32% chemical oxygen demand (COD), 9% total Kjeldahl nitrogen, 9% total phosphorus, and 47% total suspended solids. Respirometric analysis identified COD removed by settling as a new COD fraction, namely settleable slowly biodegradable COD (X(ss)), characterized by a hydrolysis rate of 1.0 day(-1) and a hydrolysis half-saturation coefficient of 0.08. A model simulation to test the fate and availability of suspended (X(s)) and settleable (X(ss)) COD fractions as carbon sources for denitrification showed that both particulate COD components were effectively removed aerobically at sludge ages higher than 1.5 to 2.0 days. Under anoxic conditions, the biodegradation of both COD fractions was reduced, especially below an anoxic sludge retention time of 3.0 days. Consequently, modeling results revealed that the settleable COD removed by primary settling could represent up to approximately 40% of the total denitrification potential of the system, depending on the specific configuration selected for the nitrogen removal process. This way, the results showed the significant effect of primary settling on denitrification, indicating that the settleable COD fraction could contribute an additional carbon source in systems where the denitrification potential associated with the influent becomes rate-limiting for the denitrification efficiency.

Validity of Monod kinetics at different sludge ages--peptone biodegradation under aerobic conditions.

The study presented an evaluation of the effect of culture history (sludge age) on the growth kinetics of a mixed culture grown under aerobic conditions. It involved an experimental setup where a lab-scale sequencing batch reactor was operated at steady-state at two different sludge ages (theta(X)) of 2 and 10 days. The system sustained a mixed culture fed with a synthetic substrate mainly consisting of peptone. The initial concentration of substrate COD was selected around 500 mg COD/L. Polyhydroxyalkanoate (PHA) storage occurred to a limited extent, around 30 mg COD/L for theta(X)=10 days and 15 mg COD/L for theta(X)=2 days. Evaluation of the experimental data based on calibration of two different models provided consistent and reliable evidence for a variable Monod kinetics where the maximum specific growth rate, was assessed as 6.1/day for theta(X)=2 days and 4.1/day for theta(X)=10 days. A similar variability was also applicable for the hydrolysis and storage kinetics. The rate of storage was significantly lower than the levels reported in the literature, exhibiting the ability of the microorganisms to regulate their metabolic mechanisms for adjusting the rate of microbial growth and storage competing for the same substrate. This adjustment evidently resulted in case-specific, variable kinetics both for microbial growth and substrate storage.

Effect of high nitrate concentration on PHB storage in sequencing batch reactor under anoxic conditions.

The study investigated effect of high influent nitrate concentration on poly-beta-hydroxybutyrate, (PHB), storage in a sequencing batch reactor, (SBR), under anoxic conditions. Acetate was fed as pulse during anoxic phase, sustained with external nitrate feeding. SBR operation involved three runs at steady state with COD/N ratios of 3.84, 2.93 and 1.54 gCOD/gN, where external nitrate concentrations gradually increased from 50 mg N/l to 114 mg N/l and 226 mg N/l, in 1st, 2nd and 3rd runs, respectively. In 1st run, acetate was fully converted into PHB with the storage yield value of 0.57-0.59 gCOD/gCOD, calculated both in terms of PHB formation and NO(X) utilization, confirming storage was the sole substrate utilization mechanism. In the following runs, PHB formation was reduced and the storage yield based on PHB dropped down to 0.40 and 0.33 gCOD/gCOD with increasing influent nitrate concentrations, indicating that higher portions of acetate were diverted to simultaneous direct growth. The observations suggested that nitrite accumulation detected at low COD/N ratios was responsible for inhibition of PHB storage.

Simultaneous storage and utilization of polyhydroxyalkanoates and glycogen under aerobic conditions.

This study aims to investigate the storage response of an activated sludge system in the presence of two different substrates which are stored as two different polymers. The objective of the study was to determine the changes in the response of an activated sludge system when two different storage mechanisms could occur simultaneously. Acetic acid (HAc) and soluble starch (SolS) were selected as model substrates and three different feeding conditions, namely (i) when both HAc and SolS were initially present in the reactor, (ii) only HAc was present, and (iii) only SolS was present in the substrate solution. The batch reactors were monitored for acetic acid, polyhydroxyalkanoates (PHA), poly-glucose (glycogen like substances) and oxygen uptake rate (OUR). The experiments have shown that, while the main portion of hydrolyzed starch was stored as poly-glucose, which was further used for heterotrophic growth, the rest was utilized for direct growth. However, acetic acid was totally stored as PHA and the stored PHA was used for biomass growth under the presented experimental conditions. When the system was fed with the substrate mixture, the storage mechanism was not significantly affected. Both PHA and poly-glucose storage took place simultaneously with the same stoichiometry and kinetics defined for single substrate utilization.

The effect of mixing pharmaceutical and tannery wastewaters on the biodegradation characteristics of the effluents.

This paper evaluated the effect of mixing the effluent of a pharmaceutical plant producing acetylsalicylic acid with tannery wastewater, on the biodegradation of the effluents. The evaluation involved the analysis of the oxygen uptake rate (OUR), profiles of each wastewater and the mixture by respirometry. Model calibration using the experimental OUR data identified major COD fractions and associated process kinetics for all samples analyzed. The tannery sample was a plain-settled effluent having a total COD of around 2200 mg/L with a readily biodegradable fraction of 15%. The same fraction was 57% in the pharmaceutical wastewater sample having a much stronger total COD content of 40,435 mg/L. Consequently, mixing of the pharmaceutical effluent with the tannery wastewater up to 38% of the total COD in the mixture increased the readily biodegradable COD fraction but had an inhibitory effect on the biodegradation kinetics. This effect was relatively lower on growth, but quite significant on the hydrolysis of the slowly biodegradable COD decreasing the maximum hydrolysis rate from 2.0 day(-1) to 1.2 day(-1). Model evaluation of the respirometric data, as performed in this study sets a workable protocol for the assessment of the compatibility of different wastewater mixtures for biological treatability.

Substrate storage concepts in modeling activated sludge systems for tannery wastewaters.

In spite of a variety of model structures proposed for activated sludge systems, calibration of these models for industrial wastewaters still stands untouched. In the scope of this study, a conceptual framework for the application of ASM1, ASM3 and 3 models, involving simultaneous growth and storage under dynamic conditions is presented and these models have been used for simulating biodegradation/tannery wastewaters. A comparative representation of the modeling results obtained with 5 different models is provided. The comparison of the simulation results showed that the possibility of describing the real case increases as the model gets more detailed. Although structured models are supposed to provide a better description of the dynamic behavior observed for tannery effluents, the insufficiency experienced in the experimental determination of all the storage products when complex substrate compositions are concerned, hindered the accurate determination of model coefficients. Furthermore, modeling results for different F/M ratios clearly emphasized the challenge in the definition of readily biodegradable COD. Process stoichiometry and wastewater fractionation should be defined cautiously with additional data in order to provide substantial basis for the evaluation of the respirometric response in batch tests for model calibration.

Effect of feeding pattern on biochemical storage by activated sludge under anoxic conditions.

This study investigated the effect of feeding pattern on bacterial storage under anoxic conditions, emphasizing previous adaptation of biomass to a long term feeding condition, under steady-state operation. Storage was evaluated in a sequencing batch reactor (SBR) system operated in a sequence of anoxic/aerobic phases, fed with acetate as the sole carbon source during anoxic conditions. The experimental results indicated that biochemical storage of acetate as PHB occurred when substrate was fed as a pulse, while acetate was removed mostly through direct microbial growth under continuous feeding. For pulse feeding, the anoxic yield, Y(STOD) was calculated as 0.58mg COD (mgCOD)(-1) in two different ways, using mass balances on acetate utilization, PHB generation and nitrate consumption. This value was supported by parallel batch tests and similar results in the literature. Similarly, the rate coefficient for storage under anoxic conditions, k(STOD) was computed as 9.3day(-1) based on basic stoichiometry and model calibration of experimental data. Batch tests conducted with biomass adapted to different feeding patterns showed that substrate storage was insignificant when the feed was added continuously at low concentrations, even if the biomass was previously adapted to storage. Similarly biomass acclimated to continuous feeding could not store the excess substrate although fed instantly. For the operating conditions selected for the study, storage response was significant only with a microbial culture with metabolic activities previously adapted to storage and with short-term substrate feeding at high concentrations.

Effect of perozonation on biodegradability and toxicity of a penicillin formulation effluent.

The pretreatment of synthetic penicillin formulation effluent containing Procain Penicillin G (PPG) with the O(3)/H(2)O(2) process (applied ozone dose = 1440 mg h-1 treatment time = 60 minutes; pH 7; H(2)O(2) = 10 mM) was investigated. The effect of chemical pretreatment was assessed on the basis of acute toxicity and biodegradability with activated sludge using water flea Daphnia magna toxicity and activated sludge inhibition tests. Biological treatability studies were performed with a mixture of untreated or pretreated PPG effluent (25% on volume basis) and synthetic domestic wastewater simulating readily biodegradable organic substrate to simulate the characteristics of domestic wastewater (75% on volume basis). Pretreatment of PPG effluent the O(3)/H(2)O(2) process resulted in more than 70% chemical oxygen demand (COD) removal and a 50% decrease in the acute toxicity towards Daphnia magna. On the other hand, biodegradation of untreated PPG effluent needed prolonged acclimation periods to obtain a significant biological COD removal (= 80%). Pretreatment employing the O(3)/H(2)O(2) process not only decreased the ultimate biodegradability of PPG effluent but also increased its inhibitory effects on activated sludge treatment speculatively due to the formation of less biodegradable oxidation by-products.

Modeling the utilization of starch by activated sludge for simultaneous substrate storage and microbial growth.

This paper presents a mechanistic model incorporating microbial growth on external substrate with simultaneous formation of storage biopolymers (activated sludge model for growth and storage-ASMGS) for the utilization of starch by activated sludge. Model description and calibration utilized experimental data of an SBR fed with particulate native potato starch (NPS) and soluble starch (SolS) selected as model substrates. The fate of starch was monitored in a cycle together with glycogen and oxygen uptake rate (OUR) profiles. In the experiments, glycogen formation was significantly lower than predicted by total conversion of starch to glycogen, justifying the need to account for primary growth on starch. The proposed model basically modified Activated Sludge Model No.3 (ASM3), to include adsorption of starch, its hydrolysis and simultaneous growth and glycogen formation using the hydrolysis products, which was mainly maltose. Model simulations indicated hydrolysis of the adsorbed starch as the rate limiting process. The proposed model calibrated well the fate of all major model components, namely, starch, glycogen, and OUR. Particulate NPS and SolS were hydrolyzed with similar rates; however, primary and secondary growth processes on SolS were more efficient, with higher yields, due to the more easily utilizable products of SolS, both in terms of extracellular hydrolysis and of stored poly-glucose. Modeling with ASM3, assuming starch as either readily or slowly biodegradable, did not provide an equally acceptable fit for the glycogen and OUR curves; supporting the need to consider primary growth together with storage as defined in the proposed model.

A computational study on the amine-oxidation mechanism of monoamine oxidase: insight into the polar nucleophilic mechanism.

The proposed polar nucleophilic mechanism of MAO was investigated using quantum chemical calculations employing the semi-empirical PM3 method. In order to mimic the reaction at the enzyme's active site, the reactions between the flavin and the p-substituted benzylamine substrate analogs were modeled. Activation energies and rate constants of all the reactions were calculated and compared with the published experimental data. The results showed that electron-withdrawing groups at the para position of benzylamine increase the reaction rate. A good correlation between the log of the calculated rate constants and the electronic parameter (sigma) of the substituent was obtained. These results agree with the previous kinetic experiments on the effect of p-substituents on the reduction of MAO-A by benzylamine analogs. In addition, the calculated rate constants showed a correlation with the rate of reduction of the flavin in MAO-A. In order to verify the results obtained from the PM3 method single-point B3LYP/6-31G*//PM3 calculations were performed. These results demonstrated a strong reduction in the activation energy for the reaction of benzylamine derivatives having electron-withdrawing substituents, which is in agreement with the PM3 calculations and the previous experimental QSAR study. PM3 and B3LYP/6-31G* energy surfaces were obtained for the overall reaction of benzylamine with flavin. Results suggest that PM3 is a reasonable method for studying this kind of reaction. These theoretical findings support the proposed polar nucleophilic mechanism for MAO-A.

Experimental evaluation of starch utilization mechanism by activated sludge.

The study aimed to explore the conversion processes of hydrolysable substrates by activated sludge. Experimental data were collected from a sequencing batch reactor (SBR) and from batch tests using activated sludge acclimated to native potato starch (NPS). Parallel batch tests were run with NPS (particulate), soluble starch (SolS), maltose, and glucose for comparative evaluation. The fate of organic carbon in the reactor was followed directly by measuring substrate, poly-glucose, and oxygen uptake rate. Results indicated that adsorption was the dominant mechanism for starch removal with subsequent enzymatic hydrolysis inside the flocs. The role of bulk liquid enzyme activity was minimal. Starch was observed to hydrolyze to maltose rather than glucose. The behavior of NPS and SolS was quite similar to maltose in terms of poly-glucose formation and oxygen uptake. Since the simplest hydrolysis product was maltose, the biomass was not acclimated to glucose and thus, glucose exhibited a significantly different removal and storage pattern. The study also showed that differentiation of readily biodegradable and slowly biodegradable COD should better be based on the kinetics of their utilization rather than simple physical characterization.

Size distribution of wastewater COD fractions as an index for biodegradability.

The study proposes direct particle size measurement by sequential filtration and ultrafiltration as a convenient method for wastewater characterization for appropriate treatment technology. It also explores the correlation between particle size distribution (PSD) and chemical oxygen demand (COD) fractionation, as an index for biological treatability. Profiles obtained through PSD-based COD fractionation serve as the fingerprints for wastewaters, and as demonstrated in this study, reflect different pictures for textile wastewater and domestic sewage. PSD-based COD fractionation profiles identify the soluble range below 2 nm as the size interval housing both the soluble inert COD initially present in the wastewater and soluble inert microbial products generated during biological treatment, as also supported by the metabolic fractionation attained through respirometric analyses. Moreover, PSD-based color profiling offers a good index for the fate of biologically resistant chemicals passing through biological treatment. Compatible results obtained from comparative evaluation of PSD-based COD and color profiles provide useful information on the biodegradability of the textile wastewater studied.

Biological treatability of raw and ozonated penicillin formulation effluent.

In the present study, oxidative pre-treatment of pharmaceutical wastewater originating from the formulation of the penicillin Sultamycillin Tosylate Diydrate via ozonation at varying pH and ozone feed rates was investigated. Biological treatability studies were performed with a synthetic wastewater alone and supplemented with raw and ozonated penicillin formulation effluents. The highest COD (34%) and TOC (24%) removal efficiencies were obtained at pH 11.0, whereas the BOD5 value increased from 16 mg l(-1) to 128 mg l(-1) after 40 min of ozonation, corresponding to an applied ozone dose of 1670 mg l(-1) and 33% relative ozone absorption. The studies showed that no degradation of raw penicillin fraction (30% of total COD) occurred, and degradation of the synthetic wastewater being completely treatable without penicillin addition, was inhibited by 7%. Upon 40 min ozonation, the synthetic wastewater could be completely oxidized and at the same time 35% of ozonated penicillin wastewater removal was obtained. Respirometric studies were conducted in parallel and produced results indicating a 22% decrease in the total oxygen consumption rate established for raw penicillin formulation effluent compared to the results obtained from the aerobic batch reactor. No inhibition of the synthetic fraction was observed for the 40 min-ozonated penicillin formulation effluent, biodegradability of the 60 min-ozonated penicillin effluent decreased possibly due to recalcitrant oxidation product accumulation. The modeling study provided experimental support and information on inhibition kinetics in activated sludge model no. 3 (ASM3) by means of respirometric tests for the first time.