International Science Index

International Journal of Chemical and Molecular Engineering

Laminar Periodic Vortex Shedding over a Square Cylinder in Pseudoplastic Fluid Flow
Pseudoplastic (n < 1, n being the power index) fluid flow can be found in food, pharmaceutical and process industries and has very complex flow nature. To our knowledge, inadequate research work has been done in this kind of flow even at very low Reynolds numbers. Here, in the present computation, we have considered unsteady laminar flow over a square cylinder in pseudoplastic flow environment. For Newtonian fluid flow, this laminar vortex shedding range lies between Re = 47-180. In this problem, we consider Re = 100 (Re = U∞ a/ ν, U∞ is the free stream velocity of the flow, a is the side of the cylinder and ν is the kinematic viscosity of the fluid). The pseudoplastic fluid range has been chosen from close to the Newtonian fluid (n = 0.8) to very high pseudoplasticity (n = 0.1). The flow domain is constituted using Gambit 2.2.30 and this software is also used to generate mesh and to impose the boundary conditions. For all places, the domain size is considered as 36a × 16a with 280 ×192 grid point in the streamwise and flow normal directions respectively. The domain and the grid points are selected after a thorough grid independent study at n = 1.0. Fine and equal grid spacing is used close to the square cylinder to capture the upper and lower shear layers shed from the cylinder. Away from the cylinder the grid is unequal in size and stretched out in all direction. Velocity inlet (u = U∞), pressure outlet (Neumann condition), symmetry (free-slip boundary condition du/dy = 0, v = 0) at upper and lower domain boundary conditions are used for this simulation. Wall boundary (u = v = 0) is considered on the square cylinder surface. Fully conservative 2-D unsteady Navier-Stokes equations are discretized and then solved by Ansys Fluent 14.5 to understand the flow nature. SIMPLE algorithm written in finite volume method is selected for this purpose which is the default solver in scripted in Fluent. The result obtained for Newtonian fluid flow agrees well with previous work supporting Fluent’s usefulness in academic research. A minute analysis of instantaneous and time averaged flow field is obtained both for Newtonian and pseudoplastic fluid flow. It has been observed that drag coefficient increases continuously with the reduced value of n. Also, the vortex shedding phenomenon changes at n = 0.4 due to flow instability. These are some of the remarkable findings for laminar periodic vortex shedding regime in pseudoplastic flow environment.
Effect of Cognitive Rehabilitation in Pediatric Population with Acquired Brain Injury: A Pilot Study
Acquired brain injury (ABI) is any physical and functional injury secondary to events that affect the brain tissue. It is one of the biggest causes of disability in the world and it has a high annual incidence in the pediatric population. There are several causes of ABI such as traumatic brain injury, central nervous system infection, stroke, hypoxia, tumors and others. The consequences can be cognitive, behavioral, emotional and functional. The cognitive rehabilitation is necessary to achieve the best outcomes for pediatric people with ABI. Cognitive orientation to daily occupational performance (CO-OP) is an individualized client-centered, performance-based, problem-solving approach that focuses on the strategy used to support the acquisition of three client-chosen goals. It has demonstrated improvements in the pediatric population with other neurological disorder but not in Spanish speakers with ABI. Aim: The main objective of this study was to determine the efficacy of cognitive orientation to daily occupational performances (CO-OP) adapted to Spanish speakers, in the level of independence and behavior in a pediatric population with ABI. Methods: Case studies with measure pre/post-treatment were used in three children with ABI, sustained at least before 6 months assessment, in school, aged 8 to 16 years, age ABI after 6 years old and above average intellectual ability. Twelve sessions of CO-OP adapted to Spanish speakers were used and videotaped. The outcomes were based on cognitive, behavior and functional independence measurements such as Child Behavior Checklist (CBCL), Behavior Rating Inventory of Executive Function (BRIEF), The Vineland Adaptive Behavior Scales (VINELAND, Social Support Scale (MOS-SSS) and others neuropsychological measures. This study was approved by the ethics committee of Universidad del Norte in Colombia. Informed parental written consent was obtained for all participants. Results: children were able to identify three goals and use the global strategy ‘goal-plan-do-check’ during each session. Verbal self-instruction was used by all children. CO-OP showed a clinically significant improvement in goals regarding with independence level and behavior according to parents and teachers. Conclusion: The results indicated that CO-OP and the use of a global strategy such as ‘goal-plan-do-check’ can be used in children with ABI in order to improve their specific goals. This is a preliminary version of a big study carrying in Colombia as part of the experimental design.
Ultrathin Tin-Silicalite 1 Zeolite Membrane in Ester Solvent Recovery
Ester solvents are widely used in pharmaceutical, printing and flavor industry due to their good miscibility, low toxicity, and high volatility. Through pervaporation, these ester solvents can be recovered from industrial wastewater. While metal-doped silicalite 1 zeolite membranes are commonly used in organic solvent recovery in the pervaporation process, these ceramic membranes suffer from low membrane permeation flux, mainly due to the high thickness of the metal-doped zeolite membrane. Herein, a simple method of fabricating an ultrathin tin-silicalite 1 membrane supported on alumina tube is reported. This ultrathin membrane is able to achieve high permeation flux and separation factor for an ester in a diluted aqueous solution. Nanosized tin-Silicalite 1 seeds which are smaller than 500nm has been formed through hydrothermal synthesis. The sn-Silicalite 1 seeds were then seeded onto alumina tube through dip coating, and the tin-Silicalite 1 membrane was then formed by hydrothermal synthesis in an autoclave through secondary growth method. Multiple membrane synthesis factors such as seed size, ceramic substrate surface pore size selection, and secondary growth conditions were studied for their effects on zeolite membrane growth. The microstructure, morphology and the membrane thickness of tin-Silicalite 1 zeolite membrane were examined. The membrane separation performance and stability will also be reported.
Enhancement in Bactericidal Activity of Hydantoin Based Microsphere from Smooth to Rough
There have been several attempts to prepare polymers with antimicrobial properties by doping with various N-halamines. Hydantoins (Cyclic N-halamine) is of importance due to their stability rechargeable chloroamide function, broad-spectrum anti-microbial action and ability to prevent resistance to the organisms. Polymerizable hydantoins are synthesized by tethering vinyl moieties to 5,5,-dialkyl hydantoin sacrificing the imide hydrogen in the molecule thereby restricting the halogen capture only to the amide nitrogen that results in compromised antibacterial activity. In order to increase the activity of the antimicrobial polymer, we have developed a scheme to maximize the attachment of chlorine to the amide and the imide moieties of hydantoin. Vinyl hydantoin monomer, (Z)-5-(4-((3-methylbuta-1,3-dien-2-yl)oxy)benzylidene)imidazolidine-2,4-dione (MBBID) was synthesized and copolymerized with a commercially available monomer, methyl methacrylate, by free radical polymerization. The antimicrobial activity of hydantoin is strongly dependent on their surface area and hence their microbial activity increases when incorporated in microspheres or nanoparticles as compared to their bulk counterpart. In this regard, smooth and rough surface microsphere of the vinyl monomer (MBBID) with commercial monomer was synthesized. The oxidative chlorine content of the copolymer ranged from 1.5 to 2.45 %. Further, to demonstrate the water purification potential, the thin column was packed with smooth or rough microspheres and challenged with simulated contaminated water that exhibited 6 log kill (total kill) of the bacteria in 20 minutes of exposure with smooth (25 mg/ml) and rough microsphere (15.0 mg/ml).
Solvent Recovery via Zinc Oxide and Metal Organic Framework Nanocomposite on the Ceramic Support Using Pervaporation Method
Solvent recovery process is becoming very popular, which not only recover and reuse the costly solvents, but also eco-friendly and curtail the rising production costs in many industries such as petrochemical and pharmaceuticals. Pervaporation method has been widely used for a varieties of separations such as azeotropic mixtures, close-boiling mixtures, heat-sensitive mixtures, isomers, and volatile removal from fermentation broth. Polymeric- and ceramic membranes are used in the pervaporation (PV) process. When compared to the former, ceramic membranes are promising material due to their relatively high chemical- and thermal resistances. When compared to other metal–organic frameworks (MOFs) that has been studied in membrane separation, Zeolitic imidazolate frameworks (ZIFs, tetrahedral metal ions bridged by Imidazolate linkers) are shown as promising materials due to their interesting structural topologies, stability and a facility to alter different sized pores. In this study, thin layers of ZnO2 and ZIFs were subsequently coated on to a porous and mechanically stable ceramic substrate. The packing density, thickness and distribution of seed layers and variation of permeation rate of solvent mixture (Isopropyl alcohol (IPA)/butyl acetate) with ZIF layer thickness and other parameters studied are highlighted. The seed and crystal growth of both ZnO2 and ZIF layers were characterized by SEM, XRD and other microscopic methods respectively. The chemical composition of ZIF films were studied by using X-ray absorption near-edge structure (XANES) spectroscopy.
A Socio-Technical Approach on Decentralisation for De-Carbonization in Tunisia
In the past few years, most Middle East North Africa (MENA) countries have rolled out national energy transition policies for the objective of decarbonising their energy systems. Meanwhile, several of them are also venturing into some form of decentralization. The linkages and dynamics between the two processes (decentralization and decarbonisation) remain understudied. This is especially the case in developing countries in the MENA, which on the one hand face tangible adverse climate change impacts and on the other suffer a challenging political landscape influencing the success of their public policy endeavors. The paper uses a content analysis methodology, focusing on the case study of Tunisia particularly the Local Authority code of 2018 and the updated version of the Tunisian Solar Plan 2012. This paper aims to look into how the recently initialed political decentralisation process empowers local communities to play an active role in the country’s energy transition. The paper finds that the decentralisation process prompted by a post-revolution democratization path since 2011 provides a window of opportunity for local authorities to take on an active role in advancing the energy transition on the local community and municipality level. However, this potential role needs to be initiated and claimed by the local authorities themselves which in turn necessitate a mobilization of the Tunisian civil society to raise awareness on energy literacy, call for capacity building and claim financial prerogatives for local communities to assume such roles.
Removal of Lead Ions from Aqueous Medium Using Devised Column Filters Packed with Chitosan from Trash Crab Shells: A Characterization Study
Chitosan is a promising biopolymer commonly found in crustacean shells that has plausible effects in water purification and wastewater treatment. It is a primary derivative of chitin and considered second of the most abundant biopolymer prior to cellulose. Morphological analysis had been done using Scanning Electron Microscopy with Energy Dispersive Microscopy (SEM/EDS), and due to its porous nature, it showcases a certain degree of porosity, hence, larger adsorption site of heavy metal. The Energy Dispersive Spectroscopy of the chitosan and ‘lead-bound’ chitosan, shows a relative increase of percent abundance of lead cation from 1.44% to 2.08% hence, adsorption occurs. Chitosan, as a nitrogenous polysaccharide, subjected to Fourier transform infrared spectroscopy (FTIR) analysis shows amide bands ranging from 1635.36 cm⁻¹ for amide 1 band and 1558.40 cm-1 for amide 2 band with NH stretching. For ‘lead-bound’ chitosan, the FT-IR analysis shows a change in peaks upon adsorption of Pb(II) cation. The spectrum shows broadening of OH and NH stretching band. Such observation can be attributed to the probability that the attachment of Pb(II) ions is in these functional groups. A column filter was devised with lead-bound chitosan to determine the zero point charge (pHzpc) of the biopolymer. The results show that at pH 8.34, below than the zpc level of literatures cited for lead which ranges from pH 4 to 7, favors the adsorption site of chitosan and its capability to adsorb traces amount of aqueous lead.
Selective Guest Accommodation in Zn(II) Bimetallic: Organic Coordination Frameworks
The synthesis and characterization of metal-organic frameworks (MOFs) is an area of coordination chemistry which has grown rapidly in recent years. Worldwide there has been growing concerns about future energy supplies, and its environmental impacts. A good number of MOFs have been tested for the adsorption of small molecules in the vapour phase. An important issue for potential applications of MOFs for gas adsorption and storage materials is the stability of their structure upon sorption. Therefore, study on the thermal stability of MOFs upon adsorption is important. The incorporation of two or more transition metals in a coordination polymer is a current challenge for designed synthesis. This work focused on the synthesis, characterization and small molecule adsorption properties of three microporous (one zinc monometal and two bimetallics) complexes involving Cu(II), Zn(II) and 1,2,4,5-benzenetetracarboxylic acid using the ambient precipitation and solvothermal method. The complexes were characterized by elemental analysis, Infrared spectroscopy, Scanning Electron microscopy, Thermogravimetry analysis and X-ray Powder diffraction. The N2-adsorption Isotherm showed the complexes to be of TYPE III in reference to IUPAC classification, with very small pores only capable for small molecule sorption. All the synthesized compounds were observed to contain water as guest. Investigations of their inclusion properties for small molecules in the vapour phase showed water and methanol as the only possible inclusion candidates with 10.25H2O in the monometal complex [Zn4(H2B4C)2.5(OH)3(H2O)]·10H2O but not reusable after a complete structural collapse. The ambient precipitation bimetallic; [(CuZnB4C(H2O)2]·5H2O, was found to be reusable and recoverable from structure collapse after adsorption of 5.75H2O. In addition, Solvo-[CuZnB4C(H2O)2.5]·2H2O obtained from solvothermal method show two cycles of rehydration with 1.75H2O and 0.75MeOH inclusion while structure remains unaltered upon dehydration and adsorption.
Enhanced Thermal and Electrical Properties of Terbium Manganate-Polyvinyl Alcohol Nanocomposite Film
Polymer nanocomposites are very significant materials both in academia and industry for diverse potential applicability in electronics. Polymer plays the role of matrix element which has low density, flexibility, good mechanical strength and electrical properties. Use of nanosized multiferroic filler in the polymer matrix is suitable to achieve nanocomposites with enhanced magneto-dielectric effect and good mechanical properties both at the same time. Multiferroic terbium manganate (TbMnO₃) nanoparticles have been synthesized by sol-gel method using chloride precursors. Terbium manganate-polyvinyl alcohol (TbMnO₃-PVA) nanocomposite film has been prepared by solution casting method. Crystallite size of TbMnO₃ nanoparticle has been calculated to be ~ 40 nm from XRD analysis. Morphological study of the samples has been done by scanning electron microscopy and a well dispersion of the nanoparticles in the PVA matrix has been found. Thermogravimetric analysis (TGA) exhibits enhancement of thermal stability of the nanocomposite film with the inclusion of TbMnO₃ nanofiller in PVA matrix. The electrical transport properties of the nanocomposite film sample have been studied in the frequency range 20Hz - 2MHz at and above room temperature. The frequency dependent variation of ac conductivity follows universal dielectric response (UDR) obeying Jhonscher’s sublinear power law. Correlated barrier hopping (CBH) mechanism is the dominant charge transport mechanism with maximum barrier height 19 meV above room temperature. The variation of dielectric constant of the sample with frequency has been studied at different temperatures. Real part of dielectric constant at 1 KHz frequency at room temperature of the sample is found to be ~ 8 which is higher than that of the pure PVA film sample (~ 6). Dielectric constant decreases with the increase in frequency. Relaxation peaks have been observed in the variation of imaginary part of electric modulus with frequency. The relaxation peaks shift towards higher frequency as temperature increases probably due to the existence of interfacial polarization in the sample in presence of applied electric field. The current-voltage (I-V) characteristics of the nanocomposite film have been studied under ±40 V applied at different temperatures. I-V characteristic exhibits temperature dependent rectifying nature indicating the formation of Schottky barrier diode (SBD) with barrier height 23 meV. In conclusion, using multiferroic TbMnO₃ nanofiller in PVA matrix, enhanced thermal stability and electrical properties can be achieved.
Removal of Iron (II) from Wastewater in Oil Field Using 3-(P-Methyl) Phenyl-5-Thionyl-1,2,4-Triazoline Assembled on Silver Nanoparticles
In this work we prepared 3-(p-methyl) phenyl-5-thionyl-1,2,4-triazoline (C1). The nanostructure of the prepared C1 compound was fabricated by assembling on silver nanoparticles. The UV and TEM analyses confirm the assembling of C1 compound on silver nanoparticles. The effect of C1 compound on the removal of Iron (II) from Iron contaminated samples and industrial wastewater samples (produced water from oil processing facility) were studied before and after their assembling on silver nanoparticles. The removal of Iron was studied at different concentrations of FeSO4 solution (5, 14 and 39 mg/l) and field sample concentration (661 mg/l). In addition, the removal of Iron (II) was investigated at different times. The Prepared compound and its nanostructure with AgNPs show highly efficient in removing the Iron ions. Quantum chemical descriptors using DFT was discussed. The output of the study pronounces that the C1 molecule can act as chelating agent for Iron (II).
Development of Metal-Organic Frameworks-Type Hybrid Functionalized Materials for Selective Uranium Extraction
Different types of materials have been developed for the solid/liquid uranium extraction processes, such as functionalized organic polymers, hybrid silica or inorganic adsorbents. In general, these materials exhibit a moderate affinity for uranyl ions and poor selectivity against impurities like iron, vanadium or molybdenum. Moreover, the structural organization deficiency of these materials generates ion diffusion issues inside the material. Therefore, the aim of our study is to developed efficient and organized materials, stable in the acid media encountered in uranium extraction processes. Metal organic frameworks (MOFs) are hybrid crystalline materials consisting of an inorganic part (cluster or metal ions) and tailored organic linkers connected via coordination bonds. These hierarchical materials have exceptional surface area, thermal stability and a large variety of tunable structures. However, due to the reversibility of constitutive coordination bonds, MOFs have moderate stability in strongly complexing or acidic media. Only few of them are known to be stable in aqueous media and only one example is described in strong acidic media. However, these conditions are very often encountered in the environmental pollution remediation of mine wastewaters. To tackle the challenge of developing MOFs adapted for uranium extraction from acid mine waters, we have investigated the stability of several materials. To ensure a good stability we have synthetized and characterized different materials based on highly coordinated metal clusters, such as LnOFs and Zirconium based materials. Among the latter, the UiO family shows a great stability in sulfuric acid media even in the presence of 1.4 M sodium sulfate at pH 2. However, the stability in phosphoric media is reduced due to the high affinity between zirconium and phosphate ligand. Based on these results, we have developed a tertiary amine functionalized MOF denoted UiO-68-NMe2 particularly adapted for the extraction of anionic uranyl (VI) sulfate complexes mainly present in the acid mine solutions. The adsorption capacity of the material has been determined upon varying total sulfate concentration, contact time and uranium concentration. The extraction tests put in evidence different phenomena due to the complexity of the extraction media and the interaction between the MOF and sulfate anion. Finally, the extraction mechanisms and the interaction between uranyl and the MOF structure have been investigated. The functionalized material UiO-68-NMe2 has been characterized in the presence and absence of uranium by FT-IR, UV and Raman techniques. Moreover, the stability of the protonated amino functionalized MOF has been evaluated. The synthesis, characterization and evaluation of this type of hybrid material, particularly adapted for uranium extraction in sulfuric acid media by an anionic exchange mechanism, paved the way for the development of metal organic frameworks functionalized by different other chelating motifs, such as bifunctional ligands showing an enhanced affinity and selectivity for uranium in acid and complexing media. Work in this direction is currently in progress.
Amino Acid Derivatives as Green Corrosion Inhibitors for Mild Steel in 1M HCl: Electrochemical, Surface and Density Functional Theory Studies
The amino acids based corrosion inhibitors 2-(3-(carboxymethyl)-1H-imidazol-3-ium-1-yl) acetate (Z-1),2-(3-(1-carboxyethyl)-1H-imidazol-3-ium-1-yl) propanoate (Z-2) and 2-(3-(1-carboxy-2-phenylethyl)-1H-imidazol-3-ium-1-yl)-3- phenylpropanoate (Z-3) were synthesized by the reaction of amino acids, glyoxal and formaldehyde, and characterized by the FTIR and NMR spectroscopy. The corrosion inhibition performance of synthesized inhibitors was studied by electrochemical (EIS and PDP), surface and DFT methods. The results show, the studied Z-1, Z-2 and Z-3 are effective inhibitors, showed the maximum inhibition efficiency of 88.52 %, 89.48 and 96.08% at concentration 200ppm, respectively. The results of potentiodynamic polarization (PDP) study showed that Z-1 act as a cathodic inhibitor, while Z-2 and Z-3 act as mixed type inhibitors. The results of electrochemical impedance spectroscopy (EIS) studies showed that zwitterions inhibit the corrosion through adsorption mechanism. The adsorption of synthesized zwitterions on the mild steel surface was followed the Langmuir adsorption isotherm. The formation of zwitterions film on mild steel surface was confirmed by the scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDX). The quantum chemical parameters were used to study the reactivity of inhibitors and supported the experimental results. An inhibitor adsorption model is proposed.
Enhanced Performance of Supercapacitor Based on Boric Acid Doped Polyvinyl Alcohol-H₂SO₄ Gel Polymer Electrolyte System
Recently, Proton Conducting Gel Polymer Electrolytes (GPEs) have drawn much attention in supercapacitor applications due to their physical and electrochemical characteristics and stability conditions for low temperatures. In this research, PVA-H2SO4-H3BO3 GPE has been used for electric-double layer capacitor (EDLCs) application, in which electrospun free-standing carbon nanofibers are used as electrodes. Introduced PVA-H2SO4-H3BO3 GPE behaves as both separator and the electrolyte in the supercapacitor. Symmetric Swagelok cells including GPEs were assembled via using two electrode arrangements and the electrochemical properties were searched. Electrochemical performance studies demonstrated that PVA-H2SO4-H3BO3 GPE had a maximum specific capacitance (Cs) of 134 F g-1 and showed great capacitance retention (%100) after 1000 charge/discharge cycles. Furthermore, PVA-H2SO4-H3BO3 GPE yielded an energy density of 67 Wh kg-1 with a corresponding power density of 1000 W kg-1 at a current density of 1 A g-1. PVA-H2SO4 based polymer electrolyte was produced according to following procedure; Firstly, 1 g of commercial PVA was dissolved in distilled water at 90°C and stirred until getting transparent solution. This was followed by addition of the diluted H2SO4 (1 g of H2SO4 in a distilled water) to the solution to obtain PVA-H2SO4. PVA-H2SO4-H3BO3 based polymer electrolyte was produced by dissolving H3BO3 in hot distilled water and then inserted into the PVA-H2SO4 solution. The mole fraction was arranged to ¼ of the PVA repeating unit. After the stirring 2 h at RT, gel polymer electrolytes were obtained. The final electrolytes for supercapacitor testing included 20% of water in weight. Several blending combinations of PVA/H2SO4 and H3BO3 were studied to observe the optimized combination in terms of conductivity as well as electrolyte stability. As the amount of boric acid increased in the matrix, excess sulfuric acid was excluded due to cross linking, especially at lower solvent content. This resulted in the reduction of proton conductivity. Therefore, the mole fraction of H3BO3 was chosen as ¼ of PVA repeating unit. Within this optimized limits, the polymer electrolytes showed better conductivities as well as stability.
Electrolyte Loaded Hexagonal Boron Nitride/Polyacrylonitrile Nanofibers for Lithium Ion Battery Application
In the present work, novel hBN/polyacrylonitrile composite nanofibers were produced via electrospinning approach and loaded with the electrolyte for rechargeable lithium-ion battery applications. The electrospun nanofibers comprising various hBN contents were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The influence of hBN/PAN ratios onto the properties of the porous composite system, such as fiber diameter, porosity, and the liquid electrolyte uptake capability were systematically studied. Ionic conductivities and electrochemical characterizations were evaluated after loading electrospun hBN/PAN composite nanofiber with liquid electrolyte, i.e., 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). The electrolyte loaded nanofiber has a highest ionic conductivity of 10−3 S cm⁻¹ at room temperature. According to cyclic voltammetry (CV) results it exhibited a high electrochemical stability window up to 4.7 V versus Li+/Li. Li//10 wt% hBN/PAN//LiCO₂ cell was produced which delivered high discharge capacity of 144 mAhg⁻¹ and capacity retention of 92.4%. Considering high safety and low cost properties of the resulting hBN/PAN fiber electrolytes, these materials can be suggested as potential separator materials for lithium-ion batteries.
Study of Intermolecular Interactions in Binary Mixtures of 1-Butyl-3-Methyl Imidazolium Bis (Trifluoro Methyl Sulfonyl) Imide and 1-Ethyl-3-Methyl Imidazolium Ethyl Sulphate at Different Temperature from 293.18 to 342.15 K
The densities of pure and its binary mixtures of 1-Butyl-3-methyl imidazolium bis (trifluoro methyl sulfonyl) imide and 1–Ethyl-3-methyl imidazolium ethyl sulphate at different temperature, over the entire composition range were measured at 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, 323.15, 328.15, 33.15, 338.15, 343.15 K. In this study, the liquid-liquid extraction procedure was used. From this experimental data, the excess molar volumes, apparent molar volume, partial molar volumes and the excess partial molar volumes have been calculated for over the whole composition range. Hence, the effect of temperature and composition on all derived thermodynamic properties of this binary mixture will be discussed in terms of intermolecular interactions.
Experimental and Numerical Studies on Hydrogen Behavior in a Small-Scale Container with Passive Autocatalytic Recombiner
One of the most important issue is to ensure the safety of long-term waste storage containers in which fuel debris and radioactive materials are accumulated. In this case, hydrogen generated by water decomposition by radiation is accumulated in the container for a long period of time, so it is necessary to reduce the concentration of hydrogen in the container. In addition, a condition that any power supplies from the outside of the container are unnecessary is requested. Then, radioactive waste storage containers with the passive autocatalytic recombiner (PAR) would be effective. The radioactive waste storage container with PAR was used for moving the fuel debris of the Three Mile Island Unit 2 to the storage location. However, the effect of PAR is not described in detail. Moreover, the reduction of hydrogen concentration during the long-term storage period was performed by the venting system, which was installed on the top of the container. Therefore, development of a long-term storage container with PAR was started with the aim of safely storing fuel debris picked up at the Fukushima Daiichi Nuclear Power Plant for a long period of time. A fundamental experiment for reducing the concentration of hydrogen which generates in a nuclear waste long-term storage container was carried out using a small-scale container with PAR. Moreover, the circulation flow behavior of hydrogen in the small-scale container resulting from the natural convection by the decay heat was clarified. In addition, preliminary numerical analyses were performed to predict the experimental results regarding the circulation flow behavior and the reduction of hydrogen concentration in the small-scale container. From the results of the present study, the validity of the container with PAR was experimentally confirmed on the reduction of hydrogen concentration. In addition, it was predicted numerically that the circulation flow behavior of hydrogen in the small-scale container is blocked by steam which generates by chemical reaction of hydrogen and oxygen.
Research and Development on Technology for Reducing Concentration of Hydrogen Gas Generated in Long-Term Waste Storage Containers
Research and development (R&D) of hydrogen concentration reduction technology using a passive autocatalytic recombiner (PAR) has been conducted with the purpose of suppressing the risk of burning and explosion of hydrogen generated in long-term waste storage containers. In this R&D, the effectiveness and feasibility of long-term waste storage containers with PAR for reduction of hydrogen concentration were experimentally confirmed. In addition, a numerical analysis method for predicting hydrogen behavior inside the container was developed. The following studies were carried out: as PAR which can be used within a storage container, the ceramic catalyst, and the geopolymer catalyst were developed. These performances, as the catalysts, were experimentally investigated. Moreover, the effectiveness as PAR was clarified; after the ceramic catalyst or the geopolymer catalyst were installed inside a small-scale container, hydrogen gas was supplied from the outside at the bottom of the container to the inside, and the reduction of hydrogen concentration by PAR was experimentally confirmed; and, the analysis method which can evaluate the hydrogen behavior in a long-term waste storage container with PAR was developed. A natural convection model of hydrogen circulating in the container and a chemical reaction model in which oxygen and hydrogen react were made. Simulations were performed using the analysis code which introduced these numerical models, and the verification of each model and the validation of predicted results were conducted. From the results of the present studies, it was confirmed that the hydrogen concentration in long-term waste storage containers can be reduced to less than an explosion limit value using the presently developed PAR.
Ternary Oxovanadium(V) Complexes Containing Unusual Pentagonal-Bipyramidal Metal Centers: Syntheses, Structures, and Properties
Reactions of bis(acetylacetonato)oxovanadium(IV) [VO(acac)₂] with H₂L¹ (diacetyl bis(benzoylhydrazone)) and H₂L² (dibenzoyl bis(benzoylhydrazone)) in methanol and chloroform-methanol (1:3) mixture, respectively, afford two novel oxovanadium(V) complexes of formula [VO(Lₙ)(acac)] (1 and 2) in good yields (52 and 60%). Both complexes have been characterized by elemental analysis, mass spectrometric, various spectroscopic (IR (Infrared Spectroscopy), UV-Vis (Ultraviolet-Visible Spectroscopy), and ¹H NMR (Proton Nuclear Magnetic Resonance)) and electrochemical measurements. The complexes are brown in color. They are diamagnetic and non-electrolytes. Molecular structures of both 1 and 2 have been determined by single crystal X-ray crystallography. The metal center in each complex is in a distorted pentagonal-bipyramidal N₂O₅ coordination sphere. The ONNO-donor fused 5,5,5-membered chelate rings forming (Lⁿ)²⁻ and one of the acetylacetonate-O form a N₂O₃ pentagonal plane around the metal center, while the second acetylacetonate-O and the oxo group occupy the axial positions. In the crystal lattice, intermolecular trifurcated O-H∙∙∙O and bifurcated C-H∙∙∙O interactions lead to the formation of discrete tetranuclear 14∙MeOH units, while the molecules of 2 form a ladder-like one-dimensional structure via intermolecular π-π and C-H∙∙∙π interactions. The spectroscopic features of 1 and 2 are consistent with their molecular structures. Both complexes are redox active and display the metal-centered 1/1⁻ and 2/2⁻ couples at -0.87 and -0.95 V, respectively.
Unsteady Three-Dimensional Adaptive Spatial-Temporal Multi-Scale Direct Simulation Monte Carlo Solver to Simulate Rarefied Gas Flows in Micro/Nano Devices
We present an efficient, three-dimensional parallel multi-scale Direct Simulation Monte Carlo (DSMC) algorithm for the simulation of unsteady rarefied gas flows in micro/nanosystems. The algorithm employs a novel spatiotemporal adaptivity scheme. The scheme performs a fully dynamic multi-level grid adaption based on the gradients of flow macro-parameters and an automatic temporal adaptation. The computational domain consists of a hierarchical octree-based Cartesian grid representation of the flow domain and a triangular mesh for the solid object surfaces. The hybrid mesh, combined with the spatiotemporal adaptivity scheme, allows for increased flexibility and efficient data management, rendering the framework suitable for efficient particle-tracing and dynamic grid refinement and coarsening. The parallel algorithm is optimized to run DSMC simulations of strongly unsteady, non-equilibrium flows over multiple cores. The presented method is validated by comparing with benchmark studies and then employed to improve the design of micro-scale hotwire thermal sensors in rarefied gas flows.
Effect of the Support Shape on Fischer-Tropsch Cobalt Catalyst Performance
Cobalt catalysts were supported on extruded silica carrier and different-type (SiO₂, γ-Al₂O₃) commercial supports with different shape and size to produce heavy hydrocarbons for Fischer-Tropsch synthesis. The catalysts were characterized by N2 physisorption and H2-TPR. The catalytic performance of the catalysts was tested in a fixed bed reactor. The results of Fischer-Tropsch synthesis performance showed that the cobalt catalyst supported on spherical silica supports displayed a higher activity and a higher selectivity to C₅⁺ products, due to the fact that the active components were only distributed in the surface layer of the spherical carrier, and the influence of gas diffusion restriction on catalytic performance was weakened. Therefore, it can be concluded that the eggshell cobalt catalyst was superior to precious metals modified catalysts in the synthesis of heavy hydrocarbons.
One Dimensional Reactor Modeling for Methanol Steam Reforming to Hydrogen
One dimensional pseudo-homogenous modeling has been performed for methanol steam reforming reactor. The results show that the models can well predict the industrial data. The reactor had minimum temperature along axial because of the endothermic reaction. Hydrogen productions and temperature profiles along axial were investigated in regard to operating conditions such as inlet mass flow rate and mass fraction of methanol, inlet temperature of external thermal oil. Low inlet mass flow rate of methanol, low inlet temperature and high mass fraction of methanol decreased minimum temperature along axial. Low inlet mass flow rate of methanol, high mass fraction of methanol and high inlet temperature of thermal oil made cold point forward. Low mass fraction, high mass flow rate and high inlet temperature of thermal oil increased hydrogen production. One dimensional model can be a guide for industrial operation.
Enzyme Immobilization in Multi-Chamber Microfluidic Reactors for Multistep Biocatalytic Conversions
Miniaturizing chemical reactors is of great interest due to a reduced consumption of chemicals and costs. By immobilizing biocatalysts into accordingly designed microfluidic reactors, specific conversions with high turnover rates may be carried out under mild conditions. The herein presented study focuses on the development of multi-chamber PDMS-on-glass microfluidic reactors and the immobilization of biocatalysts for the performance of enzymatic cascade reactions. Using this approach, the benefits of enzyme catalysis (e.g. high substrate and reaction specificity) and microfluidics (e.g. low consumption of chemicals and costs, precise control of reaction parameters) are combined. Additionally, by establishing several spatially separated reaction chambers for serial and parallel enzymatic conversions crosstalk between the enzymes can be eliminated. These characteristics make the developed system highly interesting for applications in biosensing as well as in the synthesis of fine chemicals. To start with, the enzymatic cascade of beta-galactosidase, glucose oxidase, and horseradish peroxidase was selected, as these robust enzymes are suited for proof-of-concept studies. A PEGDA-based hydrogel was developed and applied as a matrix to physically entrap the enzymes. The UV-initiated polymerization and precise photo structuring of hydrogels on glass was optimized for that purpose. Additionally, the material characteristics (e.g. pore size, swelling degree, stress-strain profile) were tuned to obtain a mechanically stable hydrogel which is well permeable for reaction educts and products and safely entraps the enzymes without significantly influencing their conformation. By establishing a colorimetric assay, the enzymatic activity of free and immobilized enzymes was determined with UV spectroscopy. Microfluidic reactors with up to three separated chambers were designed such that a bubble-free filling, smooth fluid flow and a low flow velocity could be obtained. The fluid flow within the microfluidic chips was simulated with Computational Fluid Dynamics and experimentally validated using various fluorescent dyes. Enzymes were immobilized in the microfluidic reactors by photopolymerization of the enzyme-containing hydrogel precursor solution. Finally, the enzymatic activity within the thereby obtained microfluidic chips was investigated especially focusing on long-term stability and reusability. It was shown that the hydrogel matrix is suited for enzyme immobilization, since only minor leakage occurred and the long-time activity could be even increased. Using a molding process, clearly photopatterned hydrogels with adjustable dimensions were obtained and integrated in microfluidic reactors. Additionally, the approach allowed the production of advanced multi-chamber reactors and the successful performance of serial enzymatic reactions. Thereby, a platform of several reactor geometries was developed, which is suited for the immobilization of complex reaction cascades. In the future, enzymatic reactions relevant for biosensing shall be established within the microfluidic reactor. In this respect, further work will focus on new strategies for enzyme immobilization (e.g. pre-encapsulation into polymersomes and covalent attachment to the hydrogel).
Synthesis and Characterization of Highly Oriented Bismuth Oxyiodide Thin Films for the Photocatalytical Degradation of Pharmaceuticals Compounds in Water
Heterogeneous photocatalysis is a promising method to achieve the complete degradation and mineralization of organic pollutants in water via their exhaustive oxidation. In order to take this advanced oxidation process towards sustainability, it is necessary to reduce the energy consumption, referred as the light sources and the post-treatment operations. For this, the synthesis of new nanostructures of low band gap semiconductors in the form of thin films is in continuous development. In this work, thin films of the low band gap semiconductor bismuth oxyiodide (BiOI) were synthesized via the Successive Ionic Layer Adsorption and Reaction (SILAR) method. For this, Bi(NO3)3 and KI solutions were prepared, and glass supports were immersed in each solution under strict rate and time immersion conditions. Synthesis was performed at room temperature and a washing step was set prior to each immersion. Thin films with an average thickness below 100 nm were obtained upon a cycle of 30 immersions, as determined by AFM and profilometry measurements. Cubic BiOI nanocrystals with average size of 17 nm and a high orientation to the 001 plane were observed by XRD. In order to optimize the synthesis method, several Bi/I ratios were tested, namely 1/1, 1/5, 1/10, 1/20 and 1/50. The highest crystallinity of the BiOI films was observed when the 1/5 ratio was used in the synthesis. Non-stoichiometric conditions also resulted in the highest uniformity of the thin layers. PVP was used as an additive to improve the adherence of the BiOI thin films to the support. The addition of 0.1 mg/mL of PVP during the washing step resulted in the highest adherence of the thin films. In photocatalysis tests, degradation rate of the antibiotic ciprofloxacin as high as 75% was achieved using visible light (380 to 700 nm) irradiation for 5 h in batch tests. Mineralization of the antibiotic was also observed, although in a lower extent; ~ 30% of the total organic carbon was removed upon 5 h of visible light irradiation. Some ciprofloxacin by-products were identified throughout the reaction; and some of these molecules displayed residual antibiotic activity. In conclusion, it is possible to obtain highly oriented BiOI thin films under ambient conditions via the SILAR method. Non-stoichiometric conditions using PVP additive are necessary to increase the crystallinity and adherence of the films, which are photocatalytically active to remove recalcitrant organic pollutants under visible light irradiation.
Incorporation of Copper for Performance Enhancement in Metal-Oxides Resistive Switching Device and Its Potential Electronic Application
In this work, fabrication and characterization of copper-doped zinc oxide (Cu:ZnO) based memristor devices with aluminium (Al) and indium tin oxide (ITO) metal electrodes are reported. The thin films of Cu:ZnO was synthesized using low-cost and low-temperature chemical process. The Cu:ZnO was then deposited onto ITO bottom electrodes using spin-coater technique, whereas the top electrode Al was deposited utilizing physical vapor evaporation technique. Ellipsometer was employed in order to measure the Cu:ZnO thickness and it was found to be 50 nm. Several surface and materials characterization techniques were used to study the thin-film properties of Cu:ZnO. To ascertain the efficacy of Cu:ZnO for memristor applications, electrical characterizations such as current-voltage (I-V), data retention and endurance were obtained, all being the critical parameters for next-generation memory. The I-V characteristic exhibits switching behavior with asymmetrical hysteresis loops. This work imputes the resistance switching to the positional drift of oxygen vacancies associated with respect to the Al/Cu:ZnO junction. Further, a non-linear curve fitting regression techniques were utilized to determine the equivalent circuit for the fabricated Cu:ZnO memristors. Efforts were also devoted in order to establish its potentiality for different electronic applications. This study explains a new approach towards the realization of metal-oxides based resistive-switching devices integrated on ITO coated glass platform and also opens up a new possibility for future generation transparent electronics.
Dimensional-Controlled Functional Gold Nanoparticles and Zinc Oxide Nanorods for Solar Water Splitting
Semiconductor photocatalyst is known as one of the key roles in developing clean and sustainable energy. However, most of the semiconductor only possesses photoactivity within the UV light region, and hence, decreases the overall photocatalyst efficiency. Generally, the overall effectiveness of the photocatalyst activity is determined by three critical steps: (i) light absorption efficiency and photoexcitation electron-hole pair generation, (ii) separation and migration of charge carriers to the surface of the photocatalyst, and (iii) surface reaction of the carriers with its environment. Much effort has been invested on optimizing hierarchical nanostructures of semiconductors for efficient photoactivity due to the fact that the visible light absorption capability and occurrence of the chemical reactions mostly depend on the dimension of photocatalysts. In this work, we incorporated zero-dimensional (0D) gold nanoparticles (AuNPs) and one dimensional (1D) Zinc Oxide (ZnO) nanorods (NRs) onto strontium titanate (STO) for efficient visible light absorption, charge transfer, and separation. We demonstrate that the electrical and optical properties of the photocatalyst can be tuned by controlling the dimensional structures of AuNPs and ZnO NRs. We found that smaller AuNPs sizes exhibited higher photoactivity because of Fermi level shifting toward the conductive band of STO, STO band gap narrowing and broadening of absorption spectrum to the visible light region. For ZnO NRs, it was found that the average ZnO NRs c-axis length must achieve of certain length to induce multiphoton absorption as a result of light reflection and trapping behavior in the free space between adjacent ZnO NRs hence broadening the absorption spectrum of ZnO from UV to visible light region. This work opens up a new way of broadening the absorption spectrum by incorporating controllable nanostructures of semiconductors, which is important in optimizing the solar water splitting process.
Tetracycline as Chemosensor for Simultaneous Recognition of Al³⁺: Application to Bio-Imaging for Living Cells
Antibiotic tetracycline presents as a micro-contaminant in fresh water, wastewater and soils, causing environmental and health problems. In this work, tetracycline (TC) has been employed as chemo-sensor for the recognition of Al³⁺ without interring other ions, and the results show that it enhances the fluorescence intensity for Al³⁺ and there is no interference from other coexisting cation ions (Cd²⁺, Ni²⁺, Co²⁺, Sr²⁺, Mg²⁺, Fe³⁺, K⁺, Sm³⁺, Ag⁺, Na⁺, Ba²⁺, Zn²⁺, and Mn²⁺). For the addition of Cu²⁺ to [TET-Al³⁺], it appears that the intensity of fluorescence has been quenched. Other combinations of metal ions in addition to TC do not change the fluorescence behavior. The stoichiometry determined by Job´s plot for the interaction of TC with Al³⁺ was found to be 1:1. Importantly, the detection of Al³⁺⁺ successfully employed in the real samples like living cells, and it was found that TC efficiently performs as a fluorescent probe for Al³⁺ ion in living systems, especially in Saccharomyces cerevisiae; this is confirmed by confocal laser scanning microscopy.
Therapeutic Effects of Guar Gum Nanoparticle in Oxazolone-Induced Atopic Dermatitis
Atopic dermatitis (AD) is a chronic disease of the skin, involving itchy, reddish, and scaly lesions. It mainly affects children and has a high prevalence in developing countries. The AD may occur due to environmental or genetic factors. There is no permanent cure for the AD. Currently, all therapeutic strategies involve methods to simply alleviate the symptoms, and include lotions and corticosteroids, which have adverse effects. Use of phytochemicals and natural products has not yet been exploited fully. The particle used in this study is derived from Cyamopsis tetragonoloba, an edible polysaccharide with a galactomannan component. The mannose component mainly increases its specificity towards cellular uptake by mannose receptors, highly expressed by the macrophage. The aim of this study was to determine the therapeutic effect of guar gum nanoparticles (GN) in vitro and in vivo in the AD. To assess the wound healing capacity of the guar gum nanoparticle (GN), we first treated adherent NIH3T3 cells, with a scratch injury, with GN. GN successfully healed the wound caused by the scratch. In the in vivo experiment, Balb/c mice ear were topically treated with oxazolone (oxa) to induce AD and then were topically treated with GN. The ear thickness was increased significantly till day 28 on the treatment of Oxa. The GN application showed a significant decrease in the thickness as assessed on day 28. The total cell count of skin cells showed fold increase when treated with oxa, was again decreased on topical application of GN on the affected skin. The eosinophil count, as assessed by Giemsa staining was also increased when treated with oxa, GN application led to a significant decrease. The IgE level was assessed in the serum samples which showed that GN helped in restoring the alleviated IgE level. The T helper cells and the macrophage population showed increased percentage when treated with oxa, the GN application. This was examined by flow cytometry. The H&E staining of the ear tissue showed epidermal thickness in the oxa treated mice, GN application showed reduced cellular filtration followed by epidermal thickness. Thus our assays showed that GN was successful in alleviating the disease caused by Oxa when administered topically.
Consequence of Multi-Templating of Closely Related Structural Analogues on a Chitosan-Methacryllic Acid Molecularly Imprinted Polymer Matrix-Thermal and Chromatographic Traits
Most polluted environments, most challengingly, aerosol types, contain a cocktail of different toxicants. Multi-templating of matrices have been the recent target by researchers in a bid to solving complex mixed-toxicant challenges using single or common remediation systems. This investigation looks at the effect of such multi-templated system vis-a-vis the synthesis by non-covalent interaction, of a molecularly imprinted polymer architecture using nicotine and its structural analogue Phenylalanine amide individually and, in the blend, (50:50), as template materials in a Chitosan-Methacrylic acid functional monomer matrix. The temperature for polymerization is 60OC and time for polymerization, 12hrs (water bath heating), 4mins for (microwave heating). The characteristic thermal properties of the molecularly imprinted materials are investigated using Simultaneous Thermal Analysis (STA) profiling, while the absorption and separation efficiencies based on the relative retention times and peak areas of templates were studied amongst other properties. Transmission Electron Microscopy (TEM) results obtained, show the creation of heterogeneous nanocavities, regardless, the introduction of Caffeine a close structural analogue presented near-zero perfusion. This confirms the selectivity and specificity of the templated polymers despite its dual-templated nature. The STA results presented the materials as having decomposition temperatures above 250OC and a relative loss in mass of less than19% over a period within 50mins of heating. Consequent to this outcome, multi-templated systems can be fabricated to sequester specifically and selectively targeted toxicants in a mixed toxicant populated system effectively.
Development of Electrospun Porous Carbon Fibers from Cellulose/Polyacrylonitrile Blend
Carbon fibers are one of the most demanding materials on earth due to their potential application in energy, high strength materials, and conductive materials. The nanostructure of carbon fibers offers enhanced properties of conductivity due to the larger surface area. The next generation carbon nanofibers demand the porous structure as it offers more surface area. Multiple techniques are used to produce carbon fibers. However, electrospinning followed by carbonization of the polymeric materials is easy to carry process on a laboratory scale. Also, it offers multiple diversity of changing parameters to acquire the desired properties of carbon fibers. Polyacrylonitrile (PAN) is the most used material for the production of carbon fibers due to its promising processing parameters. Also, cellulose is one of the highest yield producers of carbon fibers. However, the electrospinning of cellulosic materials is difficult due to its rigid chain structure. The combination of PAN and cellulose can offer a suitable solution for the production of carbon fibers. Both materials are miscible in the mixed solvent of N, N, Dimethylacetamide and lithium chloride. This study focuses on the production of porous carbon fibers as a function of PAN/Cellulose blend ratio, solution properties, and electrospinning parameters. These single polymer and blend with different ratios were electrospun to give fine fibers. The higher amount of cellulose offered more difficulty in electrospinning of nanofibers. After carbonization, the carbon fibers were studied in terms of their blend ratio, surface area, and texture. Cellulose contents offered the porous structure of carbon fibers. Also, the presence of LiCl contributed to the porous structure of carbon fibers.
Greywater Treatment Using Activated Bio-Char Produced from Agricultural Waste
The increase in urbanisation in South Africa has led to an increase in water demand and a decline in freshwater supply. Despite this, poor water usage is still a major challenge in South Africa, for instance, freshwater is still used for non-drinking applications. The freshwater shortage can be alleviated by using other sources of water for non-portable purposes such as greywater treated with activated biochar produced from agricultural waste. The success of Activated biochar produced from agricultural waste to treat greywater can be both economically and environmentally beneficial. Greywater treatment with activated biochar produced from agricultural waste is considered a cost-effective wastewater treatment. This work was aimed at determining the ability of Activated Bio-char to remove Total Suspended Solids (TSS), Ammonium (NH4-N), Nitrate (NO3-N, and Chemical Oxygen Demand (COD) from greywater. The experiments were carried out in 200ml laboratory plastic cylinders used as filter columns. 2.5 cm layer of gravel was used at the bottom and top of the column to sandwich the Activated Bio-char material. A measured amount (200g and 400g) of Activated Bio-char material was loaded in a column and used as a filter medium for greywater. Samples were collected once a week for four weeks and sent for analysis. Four types of greywater were treated, namely: Kitchen, floor cleaning water, shower and laundry water. The results showed that activated biochar produced from agricultural waste reduces a certain amount of pollutants from greywater. The highest reduction of pollutants were: TSS (95 % on kitchen greywater), NH4-N (85% on Bathroom greywater), NO3-N (76 % on kitchen greywater) and COD (63% on kitchen greywater). These results indicated the ability of Activated Bio-char to treat greywater for onsite reuse purposes.