Search results for: Cd coordination polymer

Authors: Glykeria A. Visvini, George Ν. Mathioudakis, Amaia Soto Beobide, George A. Voyiatzis

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Polymer nanocomposites are materials in which a polymer matrix is reinforced with nanoscale inclusions, such as nanoparticles, nanoplates, or nanofibers. These nanoscale inclusions can significantly enhance the mechanical, thermal, electrical, and other properties of the polymer matrix, making them attractive for a wide range of industrial applications. These properties can be tailored by adjusting the type and the concentration of the nanoinclusions, which provides a high degree of flexibility in their design and development. An important property that polymeric membranes can exhibit is water vapor permeability (WVP). This can be accomplished by various methods, including the incorporation of micro/nano-fillers into the polymer matrix. In this way, a micro/nano-pore network can be formed, allowing water vapor to permeate through the membrane. At the same time, the membrane can be stretched uni- or bi-axially, creating aligned or cross-linked micropores in the composite, respectively, which can also increase the WVP. Nowadays, in industry, stretched films reinforced with CaCO3 develop micro-porosity sufficient to give them breathability characteristics. Carbon-based nanomaterials, such as graphene oxide (GO), are tentatively expected to be able to effectively improve the WVP of corresponding composite polymer films. The presence in the GO structure of various functional oxidizing groups enhances its ability to attract and channel water molecules, exploiting the unique large surface area of graphene that allows the rapid transport of water molecules. Polypropylene (PP) is widely used in various industrial applications due to its desirable properties, including good chemical resistance, excellent thermal stability, low cost, and easy processability. The specific properties of PP are highly influenced by its crystalline behavior, which is determined by its processing conditions. The development of the β-crystalline phase in PP, in combination with stretching, is anticipating improving the microporosity of the polymer matrix, thereby enhancing its WVP. The aim of present study is to create breathable PP composite membranes using carbon-based nanomaterials, such as graphene oxide (GO), reduced graphene oxide (rGO), and graphene nanoplatelets (GNPs). Unlike traditional methods that rely on the drawing process to enhance the WVP of PP, this study intents to develop a low-cost approach using melt mixing with β-nucleating agents and carbon fillers to create highly breathable PP composite membranes. The study aims to investigate how the concentration of these additives affects the water vapor transport properties of the resulting PP films/membranes. The presence of β-nucleating agents and carbon fillers is expected to enhance β-phase growth in PP, while an alternation between β- and α-phase is expected to lead to improved microporosity and WVP. Our ambition is to develop highly breathable PP composite films with superior performance and at a lower cost compared to the benchmark. Acknowledgment: This research has been co‐financed by the European Union and Greek national funds through the Operational Program Competitiveness, Entrepreneurship and Innovation, under the call «Special Actions "AQUACULTURE"-"INDUSTRIAL MATERIALS"-"OPEN INNOVATION IN CULTURE"» (project code: Τ6YBP-00337)

Keywords: carbon based nanomaterials, nanocomposites, nucleating agent, polypropylene, water vapor permeability

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Authors: Z. Miao, Y. Chu, Y. Zhang

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The unique cholesteric phase liquid crystals obtained by mixing nematic liquid crystals with chiral dopants have gained valuable applications in the display field for their selective reflection and circular dichroism properties. The periodic arrangement of the helical structure of cholesteric liquid crystals makes it possible to produce Bragg reflection of circularly polarized light irradiated perpendicularly to the liquid crystals and, therefore, to acquire semi- or fully reflective surfaces or films. If the polymer-liquid crystal composites are combined with polymeric monomers, commercialized reflective broadband films can be fabricated. In this study, the polymer-liquid crystal composites reflecting visible light region (wavelength centered at 550 nm) were studied to analyze the effects of AC electric field at different voltages and frequencies on the optical texture of the composites, as well as the effects of polymerization temperature and ultraviolet (UV) intensity on the polymerization reaction and reflection bandwidth. The optimal sample was finally obtained at 100Hz, 120V, 30℃, 1.00 mW/cm², which provides a research suggestion to solve the influencing factors of visible light reflection bandwidths.

Keywords: cholesteric liquid crystal, reflection bandwidths, negative dielectric anisotropy, planar texture

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Authors: Gamze Karanfil Celep, Kevser Dincer

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The effects of polymer concentration and electrospinning process parameters on the average diameters of electrospun polyacrylonitrile (PAN) nanofibers were experimentally investigated. Besides, mechanical and thermal properties of PAN nanofibers were examined by tensile test and thermogravimetric analysis (TGA), respectively. For this purpose, the polymer concentration, solution feed rate, supply voltage and tip-to-collector distance were determined as the control factors. To succeed these aims, Taguchi’s L16 orthogonal design (4 parameters, 4 level) was employed for the experimental design. Optimal electrospinning conditions were defined using the signal-to-noise (S/N) ratio that was calculated from diameters of the electrospun PAN nanofibers according to "the-smaller-the-better" approachment. In addition, analysis of variance (ANOVA) was evaluated to conclude the statistical significance of the process parameters. The smallest diameter of PAN nanofibers was observed. According to the S/N ratio response results, the most effective parameter on finding out of nanofiber diameter was determined. Finally, the Taguchi design of experiments method has been found to be an effective method to statistically optimize the critical electrospinning parameters used in nanofiber production. After determining the optimum process parameters of nanofiber production, electrical conductivity and fuel cell performance of electrospun PAN nanofibers on the carbon papers will be evaluated.

Keywords: nanofiber, electrospinning, polyacrylonitrile, Taguchi method

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Authors: Vadim V. Zefirov, Victor E. Sizov, Marina A. Pigaleva, Igor V. Elmanovich, Mikhail S. Kondratenko, Marat O. Gallyamov

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This work presents a novel method for treating porous hydrophobic polyolefin membranes using supercritical carbon dioxide that allows usage of the modified membrane in redox flow batteries with an aqueous electrolyte. Polyolefin membranes are well known and widely used, however, they cannot be used as separators in redox flow batteries with an aqueous electrolyte since they have insufficient wettability, and therefore do not provide sufficient proton conductivity. The main aim of the presented work was the development of hydrophilic composites based on cheap membranes and precursors. Supercritical fluid was used as a medium for the deposition of the hydrophilic phase on the hydrophobic surface of the membrane. Due to the absence of negative capillary effects in a supercritical medium, a homogeneous composite is obtained as a result of synthesis. The in-situ synthesized silicon oxide nanoparticles and the chitosan polymer layer act as the hydrophilic phase and not only increase the affinity of the membrane towards the electrolyte, but also reduce the pore size of the polymer matrix, which positively affects the ion selectivity of the membrane. The composite material obtained as a result of synthesis has enhanced hydrophilic properties and is capable of providing proton conductivity in redox flow batteries. The morphology of the obtained composites was characterized by electron microscopy. To analyze the phase composition, infrared spectroscopy was used. The hydrophilic properties were studied by water contact angle measurements. In addition, the proton conductivity and ion selectivity of the obtained samples were studied, and tests in real redox flow batteries were performed. As a result, modified membrane was characterised in detail and moreover it was shown that modified cheap polyolefin membranes have pronounced proton conductivity and high ion selectivity, so their performance in a real redox flow battery approaches expensive commercial analogues, reaching 70% of energy efficiency.

Keywords: carbon dioxide, chitosan, polymer membrane, redox flow batteries, silica nanoparticles, supercritical fluid

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Authors: Ho-Wa Li, Sai-Wing Tsang

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The excitonic effect in organic semiconductors plays a key role in determining the electronic devices performance. Strong exciton binding energy has been regarded as the detrimental factor limiting the further improvement in organic photovoltaic cells. To the best of our knowledge, only limited reported can be found in measuring the exciton binding energy in organic photovoltaic materials. Conventional sophisticated approach using photoemission spectroscopy (UPS and IPES) would limit the wide access of the investigation. Here, we demonstrate a facile approach to study the electrical and optical quantum efficiencies of a series of conjugated photovoltaic polymer, fullerene and non-fullerene materials. Quantitative values of the exciton binding energy in those prototypical materials were obtained with concise photovoltaic device structure. And the extracted binding energies have excellent agreement with those determined by the conventional photoemission technique. More importantly, our findings can provide valuable information on the excitonic dissociation in the first excited state. Particularly, we find that the high binding energy of some non-fullerene acceptors limits the combination of polymer acceptors for efficiency exciton dissociation. The results bring insight into the engineering of excitonic effect for the development of efficient organic photovoltaic cells.

Keywords: organic photovoltaics, quantum efficiency, exciton binding energy, device physics

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Authors: Julian Mehler, Marcus Fischer, Martin Hartmann, Peter S. Schulz

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During the last two decades, the synthesis of metal-organic frameworks (MOFs) has gained ever increasing attention. Based on their pore size and shape as well as host-guest interactions, they are of interest for numerous fields related to porous materials, like catalysis and gas separation. Usually, MOF-synthesis takes place in an organic solvent between room temperature and approximately 220 °C, with mixtures of polyfunctional organic linker molecules and metal precursors as substrates. Reaction temperatures above the boiling point of the solvent, i.e. solvothermal reactions, are run in autoclaves or sealed glass vessels under autogenous pressures. A relatively new approach for the synthesis of MOFs is the so-called ionothermal synthesis route. It applies an ionic liquid as a solvent, which can serve as a structure-directing template and/or a charge-compensating agent in the final coordination polymer structure. Furthermore, this method often allows for less harsh reaction conditions than the solvothermal route. Here a variation of the ionothermal approach is reported, where the ionic liquid also serves as an organic linker source. By using 1-ethyl-3-methylimidazolium terephthalates ([EMIM][Hbdc] and [EMIM]₂[bdc]), the one-step synthesis of MIL-53(Al)/Boehemite composites with interesting features is possible. The resulting material is already formed at moderate temperatures (90-130 °C) and is stabilized in the usually unfavored ht-phase. Additionally, in contrast to already published procedures for MIL-53(Al) synthesis, no further activation at high temperatures is mandatory. A full characterization of this novel composite material is provided, including XRD, SS-NMR, El-Al., SEM as well as sorption measurements and its interesting features are compared to MIL-53(Al) samples produced by the classical solvothermal route. Furthermore, the syntheses of the applied ionic liquids and salts is discussed. The influence of the degree of ionicity of the linker source [EMIM]x[H(2-x)bdc] on the crystal structure and the achievable synthesis temperature are investigated and give insight into the role of the IL during synthesis. Aside from the synthesis of MIL-53 from EMIM terephthalates, the use of the phosphonium cation in this approach is discussed as well. Additionally, the employment of ILs in the preparation of other MOFs is presented briefly. This includes the ZIF-4 framework from the respective imidazolate ILs and chiral camphorate based frameworks from their imidazolium precursors.

Keywords: ionic liquids, ionothermal synthesis, material synthesis, MIL-53, MOFs

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Authors: Giulia Magi Meconi, Nicholas Ballard, José M. Asua, Ronen Zangi

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Experimental and computational studies are combined to elucidate the adsorption proprieties of ionic and nonionic surfactants on hydrophobic polymer surface such us poly(styrene). To present these two types of surfactants, sodium dodecyl sulfate and poly(ethylene glycol)-block-poly(ethylene), commonly utilized in emulsion polymerization, are chosen. By applying quartz crystal microbalance with dissipation monitoring it is found that, at low surfactant concentrations, it is easier to desorb (as measured by rate) ionic surfactants than nonionic surfactants. From molecular dynamics simulations, the effective, attractive force of these nonionic surfactants to the surface increases with the decrease of their concentration, whereas, the ionic surfactant exhibits mildly the opposite trend. The contrasting behavior of ionic and nonionic surfactants critically relies on two observations obtained from the simulations. The first is that there is a large degree of interweavement between head and tails groups in the adsorbed layer formed by the nonionic surfactant (PEO/PE systems). The second is that water molecules penetrate this layer. In the disordered layer, these nonionic surfactants generate at the surface, only oxygens of the head groups present at the interface with the water phase or oxygens next to the penetrating waters can form hydrogen bonds. Oxygens inside this layer lose this favorable energy, with a magnitude that increases with the surfactants density at the interface. This reduced stability of the surfactants diminishes their driving force for adsorption. All that is shown to be in accordance with experimental results on the dynamics of surfactants desorption. Ionic surfactants assemble into an ordered structure and the attraction to the surface was even slightly augmented at higher surfactant concentration, in agreement with the experimentally determined adsorption isotherm. The reason these two types of surfactants behave differently is because the ionic surfactant has a small head group that is strongly hydrophilic, whereas the head groups of the nonionic surfactants are large and only weakly attracted to water.

Keywords: emulsion polymerization process, molecular dynamics simulations, polymer surface, surfactants adsorption

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Authors: Mihai Gheorghe

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Freelancing in IT has seen an increased popularity during the last years mainly because of the fast Internet adoption in the countries with emerging economies, correlated with the continuous seek for reduced development costs as well with the rise of online platforms which address planning, coordination, and various development tasks. This paper conducts an overview of the most relevant Freelance Marketplaces available and studies the market structure, distribution of the workforce and trends in IT freelancing.

Keywords: freelancing in IT, freelance marketplaces, freelance market structure, globalization, online staffing, trends in freelancing

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Authors: Muhammad Nur Haniff Mohd Noor, Rokiah Kadir, Suriyani Muhamad

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Sustainable forest management and forest protection can be hampered by illegal logging. Illegal logging is not uncommon in many wood-producing countries. Hence, law enforcement, especially in timber-producing countries, is crucial in ensuring compliance with forestry related regulations, as well as confirming that all parties obey the rules and regulations prescribed by the authorities. However, enforcement officers are encountering various challenges and difficulties which have undermined the enforcement capacity and efficiency. The appropriate policy responses for these issues are important to resolve the problems in the long term and empowering enforcement capacity to meet future challenges of forest law enforcement. This paper is written according to extensive review of the articles and publications by The International Criminal Police Organization (INTERPOL), The International Tropical Timber Organization (ITTO), Chatham House and The Food and Agriculture Organization of the United Nations (FAO). Subsequently, various books and journal articles are reviewed to gain further insight towards enforcement issues and challenges. This paper identifies several issues which consist of (1) insufficient enforcement capacity and resources (2) lack of coordination between various enforcement agencies, (3) corruption in the government and private sectors and (4) unclear legal frameworks related to the forestry sector. Next, this paper discusses appropriate policy responses to address each enforcement challenges according to various publications. This includes specific reports concerning forest law enforcement published by international forestry-related organizations. Therefore, lack of resources, inadequate synchronization between agencies, corruption, and legal issues present challenges to enforcement officers in their daily routines. Recommendations regarding proper policy responses to overcome the issues are of great importance in assisting forest authorities in prioritizing their resources appropriately.

Keywords: corruption, enforcement challenges, enforcement capacity, forest law enforcement, insufficient agency coordination, legislative ambiguity

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Authors: Ana Lucia Molina

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Introduction: Fine motor skills refer to the use of the hands and coordination of the small muscles that control the fingers. A deficiency in fine motor skills is as important as a change in global movements, as fine motor skills directly affect activities of daily living. Fine movements are involved in some functions, such as motor control of the extremities, sensitivity, strength and tonus of the hands. A growing interest in the effects of non-invasive neuromodulation, such as transcranial stimulation technologies, through transcranial magnetic stimulation (TMS), has been observed in the scientific literature, with promising results in fine motor rehabilitation, as it provides modulation of the corresponding cortical activity in the area primary motor skills of the hands in both hemispheres (according to the International System 10-20, corresponding to C3 and C4). Objectives: to carry out a literature review about the effects of TMS on the cortical motor area corresponding to hand motricity. Methodology: This is a bibliographic survey carried out between October 2022 and March 2023 at Pubmed, Google Scholar, Lillacs and Virtual Health Library (BVS), with a national and international database. Some books on neuromodulation were included. Results: 28 articles and 5 books were initially found, and after reading the abstracts, only 14 articles and 3 books were selected, with publication dates between 2008 and 2022, to compose the literature review since it suited the purpose of this study. Conclusion: TMS has shown promising results in the treatment of fine motor rehabilitation, such as improving coordination, muscle strength and range of motion of the hands, being a complementary technique to existing treatments and thus providing more potent results for manual skills in activities of daily living. It is important to emphasize the need for more specific studies on the application of TMS for the treatment of manual disorders, which describe the uniqueness of each movement.

Keywords: transcranial magnetic stimulation, fine motor skills, motor rehabilitation, non-invasive neuromodulation

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Authors: Michael K. O. Ayomoh, Oyindamola A. Omotuyi

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Autonomous mobile robots deployed to explore or operate in a never explored or an abandoned sub-surface mine requires extreme effectiveness in coordination and communication. In a bid to transmit information from the depth of the mine to the external surface in real-time and amidst diverse physical, chemical and virtual impediments, the concept of unified cooperative robots is seen to be a proficient approach. This paper presents an effective [human → robot → task] coordination framework for effective exploration of an abandoned underground mine. The problem addressed in this research is basically the development of a globalized optimization model premised on time series differentiation and geometrical configurations for effective positioning of the two classes of robots in the cooperation namely the outermost stationary master (OSM) robots and the innermost dynamic task (IDT) robots for effective bi-directional signal transmission. In addition, the synchronization of a vision system and wireless communication system for both categories of robots, fiber optics system for the OSM robots in cases of highly sloppy or vertical mine channels and an autonomous battery recharging capability for the IDT robots further enhanced the proposed concept. The OSM robots are the master robots which are positioned at strategic locations starting from the mine open surface down to its base using a fiber-optic cable or a wireless communication medium all subject to the identified mine geometrical configuration. The OSM robots are usually stationary and function by coordinating the transmission of signals from the IDT robots at the base of the mine to the surface and in a reverse order based on human decisions at the surface control station. The proposed scheme also presents an optimized number of robots required to form the cooperation in a bid to reduce overall operational cost and system complexity.

Keywords: sub-surface mine, wireless communication, outermost stationary master robots, inner-most dynamic robots, fiber optic

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Authors: Mohammad S. Razai, Jan Williams, Rachel Nestel, Dermot Dalton

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Purpose: This descriptive qualitative study aimed to obtain parents recommendations for improving the notification process and communication of positive newborn screening result for cystic fibrosis (CF). Methods: Thematic analysis of semi-structured open-ended interviews with 11 parents of 7 children with confirmed diagnosis of CF between 2 months — 2 years of age. Results: Parents preferred face to face disclosure of positive NBS results by a pediatrician with CF professional qualification. They trusted a pediatrician more than any other professional in providing accurate, credible and comprehensive information about the diagnosis and its implications. Parents recommended that health professionals be knowledgeable and provide clear, succinct and understandable information. Providers should also explore parents concerns and acknowledge feelings and emotions. Most parents reported that they preferred to be notified immediately as soon as the results were available. Several parents preferred to be told once the diagnosis was certain. Most parents regarded open access to CF team as the most significant part of care coordination. In addition to health professionals, most parents used internet as an important source of information, interaction and exchange of experiences. Most parents also used social networking sites such as Facebook groups and smart phone apps. Conclusion: This study provides significant new evidence from parental perspective in emphasizing the pivotal role of good communication skills deployed by a knowledgeable CF specialist in person. Parents use of social media and internet has replaced some traditional methods of information exchange and may reduce the need for professional input for newly diagnosed CF patients.

Keywords: care coordination, cystic fibrosis, newborn screening, notification process, parental preferences, professional-paren communication

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Authors: Mihaela Beregoi, Horia Iovu, Cristina Busuioc, Alexandru Evanghelidis, Elena Matei, Monica Enculescu, Ionut Enculescu

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Nanomaterials field is very attractive for all researchers who are attempting to develop new devices with the same or improved properties than the micro-sized ones, while reducing the reagents and power consumptions. In this way, a wide range of nanomaterials were fabricated and integrated in applications for electronics, optoelectronics, solar cells, tissue reconstruction and drug delivery. Obviously, the most appealing ones are those dedicated to the medical domain. Different types of nano-sized materials, such as particles, fibers, films etc., can be synthesized by using physical, chemical or electrochemical methods. One of these techniques is electrospinning, which enable the production of fibers with nanometric dimensions by pumping a polymeric solution in a high electric field; due to the electrostatic charging and solvent evaporation, the precursor mixture is converted into nonwoven meshes with different fiber densities and mechanical properties. Moreover, polyaniline is a conducting polymer with interesting optical properties, suitable for displays and electrochromic windows. Otherwise, polyaniline is an electroactive polymer that can contract/expand by applying electric stimuli, due to the oxidation/reduction reactions which take place in the polymer chains. These two main properties can be exploited in order to synthesize smart materials that change their dimensions, exhibiting in the same time good electrochromic properties. In the context aforesaid, a poly(methyl metacrylate) solution was spun to get webs composed of fibers with diameter values between 500 nm and 1 µm. Further, the polymer meshes were covered with a gold layer in order to make them conductive and also appropriate as working electrode in an electrochemical cell. The gold shell was deposited by DC sputtering. Such metalized fibers can be transformed into smart materials by covering them with a thin layer of conductive polymer. Thus, the webs were coated with a polyaniline film by the electrochemical route, starting from and aqueous solution of aniline and sulfuric acid, where sulfuric acid acts as oxidant agent. For the polymerization of aniline, a saturated calomel electrode was employed as reference, a platinum plate as counter electrode and the gold covered webs as working electrode. Chronoamperometry was selected as deposition method for polyaniline, by modifying the deposition time. Metalized meshes with different fiber densities were used, the transmission ranging between 70 and 80 %. The morphological investigation showed that polyaniline layer has a granular structure for all deposition experiments. As well, some preliminary optical tests were done by using sulfuric acid as electrolyte, which revealed the modification of polyaniline colour from green to dark blue when applying a voltage. In conclusion, new multilayered materials were obtained by a simple approach: the merge of the electrospinning method benefits with polyaniline chemistry. This synthesis method allows the fabrication of structures with reproducible characteristics, suitable for display or tissue substituents.

Keywords: electrospinning, fibers, smart materials, polyaniline

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Authors: Kathleen Moyer, Nora Ait Boucherbil, Murtaza Zohair, Janna Eaves-Rathert, Cary Pint

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This study demonstrates the significance of interface engineering in the field of structural energy by being the first case where the performance of the system with the structural battery is greater than the performance of the same system with a battery separate from the system. The benefits of improving the interface in the structural battery were tested by creating carbon fiber composite batteries (and independent graphite electrodes and lithium iron phosphate electrodes) with and without an improved interface. Mechanical data on the structural batteries were collected using tensile tests and electrochemical data was collected using scanning electron microscopy equipment. The full-cell lithium-ion structural batteries had capacity retention of over 80% exceeding 100 cycles with an average energy density of 52 W h kg−1 and a maximum energy density of 58 W h kg−1. Most scientific developments in the field of structural energy have been done with supercapacitors. Most scientific developments with structural batteries have been done where batteries are simply incorporated into the structural element. That method has limited advantages and can create mechanical disadvantages. This study aims to show that a large improvement in structure energy research can be made by improving the interface between the structural device and the battery.

Keywords: composite materials, electrochemical performance, mechanical properties, polymer interface, structural batteries

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Authors: Khaled Barkaoui

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Research on second-language (L2) learning tends to focus on comparing students with different levels of proficiency at one point in time. However, to understand L2 development, we need more longitudinal research. In this study, we adopt a longitudinal approach to examine changes in three indicators of L2 ability, complexity, accuracy, and fluency (CAF), as reflected in the writing of L2 learners when writing on different tasks before and after a period L2 instruction. Each of 85 Chinese learners of English at three levels of English language proficiency responded to two writing tasks (independent and integrated) before and after nine months of English-language study in China. Each essay (N= 276) was analyzed in terms of numerous CAF indices using both computer coding and human rating: number of words written, number of errors per 100 words, ratings of error severity, global syntactic complexity (MLS), complexity by coordination (T/S), complexity by subordination (C/T), clausal complexity (MLC), phrasal complexity (NP density), syntactic variety, lexical density, lexical variation, lexical sophistication, and lexical bundles. Results were then compared statistically across tasks, L2 proficiency levels, and time. Overall, task type had significant effects on fluency and some syntactic complexity indices (complexity by coordination, structural variety, clausal complexity, phrase complexity) and lexical density, sophistication, and bundles, but not accuracy. L2 proficiency had significant effects on fluency, accuracy, and lexical variation, but not syntactic complexity. Finally, fluency, frequency of errors, but not accuracy ratings, syntactic complexity indices (clausal complexity, global complexity, complexity by subordination, phrase complexity, structural variety) and lexical complexity (lexical density, variation, and sophistication) exhibited significant changes after instruction, particularly for the independent task. We discuss the findings and their implications for assessment, instruction, and research on CAF in the context of L2 writing.

Keywords: second language writing, Fluency, accuracy, complexity, longitudinal

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Authors: Marianna Maiaru, Gregory M. Odegard, Josh Kemppainen, Ivan Gallegos, Michael Olaya

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Ceramic matrix composites (CMCs) are typically used in applications that require long-term mechanical integrity at elevated temperatures. CMCs are usually fabricated using a polymer precursor that is initially polymerized in situ with fiber reinforcement, followed by a series of cycles of pyrolysis to transform the polymer matrix into a rigid glass or ceramic. The pyrolysis step typically generates volatile gasses, which creates porosity within the polymer matrix phase of the composite. Subsequent cycles of monomer infusion, polymerization, and pyrolysis are often used to reduce the porosity and thus increase the durability of the composite. Because of the significant expense of such iterative processing cycles, new generations of CMCs with improved durability and manufacturability are difficult and expensive to develop using standard Edisonian approaches. The goal of this research is to develop a computational process-modeling-based approach that can be used to design the next generation of CMC materials with optimized material and processing parameters for maximum strength and efficient manufacturing. The process modeling incorporates computational modeling tools, including molecular dynamics (MD), to simulate the material at multiple length scales. Results from MD simulation are used to inform the continuum-level models to link molecular-level characteristics (material structure, temperature) to bulk-level performance (strength, residual stresses). Processing parameters are optimized such that process-induced residual stresses are minimized and laminate strength is maximized. The multiscale process modeling method developed with this research can play a key role in the development of future CMCs for high-temperature and high-strength applications. By combining multiscale computational tools and process modeling, new manufacturing parameters can be established for optimal fabrication and performance of CMCs for a wide range of applications.

Keywords: digital engineering, finite elements, manufacturing, molecular dynamics

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Authors: Rabindranath Jana, Biswajit Maity, Keka Rana

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

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

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Authors: Y. K. Leong, J. C. W. Lan, H. S. Loh, P. L. Show

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Being biodegradable, non-toxic, renewable and have similar or better properties as commercial plastics, polyhydroxy alkanoates (PHAs) can be a potential game changer in the polymer industry. PHAs are the biodegradable polymer produced by bacteria, which are in interest as a sustainable alternative to petrochemical-derived plastics; however, its commercial value has significantly limited by high production and recovery cost of PHA. Aqueous two-phase system (ATPS) offers different chemical and physical environments, which contains about 80-90% water delivers an excellent environment for partitioning of cells, cell organelles and biologically active substances. Extractive bioconversion via ATPS allows the integration of PHA upstream fermentation and downstream purification process, which reduces production steps and time, thus lead to cost reduction. The ability of Ralstonia eutropha to grow under different ATPS conditions was investigated for its potential to be used in a bioconversion system. Changes in tie-line length (TLL) and a volume ratio (Vr) were shown to have an effect on PHA partition coefficient. High PHA recovery yield of 65% with a relatively high purity of 73% was obtained in PEG 6000/Sodium sulphate system with 42.6 wt/wt % TLL and 1.25 Vr. Extractive bioconversion via ATPS is an attractive approach for the combination of PHA production and recovery process.

Keywords: aqueous two-phase system, extractive bioconversion, polyhydroxy alkanoates, purification

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Authors: Li Shuping, Shu Huaping, Yi Chaofan, Tao Jiang

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Equestrian practice is often considered having a unique effect on improving symptoms in children with autism. This study evaluated and measured the changes in daily behavior, morphological, physical function, and fitness indexes of two group children with autism by means of 12 weeks of equestrian and basketball exercises. 19 clinically diagnosed children with moderate/mild autism were randomly divided into equestrian group (9 children, age=10.11±1.90y) and basketball group (10 children, age=10.70±2.16y). Both the equestrian and basketball groups practiced twice a week for 45 to 60 minutes each time. Three scales, the Autism Behavior Checklist (ABC), the Childhood Autism Rating Scale (CARS) and the Clancy Autism Behavior Scale (CABS) were used to assess their human behavior and psychology. Four morphological, seven physical function and fitness indicators were measured to evaluate the effects of the two exercises on the children’s body. The evaluations were taken by every four weeks ( pre-exercise, the 4th week, the 8th week and 12th week (post exercise). The result showed that the total scores of ABC, CARS and CABS, the dimension scores of ABC on the somatic motor, language and life self-care obtained after exercise were significantly lower than those obtained before 12 week exercises in both groups. The ABC feeling dimension scores of equestrian group and ABC communication dimension score of basketball group were significantly lower,and The upper arm circumference, sitting forward flexion, 40 second sit-up, 15s lateral jump, vital capacity, and single foot standing of both groups were significantly higher than that of before exercise.. The BMI of equestrian group was significantly reduced. The handgrip strength of basketball group was significantly increased. In conclusion, both types of exercises could improve daily behavior, morphological, physical function, and fitness indexes of the children with autism. However, the behavioral psychological scores, body morphology and function indicators and time points were different in the middle and back of the two interventions.But the indicators and the timing of the improvement were different. To the group of equestrian, the improvement of the flexibility occurred at week 4, the improvement of the sensory perception, control and use their own body, and promote the development of core strength endurance, coordination and cardiopulmonary function occurred at week 8，and the improvement of core strength endurance, coordination and cardiopulmonary function occurred at week 12. To the group of basketball, the improvement of the hand strength, balance, flexibility and cardiopulmonary function occurred at week 4, the improvement of the self-care ability and language expression ability, and core strength endurance and coordination occurred at week 8, the improvement of the control and use of their own body and social interaction ability occurred at week 12. In comparison of the exercise effects, the equestrian exercise improved the physical control and application ability appeared earlier than that of basketball group. Basketball exercise improved the language expression ability, self-care ability, balance ability and cardiopulmonary function of autistic children appeared earlier than that of equestrian group.

Keywords: intervention, children with autism, equestrain, basketball

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Authors: Valeria Piccioni, Matthias Leschok, Ina Cheibas, Illias Hischier, Benjamin Dillenburger, Arno Schlueter, Matthias Kohler, Fabio Gramazio

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The decarbonisation of the building sector requires the development of building components that provide energy efficiency while producing minimal environmental impact. Recent advancements in large-scale 3D printing have shown that it is possible to fabricate components with embedded performances that can be tuned for their specific application. We investigate the potential of polymer 3D printing for the fabrication of translucent facade components. In this study, we explore the effect of geometry on thermal insulation of printed cavity structures following a Hot Box test method. The experimental results are used to calibrate a finite-element simulation model which can support the informed design of 3D printed insulation structures. We show that it is possible to fabricate components providing thermal insulation ranging from 1.7 to 0.95 W/m2K only by changing the internal cavity distribution and size. Moreover, we identify design guidelines that can be used to fabricate components for different climatic conditions and thermal insulation requirements. The research conducted provides the first insights into the thermal behaviour of polymer 3DP facades on a large scale. These can be used as design guidelines for further research toward performant and low-embodied energy 3D printed facade components.

Keywords: 3D printing, thermal performance, polymers, facade components, hot-box method

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Authors: O. Squillace, R. L. Thompson

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Migration of small molecules to, and across the surface of polymer matrices is a little-studied problem with important industrial applications. Tackifiers in adhesives, flavors in foods and binding agents in paints all present situations where the function of a product depends on the ability of small molecules to migrate through a polymer matrix to achieve the desired properties such as softness, dispersion of fillers, and to deliver an effect that is felt (or tasted) on a surface. It’s been shown that the chemical and molecular structure, surface free energies, phase behavior, close environment and compatibility of the system, influence the migrants’ motion. When differences in behavior, such as occurrence of segregation to the surface or not, are observed it is then of crucial importance to identify and get a better understanding of the driving forces involved in the process of molecular migration. In this aim, experience is meant to be allied with theory in order to deliver a validated theoretical and computational toolkit to describe and predict these phenomena. The systems that have been chosen for this study aim to address the effect of polarity mismatch between the migrants and the polymer matrix and that of a second migrant over the first one. As a non-polar resin polymer, polyvinyl acetate is used as the material to which more or less polar migrants (sorbitol, carvone, octanoic acid (OA), triacetin) are to be added. Through contact angle measurement a surface excess is seen for sorbitol (polar) mixed with PVAc as the surface energy is lowered compare to the one of pure PVAc. This effect is increased upon the addition of carvon or triacetin (non-polars). Surface micro-structures are also evidenced by atomic force microscopy (AFM). Ion beam analysis (Nuclear Reaction Analysis), supplemented by neutron reflectometry can accurately characterize the self-organization of surfactants, oligomers, aromatic molecules in polymer films in order to relate the macroscopic behavior to the length scales that are amenable to simulation. The nuclear reaction analysis (NRA) data for deuterated OA 20% shows the evidence of a surface excess which is enhanced after annealing. The addition of 10% triacetin, as a second migrant, results in the formation of an underlying layer enriched in triacetin below the surface excess of OA. The results show that molecules in polarity mismatch with the matrix tend to segregate to the surface, and this is favored by the addition of a second migrant of the same polarity than the matrix. As studies have been restricted to materials that are model supported films under static conditions in a first step, it is also wished to address the more challenging conditions of materials under controlled stress or strain. To achieve this, a simple rig and PDMS cell have been designed to stretch the material to a defined strain and to probe these mechanical effects by ion beam analysis and atomic force microscopy. This will make a significant step towards exploring the influence of extensional strain on surface segregation, flavor release in cross-linked rubbers.

Keywords: polymers, surface segregation, thin films, molecular migration

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Authors: A. M. Metak, T. T. Ajaal, Amal Metak, Tawfik Ajaal

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Commercial nanocomposite food packaging type nano-silver containers were characterised using scanning electron microscopy (SEM) and energy-dispersive X-Ray spectroscopy (EDX). The presence of nanoparticles consistent with the incorporation of 1% nano-silver (Ag) and 0.1% titanium dioxide (TiO2) nanoparticle into polymeric materials formed into food containers was confirmed. Both nanomaterials used in this type of packaging appear to be embedded in a layered configuration within the bulk polymer. The dimensions of the incorporated nanoparticles were investigated using X-Ray diffraction (XRD) and determined by calculation using the Scherrer Formula; these were consistent with Ag and TiO2 nanoparticles in the size range 20-70nm both were spherical shape nanoparticles. Antimicrobial assessment of the nanocomposite container has also been performed and the results confirm the antimicrobial activity of Ag and TiO2 nanoparticles in food packaging containers. Migration assessments were performed in a wide range of food matrices to determine the migration of nanoparticles from the packages. The analysis was based on the relevant European safety directives and involved the application of inductively coupled plasma mass spectrometry (ICP-MS) to identify the range of migration risk. The data pertain to insignificance levels of migration of Ag and TiO2 nanoparticles into the selected food matrices.

Keywords: nano-silver, antimicrobial food packaging, migration, titanium dioxide

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Authors: Sameh Ahmed, Khaled Galal

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Fiber-reinforced polymer (FRP) sandwich panels are increasingly making their way into structural engineering applications. One of these applications is the blast mitigation. This is attributed to FRP ability of absorbing considerable amount of energy relative to their low density. In this study, FRP sandwich panels are numerically studied using an explicit finite element code ANSYS AUTODYN. The numerical model is then validated with the experimental field tests in the literature. The inner core configurations that have been studied in the experimental field tests were formed from different orientations of the honeycomb shape. On the other hand, the conducted numerical study has proposed a new core configuration. The new core configuration is formulated from a combination of woven and honeycomb shapes. Throughout this study, two performance parameters are considered; the amount of the energy absorbed by the panels and the peak deformation of the panels. Following, a parametric study has been conducted with more variations of the studied parameters to examine the enhancement of the panels' performance. It is found that the numerical results have shown a good agreement with the experimental measurements. Furthermore, the analyses have revealed that using the proposed core configuration obviously enhances the FRP panels’ behavior when subjected to blast loads.

Keywords: blast load, fiber reinforced polymers, finite element modeling, sandwich panels

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Authors: Sudhakara Naidu Neppalli, Tejas S. Bhosale

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It is well known that the block copolymer (BCP) can form a complex molecule, through non-covalent bonds such as hydrogen bond, ionic bond and co-ordination bond, with low molecular weight compound as well as with macromolecules, which provide vast applications, includes the alteration of morphology and properties of polymers. Hence we covered the research that, the importance of non-covalent bonds in increasing the non-favourable segmental interactions of the blocks was well examined by attaching and detaching the bonds between the BCP and additive. We also monitored the phase transition of block copolymer and effective interaction parameter (χeff) for Li-doped polymers using small angle x-ray scattering and transmission electron microscopy. The effective interaction parameter (χeff) between two block components was evaluated using Leibler theory based on the incompressible random phase approximation (RPA) for ionized BCP in a disordered state. Furthermore, conductivity experiments demonstrate that the ionic conductivity in the samples quenched from the different structures is morphology-independent, while it increases with increasing ion salt concentration. Morphological transitions, interaction parameter, and thermal stability also examined in quarternized block copolymer. D-spacing was used to estimate effective interaction parameter (χeff) of block components in weak and strong segregation regimes of ordered phase. Metal-containing polymer has been the topic of great attention in recent years due to their wide range of potential application. Similarly, metal- ligand complex is used as a supramolecular linker between the polymers giving rise to a ‘Metallo-Supramolecule assembly. More precisely, functionalized polymer end capped with 2, 2’:6’, 2”- terpyridine ligand can be selectively complexed with wide range of transition metal ions and then subsequently attached to other terpyridine terminated polymer block. In compare to other supramolecular assembly, BCP involved metallo-supramolecule assembly offers vast applications such as optical activity, electrical conductivity, luminescence and photo refractivity.

Keywords: band gap, block copolymer, conductivity, interaction parameter, phase transition

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Authors: E. Erdem, M. Şahin, M. Saçak

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Smectite is a layered silicate and modified with alkyl ammonium salts to make both the hydrophilic silicate surfaces organophilic, and to expand the clay layers. Thus, a nanocomposite structure can be formed enabling to enter various types of polymers between the layers. In this study, Na-smectite crystals were prepared by purification of bentonite. Benzyltributylammonium bromide (BTBAB) was used as a swelling agent. The mixing time and additive concentration were changed during the swelling process. It was determined that the 4 h of mixing time and 0.2 g of BTBAB were sufficient and the usage of higher amounts of salt did not increase the interlayer space between the clay layers. Then, the conductive poly(o-toluidine) (POT)/smectite nanocomposite was prepared in the presence of swollen Na-smectite using ammonium persulfate (APS) as oxidant in aqueous acidic medium. The POT content and conductivity of the prepared nanocomposite were systematically investigated as a function of polymerization conditions such as the treatment time of swollen smectite in monomer solution and o-toluidine/APS mol ratio. The POT content and conductivity of nanocomposite increased with increasing monomer/oxidant mol ratio up to 1 and did not change at higher ratios. The maximum polymer yield and the highest conductivity value of the composite were 26.0% and 4.0×10-5 S/cm, respectively. The structural and morphological analyses of the POT/smectite nanocomposite were carried out by XRD, FTIR and SEM techniques, respectively.

Keywords: clay, composite, conducting polymer, poly(o-anisidine)

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Authors: Franca De Sarno, Alfonso Maria Ponsiglione, Enza Torino

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Recent advances in diagnostic imaging technology have significantly contributed to a better understanding of specific changes associated with diseases progression. Among different imaging modalities, Magnetic Resonance Imaging (MRI) represents a noninvasive medical diagnostic technique, which shows low sensitivity and long acquisition time and it can discriminate between healthy and diseased tissues by providing 3D data. In order to improve the enhancement of MRI signals, some imaging exams require intravenous administration of contrast agents (CAs). Recently, emerging research reports a progressive deposition of these drugs, in particular, gadolinium-based contrast agents (GBCAs), in the body many years after multiple MRI scans. These discoveries confirm the need to have a biocompatible system able to boost a clinical relevant Gd-chelate. To this aim, several approaches based on engineered nanostructures have been proposed to overcome the common limitations of conventional CAs, such as the insufficient signal-to-noise ratios due to relaxivity and poor safety profile. In particular, nanocarriers, labeling or loading with CAs, capable of carrying high payloads of CAs have been developed. Currently, there’s no a comprehensive understanding of the thermodynamic contributions enable of boosting the efficacy of conventional CAs by using biopolymers matrix. Thus, considering the importance of MRI in diagnosing diseases, here it is reported a successful example of the next generation of these drugs where the commercial gadolinium chelate is incorporate into a biopolymer nanostructure, formed by cross-linked hyaluronic acid (HA), with improved relaxation properties. In addition, they are highlighted the basic principles ruling biopolymer-CA interactions in the perspective of their influence on the relaxometric properties of the CA by adopting a multidisciplinary experimental approach. On the basis of these discoveries, it is clear that the main point consists in increasing the rigidification of readily-available Gd-CAs within the biopolymer matrix by controlling the water dynamics, the physicochemical interactions, and the polymer conformations. In the end, the acquired knowledge about polymer-CA systems has been applied to develop of Gd-based HA nanoparticles with enhanced relaxometric properties.

Keywords: biopolymers, MRI, nanoparticles, contrast agent

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Authors: Amine Rezzoug, Said Abdi, Nadjet Bouhelal, Ismail Daoud

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This paper investigates the application of metallic coatings on high fiber volume fraction carbon/epoxy polymer matrix composites. For the grip of the metallic layer, a method of modifying the surface of the composite by introducing a mixture of copper and steel powder (filler powders) which can reduce the impact of thermal spray particles. The powder was introduced to the surface at the time of the forming. Arc spray was used to project the zinc coating layer. The substrate was grit blasted to avoid poor adherence. The porosity, microstructure, and morphology of layers are characterized by optical microscopy, SEM and image analysis. The samples were studied also in terms of hardness and erosion resistance. This investigation did not reveal any visible evidence damage to the substrates. The hardness of zinc layer was about 25.94 MPa and the porosity was around (∼6.70%). The erosion test showed that the zinc coating improves the resistance to erosion. Based on the results obtained, we can conclude that thermal spraying allows the production of protective coating on PMC. Zinc coating has been identified as a compatible material with the substrate. The filler powders layer protects the substrate from the impact of hot particles and allows avoiding the rupture of brittle carbon fibers.

Keywords: arc spray, coating, composite, erosion

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Authors: Timine Suoware, Sylvester Edelugo, Charles Amgbari

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The susceptibility of natural fibre polymer composites to flame has necessitated research to improve and develop flame retardant (FR) to delay the escape of combustible volatiles. Previous approaches relied mostly on FR such as aluminium tri-hydroxide (ATH) and ammonium polyphosphate (APP) to improve fire performances of wood sawdust polymer composites (WSPC) with emphasis on non-structural building applications. In this paper, APP was modified with gum Arabic powder (GAP) and then hybridized with ATH at 0, 12 and 18% loading ratio to form new FR species; WSPC12%APP-GAP and WSPC18%ATH/APP-GAP. The FR species were incorporated in wood sawdust waste reinforced in polyester resin to form panels for fireproof doors. The panels were produced using hand lay compression moulding technique and cured at room temperature. Specimen cut from panels were then tested for tensile strength (TS), flexural strength (FS) and impact strength (IS) using universal testing machine and impact tester; thermal stability using (TGA/DSC 1: Metler Toledo); time-to-ignition (Tig), heat release rates (HRR); peak HRR (HRRp), average HRR (HRRavg), total HRR (THR), peak mass loss rate (MLRp), average smoke production rate (SPRavg) and carbon monoxide production (COP ) were obtained using the cone calorimeter apparatus. From the mechanical properties obtained, improvements of IS for the panels were not noticeable whereas TS and FS for WSPC12%APP-GAP respectively stood at 12.44 MPa and 85.58 MPa more than those without FR (WSPC0%). For WSC18%ATH/APP-GAP TS and FS respectively stood at 16.45 MPa and 50.49 MPa more compared to (WSPC0%). From the thermal analysis, the panels did not exhibit any significant change as early degradation was observed. At 900 OC, the char residues improved by 15% for WSPC12%APP-GAP and 19% for WSPC18%ATH/APP-GAP more than (WSC0%) at 5%, confirming the APP-GAP to be a good FR. At 50 kW/m2 heat flux (HF), WSPC12%APP-GAP improved better the fire behaviour of the panels when compared to WSC0% as follows; Tig = 46 s, HRRp = 56.1 kW/2, HRRavg = 32.8 kW/m2, THR = 66.6 MJ/m2, MLRp = 0.103 g/s, TSR = 0.04 m2/s and COP = 0.051 kg/kg. These were respectively more than WSC0%. It can be concluded that the new concept of modifying FR with GAP in WSC could meet the requirement of a fireproof door for building applications.

Keywords: composite, flame retardant, wood sawdust, fireproof doors

Procedia PDF Downloads 107

Authors: Mohammed A. Sakr, Tarek M. Khalifa, Walid N. Mansour

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External bonding of fiber reinforced polymer (FRP) plates to reinforced concrete (RC) beams is an effective technique for flexural strengthening. This paper presents an analytical parametric study on the behavior of RC continuous beams flexurally strengthened with externally bonded FRP plates on the upper and lower fibers, conducted using simple uniaxial nonlinear finite element model (UNFEM). UNFEM is able to estimate the load-carrying capacity, different failure modes and the interfacial stresses of RC continuous beams flexurally strengthened with externally bonded FRP plates on the upper and lower fibers. The study investigated the effect of five key parameters on the behavior and moment redistribution of FRP-reinforced continuous beams. The investigated parameters were the length of the FRP plate, the width and the thickness of the FRP plate, the ratio between the area of the FRP plate to the concrete area, the cohesive shear strength of the adhesive layer, and the concrete compressive strength. The investigation resulted in a number of important conclusions reflecting the effects of the studied parameters on the behavior of RC continuous beams flexurally strengthened with externally bonded FRP plates.

Keywords: continuous beams, parametric study, finite element, fiber reinforced polymer

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Authors: Fateme Nokhodchi Bonab

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Studies related to magnetic resonance imaging (MRI) and drug delivery are reviewed in this study to demonstrate the role of transport theory in porous media in facilitating advances in biomedical applications. Diffusion processes are believed to be important in many therapeutic modalities such as: B. Delivery of drugs to the brain. We analyse the progress in the development of diffusion equations using the local volume average method and the evaluation of applications related to diffusion equations. Torsion and porosity have significant effects on diffusive transport. In this study, various relevant models of torsion are presented and mathematical modeling of drug release from biodegradable delivery systems is analysed. In this study, a new model of drug release kinetics from porous biodegradable polymeric microspheres under bulk and surface erosion of the polymer matrix is presented. Solute drug diffusion, drug dissolution from the solid phase, and polymer matrix erosion have been found to play a central role in controlling the overall drug release process. This work paves the way for MRI and drug delivery researchers to develop comprehensive models based on porous media theory that use fewer assumptions compared to other approaches.

Keywords: MRI, porous media, drug delivery, biomedical applications

Procedia PDF Downloads 89