Search results for: kinetics diagrams

Authors: Adebisi Moruf Ademola

Abstract:

Hematite (Fe2O3),commonly known as ‘rust’ which usually surfaced on metal when exposed to some climatic materials. This emerges as a promising candidate for photoelectrochemical (PEC) water splitting due to its favorable physiochemical properties of the narrow band gap (2.1–2.2 eV), chemical stability, nontoxicity, abundance, and low cost. However, inherent limitations such as short hole diffusion length (2–4 nm), high charge recombination rate, and slow oxygen evolution reaction kinetics inhibit the PEC performances of a-Fe2O3 photoanodes. As such, given the narrow bandgap enabling excellent optical absorption, increased charge carrier density and accelerated surface oxidation reaction kinetics become the key points for improved photoelectrochemical performances for a-Fe2O3 photoanodes and metal ion doping as an effective way to promote charge transfer by increasing donor density and improving the electronic conductivity of a-Fe2O3. Hematite attracts enormous efforts with a number of metal ions (Ti, Zr, Sn, Pt ,etc.) as dopants. A facile deposition-annealing process showed greatly enhanced PEC performance due to the increased donor density and reduced electron-hole recombination at the time scale beyond a few picoseconds. Zr doping was also found to enhance the PEC performance of a-Fe2O3 nanorod arrays by reducing the rate of electron-hole recombination. Slow water oxidation reaction kinetics, another main factor limiting the PEC water splitting efficiency of aFe2O3 as photoanodes, was previously found to be effectively improved by surface treatment.

Keywords: deposition-annealing, hematite, metal ion doping, nanorod

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Authors: Nisrine Benzbiria, Mohammed Azzi, Mustapha Zertoubi

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2XXX series of aluminum alloys are widely employed in several applications, such as beverages, automotive, and aerospace industries. However, they are particularly prone to localized corrosion, such as pitting, often induced by a difference in corrosion potential measured for intermetallic phases and pure metal. The galvanic cells comprising Al–Cu– Mn–Fe intermetallic phases control cathodically the dissolution rate as oxygen reduction reaction kinetics are privileged on Al–Cu–Mn–Fe particles. Hence, understanding the properties of cathode sites and the processes involved must be carried out. Our interest is to outline the cathodic behavior of AA2024-T3 in sodium sulfate solution using electrochemical techniques. Oxygen reduction reaction (ORR) was investigated in the mixed charge transfer and mass transport regime using the Koutecky-Levich approach. An environmentally benign inhibitor was considered to slow the ORR on the Cu-rich cathodic phases. The surface morphology of the electrodes was investigated with SEM/EDS and AFM. The obtained results were discussed accordingly.

Keywords: AA2024-T3, neutral medium, ORR kinetics, Koutecky-Levich, DFT

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Authors: Preshanthan Moodley, E. B. Gueguim Kana

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This study examines the kinetics of S. cerevisiae BY4743 growth and bioethanol production from sugarcane leaf waste (SLW), utilizing two different optimized pretreatment regimes; under two fermentation modes: steam salt-alkali filtered enzymatic hydrolysate (SSA-F), steam salt-alkali unfiltered (SSA-U), microwave salt-alkali filtered (MSA-F) and microwave salt-alkali unfiltered (MSA-U). The kinetic coefficients were determined by fitting the Monod, modified Gompertz, and logistic models to the experimental data with high coefficients of determination R² > 0.97. A maximum specific growth rate (µₘₐₓ) of 0.153 h⁻¹ was obtained under SSA-F and SSA-U whereas, 0.150 h⁻¹ was observed with MSA-F and MSA-U. SSA-U gave a potential maximum bioethanol concentration (Pₘ) of 31.06 g/L compared to 30.49, 23.26 and 21.79g/L for SSA-F, MSA-F and MSA-U respectively. An insignificant difference was observed in the μmax and Pm for the filtered and unfiltered enzymatic hydrolysate for both SSA and MSA pretreatments, thus potentially reducing a unit operation. These findings provide significant insights for process scale up.

Keywords: lignocellulosic bioethanol, microwave pretreatment, sugarcane leaves, kinetics

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Authors: B. V. Feujofack Kemda, N. Barka, M. Jahazi, D. Osmani

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Automobile manufacturers are constantly seeking means to reduce the weight of car bodies. The usage of several steel grades in auto body assembling has been found to be a good technique to enlighten vehicles weight. This few years, the usage of dual phase (DP) steels, transformation induced plasticity (TRIP) steels and boron steels in some parts of the auto body have become a necessity because of their lightweight. However, these steels are martensitic, when they undergo a fast heat treatment, the resultant microstructure is essential, made of martensite. Resistance spot welding (RSW), one of the most used techniques in assembling auto bodies, becomes problematic in the case of these steels. RSW being indeed a process were steel is heated and cooled in a very short period of time, the resulting weld nugget is mostly fully martensitic, especially in the case of DP, TRIP and boron steels but that also holds for plain carbon steels as AISI 1010 grade which is extensively used in auto body inner parts. Martensite in its turn must be avoided as most as possible when welding steel because it is the principal source of brittleness and it weakens weld nugget. Thus, this work aims to find a mean to reduce martensite fraction in weld nugget when using RSW for assembling. The prediction of phase transformation kinetics during RSW has been done. That phase transformation kinetics prediction has been made possible through the modelling of the whole welding process, and a technique called post weld heat treatment (PWHT) have been applied in order to reduce martensite fraction in the weld nugget. Simulation has been performed for AISI 1010 grade, and results show that the application of PWHT leads to the formation of not only martensite but also ferrite, bainite and pearlite during the cooling of weld nugget. Welding experiments have been done in parallel and micrographic analyses show the presence of several phases in the weld nugget. Experimental weld geometry and phase proportions are in good agreement with simulation results, showing here the validity of the model.

Keywords: resistance spot welding, AISI 1010, modeling, post weld heat treatment, phase transformation, kinetics

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Authors: Nikolai Nosik, Vladislav Podmasterjev, Nina Kondrashina, Marina Chataeva, Olga Lobach, Dmitry Noosik, Sergei Razumovskii

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Virucidal activity of ozone is well known: dissolved in water it kill viruses very fast. The virucidal capacity of ozone in ozone-air mixture is less known. The goal of the study was to investigate the virucidal potentials of the ozone–air mixture and kinetics of virus inactivation. Materials and methods. Ozone (O3 ) was generated from oxygen with ozonizer ( 1.0 – 75.0 mg\l). The ozone concentration was determined by the spectrophotometric methods. Virus contaminated samples were placed into the flowing reactor. Viruses: poliovirus type 1, vaccine strain (Sabin) and adenovirus, type 5, were obtained from the State virus collection. Titrations of viruses were carried out in appropriate cell cultures. CxT value ( mg\l x min) was calculated. Results. Metallic, polycarbonic and fiber “Kevlar” samples were contaminated with virus, dried and treated with ozone-air mixture in the flowing reactor. Kinetics of poliovirus inactivation: in 15 min at 5.0 mg\l -2.0 lg TCID50 inhibition , in 15 min at 10 mg\l – 2.5 lg TCID50 , 4.0 lg TCID50 inactivation of poliovirus was achieved after 75min at ozone concentration 20.0mg\l (99.99%). ( CxT = 75, 150 and 1500 mg\l x min on all three types of surfaces). It was found that the inactivation of poliovirus was more effective when the virus contaminated samples were wet (in 15 min at 20mg\l inhibition of virus in dry samples was 2.0 TCID50 , in wet samples – 4.0 TCID50). Adenovirus was less resistant to ozone treatment then poliovirus: 4.0 lg TCID50 inhibition was observed after 30 min of the treatment with ozone at 20mg\l ( CxT mg\l x min = 300 for adenovirus as for poliovirus it was 1500). Conclusion. It was found that ozone-air mixture inactivates viruses at rather high concentrations (compared to the reported effect of ozone dissolved in water). Despite of that there is a difference in the resistance to ozone action between viruses – poliovirus is more resistant then adenovirus-ozone-air mixture can be used for disinfection of large rooms. The maintaining of the virus-contaminated surfaces in wet condition allow to decrease the ozone load for virus inactivation.

Keywords: adenovirus, disinfection, ozone, poliovirus

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Authors: Pavlo Selyshchev, Samuel Akintunde

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A theoretical approach to consider formation of chemical compound layer at the interface between initial substances A and B due to the interfacial interaction and diffusion is developed. It is considered situation when speed of interfacial interaction is large enough and diffusion of A-atoms through AB-layer is much more then diffusion of B-atoms. Atoms from A-layer diffuse toward B-atoms and form AB-atoms on the surface of B-layer. B-atoms are assumed to be immobile. The growth kinetics of the AB-layer is described by two differential equations with non-linear coupling, producing a good fit to the experimental data. It is shown that growth of the thickness of the AB-layer determines by dependence of chemical reaction rate on reactants concentration. In special case the thickness of the AB-layer can grow linearly or parabolically depending on that which of processes (interaction or the diffusion) controls the growth. The thickness of AB-layer as function of time is obtained. The moment of time (transition point) at which the linear growth are changed by parabolic is found.

Keywords: phase formation, binary systems, interfacial reaction, diffusion, compound layers, growth kinetics

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Authors: Nouria Bouchikhi, Soufiane Bedjaoui, C. Tewfik Bouchaour, Lamia Alachaher Bedjaoui, Ulrich Maschke

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Swelling properties and phase diagrams of binary systems composed of liquid crystalline networks and a low molecular mass liquid crystal (LMWLC) have been investigated. The networks were prepared by ultraviolet (UV) irradiation of reactive mixtures including a monomer, a cross-linking agent and a photo-initiator. These networks were prepared using two cross-linking agents: 1,6 hexanedioldiacrylate (HDDA) and a mesogenic acrylic acid 6-(4’-(6-acryloyloxy-hexyloxy) biphenyl-4-yl oxy) hexyl ester (AHBH). The obtained dry networks were characterized by differential scanning calorimetry, and immersed in an excess of a LMWLC solvent 4-cyano-4’-pentylbiphenyl (5CB), forming polymer gels. A detailed study by polarized optical microscopy allowed to determine the swelling degree of the gels and to follow the phase behavior of the solvent inside the polymer matrix in a wide range of temperature. It has been found that the gels undergo a sharp decrease of their swelling degree in response to an infinitesimal change of temperature. This finding adds new and interesting aspects on the actuators applications. We have subsequently explored the effect of different parameters on volume phase transition of these liquid crystalline materials. Such as the cross-linking density (CD), a nature of cross-linking agent and the photo initiator concentration.

Keywords: cross-linking density, liquid crystalline elastomers, phase diagrams, swelling

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Authors: A. Amirouche, M. Mouzali, D. C. Watts

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During polymerization of dental composites, the volumic shrinkage is related to the conversion degree. The variation of the volumic shrinkage (S max according to the degree of conversion CD.), was examined for the experimental composites: (BisGMA/TEGDMA): (50/50), (75/25), (25/75) mixed with seven radiopac fillers: La2O3, BaO, BaSO4, SrO, ZrO2 , SrZrO3 and BaZrO 3 with different contents in weight, from 0 to 80%. We notice that whatever the filler and the composition in monomers, Smax increases with the increase in CD. This variation is, linear in particular in the case of the fillers containing only one heavy metal, and that whatever the composition in monomers. For a given salt, the increase of BisGMA composition leads to significant increase of S max more pronounced than the increase in CD. The variation of ratio (S max / CD.) with the increase of filler content is negligible. However the fillers containing two types of heavy metals have more effect on the volumic shrinkage than on the degree of conversion. Whatever the composition in monomer, and the content of filler containing only one heavy atom, S max increases with the increase in CD. Nevertheless, S max is affected by the viscosity of the medium compared with CD. For high percentages of mineral fillers (≥ 70% in weight), the diagrams S max according to CD are deviated of the linearity, owing to the fact that S max is affected by the high percentage of fillers compared with CD. The number of heavy atoms influences directly correlation (S max / CD.). In the case of the two mineral fillers: SrZrO3 and BaZrO3 ratio (S max / CD) moves away from the proportionality. The linearity of the diagrams Smax according to CD is less regular, due to the viscosity of high content of BisGMA. The study of Smax and DC of four commercial composites are presented and compared to elaborate experimental composites.

Keywords: Dental composites, degree of conversion, volumic shrinkage, photopolymerization

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Authors: Alireza Nikravanshallmani, Jamshid Dehmeshki, Mojtaba Ahmadi

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Modeling of business processes, based on BPMN (Business Process Modeling Notation), helps analysts and managers to understand business processes, and, identify their shortages. These models provide a context to make rational decision of organizing business processes activities in an understandable manner. The purpose of this paper is to provide a framework for better understanding of business processes and their problems by reducing the cognitive load of displayed information for their audience at different managerial levels while keeping the essential information which are needed by them. For this reason, we integrate business process diagrams across the different managerial levels to develop a framework to improve the performance of business process management (BPM) projects. The proposed framework is entitled ‘Business process improvement framework based on managerial levels (BPIML)’. This framework, determine a certain type of business process diagrams (BPD) based on BPMN with respect to the objectives and tasks of the various managerial levels of organizations and their roles in BPM projects. This framework will make us able to provide the necessary support for making decisions about business processes. The framework is evaluated with a case study in a real business process improvement project, to demonstrate its superiority over the conventional method. A questionnaire consisted of 10 questions using Likert scale was designed and given to the participants (managers of Bank Refah Kargaran three managerial levels). By examining the results of the questionnaire, it can be said that the proposed framework provide support for correct and timely decisions by increasing the clarity and transparency of the business processes which led to success in BPM projects.

Keywords: business process management (BPM), business process modeling, business process reengineering (BPR), business process optimizing, BPMN

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Authors: Habtamu Anagaw Muluneh, Gebregziabher Kahsay, Tamiru Negussie

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Theoretical study of the density of state, condensation energy, specific heat, and magnetization in a spin-triplet superconductor are the main goals of this work. Utilizing the retarded double-time temperature-dependent Green's function formalism and building a model Hamiltonian for the system at hand, we were able to derive the expressions for the parameters mentioned above. The phase diagrams are plotted using MATLAB scripts. From the phase diagrams, the density of electrons increases as the excitation energy increases, and the maximum excitation energy is equal to the superconducting gap, but it decreases when the value exceeds the gap and finally becomes the same as the density of the normal state. On the other hand, the condensation energy decreases with the increase in temperature and attains its minimum value at the superconducting transition temperature but increases with the increase in superconducting transition temperature (TC) and finally becomes zero, implying the superconducting energy is equal to the normal state energy. The specific heat increases with the increase in temperature, attaining its maximum value at the TC and then undergoing a jump, showing the presence of a second-order phase transition from the superconducting state to the normal state. Finally, the magnetization of both the itinerant and localized electrons decreases with the increase in temperature and finally becomes zero at TC = 1.6 K and magnetic phase transition temperature T = 2 K, respectively, which results in a magnetic phase transition from a ferromagnetic to a paramagnetic state. Our finding is in good agreement with the previous findings.

Keywords: spin triplet superconductivity, Green’s function, condensation energy, density of state, specific heat, magnetization

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Authors: Marine Regnier, Pascal Bost, Matthieu Horgnies

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Some of the problems to be solved for the concrete industry are linked to the use of low-reactivity cement, the hardening of concrete under cold-weather and the manufacture of pre-casted concrete without costly heating step. The development of these applications needs to accelerate the hydration kinetics, in order to decrease the setting time and to obtain significant compressive strengths as soon as possible. The mechanisms enhancing the hydration kinetics of alite or Portland cement (e.g. the creation of nucleation sites) were already studied in literature (e.g. by using distinct additions such as titanium dioxide nanoparticles, calcium carbonate fillers, water-soluble polymers, C-S-H, etc.). However, the goal of this study was to establish a clear ranking of the efficiency of several types of additions by using a robust and reproducible methodology based on isothermal calorimetry (performed at 20°C). The cement was a CEM I 52.5N PM-ES (Blaine fineness of 455 m²/kg). To ensure the reproducibility of the experiments and avoid any decrease of the reactivity before use, the cement was stored in waterproof and sealed bags to avoid any contact with moisture and carbon dioxide. The experiments were performed on Portland cement pastes by using a water-to-cement ratio of 0.45, and incorporating different compounds (industrially available or laboratory-synthesized) that were selected according to their main composition and their specific surface area (SSA, calculated using the Brunauer-Emmett-Teller (BET) model and nitrogen adsorption isotherms performed at 77K). The intrinsic effects of (i) dry powders (e.g. fumed silica, activated charcoal, nano-precipitates of calcium carbonate, afwillite germs, nanoparticles of iron and iron oxides , etc.), and (ii) aqueous solutions (e.g. containing calcium chloride, hydrated Portland cement or Master X-SEED 100, etc.) were investigated. The influence of the amount of addition, calculated relatively to the dry extract of each addition compared to cement (and by conserving the same water-to-cement ratio) was also studied. The results demonstrated that the X-SEED®, the hydrated calcium nitrate, the calcium chloride (and, at a minor level, a solution of hydrated Portland cement) were able to accelerate the hydration kinetics of Portland cement, even at low concentration (e.g. 1%wt. of dry extract compared to cement). By using higher rates of additions, the fumed silica, the precipitated calcium carbonate and the titanium dioxide can also accelerate the hydration. In the case of the nano-precipitates of calcium carbonate, a correlation was established between the SSA and the accelerating effect. On the contrary, the nanoparticles of iron or iron oxides, the activated charcoal and the dried crystallised hydrates did not show any accelerating effect. Future experiments will be scheduled to establish the ranking of these additions, in terms of accelerating effect, by using low-reactivity cements and other water to cement ratios.

Keywords: acceleration, hydration kinetics, isothermal calorimetry, Portland cement

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Authors: Giorgi Chichinadze, David Shengelia, Tamara Tsutsunava, Nikoloz Maisuradze, Giorgi Beridze

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The Jalovchat gabbro intrusive is exposed on the northern and southern slopes of Main Range zone of the Greater Caucasus, on an area about 25km2. It is intruded in Precambrian crystalline schists and amphibolites intensively metamorphose them along the contact zone. The intrusive is represented by hornblende-bearing gabbro, gabbro-norites and norites including thin vein bodies of gabbro-pegmatites, anorthosites and micro-gabbros. Especially should be noted the veins of gabbro-pegmatites with the gigantic (up to 0.5m) hornblende crystals. From this point of view, the Jalovchat gabbroid intrusive is particularly interesting and by its unusual composition has no analog in the Caucasus overall. The comprehensive petrologic and geochemical study of the intrusive was carried out by the authors. The results of investigations are following. Amphiboles correspond to magnesiohastingsite and magnesiohornblende. In hastingsite and hornblende as a result of isovalent isomorphism of Fe2+ by Mg, content of the latter has been increased. By AMF and Na20+K diagrams the intrusive rocks correspond to tholeiitic basalts or to basalts close to it by composition. According to ACM-AMF double diagram the samples distributed in the fields of MORB and alkali cumulates. In TiO2/FeO+Fe2O3, Zr/Y-Zr and Ti-Cr/Ni diagrams and Ti-Cr-Y triangular diagram samples are arranged in the fields of island-arc and mid-oceanic basalts or along the trends reflecting mid-oceanic ridges or island arcs. K2O/TiO2 diagram shows that these rocks belong to normal and enriched MORB type. According to Th/Nb/Y ratio, the Jalovchat intrusive composition corresponds to depleted mantle, but by Sm/Y-Ce/Sm - to the MORB area. Th/Y and Nb/Y ratios coincide with the MORB composition, Th/Yb-Ta/Yb and La/Nb-Ti ratios correspond to N MORB, and Rb/Y and N/Y - to the lower crust formations. Exceptional are Ce/Pb-Ce and Nb/Th-Nb diagrams, showing the area of primitive mantle. Spidergrams are characterized by almost horizontal trend, weakly expressed Eu minimums and by a slight depletion of light REE. Similar are characteristic of typical tholeiit basalts. In comparison to MORB spidergrams, they are characterized by depletion of light REE. Their correlation to the spidergrams of Jalovchat intrusive proves that they are more depleted. The above cited points to the gradual depletion of mantle with the light REE in geological time. The RE and REE diagrams reveal unexpected regularity. In particular, petro-geochemical characteristics of Jalovchat gabbroid intrusive predominantly correspond to MORB, that usually is an anomalous phenomenon, since in ‘ophiolitic’ section magmatic formations represented mainly by gigantic prismatic hornblende-bearing gabbro and gabbro-pegmatite are not indicated. On the basis of petro-mineralogical and petro-geochemical data analysis, the authors consider that the Jalovchat intrusive belongs to the subduction geodynamic type. In the depleted mantle rich in water the MORB rock system has subducted, where the favorable conditions for crystallization of hornblende and especially for its gigantic crystals occurred. It is considered that the Jalovchat intrusive was formed in deep horizons of the Earth’s crust as a result of crystallization of water-bearing Bajocian basalt magma.

Keywords: The Greater Caucasus, gabbro-pegmatite, hornblende-bearing gabbro, petrogenesis

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Authors: H. Shokouhmand, H. Sobhani, B. Sajadi, M. Degheh

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In recent years, experimental and numerical investigation of water UV reactors has increased significantly. The main drawback of experimental methods is confined and expensive survey of UV reactors features. In this study, a CFD model utilizing the eulerian-lagrangian framework is applied to analysis the disinfection performance of a closed conduit reactor which contains four UV lamps perpendicular to the flow. A discrete ordinates (DO) model was employed to evaluate the UV irradiance field. To investigate the importance of each of lamps on the inactivation performance, in addition to the reference model (with 4 bright lamps), several models with one or two bright lamps in various arrangements were considered. All results were reported in three inactivation kinetics. The results showed that the log inactivation of the two central bright lamps model was between 88-99 percent, close to the reference model results. Also, whatever the lamps are closer to the main flow region, they have more effect on microbial inactivation. The effect of some operational parameters such as water flow rate, inlet water temperature, and lamps power were also studied.

Keywords: Eulerian-Lagrangian framework, inactivation kinetics, log inactivation, water UV reactor

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Authors: Bikram K. Das, Kalyan K. Chattopadhyay

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The advent of 2-D materials in the last decade has induced a fresh spur of growth in fuel cell technology as these materials have some highly promising traits that can be exploited to felicitate Oxygen Reduction Reaction (ORR) in an efficient way. Among the various 2-D carbon materials, graphyne (Gy) and graphdiyne (Gdy)1 with their intrinsic non-uniform charge distribution holds promises in this purpose and it is expected2 that substitutional Nitrogen (N) doping could further enhance their efficiency. In this regard, dispersive force corrected density functional theory is used to map the oxygen reduction reaction (ORR) kinetics of five different kinds of N doped graphyne and graphdiyne systems (namely αGy, βGy, γGy, RGy and 6,6,12Gy and Gdy) in alkaline medium. The best doping site for each of the Gy/ Gdy system is determined comparing the formation energies of the possible doping configurations. Similarly, the best di-oxygen (O₂) adsorption sites for the doped systems are identified by comparing the adsorption energies. O₂ adsorption on all N doped Gy/ Gdy systems is found to be energetically favorable. ORR on a catalyst surface may occur either via the Eley-Rideal (ER) or the Langmuir–Hinschelwood (LH) pathway. Systematic studies performed on the considered systems reveal that all of them favor the ER pathway. Further, depending on the nature of di-oxygen adsorption ORR can follow either associative or dissociative mechanism; the possibility of occurrence of both the mechanisms is tested thoroughly for each N doped Gy/ Gdy. For the ORR process, all the Gy/Gdy systems are observed to prefer the efficient four-electron pathway but the expected monotonically exothermic reaction pathway is found only for N doped 6,6,12Gy and RGy following the associative pathway and for N doped βGy, γGy and Gdy following the dissociative pathway. Further computation performed for these systems reveals that for N doped 6,6,12Gy, RGy, βGy, γGy and Gdy the overpotentials are 1.08 V, 0.94 V, 1.17 V, 1.21 V and 1.04 V respectively depicting N doped RGy is the most promising material, to carry out ORR in alkaline medium, among the considered ones. The stability of the ORR intermediate states with the variation of pH and electrode potentials is further explored with Pourbiax diagrams and the activities of these systems in the alkaline medium are compared with the prior reported B/N doped identical systems for ORR in an acidic medium in terms of a common descriptor.

Keywords: graphdiyne, graphyne, nitrogen-doped, ORR

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Authors: Tumisang Seodigeng, Hilary Rutto

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In this study we investigate the use of a laboratory batch digester to derive kinetic parameters for anaerobic digestion of garden grass and cattle dung. Laboratory experimental data from a 5 liter batch digester operating at mesophilic temperature of 32 C is used to derive parameters for Michaelis-Menten kinetic model. These fitted kinetics are further used to predict the scale-up parameters of a batch digester using DynoChem modeling and scale-up software. The scale-up model results are compared with performance data from 20 liter, 50 liter, and 200 liter batch digesters. Michaelis-Menten kinetic model shows to be a very good and easy to use model for kinetic parameter fitting on DynoChem and can accurately predict scale-up performance of 20 liter and 50 liter batch reactor based on parameters fitted on a 5 liter batch reactor.

Keywords: Biogas, kinetics, DynoChem Scale-up, Michaelis-Menten

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Authors: Tatiana R. Simonyan, Elena A. Protasova, Anastasia V. Mamontova, Eugene G. Maksimov, Konstantin A. Lukyanov, Alexey M. Bogdanov

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Here, we describe two variants of the calcium indicators based on the GCaMP sensitive core and BrUSLEE fluorescent protein (GCaMP-BrUSLEE and GCaMP-BrUSLEE-145). In contrast to the conventional GCaMP6-family indicators, these fluorophores are characterized by the well-marked responsiveness of their fluorescence decay kinetics to external calcium concentration both in vitro and in cellulo. Specifically, we show that the purified GCaMP-BrUSLEE and GCaMP-BrUSLEE-145 exhibit three-component fluorescence decay kinetics, with the amplitude-normalized lifetime component (t3*A3) of GCaMP-BrUSLEE-145 changing four-fold (500-2000 a.u.) in response to a Ca²⁺ concentration shift in the range of 0—350 nM. Time-resolved fluorescence microscopy of live cells displays the two-fold change of the GCaMP-BrUSLEE-145 mean lifetime upon histamine-stimulated calcium release. The aforementioned Ca²⁺-dependence calls considering the GCaMP-BrUSLEE-145 as a prospective Ca²⁺-indicator with the signal read-out in the time domain.

Keywords: calcium imaging, fluorescence lifetime imaging microscopy, fluorescent proteins, genetically encoded indicators

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Authors: Nicolas Bigot, M'hamed Boutaous, Nahiene Hamila, Shihe Xin

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Composite materials with polymer matrices are widely used in most industrial areas, particularly in aeronautical and automotive ones. Thanks to the development of a high-performance thermoplastic semicrystalline polymer matrix, those materials exhibit more and more efficient properties. The polymer matrix in composite materials can manifest a specific crystalline structure characteristic of crystallization in a fibrous medium. In order to guarantee a good mechanical behavior of structures and to optimize their performances, it is necessary to define realistic mechanical constitutive laws of such materials considering their physical structure. The interaction between fibers and matrix is a key factor in the mechanical behavior of composite materials. Transcrystallization phenomena which develops in the matrix around the fibers constitute the interphase which greatly affects and governs the nature of the fiber-matrix interaction. Hence, it becomes fundamental to quantify its impact on the thermo-mechanical behavior of composites material in relationship with processing conditions. In this work, we propose a numerical model coupling the thermal and crystallization kinetics in long fiber-based composite materials, considering both the spherulitic and transcrystalline types of the induced structures. After validation of the model with comparison to results from the literature and noticing a good correlation, a parametric study has been led on the effects of the thermal kinetics, the fibers volume fractions, the deformation, and the pressure on the crystallization rate in the material, under processing conditions. The ratio of the transcrystallinity is highlighted and analyzed with regard to the thermal kinetics and gradients in the material. Experimental results on the process are foreseen and pave the way to establish a mechanical constitutive law describing, with the introduction of the role on the crystallization rates and types on the thermo-mechanical behavior of composites materials.

Keywords: composite materials, crystallization, heat transfer, modeling, transcrystallization

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Authors: Dheepshika Kodieswaran

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The persisting problem in the world that continuously impose our planet at risk is the increasing amounts of recalcitrant. One such issue is the disposal of the Petroleum Refinery Sludge (PRS) which constitutes hydrocarbons that are hazardous to terrestrial and aquatic life. The comparatively safe approach to handling these wastes is by microbial degradation, while the other chemical and physical methods are either expensive and/or produce secondary pollutants. The bacterial and algal systems have different pathways for the degradation of hydrocarbons, and their growth rates vary. This study shows how different bacterial and microalgal strains degrade the polyaromatic hydrocarbon PAHs individually and their symbiotic influence on degradation as well. In this system, the metabolites and gaseous exchange help each other in growth. This method using also aids in the accumulation of lipids in microalgal cells and from which bio-oils can also be extracted. The bacterial strains used in this experiment are reported to be indigenous strains isolated from PRS. The target PAH studied were anthracene and pyrene for a period of 28 days. The PAH degradation kinetics best fitted the Gompertz model, and the order of the kinetics, rate constants, and half-life was determined.

Keywords: petroleum refinery sludge, co-culturing, polycyclic hydrocarbons, microalgal-bacterial consortia

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Authors: Sujin Hong, Seokyoon Moon, Heejoong Kim, Yunseok Lee, Youngjune Park

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Gas hydrate is an inclusion compound in which a low-molecular-weight gas or organic molecule is trapped inside a three-dimensional lattice structure created by water-molecule via intermolecular hydrogen bonding. It is generally formed at low temperature and high pressure, and exists as crystal structures of cubic systems − structure I, structure II, and hexagonal system − structure H. Many efforts have been made to apply them to various energy and environmental fields such as gas transportation and storage, CO₂ capture and separation, and desalination of seawater. Particularly, studies on the behavior of gas hydrates by new organic materials for CO₂ storage and various applications are underway. In this study, thermodynamic and spectroscopic analyses of the gas hydrate system were performed focusing on cyclopentanol, an organic molecule that forms gas hydrate at relatively low pressure. The thermodynamic equilibria of CH₄ and CO₂ hydrate systems including cyclopentanol were measured and spectroscopic analyses of XRD and Raman were performed. The differences in thermodynamic systems and formation kinetics of CO₂ added cyclopentane, cyclopentanol and cyclopentanone hydrate systems were compared. From the thermodynamic point of view, cyclopentanol was found to be a hydrate promotor. Spectroscopic analyses showed that cyclopentanol formed a hydrate crystal structure of cubic structure II in the presence of CH₄ and CO₂. It was found that the differences in the functional groups among the organic guest molecules significantly affected the rate of hydrate formation and the total amounts of CO₂ stored in the hydrate systems. The total amount of CO₂ stored in the cyclopentanone hydrate was found to be twice that of the amount of CO₂ stored in the cyclopentane and the cyclopentanol hydrates. The findings are expected to open up new opportunity to develop the gas hydrate based wastewater desalination technology.

Keywords: gas hydrate, CO₂, separation, desalination, formation kinetics, thermodynamic equilibria

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Authors: Chukwudalu C. Nwazojie, Wole W. Soboyejo, John Obayemi, Ali Salifu Azeko, Sandra M. Jusu, Chinyerem M. Onyekanne

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The conventional methods for the diagnosis and treatment of breast cancer include bulk systematic mammography, ultrasound, dynamic contrast-enhanced fast 3D gradient-echo (GRE) magnetic resonance imaging (MRI), surgery, chemotherapy, and radiotherapy. However, nanoparticles and drug-loaded polymer microspheres for disease (cancer) targeting and treatment have enormous potential to enhance the approaches that are used today. The goal is to produce an implantable biomedical device for localized breast cancer drug delivery within Africa and the world. The main advantage of localized delivery is that it reduces the amount of drug that is needed to have a therapeutic effect. Polymer blends of poly (D,L-lactide-co-glycolide) (PLGA) and polycaprolactone (PCL), which are biodegradable, is used as a drug excipient. This work focuses on the development of PLGA-PCL (poly (D,L-lactide-co-glycolide) (PLGA) blended with based injectable drug microspheres and are loaded with anticancer drugs (prodigiosin (PG), and paclitaxel (PTX) control) and also the conjugated forms of the drug functionalized with LHRH (luteinizing hormone-releasing hormone) (PG-LHRH, and PTX- LHRH control), using a single-emulsion solvent evaporation technique. The encapsulation was done in the presence of PLGA-PCL (as a polymer matrix) and poly-(vinyl alcohol) (PVA) (as an emulsifier). Comparative study of the various drugs release kinetics and degradation mechanisms of the PLGA-PCL with an encapsulated drug is achieved, and the implication of this study is for the potential application of prodigiosin PLGA-PCL loaded microparticles for controlled delivery of cancer drug and treatment to prevent the regrowth or locoregional recurrence, following surgical resection of triple-negative breast tumor.

Keywords: cancer, polymers, drug kinetics, nanoparticles

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Authors: Eman H. El-Gamal, Mai E. Khedr, Randa Ghonim, Mohamed Rashad

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In the past few years, biochar - a highly carbon-rich material produced from agro-wastes by pyrolysis process - was used as an effective adsorbent for heavy metals removal from polluted water. In this study, different types of biochar (rice straw 'RSB', corn cob 'CCB', and Jatropha shell 'JSB' were used to evaluate the adsorption capacity of heavy metals removal from multiple-metal solutions (Cu, Mn, Zn, and Cd). Kinetics modeling has been examined to illustrate potential adsorption mechanisms. The results showed that the potential removal of metal is dependent on the metal and biochar types. The adsorption capacity of the biochars followed the order: RSB > JSB > CCB. In general, RSB and JSB biochars presented high potential removal of heavy metals from polluted water, which was higher than 90 and 80% after 2 hrs of contact time for all metals, respectively. According to the kinetics data, the pseudo-second-order model was agreed strongly with Cu, Mn, Zn, and Cd adsorption onto the biochars (R2 ≥ 0.97), indicating the dominance of specific adsorption process, i.e., chemisorption. In conclusion, this study revealed that RSB and JSB biochar have the potential to be a strong adsorbent for multiple-metal removal from wastewater.

Keywords: adsorption, biochar, chemisorption, polluted water

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Authors: Makhlouf Mourad, Messabih Sidi Mohamed, Bouchher Omar, Houali Farida, Benrachedi Khaled

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Mesoporous materials are very commonly used as adsorbent materials for removing phenolic compounds. However, the adsorption mechanism of these compounds is still poorly controlled. However, understanding the interactions mesoporous materials/adsorbed molecules is very important in order to optimize the processes of liquid phase adsorption. The difficulty of synthesis is to keep an orderly and cubic pore structure and achieve a homogeneous surface modification. The grafting of Si(CH₃)₃ was chosen, to transform hydrophilic surfaces hydrophobic surfaces. The aim of this work is to study the kinetics and thermodynamics of two volatile organic compounds VOC phenol (PhOH) and P hydroxy benzoic acid (4AHB) on a mesoporous material of type MCM-48 grafted with an organosilane of the Trimethylchlorosilane (TMCS) type, the material thus grafted or functionalized (hereinafter referred to as MCM-48-G). In a first step, the kinetic and thermodynamic study of the adsorption isotherms of each of the VOCs in mono-solution was carried out. In a second step, a similar study was carried out on a mixture of these two compounds. Kinetic models (pseudo-first order, pseudo-second order) were used to determine kinetic adsorption parameters. The thermodynamic parameters of the adsorption isotherms were determined by the adsorption models (Langmuir, Freundlich). The comparative study of adsorption of PhOH and 4AHB proved that MCM-48-G had a high adsorption capacity for PhOH and 4AHB; this may be related to the hydrophobicity created by the organic function of TMCS in MCM-48-G. The adsorption results for the two compounds using the Freundlich and Langmuir models show that the adsorption of 4AHB was higher than PhOH. The values ​​obtained by the adsorption thermodynamics show that the adsorption interactions for our sample with the phenol and 4AHB are of a physical nature. The adsorption of our VOCs on the MCM-48 (G) is a spontaneous and exothermic process.

Keywords: adsorption, kinetics, isotherm, mesoporous materials, Phenol, P-hydroxy benzoique acid

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Authors: Sergei Zhevnenko

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Сontinuous layer of tantalum boride is formed on the surface as a result of reactive wetting of oxidized tantalum by copper melt with boron at a temperatures above 1150 °C. An increase in the wetting temperature above 1400 °C leads to a change in the formation mechanism of tantalum borides, they are formed in the nanosized flakes. In the presented work, we studied the process of copper-based in-situ composite formation, strengthened by the particles of tantalum borides. We investigated the structure of the formed particles, the conditions, and the kinetics of their formation. Dissolving boride particles do not have time to mix uniformly in the melt upon sufficiently rapid cooling and form a macrostructure, partly repeating the shape of the metallic tantalum. This allows to set different gradient structures in the copper alloy. Such macrostructures have been obtained. Boride particles and microstructures were studied by scanning and transmission electron microscopy, and regions with particles were investigated by nanoindentation. In this work, we also measured the kinetics of impregnation of porous tantalum with copper-boron melt and studied the structures of the composite, in which the melt filling the interpore space is saturated with boride particles.

Keywords: copper, tantalum borides, in-situ composites, wetting, imbibition

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Authors: Jihane Saad, Thomas Lendormi, Caroline Le Marechal, Anne-marie Pourcher, Céline Druilhe, Jean-louis Lanoiselle

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Agricultural anaerobic digestion consists in the conversion of animal slurry and manure into biogas and digestate. They need, however, to be treated at 70 ºC during 60 min before anaerobic digestion according to the European regulation (EC n°1069/2009 & EU n°142/2011). The impact of such heat treatment on the outcome of bacteria has been poorly studied up to now. Moreover, a recent study¹ has shown that enterococci and clostridia are still detected despite the application of such thermal treatment, questioning the relevance of this approach for the hygienisation of digestate. The aim of this study is to establish the heat inactivation kinetics of two species of enterococci (Enterococcus faecalis and Enterococcus faecium) and two species of clostridia (Clostridioides difficile and Clostridium novyi as a non-toxic model for Clostridium botulinum of group III). A pure culture of each strain was prepared in a specific sterile medium at concentration of 10⁴ – 10⁷ MPN / mL (Most Probable number), depending on the bacterial species. Bacterial suspensions were then filled in sterilized capillary tubes and placed in a water or oil bath at desired temperature for a specific period of time. Each bacterial suspension was enumerated using a MPN approach, and tests were repeated three times for each temperature/time couple. The inactivation kinetics of the four indicator bacteria is described using the Weibull model and the classical Bigelow model of first-order kinetics. The Weibull model takes biological variation, with respect to thermal inactivation, into account and is basically a statistical model of distribution of inactivation times as the classical first-order approach is a special case of the Weibull model. The heat treatment at 70 ºC / 60 min contributes to a reduction greater than 5 log10 for E. faecium and E. faecalis. However, it results only in a reduction of about 0.7 log10 for C. difficile and an increase of 0.5 log10 for C. novyi. Application of treatments at higher temperatures is required to reach a reduction greater or equal to 3 log10 for C. novyi (such as 30 min / 100 ºC, 13 min / 105 ºC, 3 min / 110 ºC, and 1 min / 115 ºC), raising the question of the relevance of the application of heat treatment at 70 ºC / 60 min for these spore-forming bacteria. To conclude, the heat treatment (70 ºC / 60 min) defined by the European regulation is sufficient to inactivate non-sporulating bacteria. Higher temperatures (> 100 ºC) are required as far as spore-forming bacteria concerns to reach a 3 log10 reduction (sporicidal activity).

Keywords: heat treatment, enterococci, clostridia, inactivation kinetics

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Authors: C. Mekala, Indumathi M. Nambi

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Nitrogen pollution in groundwater arising from wastewater and fertilizer application through vadose zone is a major problem and it causes a prime risk to groundwater based drinking water supplies. Nitrogenous compounds namely ammonium, nitrate and nitrite fate and transport in soil subsurface were studied experimentally. The major process like sorption, leaching, biotransformation involving microbial growth kinetics, and biological clogging due to biomass growth were assessed and modeled with advection-dispersion reaction equations for ammonium, nitrate and acetate in a saturated, heterogeneous soil medium. The transport process was coupled with freundlich sorption and monod inhibition kinetics for immobile bacteria and permeability reduction due to biomass growth will be verified and validated with the numerical model. This proposed mathematical model will be very helpful in the development of a management model for a sustainable and safe wastewater reuse strategies such as irrigation and groundwater recharge.

Keywords: nitrogen species transport, transformation, biological clogging, biokinetic parameters, contaminant transport model, saturated soil

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Authors: Niharika Keot, Manabendra Sarma

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A thorough investigation of Ln3+ complexes with more than one inner-sphere water molecule is crucial for designing high relaxivity contrast agents (CAs) used in magnetic resonance imaging (MRI). This study accomplished a comparative stability analysis of two hexadentate (H3cbda and H3dpaa) and two heptadentate (H4peada and H3tpaa) ligands with Ln3+ ions. The higher stability of the hexadentate H3cbda and heptadentate H4peada ligands has been confirmed by the binding affinity and Gibbs free energy analysis in aqueous solution. In addition, energy decomposition analysis (EDA) reveals the higher binding affinity of the peada4− ligand than the cbda3− ligand towards Ln3+ ions due to the higher charge density of the peada4− ligand. Moreover, a mechanistic overview of water exchange kinetics has been carried out based on the strength of the metal–water bond. The strength of the metal–water bond follows the trend Gd–O47 (w) > Gd–O39 (w) > Gd–O36 (w) in the case of the tris-aquated [Gd(cbda)(H2O)3] and Gd–O43 (w) > Gd–O40 (w) for the bis-aquated [Gd(peada)(H2O)2]− complex, which was confirmed by bond length, electron density (ρ), and electron localization function (ELF) at the corresponding bond critical points. Our analysis also predicts that the activation energy barrier decreases with the decrease in bond strength; hence kex increases. The 17O and 1H hyperfine coupling constant values of all the coordinated water molecules were different, calculated by using the second-order Douglas–Kroll–Hess (DKH2) approach. Furthermore, the ionic nature of the bonding in the metal–ligand (M–L) bond was confirmed by the Quantum Theory of Atoms-In-Molecules (QTAIM) and ELF along with energy decomposition analysis (EDA). We hope that the results can be used as a basis for the design of highly efficient Gd(III)-based high relaxivity MRI contrast agents for medical applications.

Keywords: MRI contrast agents, lanthanide chemistry, thermodynamic stability, water exchange kinetics

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Authors: Sameena Malik, Ghosh Prakash, Sandeep Mudliar, Vishal Waindeskar, Atul Vaidya

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In this study, the biodegradability enhancement along with COD color and toxicity removal of pharmaceutical effluent by O₃, O₃/Fe²⁺, O₃/nZVI processes has been evaluated. The nZVI particles were synthesized and characterized by XRD and SEM analysis. Kinetic model was reasonably developed to select the ozone doses to be applied based on the ozonation kinetic and mass transfer coefficient values. Nano catalytic ozonation process (O₃/nZVI) effectively enhanced the biodegradability (BI=BOD₅/COD) of pharmaceutical effluent up to 0.63 from 0.18 of control with a COD, color and toxicity removal of 62.3%, 93%, and 75% respectively compared to O₃, O₃/Fe²⁺ pretreatment processes. From the GC-MS analysis, 8 foremost organic compounds were predominantly detected in the pharmaceutical effluent. The disappearance of the corresponding GC-MS spectral peaks during catalyzed ozonation process indicated the degradation of the effluent. The changes in the FTIR spectra confirms the transformation/destruction of the organic compounds present in the effluent to new compounds. Subsequent aerobic biodegradation of pretreated effluent resulted in biodegradation rate enhancement by 5.31, 2.97, and 1.22 times for O₃, O₃/Fe²⁺ and O₃/nZVI processes respectively.

Keywords: iron nanoparticles, pharmaceutical effluent, ozonation, kinetics, mass transfer

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Authors: Melike Sultan Karasu Asnaz, Ayse Ozdogan Dolcek

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Crop drying, which aims to reduce the moisture content to a certain level, is a method used to extend the shelf life and prevent it from spoiling. One of the oldest food preservation techniques is open sunor shade drying. Even though this technique is the most affordable of all drying methods, there are some drawbacks such as contamination by insects, environmental pollution, windborne dust, and direct expose to weather conditions such as wind, rain, hail. However, solar dryers that provide a hygienic and controllable environment to preserve food and extend its shelf life have been developed and used to dry agricultural products. Thus, foods can be dried quickly without being affected by weather variables, and quality products can be obtained. This research is mainly devoted to investigating the modelling of drying kinetics of cantaloupe in a forced convection solar dryer. Mathematical models for the drying process should be defined to simulate the drying behavior of the foodstuff, which will greatly contribute to the development of solar dryer designs. Thus, drying experiments were conducted and replicated five times, and various data such as temperature, relative humidity, solar irradiation, drying air speed, and weight were instantly monitored and recorded. Moisture content of sliced and pretreated cantaloupe were converted into moisture ratio and then fitted against drying time for constructing drying curves. Then, 10 quasi-theoretical and empirical drying models were applied to find the best drying curve equation according to the Levenberg-Marquardt nonlinear optimization method. The best fitted mathematical drying model was selected according to the highest coefficient of determination (R²), and the mean square of the deviations (χ^²) and root mean square error (RMSE) criterial. The best fitted model was utilized to simulate a thin layer solar drying of cantaloupe, and the simulation results were compared with the experimental data for validation purposes.

Keywords: solar dryer, mathematical modelling, drying kinetics, cantaloupe drying

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Authors: Madhuresh Dwivedi, Navneet Singh Deora, Aastha Deswal, H. N. Mishra

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FT-NIR spectroscopy and electronic nose was used to study the kinetics of dough proofing. Spectroscopy was conducted with an optic probe in the diffuse reflectance mode. The dough leavening was carried out at different temperatures (25 and 35°C) and constant RH (80%). Spectra were collected in the range of wave numbers from 12,000 to 4,000 cm-1 directly on the samples, every 5 min during proofing, up to 2 hours. NIR spectra were corrected for scatter effect and second order derivatization was done to transform the spectra. Principal component analysis (PCA) was applied for the leavening process and process kinetics was calculated. PCA was performed on data set and loadings were calculated. For leavening, four absorption zones (8,950-8,850, 7,200-6,800, 5,250-5,150 and 4,700-4,250 cm-1) were involved in describing the process. Simultaneously electronic nose was also used for understanding the development of odour compounds during fermentation. The electronic nose was able to differential the sample on the basis of aroma generation at different time during fermentation. In order to rapidly differentiate samples based on odor, a Principal component analysis is performed and successfully demonstrated in this study. The result suggests that electronic nose and FT-NIR spectroscopy can be utilized for the online quality control of the fermentation process during leavening of bread dough.

Keywords: FT-NIR, dough, e-nose, proofing, principal component analysis

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Authors: Christian Fercher, Jiaul Islam, Simon R. Corrie

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Fluorescence-based immunodiagnostics are an emerging field in biosensor development and exhibit several advantages over traditional detection methods. While various affinity biosensors have been developed to generate a fluorescence signal upon sensing varying concentrations of analytes, reagentless, reversible, and continuous monitoring of complex biological samples remains challenging. Here, we aimed to genetically engineer biosensors based on single-chain antibody fragments (scFv) that are site-specifically labeled with environmentally sensitive fluorescent unnatural amino acids (UAA). A rational design approach resulted in quantifiable analyte-dependent changes in peak fluorescence emission wavelength and enabled antigen detection in vitro. Incorporation of a polarity indicator within the topological neighborhood of the antigen-binding interface generated a titratable wavelength blueshift with nanomolar detection limits. In order to ensure continuous analyte monitoring, scFv candidates with fast binding and dissociation kinetics were selected from a genetic library employing a high-throughput phage display and affinity screening approach. Initial rankings were further refined towards rapid dissociation kinetics using bio-layer interferometry (BLI) and surface plasmon resonance (SPR). The most promising candidates were expressed, purified to homogeneity, and tested for their potential to detect biomarkers in a continuous microfluidic-based assay. Variations of dissociation kinetics within an order of magnitude were achieved without compromising the specificity of the antibody fragments. This approach is generally applicable to numerous antibody/antigen combinations and currently awaits integration in a wide range of assay platforms for one-step protein quantification.

Keywords: antibody engineering, biosensor, phage display, unnatural amino acids

Procedia PDF Downloads 146