Search results for: vacuum evaporation
13 Poly (3,4-Ethylenedioxythiophene) Prepared by Vapor Phase Polymerization for Stimuli-Responsive Ion-Exchange Drug Delivery
Authors: M. Naveed Yasin, Robert Brooke, Andrew Chan, Geoffrey I. N. Waterhouse, Drew Evans, Darren Svirskis, Ilva D. Rupenthal
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Poly(3,4-ethylenedioxythiophene) (PEDOT) is a robust conducting polymer (CP) exhibiting high conductivity and environmental stability. It can be synthesized by either chemical, electrochemical or vapour phase polymerization (VPP). Dexamethasone sodium phosphate (dexP) is an anionic drug molecule which has previously been loaded onto PEDOT as a dopant via electrochemical polymerisation; however this technique requires conductive surfaces from which polymerization is initiated. On the other hand, VPP produces highly organized biocompatible CP structures while polymerization can be achieved onto a range of surfaces with a relatively straight forward scale-up process. Following VPP of PEDOT, dexP can be loaded and subsequently released via ion-exchange. This study aimed at preparing and characterising both non-porous and porous VPP PEDOT structures including examining drug loading and release via ion-exchange. Porous PEDOT structures were prepared by first depositing a sacrificial polystyrene (PS) colloidal template on a substrate, heat curing this deposition and then spin coating it with the oxidant solution (iron tosylate) at 1500 rpm for 20 sec. VPP of both porous and non-porous PEDOT was achieved by exposing to monomer vapours in a vacuum oven at 40 mbar and 40 °C for 3 hrs. Non-porous structures were prepared similarly on the same substrate but without any sacrificial template. Surface morphology, compositions and behaviour were then characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) respectively. Drug loading was achieved by 50 CV cycles in a 0.1 M dexP aqueous solution. For drug release, each sample was exposed to 20 mL of phosphate buffer saline (PBS) placed in a water bath operating at 37 °C and 100 rpm. Film was stimulated (continuous pulse of ± 1 V at 0.5 Hz for 17 mins) while immersed into PBS. Samples were collected at 1, 2, 6, 23, 24, 26 and 27 hrs and were analysed for dexP by high performance liquid chromatography (HPLC Agilent 1200 series). AFM and SEM revealed the honey comb nature of prepared porous structures. XPS data showed the elemental composition of the dexP loaded film surface, which related well with that of PEDOT and also showed that one dexP molecule was present per almost three EDOT monomer units. The reproducible electroactive nature was shown by several cycles of reduction and oxidation via CV. Drug release revealed success in drug loading via ion-exchange, with stimulated porous and non-porous structures exhibiting a proof of concept burst release upon application of an electrical stimulus. A similar drug release pattern was observed for porous and non-porous structures without any significant statistical difference, possibly due to the thin nature of these structures. To our knowledge, this is the first report to explore the potential of VPP prepared PEDOT for stimuli-responsive drug delivery via ion-exchange. The produced porous structures were ordered and highly porous as indicated by AFM and SEM. These porous structures exhibited good electroactivity as shown by CV. Future work will investigate porous structures as nano-reservoirs to increase drug loading while sealing these structures to minimize spontaneous drug leakage.Keywords: PEDOT for ion-exchange drug delivery, stimuli-responsive drug delivery, template based porous PEDOT structures, vapour phase polymerization of PEDOT
Procedia PDF Downloads 22712 Wideband Performance Analysis of C-FDTD Based Algorithms in the Discretization Impoverishment of a Curved Surface
Authors: Lucas L. L. Fortes, Sandro T. M. Gonçalves
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In this work, it is analyzed the wideband performance with the mesh discretization impoverishment of the Conformal Finite Difference Time-Domain (C-FDTD) approaches developed by Raj Mittra, Supriyo Dey and Wenhua Yu for the Finite Difference Time-Domain (FDTD) method. These approaches are a simple and efficient way to optimize the scattering simulation of curved surfaces for Dielectric and Perfect Electric Conducting (PEC) structures in the FDTD method, since curved surfaces require dense meshes to reduce the error introduced due to the surface staircasing. Defined, on this work, as D-FDTD-Diel and D-FDTD-PEC, these approaches are well-known in the literature, but the improvement upon their application is not quantified broadly regarding wide frequency bands and poorly discretized meshes. Both approaches bring improvement of the accuracy of the simulation without requiring dense meshes, also making it possible to explore poorly discretized meshes which bring a reduction in simulation time and the computational expense while retaining a desired accuracy. However, their applications present limitations regarding the mesh impoverishment and the frequency range desired. Therefore, the goal of this work is to explore the approaches regarding both the wideband and mesh impoverishment performance to bring a wider insight over these aspects in FDTD applications. The D-FDTD-Diel approach consists in modifying the electric field update in the cells intersected by the dielectric surface, taking into account the amount of dielectric material within the mesh cells edges. By taking into account the intersections, the D-FDTD-Diel provides accuracy improvement at the cost of computational preprocessing, which is a fair trade-off, since the update modification is quite simple. Likewise, the D-FDTD-PEC approach consists in modifying the magnetic field update, taking into account the PEC curved surface intersections within the mesh cells and, considering a PEC structure in vacuum, the air portion that fills the intersected cells when updating the magnetic fields values. Also likewise to D-FDTD-Diel, the D-FDTD-PEC provides a better accuracy at the cost of computational preprocessing, although with a drawback of having to meet stability criterion requirements. The algorithms are formulated and applied to a PEC and a dielectric spherical scattering surface with meshes presenting different levels of discretization, with Polytetrafluoroethylene (PTFE) as the dielectric, being a very common material in coaxial cables and connectors for radiofrequency (RF) and wideband application. The accuracy of the algorithms is quantified, showing the approaches wideband performance drop along with the mesh impoverishment. The benefits in computational efficiency, simulation time and accuracy are also shown and discussed, according to the frequency range desired, showing that poorly discretized mesh FDTD simulations can be exploited more efficiently, retaining the desired accuracy. The results obtained provided a broader insight over the limitations in the application of the C-FDTD approaches in poorly discretized and wide frequency band simulations for Dielectric and PEC curved surfaces, which are not clearly defined or detailed in the literature and are, therefore, a novelty. These approaches are also expected to be applied in the modeling of curved RF components for wideband and high-speed communication devices in future works.Keywords: accuracy, computational efficiency, finite difference time-domain, mesh impoverishment
Procedia PDF Downloads 12511 Environmentally Sustainable Transparent Wood: A Fully Green Approach from Bleaching to Impregnation for Energy-Efficient Engineered Wood Components
Authors: Francesca Gullo, Paola Palmero, Massimo Messori
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Transparent wood is considered a promising structural material for the development of environmentally friendly, energy-efficient engineered components. To obtain transparent wood from natural wood materials two approaches can be used: i) bottom-up and ii) top-down. Through the second method, the color of natural wood samples is lightened through a chemical bleaching process that acts on chromophore groups of lignin, such as the benzene ring, quinonoid, vinyl, phenolics, and carbonyl groups. These chromophoric units form complex conjugate systems responsible for the brown color of wood. There are two strategies to remove color and increase the whiteness of wood: i) lignin removal and ii) lignin bleaching. In the lignin removal strategy, strong chemicals containing chlorine (chlorine, hypochlorite, and chlorine dioxide) and oxidizers (oxygen, ozone, and peroxide) are used to completely destroy and dissolve the lignin. In lignin bleaching methods, a moderate reductive (hydrosulfite) or oxidative (hydrogen peroxide) is commonly used to alter or remove the groups and chromophore systems of lignin, selectively discoloring the lignin while keeping the macrostructure intact. It is, therefore, essential to manipulate nanostructured wood by precisely controlling the nanopores in the cell walls by monitoring both chemical treatments and process conditions, for instance, the treatment time, the concentration of chemical solutions, the pH value, and the temperature. The elimination of wood light scattering is the second step in the fabrication of transparent wood materials, which can be achieved through two-step approaches: i) the polymer impregnation method and ii) the densification method. For the polymer impregnation method, the wood scaffold is treated with polymers having a corresponding refractive index (e.g., PMMA and epoxy resins) under vacuum to obtain the transparent composite material, which can finally be pressed to align the cellulose fibers and reduce interfacial defects in order to have a finished product with high transmittance (>90%) and excellent light-guiding. However, both the solution-based bleaching and the impregnation processes used to produce transparent wood generally consume large amounts of energy and chemicals, including some toxic or pollutant agents, and are difficult to scale up industrially. Here, we report a method to produce optically transparent wood by modifying the lignin structure with a chemical reaction at room temperature using small amounts of hydrogen peroxide in an alkaline environment. This method preserves the lignin, which results only deconjugated and acts as a binder, providing both a strong wood scaffold and suitable porosity for infiltration of biobased polymers while reducing chemical consumption, the toxicity of the reagents used, polluting waste, petroleum by-products, energy and processing time. The resulting transparent wood demonstrates high transmittance and low thermal conductivity. Through the combination of process efficiency and scalability, the obtained materials are promising candidates for application in the field of construction for modern energy-efficient buildings.Keywords: bleached wood, energy-efficient components, hydrogen peroxide, transparent wood, wood composites
Procedia PDF Downloads 4210 Gas-Phase Noncovalent Functionalization of Pristine Single-Walled Carbon Nanotubes with 3D Metal(II) Phthalocyanines
Authors: Vladimir A. Basiuk, Laura J. Flores-Sanchez, Victor Meza-Laguna, Jose O. Flores-Flores, Lauro Bucio-Galindo, Elena V. Basiuk
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Noncovalent nanohybrid materials combining carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of increasing research effort, with a particular emphasis on the design of new heterogeneous catalysts, efficient organic photovoltaic cells, lithium batteries, gas sensors, field effect transistors, among other possible applications. The possibility of using unsubstituted Pcs for CNT functionalization is very attractive due to their very moderate cost and easy commercial availability. However, unfortunately, the deposition of unsubstituted Pcs onto nanotube sidewalls through the traditional liquid-phase protocols turns to be very problematic due to extremely poor solubility of Pcs. On the other hand, unsubstituted free-base H₂Pc phthalocyanine ligand, as well as many of its transition metal complexes, exhibit very high thermal stability and considerable volatility under reduced pressure, which opens the possibility for their physical vapor deposition onto solid surfaces, including nanotube sidewalls. In the present work, we show the possibility of simple, fast and efficient noncovalent functionalization of single-walled carbon nanotubes (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me= Co, Ni, Cu, and Zn. The functionalization can be performed in a temperature range of 400-500 °C under moderate vacuum and requires about 2-3 h only. The functionalized materials obtained were characterized by means of Fourier-transform infrared (FTIR), Raman, UV-visible and energy-dispersive X-ray spectroscopy (EDS), scanning and transmission electron microscopy (SEM and TEM, respectively) and thermogravimetric analysis (TGA). TGA suggested that Me(II)Pc weight content is 30%, 17% and 35% for NiPc, CuPc, and ZnPc, respectively (CoPc exhibited anomalous thermal decomposition behavior). The above values are consistent with those estimated from EDS spectra, namely, of 24-39%, 27-36% and 27-44% for CoPc, CuPc, and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Me(II)Pc hybrids, as compared to that of pristine nanotubes, implies very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) distribution patterns, calculated with density functional theory by using Perdew-Burke-Ernzerhof general gradient approximation correlation functional in combination with the Grimme’s empirical dispersion correction (PBE-D) and the double numerical basis set (DNP), also suggested that the interactions between Me(II) phthalocyanines and nanotube sidewalls are very strong. The authors thank the National Autonomous University of Mexico (grant DGAPA-IN200516) and the National Council of Science and Technology of Mexico (CONACYT, grant 250655) for financial support. The authors are also grateful to Dr. Natalia Alzate-Carvajal (CCADET of UNAM), Eréndira Martínez (IF of UNAM) and Iván Puente-Lee (Faculty of Chemistry of UNAM) for technical assistance with FTIR, TGA measurements, and TEM imaging, respectively.Keywords: carbon nanotubes, functionalization, gas-phase, metal(II) phthalocyanines
Procedia PDF Downloads 1249 Flexural Response of Sandwiches with Micro Lattice Cores Manufactured via Selective Laser Sintering
Authors: Emre Kara, Ali Kurşun, Halil Aykul
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The lightweight sandwiches obtained with the use of various core materials such as foams, honeycomb, lattice structures etc., which have high energy absorbing capacity and high strength to weight ratio, are suitable for several applications in transport industry (automotive, aerospace, shipbuilding industry) where saving of fuel consumption, load carrying capacity increase, safety of vehicles and decrease of emission of harmful gases are very important aspects. While the sandwich structures with foams and honeycombs have been applied for many years, there is a growing interest on a new generation sandwiches with micro lattice cores. In order to produce these core structures, various production methods were created with the development of the technology. One of these production technologies is an additive manufacturing technique called selective laser sintering/melting (SLS/SLM) which is very popular nowadays because of saving of production time and achieving the production of complex topologies. The static bending and the dynamic low velocity impact tests of the sandwiches with carbon fiber/epoxy skins and the micro lattice cores produced via SLS/SLM were already reported in just a few studies. The goal of this investigation was the analysis of the flexural response of the sandwiches consisting of glass fiber reinforced plastic (GFRP) skins and the micro lattice cores manufactured via SLS under thermo-mechanical loads in order to compare the results in terms of peak load and absorbed energy values respect to the effect of core cell size, temperature and support span length. The micro lattice cores were manufactured using SLS technology that creates the product drawn by a 3D computer aided design (CAD) software. The lattice cores which were designed as body centered cubic (BCC) model having two different cell sizes (d= 2 and 2.5 mm) with the strut diameter of 0.3 mm were produced using titanium alloy (Ti6Al4V) powder. During the production of all the core materials, the same production parameters such as laser power, laser beam diameter, building direction etc. were kept constant. Vacuum Infusion (VI) method was used to produce skin materials, made of [0°/90°] woven S-Glass prepreg laminates. The combination of the core and skins were implemented under VI. Three point bending tests were carried out by a servo-hydraulic test machine with different values of support span distances (L = 30, 45, and 60 mm) under various temperature values (T = 23, 40 and 60 °C) in order to analyze the influences of support span and temperature values. The failure mode of the collapsed sandwiches has been investigated using 3D computed tomography (CT) that allows a three-dimensional reconstruction of the analyzed object. The main results of the bending tests are: load-deflection curves, peak force and absorbed energy values. The results were compared according to the effect of cell size, support span and temperature values. The obtained results have particular importance for applications that require lightweight structures with a high capacity of energy dissipation, such as the transport industry, where problems of collision and crash have increased in the last years.Keywords: light-weight sandwich structures, micro lattice cores, selective laser sintering, transport application
Procedia PDF Downloads 3348 Investigation of Chemical Effects on the Lγ2,3 and Lγ4 X-ray Production Cross Sections for Some Compounds of 66dy at Photon Energies Close to L1 Absorption-edge Energy
Authors: Anil Kumar, Rajnish Kaur, Mateusz Czyzycki, Alessandro Migilori, Andreas Germanos Karydas, Sanjiv Puri
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The radiative decay of Li(i=1-3) sub-shell vacancies produced through photoionization results in production of the characteristic emission spectrum comprising several X-ray lines, whereas non-radiative vacancy decay results in Auger electron spectrum. Accurate reliable data on the Li(i=1-3) sub-shell X-ray production (XRP) cross sections is of considerable importance for investigation of atomic inner-shell ionization processes as well as for quantitative elemental analysis of different types of samples employing the energy dispersive X-ray fluorescence (EDXRF) analysis technique. At incident photon energies in vicinity of the absorption edge energies of an element, the many body effects including the electron correlation, core relaxation, inter-channel coupling and post-collision interactions become significant in the photoionization of atomic inner-shells. Further, in case of compounds, the characteristic emission spectrum of the specific element is expected to get influenced by the chemical environment (coordination number, oxidation state, nature of ligand/functional groups attached to central atom, etc.). These chemical effects on L X-ray fluorescence parameters have been investigated by performing the measurements at incident photon energies much higher than the Li(i=1-3) sub-shell absorption edge energies using EDXRF spectrometers. In the present work, the cross sections for production of the Lk(k= γ2,3, γ4) X-rays have been measured for some compounds of 66Dy, namely, Dy2O3, Dy2(CO3)3, Dy2(SO4)3.8H2O, DyI2 and Dy metal by tuning the incident photon energies few eV above the L1 absorption-edge energy in order to investigate the influence of chemical effects on these cross sections in presence of the many body effects which become significant at photon energies close to the absorption-edge energies. The present measurements have been performed under vacuum at the IAEA end-station of the X-ray fluorescence beam line (10.1L) of ELETTRA synchrotron radiation facility (Trieste, Italy) using self-supporting pressed pellet targets (1.3 cm diameter, nominal thicknesses ~ 176 mg/cm2) of 66Dy compounds (procured from Sigma Aldrich) and a metallic foil of 66Dy (nominal thickness ~ 3.9 mg/cm2, procured from Good Fellow, UK). The present measured cross sections have been compared with theoretical values calculated using the Dirac-Hartree-Slater(DHS) model based fluorescence and Coster-Kronig yields, Dirac-Fock(DF) model based X-ray emission rates and two sets of L1 sub-shell photoionization cross sections based on the non-relativistic Hartree-Fock-Slater(HFS) model and those deduced from the self-consistent Dirac-Hartree-Fock(DHF) model based total photoionization cross sections. The present measured XRP cross sections for 66Dy as well as for its compounds for the L2,3 and L4 X-rays, are found to be higher by ~14-36% than the two calculated set values. It is worth to be mentioned that L2,3 and L4 X-ray lines are originated by filling up of the L1 sub-shell vacancies by the outer sub-shell (N2,3 and O2,3) electrons which are much more sensitive to the chemical environment around the central atom. The present observed differences between measured and theoretical values are expected due to combined influence of the many-body effects and the chemical effects.Keywords: chemical effects, L X-ray production cross sections, Many body effects, Synchrotron radiation
Procedia PDF Downloads 1247 Listeria and Spoilage Inhibition Using Neutralized and Sodium Free Vinegar Powder
Authors: E. Heintz, H. J. van Lent, K. Glass, J. Lim
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The trend for sodium reduction in food products is clear. Following the World Health Organization (WHO) publication on sodium usage and intake, several countries have introduced initiatives to reduce food-related sodium intake. As salt is a common food preservative, this trend motivates the formulation of a suitable additive with comparable benefits of shelf life extension and microbial safety. Organic acid derivatives like acetates are known as generic microbial growth inhibitors and are commonly applied as additives to meet food safety demands. However, modern consumers have negative perceptions towards -synthetic-derived additives and increasingly prefer natural alternatives. Vinegar, for example, is a well-known natural fermentation product used in food preservation. However, the high acidity of vinegar often makes it impractical for direct use in meat products and a neutralized form would be desirable. This research demonstrates the efficacy of powdered vinegar (Provian DV) in inhibiting Listeria and spoilage organisms (LAB) to increase safety and shelf life of meat products. For this, the efficacy of Provian DV was compared to the efficacy of Provian K, a commonly used sodium free acetate-based preservative, which is known for its inhibition against Listeria. Materials & methods— Cured pork hams: Ingredients: Pork ham muscle, water, salt, dextrose, sodium tripolyphosphate, carrageenan, sodium nitrite, sodium erythorbate, and starch. Targets: 73-74% moisture, 1.75+0.1% salt, and pH 6.4+0.1. Treatments: Control (no antimicrobials), Provian®K 0.5% and 0.75%, Provian®DV 0.5%, 0.65%, 0.8% and 1.0%. Meat formulations in casings were cooked reaching an internal temperature of 73.9oC, cooled overnight and stored for 4 days at 4oC until inoculation. Inoculation: Sliced products were inoculated with approximately 3-log per gram of a cocktail of L. monocytogenes (including serotypes 4b, 1/2a and 1/2b) or LAB-cocktail (C. divergens and L. mesenteroides). Inoculated slices were vacuum packaged and stored at 4oC and 7°C. Samples were incubated 28 days (LAB) or 12 weeks (L. monocytogenes) Microbial analysis: Microbial populations were enumerated in rinsate obtained after adding 100ml of sterile Butterfield’s phosphate buffer to each package and massaging the contents externally by hand. L. monocytogenes populations were determined on triplicate samples by surface plating on Modified Oxford agar whereas LAB plate counts were determined on triplicate samples by surface plating on All Purpose Tween agar with 0.4% bromocresol purple. Proximate analysis: Triplicate non-inoculated ground samples were analyzed for the moisture content, pH, aw, salt, and residual nitrite. Results—The results confirmed the no growth of Listeria on cured ham with 0.5% Provian K stored at 4°C and 7°C for 12 weeks, whereas the no-antimicrobial control showed a 1-log increase within two weeks. 0.5% Provian DV demonstrated similar efficacy towards Listeria inhibition at 4°C while 0.65% Provian DV was required to match the Listeria control at 7°C. 0.75% Provian K and 1% Provian DV were needed to show inhibition of the LAB for 4 weeks at both temperatures. Conclusions—This research demonstrated that it is possible to increase safety and shelf life of cured ready-to-eat ham using preservatives that meet current food trends, like sodium reduction and natural origin.Keywords: food safety, natural preservation, listeria control, shelf life extension
Procedia PDF Downloads 1246 In-Process Integration of Resistance-Based, Fiber Sensors during the Braiding Process for Strain Monitoring of Carbon Fiber Reinforced Composite Materials
Authors: Oscar Bareiro, Johannes Sackmann, Thomas Gries
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Carbon fiber reinforced polymer composites (CFRP) are used in a wide variety of applications due to its advantageous properties and design versatility. The braiding process enables the manufacture of components with good toughness and fatigue strength. However, failure mechanisms of CFRPs are complex and still present challenges associated with their maintenance and repair. Within the broad scope of structural health monitoring (SHM), strain monitoring can be applied to composite materials to improve reliability, reduce maintenance costs and safely exhaust service life. Traditional SHM systems employ e.g. fiber optics, piezoelectrics as sensors, which are often expensive, time consuming and complicated to implement. A cost-efficient alternative can be the exploitation of the conductive properties of fiber-based sensors such as carbon, copper, or constantan - a copper-nickel alloy – that can be utilized as sensors within composite structures to achieve strain monitoring. This allows the structure to provide feedback via electrical signals to a user which are essential for evaluating the structural condition of the structure. This work presents a strategy for the in-process integration of resistance-based sensors (Elektrisola Feindraht AG, CuNi23Mn, Ø = 0.05 mm) into textile preforms during its manufacture via the braiding process (Herzog RF-64/120) to achieve strain monitoring of braided composites. For this, flat samples of instrumented composite laminates of carbon fibers (Toho Tenax HTS40 F13 24K, 1600 tex) and epoxy resin (Epikote RIMR 426) were manufactured via vacuum-assisted resin infusion. These flat samples were later cut out into test specimens and the integrated sensors were wired to the measurement equipment (National Instruments, VB-8012) for data acquisition during the execution of mechanical tests. Quasi-static tests were performed (tensile, 3-point bending tests) following standard protocols (DIN EN ISO 527-1 & 4, DIN EN ISO 14132); additionally, dynamic tensile tests were executed. These tests were executed to assess the sensor response under different loading conditions and to evaluate the influence of the sensor presence on the mechanical properties of the material. Several orientations of the sensor with regards to the applied loading and sensor placements inside the laminate were tested. Strain measurements from the integrated sensors were made by programming a data acquisition code (LabView) written for the measurement equipment. Strain measurements from the integrated sensors were then correlated to the strain/stress state for the tested samples. From the assessment of the sensor integration approach it can be concluded that it allows for a seamless sensor integration into the textile preform. No damage to the sensor or negative effect on its electrical properties was detected during inspection after integration. From the assessment of the mechanical tests of instrumented samples it can be concluded that the presence of the sensors does not alter significantly the mechanical properties of the material. It was found that there is a good correlation between resistance measurements from the integrated sensors and the applied strain. It can be concluded that the correlation is of sufficient accuracy to determinate the strain state of a composite laminate based solely on the resistance measurements from the integrated sensors.Keywords: braiding process, in-process sensor integration, instrumented composite material, resistance-based sensor, strain monitoring
Procedia PDF Downloads 1005 Thermally Conductive Polymer Nanocomposites Based on Graphene-Related Materials
Authors: Alberto Fina, Samuele Colonna, Maria del Mar Bernal, Orietta Monticelli, Mauro Tortello, Renato Gonnelli, Julio Gomez, Chiara Novara, Guido Saracco
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Thermally conductive polymer nanocomposites are of high interest for several applications including low-temperature heat recovery, heat exchangers in a corrosive environment and heat management in electronics and flexible electronics. In this paper, the preparation of thermally conductive nanocomposites exploiting graphene-related materials is addressed, along with their thermal characterization. In particular, correlations between 1- chemical and physical features of the nanoflakes and 2- processing conditions with the heat conduction properties of nanocomposites is studied. Polymers are heat insulators; therefore, the inclusion of conductive particles is the typical solution to obtain a sufficient thermal conductivity. In addition to traditional microparticles such as graphite and ceramics, several nanoparticles have been proposed, including carbon nanotubes and graphene, for the use in polymer nanocomposites. Indeed, thermal conductivities for both carbon nanotubes and graphenes were reported in the wide range of about 1500 to 6000 W/mK, despite such property may decrease dramatically as a function of the size, number of layers, the density of topological defects, re-hybridization defects as well as on the presence of impurities. Different synthetic techniques have been developed, including mechanical cleavage of graphite, epitaxial growth on SiC, chemical vapor deposition, and liquid phase exfoliation. However, the industrial scale-up of graphene, defined as an individual, single-atom-thick sheet of hexagonally arranged sp2-bonded carbons still remains very challenging. For large scale bulk applications in polymer nanocomposites, some graphene-related materials such as multilayer graphenes (MLG), reduced graphene oxide (rGO) or graphite nanoplatelets (GNP) are currently the most interesting graphene-based materials. In this paper, different types of graphene-related materials were characterized for their chemical/physical as well as for thermal properties of individual flakes. Two selected rGOs were annealed at 1700°C in vacuum for 1 h to reduce defectiveness of the carbon structure. Thermal conductivity increase of individual GNP with annealing was assessed via scanning thermal microscopy. Graphene nano papers were prepared from both conventional RGO and annealed RGO flakes. Characterization of the nanopapers evidenced a five-fold increase in the thermal diffusivity on the nano paper plane for annealed nanoflakes, compared to pristine ones, demonstrating the importance of structural defectiveness reduction to maximize the heat dissipation performance. Both pristine and annealed RGO were used to prepare polymer nanocomposites, by melt reactive extrusion. Thermal conductivity showed two- to three-fold increase in the thermal conductivity of the nanocomposite was observed for high temperature treated RGO compared to untreated RGO, evidencing the importance of using low defectivity nanoflakes. Furthermore, the study of different processing paremeters (time, temperature, shear rate) during the preparation of poly (butylene terephthalate) nanocomposites evidenced a clear correlation with the dispersion and fragmentation of the GNP nanoflakes; which in turn affected the thermal conductivity performance. Thermal conductivity of about 1.7 W/mK, i.e. one order of magnitude higher than for pristine polymer, was obtained with 10%wt of annealed GNPs, which is in line with state of the art nanocomposites prepared by more complex and less upscalable in situ polymerization processes.Keywords: graphene, graphene-related materials, scanning thermal microscopy, thermally conductive polymer nanocomposites
Procedia PDF Downloads 2594 Metal-Organic Frameworks-Based Materials for Volatile Organic Compounds Sensing Applications: Strategies to Improve Sensing Performances
Authors: Claudio Clemente, Valentina Gargiulo, Alessio Occhicone, Giovanni Piero Pepe, Giovanni Ausanio, Michela Alfè
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Volatile organic compound (VOC) emissions represent a serious risk to human health and the integrity of the ecosystems, especially at high concentrations. For this reason, it is very important to continuously monitor environmental quality and develop fast and reliable portable sensors to allow analysis on site. Chemiresistors have become promising candidates for VOC sensing as their ease of fabrication, variety of suitable sensitive materials, and simple sensing data. A chemoresistive gas sensor is a transducer that allows to measure the concentration of an analyte in the gas phase because the changes in resistance are proportional to the amount of the analyte present. The selection of the sensitive material, which interacts with the target analyte, is very important for the sensor performance. The most used VOC detection materials are metal oxides (MOx) for their rapid recovery, high sensitivity to various gas molecules, easy fabrication. Their sensing performance can be improved in terms of operating temperature, selectivity, and detection limit. Metal-organic frameworks (MOFs) have attracted a lot of attention also in the field of gas sensing due to their high porosity, high surface area, tunable morphologies, structural variety. MOFs are generated by the self-assembly of multidentate organic ligands connecting with adjacent multivalent metal nodes via strong coordination interactions, producing stable and highly ordered crystalline porous materials with well-designed structures. However, most MOFs intrinsically exhibit low electrical conductivity. To improve this property, MOFs can be combined with organic and inorganic materials in a hybrid fashion to produce composite materials or can be transformed into more stable structures. MOFs, indeed, can be employed as the precursors of metal oxides with well-designed architectures via the calcination method. The MOF-derived MOx partially preserved the original structure with high surface area and intrinsic open pores, which act as trapping centers for gas molecules, and showed a higher electrical conductivity. Core-shell heterostructures, in which the surface of a metal oxide core is completely coated by a MOF shell, forming a junction at the core-shell heterointerface, can also be synthesized. Also, nanocomposite in which MOF structures are intercalated with graphene related materials can also be produced, and the conductivity increases thanks to the high mobility of electrons of carbon materials. As MOF structures, zinc-based MOFs belonging to the ZIF family were selected in this work. Several Zn-based materials based and/or derived from MOFs were produced, structurally characterized, and arranged in a chemo resistive architecture, also exploring the potentiality of different approaches of sensing layer deposition based on PLD (pulsed laser deposition) and, in case of thermally labile materials, MAPLE (Matrix Assisted Pulsed Laser Evaporation) to enhance the adhesion to the support. The sensors were tested in a controlled humidity chamber, allowing for the possibility of varying the concentration of ethanol, a typical analyte chosen among the VOCs for a first survey. The effect of heating the chemiresistor to improve sensing performances was also explored. Future research will focus on exploring new manufacturing processes for MOF-based gas sensors with the aim to improve sensitivity, selectivity and reduce operating temperatures.Keywords: chemiresistors, gas sensors, graphene related materials, laser deposition, MAPLE, metal-organic frameworks, metal oxides, nanocomposites, sensing performance, transduction mechanism, volatile organic compounds
Procedia PDF Downloads 533 Continuity Through Best Practice. A Case Series of Complex Wounds Manage by Dedicated Orthopedic Nursing Team
Authors: Siti Rahayu, Khairulniza Mohd Puat, Kesavan R., Mohammad Harris A., Jalila, Kunalan G., Fazir Mohamad
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The greatest challenge has been in establishing and maintaining the dedicated nursing team. Continuity is served when nurses are assigned exclusively for managing wound, where they can continue to build expertise and skills. In addition, there is a growing incidence of chronic wounds and recognition of the complexity involved in caring for these patients. We would like to share 4 cases with different techniques of wound management. 1st case, 39 years old gentleman with underlying rheumatoid arthritis with chronic periprosthetic joint infection of right total knee replacement presented with persistent drainage over right knee. Patient was consulted for two stage revision total knee replacement. However, patient only agreed for debridement and retention of implant. After debridement, large medial and lateral wound was treated with Instillation Negative Pressure Wound Therapy Dressings. After several cycle, the wound size reduced, and conventional dressing was applied. 2nd case, 58 years old gentleman with underlying diabetes presented with right foot necrotizing fasciitis with gangrene of 5th toe. He underwent extensive debridement of foot with rays’ amputation of 5th toe. Post debridement patient was started on Instillation Negative Pressure Wound Therapy Dressings. After several cycle of VAC, the wound bed was prepared, and he underwent split skin graft over right foot. 3 rd case, 60 years old gentleman with underlying diabetes mellitus presented with right foot necrotizing soft tissue infection. He underwent rays’ amputation and extensive wound debridement. Upon stabilization of general condition, patient was discharge with regular wound dressing by same nurse and doctor during each visit to clinic follow up. After 6 months of follow up, the wound healed well. 4th case, 38-year-old gentleman had alleged motor vehicle accident and sustained closed fracture right tibial plateau. Open reduction and proximal tibial locking plate were done. At 2 weeks post-surgery, the patient presented with warm, erythematous leg and pus discharge from the surgical site. Empirical antibiotic was started, and wound debridement was done. Intraoperatively, 50cc pus was evacuated, unhealthy muscle and tissue debrided. No loosening of the implant. Patient underwent multiple wound debridement. At 2 weeks post debridement wound healed well, but the proximal aspect was unable to close immediately. This left the proximal part of the implant to be exposed. Patient was then put on VAC dressing for 3 weeks until healthy granulation tissue closes the implant. Meanwhile, antibiotic was change according to culture and sensitivity. At 6 weeks post the first debridement, the wound was completely close, and patient was discharge home well. At 3 months post operatively, patient wound and fracture healed uneventfully and able to ambulate independently. Complex wounds are too serious to be dealt with. Team managing complex wound need continuous support through the provision of educational tools to support their professional development, engagement with local and international expert, as well as highquality products that increase efficiencies in servicesKeywords: VAC (Vacuum Assisted Closure), empirical- initial antibiotics, NPWT- negative pressure wound therapy, NF- necrotizing fasciitis, gangrene- blackish discoloration due to poor blood supply
Procedia PDF Downloads 1002 Highly Robust Crosslinked BIAN-based Binder to Stabilize High-Performance Silicon Anode in Lithium-Ion Secondary Battery
Authors: Agman Gupta, Rajashekar Badam, Noriyoshi Matsumi
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Introduction: Recently, silicon has been recognized as one of the potential alternatives as anode active material in Li-ion batteries (LIBs) to replace the conventionally used graphite anodes. Silicon is abundantly present in the nature, it can alloy with lithium metal, and has a higher theoretical capacity (~4200 mAhg-1) that is approximately 10 times higher than graphite. However, because of a large volume expansion (~400%) upon repeated de-/alloying, the pulverization of Si particles causes the exfoliation of electrode laminate leading to the loss of electrical contact and adversely affecting the formation of solid-electrolyte interface (SEI).1 Functional polymers as binders have emerged as a competitive strategy to mitigate these drawbacks and failure mechanism of silicon anodes.1 A variety of aqueous/non-aqueous polymer binders like sodium carboxy-methyl cellulose (CMC-Na), styrene butadiene rubber (SBR), poly(acrylic acid), and other variants like mussel inspired binders have been investigated to overcome these drawbacks.1 However, there are only a few reports that mention the attempt of addressing all the drawbacks associated with silicon anodes effectively using a single novel functional polymer system as a binder. In this regard, here, we report a novel highly robust n-type bisiminoacenaphthenequinone (BIAN)-paraphenylene-based crosslinked polymer as a binder for Si anodes in lithium-ion batteries (Fig. 1). On its application, crosslinked-BIAN binder was evaluated to provide mechanical robustness to the large volume expansion of Si particles, maintain electrical conductivity within the electrode laminate, and facilitate in the formation of a thin SEI by restricting the extent of electrolyte decomposition on the surface of anode. The fabricated anodic half-cells were evaluated electrochemically for their rate capability, cyclability, and discharge capacity. Experimental: The polymerized BIAN (P-BIAN) copolymer was synthesized as per the procedure reported by our group.2 The synthesis of crosslinked P-BIAN: a solution of P-BIAN copolymer (1.497 g, 10 mmol) in N-methylpyrrolidone (NMP) (150 ml) was set-up to stir under reflux in nitrogen atmosphere. To this, 1,6-dibromohexane (5 mmol, 0.77 ml) was added dropwise. The resultant reaction mixture was stirred and refluxed at 150 °C for 24 hours followed by refrigeration for 3 hours at 5 °C. The product was obtained by evaporating the NMP solvent under reduced pressure and drying under vacuum at 120 °C for 12 hours. The obtained product was a black colored sticky compound. It was characterized by 1H-NMR, XPS, and FT-IR techniques. Results and Discussion: The N 1s XPS spectrum of the crosslinked BIAN polymer showed two characteristic peaks corresponding to the sp2 hybridized nitrogen (-C=N-) at 399.6 eV of the diimine backbone in the BP and quaternary nitrogen at 400.7 eV corresponding to the crosslinking of BP via dibromohexane. The DFT evaluation of the crosslinked BIAN binder showed that it has a low lying lowest unoccupied molecular orbital (LUMO) that enables it to get doped in the reducing environment and influence the formation of a thin (SEI). Therefore, due to the mechanically robust crosslinked matrices as well as its influence on the formation of a thin SEI, the crosslinked BIAN binder stabilized the Si anode-based half-cell for over 1000 cycles with a reversible capacity of ~2500 mAhg-1 and ~99% capacity retention as shown in Fig. 2. The dynamic electrochemical impedance spectroscopy (DEIS) characterization of crosslinked BIAN-based anodic half-cell confirmed that the SEI formed was thin in comparison with the conventional binder-based anodes. Acknowledgement: We are thankful to the financial support provided by JST-Mirai Program, Grant Number: JP18077239Keywords: self-healing binder, n-type binder, thin solid-electrolyte interphase (SEI), high-capacity silicon anodes, low-LUMO
Procedia PDF Downloads 1591 Regenerative Agriculture Standing at the Intersection of Design, Mycology, and Soil Fertility
Authors: Andrew Gennett
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Designing for fungal development means embracing the symbiotic relationship between the living system and built environment. The potential of mycelium post-colonization is explored for the fabrication of advanced pure mycelium products, going beyond the conventional methods of aggregating materials. Fruiting induction imparts desired material properties such as enhanced environmental resistance. Production approach allows for simultaneous generation of multiple products while scaling up raw materials supply suitable for architectural applications. The following work explores the integration of fungal environmental perception with computational design of built fruiting chambers. Polyporales, are classified by their porous reproductive tissues supported by a wood-like context tissue covered by a hard waterproofing coat of hydrobpobins. Persisting for years in the wild, these species represent material properties that would be highly desired in moving beyond flat sheets of arial mycelium as with leather or bacon applications. Understanding the inherent environmental perception of fungi has become the basis for working with and inducing desired hyphal differentiation. Working within the native signal interpretation of a mycelium mass during fruiting induction provides the means to apply textures and color to the final finishing coat. A delicate interplay between meeting human-centered goals while designing around natural processes of living systems represents a blend of art and science. Architecturally, physical simulations inform model design for simple modular fruiting chambers that change as fungal growth progresses, while biological life science principles describe the internal computations occurring within the fungal hyphae. First, a form filling phase of growth is controlled by growth chamber environment. Second, an initiation phase of growth forms the final exterior finishing texture. Hyphal densification induces cellular cascades, in turn producing the classical hardened cuticle, UV protective molecule production, as well, as waterproofing finish. Upon fruiting process completion, the fully colonized spent substrate holds considerable value and is not considered waste. Instead, it becomes a valuable resource in the next cycle of production scale-up. However, the acquisition of new substrate resources poses a critical question, particularly as these resources become increasingly scarce. Pursuing a regenerative design paradigm from the environmental perspective, the usage of “agricultural waste” for architectural materials would prove a continuation of the destructive practices established by the previous industrial regime. For these residues from fields and forests serve a vital ecological role protecting the soil surface in combating erosion while reducing evaporation and fostering a biologically diverse food web. Instead, urban centers have been identified as abundant sources of new substrate material. Diverting the waste from secondary locations such as food processing centers, papers mills, and recycling facilities not only reduces landfill burden but leverages the latent value of these waste steams as precious resources for mycelium cultivation. In conclusion, working with living systems through innovative built environments for fungal development, provides the needed gain of function and resilience of mycelium products. The next generation of sustainable fungal products will go beyond the current binding process, with a focus upon reducing landfill burden from urban centers. In final considerations, biophilic material builds to an ecologically regenerative recycling production cycle.Keywords: regenerative agriculture, mycelium fabrication, growth chamber design, sustainable resource acquisition, fungal morphogenesis, soil fertility
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