Search results for: covalent separation

Authors: Kenichi Hirota, Jifeng Wang, Sadao Araki, Koji Endo, Hideki Yamamoto

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Zirconium (Zr) has been used as a fuel cladding tube for nuclear reactors, because of the excellent corrosion resistance and the low adsorptive material for neutron. Generally speaking, the natural resource of Zr is often containing Hf that has similar properties. The content of Hf in the Zr resources is about 2~4 wt%. In the industrial use, the content of Hf in Zr resources should be lower than the 100 ppm. However, the separation of Zr and Hf is not so easy, because of similar chemical and physical properties such as melting point, boiling point and things. Solvent extraction method has been applied for the separation of Zr and Hf from Zr natural resources. This method can separate Hf with high efficiency (Hf < 100ppm), however, it needs much amount of organic solvents for solvent extraction and the cost of its disposal treatment is high. Therefore, we attached attention for the fractional crystallization. This separation method depends on the solubility difference of Zr and Hf in the solvent. In this work, hexafluorozirconate (hafnate) (K2Zr(Hf)F6) was used as model compound. Solubility of K2ZrF6 in water showed lower than that of K2HfF6. By repeating of this treatment, it is possible to purify Zr, practically. In this case, 16-18 times of recrystallization stages were needed for its high purification. The improvement of the crystallization process was carried out in this work. Water, hydrofluoric acid (HF) and hydrofluoric acid (HF) +hydrochloric acid (HCl) mixture were chosen as solvent for dissolution of Zr and Hf. In the experiment, 10g of K2ZrF6 was added to each solvent of 100mL. Each solution was heated for 1 hour at 353K. After 1h of this operation, they were cooled down till 293K, and were held for 5 hours at 273K. Concentration of Zr or Hf was measured using ICP analysis. It was found that Hf was separated from Zr-Hf mixed compound with high efficiency, when HF-HCl solution was used for solvent of crystallization. From the comparison of the particle size of each crystal by SEM, it was confirmed that the particle diameter of the crystal showed smaller size with decreasing of Hf content. This paper concerned with purification of Zr from Zr-Hf mixture using crystallization method.

Keywords: crystallization, zirconium, hafnium, separation

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Authors: Noe Brice Nkoumbou Kaptchouang, Pierre-Guy Vincent, Yann Monerie

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The present work addresses the modelling and the simulation of crack initiation and propagation in ductile materials which failed by void nucleation, growth, and coalescence. One of the current research frameworks on crack propagation is the use of cohesive-volumetric approach where the crack growth is modelled as a decohesion of two surfaces in a continuum material. In this framework, the material behavior is characterized by two constitutive relations, the volumetric constitutive law relating stress and strain, and a traction-separation law across a two-dimensional surface embedded in the three-dimensional continuum. Several cohesive models have been proposed for the simulation of crack growth in brittle materials. On the other hand, the application of cohesive models in modelling crack growth in ductile material is still a relatively open field. One idea developed in the literature is to identify the traction separation for ductile material based on the behavior of a continuously-deforming unit cell failing by void growth and coalescence. Following this method, the present study proposed a semi-analytical cohesive model for ductile material based on a micromechanical approach. The strain localization band prior to ductile failure is modelled as a cohesive band, and the Gurson-Tvergaard-Needleman plasticity model (GTN) is used to model the behavior of the cohesive band and derived a corresponding traction separation law. The numerical implementation of the model is realized using the non-smooth contact method (NSCD) where cohesive models are introduced as mixed boundary conditions between each volumetric finite element. The present approach is applied to the simulation of crack growth in nuclear ferritic steel. The model provides an alternative way to simulate crack propagation using the numerical efficiency of cohesive model with a traction separation law directly derived from porous continuous model.

Keywords: ductile failure, cohesive model, GTN model, numerical simulation

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Authors: Robert van Ling, Alexander Schwahn, Shanhua Lin, Ken Cook, Frank Steiner, Rowan Moore, Mauro de Pra

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Purpose: Demonstration of fast high resolution charge variant analysis for monoclonal antibody (mAb) therapeutics within 5 minutes. Methods: Three commercially available mAbs were used for all experiments. The charge variants of therapeutic mAbs (Bevacizumab, Cetuximab, Infliximab, and Trastuzumab) are analyzed on a strong cation exchange column with a linear pH gradient separation method. The linear gradient from pH 5.6 to pH 10.2 is generated over time by running a linear pump gradient from 100% Thermo Scientific™ CX-1 pH Gradient Buffer A (pH 5.6) to 100% CX-1 pH Gradient Buffer B (pH 10.2), using the Thermo Scientific™ Vanquish™ UHPLC system. Results: The pH gradient method is generally applicable to monoclonal antibody charge variant analysis. In conjunction with state-of-the-art column and UHPLC technology, ultra fast high-resolution separations are consistently achieved in under 5 minutes for all mAbs analyzed. Conclusion: The linear pH gradient method is a platform method for mAb charge variant analysis. The linear pH gradient method can be easily optimized to improve separations and shorten cycle times. Ultra-fast charge variant separation is facilitated with UHPLC that complements, and in some instances outperforms CE approaches in terms of both resolution and throughput.

Keywords: charge variants, ion exchange chromatography, monoclonal antibody, UHPLC

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Authors: M. Benhamida, Kh. Bouamama, P. Djemia

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We investigate by first-principles pseudo-potential calculations the composition dependence of lattice parameter, hardness and elastic properties of ternary disordered solid solutions Ti(1-x)Ta(x)N (1>=x>=0) with B1-rocksalt structure. Calculations use the coherent potential approximation with the exact muffin-tin orbitals (EMTO) and hardness formula for multicomponent covalent solid solution proposed. Bulk modulus B shows a nearly linear behaviour whereas not C44 and C’=(C11-C12)/2 that are not monotonous. Influences of vacancies on hardness of off-stoichiometric transition-metal nitrides TiN(1−x) and TaN(1−x) are also considered.

Keywords: transition metal nitride materials, elastic constants, hardness, EMTO

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Authors: F. Debbat, F. T. Bendimerad

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The efficient frequency assignment for radio communications becomes more and more crucial when developing new information technologies and their applications. It is consists in defining an assignment of frequencies to radio links, to be established between base stations and mobile transmitters. Separation of the frequencies assigned is necessary to avoid interference. However, unnecessary separation causes an excess requirement for spectrum, the cost of which may be very high. This problem is NP-hard problem which cannot be solved by conventional optimization algorithms. It is therefore necessary to use metaheuristic methods to solve it. This paper proposes Hybrid approach based on simulated annealing (SA) and Tabu Search (TS) methods to solve this problem. Computational results, obtained on a number of standard problem instances, testify the effectiveness of the proposed approach.

Keywords: cellular mobile communication, frequency assignment problem, optimization, tabu search, simulated annealing

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Authors: Chukwuemeka Castro Nwabuzor

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The 2015 Administration of Criminal Justice Act in Nigeria clearly sets out conditions for bail for felonies, lesser offenses and capital offenses. Even where the conditions for bail are met, granting an application for bail is not automatic as it is subject to the discretion of the court. Where the court, however, grants bail to an accused, the detaining authority which usually is the executive arm of government is bound to comply with the order of the court. This paper discusses the constitutionality of the continued detention of criminal suspects in disobedience to an order of the court and in the absence of an appeal. Particularly, the paper looks at the rights to personal liberty, the dignity of the human person and also the presumption of innocence which remains one of the crucial pillars of our criminal jurisprudence. The paper analyses the reasons posed by the executive for the continued detention of a suspect including State security and security of the suspect and questions whether the reasons are reasonable justifiable in a constitutional democratic society and whether they breach the principles of separation of powers. The paper concludes that the continued detention criminal of suspects in disobedience to court orders constitutes contempt of court and dishonours the principles of separation of powers enshrined in the Nigerian Constitution. This paper makes a strong case for the donation of more enforceable powers to the judiciary particularly with regards to the granting of compensation orders against the executive and ensuring compliance by the executive to bail orders.

Keywords: breach of fundamental rights, contempt of court, discretion of court, right to bail, separation of powers

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Authors: Mbongeni Mabaso, Kandasamy Moodley, Gan Redhi

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The recovery of industrially valuable organic solvents from liquid waste, generated in chemical processes, is economically crucial to countries which need to import organic solvents. In view of this, the main objective of this study was to determine the ability of selected ionic liquids, namely, 1-ethyl-3-methylimidazolium ethylsulphate, [EMIM] [ESO4] and 1-ethyl-3-methylpyridinium ethylsulphate, [EMpy][ESO4] to recover aromatic components from spent paint solvents. Preliminary studies done on the liquid waste, received from a paint manufacturing company, showed that the aromatic components were present in the range 6 - 21 % by volume. The separation of the aromatic components was performed with the ionic liquids listed above. The phases, resulting from the separation of the mixtures, were analysed with a Gas Chromatograph (GC) coupled to a FID detector. Chromatograms illustrate that the chosen ZB-Wax-Plus column gave excellent separation of all components of interest from the mixtures, including the isomers of xylene. The concentrations of aromatics recovered from the spent solvents were found to be the % ranges 13-33 and 23-49 respectively for imidazolium and pyridinium ionic liquids. These results also show that there is a significant correlation between π-character of ionic liquids and the level of extraction. It is therefore concluded that ionic liquids have the potential for macro-scale recovery of re-useable solvents present in liquid waste emanating from paint manufacture.

Keywords: synthesis, ionic liquid, imidazolium, pyridinium, extraction, aromatic solvents, spent paint organic solvents

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Authors: Zita Šereš, Dragana Šoronja Simović, Ljubica Dokić, Lidietta Giorno, Biljana Pajin, Cecilia Hodur, Nikola Maravić

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Membrane technology is convenient for separation of suspended solids, colloids and high molecular weight materials that are present. The idea is that the waste stream from edible oil industry, after the separation of oil by using skimmers is subjected to microfiltration and the obtained permeate can be used again in the production process. The wastewater from edible oil industry was used for the microfiltration. For the microfiltration of this effluent a tubular membrane was used with a pore size of 200 nm at transmembrane pressure in range up to 3 bar and in range of flow rate up to 300 L/h. Box–Behnken design was selected for the experimental work and the responses considered were permeate flux and chemical oxygen demand (COD) reduction. The reduction of the permeate COD was in the range 40-60% according to the feed. The highest permeate flux achieved during the process of microfiltration was 160 L/m²h.

Keywords: ceramic membrane, edible oil, microfiltration, wastewater

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Authors: Milda Nainyte, Viktoras Masevicius

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Biological methylation is a methyl group transfer from S-adenosyl-L-methionine (AdoMet) onto N-, C-, O- or S-nucleophiles in DNA, RNA, proteins or small biomolecules. The reaction is catalyzed by enzymes called AdoMet-dependent methyltransferases (MTases), which represent more than 3 % of the proteins in the cell. As a general mechanism, the methyl group from AdoMet replaces a hydrogen atom of nucleophilic center producing methylated DNA and S-adenosyl-L-homocysteine (AdoHcy). Recently, DNA methyltransferases have been used for the sequence-specific, covalent labeling of biopolymers. Two types of MTase catalyzed labeling of biopolymers are known, referred as two-step and one-step. During two-step labeling, an alkylating fragment is transferred onto DNA in a sequence-specific manner and then the reporter group, such as biotin, is attached for selective visualization using suitable chemistries of coupling. This approach of labeling is quite difficult and the chemical hitching does not always proceed at 100 %, but in the second step the variety of reporter groups can be selected and that gives the flexibility for this labeling method. In the one-step labeling, AdoMet analog is designed with the reporter group already attached to the functional group. Thus, the one-step labeling method would be more comfortable tool for labeling of biopolymers in order to prevent additional chemical reactions and selection of reaction conditions. Also, time costs would be reduced. However, effective AdoMet analog appropriate for one-step labeling of biopolymers and containing cleavable bond, required for reduction of PCR interferation, is still not known. To expand the practical utility of this important enzymatic reaction, cofactors with activated sulfonium-bound side-chains have been produced and can serve as surrogate cofactors for a variety of wild-type and mutant DNA and RNA MTases enabling covalent attachment of these chains to their target sites in DNA, RNA or proteins (the approach named methyltransferase-directed Transfer of Activated Groups, mTAG). Compounds containing hex-2-yn-1-yl moiety has proved to be efficient alkylating agents for labeling of DNA. Herein we describe synthetic procedures for the preparation of N-biotinoyl-N’-(pent-4-ynoyl)cystamine starting from the coupling of cystamine with pentynoic acid and finally attaching the biotin as a reporter group. The synthesis of the first AdoMet based cofactor containing a cleavable reporter group and appropriate for one-step labeling was developed.

Keywords: adoMet analogs, DNA alkylation, cofactor, methyltransferases

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Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

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Organic polymers, constructed from light elements like carbon, hydrogen, nitrogen, oxygen, sulphur, and boron atoms, are the emergent class of non-toxic, metal-free, environmental benign advanced materials. Covalent triazine-based polymers with a functional triazine group are significant class of organic materials due to their remarkable stability arising out of strong covalent bonds. They can conventionally form hydrogen bonds, favour π–π contacts, and they were recently revealed to be involved in interesting anion–π interactions. The present work mainly focuses upon the development of a single-crystalline, highly cross-linked triazine-based nitrogen-rich organic polymer with nanodendritic morphology and significant thermal stability. The polymer has been synthesized through hydrothermal treatment of melamine and ethylene glycol resulting in cross-polymerization via condensation-polymerization reaction. The crystal structure of the polymer has been evaluated by employing Rietveld whole profile fitting method. The polymer has been found to be composed of monoclinic melamine having space group P21/a. A detailed insight into the chemical structure of the as synthesized polymer has been elucidated by Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopic analysis. X-Ray Photoelectron Spectroscopic (XPS) analysis has also been carried out for further understanding of the different types of linkages required to create the backbone of the polymer. The unique rod-like morphology of the triazine based polymer has been revealed from the images obtained from Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Interestingly, this polymer has been found to selectively detect mercury (Hg²⁺) ions at an extremely low concentration through fluorescent quenching with detection limit as low as 0.03 ppb. The high toxicity of mercury ions (Hg²⁺) arise from its strong affinity towards the sulphur atoms of biological building blocks. Even a trace quantity of this metal is dangerous for human health. Furthermore, owing to its small ionic radius and high solvation energy, Hg²⁺ ions remain encapsulated by water molecules making its detection a challenging task. There are some existing reports on fluorescent-based heavy metal ion sensors using covalent organic frameworks (COFs) but reports on mercury sensing using triazine based polymers are rather undeveloped. Thus, the importance of ultra-trace detection of Hg²⁺ ions with high level of selectivity and sensitivity has contemporary significance. A plausible sensing phenomenon by the polymer has been proposed to understand the applicability of the material as a potential sensor. The impressive sensitivity of the polymer sample towards Hg²⁺ is the very first report in the field of highly crystalline triazine based polymers (without the introduction of any sulphur groups or functionalization) towards mercury ion detection through photoluminescence quenching technique. This crystalline metal-free organic polymer being cheap, non-toxic and scalable has current relevance and could be a promising candidate for Hg²⁺ ion sensing at commercial level.

Keywords: fluorescence quenching , mercury ion sensing, single-crystalline, triazine-based polymer

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Authors: H. Ishii, S. Araki, H. Yamamoto

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In recent years, the carbon dioxide (CO2) separation technology is required in terms of the reduction of emission of global warming gases and the efficient use of fossil fuels. Since the emission amount of CO2 gas occupies the large part of greenhouse effect gases, it is considered that CO2 have the most influence on global warming. Therefore, we need to establish the CO2 separation technologies with high efficiency at low cost. In this study, we focused on the membrane separation compared with conventional separation technique such as distillation or cryogenic separation. In this study, we prepared carbonate-ceramic dual-phase membranes to separate CO2 at high temperature. As porous ceramic substrate, the (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+σ, La0.6Sr0.4Ti0.3 Fe0.7O3 and Ca0.8Sr0.2Ti0.7Fe0.3O3-α (PLNCG, LSTF and CSTF) were examined. PLNCG, LSTF and CSTF have the perovskite structure. The perovskite structure has high stability and shows ion-conducting doped by another metal ion. PLNCG, LSTF and CSTF have perovskite structure and has high stability and high oxygen ion diffusivity. PLNCG, LSTF and CSTF powders were prepared by a solid-phase process using the appropriate carbonates or oxides. To prepare porous substrates, these powders mixed with carbon black (20 wt%) and a few drops of polyvinyl alcohol (5 wt%) aqueous solution. The powder mixture were packed into stainless steel mold (13 mm) and uniaxially pressed into disk shape under a pressure of 20 MPa for 1 minute. PLNCG, LSTF and CSTF disks were calcined in air for 6 h at 1473, 1573 and 1473 K, respectively. The carbonate mixture (Li2CO3/Na2CO3/K2CO3: 42.5/32.5/25 in mole percent ratio) was placed inside a crucible and heated to 793 K. Porous substrates were infiltrated with the molten carbonate mixture at 793 K. Crystalline structures of the fresh membranes and after the infiltration with the molten carbonate mixtures were determined by X-ray diffraction (XRD) measurement. We confirmed the crystal structure of PLNCG and CSTF slightly changed after infiltration with the molten carbonate mixture. CO2 permeation experiments with PLNCG-carbonate, LSTF-carbonate and CSTF-carbonate membranes were carried out at 773-1173 K. The gas mixture of CO2 (20 mol%) and He was introduced at the flow rate of 50 ml/min to one side of membrane. The permeated CO2 was swept by N2 (50 ml/min). We confirmed the effect of ceramic materials and temperature on the CO2 permeation at high temperature.

Keywords: membrane, perovskite structure, dual-phase, carbonate

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Authors: Neel K. Shah

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Passive flow control on aerofoils has largely been achieved through the use of protrusions such as vane-type vortex generators. Consequently, innovative flow-control concepts should be explored in an effort to improve current component performance. Therefore, experimental research has been performed at The University of Manchester to evaluate the flow-control effectiveness of a vortex generator made in the form of a surface indentation. The surface indentation has a trapezoidal planform. A spanwise array of indentations has been applied in a convergent orientation around the maximum-thickness location of the upper surface of a NACA-0015 aerofoil. The aerofoil has been tested in a two-dimensional set-up in a low-speed wind tunnel at an angle of attack (AoA) of 3° and a chord-based Reynolds number (Re) of ~2.7 x 105. The baseline model has been found to suffer from a laminar separation bubble at low AoA. The application of the indentations at 3° AoA has considerably shortened the separation bubble. The indentations achieve this by shedding up-flow pairs of streamwise vortices. Despite the considerable reduction in bubble length, the increase in leading-edge suction due to the shorter bubble is limited by the removal of surface curvature and blockage (increase in surface pressure) caused locally by the convergent indentations. Furthermore, the up-flow region of the vortices, which locally weakens the pressure recovery around the trailing edge of the aerofoil by thickening the boundary layer, also contributes to this limitation. Due to the conflicting effects of the indentations, the changes in the pressure-lift and pressure-drag coefficients, i.e., cl,p and cd,p, are small. Nevertheless, the indentations have improved cl,p and cd,p beyond the uncertainty range, i.e., by ~1.30% and ~0.30%, respectively, at 3° AoA. The wake measurements show that turbulence intensity and Reynolds stresses have considerably increased in the indented case, thus implying that the indentations increase the viscous drag on the model. In summary, the convergent indentations are able to reduce the size of the laminar separation bubble, but conversely, they are not highly effective in reducing cd,p at the tested Reynolds number.

Keywords: aerofoil flow control, laminar separation bubbles, low Reynolds-number flows, surface indentations

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Authors: D. S. Fardhyanti, Megawati, W. B. Sediawan

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Coal tar is a liquid by-product of the process of coal gasification and carbonation. This liquid oil mixture contains various kinds of useful compounds such as aromatic compounds and phenolic compounds. These compounds are widely used as raw material for insecticides, dyes, medicines, perfumes, coloring matters, and many others. This research investigates thermodynamic modelling of liquid-liquid equilibria (LLE) in the separation of phenol from the coal tar by solvent extraction. The equilibria are modeled by ternary components of Wohl, Van Laar, and Three-Suffix Margules models. The values of the parameters involved are obtained by curve-fitting to the experimental data. Based on the comparison between calculated and experimental data, it turns out that among the three models studied, the Three-Suffix Margules seems to be the best to predict the LLE of p-Cresol mixtures for those system.

Keywords: coal tar, phenol, Wohl, Van Laar, Three-Suffix Margules

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Authors: Nice Vasconcelos Coimbra, Fábio dos Santos Gonçalves, Marisa Nascimento, Ellen Cristine Giese

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The development of chemical routes for the recovery and separation of rare earth elements (REE) is seen as a priority and strategic action by several countries demanding these elements. Among the possibilities of alternative routes, the biosorption process has been evaluated in our laboratory. In this theme, the present work attempts to assess and fit the solution equilibrium data in Langmuir, Freundlich and DKR isothermal models, based on the biosorption results of the lanthanum and samarium elements by Bacillus subtilis immobilized on calcium alginate gel. It was observed that the preference of adsorption of REE by the immobilized biomass followed the order Sm (III)> La (III). It can be concluded that among the studied isotherms models, the Langmuir model presented better mathematical results than the Freundlich and DKR models.

Keywords: rare earth elements, biosorption, Bacillus subtilis, adsorption isotherm models

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Authors: Peng Zhou, Peter Pudney

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Driver advice systems are used by many rail operators to help train drivers to improve timekeeping while minimising energy use. These systems typically operate independently of the safeworking system, because information on how far the train is allowed to travel -the “limit of authority"- is usually not available as real-time data that can be used when generating driving advice. This is not an issue when there is sufficient separation between trains. But on systems with low headways, driving advice could conflict with safeworking requirements. We describe a method for generating driving advice that takes into account a moving limit of authority that is communicated to the train in real-time. We illustrate the method with four simulated examples using data from the Zhengzhou Metro. The method will allow driver advice systems to be used more effectively on railways with low headways.

Keywords: railway transportation, energy efficient train operation, optimal train control, safe separation

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Authors: Francis Mark A. Fernandez, Chelca Ubay, Armithan Suguitan

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Regions or provinces in a definite state certainly contribute to the economy of their mainland. These regions or provinces are the ones supplying the mainland with different resources and assets. Thus, with a certain region separating from the mainland would indeed impinge the heart of an entire state to develop and expand. With these, the researchers decided to study on the effects of the separation of one’s region to its mainland and the consequences that will take place if the mainland would rule out the region to separate from them. The researchers wrote this paper to present the causes of the separation of Catalonia from Spain and the prediction regarding the pursuance of this region to revolt from its mainland, Spain. In conducting this research, the researchers utilized two analyses, namely: qualitative and quantitative. In qualitative, numerous of information regarding the existing experiences of the citizens of Catalonia were gathered by the authors to give certainty to the prediction of the researchers. Besides this undertaking, the researchers will also gather needed information and figures through books, journals and the published news and reports. In addition, to further support this prediction under qualitative analysis, the researchers intended to operate the Phenomenological research in which the examiners will exemplify the lived experiences of each citizen in Catalonia. Moreover, the researchers will utilize one of the types of Phenomenological research which is hermeneutical phenomenology by Van Manen. In quantitative analysis, the researchers utilized the regression analysis in which it will ascertain the causality in an underlying theory in understanding the relationship of the variables. The researchers assigned and identified different variables, wherein the dependent variable or the y which represents the prediction of the researchers, the independent variable however or the x represents the arising problems that grounds the partition of the region, the summation of the independent variable or the ∑x represents the sum of the problem and finally the summation of the dependent variable or the ∑y is the result of the prediction. With these variables, using the regression analysis, the researchers will be able to show the connections and how a single variable could affect the other variables. From these approaches, the prediction of the researchers will be specified. This research could help different states dealing with this kind of problem. It will further help certain states undergoing this problem by analyzing the causes of these insurgencies and the effects on it if it will obstruct its region to consign their full-pledge autonomy.

Keywords: autonomy, liberty, prediction, separation

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Authors: Ratna Dewi Kusumaningtyas, Riris Pristiyani, Heny Dewajani

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Biodiesel is commonly produced via the two main routes, i.e. the transesterification of triglycerides and the esterification of free fatty acid (FFA) using short-chain alcohols. Both the two routes have drawback in term of the side product yielded during the reaction. Transesterification reaction of triglyceride results in glycerol as side product. On the other hand, FFA esterification brings in water as side product. Both glycerol and water in the biodiesel production are managed as waste. Hence, a separation process is necessary to obtain a high purity biodiesel. Meanwhile, separation processes is generally the most capital and energy intensive part in industrial process. Therefore, to reduce the separation process, it is essential to produce biodiesel via an alternative route eliminating glycerol or water side-products. In this work, biodiesel synthesis was performed using a glycerol-free process through chemical interesterification of jatropha oil with ethyl acetate in the presence on sodium acetate catalyst. By using this method, triacetine, which is known as fuel bio-additive, is yielded instead of glycerol. This research studied the effects of catalyst concentration on the jatropha oil interesterification process in the range of 0.5 – 1.25% w/w oil. The reaction temperature and molar ratio of oil to ethyl acetate were varied at 50, 60, and 70°C, and 1:6, 1:9, 1:15, 1:30, and 1:60, respectively. The reaction time was evaluated from 0 to 8 hours. It was revealed that the best yield was obtained with the catalyst concentration of 0.5%, reaction temperature of 70 °C, molar ratio of oil to ethyl acetate at 1:60, at 6 hours reaction time.

Keywords: biodiesel, interesterification, glycerol-free, triacetine, jatropha oil

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Authors: Srinivasa Reddy Mallampati, Min Hee Park, Soo Mim Cho, Sung Hyeon Yoon

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One of the issues of End of Life Vehicles (ELVs) recycling promotion is technology for the appropriate treatment of automotive shredder residue (ASR). Owing to its high heterogeneity and variable composition (plastic (23–41%), rubber/elastomers (9–21%), metals (6–13%), glass (10–20%) and dust (soil/sand) etc.), ASR can be classified as ‘hazardous waste’, on the basis of the presence of heavy metals (HMs), PCBs, BFRs, mineral oils, etc. Considering their relevant concentrations, these metals and plastics should be properly recovered for recycling purposes before ASR residues are disposed of. Brominated flame retardant additives in ABS/HIPS and PVC may generate dioxins and furans at elevated temperatures. Moreover, these BFRs additives present in plastic materials may leach into the environment during landfilling operations. ASR thermal process removes some of the organic material but concentrates, the heavy metals and POPs present in the ASR residues. In the present study, Fe/Ca/CaO nanoparticle assisted ozone treatment has been found to selectively hydrophilize the surface of ABS/HIPS and PVC plastics, enhancing its wettability and thereby promoting its separation from ASR plastics by means of froth flotation. The water contact angles, of ABS/HIPS and PVC decreased, about 18.7°, 18.3°, and 17.9° in ASR respectively. Under froth flotation conditions at 50 rpm, about 99.5% and 99.5% of HIPS in ASR samples sank, resulting in a purity of 98% and 99%. Furthermore, at 150 rpm a 100% PVC separation in the settled fraction, with 98% of purity in ASR, respectively. Total recovery of non-ABS/HIPS and PVC plastics reached nearly 100% in the floating fraction. This process improved the quality of recycled ASR plastics by removing surface contaminants or impurities. Further, a hybrid ball-milling and with Fe/Ca/CaO nanoparticle froth flotation process was established for the recovery of HMs from ASR. After ball-milling with Fe/Ca/CaO nanoparticle additives, the flotation efficiency increased to about 55 wt% and the HMs recovery were also increased about 90% for the 0.25 mm size fractions of ASR. Coating with Fe/Ca/CaO nanoparticles associated with subsequent microbubble froth flotation allowed the air bubbles to attach firmly on the HMs. SEM–EDS maps showed that the amounts of HMs were significant on the surface of the floating ASR fraction. This result, along with the low HM concentration in the settled fraction, was confirmed by elemental spectra and semi-quantitative SEM–EDS analysis. Developed hybrid preferential hazardous plastics and metals separation process from ASR is a simple, highly efficient, and sustainable procedure.

Keywords: end of life vehicles shredder residue, hazardous plastics, nanoparticle froth flotation, separation process

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Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay

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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

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Authors: S. Pradhan, V. Kumaran

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Centrifugal gas separation processes effect separation by utilizing the difference in the mole fraction in a high speed rotating cylinder caused by the difference in molecular mass, and consequently the centrifugal force density. These have been widely used in isotope separation because chemical separation methods cannot be used to separate isotopes of the same chemical species. More recently, centrifugal separation has also been explored for the separation of gases such as carbon dioxide and methane. The efficiency of separation is critically dependent on the secondary flow generated due to temperature gradients at the cylinder wall or due to inserts, and it is important to formulate accurate models for this secondary flow. The widely used Onsager model for secondary flow is restricted to very long cylinders where the length is large compared to the diameter, the limit of high stratification parameter, where the gas is restricted to a thin layer near the wall of the cylinder, and it assumes that there is no mass difference in the two species while calculating the secondary flow. There are two objectives of the present analysis of the rarefied gas flow in a rotating cylinder. The first is to remove the restriction of high stratification parameter, and to generalize the solutions to low rotation speeds where the stratification parameter may be O (1), and to apply for dissimilar gases considering the difference in molecular mass of the two species. Secondly, we would like to compare the predictions with molecular simulations based on the direct simulation Monte Carlo (DSMC) method for rarefied gas flows, in order to quantify the errors resulting from the approximations at different aspect ratios, Reynolds number and stratification parameter. In this study, we have obtained analytical and numerical solutions for the secondary flows generated at the cylinder curved surface and at the end-caps due to linear wall temperature gradient and external gas inflow/outflow at the axis of the cylinder. The effect of sources of mass, momentum and energy within the flow domain are also analyzed. The results of the analytical solutions are compared with the results of DSMC simulations for three types of forcing, a wall temperature gradient, inflow/outflow of gas along the axis, and mass/momentum input due to inserts within the flow. The comparison reveals that the boundary conditions in the simulations and analysis have to be matched with care. The commonly used diffuse reflection boundary conditions at solid walls in DSMC simulations result in a non-zero slip velocity as well as a temperature slip (gas temperature at the wall is different from wall temperature). These have to be incorporated in the analysis in order to make quantitative predictions. In the case of mass/momentum/energy sources within the flow, it is necessary to ensure that the homogeneous boundary conditions are accurately satisfied in the simulations. When these precautions are taken, there is excellent agreement between analysis and simulations, to within 10 %, even when the stratification parameter is as low as 0.707, the Reynolds number is as low as 100 and the aspect ratio (length/diameter) of the cylinder is as low as 2, and the secondary flow velocity is as high as 0.2 times the maximum base flow velocity.

Keywords: rotating flows, generalized onsager and carrier-Maslen model, DSMC simulations, rarefied gas flow

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Authors: Gülşah Çelik Gül, Figen Kurtuluş

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The first laboratory synthesis of hard materials such as diamond proceeded to attack of developing materials with high hardness to compete diamond. Boron rich solids are good candidates owing to their short interatomic bond lengths and strong covalent character. Boron containing hard material was synthesized by modified-microwave method under nitrogen atmosphere by using a fuel (glycine or urea), amorphous boron and/or boric acid in appropriate molar ratio. Characterizations were done by x-ray diffraction (XRD), fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy/energy dispersive analyze (SEM/EDS), thermo gravimetric/differantial thermal analysis (TG/DTA).

Keywords: boron containing materials, hard materials, microwave synthesis, powder X-ray diffraction

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Authors: Cassandra Seery

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During the twentieth century, the notion of child rights at the international level began with the League of Nations’ Geneva Declaration of the Rights of the Child 1924, culminating in the development and adoption of the UN Convention on the Rights of the Child (‘the Convention’) in 1989. A key foundation of child rights lies in the development of the ‘best interests of the child’ principle and its subsequent incorporation into domestic legislation across the globe. This principle has become a key concept in child rights protection and has become a widely recognized principle in the protection of child rights. However, despite its status as the primary operating standard in child and family law and its ‘deepening hold in domestic and international instruments’, the meaning of the ‘best interests of the child’ principle has been criticised as open-ended and vague. This paper explores the evolution and development of the principle in the context of parental separation at international law throughout the 21st century and identifies opportunities for the Nation States to further improve legislative responses in associated child protection cases. An extensive review of relevant United Nations documentation (including instruments, resolutions and comments, jurisprudence, reports, guidelines and policies, training materials and so forth) explores: (i) what progress has been made to further develop the principle at the international level with regard to parental separation; and (ii) what developments participating the Nation States should consider as part of future legal and social policy reforms in this space. It will highlight opportunities for improvement and explore the benefit and relevance of international approaches for the Nation States moving forward.

Keywords: international human rights, best interests of the child, legal and social policy, child rights

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Authors: Kul Pun, F. A. Hamad, T. Ahmed, J. O. Ugwu, J. Eyers, G. Lawson, P. A. Russell

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Determining droplet size and distribution is essential when determining the separation efficiency of a two/three-phase separator. This paper investigates the effect of liquid flow and oil pad thickness on the droplet size at the lab scale. The findings show that increasing the inlet flow rates of the oil and water results in size reduction of the droplets and increasing the thickness of the oil pad increases the size of the droplets. The data were fitted with a simple Gaussian model, and the parameters of mean, standard deviation, and amplitude were determined. Trends have been obtained for the fitted parameters as a function of the Reynolds number, which suggest a way forward to better predict the starting parameters for population models when simulating separation using CFD packages. The key parameter to predict to fix the position of the Gaussian distribution was found to be the mean droplet size.

Keywords: two-phase separator, average bubble droplet, bubble size distribution, liquid-liquid phase

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Authors: Seung Moon Woo, Youn Suk Chung, Sang Yong Nam

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In the present time, we need advanced water treatment technology for separation of virus and bacteria in effluent which occur epidemic and waterborne diseases. Water purification system is mainly divided into two categorizations like reverse osmosis (RO) and ultrafiltration (UF). Membrane used in these systems requires higher durability because of operating in harsh condition. Of these, the membrane using in UF system has many advantages like higher efficiency and lower energy consume for water treatment compared with RO system. In many kinds of membrane, hollow fiber type membrane is possible to make easily and to get optimized property by control of various spinning conditions such as temperature of coagulation bath, concentration of polymer, addition of additive, air gap and internal coagulation. In this study, polysulfone hollow fiber membrane was successfully prepared by phase inversion method for separation of virus and bacteria. When we prepare the hollow fiber membrane, we controlled various factors such as the polymer concentration, air gap and internal coagulation to investigate effect to membrane property. Morphology of surface and cross section of membrane were measured by field emission scanning electron microscope (FE-SEM). Water flux of membrane was measured using test modules. Mean pore diameter of membrane was calculated using rejection of polystyrene (PS) latex beads for separation of virus and bacteria. Flux and mean flow pore diameter of prepared membrane show 1.5 LPM, 0.03 μm at 1.0 kgf/cm2. The bacteria and virus removal performance of prepared UF membranes were over 6 logs.

Keywords: hollow fiber membrane, drinking water, ultrafiltration, bacteria

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Authors: Rosmini Yanti, Safira Aviolita, Marsetio

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Indonesia has several straits that are very important as a shipping lane, including the Sunda Strait and the Lombok Strait, which are the part of the Indonesian Archipelagic Sea Lane (IASL). An increase in traffic on the Marine Archipelago makes the task of monitoring sea routes increasingly difficult. Indonesia has proposed the establishment of a Traffic Separation Scheme (TSS) in the Sunda Strait and the Lombok Strait and the country now has the right to be able to conceptualize the TSS as well as the obligation to regulate it. Indonesia has the right to maintain national safety and sovereignty. In setting the TSS, Indonesia needs to issue national regulations that are in accordance with international law and the general provisions of the IMO (International Maritime Organization) can then be used as guidelines for maritime safety and security in the Sunda Strait and the Lombok Strait. The research method used is a qualitative method with the concept of linguistic and visual data collection. The source of the data is the analysis of documents and regulations. The results show that the determination of TSS was justified by International Law, in accordance with article 22, article 41, and article 53 of the United Nations Convention on the Law of the Sea (UNCLOS) 1982. The determination of TSS by the Indonesian government would be in accordance with COLREG (International Convention on Preventing Collisions at Sea) 10, which has been designed to follow IASL. Thus, TSS can provide a function as a safety and monitoring medium to minimize ship accidents or collisions, including the warship and aircraft of other countries that cross the IASL.

Keywords: archipelago state, maritime law, maritime security, traffic separation scheme

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Authors: M. Harmel, H. Khachai

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The first principles within the full potential linearized augmented plane wave (FP-LAPW) method were applied to study the structural and electronic properties of cubic perovskite-type compounds BiAlO3 and BiGaO3. The lattice constant, bulk modulus, its pressure derivative, band structure and density of states were obtained. The results show that BiGaO3 should exhibit higher hardness and stiffness than BiAlO3. The Al–O or Ga–O bonds are typically covalent with a strong hybridization as well as Bi–O ones that have a significant ionic character. Both materials are weakly ionic and exhibit wide and indirect band gaps, which are typical of insulators.

Keywords: DFT, Ab initio, electronic structure, Perovskite structure, ferroelectrics

Procedia PDF Downloads 397

Authors: Onyinyechi Lilian Uche

Abstract:

Limiting arbitrariness and political power in governance is expressed in the concept of constitutionalism. Constitutionalism acknowledges the necessity for government but insists upon a limitation being placed upon its powers. It is therefore clear that the essence of constitutionalism is obviation of arbitrariness in governance and maximisation of liberty with adequate and expedient restraint on government. The doctrine of separation of powers accompanied by a system of checks and balances in Nigeria like many other African countries is marked by elements of ‘personal government’ and this has raised questions about whether the apparent separation of powers provided for in the Nigerian Constitution is not just a euphemism for the hegemony of the executive over the other two arms of government; the legislature and the judiciary. Another question raised in the article is whether the doctrine is merely an abstract philosophical inheritance that lacks both content and relevance to the realities of the country and region today? The current happenings in Nigeria and most African countries such as the flagrant disregard of court orders by the Executive, indicate clearly that the concept constitutionalism ordinarily goes beyond mere form and strikes at the substance of a constitution. It, therefore, involves a consideration of whether there are provisions in the constitution which limit arbitrariness in the exercise of political powers by providing checks and balances upon such exercise. These questions underscore the need for Africa to craft its own understanding of the separation of powers between the arms of government in furtherance of good governance as it has been seen that it is possible to have a constitution in place which may just be a mere statement of unenforceable ‘rights’ or may be bereft of provisions guaranteeing liberty or adequate and necessary restraint on exercise of government. This paper seeks to expatiate on the importance of the nexus between constitutionalism and democratic process and a juxtaposition of practices between Nigeria and South Africa. The article notes that an abstract analysis of constitutionalism without recourse to the democratic process is meaningless and also analyses the structure of government of some selected African countries. These are examined the extent to which the doctrine operates within the arms of government and concludes that it should not just be regarded as a general constitutional principle but made rigid or perhaps effective and binding through law and institutional reforms.

Keywords: checks and balances, constitutionalism, democratic process, separation of power

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Authors: Z. V. P. Murthy, Preeti Arunachalam, Sangeeta Balram

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Removal of metal ions from different wastewaters has become important due to their effects on living beings. Cadmium is one of the heavy metals found in different industrial wastewaters. There are many conventional methods available to remove heavy metals from wastewaters like adsorption, membrane separations, precipitation, electrolytic methods, etc. and all of them have their own advantages and disadvantages. The present work deals with the use of natural biosorbents (chitin and chitosan) to separate cadmium ions from aqueous solutions. The adsorption data were fitted with different isotherms and kinetics models. Amongst different adsorption isotherms used to fit the adsorption data, the Freundlich isotherm showed better fits for both the biosorbents. The kinetics data of adsorption of cadmium showed better fit with pseudo-second order model for both the biosorbents. Chitosan, the derivative from chitin, showed better performance than chitin. The separation results are encouraging.

Keywords: chitin, chitosan, cadmium, isotherm, kinetics

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Authors: Mahmoud A. Abdulhamid

Abstract:

Poly(ether-ether-ketone) (PEEK) has received increased attention due to its outstanding performance in different membrane applications including gas and liquid separation. However, it suffers from a semi-crystalline morphology, bad solubility and low porosity. To fabricate membranes from PEEK, the usage of harsh acid such as sulfuric acid is essential, regardless its hazardous properties. In this work, we report the molecular design of poly(ether-ether-ketones) (iPEEKs) with intrinsic porosity character, by incorporating kinked units into PEEK backbone such as spirobisindane, Tröger's base, and triptycene. The porous polymers were used to fabricate stable membranes for organic solvent nanofiltration application. To better understand the mechanism, we conducted molecular dynamics simulations to evaluate the possible interactions between the polymers and the solvents. Notable enhancement in separation performance was observed confirming the importance of molecular engineering of high-performance polymers. The iPEEKs demonstrated good solubility in polar aprotic solvents, a high surface area of 205–250 m² g⁻¹, and excellent thermal stability. Mechanically flexible nanofiltration membranes were prepared from N-methyl-2-pyrrolidone dope solution at iPEEK concentrations of 19–35 wt%. The molecular weight cutoff of the membranes was fine-tuned in the range of 450–845 g mol⁻¹ displaying 2–6 fold higher permeance (3.57–11.09 L m⁻² h⁻¹ bar⁻¹) than previous reports. The long-term stabilities were demonstrated by a 7 day continuous cross-flow filtration.

Keywords: molecular engineering, polymer synthesis, membrane fabrication, liquid separation

Procedia PDF Downloads 96

Authors: El Hatka Hicham, Hafidi Youssef, Saghiri Khalid, Ittobane Najim

Abstract:

Flexible polyurethane foam (FPUF) is a low-density cellular material generally used as a cushioning material in many applications such as furniture, bedding, packaging, etc. It is commercially produced during a continuous process, where a reactive mixture of foam chemicals is poured onto a moving conveyor. FPUFs are produced by the catalytic balancing of two reactions involved, the blowing reaction (isocyanate-water) and the gelation reaction (isocyanate-polyol). The microstructure of FPUF is generally composed of soft phases (polyol phases) and rigid domains that separate into two domains of different sizes: the rigid polyurea microdomains and the macrodomains (larger aggregates). The morphological features of FPUF are strongly influenced by the phase separation morphology that plays a key role in determining the global FPUF properties. This phase-separated morphology results from a thermodynamic incompatibility between soft segments derived from aliphatic polyether and hard segments derived from the commonly used aromatic isocyanate. In order to improve the properties of FPUF against the different stresses faced by this material during its use, we report in this work a study of the phase separation phenomenon in FPUF that has been examined using SAXS WAXS and FTIR. Indeed, we have studied with these techniques the effect of water, isocyanates, and alkaline chlorides on the phase separation behavior. SAXS was used to study the morphology of the microphase separated, WAXS to examine the nature of the hard segment packing, and FTIR to investigate the hydrogen bonding characteristics of the materials studied. The prepared foams were shown to have different levels of urea phase connectivity; the increase in water content in the FPUF formulation leads to an increase in the amount of urea formed and consequently the increase of the size of urea aggregates formed. Alkali chlorides (NaCl, KCl, and LiCl) incorporated into FPUF formulations show that is the ability to prevent hydrogen bond formation and subsequently alter the rigid domains. FPUFs prepared by different isocyanate structures showed that urea aggregates are difficult to be formed in foams prepared by asymmetric diisocyanate, while are more easily formed in foams prepared by symmetric and aliphatic diisocyanate.

Keywords: flexible polyurethane foam, hard segments, phase separation, soft segments

Procedia PDF Downloads 166