Search results for: sulfonated polymers

Authors: Sai Snehitha Yadavalli, K. Sruthi, Swati Ghosh Acharyya

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Heavy metal ions are toxic to humans and all living species when exposed in large quantities or for long durations. Though Fe acts as a nutrient, when intake is in large quantities, it becomes toxic. These toxic heavy metal ions, when consumed through water, will cause many disorders and are harmful to all flora and fauna through biomagnification. Specifically, humans are prone to innumerable diseases ranging from skin to gastrointestinal, neurological, etc. In higher quantities, they even cause cancer in humans. Detection of these toxic heavy metal ions in water is thus important. Traditionally, the detection of heavy metal ions in water has been done by techniques like Inductively Coupled Plasma Mass Spectroscopy (ICPMS) and Atomic Absorption Spectroscopy (AAS). Though these methods offer accurate quantitative analysis, they require expensive equipment and cannot be used for on-site measurements. Anodic Stripping Voltammetry is a good alternative as the equipment is affordable, and measurements can be made at the river basins or lakes. In the current study, Square Wave Anodic Stripping Voltammetry (SWASV) was used to detect the heavy metal ions in water. Literature reports various electrodes on which deposition of heavy metal ions was carried out like Bismuth, Polymers, etc. The working electrode used in this study is a polyvinyl chloride (PVC) modified glassy carbon electrode (GCE). Ag/AgCl reference electrode and Platinum counter electrode were used. Biologic Potentiostat SP 300 was used for conducting the experiments. Through this work of simultaneous detection, four heavy metal ions were successfully detected at a time. The influence of modifying GCE with PVC was studied in comparison with unmodified GCE. The simultaneous detection of Cd⁺², Fe⁺², Co⁺², Pb⁺² heavy metal ions was done using PVC modified GCE by drop casting 1 wt.% of PVC dissolved in Tetra Hydro Furan (THF) solvent onto GCE. The concentration of all heavy metal ions was 0.2 mg/L, as shown in the figure. The scan rate was 0.1 V/s. Detection parameters like pH, scan rate, temperature, time of deposition, etc., were optimized. It was clearly understood that PVC helped in increasing the sensitivity and selectivity of detection as the current values are higher for PVC-modified GCE compared to unmodified GCE. The peaks were well defined when PVC-modified GCE was used.

Keywords: cadmium, cobalt, electrochemical sensing, glassy carbon electrodes, heavy metal Ions, Iron, lead, polyvinyl chloride, potentiostat, square wave anodic stripping voltammetry

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Authors: Attila Kiss, Erzsébet Némedi, Zoltán Naár

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As natural prebiotic (non-digestible) carbohydrates stimulate the growth of colon microflora and contribute to maintain the health of the host, analytical studies aiming at revealing the chemical behavior of these beneficial food components came to the forefront of interest. Food processing (especially baking) may lead to a significant conversion of the parent compounds, hence it is of utmost importance to characterize the transformation patterns and the plausible decomposition products formed by thermal degradation. The relevance of this work is confirmed by the wide-spread use of these carbohydrates (fructo-oligosaccharides, cyclodextrins, raffinose and resistant starch) in the food industry. More and more functional foodstuffs are being developed based on prebiotics as bioactive components. 12 different types of oligosaccharides have been investigated in order to reveal their thermal degradation characteristics. Different carbohydrate derivatives (D-fructose and D-glucose oligomers and polymers) have been exposed to elevated temperatures (150 °C 170 °C, 190 °C, 210 °C, and 220 °C) for 10 min. An advanced HPLC method was developed and used to identify the decomposition products of carbohydrates formed as a consequence of thermal treatment. Gradient elution was applied with binary solvent elution (acetonitrile, water) through amine based carbohydrate column. Evaporative light scattering (ELS) proved to be suitable for the reliable detection of the UV/VIS inactive carbohydrate degradation products. These experimental conditions and applied advanced techniques made it possible to survey all the formed intermediers. Change in oligomer distribution was established in cases of all studied prebiotics throughout the thermal treatments. The obtained results indicate increased extent of chain degradation of the carbohydrate moiety at elevated temperatures. Prevalence of oligomers with shorter chain length and even the formation of monomer sugars (D-glucose and D-fructose) might be observed at higher temperatures. Unique oligomer distributions, which have not been described previously are revealed in the case of each studied, specific carbohydrate, which might result in various prebiotic activities. Resistant starches exhibited high stability when being thermal treated. The degradation process has been modeled by a plausible reaction mechanism, in which proton catalyzed degradation and chain cleavage take place.

Keywords: prebiotics, thermal degradation, fructo-oligosaccharide, HPLC, ELS detection

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Authors: N. Pérez-Rodríguez, D. García-Bernet, A. Torrado-Agrasar, J. M. Cruz, A. B. Moldes, J. M. Domínguez

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World economy is based on non-renewable, fossil fuels such as petroleum and natural gas, which entails its rapid depletion and environmental problems. In EU countries, the objective is that at least 20% of the total energy supplies in 2020 should be derived from renewable resources. Biogas, a product of anaerobic degradation of organic substrates, represents an attractive green alternative for meeting partial energy needs. Nowadays, trend to circular economy model involves efficiently use of residues by its transformation from waste to a new resource. In this sense, characteristics of agricultural residues (that are available in plenty, renewable, as well as eco-friendly) propitiate their valorisation as substrates for biogas production. Corn cob is a by-product obtained from maize processing representing 18 % of total maize mass. Corn cob importance lies in the high production of this cereal (more than 1 x 109 tons in 2014). Due to its lignocellulosic nature, corn cob contains three main polymers: cellulose, hemicellulose and lignin. Crystalline, highly ordered structures of cellulose and lignin hinders microbial attack and subsequent biogas production. For the optimal lignocellulose utilization and to enhance gas production in anaerobic digestion, materials are usually submitted to different pretreatment technologies. In the present work, enzymatic hydrolysis, ultrasounds and combination of both technologies were assayed as pretreatments of corn cob for biogas production. Enzymatic hydrolysis pretreatment was started by adding 0.044 U of Ultraflo® L feruloyl esterase per gram of dry corncob. Hydrolyses were carried out in 50 mM sodium-phosphate buffer pH 6.0 with a solid:liquid proportion of 1:10 (w/v), at 150 rpm, 40 ºC and darkness for 3 hours. Ultrasounds pretreatment was performed subjecting corn cob, in 50 mM sodium-phosphate buffer pH 6.0 with a solid: liquid proportion of 1:10 (w/v), at a power of 750W for 1 minute. In order to observe the effect of the combination of both pretreatments, some samples were initially sonicated and then they were enzymatically hydrolysed. In terms of methane production, anaerobic digestion of the corn cob pretreated by enzymatic hydrolysis was positive achieving 290 L CH4 kg MV-1 (compared with 267 L CH4 kg MV-1 obtained with untreated corn cob). Although the use of ultrasound as the only pretreatment resulted detrimentally (since gas production decreased to 244 L CH4 kg MV-1 after 44 days of anaerobic digestion), its combination with enzymatic hydrolysis was beneficial, reaching the highest value (300.9 L CH4 kg MV-1). Consequently, the combination of both pretreatments improved biogas production from corn cob.

Keywords: biogas, corn cob, enzymatic hydrolysis, ultrasound

Procedia PDF Downloads 267

Authors: A. Gürses, T. B. Barın, Ç. Doğar

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Bitumen has been widely used as the binder of aggregate in road pavement due to its good viscoelastic properties, as a viscous organic mixture with various chemical compositions. Bitumen is a liquid at high temperature and it becomes brittle at low temperatures, and this temperature-sensitivity can cause the rutting and cracking of the pavement and limit its application. Therefore, the properties of existing asphalt materials need to be enhanced. The pavement with polymer modified bitumen exhibits greater resistance to rutting and thermal cracking, decreased fatigue damage, as well as stripping and temperature susceptibility; however, they are expensive and their applications have disadvantages. Bituminous mixtures are composed of very irregular aggregates bound together with hydrocarbon-based asphalt, with a low volume fraction of voids dispersed within the matrix. Montmorillonite (MMT) is a layered silicate with low cost and abundance, which consists of layers of tetrahedral silicate and octahedral hydroxide sheets. Recently, the layered silicates have been widely used for the modification of polymers, as well as in many different fields. However, there are not too much studies related with the preparation of the modified asphalt with MMT, currently. In this study, organo-clay-modified bitumen, and calcareous aggregate and organo-clay blends were prepared by hot blending method with OMMT, which has been synthesized using a cationic surfactant (Cetyltrymethylammonium bromide, CTAB) and long chain hydrocarbon, and MMT. When the exchangeable cations in the interlayer region of pristine MMT were exchanged with hydrocarbon attached surfactant ions, the MMT becomes organophilic and more compatible with bitumen. The effects of the super hydrophobic OMMT onto the micro structural and mechanic properties (Marshall Stability and volumetric parameters) of the prepared blends were investigated. Stability and volumetric parameters of the blends prepared were measured using Marshall Test. Also, in order to investigate the morphological and micro structural properties of the organo-clay-modified bitumen and calcareous aggregate and organo-clay blends, their SEM and HRTEM images were taken. It was observed that the stability and volumetric parameters of the prepared mixtures improved significantly compared to the conventional hot mixes and even the stone matrix mixture. A micro structural analysis based on SEM images indicates that the organo-clay platelets dispersed in the bitumen have a dominant role in the increase of effectiveness of bitumen - aggregate interactions.

Keywords: hot mix asphalt, stone matrix asphalt, organo clay, Marshall test, calcareous aggregate, modified bitumen

Procedia PDF Downloads 239

Authors: I. Irska, S. Paszkiewicz, D. Pawlikowska, E. Piesowicz, A. Linares, T. A. Ezquerra

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Due to the number of advantages such as high tensile strength, sensitivity to hydrolytic degradation, and biocompatibility poly(lactic acid) (PLA) is one of the most common polyesters for biomedical and pharmaceutical applications. However, PLA is a rigid, brittle polymer with low heat distortion temperature and slow crystallization rate. In order to broaden the range of PLA applications, it is necessary to improve these properties. In recent years a number of new strategies have been evolved to obtain PLA-based materials with improved characteristics, including manipulation of crystallinity, plasticization, blending, and incorporation into block copolymers. Among the other methods, synthesis of aliphatic-aromatic copolyesters has been attracting considerable attention as they may combine the mechanical performance of aromatic polyesters with biodegradability known from aliphatic ones. Given the need for highly flexible biodegradable polymers, in this contribution, a series of aromatic-aliphatic based on poly(butylene terephthalate) and poly(lactic acid) (PBT-b-PLA) copolyesters exhibiting superior mechanical properties were copolymerized with an additional poly(tetramethylene oxide) (PTMO) soft block. The structure and properties of both series were characterized by means of attenuated total reflectance – Fourier transform infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance spectroscopy (¹H NMR), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and dynamic mechanical, thermal analysis (DMTA). Moreover, the related changes in tensile properties have been evaluated and discussed. Lastly, the viscoelastic properties of synthesized poly(ester-ether) copolymers were investigated in detail by step cycle tensile tests. The block lengths decreased with the advance of treatment, and the block-random diblock terpolymers of (PBT-ran-PLA)-b-PTMO were obtained. DSC and DMTA analysis confirmed unambiguously that synthesized poly(ester-ether) copolymers are microphase-separated systems. The introduction of polyether co-units resulted in a decrease in crystallinity degree and melting temperature. X-ray diffraction patterns revealed that only PBT blocks are able to crystallize. The mechanical properties of (PBT-ran-PLA)-b-PTMO copolymers are a result of a unique arrangement of immiscible hard and soft blocks, providing both strength and elasticity.

Keywords: aliphatic-aromatic copolymers, multiblock copolymers, phase behavior, thermoplastic elastomers

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Authors: Wei Wang, Yuan Hu

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Epoxy resins (EP), one of the most important thermosetting polymers, is widely applied in various fields due to its desirable properties, such as excellent electrical insulation, low shrinkage, outstanding mechanical stiffness, satisfactory adhesion and solvent resistance. However, like most of the polymeric materials, EP has the fatal drawbacks including inherent flammability and high yield of toxic smoke, which restricts its application in the fields requiring fire safety. So, it is still a challenge and an interesting subject to develop new flame retardants which can not only remarkably improve the flame retardancy, but also render modified resins low toxic gases generation. In recent work, polymer nanocomposites based on nanohybrids that contain two or more kinds of nanofillers have drawn intensive interest, which can realize performance enhancements. The realization of previous hybrids of carbon nanotubes (CNTs) and molybdenum disulfide provides us a novel route to decorate layered double hydroxide (LDH) nanosheets on the surface of β-FeOOH nanorods; the deposited LDH nanosheets can fill the network and promote the work efficiency of β-FeOOH nanorods. Moreover, the synergistic effects between LDH and β-FeOOH can be anticipated to have potential applications in reducing fire hazards of EP composites for the combination of condense-phase and gas-phase mechanism. As reported, β-FeOOH nanorods can act as a core to prepare hybrid nanostructures combining with other nanoparticles through electrostatic attraction through layer-by-layer assembly technique. In this work, LDH nanosheets wrapped β-FeOOH nanorods (LDH-β-FeOOH) hybrids was synthesized by a facile method, with the purpose of combining the characteristics of one dimension (1D) and two dimension (2D), to improve the fire resistance of epoxy resin. The hybrids showed a well dispersion in EP matrix and had no obvious aggregation. Thermogravimetric analysis and cone calorimeter tests confirmed that LDH-β-FeOOH hybrids into EP matrix with a loading of 3% could obviously improve the fire safety of EP composites. The plausible flame retardancy mechanism was explored by thermogravimetric infrared (TG-IR) and X-ray photoelectron spectroscopy. The reasons were concluded: condense-phase and gas-phase. Nanofillers were transferred to the surface of matrix during combustion, which could not only shield EP matrix from external radiation and heat feedback from the fire zone, but also efficiently retard transport of oxygen and flammable pyrolysis.

Keywords: fire hazards, toxic gases, self-assembly, epoxy

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Authors: Muhammad Muzamal, Anders Rasmuson

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Wood material is extensively considered as a raw material for the production of bio-polymers, bio-fuels and value-added chemicals. However, the shortcoming in using wood as raw material is that the enzymatic hydrolysis of wood material is difficult because the accessibility of enzymes to hemicelluloses and cellulose is hindered by complex chemical and physical structure of the wood. The steam explosion (SE) pre-treatment improves the digestion of wood material by creating both chemical and physical modifications in wood. In this process, first, wood chips are treated with steam at high pressure and temperature for a certain time in a steam treatment vessel. During this time, the chemical linkages between lignin and polysaccharides are cleaved and stiffness of material decreases. Then the steam discharge valve is rapidly opened and the steam and wood chips exit the vessel at very high speed. These fast moving wood chips collide with each other and with walls of the equipment and disintegrate to small pieces. More damaged and disintegrated wood have larger surface area and increased accessibility to hemicelluloses and cellulose. The energy required for an increase in specific surface area by same value is 70 % more in conventional mechanical technique, i.e. attrition mill as compared to steam explosion process. The mechanism of wood disintegration during the SE pre-treatment is very little studied. In this study, we have simulated collision and impact of wood chips (dimension 20 mm x 20 mm x 4 mm) with each other and with walls of the vessel. The wood chips are simulated as a 3D orthotropic material. Damage and fracture in the wood material have been modelled using 3D Hashin’s damage model. This has been accomplished by developing a user-defined subroutine and implementing it in the FE software ABAQUS. The elastic and strength properties used for simulation are of spruce wood at 12% and 30 % moisture content and at 20 and 160 OC because the impacted wood chips are pre-treated with steam at high temperature and pressure. We have simulated several cases to study the effects of elastic and strength properties of wood, velocity of moving chip and orientation of wood chip at the time of impact on the damage in the wood chips. The disintegration patterns captured by simulations are very similar to those observed in experimentally obtained steam exploded wood. Simulation results show that the wood chips moving with higher velocity disintegrate more. Moisture contents and temperature decreases elastic properties and increases damage. Impact and collision in specific directions cause easy disintegration. This model can be used to efficiently design the steam explosion equipment.

Keywords: dynamic simulation, disintegration of wood, impact, steam explosion pretreatment

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Authors: Inês N. Peça , A. Bicho, Rui Gardner, M. Margarida Cardoso

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Inorganic/organic nanocomplexes offer tremendous scope for future biomedical applications, including imaging, disease diagnosis and drug delivery. The combination of Fe3O4 with biocompatible polymers to produce smart drug delivery systems for use in pharmaceutical formulation present a powerful tool to target anti-cancer drugs to specific tumor sites through the application of an external magnetic field. In the present study, we focused on the evaluation of the effect of the magnetic field application time on the rate of drug release from iron oxide polymeric nanoparticles. Doxorubicin, an anticancer drug, was selected as the model drug loaded into the nanoparticles. Nanoparticles composed of poly(d-lactide-co-glycolide (PLGA), a biocompatible polymer already approved by FDA, containing iron oxide nanoparticles (MNP) for magnetic targeting and doxorubicin (DOX) were synthesized by the o/w solvent extraction/evaporation method and characterized by scanning electron microscopy (SEM), by dynamic light scattering (DLS), by inductively coupled plasma-atomic emission spectrometry and by Fourier transformed infrared spectroscopy. The produced particles yielded smooth surfaces and spherical shapes exhibiting a size between 400 and 600 nm. The effect of the magnetic doxorubicin loaded PLGA nanoparticles produced on cell viability was investigated in mammalian CHO cell cultures. The results showed that unloaded magnetic PLGA nanoparticles were nontoxic while the magnetic particles without polymeric coating show a high level of toxicity. Concerning the therapeutic activity doxorubicin loaded magnetic particles cause a remarkable enhancement of the cell inhibition rates compared to their non-magnetic counterpart. In vitro drug release studies performed under a non-permanent magnetic field show that the application time and the on/off cycle duration have a great influence with respect to the final amount and to the rate of drug release. In order to determine the mechanism of drug release, the data obtained from the release curves were fitted to the semi-empirical equation of the the Korsmeyer-Peppas model that may be used to describe the Fickian and non-Fickian release behaviour. Doxorubicin release mechanism has shown to be governed mainly by Fickian diffusion. The results obtained show that the rate of drug release from the produced magnetic nanoparticles can be modulated through the magnetic field time application.

Keywords: drug delivery, magnetic nanoparticles, PLGA nanoparticles, controlled release rate

Procedia PDF Downloads 261

Authors: Sonia Amariei, Ionut Avramia, Florin Ursachi, Ancuta Chetrariu, Ancuta Petraru

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The food industry is one of the major generators of plastic waste derived from conventional synthetic petroleum-based polymers, which are non-biodegradable, used especially for packaging. These packaging materials, after the food is consumed, accumulate serious environmental concerns due to the materials but also to the organic residues that adhere to them. It is the concern of specialists, researchers to eliminate problems related to conventional materials that are not biodegradable or unnecessary plastic and replace them with biodegradable and edible materials, supporting the common effort to protect the environment. Even though environmental and health concerns will cause more consumers to switch to a plant-based diet, most people will continue to add more meat to their diet. The paper presents the possibility of replacing the polyethylene packaging from the surface of the trays for meat preparations with biodegradable packaging obtained from biopolymers. During the storage of meat products may occur deterioration by lipids oxidation and microbial spoilage, as well as the modification of the organoleptic characteristics. For this reason, different compositions of polymer mixtures and film conditions for obtaining must be studied to choose the best packaging material to achieve food safety. The compositions proposed for packaging are obtained from alginate, agar, starch, and glycerol as plasticizers. The tensile strength, elasticity, modulus of elasticity, thickness, density, microscopic images of the samples, roughness, opacity, humidity, water activity, the amount of water transferred as well as the speed of water transfer through these packaging materials were analyzed. A number of 28 samples with various compositions were analyzed, and the results showed that the sample with the highest values for hardness, density, and opacity, as well as the smallest water vapor permeability, of 1.2903E-4 ± 4.79E-6, has the ratio of components as alginate: agar: glycerol (3:1.25:0.75). The water activity of the analyzed films varied between 0.2886 and 0.3428 (aw< 0.6), demonstrating that all the compositions ensure the preservation of the products in the absence of microorganisms. All the determined parameters allow the appreciation of the quality of the packaging films in terms of mechanical resistance, its protection against the influence of light, the transfer of water through the packaging. Acknowledgments: This work was supported by a grant of the Ministry of Research, Innovation, and Digitization, CNCS/CCCDI – UEFISCDI, project number PN-III-P2-2.1-PED-2019-3863, within PNCDI III.

Keywords: meat products, alginate, agar, starch, glycerol

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Authors: D. Berdous, H. Ferfera-Harrar

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Superabsorbent polymers (SAPs) or hydrogels with three-dimensional hydrophilic network structure are high-performance water absorbent and retention materials. The in situ synthesis of metal nanoparticles within polymeric network as antibacterial agents for bio-applications is an approach that takes advantage of the existing free-space into networks, which not only acts as a template for nucleation of nanoparticles, but also provides long term stability and reduces their toxicity by delaying their oxidation and release. In this work, SAP/nanosilver nanocomposites were successfully developed by a unique green process at room temperature, which involves in situ formation of silver nanoparticles (AgNPs) within hydrogels as a template. The aim of this study is to investigate whether these AgNPs-loaded hydrogels are potential candidates for antimicrobial applications. Firstly, the superabsorbents were prepared through radical copolymerization via grafting and crosslinking of acrylamide (AAm) onto chitosan backbone (Cs) using potassium persulfate as initiator and N,N’-methylenebisacrylamide as the crosslinker. Then, they were hydrolyzed to achieve superabsorbents with ampholytic properties and uppermost swelling capacity. Lastly, the AgNPs were biosynthesized and entrapped into hydrogels through a simple, eco-friendly and cost-effective method using aqueous silver nitrate as a silver precursor and curcuma longa tuber-powder extracts as both reducing and stabilizing agent. The formed superabsorbents nanocomposites (Cs-g-PAAm)/AgNPs were characterized by X-ray Diffraction (XRD), UV-visible Spectroscopy, Attenuated Total reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Inductively Coupled Plasma (ICP), and Thermogravimetric Analysis (TGA). Microscopic surface structure analyzed by Transmission Electron Microscopy (TEM) has showed spherical shapes of AgNPs with size in the range of 3-15 nm. The extent of nanosilver loading was decreased by increasing Cs content into network. The silver-loaded hydrogel was thermally more stable than the unloaded dry hydrogel counterpart. The swelling equilibrium degree (Q) and centrifuge retention capacity (CRC) in deionized water were affected by both contents of Cs and the entrapped AgNPs. The nanosilver-embedded hydrogels exhibited antibacterial activity against Escherichia coli and Staphylococcus aureus bacteria. These comprehensive results suggest that the elaborated AgNPs-loaded nanomaterials could be used to produce valuable wound dressing.

Keywords: antibacterial activity, nanocomposites, silver nanoparticles, superabsorbent Hydrogel

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Authors: Alice Robba, Renaud Bouchet, Celine Barchasz, Jean-Francois Colin, Erik Elkaim, Kristina Kvashnina, Gavin Vaughan, Matjaz Kavcic, Fannie Alloin

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With their high theoretical energy density (~2600 Wh.kg-1), lithium/sulfur (Li/S) batteries are highly promising, but these systems are still poorly understood due to the complex mechanisms/equilibria involved. Replacing S8 by Li2S as the active material allows the use of safer negative electrodes, like silicon, instead of lithium metal. S8 and Li2S have different conductivity and solubility properties, resulting in a profoundly changed activation process during the first cycle. Particularly, during the first charge a high polarization and a lack of reproducibility between tests are observed. Differences observed between raw Li2S material (micron-sized) and that electrochemically produced in a battery (nano-sized) may indicate that the electrochemical process depends on the particle size. Then the major focus of the presented work is to deepen the understanding of the Li2S material charge mechanism, and more precisely to characterize the effect of the initial Li2S particle size both on the mechanism and the electrode preparation process. To do so, Li2S nanoparticles were synthetized according to two ways: a liquid path synthesis and a dissolution in ethanol, allowing Li2S nanoparticles/carbon composites to be made. Preliminary chemical and electrochemical tests show that starting with Li2S nanoparticles could effectively suppress the high initial polarization but also influence the electrode slurry preparation. Indeed, it has been shown that classical formulation process - a slurry composed of Polyvinylidone Fluoride polymer dissolved in N-methyle-2-pyrrolidone - cannot be used with Li2S nanoparticles. This reveals a complete different Li2S material behavior regarding polymers and organic solvents when going at the nanometric scale. Then the coupling between two operando characterizations such as X-Ray Diffraction (XRD) and X-Ray Absorption and Emission Spectroscopy (XAS/XES) have been carried out in order to interpret the poorly understood first charge. This study discloses that initial particle size of the active material has a great impact on the working mechanism and particularly on the different equilibria involved during the first charge of the Li2S based Li-ion batteries. These results explain the electrochemical differences and particularly the polarization differences observed during the first charge between micrometric and nanometric Li2S-based electrodes. Finally, this work could lead to a better active material design and so to more efficient Li2S-based batteries.

Keywords: Li-ion/Sulfur batteries, Li2S nanoparticles effect, Operando characterizations, working mechanism

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Authors: Jafar S. Noori, Jan Romano-deGea, Maria Dimaki, John Mortensen, Winnie E. Svendsen

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Pesticides have been intensively used in agriculture to control weeds, insects, fungi, and pest. One of the most commonly used pesticides is glyphosate. Glyphosate has the ability to attach to the soil colloids and degraded by the soil microorganisms. As glyphosate led to the appearance of resistant species, the pesticide was used more intensively. As a consequence of the heavy use of glyphosate, residues of this compound are increasingly observed in food and water. Recent studies reported a direct link between glyphosate and chronic effects such as teratogenic, tumorigenic and hepatorenal effects although the exposure was below the lowest regulatory limit. Today, pesticides are detected in water by complicated and costly manual procedures conducted by highly skilled personnel. It can take up to several days to get an answer regarding the pesticide content in water. An alternative to this demanding procedure is offered by electrochemical measuring techniques. Electrochemistry is an emerging technology that has the potential of identifying and quantifying several compounds in few minutes. It is currently not possible to detect glyphosate directly in water samples, and intensive research is underway to enable direct selective and quantitative detection of glyphosate in water. This study focuses on developing and modifying a sensor chip that has the ability to selectively measure glyphosate and minimize the signal interference from other compounds. The sensor is a silicon-based chip that is fabricated in a cleanroom facility with dimensions of 10×20 mm. The chip is comprised of a three-electrode configuration. The deposited electrodes consist of a 20 nm layer chromium and 200 nm gold. The working electrode is 4 mm in diameter. The working electrodes are modified by creating molecularly imprinted polymers (MIP) using electrodeposition technique that allows the chip to selectively measure glyphosate at low concentrations. The modification included using gold nanoparticles with a diameter of 10 nm functionalized with 4-aminothiophenol. This configuration allows the nanoparticles to bind to the working electrode surface and create the template for the glyphosate. The chip was modified using electrodeposition technique. An initial potential for the identification of glyphosate was estimated to be around -0.2 V. The developed sensor was used on 6 different concentrations and it was able to detect glyphosate down to 0.5 mgL⁻¹. This value is below the accepted pesticide limit of 0.7 mgL⁻¹ set by the US regulation. The current focus is to optimize the functionalizing procedure in order to achieve glyphosate detection at the EU regulatory limit of 0.1 µgL⁻¹. To the best of our knowledge, this is the first attempt to modify miniaturized sensor electrodes with functionalized nanoparticles for glyphosate detection.

Keywords: pesticides, glyphosate, rapid, detection, modified, sensor

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Authors: Pesaru Vigneshwar Reddy, Parvathaneni Pavan

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Green organic chemistry which is the latest and one of the most researched topics now-a- days has been in demand since 1990’s. Majority of the research in green organic chemistry chemicals are some of the important starting materials for greater number of major chemical industries. The production of organic chemicals has raw materials (or) reagents for other application is major sector of manufacturing polymers, pharmaceuticals, pesticides, paints, artificial fibers, food additives etc. organic synthesis on a large scale compound to the labratory scale, involves the use of energy, basic chemical ingredients from the petro chemical sectors, catalyst and after the end of the reaction, seperation, purification, storage, packing distribution etc. During these processes there are many problems of health and safety for workers in addition to the environmental problems caused there by use and deposition as waste. Green chemistry with its 12 principles would like to see changes in conventional way that were used for decades to make synthetic organic chemical and the use of less toxic starting materials. Green chemistry would like to increase the efficiency of synthetic methods, to use less toxic solvents, reduce the stage of synthetic routes and minimize waste as far as practically possible. In this way, organic synthesis will be part of the effort for sustainable development Green chemistry is also interested for research and alternatives innovations on many practical aspects of organic synthesis in the university and research labaratory of institutions. By changing the methodologies of organic synthesis, health and safety will be advanced in the small scale laboratory level but also will be extended to the industrial large scale production a process through new techniques. The three key developments in green chemistry include the use of super critical carbondioxide as green solvent, aqueous hydrogen peroxide as an oxidising agent and use of hydrogen in asymmetric synthesis. It also focuses on replacing traditional methods of heating with that of modern methods of heating like microwaves traditions, so that carbon foot print should reduces as far as possible. Another beneficiary of this green chemistry is that it will reduce environmental pollution through the use of less toxic reagents, minimizing of waste and more bio-degradable biproducts. In this present paper some of the basic principles, approaches, and early achievements of green chemistry has a branch of chemistry that studies the laws of passing of chemical reactions is also considered, with the summarization of green chemistry principles. A discussion about E-factor, old and new synthesis of ibuprofen, microwave techniques, and some of the recent advancements also considered.

Keywords: energy, e-factor, carbon foot print, micro-wave, sono-chemistry, advancement

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Authors: Chrislaura Carmo, Luca Deiana, Mafalda Laranjo, Abilio Sobral, Armando Cordova

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Photodynamic therapy (PDT) is currently used for the treatment of malignancies and premalignant tumors. It is based on the capture of a photosensitizing molecule (PS) which, when excited by light at a certain wavelength, reacts with oxygen and generates oxidizing species (radicals, singlet oxygen, triplet species) in target tissues, leading to cell death. BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno) derivatives are emerging as important candidates for photosensitizer in photodynamic therapy of cancer cells due to their high triplet quantum yield. Today these dyes are relevant molecules in photovoltaic materials and fluorescent sensors. In this study, it will be demonstrated the possibility that BODIPY can be covalently linked to thioglycolic acid through the click reaction. Thiol−ene click chemistry has become a powerful synthesis method in materials science and surface modification. The design of biobased allyl-terminated precursors with high renewable carbon content for the construction of the thiol-ene polymer networks is essential for sustainable development and green chemistry. The work aims to synthesize the BODIPY (10-(4-(allyloxy) phenyl)-2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-dipyrrolo[1,2-c:2',1'-f] [1,3,2] diazaborinin-4-ium-5-uide) and to click reaction with Thioglycolic acid. BODIPY was synthesized by the condensation reaction between aldehyde and pyrrole in dichloromethane, followed by in situ complexation with BF3·OEt2 in the presence of the base. Then it was functionalized with allyl bromide to achieve the double bond and thus be able to carry out the click reaction. The thiol−ene click was performed using DMPA (2,2-Dimethoxy-2-phenylacetophenone) as a photo-initiator in the presence of UV light (320–500 nm) in DMF at room temperature for 24 hours. Compounds were characterized by standard analytical techniques, including UV-Vis Spectroscopy, 1H, 13C, 19F NMR and mass spectroscopy. The results of this study will be important to link BODIPY to polymers through the thiol group offering a diversity of applications and functionalization. This new molecule can be tested as third-generation photosensitizers, in which the dye is targeted by antibodies or nanocarriers by cells, mainly in cancer cells, PDT and Photodynamic Antimicrobial Chemotherapy (PACT). According to our studies, it was possible to visualize a click reaction between allyl BODIPY and thioglycolic acid. Our team will also test the reaction with other thiol groups for comparison. Further, we will do the click reaction of BODIPY with a natural polymer linked with a thiol group. The results of the above compounds will be tested in PDT assays on various lung cancer cell lines.

Keywords: bodipy, click reaction, thioglycolic acid, allyl, thiol-ene click

Procedia PDF Downloads 133

Authors: Rangrong Yoksan, Amporn Sane, Nattaporn Khanoonkon, Chanakorn Yokesahachart, Narumol Noivoil, Khanh Minh Dang

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Polylactic acid (PLA) is the most commercially available bio-based and biodegradable plastic at present. PLA has been used in plastic related industries including single-used containers, disposable and environmentally friendly packaging owing to its renewability, compostability, biodegradability, and safety. Although PLA demonstrates reasonably good optical, physical, mechanical, and barrier properties comparable to the existing petroleum-based plastics, its brittleness and mold shrinkage as well as its price are the points to be concerned for the production of rigid and semi-rigid packaging. Blending PLA with other bio-based polymers including thermoplastic starch (TPS) is an alternative not only to achieve a complete bio-based plastic, but also to reduce the brittleness, shrinkage during molding and production cost of the PLA-based products. TPS is a material produced mainly from starch which is cheap, renewable, biodegradable, compostable, and non-toxic. It is commonly prepared by a plasticization of starch under applying heat and shear force. Although glycerol has been reported as one of the most plasticizers used for preparing TPS, its migration caused the surface stickiness of the TPS products. In some cases, mixed plasticizers or natural fibers have been applied to impede the retrogradation of starch or reduce the migration of glycerol. The introduction of fibers into TPS-based materials could reinforce the polymer matrix as well. Therefore, the objective of the present research is to study the effect of starch type (i.e. native starch and phosphate starch), plasticizer type (i.e. glycerol and xylitol with a weight ratio of glycerol to xylitol of 100:0, 75:25, 50:50, 25:75, and 0:100), and fiber content (i.e. in the range of 1-25 % wt) on properties of PLA/TPS blend and composite. PLA/TPS blends and composites were prepared using a twin-screw extruder and then converted into dumbbell-shaped specimens using an injection molding machine. The PLA/TPS blends prepared by using phosphate starch showed higher tensile strength and stiffness than the blends prepared by using the native one. In contrast, the blends from native starch exhibited higher extensibility and heat distortion temperature (HDT) than those from the modified starch. Increasing xylitol content resulted in enhanced tensile strength, stiffness, and water resistance, but decreased extensibility and HDT of the PLA/TPS blend. Tensile properties and hydrophobicity of the blend could be improved by incorporating silane treated-jute fibers.

Keywords: polylactic acid, thermoplastic starch, Jute fiber, composite, blend

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Authors: T. Sadunishvili, L. Kutateladze, T. Urushadze, R. Khvedelidze, N. Zakariashvili, M. Jobava, G. Kvesitadze

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Multiple repeated soil-climatic zones in Georgia determines the diversity of microorganisms. Hundreds of microscopic fungi of different genera have been isolated from different ecological niches, including some extreme environments. Biosynthetic ability of microscopic fungi has been studied. Trichoderma ressei, representative of the Ascomycetes secrete cellulolytic and xylanolytic enzymes that act in synergy to hydrolyze polysaccharide polymers to glucose, xylose and arabinose, which can be fermented to biofuels. The other mesophilic strains producing cellulases are Allesheria terrestris, Chaetomium thermophile, Fusarium oxysporium, Piptoporus betulinus, Penicillium echinulatum, P. purpurogenum, Aspergillus niger, A. wentii, A. versicolor, A. fumigatus etc. In the majority of the cases the cellulases produced by strains of genus Aspergillus usually have high β-glucosidase activity and average endoglucanases levels (with some exceptions), whereas strains representing Trichoderma have high endo enzyme and low β-glucosidase, and hence has limited efficiency in cellulose hydrolysis. Six producers of stable cellulases and xylanases from mesophilic and thermophilic fungi have been selected. By optimization of submerged cultivation conditions, high activities of cellulases and xylanases were obtained. For enzymes purification, their sedimentation by organic solvents such as ethyl alcohol, acetone, isopropanol and by ammonium sulphate in different ratios have been carried out. Best results were obtained with precipitation by ethyl alcohol (1:3.5) and ammonium sulphate. The yields of enzyme according to cellulase activities were 80-85% in both cases. Cellulase activity of enzyme preparation obtained from the strain Trichoderma viride X 33 is 126 U/g, from the strain Penicillium canescence D 85–185U/g and from the strain Sporotrichum pulverulentum T 5-0 110 U/g. Cellulase activity of enzyme preparation obtained from the strain Aspergillus sp. Av10 is 120 U/g, xylanase activity of enzyme preparation obtained from the strain Aspergillus niger A 7-5–1155U/g and from the strain Aspergillus niger Aj 38-1250 U/g. Optimum pH and temperature of operation and thermostability, of the enzyme preparations, were established. The efficiency of hydrolyses of different agricultural residues by the microscopic fungi cellulases has been studied. The glucose yield from the residues as a result of enzymatic hydrolysis is highly determined by the ratio of enzyme to substrate, pH, temperature, and duration of the process. Hydrolysis efficiency was significantly increased as a result of different pretreatment of the residues by different methods. Acknowledgement: The Study was supported by the ISTC project G-2117, funded by Korea.

Keywords: cellulase, xylanase, microscopic fungi, enzymatic hydrolysis

Procedia PDF Downloads 393

Authors: V. Samulionis, J. Banys, A. Sánchez-Ferrer

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Inorganic nanoparticles are used for fabrication of various composites based on polymer materials because they exhibit a good homogeneity and solubility of the composite material. Multifunctional materials based on composites of a polymer containing inorganic nanotubes are expected to have a great impact on industrial applications in the future. An emerging family of such composites are polyurea elastomers with inorganic MoS2 nanotubes or MoSI nanowires. Polyurea elastomers are a new kind of materials with higher performance than polyurethanes. The improvement of mechanical, chemical and thermal properties is due to the presence of hydrogen bonds between the urea motives which can be erased at high temperature softening the elastomeric network. Such materials are the combination of amorphous polymers above glass transition and crosslinkers which keep the chains into a single macromolecule. Polyurea exhibits a phase separated structure with rigid urea domains (hard domains) embedded in a matrix of flexible polymer chains (soft domains). The elastic properties of polyurea can be tuned over a broad range by varying the molecular weight of the components, the relative amount of hard and soft domains, and concentration of nanoparticles. Ultrasonic methods as non-destructive techniques can be used for elastomer composites characterization. In this manner, we have studied the temperature dependencies of the longitudinal ultrasonic velocity and ultrasonic attenuation of these new polyurea elastomers and composites with inorganic nanoparticles. It was shown that in these polyurea elastomers large ultrasonic attenuation peak and corresponding velocity dispersion exists at 10 MHz frequency below room temperature and this behaviour is related to glass transition Tg of the soft segments in the polymer matrix. The relaxation parameters and Tg depend on the segmental molecular weight of the polymer chains between crosslinking points, the nature of the crosslinkers in the network and content of MoS2 nanotubes or MoSI nanowires. The increase of ultrasonic velocity in composites modified by nanoparticles has been observed, showing the reinforcement of the elastomer. In semicrystalline polyurea elastomer matrices, above glass transition, the first order phase transition from quasi-crystalline to the amorphous state has been observed. In this case, the sharp ultrasonic velocity and attenuation anomalies were observed near the transition temperature TC. Ultrasonic attenuation maximum related to glass transition was reduced in quasicrystalline polyureas indicating less influence of soft domains below TC. The first order phase transition in semicrystalline polyurea elastomer samples has large temperature hysteresis (> 10 K). The impact of inorganic MoS2 nanotubes resulted in the decrease of the first order phase transition temperature in semicrystalline composites.

Keywords: inorganic nanotubes, polyurea elastomer composites, ultrasonic velocity, ultrasonic attenuation

Procedia PDF Downloads 301

Authors: Sara A. Pakvis, Giulia Scalet, Stefania Marconi, Ferdinando Auricchio, Matthijs Langelaar

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In recent developments in the field of multi-material additive manufacturing, differences in material properties are exploited to create printed shape-memory structures, which are referred to as 4D-printed structures. New printing techniques allow for the deliberate introduction of prestresses in the specimen during manufacturing, and, in combination with the right design, this enables new functionalities. This research focuses on bi-polymer 4D-printed structures, where the transformation process is based on a heat-induced glass transition in one material lowering its Young’s modulus, combined with an initial prestress in the other material. Upon the decrease in stiffness, the prestress is released, which results in the realization of an essentially pre-programmed deformation. As the design of such functional multi-material structures is crucial but far from trivial, a systematic methodology to find the design of 4D-printed structures is developed, where a finite element model is combined with a density-based topology optimization method to describe the material layout. This modeling approach is verified by a convergence analysis and validated by comparing its numerical results to analytical and published data. Specific aspects that are addressed include the interplay between the definition of the prestress and the material interpolation function used in the density-based topology description, the inclusion of a temperature-dependent stiffness relationship to simulate the glass transition effect, and the importance of the consideration of geometric nonlinearity in the finite element modeling. The efficacy of topology optimization to design 4D-printed structures is explored by applying the methodology to a variety of design problems, both in 2D and 3D settings. Bi-layer designs composed of thermoplastic polymers are printed by means of the fused deposition modeling (FDM) technology. Acrylonitrile butadiene styrene (ABS) polymer undergoes the glass transition transformation, while polyurethane (TPU) polymer is prestressed by means of the 3D-printing process itself. Tests inducing shape transformation in the printed samples through heating are performed to calibrate the prestress and validate the modeling approach by comparing the numerical results to the experimental findings. Using the experimentally obtained prestress values, more complex designs have been generated through topology optimization, and samples have been printed and tested to evaluate their performance. This study demonstrates that by combining topology optimization and 4D-printing concepts, stimuli-responsive structures with specific properties can be designed and realized.

Keywords: 4D-printing, glass transition, shape memory polymer, topology optimization

Procedia PDF Downloads 211

Authors: Sofia Lazareva, Artem Smolentsev

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Fluorescent photochromic materials collect strong interest due to their possible application in organic photonics such as optical logic systems, optical memory, visualizing sensors, as well as characterization of polymers and biological systems. In photochromic fluorescence switching systems the emission of fluorophore is modulated between ‘on’ and ‘off’ via the photoisomerization of photochromic moieties resulting in effective resonance energy transfer (FRET). In current work, we have studied both photochromic and fluorescent properties of several diarylethenes. It was found that coloured forms of these compounds are not fluorescent because of the efficient intramolecular energy transfer. Spectral and photochromic parameters of investigated substances have been measured in five solvents having different polarity. Quantum yields of photochromic transformation A↔B ΦA→B and ΦB→A as well as B isomer extinction coefficients were determined by kinetic method. It was found that the photocyclization reaction quantum yield of all compounds decreases with the increase of solvent polarity. In addition, the solvent polarity is revealed to affect fluorescence significantly. Increasing of the solvent dielectric constant was found to result in a strong shift of emission band position from 450 nm (nhexane) to 550 nm (DMSO and ethanol) for all three compounds. Moreover, the emission intensive in polar solvents becomes weak and hardly detectable in n-hexane. The only one exception in the described dependence is abnormally low fluorescence quantum yield in ethanol presumably caused by the loss of electron-donating properties of nitrogen atom due to the protonation. An effect of the protonation was also confirmed by the addition of concentrated HCl in solution resulting in a complete disappearance of the fluorescent band. Excited state dynamics were investigated by ultrafast optical spectroscopy methods. Kinetic curves of excited states absorption and fluorescence decays were measured. Lifetimes of transient states were calculated from the data measured. The mechanism of ring opening reaction was found to be polarity dependent. Comparative analysis of kinetics measured in acetonitrile and hexane reveals differences in relaxation dynamics after the laser pulse. The most important fact is the presence of two decay processes in acetonitrile, whereas only one is present in hexane. This fact supports an assumption made on the basis of steady-state preliminary experiments that in polar solvents occur stabilization of TICT state. Thus, results achieved prove the hypothesis of two channel mechanism of energy relaxation of compounds studied.

Keywords: diarylethenes, fluorescence switching, FRET, photochromism, TICT state

Procedia PDF Downloads 680

Authors: Tsvetanka Filipova

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Entrepreneurial mindset learning (EML) is the combined process of instilling curiosity and invention, developing insight and value creation while building on other active pedagogy, such as project-based learning (PBL). It is essential to introduce students to chemistry and chemical engineering entrepreneurship in a manner that gives a holistic approach by first educating students on diverse entrepreneurial skills and then providing an opportunity to build their innovation. Chemistry and chemical engineering students have an opportunity to be engaged in an entrepreneurial class project in the Green Chemistry and Processes course at South Dakota Mines. The course provides future chemists and chemical engineers with the knowledge and skills required to enable them to design materials and processes in an environmentally benign way. This paper presents findings from implementing an open-ended design project in the Green Chemistry and Processes course. The goal of this team project is to have student teams design sustainable polymer materials to fulfill a need and/or opportunity related to a fictitious aerospace company that satisfies technical, safety, environmental, regulatory, economic, and social needs. Each student team is considered a start-up company charged with the task of designing sustainable polymer materials for aerospace applications. Through their work on the project, students utilize systems and entrepreneurial thinking in selecting their design project, being aware of the existent technologies (literature and patent search) and users and clients (connections), determining the goals and motivations (creating value), and what need or problem they are trying to address (curiosity). The project draws systems boundaries by focusing on student exploration of feedstocks to end-of-life of polymeric materials and products. Additional subtopics to explore are green processes for syntheses, green engineering for process design, and the economics of sustainable polymers designed for circularity. Project deliverables are team project reports and project presentations to a panel of industry, chemistry, and engineering professionals. Project deliverables are team project reports and project presentations to a panel of industry, chemistry, and engineering professionals. The impact of the entrepreneurial mindset project is evaluated through a student survey at the end of the semester. It has been found that the Innovative Solution project was excellent in promoting student curiosity, creativity, critical and systems thinking and teamwork. The results of this study suggest that incorporating EML positively impacted students’ professional skill development, their ability to understand and appreciate the socio-technical context of chemistry and engineering, and the cultivation of an entrepreneurial mindset to discover, evaluate and exploit opportunities.

Keywords: curriculum, entrepreneurial mindset learning, green chemistry and engineering, systems thinking

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Authors: Ahmad Kayvani Fard, Gordon Mckay, Muataz Hussien

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Adsorption/sorption is believed to be one of the optimal processes for the removal of heavy metals from water due to its low operational and capital cost as well as its high removal efficiency. Different materials have been reported in literature as adsorbent for heavy metal removal in waste water such as natural sorbents, organic polymers (synthetic) and mineral materials (inorganic). The selection of adsorbents and development of new functional materials that can achieve good removal of heavy metals from water is an important practice and depends on many factors, such as the availability of the material, cost of material, and material safety and etc. In this study we reported the synthesis of doped Activated carbon and Carbon nanotube (CNT) with different loading of metal oxide nanoparticles such as Fe2O3, Fe3O4, Al2O3, TiO2, SiO2 and Ag nanoparticles and their application in removal of heavy metals, hydrocarbon, and organics from waste water. Commercial AC and CNT with different loadings of mentioned nanoparticle were prepared and effect of pH, adsorbent dosage, sorption kinetic, and concentration effects are studied and optimum condition for removal of heavy metals from water is reported. The prepared composite sorbent is characterized using field emission scanning electron microscopy (FE-SEM), high transmission electron microscopy (HR-TEM), thermogravimetric analysis (TGA), X-ray diffractometer (XRD), the Brunauer, Emmett and Teller (BET) nitrogen adsorption technique, and Zeta potential. The composite materials showed higher removal efficiency and superior adsorption capacity compared to commercially available carbon based adsorbent. The specific surface area of AC increased by 50% reaching up to 2000 m2/g while the CNT specific surface area of CNT increased by more than 8 times reaching value of 890 m2/g. The increased surface area is one of the key parameters along with surface charge of the material determining the removal efficiency and removal efficiency. Moreover, the surface charge density of the impregnated CNT and AC have enhanced significantly where can benefit the adsorption process. The nanoparticles also enhance the catalytic activity of material and reduce the agglomeration and aggregation of material which provides more active site for adsorbing the contaminant from water. Some of the results for treating wastewater includes 100% removal of BTEX, arsenic, strontium, barium, phenolic compounds, and oil from water. The results obtained are promising for the use of AC and CNT loaded with metal oxide nanoparticle in treatment and pretreatment of waste water and produced water before desalination process. Adsorption can be very efficient with low energy consumption and economic feasibility.

Keywords: carbon nanotube, activated carbon, adsorption, heavy metal, water treatment

Procedia PDF Downloads 234

Authors: Majid Farsadrouh Rashti, Alireza Mohammadinejad, Amir Shafiee Kisomi

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Lead (Pb²⁺), a cation, is a prime constituent of the majority of the industrial effluents such as mining, smelting and coal combustion, Pb-based painting and Pb containing pipes in water supply systems, paper and pulp refineries, printing, paints and pigments, explosive manufacturing, storage batteries, alloy and steel industries. The maximum permissible limit of lead in the water used for drinking and domesticating purpose is 0.01 mg/L as advised by Bureau of Indian Standards, BIS. This becomes the acceptable 'safe' level of lead(II) ions in water beyond which, the water becomes unfit for human use and consumption, and is potential enough to lead health problems and epidemics leading to kidney failure, neuronal disorders, and reproductive infertility. Superabsorbent hydrogels are loosely crosslinked hydrophilic polymers that in contact with aqueous solution can easily water and swell to several times to their initial volume without dissolving in aqueous medium. Superabsorbents are kind of hydrogels capable to swell and absorb a large amount of water in their three-dimensional networks. While the shapes of hydrogels do not change extensively during swelling, because of tremendously swelling capacity of superabsorbent, their shape will broadly change.Because of their superb response to changing environmental conditions including temperature pH, and solvent composition, superabsorbents have been attracting in numerous industrial applications. For instance, water retention property and subsequently. Natural-based superabsorbent hydrogels have attracted much attention in medical pharmaceutical, baby diapers, agriculture, and horticulture because of their non-toxicity, biocompatibility, and biodegradability. Novel superabsorbent hydrogel nanocomposites were prepared by graft copolymerization of acrylamide and itaconic acid in the presence of nanoclay (laponite), using methylene bisacrylamide (MBA) and potassium persulfate, former as a crosslinking agent and the second as an initiator. The superabsorbent hydrogel nanocomposites structure was characterized by FTIR spectroscopy, SEM and TGA Spectroscopy adsorption of metal ions on poly (AAm-co-IA). The equilibrium swelling values of copolymer was determined by gravimetric method. During the adsorption of metal ions on polymer, residual metal ion concentration in the solution and the solution pH were measured. The effects of the clay content of the hydrogel on its metal ions uptake behavior were studied. The NC hydrogels may be considered as a good candidate for environmental applications to retain more water and to remove heavy metals.

Keywords: adsorption, hydrogel, nanocomposite, super adsorbent

Procedia PDF Downloads 189

Authors: Pedro G. Morouço

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One utmost challenge in Tissue Engineering is the production of 3D constructs capable of mimicking the functional hierarchy of native tissues. This is well stated for osteochondral tissue due to the complex mechanical functional unit based on the junction of articular cartilage and bone. Thus, the aim of the present study was to develop a new additive manufacturing system coupling micro-extrusion with hydrogels printing. An integrated system was developed with 2 main features: (i) the printing of up to three distinct hydrogels; (ii) in coordination with the printing of a thermoplastic structural support. The hydrogel printing module was projected with a ‘revolver-like’ system, where the hydrogel selection was made by a rotating mechanism. The hydrogel deposition was then controlled by pressured air input. The use of specific components approved for medical use was incorporated in the material dispensing system (Nordson EDF Optimum® fluid dispensing system). The thermoplastic extrusion modulus enabled the control of required extrusion temperature through electric resistances in the polymer reservoir and the extrusion system. After testing and upgrades, a hydrogel modulus with 3 syringes (3cm3 capacity each), with a pressure range of 0-2.5bar, a rotational speed of 0-5rpm, and working with needles from 200-800µm was obtained. This modulus was successfully coupled to the extrusion system that presented a temperature up to 300˚C, a pressure range of 0-12bar, and working with nozzles from 200-500µm. The applied motor could provide a velocity range 0-2000mm/min. Although, there are distinct printing requirements for hydrogels and polymers, the novel system could develop hybrid scaffolds, combining the 2 moduli. The morphological analysis showed high reliability (n=5) between the theoretical and obtained filament and pore size (350µm and 300µm vs. 342±4µm and 302±3µm, p>0.05, respectively) of the polymer; and multi-material 3D constructs were successfully obtained. Human tissues present very distinct and complex structures regarding their mechanical properties, organization, composition and dimensions. For osteochondral regenerative medicine, a multiphasic scaffold is required as subchondral bone and overlying cartilage must regenerate at the same time. Thus, a scaffold with 3 layers (bone, intermediate and cartilage parts) can be a promising approach. The developed system may give a suitable solution to construct those hybrid scaffolds with enhanced properties. The present novel system is a step-forward regarding osteochondral tissue engineering due to its ability to generate layered mechanically stable implants through the double-printing of hydrogels with thermoplastics.

Keywords: 3D bioprinting, bone regeneration, cartilage regeneration, regenerative medicine, tissue engineering

Procedia PDF Downloads 167

Authors: Catariny C. Aleman, Flavio B. Campos, Matheus A. Caliman, Everardo C. Mantovani

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The seedling production stage is a critical point in the vegetable production system. Obtaining high-quality seedlings is a prerequisite for subsequent cropping to occur well and productivity optimization is required. The water management is an important step in agriculture production. The adequate water requirement in horticulture seedlings can provide higher quality and increase field production. The practice of irrigation is indispensable and requires a duly adjusted quality irrigation system, together with a specific water management plan to meet the water demand of the crop. Irrigation management in seedling management requires a great deal of specific information, especially when it involves the use of inputs such as hydrorentering polymers and automation technologies of the data acquisition and irrigation system. The experiment was conducted in a greenhouse at the Federal University of Viçosa, Viçosa - MG. Tomato seedlings (Lycopersicon esculentum Mill) were produced in plastic trays of 128 cells, suspended at 1.25 m from the ground. The seedlings were irrigated by 4 micro sprinklers of fixed jet 360º per tray, duly isolated by sideboards, following the methodology developed for this work. During Phase 1, in January / February 2017 (duration of 24 days), the cultivation coefficient (Kc) of seedlings cultured in the presence and absence of hydrogel was evaluated by weighing lysimeter. In Phase 2, September 2017 (duration of 25 days), the seedlings were submitted to 4 irrigation managements (Kc, timer, 0.50 ETo, and 1.00 ETo), in the presence and absence of hydrogel and then evaluated in relation to quality parameters. The microclimate inside the greenhouse was monitored with the use of air temperature, relative humidity and global radiation sensors connected to a microcontroller that performed hourly calculations of reference evapotranspiration by Penman-Monteith standard method FAO56 modified for the balance of long waves according to Walker, Aldrich, Short (1983), and conducted water balance and irrigation decision making for each experimental treatment. Kc of seedlings cultured on a substrate with hydrogel (1.55) was higher than Kc on a pure substrate (1.39). The use of the hydrogel was a differential for the production of earlier tomato seedlings, with higher final height, the larger diameter of the colon, greater accumulation of a dry mass of shoot, a larger area of crown projection and greater the rate of relative growth. The handling 1.00 ETo promoted higher relative growth rate.

Keywords: automatic system; efficiency of water use; precision irrigation, micro sprinkler.

Procedia PDF Downloads 116

Authors: Olga Gomez De Miranda, Jose R. Ochoa-Gomez, Stefaan De Wildeman, Luciano Monsegue, Soraya Prieto, Leire Lorenzo, Cristina Dineiro

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The chemical industry is facing a new revolution. As long as processes based on the exploitation of fossil resources emerged with force in the XIX century, Society currently demands a new radical change that will lead to the complete and irreversible implementation of a circular sustainable economic model. The implementation of biorefineries will be essential for this. There, renewable raw materials as sugars and other biomass resources are exploited for the development of new materials that will partially replace their petroleum-derived homologs in a safer, and environmentally more benign approach. Isosorbide, (1,4:3,6-dianhydro-d-glucidol) is a primary bio-based derivative obtained from the plant (poly) saccharides and a very interesting example of a useful chemical produced in biorefineries. It can, in turn, be converted to other secondary monomers as isosorbide bis-methyl carbonate (IBMC), whose main field of application can be as a key biodegradable intermediary substitute of bisphenol-A in the manufacture of polycarbonates, or as an alternative to the toxic isocyanates in the synthesis of new polyurethanes (non-isocyanate polyurethanes) both with a huge application market. New products will present advantageous mechanical or optical properties, as well as improved behavior in non-toxicity and biodegradability aspects in comparison to their petro-derived alternatives. A robust production process of IBMC, a biomass-derived chemical, is here presented. It can be used with different raw material qualities using dimethyl carbonate (DMC) as both co-reactant and solvent. It consists of the transesterification of isosorbide with DMC under soft operational conditions, using different basic catalysts, always active with the isosorbide characteristics and purity. Appropriate isolation processes have been also developed to obtain crude IBMC yields higher than 90%, with oligomers production lower than 10%, independently of the quality of the isosorbide considered. All of them are suitable to be used in polycondensation reactions for polymers obtaining. If higher qualities of IBMC are needed, a purification treatment based on nanofiltration membranes has been also developed. The IBMC reaction-isolation conditions established in the laboratory have been successfully modeled using appropriate software programs and moved to a pilot-scale (production of 100 kg of IBMC). It has been demonstrated that a highly efficient IBMC production process able to be up-scaled under suitable market conditions has been obtained. Operational conditions involved the production of IBMC involve soft temperature and energy needs, no additional solvents, and high operational efficiency. All of them are according to green manufacturing rules.

Keywords: biomass, catalyst, isosorbide bis-methyl carbonate, polycarbonate, polyurethane, transesterification

Procedia PDF Downloads 133

Authors: Rabindranath Jana, Biswajit Maity, Keka Rana

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The most promising clean energy source is the fuel cell, since it does not generate toxic gases and other hazardous compounds. Again the direct methanol fuel cell (DMFC) is more user-friendly as it is easy to be miniaturized and suited as energy source for automobiles as well as domestic applications and portable devices. And unlike the hydrogen used for some fuel cells, methanol is a liquid that is easy to store and transport in conventional tanks. The most important part of a fuel cell is its membrane. Till now, an overall efficiency for a methanol fuel cell is reported to be about 20 ~ 25%. The lower efficiency of the cell may be due to the critical factors, e.g. slow reaction kinetics at the anode and methanol crossover. The oxidation of methanol is composed of a series of successive reactions creating formaldehyde and formic acid as intermediates that contribute to slow reaction rates and decreased cell voltage. Currently, the investigation of new anode catalysts to improve oxidation reaction rates is an active area of research as it applies to the methanol fuel cell. Surprisingly, there are very limited reports on nanostructured membranes, which are rather simple to manufacture with different tuneable compositions and are expected to allow only the proton permeation but not the methanol due to their molecular sizing effects and affinity to the membrane surface. We have developed a nanostructured fuel cell membrane from polydimethyl siloxane rubber (PDMS), ethylene methyl co-acrylate (EMA) and multi-walled carbon nanotubes (MWNTs). The effect of incorporating different proportions of f-MWNTs in polymer membrane has been studied. The introduction of f-MWNTs in polymer matrix modified the polymer structure, and therefore the properties of the device. The proton conductivity, measured by an AC impedance technique using open-frame and two-electrode cell and methanol permeability of the membranes was found to be dependent on the f-MWNTs loading. The proton conductivity of the membranes increases with increase in concentration of f-MWNTs concentration due to increased content of conductive materials. Measured methanol permeabilities at 60oC were found to be dependant on loading of f-MWNTs. The methanol permeability decreased from 1.5 x 10-6 cm²/s for pure film to 0.8 x 10-7 cm²/s for a membrane containing 0.5wt % f-MWNTs. This is due to increasing proportion of f-MWNTs, the matrix becomes more compact. From DSC melting curves it is clear that the polymer matrix with f-MWNTs is thermally stable. FT-IR studies show good interaction between EMA and f-MWNTs. XRD analysis shows good crystalline behavior of the prepared membranes. Significant cost savings can be achieved when using the blended films which contain less expensive polymers.

Keywords: fuel cell membrane, polydimethyl siloxane rubber, carbon nanotubes, proton conductivity, methanol permeability

Procedia PDF Downloads 413

Authors: Boriana Karamanova, Svetlana Veleva, Luybomir Soserov, Ana Arenillas, Francesco Lufrano, Antonia Stoyanova

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Supercapacitors have received a lot of research attention and are promising energy storage devices due to their high power and long cycle life. In order to developed an advanced device with significant capacity for storing charge and cheap carbon materials, efforts must focus not only on improving synthesis by controlling the morphology and pore size but also on improving electrode-electrolyte compatibility of the resulting systems. The present study examines the relationship between the surface chemistry of two activated carbon xerogels, the electrolyte type, and the electrochemical properties of supercapacitors. Activated carbon xerogels were prepared by varying the initial pH of the resorcinol-formaldehyde aqueous solution. The materials produced are physicochemical characterized by DTA/TGA, porous characterization, and SEM analysis. The carbon xerogel based electrodes were prepared by spreading over glass plate a slurry containing the carbon gel, graphite, and poly vinylidene difluoride (PVDF) binder. The layer formed was dried consecutively at different temperatures and then detached by water. After, the layer was dried again to improve its mechanical stability. The developed electrode materials and the Aquivion® E87-05S membrane (Solvay Specialty Polymers), socked in Na2SO4 as a polymer electrolyte, were used to assembly the solid-state supercapacitor. Symmetric supercapacitor cells composed by same electrodes and 1 M KOH electrolytes are also assembled and tested for comparison. The supercapacitor performances are verified by different electrochemical methods - cyclic voltammetry, galvanostatic charge/discharge measurements, electrochemical impedance spectroscopy, and long-term durability tests in neutral and alkaline electrolytes. Specific capacitances, energy, and power density, energy efficiencies, and durability were compared into studied supercapacitors. Ex-situ physicochemical analyses on the synthesized materials have also been performed, which provide information about chemical and structural changes in the electrode morphology during charge / discharge durability tests. They are discussed on the basis of electrode-electrolyte interaction. The obtained correlations could be of significance in order to design sustainable solid-state supercapacitors with high power and energy density. Acknowledgement: This research is funded by the Ministry of Education and Science of Bulgaria under the National Program "European Scientific Networks" (Agreement D01-286 / 07.10.2020, D01-78/30.03.2021). Authors gratefully acknowledge.

Keywords: carbon xerogel, electrochemical tests, neutral and alkaline electrolytes, supercapacitors

Procedia PDF Downloads 137

Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay

Abstract:

Pervaporation (PV), a membrane-based separation technology, has gained much attention because of its energy saving capability and low-cost, especially for separation of azeotropic or close-boiling liquid mixtures. There are two crucial issues for industrial application of pervaporation process. The first is developing membrane material and tailoring membrane structure to obtain high pervaporation performances. The second is modeling pervaporation transport to better understand of the above-mentioned structure–pervaporation relationship. Many models were proposed to predict the mass transfer process, among them, solution-diffusion model is most widely used in describing pervaporation transport including preferential sorption, diffusion and evaporation steps. For modeling pervaporation transport, the permeation flux, which depends on the solubility and diffusivity of components in the membrane, should be obtained first. Traditionally, the solubility was calculated according to the Flory–Huggins theory. Separation of the benzene (Bz)/cyclohexane (Cx) mixture is industrially significant. Numerous papers have been focused on the Bz/Cx system to assess the PV properties of membrane materials. Membranes with both high permeability and selectivity are desirable for practical application. Several new polymers have been prepared to get both high permeability and selectivity. Styrene-butadiene rubbers (SBR), dense membranes cross-linked by chloromethylation were used in the separation of benzene/cyclohexane mixtures. The impact of chloromethylation reaction as a new method of cross-linking SBR on the pervaporation performance have been reported. In contrast to the vulcanization with sulfur, the cross-linking takes places on styrene units of polymeric chains via a methylene bridge. The partial pervaporative (PV) fluxes of benzene/cyclohexane mixtures in styrene-butadiene rubber (SBR) were predicted using Fick's first law. The predicted partial fluxes and the PV separation factor agreed well with the experimental data by integrating Fick's law over the benzene concentration. The effects of feed concentration and operating temperature on the predicted permeation flux by this proposed model are investigated. The predicted permeation fluxes are in good agreement with experimental data at lower benzene concentration in feed, but at higher benzene concentration, the model overestimated permeation flux. The predicted and experimental permeation fluxes all increase with operating temperature increasing. Solvent sorption levels for benzene/ cyclohexane mixtures in a SBR membrane were determined experimentally. The results showed that the solvent sorption levels were strongly affected by the feed composition. The Flory- Huggins equation generates higher R-square coefficient for the sorption selectivity.

Keywords: benzene, cyclohexane, pervaporation, permeation, sorption modeling, SBR

Procedia PDF Downloads 328

Authors: Dongwoo Kang, Yunsung Yoo, Injun Kim, Jongin Lee, Jinwon Park

Abstract:

Since industrial revolution, energy usage by human-beings has been drastically increased resulting in the enormous emissions of carbon dioxide into the atmosphere. High concentration of carbon dioxide is well recognized as the main reason for the climate change by breaking the heat equilibrium of the earth. In order to decrease the amount of carbon dioxide emission, lots of technologies have been developed. One of the methods is to capture carbon dioxide after combustion process using liquid type absorbents. However, for some nations, captured carbon dioxide cannot be treated and stored properly due to their geological structures. Also, captured carbon dioxide can be leaked out when crust activities are active. Hence, the method to convert carbon dioxide as stable and useful products were developed. It is usually called CCU, that is, Carbon Capture and Utilization. There are several ways to convert carbon dioxide into useful substances. For example, carbon dioxide can be converted and used as fuels such as diesel, plastics, and polymers. However, these types of technologies require lots of energy to make stable carbon dioxide into a reactive one. Hence, converting it into metal carbonates salts have been studied widely. When carbon dioxide is captured by alkanolamine-based liquid absorbents, it exists as ionic forms such as carbonate, carbamate, and bicarbonate. When adequate metal ions are added, metal carbonate salt can be produced by ionic reaction with fast reaction kinetics. However, finding metal sources can be one of the problems for this method to be commercialized. If natural resources such as calcium oxide were used to supply calcium ions, it is not thought to have the economic feasibility to use natural resources to treat carbon dioxide. In this research, high concentrated industrial wastewater produced from refined salt production facility have been used as metal supplying source, especially for calcium cations. To ensure purity of final products, calcium ions were selectively separated in the form of gypsum dihydrate. After that, carbon dioxide is captured using alkanolamine-based absorbents making carbon dioxide into reactive ionic form. And then, high purity calcium carbonate salt was produced. The existence of calcium carbonate was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) images. Also, carbon dioxide loading curves for absorption, conversion, and desorption were provided. Also, in order to investigate the possibility of the absorbent reuse, reabsorption experiments were performed either. Produced calcium carbonate as final products is seemed to have potential to be used in various industrial fields including cement and paper making industries and pharmaceutical engineering fields.

Keywords: alkanolamine, calcium carbonate, climate change, seawater, industrial wastewater

Procedia PDF Downloads 187

Authors: Małgorzata Golonka, Jadwiga Laska

Abstract:

Self-healing polymers are one of the most investigated groups of smart materials. As materials engineering has recently focused on the design, production and research of modern materials and future technologies, researchers are looking for innovations in structural, construction and coating materials. Based on available scientific articles, it can be concluded that most of the research focuses on the self-healing of cement, concrete, asphalt and anticorrosion resin coatings. In our study, a method of obtaining and testing the properties of several types of microcapsules for use in self-healing polymer materials was developed. A method to obtain microcapsules exhibiting various mechanical properties, especially compressive strength was developed. The effect was achieved by using various polymer materials to build the shell: urea-formaldehyde resin (UFR), melamine-formaldehyde resin (MFR), melamine-urea-formaldehyde resin (MUFR). Dicyclopentadiene (DCPD) was used as the core material due to the possibility of its polymerization according to the ring-opening olefin metathesis (ROMP) mechanism in the presence of a solid Grubbs catalyst showing relatively high chemical and thermal stability. The ROMP of dicyclopentadiene leads to a polymer with high impact strength, high thermal resistance, good adhesion to other materials and good chemical and environmental resistance, so it is potentially a very promising candidate for the self-healing of materials. The capsules were obtained by condensation polymerization of formaldehyde with urea, melamine or copolymerization with urea and melamine in situ in water dispersion, with different molar ratios of formaldehyde, urea and melamine. The fineness of the organic phase dispersed in water, and consequently the size of the microcapsules, was regulated by the stirring speed. In all cases, to establish such synthesis conditions as to obtain capsules with appropriate mechanical strength. The microcapsules were characterized by determining the diameters and their distribution and measuring the shell thickness using digital optical microscopy and scanning electron microscopy, as well as confirming the presence of the active substance in the core by FTIR and SEM. Compression tests were performed to determine mechanical strength of the microcapsules. The highest repeatability of microcapsule properties was obtained for UFR resin, while the MFR resin had the best mechanical properties. The encapsulation efficiency of MFR was much lower compared to UFR, though. Therefore, capsules with a MUFR shell may be the optimal solution. The chemical reaction between the active substance present in the capsule core and the catalyst placed outside the capsules was confirmed by FTIR spectroscopy. The obtained autonomous repair systems (microcapsules + catalyst) were introduced into polyethylene in the extrusion process and tested for the self-repair of the material.

Keywords: autonomic self-healing system, dicyclopentadiene, melamine-urea-formaldehyde resin, microcapsules, thermoplastic materials

Procedia PDF Downloads 47