Aqueous Manufacturing of Defect-Free Thick Multi-Layer NMC811 Electrodes.

Manufacturing thick electrodes for Li-ion batteries is a challenging task to fulfill, but leads to higher energy densities inside the cell. Water-based processing even adds an extra level of complexity to the procedure. The focus of this work is to implement a multi-layered coating in an industrially relevant process, to overcome issues in electrode integrity and to enable high electrochemical performance. LiNi0.8Mn0.1Co0.1O2 (NMC811) was used as the active material to fabricate single- and multi-layered cathodes with areal capacities of 8.6 mA h cm-2. A detailed description of the manufacturing process is given to establish thick defect-free aqueous electrodes. Good inter-layer cohesion and adhesion to the current collector foil are achieved by multi-layering, as confirmed by optical analysis and peel testing. Furthermore, full cells were assembled and rate capability tests were performed. These tests show that by multi-layering, an increase in specific discharge capacity (e.g., 20.7% increase for C/10) can be established for all tested C-rates.

Considerations on Temperature Dependent Effective Diffusion and Permeability of Natural Clays.

A series of porous clay samples prepared at different pretreatment temperatures have been tested in a diffusion chamber. Diffusivity and permeability were examined in a temperature range from ambient to 900 °C. Gaseous mixtures of O2, CO2, and N2 have been applied, as these species are the relevant gases in the context of clay brick firing and similar thermochemical processes. Diffusive transport characteristics have been determined by means of the mean transport-pore model, and permeability has been evaluated by Darcy's law. CO2 diffusivity increased strongly with temperature, whereas O2 diffusion was limited to a certain level. It is proposed that one should consider CO2 surface diffusion in order to explain this phenomenon. The diffusion model was expanded and surface diffusion was included in the model equation. The results of the model fit reflected the important role of incorporated carbonates of the clay foundation in gas-phase (molecular or Knudsen) diffusivity. CO2 surface diffusion was observed to exhibit similar coefficients for two different investigated clays, and is therefore indicated as a property of natural clays. Permeability showed a progressive rise with temperature, in line with related literature.

Synthesis of Polyaniline Coated Magnesium and Cobalt Oxide Nanoparticles through Eco-Friendly Approach and Their Application as Antifungal Agents.

Plant-mediated synthesis of nanoparticles exhibits great potential to minimize the generation of chemical waste through the utilization of non-toxic precursors. In this research work, we report the synthesis of magnesium oxide (MgO) and cobalt oxide (Co3O4) nanoparticles through a green approach using Manilkara zapota leaves extract, their surface modification by polyaniline (PANI), and antifungal properties against Aspergillus niger. Textural and structural characterization of modified and unmodified metal oxide nanoparticles were evaluated using FT-IR, SEM, and XRD. The optimal conditions for inhibition of Aspergillus niger were achieved by varying nanoparticles' concentration and time exposure. Results demonstrate that PANI/MgO nanoparticles were superior in function relative to PANI/Co3O4 nanoparticles to control the growth rate of Aspergillus niger at optimal conditions (time exposure of 72 h and nanoparticles concentration of 24 mM). A percentage decrease of 73.2% and 65.1% in fungal growth was observed using PANI/MgO and PANI/Co3O4 nanoparticles, respectively, which was higher than the unmodified metal oxide nanoparticles (67.5% and 63.2%).

Status, characterization, and potential utilization of municipal solid waste as renewable energy source: Lahore case study in Pakistan.

With rapid increases in population and urbanization, uncontrolled municipal solid waste (MSW) is a threat to public health and environmental safety. In this study, we explore its generation, treatment, and characteristics of physical/chemical composition and assess the potential of MSW as a renewable energy source in Lahore, the second largest city in Pakistan. Based on the average generation rate of MSW (i.e., 0.65 kg/capita/day), the daily production of MSW in this city would reach 7150 tons/day. However, its disposal in a safely engineered way has been restricted due to the lack of: (a) pre-planning, (b) infrastructure, (c) political will, and (d) public awareness. Various samples of MSW considering socio-economic structure were collected. The physical components of MSW in Lahore were found to be in the descending order of biodegradable, nylon plastic bags, textile, diaper, and paper. The inductively coupled plasma optical emission spectroscopy (ICP-OES) technique was used to determine the heavy metal content and leachability of the MSW components to check for the environmental contamination risk. The proximate and ultimate analysis of this MSW was also carried out along with its heating values. The average high heating value of MSW was measured as 14,490 kJ kg-1. Energy recovery potential of 48 MW was assessed further from 2000 tons of MSW/day. The results of this study should be helpful for policy makers to establish a MSW management strategy for the potential renewable energy alternative.

Comparing Fly Ash Samples from Different Types of Incinerators for Their Potential as Storage Materials for Thermochemical Energy and CO2.

This study aims to investigate the physical and chemical characterization of six fly ash samples obtained from different municipal solid waste incinerators (MSWIs), namely grate furnaces, rotary kiln, and fluidized bed reactor, to determine their potential for CO2 and thermochemical energy storage (TCES). Representative samples were characterized via simultaneous thermal analysis (STA) in different atmospheres, i.e., N2, air, H2O, CO2, and H2O/CO2, to identify fly ash samples that can meet the minimum requirements, i.e., charging, discharging, and cycling stability, for its consideration as TCES and CO2-storage materials and to determine their energy contents. Furthermore, other techniques, such as inductively coupled plasma optical emission spectroscopy, X-ray fluorescence (XRF) spectrometry, X-ray diffraction (XRD), scanning electron microscopy, leachability tests, specific surface area measurement based on the Brunauer-Emmett-Teller method, and particle-size distribution measurement, were performed. XRF analysis showed that calcium oxide is one of the main components in fly ash, which is a potentially suitable component for TCES systems. XRD results revealed information regarding the crystal structure and phases of various elements, including that of Ca. The STA measurements showed that the samples can store thermal heat with energy contents of 50-394 kJ/kg (charging step). For one fly ash sample obtained from a grate furnace, the release of the stored thermal heat under the selected experimental conditions (discharging step) was demonstrated. The cycling stability tests were conducted thrice, and they were successful for the selected sample. One fly ash sample could store CO2 with a storage capacity of 27 kg CO2/ton based on results obtained under the selected experimental conditions in STA. Samples from rotary kiln and fluidized bed were heated up to 1150 °C in an N2 atmosphere, resulting in complete melting of samples in crucibles; however, other samples obtained from grate furnaces formed compacted powders after undergoing the same thermal treatment in STA. Samples from different grate furnaces showed similarities in their chemical and physical characterization. The leachability test according to the standard (EN 12457-4 (2002)) using water in a ratio of 10 L/S and showed that the leachate of heavy metals is below the maximum permissible values for nonhazardous materials (except for Pb), excluding the fly ash sample obtained using fluidized bed technology. The leachate contents of Cd and Mn in the fly ash samples obtained from the rotary kiln were higher than those in other samples. Characterization performed herein helped in determining the suitable fly ash samples that can be considered as potential CO2-storage and TCES materials.

Comparison of the Characteristics of Fly Ash Generated from Bio and Municipal Waste: Fluidized Bed Incinerators.

European solid waste incinerator plants still primarily use grate furnace technology, although circulating fluidized bed (CFB) technology is steadily expanding. Therefore, few investigations have reported on the environmental assessment of fly ash from fluidized incinerators. This research project aims to integrate information on fly ash derived from the combustion of municipal solid waste (FA1) and biomass (FA2) in fluidized bed incinerator facilities. Fly ash samples were comparatively analyzed by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), and inductively coupled plasma optical emission spectroscopy (ICP-OES) to study the mineralogy, morphology, total heavy metal content, and leaching behavior, respectively. The analysis revealed that the two types of fly ash differ in their characteristics and leaching behavior. The concentration of most of the heavy metals in both is low compared to the literature values, but higher than the regulatory limits for use as a soil conditioner, whereas the high contents of Fe, Cu, and Al suggest good potential for metal recovery. The leaching ability of most elements is within the inert waste category, except for Hg, which is slightly above the non-hazardous waste limit.

Thermal co-treatment of combustible hazardous waste and waste incineration fly ash in a rotary kiln.

As current disposal practices for municipal solid waste incineration (MSWI) fly ash are either associated with significant costs or negative environmental impacts, an alternative treatment was investigated in a field scale experiment. Thereto, two rotary kilns were fed with hazardous waste, and moistened MSWI fly ash (water content of 23%) was added to the fuel of one kiln with a ratio of 169kg/Mg hazardous waste for 54h and 300kg/Mg hazardous waste for 48h while the other kiln was used as a reference. It was shown that the vast majority (>90%) of the inserted MSWI fly ash was transferred to the bottom ash of the rotary kiln. This bottom ash complied with the legal limits for non-hazardous waste landfills, thereby demonstrating the potential of the investigated method to transfer hazardous waste (MSWI fly ash) into non-hazardous waste (bottom ash). The results of a simple mixing test (MSWI fly ash and rotary kiln bottom ash have been mixed accordingly without thermal treatment) revealed that the observed transformation of hazardous MSWI fly ash into non-hazardous bottom ash during thermal co-treatment cannot be referred to dilution, as the mixture did not comply with legal limits for non-hazardous waste landfills. For the newly generated fly ash of the kiln, an increase in the concentration of Cd, K and Pb by 54%, 57% and 22%, respectively, was observed. In general, the operation of the rotary kiln was not impaired by the MSWI fly ash addition.

Possibilities of municipal solid waste incinerator fly ash utilisation.

Properties of the waste treatment residual fly ash generated from municipal solid waste incinerator fly ash were investigated in this study. Six different mortar blends with the addition of the municipal solid waste incinerator fly ash were evaluated. The Portland cement replacement levels of the municipal solid waste incinerator fly ash used were 25%, 30% and 50%. Both, raw and washed municipal solid waste incinerator fly ash samples were examined. According to the mineralogical composition measurements, a 22.6% increase in the pozzolanic/hydraulic properties was observed for the washed municipal solid waste incinerator fly ash sample. The maximum replacement level of 25% for the washed municipal solid waste incinerator fly ash in mortar blends was established in order to preserve the compressive strength properties. Moreover, the leaching characteristics of the crushed mortar blend was analysed in order to examine the immobilisation of its hazardous contents.

Sewage sludge ash to phosphate fertilizer by chlorination and thermal treatment: residence time requirements for heavy metal removal.

Heavy metal removal from sewage sludge ash can be performed by mixing the ash with environmentally compatible chlorides (e.g. CaCl2 or MgCl2) and water, pelletizing the mixture and treating the pellets in a rotary reactor at about 1000 degrees C. Thermogravimetry-mass spectroscopy, muffle oven tests (500-1150 degrees C) and investigations in a laboratory-scale rotary reactor (950-1050 degrees C, residence time 1-25 min) were carried out. In the rotary reactor, up to 97% of Cu, 95% Pb and 95% Zn can be removed at 1050 degrees C. As Cl release starts from 400 degrees C (obtained from thermogravimetry-mass spectrometry experiments), heavy metals are already removed partially within the heating period. This heavy metal removal can be described as being similar to a first-order rate law. To meet the limit values specified in the Austrian and German fertilizer ordinances, residence times of the order of minutes are sufficient at 950 degrees C.

Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash.

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100°C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl(2). Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900°C, 10 and 30 min and 3.4 and 4.6 ms(-1). Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu. In the pellet, three major reactions occur: formation of HCl and Cl(2) from CaCl(2); diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl(2) out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.

CO and CO2 spectroscopy using a 60 nm broadband tunable MEMS-VCSEL at approximately 1.55 microm.

The spectroscopic application of a new broadband microelectromechanical-system-tunable vertical cavity surface-emitting laser with single-mode coverage of 60 nm (245 cm(-1)) in a single, continuous sweep is described. The operation of the device is illustrated with high-resolution spectra of CO and CO2 over 110 cm(-1) (27 nm) and 67 cm(-1) (17 nm), respectively, with the CO band shown for high-pressure scans between 1 and 3 bars (0.1-0.3 MPa). The achieved tuning range opens up new opportunities for tunable diode laser absorption spectroscopy. The spectra were compared with HITRAN-derived model calculations. The benefits of a sensor based on this laser are greater speed, laser power, and tuning range.

In situ investigation of laser-induced ignition and the early stages of methane-air combustion at high pressures using a rapidly tuned diode laser at 2.55 microm.

The laser-induced ignition of methane/air-mixtures at elevated pressures was investigated by an absorption spectroscopic technique. A room temperature continuous wave InGaAsSb/AlGaAsSb quantum well ridge diode laser was wavelength tuned around 2.55 mum by periodically modulating the injection current from 0 to 174 mA at a 5 kHz repetition rate. The laser heat sink temperature was fixed at 291 K. The infrared laser beam was sent through the pressurized combustion vessel perpendicularly to the igniting laser beam (Nd:YAG laser, 10 ns pulse duration, 20 mJ) at the position of the ignition spark. Fuel-rich to fuel-lean mixtures of methane/air (air equivalence ratio 0.89, 1.06, 1.42, 2.50) were investigated at initial pressures of up to 3 MPa. The initial temperature was 473 K, the volume of the combustion vessel 0.9x10(-3) m(3). The formation of water vapor in the vicinity of the laser spark was tracked by the diode laser. The time resolution of the measurements was 0.2 ms for a total continuous measurement time of up to 1 s. In this way, the laser-induced ignition and its accompanying effects could be investigated on a time scale spanning four orders of magnitude. Apart from the absorbance of water vapor which could be determined semi-quantitatively (due to the effects of severe pressure broadening at high pressures and the ignorance of the exact temperature distribution after ignition), the emissions from the flame (broadband, 1-10 mum) and a gas inhomogeneity index were recorded. The gas inhomogeneity index was obtained by extracting a frequency variable from the time-dependent fluctuations of the transmitted laser intensities and calculating its derivation. The absorbance of water vapor, the emissions from the flame and the gas inhomogeneity index were found to be a powerful tool to characterize laser-induced ignition. Major implications of in situ species concentration measurements at high pressures for the design and development of high-load combustors are presented.