Search results for: inductively coupled plasma-mass spectroscopy

Authors: M. François, L. Sigot, C. Vallières

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Volatile Organic Compounds (VOCs) are a real health issue, particularly in domestic indoor environments. Among these VOCs, acetaldehyde is frequently monitored in dwellings ‘air, especially due to smoking and spontaneous emissions from the new wall and soil coverings. It is responsible for respiratory complaints and is classified as possibly carcinogenic to humans. Adsorption processes are commonly used to remove VOCs from the air. Metal-Organic Frameworks (MOFs) are a promising type of material for high adsorption performance. These hybrid porous materials composed of metal inorganic clusters and organic ligands are interesting thanks to their high porosity and surface area. The HKUST-1 (also referred to as MOF-199) is a copper-based MOF with the formula [Cu₃(BTC)₂(H₂O)₃]n (BTC = benzene-1,3,5-tricarboxylate) and exhibits unsaturated metal sites that can be attractive sites for adsorption. The objective of this study is to investigate the impact of HKUST-1 pretreatment on acetaldehyde adsorption. Thus, dynamic adsorption experiments were conducted in 1 cm diameter glass column packed with 2 cm MOF bed height. MOF were sieved to 630 µm - 1 mm. The feed gas (Co = 460 ppmv ± 5 ppmv) was obtained by diluting a 1000 ppmv acetaldehyde gas cylinder in air. The gas flow rate was set to 0.7 L/min (to guarantee a suitable linear velocity). Acetaldehyde concentration was monitored online by gas chromatography coupled with a flame ionization detector (GC-FID). Breakthrough curves must allow to understand the interactions between the MOF and the pollutant as well as the impact of the HKUST-1 humidity in the adsorption process. Consequently, different MOF water content conditions were tested, from a dry material with 7 % water content (dark blue color) to water saturated state with approximately 35 % water content (turquoise color). The rough material – without any pretreatment – containing 30 % water serves as a reference. First, conclusions can be drawn from the comparison of the evolution of the ratio of the column outlet concentration (C) on the inlet concentration (Co) as a function of time for different HKUST-1 pretreatments. The shape of the breakthrough curves is significantly different. The saturation of the rough material is slower (20 h to reach saturation) than that of the dried material (2 h). However, the breakthrough time defined for C/Co = 10 % appears earlier in the case of the rough material (0.75 h) compared to the dried HKUST-1 (1.4 h). Another notable difference is the shape of the curve before the breakthrough at 10 %. An abrupt increase of the outlet concentration is observed for the material with the lower humidity in comparison to a smooth increase for the rough material. Thus, the water content plays a significant role on the breakthrough kinetics. This study aims to understand what can explain the shape of the breakthrough curves associated to the pretreatments of HKUST-1 and which mechanisms take place in the adsorption process between the MOF, the pollutant, and the water.

Keywords: acetaldehyde, dynamic adsorption, HKUST-1, pretreatment influence

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Authors: C. D. Ellis, H. Xia, X. Chen

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Experimental and computational studies investigating heat transfer in separated flows have been of increasing importance over the last 60 years, as efforts are being made to understand and improve the efficiency of components such as combustors, turbines, heat exchangers, nuclear reactors and cooling channels. Understanding of not only the time-mean heat transfer properties but also the unsteady properties is vital for design of these components. As computational power increases, more sophisticated methods of modelling these flows become available for use. The hybrid LES-RANS approach has been applied to a blunt leading edge flat plate, utilising a structured grid at a moderate Reynolds number of 20300 based on the plate thickness. In the region close to the wall, the RANS method is implemented for two turbulence models; the one equation Spalart-Allmaras model and Menter’s two equation SST k-ω model. The LES region occupies the flow away from the wall and is formulated without any explicit subgrid scale LES modelling. Hybridisation is achieved between the two methods by the blending of the nearest wall distance. Validation of the flow was obtained by assessing the mean velocity profiles in comparison to similar studies. Identifying the vortex structures of the flow was obtained by utilising the λ2 criterion to identify vortex cores. The qualitative structure of the flow compared with experiments of similar Reynolds number. This identified the 2D roll up of the shear layer, breaking down via the Kelvin-Helmholtz instability. Through this instability the flow progressed into hairpin like structures, elongating as they advanced downstream. Proper Orthogonal Decomposition (POD) analysis has been performed on the full flow field and upon the surface temperature of the plate. As expected, the breakdown of POD modes for the full field revealed a relatively slow decay compared to the surface temperature field. Both POD fields identified the most energetic fluctuations occurred in the separated and recirculation region of the flow. Latter modes of the surface temperature identified these levels of fluctuations to dominate the time-mean region of maximum heat transfer and flow reattachment. In addition to the current research, work will be conducted in tracking the movement of the vortex cores and the location and magnitude of temperature hot spots upon the plate. This information will support the POD and statistical analysis performed to further identify qualitative relationships between the vortex dynamics and the response of the surface heat transfer.

Keywords: heat transfer, hybrid LES-RANS, separated and reattached flow, vortex dynamics

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Authors: Joseph Mwiti Marangu, Joseph Karanja Thiong'o, Jackson Muthengia Wachira

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The mechanical performance of hydrated cements mortars mainly depends on its compressive strength and setting time. These properties are crucial in the construction industry. Pozzolana based cements are mostly characterized by low 28 day compressive strength and long setting times. These are some of the major impediments to their production and diverse uses despite numerous technological and environmental benefits associated with them. The study investigated the effects of potential chemical activators on calcined clay- Portland cement blends with an aim to achieve high early compressive strength and shorter setting times in cement mortar. In addition, standard consistency, soundness and insoluble residue of all cement categories was determined. The test cement was made by blending calcined clays with Ordinary Portland Cement (OPC) at replacement levels from 35 to 50 percent by mass of the OPC to make test cement labeled PCC for the purposes of this study. Mortar prisms measuring 40mmx40mmx160mm were prepared and cured in accordance with KS EAS 148-3:2000 standard. Solutions of Na2SO4, NaOH, Na2SiO3 and Na2CO3 containing 0.5- 2.5M were separately added during casting. Compressive strength was determined at 2rd, 7th, 28th and 90th day of curing. For comparison purposes, commercial Portland Pozzolana cement (PPC) and Ordinary Portland Cement (OPC) were also investigated without activators under similar conditions. X-Ray Florescence (XRF) was used for chemical analysis while X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) were used for mineralogical analysis of the test samples. The results indicated that addition of activators significantly increased the 2nd and 7th day compressive strength but minimal increase on the 28th and 90th day compressive strength. A relatively linear relationship was observed between compressive strength and concentration of activator solutions up to 28th of curing. Addition of the said activators significantly reduced both initial and final setting time. Standard consistency and soundness varied with increased amount of clay in the test cement and concentration of activators. Amount of insoluble residues increased with increased replacement of OPC with calcined clays. Mineralogical studies showed that N-A-S-H is formed in addition to C-S-H. In conclusion, the concentration of 2 molar for all activator solutions produced the optimum compressive strength and greatly reduced the setting times for all cement mortars.

Keywords: activators, admixture, cement, clay, pozzolana

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Authors: Benoit Atge, Alice Dhersin, Oscar Da Silva Cacao, Beatrice Martinez, Dominique Ducint, Catherine Verdun-Esquer, Isabelle Baldi, Mathieu Molimard, Antoine Villa, Mireille Canal-Raffin

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Introduction: Healthcare workers' exposure to antineoplastic drugs (AD) is a burning issue for occupational medicine practitioners. Biological monitoring of occupational exposure (BMOE) is an essential tool for assessing AD contamination of healthcare workers. In addition to BMOE, surface sampling is a useful tool in order to understand how workers get contaminated, to identify sources of environmental contamination, to verify the effectiveness of surface decontamination way and to ensure monitoring of these surfaces. The objective of this work was to develop a complete tool including a kit for surface sampling and a quantification analytical method for AD traces detection. The development was realized with the three following criteria: the kit capacity to sample in every professional environment (healthcare services, veterinaries, etc.), the detection of very low AD traces with a validated analytical method and the easiness of the sampling kit use regardless of the person in charge of sampling. Material and method: AD mostly used in term of quantity and frequency have been identified by an analysis of the literature and consumptions of different hospitals, veterinary services, and home care settings. The kind of adsorbent device, surface moistening solution and mix of solvents for the extraction of AD from the adsorbent device have been tested for a maximal yield. The AD quantification was achieved by an ultra high-performance liquid chromatography method coupled with tandem mass spectrometry (UHPLC-MS/MS). Results: With their high frequencies of use and their good reflect of the diverse activities through healthcare, 15 AD (cyclophosphamide, ifosfamide, doxorubicin, daunorubicin, epirubicin, 5-FU, dacarbazin, etoposide, pemetrexed, vincristine, cytarabine, methothrexate, paclitaxel, gemcitabine, mitomycin C) were selected. The analytical method was optimized and adapted to obtain high sensitivity with very low limits of quantification (25 to 5000ng/mL), equivalent or lowest that those previously published (for 13/15 AD). The sampling kit is easy to use, provided with a didactic support (online video and protocol paper). It showed its effectiveness without inter-individual variation (n=5/person; n= 5 persons; p=0,85; ANOVA) regardless of the person in charge of sampling. Conclusion: This validated tool (sampling kit + analytical method) is very sensitive, easy to use and very didactic in order to control the chemical risk brought by AD. Moreover, BMOE permits a focal prevention. Used in routine, this tool is available for every intervention of occupational health.

Keywords: surface contamination, sampling kit, analytical method, sensitivity

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Authors: S.I.Mukhin, S. Seidov, A. Mukherjee

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The Dicke model is a key tool for the description of correlated states of quantum atomic systems, excited by resonant photon absorption and subsequently emitting spontaneous coherent radiation in the superradiant state. The Dicke Hamiltonian (DH) is successfully used for the description of the dynamics of the Josephson Junction (JJ) array in a resonant cavity under applied current. In this work, we have investigated a generalized model, which is described by DH with a frustrating interaction term. This frustrating interaction term is explicitly the infinite coordinated interaction between all the spin half in the system. In this work, we consider an array of N superconducting islands, each divided into two sub-islands by a Josephson Junction, taken in a charged qubit / Cooper Pair Box (CPB) condition. The array is placed inside the resonant cavity. One important aspect of the problem lies in the dynamical nature of the physical observables involved in the system, such as condensed electric field and dipole moment. It is important to understand how these quantities behave with time to define the quantum phase of the system. The Dicke model without frustrating term is solved to find the dynamical solutions of the physical observables in analytic form. We have used Heisenberg’s dynamical equations for the operators and on applying newly developed Rotating Holstein Primakoff (HP) transformation and DH we have arrived at the four coupled nonlinear dynamical differential equations for the momentum and spin component operators. It is possible to solve the system analytically using two-time scales. The analytical solutions are expressed in terms of Jacobi's elliptic functions for the metastable ‘bound luminosity’ dynamic state with the periodic coherent beating of the dipoles that connect the two double degenerate dipolar ordered phases discovered previously. In this work, we have proceeded the analysis with the extended DH with a frustrating interaction term. Inclusion of the frustrating term involves complexity in the system of differential equations and it gets difficult to solve analytically. We have solved semi-classical dynamic equations using the perturbation technique for small values of Josephson energy EJ. Because the Hamiltonian contains parity symmetry, thus phase transition can be found if this symmetry is broken. Introducing spontaneous symmetry breaking term in the DH, we have derived the solutions which show the occurrence of finite condensate, showing quantum phase transition. Our obtained result matches with the existing results in this scientific field.

Keywords: Dicke Model, nonlinear dynamics, perturbation theory, superconductivity

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Authors: Monica Enculescu, A. Evanghelidis, I. Enculescu

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Among the numerous methods for obtaining polymer nanofibers, the electrospinning technique distinguishes itself due to the more growing interest induced by its proved utility leading to developing and improving of the method and the appearance of novel materials. In particular, production of polymeric nanofibers in which different dopants are introduced was intensively studied in the last years because of the increased interest for the obtaining of functional electrospun nanofibers. Electrospinning is a facile method of obtaining polymer nanofibers with diameters from tens of nanometers to micrometrical sizes that are cheap, flexible, scalable, functional and biocompatible. Besides the multiple applications in medicine, polymeric nanofibers obtained by electrospinning permit manipulation of light at nanometric dimensions when doped with organic dyes or different nanoparticles. It is a simple technique that uses an electrical field to draw fine polymer nanofibers from solutions and does not require complicated devices or high temperatures. Different morphologies of the electrospun nanofibers can be obtained for the same polymeric host when different parameters of the electrospinning process are used. Consequently, we can obtain tuneable optical properties of the electrospun nanofibers (e.g. changing the wavelength of the emission peak) by varying the parameters of the fabrication method. We focus on obtaining doped polymer nanofibers with enhanced optical properties using the electrospinning technique. The aim of the paper is to produce dye-doped polymer nanofibers’ mats incorporating uniformly dispersed dyes. Transmission and fluorescence of the fibers will be evaluated by spectroscopy methods. The morphological properties of the electrospun dye-doped polymer fibers will be evaluated using scanning electron microscopy (SEM). We will tailor the luminescent properties of the material by doping the polymer (polyvinylpyrrolidone or polymethylmetacrilate) with different dyes (coumarins, rhodamines and sulforhodamines). The tailoring will be made taking into consideration the possibility of changing the luminescent properties of electrospun polymeric nanofibers that are doped with different dyes by using different parameters for the electrospinning technique (electric voltage, distance between electrodes, flow rate of the solution, etc.). Furthermore, we can evaluated the influence of the concentration of the dyes on the emissive properties of dye-doped polymer nanofibers using different concentrations. The advantages offered by the electrospinning technique when producing polymeric fibers are given by the simplicity of the method, the tunability of the morphology allowed by the possibility of controlling all the process parameters (temperature, viscosity of polymeric solution, applied voltage, distance between electrodes, etc.), and by the absence of necessity of using harsh and supplementary chemicals such as the ones used in the traditional nanofabrication techniques. Acknowledgments: The authors acknowledge the financial support received through IFA CEA Project No. C5-08/2016.

Keywords: electrospinning, luminescence, polymer nanofibers, scanning electron microscopy

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Authors: Smita Mondal, Dinesh Kumar Pandey, Prakash Biswas

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During past two decades, considerable attention has been given to the value addition of biodiesel derived glycerol (~10wt.%) to make the biodiesel industry economically viable. Among the various glycerol value-addition methods, hydrogenolysis of glycerol to 1,2-propanediol is one of the attractive and promising routes. In this study, highly active and selective γ-Al₂O₃ supported bimetallic Cu-Ni catalyst was developed for selective hydrogenolysis of glycerol to 1,2-propanediol in the liquid phase. The catalytic performance was evaluated in a high-pressure autoclave reactor. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. Experimental results demonstrated that bimetallic copper-nickel catalyst was more active and selective to 1,2-PDO as compared to monometallic catalysts due to bifunctional behavior. To verify the effect of calcination temperature on the formation of Cu-Ni mixed oxide phase, the calcination temperature of 20wt.% Cu:Ni(1:1)/Al₂O₃ catalyst was varied from 300°C-550°C. The physicochemical properties of the catalysts were characterized by various techniques such as specific surface area (BET), X-ray diffraction study (XRD), temperature programmed reduction (TPR), and temperature programmed desorption (TPD). The BET surface area and pore volume of the catalysts were in the range of 71-78 m²g⁻¹, and 0.12-0.15 cm³g⁻¹, respectively. The peaks at the 2θ range of 43.3°-45.5° and 50.4°-52°, was corresponded to the copper-nickel mixed oxidephase [JCPDS: 78-1602]. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. The crystallite size decreased with increasing the calcination temperature up to 450°C. Further, the crystallite size was increased due to agglomeration. Smaller crystallite size of 16.5 nm was obtained for the catalyst calcined at 400°C. Total acidic sites of the catalysts were determined by NH₃-TPD, and the maximum total acidic of 0.609 mmol NH₃ gcat⁻¹ was obtained over the catalyst calcined at 400°C. TPR data suggested the maximum of 75% degree of reduction of catalyst calcined at 400°C among all others. Further, 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst calcined at 400°C exhibited highest catalytic activity ( > 70%) and 1,2-PDO selectivity ( > 85%) at mild reaction condition due to highest acidity, highest degree of reduction, smallest crystallite size. Further, the modified Power law kinetic model was developed to understand the true kinetic behaviour of hydrogenolysis of glycerol over 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst. Rate equations obtained from the model was solved by ode23 using MATLAB coupled with Genetic Algorithm. Results demonstrated that the model predicted data were very well fitted with the experimental data. The activation energy of the formation of 1,2-PDO was found to be 45 kJ mol⁻¹.

Keywords: glycerol, 1, 2-PDO, calcination, kinetic

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Authors: Burçak Boztemur, Yue Xu, Laima Luo, M. Lütfi Öveçoğlu, Duygu Ağaoğulları

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Tungsten (W) is used chiefly as plasma-facing material. However, it has some problems, such as brittleness after plasma exposure. High-entropy alloys (RHEAs) are a new opportunity for this deficiency. So, the neutron shielding behavior of WNbMoVTa and WNbMoVTaCr₀.₅Al compositions were examined against He⁺ irradiation in this study. The mechanical and irradiation properties of the WNbMoVTa base composition were investigated by adding the Al and Cr elements. The mechanical alloying (MA) for 6 hours was applied to obtain RHEA powders. According to the X-ray diffraction (XRD) method, the body-centered cubic (BCC) phase and NbTa phase with a small amount of WC impurity that comes from vials and balls were determined after 6 h MA. Also, RHEA powders were consolidated with the spark plasma sintering (SPS) method (1500 ºC, 30 MPa, and 10 min). After the SPS method, (Nb,Ta)C and W₂C₀.₈₅ phases were obtained with the decomposition of WC and stearic acid that is added during MA based on XRD results. Also, the BCC phase was obtained for both samples. While the Al₂O₃ phase with a small intensity was seen for the WNbMoVTaCr₀.₅Al sample, the Ta₂VO₆ phase was determined for the base sample. These phases were observed as three different regions according to scanning electron microscopy (SEM). All elements were distributed homogeneously on the white region by measuring an electron probe micro-analyzer (EPMA) coupled with a wavelength dispersive spectroscope (WDS). Also, the grey region of the WNbMoVTa sample was rich in Ta, V, and O elements. However, the amount of Al and O elements was higher for the grey region of the WNbMoVTaCr₀.₅Al sample. The high amount of Nb, Ta, and C elements were determined for both samples. Archimedes’ densities that were measured with alcohol media were closer to the theoretical densities of RHEAs. These values were important for the microhardness and irradiation resistance of compositions. While the Vickers microhardness value of the WNbMoVTa sample was measured as ~11 GPa, this value increased to nearly 13 GPa with the WNbMoVTaCr₀.₅Al sample. These values were compatible with the wear behavior. The wear volume loss was decreased to 0.16×10⁻⁴ from 1.25×10⁻⁴ mm³ by the addition of Al and Cr elements to the WNbMoVTa. The He⁺ irradiation was conducted on the samples to observe surface damage. After irradiation, the XRD patterns were shifted to the left because of defects and dislocations. He⁺ ions were infused under the surface, so they created the lattice expansion. The peak shifting of the WNbMoVTaCr₀.₅Al sample was less than the WNbMoVTa base sample, thanks to less impact. A small amount of fuzz was observed for the base sample. This structure was removed and transformed into a wavy structure with the addition of Cr and Al elements. Also, the deformation hardening was actualized after irradiation. A lower amount of hardening was obtained with the WNbMoVTaCr₀.₅Al sample based on the changing microhardness values. The surface deformation was decreased in the WNbMoVTaCr₀.₅Al sample.

Keywords: refractory high entropy alloy, microhardness, wear resistance, He⁺ irradiation

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Authors: Stefano Iannello, Massimiliano Materazzi

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Fluidized bed reactor technologies are one of the most valuable pathways for thermochemical conversions of biogenic fuels due to their good operating flexibility. Nevertheless, there are still issues related to the mixing and separation of heterogeneous phases during operation with highly volatile feedstocks, including biomass and waste. At high temperatures, the volatile content of the feedstock is released in the form of the so-called endogenous bubbles, which generally exert a “lift” effect on the particle itself by dragging it up to the bed surface. Such phenomenon leads to high release of volatile matter into the freeboard and limited mass and heat transfer with particles of the bed inventory. The aim of this work is to get a better understanding of the behaviour of a single reacting particle in a hot fluidized bed reactor during the devolatilization stage. The analysis has been undertaken at different fluidization regimes and temperatures to closely mirror the operating conditions of waste-to-energy processes. Beechwood and polypropylene particles were used to resemble the biomass and plastic fractions present in waste materials, respectively. The non-invasive X-ray technique was coupled to particle tracking algorithms to characterize the motion of a single feedstock particle during the devolatilization with high resolution. A high-energy X-ray beam passes through the vessel where absorption occurs, depending on the distribution and amount of solids and fluids along the beam path. A high-speed video camera is synchronised to the beam and provides frame-by-frame imaging of the flow patterns of fluids and solids within the fluidized bed up to 72 fps (frames per second). A comprehensive mathematical model has been developed in order to validate the experimental results. Beech wood and polypropylene particles have shown a very different dynamic behaviour during the pyrolysis stage. When the feedstock is fed from the bottom, the plastic material tends to spend more time within the bed than the biomass. This behaviour can be attributed to the presence of the endogenous bubbles, which drag effect is more pronounced during the devolatilization of biomass, resulting in a lower residence time of the particle within the bed. At the typical operating temperatures of thermochemical conversions, the synthetic polymer softens and melts, and the bed particles attach on its outer surface, generating a wet plastic-sand agglomerate. Consequently, this additional layer of sand may hinder the rapid evolution of volatiles in the form of endogenous bubbles, and therefore the establishment of a poor drag effect acting on the feedstock itself. Information about the mixing and segregation of solid feedstock is of prime importance for the design and development of more efficient industrial-scale operations.

Keywords: fluidized bed, pyrolysis, waste feedstock, X-ray

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Authors: Tatiana Marques Pessanha, Aurora Perez-Gramatges, Regina Sandra Veiga Nascimento

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Emulsions are commonly used in applications involving oil/water dispersions, where handling of interfaces becomes a crucial aspect. The use of emulsion technology has greatly evolved in the last decades to suit the most diverse uses, ranging from cosmetic products and biomedical adjuvants to complex industrial fluids. The stability of these emulsions is influenced by factors such as the amount of oil, size of droplets and emulsifiers used. While commercial surfactants are typically used as emulsifiers to reduce interfacial tension, and therefore increase emulsion stability, these organic amphiphilic compounds are often toxic and expensive. A suitable alternative for emulsifiers can be obtained from the chemical modification of polysaccharides. Our group has been working on modification of polysaccharides to be used as additives in a variety of fluid formulations. In particular, we have obtained promising results using chitosan, a natural and biodegradable polymer that can be easily modified due to the presence of amine groups in its chemical structure. In this way, it is possible to increase both the hydrophobic and hydrophilic character, which renders a water-soluble, amphiphilic polymer that can behave as an emulsifier. The aim of this work was the synthesis of chitosan derivatives structurally modified to act as surfactants in stable oil-in-water. The synthesis of chitosan derivatives occurred in two steps, the first being the hydrophobic modification with the insertion of long hydrocarbon chains, while the second step consisted in the cationization of the amino groups. All products were characterized by infrared spectroscopy (FTIR) and carbon magnetic resonance (13C-NMR) to evaluate the cationization and hydrofobization degrees. These modified polysaccharides were used to formulate oil-in water (O:W) emulsions with different oil/water ratios (i.e 25:75, 35:65, 60:40) using mineral paraffinic oil. The formulations were characterized according to the type of emulsion, density and rheology measurements, as well as emulsion stability at high temperatures. All emulsion formulations were stable for at least 30 days, at room temperature (25°C), and in the case of the high oil content emulsion (60:40), the formulation was also stable at temperatures up to 100°C. Emulsion density was in the range of 0.90-0.87 s.g. The rheological study showed a viscoelastic behaviour in all formulations at room temperature, which is in agreement with the high stability showed by the emulsions, since the polymer acts not only reducing interfacial tension, but also forming an elastic membrane at the oil/water interface that guarantees its integrity. The results obtained in this work are a strong evidence of the possibility of using chemically modified polysaccharides as environmentally friendly alternatives to commercial surfactants in the stabilization of oil-in water formulations.

Keywords: emulsion, polymer, polysaccharide, stability, chemical modification

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Authors: Mohammed Mesrar, Hamza El Malki, Hamza Mesrar

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In this study, ceramics of (1-x)(Na0.5Bi0.5)TiO3 x(K0.5 Bi0.5)TiO3 were synthesized through a conventional calcination process (solid-state method) at 1000°C for 4 hours, with x(%) values ranging from 0.0 to 100. Room temperature XRD patterns confirmed the phase formation of the samples. The Rietveld refinement method was employed to verify the morphotropic phase boundary (MPB) at x(%)=16-20. We investigated the average crystallite size and lattice strain using Scherrer's formula and Williamson-Hall (W-H) analysis. SEM image analyses provided additional evidence of the impact of doping on structural growth under low temperatures. Relaxation time extracted from Z″(f) and M″(f) spectra for x(%) = 0.0, 12, 16, 20, and 30 followed the Arrhenius law, revealing the presence of three distinct relaxation mechanisms with varying activation energies. The shoulder response in M″(f) indirectly indicated the existence of highly polarizable entities in the samples, serving as a signature of polar nanoregions (PNRs) within the grains.In this study, ceramics of (1-x)(Na0.5Bi0.5)TiO3 x(K0.5 Bi0.5)TiO3 were synthesized through a conventional calcination process (solid-state method) at 1000°C for 4 hours, with x(%) values ranging from 0.0 to 100. Room temperature XRD patterns confirmed the phase formation of the samples. The Rietveld refinement method was employed to verify the morphotropic phase boundary (MPB) at x(%)=16-20. We investigated the average crystallite size and lattice strain using Scherrer's formula and Williamson-Hall (W-H) analysis. SEM image analyses provided additional evidence of the impact of doping on structural growth under low temperatures. Relaxation time extracted from Z″(f) and M″(f) spectra for x(%) = 0.0, 12, 16, 20, and 30 followed the Arrhenius law, revealing the presence of three distinct relaxation mechanisms with varying activation energies. The shoulder response in M″(f) indirectly indicated the existence of highly polarizable entities in the samples, serving as a signature of polar nanoregions (PNRs) within the grains.

Keywords: (1-x)(Na0.5Bi0.5)TiO3 x(K0.5 Bi0.5)TiO3, Rietveld refinement, Scanning electron microscopy (SEM), Williamson-Hall plots, charge density distribution, dielectric properties

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Authors: Luminita Marin, Dalila Belei, Carmen Dumea

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Aggregation induced emission (AIE) is an intriguing optical phenomenon recently evidenced by Tang and his co-workers, for which aggregation works constructively in the improving of light emission. The AIE challenging phenomenon is quite opposite to the notorious aggregation caused quenching (ACQ) of light emission in the condensed phase, and comes in line with requirements of photonic and optoelectronic devices which need solid state emissive substrates. This paper reports a series of ten new aggregation induced emission (AIE) low molecular weight compounds based on triazole and pyridine-N-oxide heterocyclic units bonded by short flexible chains, obtained by a „click” chemistry reaction. The compounds present extremely weak luminescence in solution but strong light emission in solid state. To distinguish the influence of the crystallinity degree on the emission efficiency, the photophysical properties were explored by UV-vis and photoluminescence spectroscopy in solution, water suspension, amorphous and crystalline films. On the other hand, the compound morphology of the up mentioned states was monitored by dynamic light scattering, scanning electron microscopy, atomic force microscopy and polarized light microscopy methods. To further understand the structural design – photophysical properties relationship, single crystal X-ray diffraction on some understudy compounds was performed too. The UV-vis absorption spectra of the triazole water suspensions indicated a typical behaviour for nanoparticle formation, while the photoluminescence spectra revealed an emission intensity enhancement up to 921-fold higher of the crystalline films compared to solutions, clearly indicating an AIE behaviour. The compounds have the tendency to aggregate forming nano- and micro- crystals in shape of rose-like and fibres. The crystals integrity is kept due to the strong lateral intermolecular forces, while the absence of face-to-face forces explains the enhanced luminescence in crystalline state, in which the intramolecular rotations are restricted. The studied flexible triazoles draw attention to a new structural design in which small biologically friendly luminophore units are linked together by small flexible chains. This design enlarges the variety of the AIE luminogens to the flexible molecules, guiding further efforts in development of new AIE structures for appropriate applications, the biological ones being especially envisaged.

Keywords: aggregation induced emission, pyridine-N-oxide, triazole

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Authors: Ciprian Briciu-Burghina, Brendan Heery, Dermot Brabazon, Fiona Regan

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Good quality bathing water is a highly desirable natural resource which can provide major economic, social, and environmental benefits. Both in Ireland and Europe, such water bodies are managed under the European Directive for the management of bathing water quality (BWD). The BWD aims mainly: (i) to improve health protection for bathers by introducing stricter standards for faecal pollution assessment (E. coli, enterococci), (ii) to establish a more pro-active approach to the assessment of possible pollution risks and the management of bathing waters, and (iii) to increase public involvement and dissemination of information to the general public. Standard methods for E. coli and enterococci quantification rely on cultivation of the target organism which requires long incubation periods (from 18h to a few days). This is not ideal when immediate action is required for risk mitigation. Municipalities that oversee the bathing water quality and deploy appropriate signage have to wait for laboratory results. During this time, bathers can be exposed to pollution events and health risks. Although forecasting tools exist, they are site specific and as consequence extensive historical data is required to be effective. Another approach for early detection of faecal pollution is the use of marker enzymes. β-glucuronidase (GUS) is a widely accepted biomarker for E. coli detection in microbiological water quality control. GUS assay is particularly attractive as they are rapid, less than 4 h, easy to perform and they do not require specialised training. A method for on-site detection of GUS from environmental samples in less than 75 min was previously demonstrated. In this study, the capability of ColiSense as an early warning system for faecal pollution in freshwater is assessed. The system successfully detected GUS activity in all of the 45 freshwater samples tested. GUS activity was found to correlate linearly with E. coli (r2=0.53, N=45, p < 0.001) and enterococci (r2=0.66, N=45, p < 0.001) Although GUS is a marker for E. coli, a better correlation was obtained for enterococci. For this study water samples were collected from 5 rivers in the Dublin area over 1 month. This suggests a high diversity of pollution sources (agricultural, industrial, etc) as well as point and diffuse pollution sources were captured in the sample size. Such variety in the source of E. coli can account for different GUS activities/culturable cell and different ratios of viable but not culturable to viable culturable bacteria. A previously developed protocol for the recovery and detection of E. coli was coupled with a miniaturised fluorometer (ColiSense) and the system was assessed for the rapid detection FIB in freshwater samples. Further work will be carried out to evaluate the system’s performance on seawater samples.

Keywords: faecal pollution, β-glucuronidase (GUS), bathing water, E. coli

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Authors: Mohammad Emamjome Kashan, Alan S. Fung

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In Canada, more than 32% of the total energy demand is related to the building sector. Therefore, there is a great opportunity for Greenhouse Gases (GHG) reduction by integrating solar collectors to provide building heating load and domestic hot water (DHW). Despite the cold winter weather, Canada has a good number of sunny and clear days that can be considered for diurnal solar thermal energy storage. Due to the energy mismatch between building heating load and solar irradiation availability, relatively big storage tanks are usually needed to store solar thermal energy during the daytime and then use it at night. On the other hand, water tanks occupy huge space, especially in big cities, space is relatively expensive. This project investigates the possibility of using a specific building construction material (ICF – Insulated Concrete Form) as diurnal solar thermal energy storage that is integrated with a heat pump and microchannel solar thermal collector (MCST). Not much literature has studied the application of building pre-existing walls as active solar thermal energy storage as a feasible and industrialized solution for the solar thermal mismatch. By using ICF walls that are integrated into the building envelope, instead of big storage tanks, excess solar energy can be stored in the concrete of the ICF wall that consists of EPS insulation layers on both sides to store the thermal energy. In this study, two solar-based systems are designed and simulated inTransient Systems Simulation Program(TRNSYS)to compare ICF wall thermal storage benefits over the system without ICF walls. In this study, the heating load and DHW of a Canadian single-family house located in London, Ontario, are provided by solar-based systems. The proposed system integrates the MCST collector, a water-to-water HP, a preheat tank, the main tank, fan coils (to deliver the building heating load), and ICF walls. During the day, excess solar energy is stored in the ICF walls (charging cycle). Thermal energy can be restored from the ICF walls when the preheat tank temperature drops below the ICF wall (discharging process) to increase the COP of the heat pump. The evaporator of the heat pump is taking is coupled with the preheat tank. The provided warm water by the heat pump is stored in the second tank. Fan coil units are in contact with the tank to provide a building heating load. DHW is also delivered is provided from the main tank. It is investigated that the system with ICF walls with an average solar fraction of 82%- 88% can cover the whole heating demand+DHW of nine months and has a 10-15% higher average solar fraction than the system without ICF walls. Sensitivity analysis for different parameters influencing the solar fraction is discussed in detail.

Keywords: net-zero building, renewable energy, solar thermal storage, microchannel solar thermal collector

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Authors: Benjamin Mauck, Kevin Winter

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The city of Cape Town in South Africa, has shown consistent economic and population growth in the last few decades and that growth is expected to continue to increase into the future. These projected economic and population growth rates are set to place additional pressure on the city’s already strained water supply system. Thus, given Cape Town’s water scarcity, increasing water demands and stressed water supply system, coupled with global awareness around the issues of sustainable development, environmental protection and climate change, alternative water management strategies are required to ensure water is sustainably managed. Water Sensitive Urban Design (WSUD) is an approach to sustainable urban water management that attempts to assign a resource value to all forms of water in the urban context, viz. stormwater, wastewater, potable water and groundwater. WSUD employs a wide range of strategies to improve the sustainable management of urban water such as the water reuse, developing alternative available supply sources, sustainable stormwater management and enhancing the aesthetic and recreational value of urban water. Managed Aquifer Recharge (MAR) is one WSUD strategy which has proven to be a successful reuse strategy in a number of places around the world. MAR is the process where an aquifer is intentionally or artificially recharged, which provides a valuable means of water storage while enhancing the aquifers supply potential. This paper investigates the feasibility of implementing MAR in the sandy, unconfined Cape Flats Aquifer (CFA) in Cape Town. The main objective of the study is to assess if MAR is a viable strategy for stormwater management on the Cape Flats, aiding the prevention or mitigation of the seasonal flooding that occurs on the Cape Flats, while also improving the supply potential of the aquifer. This involves the infiltration of stormwater into the CFA during the wet winter months and in turn, abstracting from the CFA during the dry summer months for fit-for-purpose uses in order to optimise the recharge and storage capacity of the CFA. The fully-integrated MIKE SHE model is used in this study to simulate both surface water and groundwater hydrology. This modelling approach enables the testing of various potential recharge and abstraction scenarios required for implementation of MAR on the Cape Flats. Further MIKE SHE scenario analysis under projected future climate scenarios provides insight into the performance of MAR as a stormwater management strategy under climate change conditions. The scenario analysis using an integrated model such as MIKE SHE is a valuable tool for evaluating the feasibility of the MAR as a stormwater management strategy and its potential to contribute towards improving Cape Town’s water security into the future.

Keywords: managed aquifer recharge, stormwater management, cape flats aquifer, MIKE SHE

Procedia PDF Downloads 226

Authors: Natalia Alzate-Carvajal, Diego A. Acevedo-Guzman, Victor Meza-Laguna, Mario H. Farias, Luis A. Perez-Rey, Edgar Abarca-Morales, Victor A. Garcia-Ramirez, Vladimir A. Basiuk, Elena V. Basiuk

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Direct covalent functionalization of prefabricated free-standing graphene oxide paper (GOP) is considered as the only approach suitable for systematic tuning of thermal, mechanical and electronic characteristics of this important class of carbon nanomaterials. At the same time, the traditional liquid-phase functionalization protocols can compromise physical integrity of the paper-like material up to its total disintegration. To avoid such undesirable effects, we explored the possibility of employing an alternative, solvent-free strategy for facile and nondestructive functionalization of GOP with two representative aliphatic amines, 1-octadecylamine (ODA) and 1,12-diaminododecane (DAD), as well as with two aromatic amines, 1-aminopyrene (AP) and 1,5-diaminonaphthalene (DAN). The functionalization was performed under moderate heating at 150-180 °C in vacuum. Under such conditions, it proceeds through both amidation and epoxy ring opening reactions. Comparative characterization of pristine and amine-functionalized GOP mats was carried out by using Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopy (XPS), thermogravimetric (TGA) and differential thermal analysis, scanning electron and atomic force microscopy (SEM and AFM, respectively). Besides that, we compared the stability in water, wettability, electrical conductivity and elastic (Young's) modulus of GOP mats before and after amine functionalization. The highest content of organic species was obtained in the case of GOP-ODA, followed by GOP-DAD, GOP-AP and GOP-DAN samples. The covalent functionalization increased mechanical and thermal stability of GOP, as well as its electrical conductivity. The magnitude of each effect depends on the particular chemical structure of amine employed, which allows for tuning a given GOP property. Morphological characterization by using SEM showed that, compared to pristine graphene oxide paper, amine-modified GOP mats become relatively ordered layered assemblies, in which individual GO sheets are organized in a near-parallel pattern. Financial support from the National Autonomous University of Mexico (grants DGAPA-IN101118 and IN200516) and from the National Council of Science and Technology of Mexico (CONACYT, grant 250655) is greatly appreciated. The authors also thank David A. Domínguez (CNyN of UNAM) for XPS measurements and Dr. Edgar Alvarez-Zauco (Faculty of Science of UNAM) for the opportunity to use TGA equipment.

Keywords: amines, covalent functionalization, gas-phase, graphene oxide paper

Procedia PDF Downloads 150

Authors: Nursultan Turdakyn, Alisher Medeubayev, Didar Meiramov, Zhibek Bekezhankyzy, Desmond Adair, Gulnur Kalimuldina

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In recent years the development of sustainable energy sources is getting extensive research interest due to the ever-growing demand for energy. As an alternative energy source to power small electronic devices, ambient energy harvesting from vibration or human body motion is considered a potential candidate. Despite the enormous progress in the field of battery research in terms of safety, lifecycle and energy density in about three decades, it has not reached the level to conveniently power wearable electronic devices such as smartwatches, bands, hearing aids, etc. For this reason, the development of self-charging power units with excellent flexibility and integrated energy harvesting and storage is crucial. Self-powering is a key idea that makes it possible for the system to operate sustainably, which is now getting more acceptance in many fields in the area of sensor networks, the internet of things (IoT) and implantable in-vivo medical devices. For solving this energy harvesting issue, the self-powering nanogenerators (NGS) were proposed and proved their high effectiveness. Usually, sustainable power is delivered through energy harvesting and storage devices by connecting them to the power management circuit; as for energy storage, the Li-ion battery (LIB) is one of the most effective technologies. Through the movement of Li ions under the driving of an externally applied voltage source, the electrochemical reactions generate the anode and cathode, storing the electrical energy as the chemical energy. In this paper, we present a simultaneous process of converting the mechanical energy into chemical energy in a way that NG and LIB are combined as an all-in-one power system. The electrospinning method was used as an initial step for the development of such a system with a β-PVDF separator. The obtained film showed promising voltage output at different stress frequencies. X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR) analysis showed a high percentage of β phase of PVDF polymer material. Moreover, it was found that the addition of 1 wt.% of BTO (Barium Titanate) results in higher quality fibers. When comparing pure PVDF solution with 20 wt.% content and the one with BTO added the latter was more viscous. Hence, the sample was electrospun uniformly without any beads. Lastly, to test the sensor application of such film, a particular testing device has been developed. With this device, the force of a finger tap can be applied at different frequencies so that electrical signal generation is validated.

Keywords: electrospinning, nanogenerators, piezoelectric PVDF, self-charging li-ion batteries

Procedia PDF Downloads 140

Authors: Ivo Zution Goncalves, Christopher M. U. Neale, Hiran Medeiros, Everardo Mantovani, Natalia Souza

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Multispectral and thermal infrared imagery from satellite sensors coupled with climate and soil datasets were used to estimate evapotranspiration and biomass in center pivots planted to maize in Brazil during the 2016 season. The hybrid remote sensing based model named Spatial EvapoTranspiration Modelling Interface (SETMI) was applied using multispectral and thermal infrared imagery from the Landsat Thematic Mapper instrument. Field data collected by the IRRIGER center pivot management company included daily weather information such as maximum and minimum temperature, precipitation, relative humidity for estimating reference evapotranspiration. In addition, soil water content data were obtained every 0.20 m in the soil profile down to 0.60 m depth throughout the season. Early season soil samples were used to obtain water-holding capacity, wilting point, saturated hydraulic conductivity, initial volumetric soil water content, layer thickness, and saturated volumetric water content. Crop canopy development parameters and irrigation application depths were also inputs of the model. The modeling approach is based on the reflectance-based crop coefficient approach contained within the SETMI hybrid ET model using relationships developed in Nebraska. The model was applied to several fields located in Minas Gerais State in Brazil with approximate latitude: -16.630434 and longitude: -47.192876. The model provides estimates of real crop evapotranspiration (ET), crop irrigation requirements and all soil water balance outputs, including biomass estimation using multi-temporal satellite image inputs. An interpolation scheme based on the growing degree-day concept was used to model the periods between satellite inputs, filling the gaps between image dates and obtaining daily data. Actual and accumulated ET, accumulated cold temperature and water stress and crop water requirements estimated by the model were compared with data measured at the experimental fields. Results indicate that the SETMI modeling approach using data assimilation, showed reliable daily ET and crop water requirements for maize, interpolated between remote sensing observations, confirming the applicability of the SETMI model using new relationships developed in Nebraska for estimating mainly ET and water requirements in Brazil under tropical conditions.

Keywords: basal crop coefficient, irrigation, remote sensing, SETMI

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Authors: Antoine Dumont, Weiji Hong, Zheng-Hong Lu

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Light emitting diodes (LEDs) are steadily becoming the new standard for luminescent display devices because of their energy efficiency and relatively low cost, and the purity of the light they emit. Our research focuses on the optical properties of the lead halide perovskite CsPbBr₃ and its family that is showing steadily improving performances in LEDs and solar cells. The objective of this work is to investigate CsPbBr₃ as an emitting layer made by physical vapor deposition instead of the usual solution-processed perovskites, for use in LEDs. The deposition in vacuum eliminates any risk of contaminants as well as the necessity for the use of chemical ligands in the synthesis of quantum dots. Initial results show the versatility of the dual-source evaporation method, which allowed us to create different phases in bulk form by altering the mole ratio or deposition rate of CsBr and PbBr₂. The distinct phases Cs₄PbBr₆, CsPbBr₃ and CsPb₂Br₅ – confirmed through XPS (x-ray photoelectron spectroscopy) and X-ray diffraction analysis – have different optical properties and morphologies that can be used for specific applications in optoelectronics. We are particularly focused on the blue shift expected from quantum dots (QDs) and the stability of the perovskite in this form. We already obtained proof of the formation of QDs through our dual source evaporation method with electron microscope imaging and photoluminescence testing, which we understand is a first in the community. We also incorporated the QDs in an LED structure to test the electroluminescence and the effect on performance and have already observed a significant wavelength shift. The goal is to reach 480nm after shifting from the original 528nm bulk emission. The hole transport layer (HTL) material onto which the CsPbBr₃ is evaporated is a critical part of this study as the surface energy interaction dictates the behaviour of the QD growth. A thorough study to determine the optimal HTL is in progress. A strong blue shift for a typically green emitting material like CsPbBr₃ would eliminate the necessity of using blue emitting Cl-based perovskite compounds and could prove to be more stable in a QD structure. The final aim is to make a perovskite QD LED with strong blue luminescence, fabricated through a dual-source evaporation technique that could be scalable to industry level, making this device a viable and cost-effective alternative to current commercial LEDs.

Keywords: material physics, perovskite, light emitting diode, quantum dots, high vacuum deposition, thin film processing

Procedia PDF Downloads 135

Authors: Rio Hirakawa, Christian Gundlach, Sven Hartwig

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In recent years, the use of aluminium has further expanded and is expected to replace steel in the future as vehicles become lighter and more recyclable in order to reduce greenhouse gas (GHG) emissions and improve fuel economy. In line with this, structures and components are becoming increasingly multi-material, with different materials, including aluminium, being used in combination to improve mechanical utility and performance. A common method of assembling dissimilar materials is mechanical fastening, but it has several drawbacks, such as increased manufacturing processes and the influence of substrate-specific mechanical properties. Adhesive bonding and fusion bonding are methods that overcome the above disadvantages. In these two joining methods, surface pre-treatment of the substrate is always necessary to ensure the strength and durability of the joint. Previous studies have shown that laser surface treatment improves the strength and durability of the joint. Yan et al. showed that laser surface treatment of aluminium alloys changes α-Al2O3 in the oxide layer to γ-Al2O3. As γ-Al2O3 has a large specific surface area, is very porous and chemically active, laser-treated aluminium surfaces are expected to undergo physico-chemical changes over time and adsorb moisture and organic substances from the air or storage atmosphere. The impurities accumulated on the laser-treated surface may be released at the adhesive and bonding interface by the heat input to the bonding system during the joining phase, affecting the strength and durability of the joint. However, only a few studies have discussed the effect of such storage periods on laser-treated surfaces. This paper, therefore, investigates the ageing of laser-treated aluminium alloy surfaces through thermal analysis, electrochemical analysis and microstructural observations.AlMg3 of 0.5 mm and 1.5 mm thickness was cut using a water-jet cutting machine, cleaned and degreased with isopropanol and surface pre-treated with a pulsed fibre laser at 1060 nm wavelength, 70 W maximum power and 55 kHz repetition frequency. The aluminium surface was then analysed using SEM, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and cyclic voltammetry (CV) after storage in air for various periods ranging from one day to several months TGA and FTIR analysed impurities adsorbed on the aluminium surface, while CV revealed changes in the true electrochemically active surface area. SEM also revealed visual changes on the treated surface. In summary, the changes in the laser-treated aluminium surface with storage time were investigated, and the final results were used to determine the appropriate storage period.

Keywords: laser surface treatment, pre-treatment, adhesion, bonding, corrosion, durability, dissimilar material interface, automotive, aluminium alloys

Procedia PDF Downloads 54

Authors: Anjali Vanpariya, Priyanka Marathey, Sakshum Khanna, Roma Patel, Indrajit Mukhopadhyay

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Silicon (Si) is a promising negative electrode material for lithium-ion batteries (LiBs) due to its low cost, non-toxicity, and a high theoretical capacity of 4200 mAhg⁻¹. The primary challenge of the application of Si-based LiBs is large volume expansion (~ 300%) during the charge-discharge process. Incorporation of graphene, carbon nanotubes (CNTs), morphological control, and nanoparticles was utilized as effective strategies to tackle volume expansion issues. However, molten salt methods can resolve the issue, but high-temperature requirement limits its application. For sustainable and practical approach, room temperature (RT) based methods are essentially required. Use of ionic liquids (ILs) for electrodeposition of Si nanostructures can possibly resolve the issue of temperature as well as greener media. In this work, electrodeposition of Si nanoparticles on gold substrate was successfully carried out in the presence of ILs media, 1-butyl-3-methylimidazolium-bis (trifluoromethyl sulfonyl) imide (BMImTf₂N) at room temperature. Cyclic voltammetry (CV) suggests the sequential reduction of Si⁴⁺ to Si²⁺ and then Si nanoparticles (SiNs). The structure and morphology of the electrodeposited SiNs were investigated by FE-SEM and observed interconnected Si nanoparticles of average particle size ⁓100-200 nm. XRD and XPS data confirm the deposition of Si on Au (111). The first discharge-charge capacity of Si anode material has been found to be 1857 and 422 mAhg⁻¹, respectively, at current density 7.8 Ag⁻¹. The irreversible capacity of the first discharge-charge process can be attributed to the solid electrolyte interface (SEI) formation via electrolyte decomposition, and trapped Li⁺ inserted into the inner pores of Si. Pulverization of SiNs results in the creation of a new active site, which facilitates the formation of new SEI in the subsequent cycles leading to fading in a specific capacity. After 20 cycles, charge-discharge profiles have been stabilized, and a reversible capacity of 150 mAhg⁻¹ is retained. Electrochemical impedance spectroscopy (EIS) data shows the decrease in Rct value from 94.7 to 47.6 kΩ after 50 cycles of charge-discharge, which demonstrates the improvements of the interfacial charge transfer kinetics. The decrease in the Warburg impedance after 50 cycles of charge-discharge measurements indicates facile diffusion in fragmented and smaller Si nanoparticles. In summary, Si nanoparticles deposited on gold substrate using ILs as media and characterized well with different analytical techniques. Synthesized material was successfully utilized for LiBs application, which is well supported by CV and EIS data.

Keywords: silicon nanoparticles, ionic liquid, electrodeposition, cyclic voltammetry, Li-ion battery

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Authors: Suchhanda Ghosh, A. K. Paul

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Nickel, an industrially important metal is not mined in India, due to the lack of its primary mining resources. But, the chromite deposits occurring in the Sukinda and Baula-Nuasahi region of Odhisa, India, is reported to contain around 0.99% of nickel entrapped in the goethite matrix of the lateritic iron rich ore. Weathering of the dumped chromite mining overburden often leads to the contamination of the ground as well as the surface water with toxic nickel. Microbes inherent to this metal contaminated environment are reported to be capable of removal as well as detoxification of various metals including nickel. Nickel resistant fungal isolates obtained in pure form from the metal rich overburden were evaluated for their potential to biosorb nickel by using their dried biomass. Penicillium simplicissimum SAU203 was the best nickel biosorbant among the 20 fungi tested and was capable to sorbing 16.85 mg Ni/g biomass from a solution containing 50 mg/l of Ni. The identity of the isolate was confirmed using 18S rRNA gene analysis. The sorption capacity of the isolate was further standardized following Langmuir and Freundlich adsorption isotherm models and the results reflected energy efficient sorption. Fourier-transform infrared spectroscopy studies of the nickel loaded and control biomass in a comparative basis revealed the involvement of hydroxyl, amine and carboxylic groups in Ni binding. The sorption process was also optimized for several standard parameters like initial metal ion concentration, initial sorbet concentration, incubation temperature and pH, presence of additional cations and pre-treatment of the biomass by different chemicals. Optimisation leads to significant improvements in the process of nickel biosorption on to the fungal biomass. P. simplicissimum SAU203 could sorb 54.73 mg Ni/g biomass with an initial Ni concentration of 200 mg/l in solution and 21.8 mg Ni/g biomass with an initial biomass concentration of 1g/l solution. Optimum temperature and pH for biosorption was recorded to be 30°C and pH 6.5 respectively. Presence of Zn and Fe ions improved the sorption of Ni(II), whereas, cobalt had a negative impact. Pre-treatment of biomass with various chemical and physical agents has affected the proficiency of Ni sorption by P. simplicissimum SAU203 biomass, autoclaving as well as treatment of biomass with 0.5 M sulfuric acid and acetic acid reduced the sorption as compared to the untreated biomass, whereas, NaOH and Na₂CO₃ and Twin 80 (0.5 M) treated biomass resulted in augmented metal sorption. Hence, on the basis of the present study, it can be concluded that P. simplicissimum SAU203 has the potential for the removal as well as detoxification of nickel from contaminated environments in general and particularly from the chromite mining areas of Odhisa, India.

Keywords: nickel, fungal biosorption, Penicillium simplicissimum SAU203, Indian chromite mines, mining overburden

Procedia PDF Downloads 171

Authors: Purnima Dhall, Rita Kumar

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Introduction: River Yamuna, in the national capital territory (NCT), and also the primary source of drinking water for the city. Delhi discharges about 3,684 MLD of sewage through its 18 drains in to the Yamuna. Water quality monitoring is an important aspect of water management concerning to the pollution control. Public concern and legislation are now a day’s demanding better environmental control. Conventional method for estimating BOD5 has various drawbacks as they are expensive, time-consuming, and require the use of highly trained personnel. Stringent forthcoming regulations on the wastewater have necessitated the urge to develop analytical system, which contribute to greater process efficiency. Biosensors offer the possibility of real time analysis. Methodology: In the present study, a novel rapid method for the determination of biochemical oxygen demand (BOD) has been developed. Using the developed method, the BOD of a sample can be determined within 2 hours as compared to 3-5 days with the standard BOD3-5day assay. Moreover, the test is based on specified consortia instead of undefined seeding material therefore it minimizes the variability among the results. The device is coupled to software which automatically calculates the dilution required, so, the prior dilution of the sample is not required before BOD estimation. The developed BOD-Biosensor makes use of immobilized microorganisms to sense the biochemical oxygen demand of industrial wastewaters having low–moderate–high biodegradability. The method is quick, robust, online and less time consuming. Findings: The results of extensive testing of the developed biosensor on drains demonstrate that the BOD values obtained by the device correlated with conventional BOD values the observed R2 value was 0.995. The reproducibility of the measurements with the BOD biosensor was within a percentage deviation of ±10%. Advantages of developed BOD biosensor • Determines the water pollution quickly in 2 hours of time; • Determines the water pollution of all types of waste water; • Has prolonged shelf life of more than 400 days; • Enhanced repeatability and reproducibility values; • Elimination of COD estimation. Distinctiveness of Technology: • Bio-component: can determine BOD load of all types of waste water; • Immobilization: increased shelf life > 400 days, extended stability and viability; • Software: Reduces manual errors, reduction in estimation time. Conclusion: BiosensorBOD can be used to measure the BOD value of the real wastewater samples. The BOD biosensor showed good reproducibility in the results. This technology is useful in deciding treatment strategies well ahead and so facilitating discharge of properly treated water to common water bodies. The developed technology has been transferred to M/s Forbes Marshall Pvt Ltd, Pune.

Keywords: biosensor, biochemical oxygen demand, immobilized, monitoring, Yamuna

Procedia PDF Downloads 254

Authors: Monu Ojha, Rahul Rana, Satywati Sharma, Kavya Dashora

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The global production rate of plastics has increased enormously and global demand for polyethylene resins –High-density polyethylene (HDPE), Linear low-density polyethylene (LLDPE) and Low-density polyethylene (LDPE) is expected to rise drastically, with very high value. These get accumulated in the environment, posing a potential ecological threat as they are degrading at a very slow rate and remain in the environment indefinitely. The aim of the present study was to investigate the potential of commonly found soil microbes like Bacillus subtilus, Aspergillus niger, Pseudomonas fluroscence for their ability to biodegrade LDPE in the lab on solid and liquid media conditions as well as in presence of 1% salt in the soil. This study was conducted at Indian Institute of Technology, Delhi, India from July to September where average temperature and RH (Relative Humidity) were 33 degrees Celcius and 80% respectively. It revealed that the weight loss of LDPE strip obtained from market of approximately 4x6 cm dimensions is more in liquid broth media than in solid agar media. The percentage weight loss by P. fluroscence, A. niger and B. subtilus observed after 80 days of incubation was 15.52, 9.24 and 8.99% respectively in broth media and 6.93, 2.18 and 4.76 % in agar media. The LDPE strips from same source and on the same were subjected to soil in presence of above microbes with 1% salt (NaCl: obtained from commercial table salt) with temperature and RH 33 degree Celcius and 80%. It was found that the rate of degradation increased in the soil than under lab conditions. The rate of weight loss of LDPE strips under same conditions given in lab was found to be 32.98, 15.01 and17.09 % by P. fluroscence, A. niger and B. subtilus respectively. The breaking strength was found to be 9.65N, 29N and 23.85 N for P. fluroscence, A. niger and B. subtilus respectively. SEM analysis conducted on Zeiss EVO 50 confirmed that surface of LDPE becomes physically weak after biological treatment. There was the increase in the surface roughness indicating Surface erosion of LDPE film. FTIR (Fourier-transform infrared spectroscopy) analysis of the degraded LDPE films showed stretching of aldehyde group at 3334.92 and 3228.84 cm-1,, C–C=C symmetric of aromatic ring at 1639.49 cm-1.There was also C=O stretching of aldehyde group at 1735.93 cm-1. N=O peak bend was also observed which corresponds to 1365.60 cm-1, C–O stretching of ether group at 1217.08 and 1078.21 cm-1.

Keywords: microbial degradation, LDPE, Aspergillus niger, Bacillus subtilus, Peudomonas fluroscence, common salt

Procedia PDF Downloads 141

Authors: Luana Guerra, Silvio C. Sampaio, Vladimir Pavan Margarido, Ralpho R. Reis

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Brazil is the world's largest consumer of pesticides. The excessive use of these compounds has negative impacts on animal and human life, the environment, and food security. Bees, crucial for pollination, are exposed to pesticides during the collection of nectar and pollen, posing risks to their health and the food chain, including honey contamination. Aquatic sediments are also affected, impacting water quality and the microbiota. Therefore, the analysis of aquatic sediments and bee honey is essential to identify environmental contamination and monitor ecosystems. The aim of this study was to use samples of honey from honeybees (Apis mellifera) and aquatic sediment as bioindicators of environmental contamination by pesticides and their relationship with agricultural use in the surrounding areas. The sample collections of sediment and honey were carried out in two stages. The first stage was conducted in the Bituruna municipality region in the second half of the year 2022, and the second stage took place in the regions of Laranjeiras do Sul, Quedas do Iguaçu, and Nova Laranjeiras in the first half of the year 2023. In total, 10 collection points were selected, with 5 points in the first stage and 5 points in the second stage, where one sediment sample and one honey sample were collected for each point, totaling 20 samples. The honey and sediment samples were analyzed at the Laboratory of the Paraná Institute of Technology, with ten samples of honey and ten samples of sediment. The selected extraction method was QuEChERS, and the analysis of the components present in the sample was performed using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The pesticides Azoxystrobin, Epoxiconazole, Boscalid, Carbendazim, Haloxifope, Fomesafen, Fipronil, Chlorantraniliprole, Imidacloprid, and Bifenthrin were detected in the sediment samples from the study area in Laranjeiras do Sul, Paraná, with Carbendazim being the compound with the highest concentration (0.47 mg/kg). The honey samples obtained from the apiaries showed satisfactory results, as they did not show any detection or quantification of the analyzed pesticides, except for Point 9, which had the fungicide tebuconazole but with a concentration Keywords: contamination, water research, agrochemicals, beekeeping activity

Procedia PDF Downloads 19

Authors: Bao-Fang Wen, Meng-Na Dai, Gao-Pei Zhu, Chen-Xi Zhang, Jing Sun, Xun-Bao Yin, Yu-Han Zhao, Hong-Wei Sun, Wei-Fen Zhang

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A drug-loaded nanoparticles containing berberine hydrochloride (BH/FA-CTS-NPs) was prepared. The physicochemical characterizations of BH/FA-CTS-NPs and the inhibitory effect on the HeLa cells were investigated. Folic acid-conjugated chitosan (FA-CTS) was prepared by amino reaction of folic acid active ester and chitosan molecules; BH/FA-CTS-NPs were prepared using ionic cross-linking technique with BH as a model drug. The morphology and particle size were determined by Transmission Electron Microscope (TEM). The average diameters and polydispersity index (PDI) were evaluated by Dynamic Light Scattering (DLS). The interaction between various components and the nanocomplex were characterized by Fourier Transform Infrared Spectroscopy (FT-IR). The entrapment efficiency (EE), drug-loading (DL) and in vitro release were studied by UV spectrophotometer. The effect of cell anti-migratory and anti-invasive actions of BH/FA-CTS-NPs were investigated using MTT assays, wound healing assays, Annexin-V-FITC single staining assays, and flow cytometry, respectively. HeLa nude mice subcutaneously transplanted tumor model was established and treated with different drugs to observe the effect of BH/FA-CTS-NPs in vivo on HeLa bearing tumor. The BH/FA-CTS-NPs prepared in this experiment have a regular shape, uniform particle size, and no aggregation phenomenon. The results of DLS showed that mean particle size, PDI and Zeta potential of BH/FA-CTS NPs were (249.2 ± 3.6) nm, 0.129 ± 0.09, 33.6 ± 2.09, respectively, and the average diameter and PDI were stable in 90 days. The results of FT-IR demonstrated that the characteristic peaks of FA-CTS and BH/FA-CTS-NPs confirmed that FA-CTS cross-linked successfully and BH was encapsulated in NPs. The EE and DL amount were (79.3 ± 3.12) % and (7.24 ± 1.41) %, respectively. The results of in vitro release study indicated that the cumulative release of BH/FA-CTS NPs was (89.48±2.81) % in phosphate-buffered saline (PBS, pH 7.4) within 48h; these results by MTT assays and wund healing assays indicated that BH/FA-CTS NPs not only inhibited the proliferation of HeLa cells in a concentration and time-dependent manner but can induce apoptosis as well. The subcutaneous xenograft tumor formation rate of human cervical cancer cell line HeLa in nude mice was 98% after inoculation for 2 weeks. Compared with BH group and BH/CTS-NPs group, the xenograft tumor growth of BH/FA-CTS-NPs group was obviously slower; the result indicated that BH/FA-CTS-NPs could significantly inhibit the growth of HeLa xenograft tumor. BH/FA-CTS NPs with the sustained release effect could be prepared successfully by the ionic crosslinking method. Considering these properties, block proliferation and impairing the migration of the HeLa cell line, BH/FA-CTS NPs could be an important compound for consideration in the treatment of cervical cancer.

Keywords: folic-acid, chitosan, berberine hydrochloride, nanoparticles, cervical cancer

Procedia PDF Downloads 97

Authors: Manuel Chacon-Fuentes, Leonardo Bardehle, Marcelo Lizama, Claudio Reyes, Andres Quiroz

Abstract:

The insect-plant interaction is a complex process in which the plant is able to release chemical signaling that modifies the behavior of insects. Insect herbivory can trigger mechanisms that allow the increase in the production of secondary metabolites that allow coping against the herbivores. Monoterpenes are a kind of secondary metabolites involved in direct defense acting as repellents of herbivorous or even in indirect defense acting as attractants for insect predators. In addition, an increase of the monoterpenes concentration is an effect commonly associated with the herbivory. Hence, plants subjected to damage by herbivory increase the monoterpenes production in comparison to plants without herbivory. In this framework, co-evolutionary aspects play a fundamental role in the adaptation of the herbivorous to their host and in the counter-adaptive strategies of the plants to avoid the herbivorous. In this context, Ugni molinae 'murtilla' is a native shrub from Chile characterized by its antioxidant activity mainly related to the phenolic compounds presents in its fruits. The larval stage of the red grape caterpillar Chilesia rudis Butler (Lepidoptera: Arctiidae) has been reported as an important defoliator of U. molinae. This insect is native from Chile and probably has been involved in a co-evolutionary process with murtilla. Therefore, we hypothesized that herbivory by the red grape caterpillar increases the emission of monoterpenes in Ugni molinae. Ecotypes 19-1 and 22-1 of murtilla were established and maintained at 25° C in the Laboratorio de Química Ecológica at Universidad de La Frontera. Red grape caterpillars of ⁓40 mm were collected near to Temuco (Chile) from grasses, and they were deprived of food for 24 h before performing the assays. Ten caterpillars were placed on the foliage of the ecotypes 19-1 and 22-1 and allowed to feed during 48 h. After this time, caterpillars were removed from the ecotypes and monoterpenes were collected. A glass chamber was used to enclose the ecotypes and a Porapak-Q column was used to trap the monoterpenes. After 24 h of capturing, columns were desorbed with hexane. Then, samples were injected in a gas chromatograph coupled to mass spectrometer and monoterpenes were determined according to the NIST library. All the experiments were performed in triplicate. Results showed that α-pinene, β-phellandrene, limonene, and 1,8 cineole were the main monoterpenes released by murtilla ecotypes. For the ecotype 19-1, the abundance of α-pinene was significantly higher in plants subjected to herbivory (100%) in relation to control plants (54.58%). Moreover, β-phellandrene and 1,8 cineole were observed only in control plants. For ecotype 22-1, there was no significant difference in monoterpenes abundance. In conclusion, the results suggest a trade-off of β-phellandrene and 1,8 cineole in response to herbivory damage by red grape caterpillar generating an increase in α-pinene abundance.

Keywords: Chilesia rudis, gas chromatography, monoterpenes, Ugni molinae

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Authors: Biao Sun, Tejas Bhatelia, Vishnu Pareek, Ranjeet Utikar, Moses Tadé

Abstract:

Additive manufacturing (AM), commonly known as 3D printing, with the continuing advances in parallel processing and computational modeling, has created a paradigm shift (with significant radical thinking) in the design and operation of chemical processing plants, especially LNG plants. With the rising energy demands, environmental pressures, and economic challenges, there is a continuing industrial need for disruptive technologies such as AM, which possess capabilities that can drastically reduce the cost of manufacturing and operations of chemical processing plants in the future. However, the continuing challenge for 3D printing is its lack of adaptability in re-designing the process plant equipment coupled with the non-existent theory or models that could assist in selecting the optimal candidates out of the countless potential fabrications that are possible using AM. One of the most common packings used in the LNG process is structured packing in the packed column (which is a unit operation) in the process. In this work, we present an example of an optimum strategy for the application of AM to this important unit operation. Packed columns use a packing material through which the gas phase passes and comes into contact with the liquid phase flowing over the packing, typically performing the necessary mass transfer to enrich the products, etc. Structured packing consists of stacks of corrugated sheets, typically inclined between 40-70° from the plane. Computational Fluid Dynamics (CFD) was used to test and model various geometries to study the governing hydrodynamic characteristics. The results demonstrate that the costly iterative experimental process can be minimized. Furthermore, they also improve the understanding of the fundamental physics of the system at the multiscale level. SpiroPak, patented by Curtin University, represents an innovative structured packing solution currently at a technology readiness level (TRL) of 5~6. This packing exhibits remarkable characteristics, offering a substantial increase in surface area while significantly enhancing hydrodynamic and mass transfer performance. Recent studies have revealed that SpiroPak can reduce pressure drop by 50~70% compared to commonly used commercial packings, and it can achieve 20~50% greater mass transfer efficiency (particularly in CO2 absorption applications). The implementation of SpiroPak has the potential to reduce the overall size of columns and decrease power consumption, resulting in cost savings for both capital expenditure (CAPEX) and operational expenditure (OPEX) when applied to retrofitting existing systems or incorporated into new processes. Furthermore, pilot to large-scale tests is currently underway to further advance and refine this technology.

Keywords: Additive Manufacturing (AM), 3D printing, Computational Fluid Dynamics (CFD, structured packing (SpiroPak)

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Authors: Elaine Wong

Abstract:

Introduction: The Singapore Physical Activity and Nutrition Study (SPANS) aimed to assess the effects of a community-based intervention on physical activity (PA) and nutrition behaviours as well as chronic disease risk factors for Singaporean women aged above 50 years. This article examines the participation, dose, fidelity, reach, satisfaction and reasons for completion and non-completion of the SPANS. Methods: The SPANS program integrated constructs of Social Cognitive Theory (SCT) and is composed of PA activities; nutrition workshops; dietary counselling coupled with motivational interviewing (MI) through phone calls; and text messages promoting healthy behaviours. Printed educational resources and health incentives were provided to participants. Data were collected via a mixed-method design strategy from a sample of 295 intervention participants. Quantitative data were collected using self-completed survey (n = 209); qualitative data were collected via research assistants’ notes, post feedback sessions and exit interviews with program completers (n = 13) and non-completers (n = 12). Results: Majority of participants reported high ‘satisfactory to excellent’ ratings for the program pace, suitability of interest and overall program (96.2-99.5%). Likewise, similar ratings for clarity of presentation; presentation skills, approachability, knowledge; and overall rating of trainers and program ambassadors were achieved (98.6-100%). Phone dietary counselling had the highest level of participation (72%) at less than or equal to 75% attendance rate followed by nutrition workshops (65%) and PA classes (60%). Attrition rate of the program was 19%; major reasons for withdrawal were personal commitments, relocation and health issues. All participants found the program resources to be colourful, informative and practical for their own reference. Reasons for program completion and maintenance were: desired health benefits; social bonding opportunities and to learn more about PA and nutrition. Conclusions: Process evaluation serves as an appropriate tool to identify recruitment challenges, effective intervention strategies and to ensure program fidelity. Program participants were satisfied with the educational resources, program components and delivery strategies implemented by the trainers and program ambassadors. The combination of printed materials and intervention components, when guided by the SCT and MI, were supportive in encouraging and reinforcing lifestyle behavioural changes. Mixed method evaluation approaches are integral processes to pinpoint barriers, motivators, improvements and effective program components in optimising the health status of Singaporean women.

Keywords: process evaluation, Singapore, older adults, lifestyle changes, program challenges

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Authors: Kyohei Yoshino, Masahiko Matsumiya, Yuji Sasaki

Abstract:

Recently, studies have been conducted on Au(III) extraction using ionic liquids (ILs) as extractants or diluents. ILs such as piperidinium, pyrrolidinium, and pyridinium have been studied as extractants for noble metal extractions. Furthermore, the polarity, hydrophobicity, and solvent miscibility of these ILs can be adjusted depending on their intended use. Therefore, the unique properties of ILs make them functional extraction media. The extraction mechanism of Au(III) using phosphonium-based ILs and relevant thermodynamic studies are yet to be reported. In the present work, we focused on the mechanism of Au(III) extraction and related thermodynamic analyses using phosphonium-based ILs. Triethyl-n-pentyl, triethyl-n-octyl, and triethyl-n-dodecyl phosphonium bis(trifluoromethyl-sulfonyl)amide, [P₂₂₂ₓ][NTf₂], (X = 5, 8, and 12) were investigated for Au(III) extraction. The IL–Au complex was identified as [P₂₂₂₅][AuCl₄] using UV–Vis–NIR and Raman spectroscopic analyses. The extraction behavior of Au(III) was investigated with a change in the [P₂₂₂ₓ][NTf₂]IL concentration from 1.0 × 10–4 to 1.0 × 10–1 mol dm−3. The results indicate that Au(III) can be easily extracted by the anion-exchange reaction in the [P₂₂₂ₓ][NTf₂]IL. The slope range 0.96–1.01 on the plot of log D vs log[P₂₂₂ₓ][NTf2]IL indicates the association of one mole of IL with one mole of [AuCl4−] during extraction. Consequently, [P₂₂₂ₓ][NTf₂] is an anion-exchange extractant for the extraction of Au(III) in the form of anions from chloride media. Thus, this type of phosphonium-based IL proceeds via an anion exchange reaction with Au(III). In order to evaluate the thermodynamic parameters on the Au(III) extraction, the equilibrium constant (logKₑₓ’) was determined from the temperature dependence. The plot of the natural logarithm of Kₑₓ’ vs the inverse of the absolute temperature (T–1) yields a slope proportional to the enthalpy (ΔH). By plotting T–1 vs lnKₑₓ’, a line with a slope range 1.129–1.421 was obtained. Thus, the result indicated that the extraction reaction of Au(III) using the [P₂₂₂ₓ][NTf₂]IL (X=5, 8, and 12) was exothermic (ΔH=-9.39〜-11.81 kJ mol-1). The negative value of TΔS (-4.20〜-5.27 kJ mol-1) indicates that microscopic randomness is preferred in the [P₂₂₂₅][NTf₂]IL extraction system over [P₂₂₂₁₂][NTf₂]IL. The total negative alternation in Gibbs energy (-5.19〜-6.55 kJ mol-1) for the extraction reaction would thus be relatively influenced by the TΔS value on the number of carbon atoms in the alkyl side length, even if the efficiency of ΔH is significantly influenced by the total negative alternations in Gibbs energy. Electrochemical analysis revealed that extracted Au(III) can be reduced in two steps: (i) Au(III)/Au(I) and (ii) Au(I)/Au(0). The diffusion coefficients of the extracted Au(III) species in [P₂₂₂ₓ][NTf₂] (X = 5, 8, and 12) were evaluated from 323 to 373 K using semi-integral and semi-differential analyses. Because of the viscosity of the IL medium, the diffusion coefficient of the extracted Au(III) increases with increasing alkyl chain length. The 4f7/2 spectrum based on X-ray photoelectron spectroscopy revealed that the Au electrodeposits obtained after 10 cycles of continuous extraction and electrodeposition were in the metallic state.

Keywords: au(III), electrodeposition, phosphonium-based ionic liquids, solvent extraction

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