Commenced in January 2007
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Edition: International
Paper Count: 1708

Search results for: deep eutectic solvents

1708 An Eco-Friendly Preparations of Izonicotinamide Quaternary Salts in Deep Eutectic Solvents

Authors: Dajana Gašo-Sokač, Valentina Bušić


Deep eutectic solvents (DES) are liquids composed of two or three safe, inexpensive components, often interconnected by noncovalent hydrogen bonds which produce eutectic mixture whose melting point is lower than that of each component. No data in literature have been found on the quaternization reaction in DES. The use of DES have several advantages: they are environmentally benign and biodegradable, easy for purification and simple for preparation. An environmentally sustainable method for preparing quaternary salts of izonicotinamide and substituted 2-bromoacetophenones was demonstrated here using choline chloride-based DES. The quaternization reaction was carried out by three synthetic approaches: conventional method, microwave and ultrasonic irradiation. We showed that the highest yields were obtained by the microwave method.

Keywords: deep eutectic solvents, izonicotinamide salts, microwave synthesis, ultrasonic irradiation

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1707 COSMO-RS Prediction for Choline Chloride/Urea Based Deep Eutectic Solvent: Chemical Structure and Application as Agent for Natural Gas Dehydration

Authors: Tayeb Aissaoui, Inas M. AlNashef


In recent years, green solvents named deep eutectic solvents (DESs) have been found to possess significant properties and to be applicable in several technologies. Choline chloride (ChCl) mixed with urea at a ratio of 1:2 and 80 °C was the first discovered DES. In this article, chemical structure and combination mechanism of ChCl: urea based DES were investigated. Moreover, the implementation of this DES in water removal from natural gas was reported. Dehydration of natural gas by ChCl:urea shows significant absorption efficiency compared to triethylene glycol. All above operations were retrieved from COSMOthermX software. This article confirms the potential application of DESs in gas industry.

Keywords: COSMO-RS, deep eutectic solvents, dehydration, natural gas, structure, organic salt

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1706 Novel Synthesis of Metal Oxide Nanoparticles from Type IV Deep Eutectic Solvents

Authors: Lorenzo Gontrani, Marilena Carbone, Domenica Tommasa Donia, Elvira Maria Bauer, Pietro Tagliatesta


One of the fields where DES shows remarkable added values is the synthesis Of inorganic materials, in particular nanoparticles. In this field, the higher- ent and highly-tunable nano-homogeneities of DES structure give origin to a marked templating effect, a precious role that has led to the recent bloom of a vast number of studies exploiting these new synthesis media to prepare Nanomaterials and composite structures of various kinds. In this contribution, the most recent developments in the field will be reviewed, and some ex-citing examples of novel metal oxide nanoparticles syntheses using non-toxic type-IV Deep Eutectic Solvents will be described. The prepared materials possess nanometric dimensions and show flower-like shapes. The use of the pre- pared nanoparticles as fluorescent materials for the detection of various contaminants is under development.

Keywords: metal deep eutectic solvents, nanoparticles, inorganic synthesis, type IV DES, lamellar

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1705 Extractive Desulfurization of Fuels Using Choline Chloride-Based Deep Eutectic Solvents

Authors: T. Zaki, Fathi S. Soliman


Desulfurization process is required by most, if not all refineries, to achieve ultra-low sulfur fuel, that contains less than 10 ppm sulfur. A lot of research works and many effective technologies have been studied to achieve deep desulfurization process in moderate reaction environment, such as adsorption desulfurization (ADS), oxidative desulfurization (ODS), biodesulfurization and extraction desulfurization (EDS). Extraction desulfurization using deep eutectic solvents (DESs) is considered as simple, cheap, highly efficient and environmentally friend process. In this work, four DESs were designed and synthesized. Choline chloride (ChCl) was selected as typical hydrogen bond acceptors (HBA), and ethylene glycol (EG), glycerol (Gl), urea (Ur) and thiourea (Tu) were selected as hydrogen bond donors (HBD), from which a series of deep eutectic solvents were synthesized. The experimental data showed that the synthesized DESs showed desulfurization affinities towards the thiophene species in cyclohexane solvent. Ethylene glycol molecules showed more affinity to create hydrogen bond with thiophene instead of choline chloride. Accordingly, ethylene glycol choline chloride DES has the highest extraction efficiency.

Keywords: DES, desulfurization, green solvent, extraction

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1704 Investigation of Deep Eutectic Solvents for Microwave Assisted Extraction and Headspace Gas Chromatographic Determination of Hexanal in Fat-Rich Food

Authors: Birute Bugelyte, Ingrida Jurkute, Vida Vickackaite


The most complicated step of the determination of volatile compounds in complex matrices is the separation of analytes from the matrix. Traditional analyte separation methods (liquid extraction, Soxhlet extraction) require a lot of time and labour; moreover, there is a risk to lose the volatile analytes. In recent years, headspace gas chromatography has been used to determine volatile compounds. To date, traditional extraction solvents have been used in headspace gas chromatography. As a rule, such solvents are rather volatile; therefore, a large amount of solvent vapour enters into the headspace together with the analyte. Because of that, the determination sensitivity of the analyte is reduced, a huge solvent peak in the chromatogram can overlap with the peaks of the analyts. The sensitivity is also limited by the fact that the sample can’t be heated at a higher temperature than the solvent boiling point. In 2018 it was suggested to replace traditional headspace gas chromatographic solvents with non-volatile, eco-friendly, biodegradable, inexpensive, and easy to prepare deep eutectic solvents (DESs). Generally, deep eutectic solvents have low vapour pressure, a relatively wide liquid range, much lower melting point than that of any of their individual components. Those features make DESs very attractive as matrix media for application in headspace gas chromatography. Also, DESs are polar compounds, so they can be applied for microwave assisted extraction. The aim of this work was to investigate the possibility of applying deep eutectic solvents for microwave assisted extraction and headspace gas chromatographic determination of hexanal in fat-rich food. Hexanal is considered one of the most suitable indicators of lipid oxidation degree as it is the main secondary oxidation product of linoleic acid, which is one of the principal fatty acids of many edible oils. Eight hydrophilic and hydrophobic deep eutectic solvents have been synthesized, and the influence of the temperature and microwaves on their headspace gas chromatographic behaviour has been investigated. Using the most suitable DES, microwave assisted extraction conditions and headspace gas chromatographic conditions have been optimized for the determination of hexanal in potato chips. Under optimized conditions, the quality parameters of the prepared technique have been determined. The suggested technique was applied for the determination of hexanal in potato chips and other fat-rich food.

Keywords: deep eutectic solvents, headspace gas chromatography, hexanal, microwave assisted extraction

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1703 Devulcanization of Waste Rubber Tyre Utilizing Deep Eutectic Solvents and Ultrasonic Energy

Authors: Ricky Saputra, Rashmi Walvekar, Mohammad Khalid, Kaveh Shahbaz, Suganti Ramarad


This particular study of interest aims to study the effect of coupling ultrasonic treatment with eutectic solvents in devulcanization process of waste rubber tyre. Specifically, three different types of Deep Eutectic Solvents (DES) were utilized, namely ChCl:Urea (1:2), ChCl:ZnCl₂ (1:2) and ZnCl₂:urea (2:7) in which their physicochemical properties were analysed and proven to have permissible water content that is less than 3.0 wt%, degradation temperature below 200ᵒC and freezing point below 60ᵒC. The mass ratio of rubber to DES was varied from 1:20-1:40, sonicated for 1 hour at 37 kHz and heated at variable time of 5-30 min at 180ᵒC. Energy dispersive x-rays (EDX) results revealed that the first two DESs give the highest degree of sulphur removal at 74.44 and 76.69% respectively with optimum heating time at 15 minutes whereby if prolonged, reformation of crosslink network would be experienced. Such is supported by the evidence shown by both FTIR and FESEM results where di-sulfide peak reappears at 30 minutes and morphological structures from 15 to 30 minutes change from smooth with high voidage to rigid with low voidage respectively. Furthermore, TGA curve reveals similar phenomena whereby at 15 minutes thermal decomposition temperature is at the lowest due to the decrease of molecular weight as a result of sulphur removal but increases back at 30 minutes. Type of bond change was also analysed whereby it was found that only di-sulphide bond was cleaved and which indicates partial-devulcanization. Overall, the results show that DES has a great potential to be used as devulcanizing solvent.

Keywords: crosslink network, devulcanization, eutectic solvents, reformation, ultrasonic

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1702 The Evaluation of Fuel Desulfurization Performance of Choline-Chloride Based Deep Eutectic Solvents with Addition of Graphene Oxide as Catalyst

Authors: Chiau Yuan Lim, Hayyiratul Fatimah Mohd Zaid, Fai Kait Chong


Deep Eutectic Solvent (DES) is used in various applications due to its simplicity in synthesis procedure, biodegradable, inexpensive and easily available chemical ingredients. Graphene Oxide is a popular catalyst that being used in various processes due to its stacking carbon sheets in layer which theoretically rapid up the catalytic processes. In this study, choline chloride based DESs were synthesized and ChCl-PEG(1:4) was found to be the most effective DES in performing desulfurization, which it is able to remove up to 47.4% of the sulfur content in the model oil in just 10 minutes, and up to 95% of sulfur content after repeat the process for six times. ChCl-PEG(1:4) able to perform up to 32.7% desulfurization on real diesel after 6 multiple stages. Thus, future research works should focus on removing the impurities on real diesel before utilising DESs in petroleum field.

Keywords: choline chloride, deep eutectic solvent, fuel desulfurization, graphene oxide

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1701 Kinetic Study on Extracting Lignin from Black Liquor Using Deep Eutectic Solvents

Authors: Fatemeh Saadat Ghareh Bagh, Srimanta Ray, Jerald Lalman


Lignin, the largest inventory of organic carbon with a high caloric energy value is a major component in woody and non-woody biomass. In pulping mills, a large amount of the lignin is burned for energy. At the same time, the phenolic structure of lignin enables it to be converted to value-added compounds.This study has focused on extracting lignin from black liquor using deep eutectic solvents (DESs). Therefore, three choline chloride (ChCl)-DESs paired with lactic acid (LA) (1:11), oxalic acid.2H₂O (OX) (1:4), and malic acid (MA) (1:3) were synthesized at 90oC and atmospheric pressure. The kinetics of lignin recovery from black liquor using DES was investigated at three moderate temperatures (338, 353, and 368 K) at time intervals from 30 to 210 min. The extracted lignin (acid soluble lignin plus Klason lignin) was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR studies included comparing the extracted lignin with a model Kraft lignin. The extracted lignin was characterized spectrophotometrically to determine the acid soluble lignin (ASL) [TAPPI UM 250] fraction and Klason lignin was determined gravimetrically using TAPPI T 222 om02. The lignin extraction reaction using DESs was modeled by first-order reaction kinetics and the activation energy of the process was determined. The ChCl:LA-DES recovered lignin was 79.7±2.1% at 368K and a DES:BL ratio of 4:1 (v/v). The quantity of lignin extracted for the control solvent, [emim][OAc], was 77.5+2.2%. The activation energy measured for the LA-DES system was 22.7 KJ mol⁻¹, while the activation energy for the OX-DES and MA-DES systems were 7.16 KJ·mol⁻¹ and 8.66 KJ·mol⁻¹ when the total lignin recovery was 75.4 ±0.9% and 62.4 ±1.4, % respectively.

Keywords: black liquor, deep eutectic solvents, kinetics, lignin

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1700 Deep Eutectic Solvent/ Polyimide Blended Membranes for Anaerobic Digestion Gas Separation

Authors: Glemarie C. Hermosa, Sheng-Jie You, Chien Chih Hu


Efficient separation technologies are required for the removal of carbon dioxide from natural gas streams. Membrane-based natural gas separation has emerged as one of the fastest growing technologies, due to the compactness, higher energy efficiency and economic advantages which can be reaped. The removal of Carbon dioxide from gas streams using membrane technology will also give the advantage like environmental friendly process compared to the other technologies used in gas separation. In this study, Polyimide membranes, which are mostly used in the separation of gases, are blended with a new kind of solvent: Deep Eutectic Solvents or simply DES. The three types of DES are used are choline chloride based mixed with three different hydrogen bond donors: Lactic acid, N-methylurea and Urea. The blending of the DESs to Polyimide gave out high permeability performance. The Gas Separation performance for all the membranes involving CO2/CH4 showed low performance while for CO2/N2 surpassed the performance of some studies. Among the three types of DES used the solvent Choline Chloride/Lactic acid exhibited the highest performance for both Gas Separation applications. The values are 10.5 for CO2/CH4 selectivity and 60.5 for CO2/N2. The separation results for CO2/CH4 may be due to the viscosity of the DESs affecting the morphology of the fabricated membrane thus also impacts the performance. DES/blended Polyimide membranes fabricated are novel and have the potential of a low-cost and environmental friendly application for gas separation.

Keywords: deep eutectic solvents, gas separation, polyimide blends, polyimide membranes

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1699 Mentha piperita Formulations in Natural Deep Eutectic Solvents: Phenolic Profile and Biological Activity

Authors: Tatjana Jurić, Bojana Blagojević, Denis Uka, Ružica Ždero Pavlović, Boris M. Popović


Natural deep eutectic solvents (NADES) represent a class of modern systems that have been developed as a green alternative to toxic organic solvents, which are commonly used as extraction media. It has been considered that hydrogen bonding is the main interaction leading to the formation of NADES. The aim of this study was phytochemical characterization and determination of the antioxidant and antibacterial activity of Mentha piperita leaf extracts obtained by six choline chloride-based NADES. NADES were prepared by mixing choline chloride with different hydrogen bond donors in 1:1 molar ratio following the addition of 30% (w/w) water. The mixtures were then heated (60 °C) and stirred (650 rpm) until the clear homogenous liquids were obtained. The Mentha piperita extracts were prepared by mixing 75 mg of peppermint leaves with 1 mL of NADES following by the heating and stirring (60 °C, 650 rpm) within 30 min. The content of six phenolics in extracts was determined using HPLC-PDA. The dominant compounds presented in peppermint leaves - rosmarinic acid and luteolin 7-O-glucoside, were extracted by NADES at a similar level as 70% ethanol. The microdilution method was applied to test the antibacterial activity of extracts. Compared with 70% ethanol, all NADES systems showed higher antibacterial activity towards Pseudomonas aeruginosa (Gram -), Staphylococcus aureus (Gram +), Escherichia coli (Gram -), and Salmonella enterica (Gram -), especially NADES containing organic acids. The majority of NADES extracts showed a better ability to neutralize DPPH radical than conventional solvent and similar ability to reduce Fe3+ to Fe2+ ions in FRAP assay. The obtained results introduce NADES systems as the novel, sustainable, and low-cost solvents with a variety of applications.

Keywords: antibacterial activity, antioxidant activity, green extraction, natural deep eutectic solvents, polyphenols

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1698 Stabilizing Effects of Deep Eutectic Solvents on Alcohol Dehydrogenase Mediated Systems

Authors: Fatima Zohra Ibn Majdoub Hassani, Ivan Lavandera, Joseph Kreit


This study explored the effects of different organic solvents, temperature, and the amount of glycerol on the alcohol dehydrogenase (ADH)-catalysed stereoselective reduction of different ketones. These conversions were then analyzed by gas chromatography. It was found that when the amount of deep eutectic solvents (DES) increases, it can improve the stereoselectivity of the enzyme although reducing its ability to convert the substrate into the corresponding alcohol. Moreover, glycerol was found to have a strong stabilizing effect on the ADH from Ralstonia sp. (E. coli/ RasADH). In the case of organic solvents, it was observed that the best conversions into the alcohols were achieved with DMSO and hexane. It was also observed that temperature decreased the ability of the enzyme to convert the substrates into the products and also affected the selectivity. In addition to that, the recycling of DES up to three times gave good conversions and enantiomeric excess results and glycerol showed a positive effect in the stability of various ADHs. Using RasADH, a good conversion and enantiomeric excess into the S-alcohol were obtained. It was found that an enhancement of the temperature disabled the stabilizing effect of glycerol and decreased the stereoselectivity of the enzyme. However, for other ADHs a temperature increase had an opposite positive effect, especially with ADH-T from Thermoanaerobium sp. One of the objectives of this study was to see the effect of cofactors such as NAD(P) on the biocatlysis activities of ADHs.

Keywords: alcohol dehydrogenases, DES, gas chromatography, RasADH

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1697 Working Fluids in Absorption Chillers: Investigation of the Use of Deep Eutectic Solvents

Authors: L. Cesari, D. Alonso, F. Mutelet


The interest in cold production has been on the increase in absorption chillers for many years. In fact, the absorption cycles replace the compressor and thus reduce electrical consumption. The devices also allow waste heat generated through industrial activities to be recovered and cooled to a moderate temperature in accordance with regulatory guidelines. Many working fluids were investigated but could not compete with the commonly used {H2O + LiBr} and {H2O + NH3} to author’s best knowledge. Yet, the corrosion, toxicity and crystallization phenomena of these mixtures prevent the development of the absorption technology. This work investigates the possible use of a glyceline deep eutectic solvent (DES) and CO2 as working fluid in an absorption chiller. To do so, good knowledge of the mixtures is required. Experimental measurements (vapor-liquid equilibria, density, and heat capacity) were performed to complete the data lacking in the literature. The performance of the mixtures was quantified by the calculation of the coefficient of performance (COP). The results show that working fluids containing DES + CO2 are an interesting alternative and lead to different trails of working mixtures for absorption and chiller.

Keywords: absorption devices, deep eutectic solvent, energy valorization, experimental data, simulation

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1696 Metal-Based Deep Eutectic Solvents for Extractive Desulfurization of Fuels: Analysis from Molecular Dynamics Simulations

Authors: Aibek Kukpayev, Dhawal Shah


Combustion of sour fuels containing high amount of sulfur leads to the formation of sulfur oxides, which adversely harm the environment and has a negative impact on human health. Considering this, several legislations have been imposed to bring down the sulfur content in fuel to less than 10 ppm. In recent years, novel deep eutectic solvents (DESs) have been developed to achieve deep desulfurization, particularly to extract thiophenic compounds from liquid fuels. These novel DESs, considered as analogous to ionic liquids are green, eco-friendly, inexpensive, and sustainable. We herein, using molecular dynamic simulation, analyze the interactions of metal-based DESs with model oil consisting of thiophenic compounds. The DES used consists of polyethylene glycol (PEG-200) as a hydrogen bond donor, choline chloride (ChCl) or tetrabutyl ammonium chloride (TBAC) as a hydrogen bond acceptor, and cobalt chloride (CoCl₂) as metal salt. In particular, the combination of ChCl: PEG-200:CoCl₂ at a ratio 1:2:1 and the combination of TBAC:PEG-200:CoCl₂ at a ratio 1:2:0.25 were simulated, separately, with model oil consisting of octane and thiophenes at 25ᵒC and 1 bar. The results of molecular dynamics simulations were analyzed in terms of interaction energies between different components. The simulations revealed a stronger interaction between DESs/thiophenes as compared with octane/thiophenes, suggestive of an efficient desulfurization process. In addition, our analysis suggests that the choice of hydrogen bond acceptor strongly influences the efficiency of the desulfurization process. Taken together, the results also show the importance of the metal ion, although present in small amount, in the process, and the role of the polymer in desulfurization of the model fuel.

Keywords: deep eutectic solvents, desulfurization, molecular dynamics simulations, thiophenes

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1695 Metal Extraction into Ionic Liquids and Hydrophobic Deep Eutectic Mixtures

Authors: E. E. Tereshatov, M. Yu. Boltoeva, V. Mazan, M. F. Volia, C. M. Folden III


Room temperature ionic liquids (RTILs) are a class of liquid organic salts with melting points below 20 °C that are considered to be environmentally friendly ‘designers’ solvents. Pure hydrophobic ILs are known to extract metallic species from aqueous solutions. The closest analogues of ionic liquids are deep eutectic solvents (DESs), which are a eutectic mixture of at least two compounds with a melting point lower than that of each individual component. DESs are acknowledged to be attractive for organic synthesis and metal processing. Thus, these non-volatile and less toxic compounds are of interest for critical metal extraction. The US Department of Energy and the European Commission consider indium as a key metal. Its chemical homologue, thallium, is also an important material for some applications and environmental safety. The aim of this work is to systematically investigate In and Tl extraction from aqueous solutions into pure fluorinated ILs and hydrophobic DESs. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. The extraction efficiency of the TlXz3–z anionic species (where X = Cl– and/or Br–) is greater for ionic liquids with more hydrophobic cations. Unexpectedly high distribution ratios (> 103) of Tl(III) were determined even by applying a pure ionic liquid as receiving phase. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the co-extraction of two different anionic species, and the relative contributions of each mechanism have been determined. The first evidence of indium extraction into new quaternary ammonium- and menthol-based hydrophobic DESs from hydrochloric and oxalic acid solutions with distribution ratios up to 103 will be provided. Data obtained allow us to interpret the mechanism of thallium and indium extraction into ILs and DESs media. The understanding of Tl and In chemical behavior in these new media is imperative for the further improvement of separation and purification of these elements.

Keywords: deep eutectic solvents, indium, ionic liquids, thallium

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1694 Synthesis of 5-Substituted 1H-Tetrazoles in Deep Eutectic Solvent

Authors: Swapnil A. Padvi, Dipak S. Dalal


The chemistry of tetrazoles has been grown tremendously in the past few years because tetrazoles are important and useful class of heterocyclic compounds which have a widespread application such as anticancer, antimicrobial, analgesics, antibacterial, antifungal, antihypertensive, and anti-allergic drugs in medicinal chemistry. Furthermore, tetrazoles have application in material sciences as explosives, rocket propellants, and in information recording systems. In addition to this, they have a wide range of application in coordination chemistry as a ligand. Deep eutectic solvents (DES) have emerged over the current decade as a novel class of green reaction media and applied in various fields of sciences because of their unique physical and chemical properties similar to the ionic liquids such as low vapor pressure, non-volatility, high thermal stability and recyclability. In addition, the reactants of DES are cheaply available, low-toxic, and biodegradable, which makes them predominantly required for large-scale applications effectively in industrial production. Herein we report the [2+3] cycloaddition reaction of organic nitriles with sodium azide affords the corresponding 5-substituted 1H-tetrazoles in six different types of choline chloride based deep eutectic solvents under mild reaction condition. Choline chloride: ZnCl2 (1:2) showed the best results for the synthesis of 5-substituted 1 H-tetrazoles. This method reduces the disadvantages such as: the use of toxic metals and expensive reagents, drastic reaction conditions and the presence of dangerous hydrazoic acid. The approach provides environment-friendly, short reaction times, good to excellent yields; safe process and simple workup make this method an attractive and useful contribution to present green organic synthesis of 5-substituted-1H-tetrazoles. All synthesized compounds were characterized by IR, 1H NMR, 13C NMR and Mass spectroscopy. DES can be recovered and reused three times with very little loss in activity.

Keywords: click chemistry, choline chloride, green chemistry, deep eutectic solvent, tetrazoles

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1693 Damage Strain Analysis of Parallel Fiber Eutectic

Authors: Jian Zheng, Xinhua Ni, Xiequan Liu


According to isotropy of parallel fiber eutectic, the no- damage strain field in parallel fiber eutectic is obtained from the flexibility tensor of parallel fiber eutectic. Considering the damage behavior of parallel fiber eutectic, damage variables are introduced to determine the strain field of parallel fiber eutectic. The damage strains in the matrix, interphase, and fiber of parallel fiber eutectic are quantitatively analyzed. Results show that damage strains are not only associated with the fiber volume fraction of parallel fiber eutectic, but also with the damage degree.

Keywords: damage strain, initial strain, fiber volume fraction, parallel fiber eutectic

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1692 Thermosonic Devulcanization of Waste Ground Rubber Tires by Quaternary Ammonium-Based Ternary Deep Eutectic Solvents and the Effect of α-Hydrogen

Authors: Ricky Saputra, Rashmi Walvekar, Mohammad Khalid


Landfills, water contamination, and toxic gas emission are a few impacts faced by the environment due to the increasing number of αof waste rubber tires (WRT). In spite of such concerning issue, only minimal efforts are taken to reclaim or recycle these wastes as their products are generally not-profitable for companies. Unlike the typical reclamation process, devulcanization is a method to selectively cleave sulfidic bonds within vulcanizates to avoid polymeric scissions that compromise elastomer’s mechanical and tensile properties. The process also produces devulcanizates that are re-processable similar to virgin rubber. Often, a devulcanizing agent is needed. In the current study, novel and sustainable ammonium chloride-based ternary deep eutectic solvents (TDES), with a different number of α-hydrogens, were utilised to devulcanize ground rubber tire (GRT) as an effort to implement green chemistry to tackle such issue. 40-mesh GRT were soaked for 1 day with different TDESs and sonicated at 37-80 kHz for 60-120 mins and heated at 100-140oC for 30-90 mins. Devulcanizates were then filtered, dried, and evaluated based on the percentage of by means of Flory-Rehner calculation and swelling index. The result shows that an increasing number of α-Hs increases the degree of devulcanization, and the value achieved was around eighty-percent, thirty percent higher than the typical industrial-autoclave method. Resulting bondages of devulcanizates were also analysed by Fourier transform infrared spectrometer (FTIR), Horikx fitting, and thermogravimetric analyser (TGA). The earlier two confirms only sulfidic scissions were experienced by GRT through the treatment, while the latter proves the absence or negligibility of carbon-chains scission.

Keywords: ammonium, sustainable, deep eutectic solvent, α-hydrogen, waste rubber tire

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1691 Chitin Crystalline Phase Transition Promoted by Deep Eutectic Solvent

Authors: Diana G. Ramirez-Wong, Marius Ramirez, Regina Sanchez-Leija, Adriana Rugerio, R. Araceli Mauricio-Sanchez, Martin A. Hernandez-Landaverde, Arturo Carranza, John A. Pojman, Josue D. Mota-Morales, Gabriel Luna-Barcenas


Chitin films were prepared using alpha-chitin from shrimp shells as raw material and a simple method of precipitation-evaporation. Choline chloride: urea Deep Eutectic Solvent (DES) was used to disperse chitin and compared against hexafluoroisopropanol (HFIP). A careful analysis of the chemical and crystalline structure was followed along the synthesis of the films, revealing crystalline-phase transitions. The full conversion of alpha- to beta-, or alpha- to gamma-chitin structure were detected by XRD and NMR on the films. The synthesis of highly crystalline monophasic gamma-chitin films was achieved using a DES; whereas HFIP helps to promote the beta-phase. These results are encouraging to continue in the study of DES as good processing media to control the final properties of chitin based materials.

Keywords: chitin, deep eutectic solvent, polymorph, phase transformation

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1690 Limiting Fracture Stress of Composite Ceramics with Symmetric Triangle Eutectic

Authors: Jian Zheng, Jinfeng Yu, Xinhua Ni


The limiting fracture stress predicting model of composite ceramics with symmetric triangle eutectic was established based on its special microscopic structure. The symmetric triangle eutectic is consisted of matrix, the strong constraint inter-phase and reinforced fiber inclusions which are 120 degrees uniform symmetrical distribution. Considering the conditions of the rupture of the cohesive bond between matrix and fibers in eutectic and the stress concentration effect at the fiber end, the intrinsic fracture stress of eutectic was obtained. Based on the biggest micro-damage strain in eutectic, defining the load function, the macro-damage fracture stress of symmetric triangle eutectic was determined by boundary conditions. Introducing the conception of critical zone, the theoretical limiting fracture stress forecasting model of composite ceramics was got, and the stress was related to the fiber size and fiber volume fraction in eutectic. The calculated results agreed with the experimental results in the literature.

Keywords: symmetric triangle eutectic, composite ceramics, limiting stress, intrinsic fracture stress

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1689 Photophysics and Torsional Dynamics of Thioflavin T in Deep Eutectic Solvents

Authors: Rajesh Kumar Gautam, Debabrata Seth


Thioflavin-T (ThT) play a key role of an important biologically active fluorescent sensor for amyloid fibrils. ThT molecule has been developed a method to detect the analysis of different type of diseases such as neurodegenerative disorders, Alzheimer’s, Parkinson’s, and type II diabetes. ThT was used as a fluorescent marker to detect the formation of amyloid fibril. In the presence of amyloid fibril, ThT becomes highly fluorescent. ThT undergoes twisting motion around C-C bonds of the two adjacent benzothiazole and dimethylaniline aromatic rings, which is predominantly affected by the micro-viscosity of the local environment. The present study articulates photophysics and torsional dynamics of biologically active molecule ThT in the presence of deep-eutectic solvents (DESs). DESs are environment-friendly, low cost and biodegradable alternatives to the ionic liquids. DES resembles ionic liquids, but the constituents of a DES include a hydrogen bond donor and acceptor species, in addition to ions. Due to the presence of the H-bonding network within a DES, it exhibits structural heterogeneity. Herein, we have prepared two different DESs by mixing urea with choline chloride and N, N-diethyl ethanol ammonium chloride at ~ 340 K. It was reported that deep eutectic mixture of choline chloride with urea gave a liquid with a freezing point of 12°C. We have experimented by taking two different concentrations of ThT. It was observed that at higher concentration of ThT (50 µM) it forms aggregates in DES. The photophysics of ThT as a function of temperature have been explored by using steady-state, and picoseconds time-resolved fluorescence emission spectroscopic techniques. From the spectroscopic analysis, we have observed that with rising temperature the fluorescence quantum yields and lifetime values of ThT molecule gradually decreases; this is the cumulative effect of thermal quenching and increase in the rate of the torsional rate constant. The fluorescence quantum yield and fluorescence lifetime decay values were always higher for DES-II (urea & N, N-diethyl ethanol ammonium chloride) than those for DES-I (urea & choline chloride). This was mainly due to the presence of structural heterogeneity of the medium. This was further confirmed by comparison with the activation energy of viscous flow with the activation energy of non-radiative decay. ThT molecule in less viscous media undergoes a very fast twisting process and leads to deactivation from the photoexcited state. In this system, the torsional motion increases with increasing temperature. We have concluded that beside bulk viscosity of the media, structural heterogeneity of the medium play crucial role to guide the photophysics of ThT in DESs. The analysis of the experimental data was carried out in the temperature range 288 ≤ T = 333K. The present articulate is to obtain an insight into the DESs as media for studying various photophysical processes of amyloid fibrils sensing molecule of ThT.

Keywords: deep eutectic solvent, photophysics, Thioflavin T, the torsional rate constant

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1688 Effect of Y Addition on the Microstructure and Mechanical Properties of Sn-Zn Eutectic Alloy

Authors: Jung-Ho Moon, Tae Kwon Ha


The effect of Yttrium addition on the microstructure and mechanical properties of Sn-Zn eutectic alloy, which has been attracting intensive focus as a Pb-free solder material, was investigated in this study. Phase equilibrium has been calculated by using FactSage® to evaluate the composition and fraction of equilibrium intermetallic compounds and construct a phase diagram. In the case of Sn-8.8 Zn eutectic alloy, the as-cast microstructure was typical lamellar. With addition of 0.25 wt. %Y, a large amount of pro-eutectic phases have been observed and various YZnx intermetallic compounds were expected to successively form during cooling. Hardness of Sn-8.8 Zn alloy was not affected by Y-addition and both alloys could be rolled by 90% at room temperature.

Keywords: Sn-Zn eutectic alloy, yttrium, FactSage®, microstructure, mechanical properties

Procedia PDF Downloads 338
1687 Microstructural Characterization and Mechanical Properties of Al-2Mn-5Fe Ternary Eutectic Alloy

Authors: Emin Çadirli, Izzettin Yilmazer, Uğur Büyük, Hasan Kaya


Al-2Mn-5Fe eutectic alloy (wt.%) was prepared in a graphite crucible under vacuum atmosphere. The samples were directionally solidified upward at a constant temperature gradient in four different of growth rates by using a Bridgman method. The values of eutectic spacing were measured from longitudinal and transverse sections of the samples. The dependence of eutectic spacing on the growth rate was determined by using linear regression analysis. The microhardness and tensile strength of the studied alloy also were measured from directionally solidified samples. The dependency of the microhardness and tensile strength for directionally solidified Al-2Mn-5Fe eutectic alloy on the growth rate were investigated and the relationships between them were experimentally obtained by using regression analysis. The results obtained in present work were compared with the previous similar experimental results obtained for binary and ternary alloys.

Keywords: eutectic alloy, microhardness, microstructure, tensile strength

Procedia PDF Downloads 373
1686 The Effects of Microstructure of Directionally Solidified Al-Si-Fe Alloys on Micro Hardness, Tensile Strength, and Electrical Resistivity

Authors: Sevda Engin, Ugur Buyuk, Necmettin Marasli


Directional solidification of eutectic alloys attracts considerable attention because of microhardness, tensile strength, and electrical resistivity influenced by eutectic structures. In this research, we examined processing of Al–Si–Fe (Al–11.7wt.%Si–1wt.%Fe) eutectic by directional solidification. The alloy was prepared by vacuum furnace and directionally solidified in Bridgman-type equipment. During the directional solidification process, the growth rates utilized varied from 8.25 m/s to 164.80 m/s. The Al–Si–Fe system showed an eutectic transformation, which resulted in the matrix Al, Si and Al5SiFe plate phases. The eutectic spacing between (λ_Si-λ_Si, λ_(Al_5 SiFe)-λ_(Al_5 SiFe)) was measured. Additionally, the microhardness, tensile strength, and electrical resistivity of the alloy were determined using directionally solidified samples. The effects of growth rates on microhardness, tensile strength, and electrical resistivity for directionally solidified Al–Si–Fe eutectic alloy were investigated, and the relationships between them were experimentally obtained. It was found that the microhardness, tensile strength, and electrical resistivity were affected by both eutectic spacing and the solidification parameter.

Keywords: directional solidification, aluminum alloy, microstructure, electrical properties, tensile test, hardness test

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1685 Directional Solidification of Al–Cu–Mg Eutectic Alloy

Authors: Yusuf Kaygısız, Necmetti̇n Maraşlı


Aluminum alloys are produced and used at various areas of industry and especially in the aerospace industry. The advantages of these alloys over traditional iron-based alloys are lightweight, corrosion resistance, and very good thermal and electrical conductivity. The aim of this work is to experimentally investigate the effect of growth rates on the eutectic spacings (λ), microhardness, tensile strength and electrical resistivity in Al–30wt.%Cu–6wt.%Mg eutectic alloy. Al–Cu–Mg eutectic alloy was directionally solidified at a constant temperature gradient (G=8.55 K/mm) with different growth rates, 9.43 to 173.3 µm/s by using a Bridgman-type furnace. The dependency of microstructure, microhardness, tensile strength and electrical resistivity for directionally solidified the Al-Cu-Mg eutectic alloy were investigated. Eutectic microstructure is consisting of regular Al2CuMg lamellar and Al2Cu rod phases with in the α (Al) solid solution matrix. The lamellar eutectic spacings were measured from transverse sections of the samples. It was found that the value of microstructures decrease with the increase the value the growth rates. The microhardness, tensile strength and electrical resistivity of the alloy also were measured from sample and relationships between them were experimentally analyzed by using regression analysis. According to present results, values tensile strength and electrical resistivity increase with increasing growth rates.

Keywords: directional solidification, aluminum alloys, microstructure, electrical properties, hardness test

Procedia PDF Downloads 193
1684 Achievement of High L-Cysteine Yield from Enzymatic Conversion Using Eutectic Mixtures of the Substrate ATC

Authors: Deokyeong Choe, Sung Hun Youn, Younggon Kim, Chul Soo Shin


L-Cysteine, a sulfur-containing amino acid, has been often used in the pharmaceutical, cosmetic, food, and feed additive industries. This amino acid has been usually produced by acid-hydrolysis of human hair and poultry feathers. There are many problems, such as avoidance for use of animal hair, low yields, and formation of harmful waste material. As an alternative, the enzymatic conversion of D, L-2-amino-Δ2-thiazoline-4-carboxylic acid (ATC) to L-cysteine has been developed as an environmental-friendly method. However, the substrate solubility was too low to be used in industry. In this study, high concentrations of eutectic substrate solutions were prepared to solve the problem. Eutectic melting occurred at 39°C after mixing ATC and malonic acid at a molar ratio of 1:1. The characteristics of eutectic mixtures were analyzed by FE-SEM, EDS mapping, and XPS. However, since sorbitol, MnSO4, and NaOH should be added as supplements to the substrate mixture for the activation and stabilization of the enzyme, strategies for sequential addition of total five compounds, ATC, malonic acid, sorbitol, MnSO4, and NaOH were established. As a result, eutectic substrate mixtures of 670 mM ATC were successfully formulated. After 6 h of enzymatic reaction, 550 mM L-cysteine was made.

Keywords: D, L-2-amino-Δ2-thiazoline-4-carboxylicacid, enzymatic conversion, eutectic solution, l-cysteine

Procedia PDF Downloads 353
1683 Effect of Lead Content on Physical Properties of the Al–Si Eutectic Alloys

Authors: Hasan Kaya


Effect of lead content on the microstructure, mechanical (microhardness, ultimate tensile strength) and electrical resistivity properties of Al–Si eutectic alloys has been investigated. Al–12.6 Si–xSn (x=1, 2, 4, 6 and 8 wt. %) were prepared using metals of 99.99% high purity in the vacuum atmosphere. These alloys were directionally solidified under constant temperature gradient (5.50 K/mm) and growth rate (8.25 μm/s) by using a Bridgman–type directional solidification furnace. Eutectic spacing, microhardness, ultimate tensile strength and electrical resistivity were expressed as functions of the composition by using a linear regression analysis. The dependency of the eutectic spacing, microhardness, tensile strength and electrical resistivity on the composition (Sn content) were determined. According to experimental results, the microhardness, ultimate tensile strength and electrical resistivity of the solidified samples increase with increasing the Sn content, but decrease eutectic spacing. Variation of electrical resistivity with the temperature in the range of 300-500 K for studied alloys was also measured by using a standard d.c. four-point probe technique.

Keywords: content elements, solidification, microhardness, strength

Procedia PDF Downloads 199
1682 Phase Equilibria in Zn-Al-Sn Alloy for Lead-free Solder Application

Authors: Ji Chan Kim, Seok Hong Min, Tae Kwon Ha


The effect of Yttrium addition on the microstructure and mechanical properties of Sn-Zn eutectic alloy, which has been attracting intensive focus as a Pb-free solder material, was investigated in this study. Phase equilibrium has been calculated by using FactSage® to evaluate the composition and fraction of equilibrium intermetallic compounds and construct a phase diagram. In the case of Sn-8.8 Zn eutectic alloy, the as-cast microstructure was typical lamellar. With addition of 0.25 wt. %Y, a large amount of pro-eutectic phases have been observed and various YZnx intermetallic compounds were expected to successively form during cooling. Hardness of Sn-8.8 Zn alloy was not affected by Y-addition and both alloys could be rolled by 90% at room temperature.

Keywords: lead-free solder, zn-al-sn alloy, phase equilibrium, rolling, microstructure, hardness

Procedia PDF Downloads 227
1681 Raman Spectroscopy Analysis of MnTiO₃-TiO₂ Eutectic

Authors: Adrian Niewiadomski, Barbara Surma, Katarzyna Kolodziejak, Dorota A. Pawlak


Oxide-oxide eutectic is attracting increasing interest of scientific community because of their unique properties and numerous potential applications. Some of the most interesting examples of applications are metamaterials, glucose sensors, photoactive materials, thermoelectric materials, and photocatalysts. Their unique properties result from the fact that composite materials consist of two or more phases. As a result, these materials have additive and product properties. Additive properties originate from particular phases while product properties originate from the interaction between phases. MnTiO3-TiO2 eutectic is one of such materials. TiO2 is a well-known semiconductor, and it is used as a photocatalyst. Moreover, it may be used to produce solar cells, in a gas sensing devices and in electrochemistry. MnTiO3 is a semiconductor and antiferromagnetic. Therefore it has potential application in integrated circuits devices, and as a gas and humidity sensor, in non-linear optics and as a visible-light activated photocatalyst. The above facts indicate that eutectic MnTiO3-TiO2 constitutes an extremely promising material that should be studied. Despite that Raman spectroscopy is a powerful method to characterize materials, to our knowledge Raman studies of eutectics are very limited, and there are no studies of the MnTiO3-TiO2 eutectic. While to our knowledge the papers regarding this material are scarce. The MnTiO3-TiO2 eutectic, as well as TiO2 and MnTiO3 single crystals, were grown by the micro-pulling-down method at the Institute of Electronic Materials Technology in Warsaw, Poland. A nitrogen atmosphere was maintained during whole crystal growth process. The as-grown samples of MnTiO3-TiO2 eutectic, as well as TiO2 and MnTiO3 single crystals, are black and opaque. Samples were cut perpendicular to the growth direction. Cross sections were examined with scanning electron microscopy (SEM) and with Raman spectroscopy. The present studies showed that maintaining nitrogen atmosphere during crystal growth process may result in obtaining black TiO2 crystals. SEM and Raman experiments showed that studied eutectic consists of three distinct regions. Furthermore, two of these regions correspond with MnTiO3, while the third region corresponds with the TiO2-xNx phase. Raman studies pointed out that TiO2-xNx phase crystallizes in rutile structure. The studies show that Raman experiments may be successfully used to characterize eutectic materials. The MnTiO3-TiO2 eutectic was grown by the micro-pulling-down method. SEM and micro-Raman experiments were used to establish phase composition of studied eutectic. The studies revealed that the TiO2 phase had been doped with nitrogen. Therefore the TiO2 phase is, in fact, a solid solution with TiO2-xNx composition. The remaining two phases exhibit Raman lines of both rutile TiO2 and MnTiO3. This points out to some kind of coexistence of these phases in studied eutectic.

Keywords: compound materials, eutectic growth and characterization, Raman spectroscopy, rutile TiO₂

Procedia PDF Downloads 106
1680 Microstructure and Mechanical Properties of A201 Alloys with Additions of Si

Authors: Suzan Abd El Majid, Menachem Bamberger, Alexander Katsman


Two Al-4 wt. % Cu based alloys, A201 and A201+Si were investigated in the as-cast, solution treated and aged conditions. The addition of Si was used to improve the castability of the basic alloy. The all investigated alloys in the as-cast condition contained a eutectic structure along grain boundaries (GBs) with the composition Al-50at. %Cu that was found by HRSEM EDS. Addition of Si refined the grain structure and changed the amount of the eutectic regions, their size and shape. Additionally, the A201+Si microstructure contained Si rods and small amount of Al6Mn4Cu3Fe2Si-phase. Solution treatment (ST) at 550°C for ~ 20 hours resulted in a slight dissolution of the eutectic structure in the A201 alloy while substantial dissolution and change of the eutectic composition was detected in the A201+Si alloy. After ST, the A201alloy contained θ-Al2Cu, Al5Cu2Mn3 and Al9Cu7Mn3(Fe) phases associated to the GBs, while the ST A201+Si alloy contained θ-Al2Cu, Al6Mn4Cu3(Fe,Si) and Si94Mn3Al2Cu phases. Precipitation hardening during aging at 170°C was investigated for both alloys. The microhardness of the ST A201alloy increased during aging and reached the maximum value ~ 140 HV after 2 h of aging. Initial microhardness of the ST A201+Si alloy was distinctly higher than one of the ST A201 alloy, but it decreased during the first hour of aging, then increased and reached the same maximum value ~ 140 HV after ~ 4 h of aging. It was concluded that the Si addition influenced the precipitation sequence and slowed down the age hardening process. The Si induced grain refining and evolution of the eutectic structure during the heat treatments applied are discussed.

Keywords: A201 alloys, castability, microstructure, micro-hardness

Procedia PDF Downloads 226
1679 Ag-Cu and Bi-Cd Eutectics Ribbons under Superplastic Tensile Test Regime

Authors: Edgar Ochoa, G. Torres-Villasenor


Superplastic deformation is shown by materials with a fine grain size, usually less than 10 μm, when they are deformed within the strain rate range 10-5 10-1 s-1 at temperatures greater than 0.5Tm, where Tm is the melting point in Kelvin. According to the constitutive equation for superplastic flow, refinement of the grain size would be expected to increase the optimum strain rate and decrease the temperature required for superplastic flow. Ribbons of eutectic Ag-Cu and Bi-Cd alloys were manufactured by using a single roller melt-spinning technique to obtain a fine grain structure for later test in superplastic regime. The eutectics ribbons were examined by scanning electron microscopy and X-Ray diffraction, and the grain size was determined using the image analysis software ImageJ. The average grain size was less than 1 μm. Tensile tests were carried out from 10-4 to 10-1 s-1, at room temperature, to evaluate the superplastic behavior. The largest deformation was shown by the Bi-Cd eutectic ribbons, Ɛ=140 %, despite that these ribbons have a hexagonal unit cell. On the other hand, Ag-Cu eutectic ribbons have a minor grain size and cube unit cell, however they showed a lower deformation in tensile test under the same conditions than Bi-Cd ribbons. This is because the Ag-Cu grew in a strong cube-cube orientation relationship.

Keywords: eutectic ribbon, fine grain, superplastic deformation, cube-cube orientation

Procedia PDF Downloads 95