Search results for: spin glass
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1242

Search results for: spin glass

192 Influence of Thermal Damage on the Mechanical Strength of Trimmed CFRP

Authors: Guillaume Mullier, Jean François Chatelain

Abstract:

Carbon Fiber Reinforced Plastics (CFRPs) are widely used for advanced applications, in particular in aerospace, automotive and wind energy industries. Once cured to near net shape, CFRP parts need several finishing operations such as trimming, milling or drilling in order to accommodate fastening hardware and meeting the final dimensions. The present research aims to study the effect of the cutting temperature in trimming on the mechanical strength of high performance CFRP laminates used for aeronautics applications. The cutting temperature is of great importance when dealing with trimming of CFRP. Temperatures higher than the glass-transition temperature (Tg) of the resin matrix are highly undesirable: they cause degradation of the matrix in the trimmed edges area, which can severely affect the mechanical performance of the entire component. In this study, a 9.50 mm diameter CVD diamond coated carbide tool with six flutes was used to trim 24-plies CFRP laminates. A 300 m/min cutting speed and 1140 mm/min feed rate were used in the experiments. The tool was heated prior to trimming using a blowtorch, for temperatures ranging from 20°C to 300°C. The temperature at the cutting edge was measured using embedded K-Type thermocouples. Samples trimmed for different cutting temperatures, below and above Tg, were mechanically tested using three-points bending short-beam loading configurations. New cutting tools as well as worn cutting tools were utilized for the experiments. The experiments with the new tools could not prove any correlation between the length of cut, the cutting temperature and the mechanical performance. Thus mechanical strength was constant, regardless of the cutting temperature. However, for worn tools, producing a cutting temperature rising up to 450°C, thermal damage of the resin was observed. The mechanical tests showed a reduced mean resistance in short beam configuration, while the resistance in three point bending decreases with increase of the cutting temperature.

Keywords: composites, trimming, thermal damage, surface quality

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191 Removal of Rhodamine B from Aqueous Solution Using Natural Clay by Fixed Bed Column Method

Authors: A. Ghribi, M. Bagane

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The discharge of dye in industrial effluents is of great concern because their presence and accumulation have a toxic or carcinogenic effect on living species. The removal of such compounds at such low levels is a difficult problem. The adsorption process is an effective and attractive proposition for the treatment of dye contaminated wastewater. Activated carbon adsorption in fixed beds is a very common technology in the treatment of water and especially in processes of decolouration. However, it is expensive and the powdered one is difficult to be separated from aquatic system when it becomes exhausted or the effluent reaches the maximum allowable discharge level. The regeneration of exhausted activated carbon by chemical and thermal procedure is also expensive and results in loss of the sorbent. The focus of this research was to evaluate the adsorption potential of the raw clay in removing rhodamine B from aqueous solutions using a laboratory fixed-bed column. The continuous sorption process was conducted in this study in order to simulate industrial conditions. The effect of process parameters, such as inlet flow rate, adsorbent bed height, and initial adsorbate concentration on the shape of breakthrough curves was investigated. A glass column with an internal diameter of 1.5 cm and height of 30 cm was used as a fixed-bed column. The pH of feed solution was set at 8.5. Experiments were carried out at different bed heights (5 - 20 cm), influent flow rates (1.6- 8 mL/min) and influent rhodamine B concentrations (20 - 80 mg/L). The obtained results showed that the adsorption capacity increases with the bed depth and the initial concentration and it decreases at higher flow rate. The column regeneration was possible for four adsorption–desorption cycles. The clay column study states the value of the excellent adsorption capacity for the removal of rhodamine B from aqueous solution. Uptake of rhodamine B through a fixed-bed column was dependent on the bed depth, influent rhodamine B concentration, and flow rate.

Keywords: adsorption, breakthrough curve, clay, fixed bed column, rhodamine b, regeneration

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190 In Vivo Response of Scaffolds of Bioactive Glass-Ceramic

Authors: Ana Claudia Muniz Rennó, Karina Nogueira

Abstract:

This study aimed to investigate the in vivo tissue response of the introduction of the bioactive mesh (BM) scaffolds using a model of tibial bone defect implants in rats. Although a previous in vivo study demonstrated a highly positive response of particulate bioactive materials in the morphological and biomechanical properties of the bone callus, the effects of material with superior bioactivity, present in form of meshes have not been studied yet. Eighty male Wistar rats with 3 mm tibial defects were used. Animals were divided into four groups: intact group (IG) – tibia without any injury; bone defect day zero (0dD) – bone defects, sacrificed immediately after injury; bone defect control group (CG) – bone defects without any filler and bone defect filled with BM scaffold. The animals of BM and CG groups were sacrificed 15, 30 and 45 days post-injury to compare the temporal-special effects of the scaffolds on bone healing. The histological analysis revealed an organized newly formed bone at 30 and 45 days post-surgery in the BM. Also, this group presented an increased COX-2 expression on days 15 and 30 post-surgery. Furthermore, the immunohistochemistry analysis revealed that, BM presented a positive immunoexpression of RUNX-2 during all periods evaluated. The biomechanical analysis revealed that at 15 day after surgery, no significant statistically difference was observed between BM and CG and both groups had significantly higher values of maximal load compared to 0dG and significantly lower values than IG. On days 30 and 45 post-surgery, BM presented statistically lower values of maximal load compared to the CG. Nevertheless, at the same periods, BM did not show statistically significant difference compared to the IG maximal load values (p > 0, 05). Our results revealed that the implantation of the BM scaffolds was effective in stimulating newly bone formation.

Keywords: bone, biomaterials, scaffolds, cartilage

Procedia PDF Downloads 315
189 Effect of Hybrid Fibers on Mechanical Properties in Autoclaved Aerated Concrete

Authors: B. Vijay Antony Raj, Umarani Gunasekaran, R. Thiru Kumara Raja Vallaban

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Fibrous autoclaved aerated concrete (FAAC) is concrete containing fibrous material in it which helps to increase its structural integrity when compared to that of convention autoclaved aerated concrete (CAAC). These short discrete fibers are uniformly distributed and randomly oriented, which enhances the bond strength within the aerated concrete matrix. Conventional red-clay bricks create larger impact to the environment due to red soil depletion and it also consumes large amount to time for construction. Whereas, AAC are larger in size, lighter in weight and it is environmentally friendly in nature and hence it is a viable replacement for red-clay bricks. Internal micro cracks and corner cracks are the only disadvantages of conventional autoclaved aerated concrete, to resolve this particular issue it is preferable to make use of fibers in it.These fibers are bonded together within the matrix and they induce the aerated concrete to withstand considerable stresses, especially during the post cracking stage. Hence, FAAC has the capability of enhancing the mechanical properties and energy absorption capacity of CAAC. In this research work, individual fibers like glass, nylon, polyester and polypropylene are used they generally reduce the brittle fracture of AAC.To study the fibre’s surface topography and composition, SEM analysis is performed and then to determine the composition of a specimen as a whole as well as the composition of individual components EDAX mapping is carried out and then an experimental approach was performed to determine the effect of hybrid (multiple) fibres at various dosage (0.5%, 1%, 1.5%) and curing temperature of 180-2000 C is maintained to determine the mechanical properties of autoclaved aerated concrete. As an analytical part, the outcome experimental results is compared with fuzzy logic using MATLAB.

Keywords: fiberous AAC, crack control, energy absorption, mechanical properies, SEM, EDAX, MATLAB

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188 Research and Application of Multi-Scale Three Dimensional Plant Modeling

Authors: Weiliang Wen, Xinyu Guo, Ying Zhang, Jianjun Du, Boxiang Xiao

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Reconstructing and analyzing three-dimensional (3D) models from situ measured data is important for a number of researches and applications in plant science, including plant phenotyping, functional-structural plant modeling (FSPM), plant germplasm resources protection, agricultural technology popularization. It has many scales like cell, tissue, organ, plant and canopy from micro to macroscopic. The techniques currently used for data capture, feature analysis, and 3D reconstruction are quite different of different scales. In this context, morphological data acquisition, 3D analysis and modeling of plants on different scales are introduced systematically. The commonly used data capture equipment for these multiscale is introduced. Then hot issues and difficulties of different scales are described respectively. Some examples are also given, such as Micron-scale phenotyping quantification and 3D microstructure reconstruction of vascular bundles within maize stalks based on micro-CT scanning, 3D reconstruction of leaf surfaces and feature extraction from point cloud acquired by using 3D handheld scanner, plant modeling by combining parameter driven 3D organ templates. Several application examples by using the 3D models and analysis results of plants are also introduced. A 3D maize canopy was constructed, and light distribution was simulated within the canopy, which was used for the designation of ideal plant type. A grape tree model was constructed from 3D digital and point cloud data, which was used for the production of science content of 11th international conference on grapevine breeding and genetics. By using the tissue models of plants, a Google glass was used to look around visually inside the plant to understand the internal structure of plants. With the development of information technology, 3D data acquisition, and data processing techniques will play a greater role in plant science.

Keywords: plant, three dimensional modeling, multi-scale, plant phenotyping, three dimensional data acquisition

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187 Fabrication of Glucose/O₂ Microfluidic Biofuel Cell with Double Layer of Electrodes

Authors: Haroon Khan, Chul Min Kim, Sung Yeol Kim, Sanket Goel, Prabhat K. Dwivedi, Ashutosh Sharma, Gyu Man Kim

Abstract:

Enzymatic biofuel cells (EBFCs) have drawn the attention of researchers due to its demanding application in medical implants. In EBFCs, electricity is produced with the help of redox enzymes. In this study, we report the fabrication of membraneless EBFC with new design of electrodes to overcome microchannel related limitations. The device consists of double layer of electrodes on both sides of Y-shaped microchannel to reduce the effect of oxygen depletion layer and diffusion of fuel and oxidant at the end of microchannel. Moreover, the length of microchannel was reduced by half keeping the same area of multiwalled carbon nanotubes (MWCNT) electrodes. Polydimethylsiloxane (PDMS) stencils were used to pattern MWCNT electrodes on etched Indium Tin Oxide (ITO) glass. PDMS casting was used to fabricate microchannel of the device. Both anode and cathode were modified with glucose oxidase and laccase. Furthermore, these enzymes were covalently bound to carboxyl MWCNTs with the help of EDC/NHS. Glucose used as fuel was oxidized by glucose oxidase at anode while oxygen was reduced to water at the cathode side. The resulted devices were investigated with the help of polarization curves obtained from Chronopotentiometry technique by using potentiostat. From results, we conclude that the performance of double layer EBFC is improved 15 % as compared to single layer EBFC delivering maximum power density of 71.25 µW cm-2 at a cell potential of 0.3 V and current density of 250 µA cm-2 at micro channel height of 450-µm and flow rate of 25 ml hr-1. However, the new device was stable only for three days after which its power output was rapidly dropped by 75 %. This work demonstrates that the power output of membraneless EBFC is improved comparatively, but still efforts will be needed to make the device stable over long period of time.

Keywords: EBFC, glucose, MWCNT, microfluidic

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186 Three-Dimensional Computer Graphical Demonstration of Calcified Tissue and Its Clinical Significance

Authors: Itsuo Yokoyama, Rikako Kikuti, Miti Sekikawa, Tosinori Asai, Sarai Tsuyoshi

Abstract:

Introduction: Vascular access for hemodialysis therapy is often difficult, even for experienced medical personnel. Ultrasound guided needle placement have been performed occasionally but is not always helpful in certain cases with complicated vascular anatomy. Obtaining precise anatomical knowledge of the vascular structure is important to prevent access-related complications. With augmented reality (AR) device such as AR glasses, the virtual vascular structure is shown superimposed on the actual patient vessels, thus enabling the operator to maneuver catheter placement easily with free both hands. We herein report our method of AR guided vascular access method in dialysis treatment Methods: Three dimensional (3D) object of the arm with arteriovenous fistula is computer graphically created with 3D software from the data obtained by computer tomography, ultrasound echogram, and image scanner. The 3D vascular object thus created is viewed on the screen of the AR digital display device (such as AR glass or iPad). The picture of the vascular anatomical structure becomes visible, which is superimposed over the real patient’s arm, thereby the needle insertion be performed under the guidance of AR visualization with ease. By this method, technical difficulty in catheter placement for dialysis can be lessened and performed safely. Considerations: Virtual reality technology has been applied in various fields and medical use is not an exception. Yet AR devices have not been widely used among medical professions. Visualization of the virtual vascular object can be achieved by creation of accurate three dimensional object with the help of computer graphical technique. Although our experience is limited, this method is applicable with relative easiness and our accumulating evidence has suggested that our method of vascular access with the use of AR can be promising.

Keywords: abdominal-aorta, calcification, extraskeletal, dialysis, computer graphics, 3DCG, CT, calcium, phosphorus

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185 Crystalline Particles Dispersed Cu-Based Metallic Glassy Composites Fabricated by Spark Plasma Sintering

Authors: Sandrine Cardinal, Jean-Marc Pelletier, Guang Xie, Florian Mercier, Florent Delmas

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Bulk metallic glasses exhibit several superior properties, compared to their corresponding crystalline counterpart, such as high strength, high elastic limit or good corrosion resistance. Therefore they can be considered as good candidates for structural applications in many sectors. However, they are generally brittle and do not exhibit plastic deformation at room temperature. These materials are mainly obtained by rapid cooling from a liquid state to prevent crystallization, which limits their size. To overcome these two drawbacks: fragility and limited dimensions, composite metallic glass matrix reinforced by a second phase whose role is to slow crack growth are developed. Concerning the limited size of the pieces, the proposed solution is to get the material from amorphous powders by densifying under load. In this study, Cu50Zr45Al5 bulk metallic glassy matrix composites (MGMCs) containing different volume fraction (Vf) of Zr crystalline particles were manufactured by spark plasma sintering (SPS). Microstructure, thermal stability and mechanical properties of the MGMCs were investigated. Matrix of the composites remains a fully amorphous phase after consolidation at 420°C under 600 MPa. A good dispersion of the particles in the glassy matrix is obtained. Results show that the compressive strength decreases with Vf : 1670 MPa (Vf=0%) to 1300MPa (Vf=30%), the elastic modulus decreases but only slighty respectively 97.3GPa and 94.5 GPa and plasticity is improved from 0 to 4%. Fractographic investigation indicates a good bonding between amorphous and crystalline particles. In conclusion, present study has demonstrated that SPS method is useful for the synthesis of the bulk glassy composites. Large controlled microstructure specimens with interesting ductility can be obtained compared with others methods.

Keywords: composite, mechanical properties, metallic glasses, spark plasma sintering

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184 Mode II Fracture Toughness of Hybrid Fiber Reinforced Concrete

Authors: H. S. S Abou El-Mal, A. S. Sherbini, H. E. M. Sallam

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Mode II fracture toughness (KIIc) of fiber reinforced concrete has been widely investigated under various patterns of testing geometries. The effect of fiber type, concrete matrix properties, and testing mechanisms were extensively studied. The area of hybrid fiber addition shows a lake of reported research data. In this paper an experimental investigation of hybrid fiber embedded in high strength concrete matrix is reported. Three different types of fibers; namely steel (S), glass (G), and polypropylene (PP) fibers were mixed together in four hybridization patterns, (S/G), (S/PP), (G/PP), (S/G/PP) with constant cumulative volume fraction (Vf) of 1.5%. The concrete matrix properties were kept the same for all hybrid fiber reinforced concrete patterns. In an attempt to estimate a fairly accepted value of fracture toughness KIIc, four testing geometries and loading types are employed in this investigation. Four point shear, Brazilian notched disc, double notched cube, and double edge notched specimens are investigated in a trial to avoid the limitations and sensitivity of each test regarding geometry, size effect, constraint condition, and the crack length to specimen width ratio a/w. The addition of all hybridization patterns of fiber reduced the compressive strength and increased mode II fracture toughness in pure mode II tests. Mode II fracture toughness of concrete KIIc decreased with the increment of a/w ratio for all concretes and test geometries. Mode II fracture toughness KIIc is found to be sensitive to the hybridization patterns of fiber. The (S/PP) hybridization pattern showed higher values than all other patterns, while the (S/G/PP) showed insignificant enhancement on mode II fracture toughness (KIIc). Four point shear (4PS) test set up reflects the most reliable values of mode II fracture toughness KIIc of concrete. Mode II fracture toughness KIIc of concrete couldn’t be assumed as a real material property.

Keywords: fiber reinforced concrete, Hybrid fiber, Mode II fracture toughness, testing geometry

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183 AFM Probe Sensor Designed for Cellular Membrane Components

Authors: Sarmiza Stanca, Wolfgang Fritzsche, Christoph Krafft, Jürgen Popp

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Independent of the cell type a thin layer of a few nanometers thickness surrounds the cell interior as the cellular membrane. The transport of ions and molecules through the membrane is achieved in a very precise way by pores. Understanding the process of opening and closing the pores due to an electrochemical gradient across the membrane requires knowledge of the pore constitutive proteins. Recent reports prove the access to the molecular level of the cellular membrane by atomic force microscopy (AFM). This technique also permits an electrochemical study in the immediate vicinity of the tip. Specific molecules can be electrochemically localized in the natural cellular membrane. Our work aims to recognize the protein domains of the pores using an AFM probe as a miniaturized amperometric sensor, and to follow the protein behavior while changing the applied potential. The intensity of the current produced between the surface and the AFM probe is amplified and detected simultaneously with the surface imaging. The AFM probe plays the role of the working electrode and the substrate, a conductive glass on which the cells are grown, represent the counter electrode. For a better control of the electric potential on the probe, a third electrode Ag/AgCl wire is mounted in the circuit as a reference electrode. The working potential is applied between the electrodes with a programmable source and the current intensity in the circuit is recorded with a multimeter. The applied potential considers the overpotential at the electrode surface and the potential drop due to the current flow through the system. The reported method permits a high resolved electrochemical study of the protein domains on the living cell membrane. The amperometric map identifies areas of different current intensities on the pore depending on the applied potential. The reproducibility of this method is limited by the tip shape, the uncontrollable capacitance, which occurs at the apex and a potential local charge separation.

Keywords: AFM, sensor, membrane, pores, proteins

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182 Design of Nanoreinforced Polyacrylamide-Based Hybrid Hydrogels for Bone Tissue Engineering

Authors: Anuj Kumar, Kummara M. Rao, Sung S. Han

Abstract:

Bone tissue engineering has emerged as a potentially alternative method for localized bone defects or diseases, congenital deformation, and surgical reconstruction. The designing and the fabrication of the ideal scaffold is a great challenge, in restoring of the damaged bone tissues via cell attachment, proliferation, and differentiation under three-dimensional (3D) biological micro-/nano-environment. In this case, hydrogel system composed of high hydrophilic 3D polymeric-network that is able to mimic some of the functional physical and chemical properties of the extracellular matrix (ECM) and possibly may provide a suitable 3D micro-/nano-environment (i.e., resemblance of native bone tissues). Thus, this proposed hydrogel system is highly permeable and facilitates the transport of the nutrients and metabolites. However, the use of hydrogels in bone tissue engineering is limited because of their low mechanical properties (toughness and stiffness) that continue to posing challenges in designing and fabrication of tough and stiff hydrogels along with improved bioactive properties. For this purpose, in our lab, polyacrylamide-based hybrid hydrogels were synthesized by involving sodium alginate, cellulose nanocrystals and silica-based glass using one-step free-radical polymerization. The results showed good in vitro apatite-forming ability (biomineralization) and improved mechanical properties (under compression in the form of strength and stiffness in both wet and dry conditions), and in vitro osteoblastic (MC3T3-E1 cells) cytocompatibility. For in vitro cytocompatibility assessment, both qualitative (attachment and spreading of cells using FESEM) and quantitative (cell viability and proliferation using MTT assay) analyses were performed. The obtained hybrid hydrogels may potentially be used in bone tissue engineering applications after establishment of in vivo characterization.

Keywords: bone tissue engineering, cellulose nanocrystals, hydrogels, polyacrylamide, sodium alginate

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181 A Robust Stretchable Bio Micro-Electromechanical Systems Technology for High-Strain in vitro Cellular Studies

Authors: Tiffany Baetens, Sophie Halliez, Luc Buée, Emiliano Pallecchi, Vincent Thomy, Steve Arscott

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We demonstrate here a viable stretchable bio-microelectromechanical systems (BioMEMS) technology for use with biological studies concerned with the effect of high mechanical strains on living cells. An example of this is traumatic brain injury (TBI) where neurons are damaged with physical force to the brain during, e.g., accidents and sports. Robust, miniaturized integrated systems are needed by biologists to be able to study the effect of TBI on neuron cells in vitro. The major challenges in this area are (i) to develop micro, and nanofabrication processes which are based on stretchable substrates and to (ii) create systems which are robust and performant at very high mechanical strain values—sometimes as high as 100%. At the time of writing, such processes and systems were rapidly evolving subject of research and development. The BioMEMS which we present here is composed of an elastomer substrate (low Young’s modulus ~1 MPa) onto which is patterned robust electrodes and insulators. The patterning of the thin films is achieved using standard photolithography techniques directly on the elastomer substrate—thus making the process generic and applicable to many materials’ in based systems. The chosen elastomer used is commercial ‘Sylgard 184’ polydimethylsiloxane (PDMS). It is spin-coated onto a silicon wafer. Multistep ultra-violet based photolithography involving commercial photoresists are then used to pattern robust thin film metallic electrodes (chromium/gold) and insulating layers (parylene) on the top of the PDMS substrate. The thin film metals are deposited using thermal evaporation and shaped using lift-off techniques The BioMEMS has been characterized mechanically using an in-house strain-applicator tool. The system is composed of 12 electrodes with one reference electrode transversally-orientated to the uniaxial longitudinal straining of the system. The electrical resistance of the electrodes is observed to remain very stable with applied strain—with a resistivity approaching that of evaporated gold—up to an interline strain of ~50%. The mechanical characterization revealed some interesting original properties of such stretchable BioMEMS. For example, a Poisson effect induced electrical ‘self-healing’ of cracking was identified. Biocompatibility of the commercial photoresist has been studied and is conclusive. We will present the results of the BioMEMS, which has also characterized living cells with a commercial Multi Electrode Array (MEA) characterization tool (Multi Channel Systems, USA). The BioMEMS enables the cells to be strained up to 50% and then characterized electrically and optically.

Keywords: BioMEMS, elastomer, electrical impedance measurements of living cells, high mechanical strain, microfabrication, stretchable systems, thin films, traumatic brain injury

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180 Carbon, Nitrogen Doped TiO2 Macro/Mesoporous Monoliths with High Visible Light Absorption for Photocatalytic Wastewater Treatment

Authors: Paolo Boscaro, Vasile Hulea, François Fajula, Francis Luck, Anne Galarneau

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TiO2 based monoliths with hierarchical macropores and mesopores have been synthesized following a novel one pot sol-gel synthesis method. Taking advantage of spinodal separation that occurs between titanium isopropoxide and an acidic solution in presence of polyethylene oxide polymer, monoliths with homogeneous interconnected macropres of 3 μm in diameter and mesopores of ca. 6 nm (surface area 150 m2/g) are obtained. Furthermore, these monoliths present some carbon and nitrogen (as shown by XPS and elemental analysis), which considerably reduce titanium oxide energy gap and enable light to be absorbed up to 700 nm wavelength. XRD shows that anatase is the dominant phase with a small amount of brookite. Enhanced light absorption and high porosity of the monoliths are responsible for a remarkable photocatalytic activity. Wastewater treatment has been performed in closed reactor under sunlight using orange G dye as target molecule. Glass reactors guarantee that most of UV radiations (to almost 300 nm) of solar spectrum are excluded. TiO2 nanoparticles P25 (usually used in photocatalysis under UV) and un-doped TiO2 monoliths with similar porosity were used as comparison. C,N-doped TiO2 monolith allowed a complete colorant degradation in less than 1 hour, whereas 10 h are necessary for 40% colorant degradation with P25 and un-doped monolith. Experiment performed in the dark shows that only 3% of molecules have been adsorbed in the C,N-doped TiO2 monolith within 1 hour. The much higher efficiency of C,N-doped TiO2 monolith in comparison to P25 and un-doped monolith, proves that doping TiO2 is an essential issue and that nitrogen and carbon are effective dopants. Monoliths offer multiples advantages in respect to nanometric powders: sample can be easily removed from batch (no needs to filter or to centrifuge). Moreover flow reactions can be set up with cylindrical or flat monoliths by simple sheathing or by locking them with O-rings.

Keywords: C-N doped, sunlight photocatalytic activity, TiO2 monolith, visible absorbance

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179 Study of Electro-Chemical Properties of ZnO Nanowires for Various Application

Authors: Meera A. Albloushi, Adel B. Gougam

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The development in the field of piezoelectrics has led to a renewed interest in ZnO nanowires (NWs) as a promising material in the nanogenerator devices category. It can be used as a power source for self-powered electronic systems with higher density, higher efficiency, longer lifetime, as well as lower cost of fabrication. Highly aligned ZnO nanowires seem to exhibit a higher performance compared with nonaligned ones. The purpose of this study was to develop ZnO nanowires and to investigate their electrical and chemical properties for various applications. They were grown on silicon (100) and glass substrates. We have used a low temperature and non-hazardous method: aqueous chemical growth (ACG). ZnO (non-doped) and AZO (Aluminum doped) seed layers were deposited using RF magnetron sputteringunder Argon pressure of 3 mTorr and deposition power of 180 W, the times of growth were selected to obtain thicknesses in the range of 30 to 125 nm. Some of the films were subsequently annealed. The substrates were immersed tilted in an equimolar solution composed of zinc nitrate and hexamine (HMTA) of 0.02 M and 0.05 M in the temperature range of 80 to 90 ᵒC for 1.5 to 2 hours. The X-ray diffractometer shows strong peaks at 2Ө = 34.2ᵒ of ZnO films which indicates that the films have a preferred c-axis wurtzite hexagonal (002) orientation. The surface morphology of the films is investigated by atomic force microscope (AFM) which proved the uniformity of the film since the roughness is within 5 nm range. The scanning electron microscopes(SEM) (Quanta FEG 250, Quanta 3D FEG, Nova NanoSEM 650) are used to characterize both ZnO film and NWs. SEM images show forest of ZnO NWs grown vertically and have a range of length up to 2000 nm and diameter of 20-300 nm. The SEM images prove that the role of the seed layer is to enhance the vertical alignment of ZnO NWs at the pH solution of 5-6. Also electrical and optical properties of the NWs are carried out using Electrical Force Microscopy (EFM). After growing the ZnO NWs, developing the nano-generator is the second step of this study in order to determine the energy conversion efficiency and the power output.

Keywords: ZnO nanowires(NWs), aqueous chemical growth (ACG), piezoelectric NWs, harvesting enery

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178 Response of Yield and Morphological Characteristic of Rice Cultivars to Heat Stress at Different Growth Stages

Authors: Mohammad Taghi Karbalaei Aghamolki, Mohd Khanif Yusop, Fateh Chand Oad, Hamed Zakikhani, Hawa Zee Jaafar, Sharifh Kharidah, Mohamed Hanafi Musa, Shahram Soltani

Abstract:

The high temperatures during sensitive growth phases are changing rice morphology as well as influencing yield. In the glass house study, the treatments were: growing conditions [normal growing (32oC+2) and heat stress (38oC+2) day time and 22oC+2 night time], growth stages (booting, flowering and ripening) and four cultivars (Hovaze, Hashemi, Fajr, as exotic and MR219 as indigenous). The heat chamber was prepared covered with plastic, and automatic heater was adjusted at 38oC+2 (day) and 22oC+2 (night) for two weeks in every growth stages. Rice morphological and yield under the influence of heat stress during various growth stages showed taller plants in Hashsemi due to its tall character. The total tillers per hill were significantly higher in Fajr receiving heat stress during booting stage. In all growing conditions and growth stages, Hashemi recorded higher panicle exertion and flag leaf length. The flag leaf width in all situations was found higher in Hovaze. The total tillers per hill were more in Fajr, although heat stress was imposed during booting and flowering stages. The indigenous MR219 in all situations of growing conditions, growth stages recorded higher grain yield. However, its grain yield slightly decreased when heat stress was imposed during booting and flowering. Similar results were found in all other exotic cultivars recording to lower grain yield in the heat stress condition during booting and flowering. However, plants had no effect on heat stress during ripening stage.

Keywords: rice, growth, heat, temperature, stress, morphology, yield

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177 Development of Excellent Water-Repellent Coatings for Metallic and Ceramic Surfaces

Authors: Aditya Kumar

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One of the most fascinating properties of various insects and plant surfaces in nature is their water-repellent (superhydrophobicity) capability. The nature offers new insights to learn and replicate the same in designing artificial superhydrophobic structures for a wide range of applications such as micro-fluidics, micro-electronics, textiles, self-cleaning surfaces, anti-corrosion, anti-fingerprint, oil/water separation, etc. In general, artificial superhydrophobic surfaces are synthesized by creating roughness and then treating the surface with low surface energy materials. In this work, various super-hydrophobic coatings on metallic surfaces (aluminum, steel, copper, steel mesh) were synthesized by chemical etching process using different etchants and fatty acid. Also, SiO2 nano/micro-particles embedded polyethylene, polystyrene, and poly(methyl methacrylate) superhydrophobic coatings were synthesized on glass substrates. Also, the effect of process parameters such as etching time, etchant concentration, and particle concentration on wettability was studied. To know the applications of the coatings, surface morphology, contact angle, self-cleaning, corrosion-resistance, and water-repellent characteristics were investigated at various conditions. Furthermore, durabilities of coatings were also studied by performing thermal, ultra-violet, and mechanical stability tests. The surface morphology confirms the creation of rough microstructures by chemical etching or by embedding particles, and the contact angle measurements reveal the superhydrophobic nature. Experimentally it is found that the coatings have excellent self-cleaning, anti-corrosion and water-repellent nature. These coatings also withstand mechanical disturbances such surface bending, adhesive peeling, and abrasion. Coatings are also found to be thermal and ultra-violet stable. Additionally, coatings are also reproducible. Hence aforesaid durable superhydrophobic surfaces have many potential industrial applications.

Keywords: superhydrophobic, water-repellent, anti-corrosion, self-cleaning

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176 Structure Domains Tuning Magnetic Anisotropy and Motivating Novel Electric Behaviors in LaCoO₃ Films

Authors: Dechao Meng, Yongqi Dong, Qiyuan Feng, Zhangzhang Cui, Xiang Hu, Haoliang Huang, Genhao Liang, Huanhua Wang, Hua Zhou, Hawoong Hong, Jinghua Guo, Qingyou Lu, Xiaofang Zhai, Yalin Lu

Abstract:

Great efforts have been taken to reveal the intrinsic origins of emerging ferromagnetism (FM) in strained LaCoO₃ (LCO) films. However, some macro magnetic performances of LCO are still not well understood and even controversial, such as magnetic anisotropy. Determining and understanding magnetic anisotropy might help to find the true causes of FM in turn. Perpendicular magnetic anisotropy (PMA) was the first time to be directly observed in high-quality LCO films with different thickness. The in-plane (IP) and out of plane (OOP) remnant magnetic moment ratio of 30 unit cell (u.c.) films is as large as 20. The easy axis lays in the OOP direction with an IP/OOP coercive field ratio of 10. What's more, the PMA could be simply tuned by changing the thickness. With the thickness increases, the IP/OOP magnetic moment ratio remarkably decrease with magnetic easy axis changing from OOP to IP. Such a huge and tunable PMA performance exhibit strong potentials in fundamental researches or applications. What causes PMA is the first concern. More OOP orbitals occupation may be one of the micro reasons of PMA. A cluster-like magnetic domain pattern was found in 30 u.c. with no obvious color contrasts, similar to that of LaAlO₃/SrTiO₃ films. And the nanosize domains could not be totally switched even at a large OOP magnetic field of 23 T. It indicates strong IP characters or none OOP magnetism of some clusters. The IP magnetic domains might influence the magnetic performance and help to form PMA. Meanwhile some possible nonmagnetic clusters might be the reason why the measured moments of LCO films are smaller than the calculated values 2 μB/Co, one of the biggest confusions in LCO films.What tunes PMA seems much more interesting. Totally different magnetic domain patterns were found in 180 u.c. films with cluster magnetic domains surrounded by < 110 > cross-hatch lines. These lines were regarded as structure domain walls (DWs) determined by 3D reciprocal space mapping (RSM). Two groups of in-plane features with fourfold symmetry were observed near the film diffraction peaks in (002) 3D-RSM. One is along < 110 > directions with a larger intensity, which is well match the lines on the surfaces. The other is much weaker and along < 100 > directions, which is from the normal lattice titling of films deposited on cubic substrates. The < 110 > domain features obtained from (103) and (113) 3D-RSMs exhibit similar evolution of the DWs percentages and magnetic behavior. Structure domains and domain walls are believed to tune PMA performances by transform more IP magnetic moments to OOP. Last but not the least, thick films with lots of structure domains exhibit different electrical transport behaviors. A metal-to-insulator transition (MIT) and an angular dependent negative magnetic resistivity were observed near 150 K, higher than FM transition temperature but similar to that of spin-orbital coupling related 1/4 order diffraction peaks.

Keywords: structure domain, magnetic anisotropy, magnetic domain, domain wall, 3D-RSM, strain

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175 Monitoring the Effect of Doxorubicin Liposomal in VX2 Tumor Using Magnetic Resonance Imaging

Authors: Ren-Jy Ben, Jo-Chi Jao, Chiu-Ya Liao, Ya-Ru Tsai, Lain-Chyr Hwang, Po-Chou Chen

Abstract:

Cancer is still one of the serious diseases threatening the lives of human beings. How to have an early diagnosis and effective treatment for tumors is a very important issue. The animal carcinoma model can provide a simulation tool for the study of pathogenesis, biological characteristics and therapeutic effects. Recently, drug delivery systems have been rapidly developed to effectively improve the therapeutic effects. Liposome plays an increasingly important role in clinical diagnosis and therapy for delivering a pharmaceutic or contrast agent to the targeted sites. Liposome can be absorbed and excreted by the human body, and is well known that no harm to the human body. This study aimed to compare the therapeutic effects between encapsulated (doxorubicin liposomal, LipoDox) and un-encapsulated (doxorubicin, Dox) anti-tumor drugs using Magnetic Resonance Imaging (MRI). Twenty-four New Zealand rabbits implanted with VX2 carcinoma at left thigh were classified into three groups: control group (untreated), Dox-treated group and LipoDox-treated group, 8 rabbits for each group. MRI scans were performed three days after tumor implantation. A 1.5T GE Signa HDxt whole body MRI scanner with a high resolution knee coil was used in this study. After a 3-plane localizer scan was performed, Three-Dimensional (3D) Fast Spin Echo (FSE) T2-Weighted Images (T2WI) was used for tumor volumetric quantification. And Two-Dimensional (2D) spoiled gradient recalled echo (SPGR) dynamic Contrast-enhanced (DCE) MRI was used for tumor perfusion evaluation. DCE-MRI was designed to acquire four baseline images, followed by contrast agent Gd-DOTA injection through the ear vein of rabbits. Afterwards, a series of 32 images were acquired to observe the signals change over time in the tumor and muscle. The MRI scanning was scheduled on a weekly basis for a period of four weeks to observe the tumor progression longitudinally. The Dox and LipoDox treatments were prescribed 3 times in the first week immediately after VX2 tumor implantation. ImageJ was used to quantitate tumor volume and time course signal enhancement on DCE images. The changes of tumor size showed that the growth of VX2 tumors was effectively inhibited for both LipoDox-treated and Dox-treated groups. Furthermore, the tumor volume of LipoDox-treated group was significantly lower than that of Dox-treated group, which implies that LipoDox has better therapeutic effect than Dox. The signal intensity of LipoDox-treated group is significantly lower than that of the other two groups, which implies that targeted therapeutic drug remained in the tumor tissue. This study provides a radiation-free and non-invasive MRI method for therapeutic monitoring of targeted liposome on an animal tumor model.

Keywords: doxorubicin, dynamic contrast-enhanced MRI, lipodox, magnetic resonance imaging, VX2 tumor model

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174 Biomolecules Based Microarray for Screening Human Endothelial Cells Behavior

Authors: Adel Dalilottojari, Bahman Delalat, Frances J. Harding, Michaelia P. Cockshell, Claudine S. Bonder, Nicolas H. Voelcker

Abstract:

Endothelial Progenitor Cell (EPC) based therapies continue to be of interest to treat ischemic events based on their proven role to promote blood vessel formation and thus tissue re-vascularisation. Current strategies for the production of clinical-grade EPCs requires the in vitro isolation of EPCs from peripheral blood followed by cell expansion to provide sufficient quantities EPCs for cell therapy. This study aims to examine the use of different biomolecules to significantly improve the current strategy of EPC capture and expansion on collagen type I (Col I). In this study, four different biomolecules were immobilised on a surface and then investigated for their capacity to support EPC capture and proliferation. First, a cell microarray platform was fabricated by coating a glass surface with epoxy functional allyl glycidyl ether plasma polymer (AGEpp) to mediate biomolecule binding. The four candidate biomolecules tested were Col I, collagen type II (Col II), collagen type IV (Col IV) and vascular endothelial growth factor A (VEGF-A), which were arrayed on the epoxy-functionalised surface using a non-contact printer. The surrounding area between the printed biomolecules was passivated with polyethylene glycol-bisamine (A-PEG) to prevent non-specific cell attachment. EPCs were seeded onto the microarray platform and cell numbers quantified after 1 h (to determine capture) and 72 h (to determine proliferation). All of the extracellular matrix (ECM) biomolecules printed demonstrated an ability to capture EPCs within 1 h of cell seeding with Col II exhibiting the highest level of attachment when compared to the other biomolecules. Interestingly, Col IV exhibited the highest increase in EPC expansion after 72 h when compared to Col I, Col II and VEGF-A. These results provide information for significant improvement in the capture and expansion of human EPC for further application.

Keywords: biomolecules, cell microarray platform, cell therapy, endothelial progenitor cells, high throughput screening

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173 Effect of Phthalates on Male Infertility: Myth or Truth?

Authors: Rashmi Tomar, A. Srinivasan, Nayan K. Mohanty, Arun K. Jain

Abstract:

Phthalates have been used as additives in industrial products since the 1930s, and are universally considered to be ubiquitous environmental contaminants. The general population is exposed to phthalates through consumer products, as well as diet and medical treatments. Animal studies showing the existence of an association between some phthalates and testicular toxicity have generated public and scientific concern about the potential adverse effects of environmental changes on male reproductive health. Unprecedented declines in fertility rates and semen quality have been reported during the last half of the 20th century in developed countries and increasing interest exists on the potential relationship between exposure to environmental contaminants, including phthalates, and human male reproductive health Studies. Phthalates may be associated with altered endocrine function and adverse effects on male reproductive development and function, but human studies are limited. The aim of the present study was detection of phthalate compounds, estimation of their metabolites in infertile & fertile male. Blood and urine samples were collected from 150 infertile patients & 75 fertile volunteers recruited through Department of Urology, Safdarjung Hospital, New Delhi. Blood have been collected in separate glass tubes from the antecubital vein of the patients, serum have been separate and estimate the phthalate level in serum samples by Gas Chromatography / Mass Spectrometry using NIOSH / OSHA detailed protocol. Urine of Infertile & Fertile Subjects was collected & extracted using solid phase extraction method, analysis by HPLC. In conclusion, to the best of our knowledge the present study based on human is first to show the presence of phthalate in human serum samples and their metabolites in urine samples. Significant differences were observed between several phthalates in infertile and fertile healthy individuals.

Keywords: Gas Chromatography, HPLC, male infertility, phthalates, serum, toxicity, urine

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172 Energy Conversion for Sewage Sludge by Microwave Heating Pyrolysis and Gasification

Authors: Young Nam Chun, Soo Hyuk Yun, Byeo Ri Jeong

Abstract:

The recent gradual increase in the energy demand is mostly met by fossil fuel, but the research on and development of new alternative energy sources is drawing much attention due to the limited fossil fuel supply and the greenhouse gas problem. Biomass is an eco-friendly renewable energy that can achieve carbon neutrality. The conversion of the biomass sludge wastes discharged from a wastewater treatment plant to clean energy is an important green energy technology in an eco-friendly way. In this NRF study, a new type of microwave thermal treatment was developed to apply the biomass-CCS technology to sludge wastes. For this, the microwave dielectric heating characteristics were examined to investigate the energy conversion mechanism for the combined drying-pyrolysis/gasification of the dewatered wet sludge. The carbon dioxide gasification was tested using the CO2 captured from the pre-combustion capture process. In addition, the results of the pyrolysis and gasification test with the wet sludge were analyzed to compare the microwave energy conversion results with the results of the use of the conventional heating method. Gas was the largest component of the product of both pyrolysis and gasification, followed by sludge char and tar. In pyrolysis, the main components of the producer gas were hydrogen and carbon monoxide, and there were some methane and hydrocarbons. In gasification, however, the amount of carbon monoxide was greater than that of hydrogen. In microwave gasification, a large amount of heavy tar was produced. The largest amount of benzene among light tar was produced in both pyrolysis and gasification. NH3 and HCN which are the precursors of NOx, generated as well. In microwave heating, the sludge char had a smooth surface, like that of glass, and in the conventional heating method with an electric furnace, deep cracks were observed in the sludge char. This indicates that the gas obtained from the microwave pyrolysis and gasification of wet sewage sludge can be used as fuel, but the heavy tar and NOx precursors in the gas must be treated. Sludge char can be used as solid fuel or as a tar reduction adsorbent in the process if necessary. This work supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (No. 2015R1R1A2A2A03003044).

Keywords: microwave heating, pyrolysis gasification, precombustion CCS, sewage sludge, biomass energy

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171 On Cold Roll Bonding of Polymeric Films

Authors: Nikhil Padhye

Abstract:

Recently a new phenomenon for bonding of polymeric films in solid-state, at ambient temperatures well below the glass transition temperature of the polymer, has been reported. This is achieved by bulk plastic compression of polymeric films held in contact. Here we analyze the process of cold-rolling of polymeric films via finite element simulations and illustrate a flexible and modular experimental rolling-apparatus that can achieve bonding of polymeric films through cold-rolling. Firstly, the classical theory of rolling a rigid-plastic thin-strip is utilized to estimate various deformation fields such as strain-rates, velocities, loads etc. in rolling the polymeric films at the specified feed-rates and desired levels of thickness-reduction(s). Predicted magnitudes of slow strain-rates, particularly at ambient temperatures during rolling, and moderate levels of plastic deformation (at which Bauschinger effect can be neglected for the particular class of polymeric materials studied here), greatly simplifies the task of material modeling and allows us to deploy a computationally efficient, yet accurate, finite deformation rate-independent elastic-plastic material behavior model (with inclusion of isotropic-hardening) for analyzing the rolling of these polymeric films. The interfacial behavior between the roller and polymer surfaces is modeled using Coulombic friction; consistent with the rate-independent behavior. The finite deformation elastic-plastic material behavior based on (i) the additive decomposition of stretching tensor (D = De + Dp, i.e. a hypoelastic formulation) with incrementally objective time integration and, (ii) multiplicative decomposition of deformation gradient (F = FeFp) into elastic and plastic parts, are programmed and carried out for cold-rolling within ABAQUS Explicit. Predictions from both the formulations, i.e., hypoelastic and multiplicative decomposition, exhibit a close match. We find that no specialized hyperlastic/visco-plastic model is required to describe the behavior of the blend of polymeric films, under the conditions described here, thereby speeding up the computation process .

Keywords: Polymer Plasticity, Bonding, Deformation Induced Mobility, Rolling

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170 Effect of Polymer Molecular Structures on Properties of Dental Cement Restoratives

Authors: Dong Xie, Jun Zhao, Yiming Weng

Abstract:

One of the challenges in dental cement biomaterials is how to make a restorative with mechanical strengths and wear resistance that are comparable to contemporary dental resin composites. Currently none of the dental cement restoratives has been used in high stress-bearing sites due to their low mechanical strengths and poor wear-resistance. The objective of this study was to synthesize and characterize the poly(alkenoic acid)s with different molecular structures, use these polymers to formulate a dental cement restorative, and study the effect of molecular structures on reaction kinetics, viscosity, and mechanical strengths of the formed polymers and cement restoratives. In this study, poly(alkenoic acid)s with different molecular structures were synthesized. The purified polymers were formulated with commercial Fuji II LC glass fillers to form the experimental cement restoratives. The reaction kinetics was studied via 1HNMR spectroscopy. The formed restoratives were evaluated using compressive strength, diametral tensile strength, flexural strength, hardness and wear-resistance tests. Specimens were conditioned in distilled water at 37 oC for 24 h prior to testing. Fuji II LC restorative was used as control. The results show that the higher the arm number and initiator concentration, the faster the reaction was. It was also found that the higher the arm number and branching that the polymer had, the lower the viscosity of the polymer in water and the lower the mechanical strengths of the formed restorative. The experimental restoratives were 31-53% in compressive strength, 37-55% in compressive modulus, 80-126% in diametral tensile strength, 76-94% in flexural strength, 4-21% in fracture toughness and 53-96% in hardness higher than Fuji II LC. For wear test, the experimental restoratives were only 5.4-13% of abrasive and 6.4-12% of attritional wear depths of Fuji II LC in each wear cycle. The aging study also showed that all the experimental restoratives increased their strength continuously during 30 days, unlike Fuji II LC. It is concluded that polymer molecular structures have significant and positive impact on mechanical properties of dental cement restoratives.

Keywords: dental materials, polymers, strength, biomaterials

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169 Some Characteristics Based on Literature, for an Ideal Disinfectant

Authors: Saimir Heta, Ilma Robo, Rialda Xhizdari, Kers Kapaj

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The stability of an ideal disinfectant should be constant regardless of the change in the atmospheric conditions of the environment where it is kept. If the conditions such as temperature or humidity change, it is understood that it will also be necessary to approach possible changes in the holding materials such as plastic or glass bottles with the aim of protecting, for example, the disinfectant from the excessive lighting of the environment, which can also be translated as an increase in the temperature of disinfectant as a fluid. Material and Methods: In this study, an attempt was made to find the most recent published data about the best possible combination of disinfectants indicated for use after dental procedures. This purpose of the study was realized by comparing the basic literature that is studied in the field of dentistry by students with the most published data in the literature of recent years about this topic. Each disinfectant is represented by a number called the disinfectant count, in which different factors can influence the increase or reduction of variables whose production remains a specific statistic for a specific disinfectant. Results: The changes in the atmospheric conditions where the disinfectant is deposited and stored in the environment are known to affect the stability of the disinfectant as a fluid; this fact is known and even cited in the leaflets accompanying the manufactured boxes of disinfectants. It is these cares, in the form of advice, which are based not only on the preservation of the disinfectant but also on the application in order to have the desired clinical result. Aldehydes have the highest constant among the types of disinfectants, followed by acids. The lowest value of the constant belongs to the class of glycols, the predecessors of which were the halogens, in which class there are some representatives with disinfection applications. The class of phenols and acids have almost the same intervals of constants. Conclusions: If the goal were to find the ideal disinfectant among the large variety of disinfectants produced, a good starting point would be to find something unchanging or a fixed, unchanging element on the basis of which the comparison can be made properties of different disinfectants. Precisely based on the results of this study, the role of the specific constant according to the specific disinfectant is highlighted. Finding an ideal disinfectant, like finding a medication or the ideal antibiotic, is an ongoing but unattainable goal.

Keywords: different disinfectants, ideal, specific constant, dental procedures

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168 Effect of Electropolymerization Method in the Charge Transfer Properties and Photoactivity of Polyaniline Photoelectrodes

Authors: Alberto Enrique Molina Lozano, María Teresa Cortés Montañez

Abstract:

Polyaniline (PANI) photoelectrodes were electrochemically synthesized through electrodeposition employing three techniques: chronoamperometry (CA), cyclic voltammetry (CV), and potential pulse (PP) methods. The substrate used for electrodeposition was a fluorine-doped tin oxide (FTO) glass with dimensions of 2.5 cm x 1.3 cm. Subsequently, structural and optical characterization was conducted utilizing Fourier-transform infrared (FTIR) spectroscopy and UV-visible (UV-vis) spectroscopy, respectively. The FTIR analysis revealed variations in the molar ratio of benzenoid to quinonoid rings within the PANI polymer matrix, indicative of differing oxidation states arising from the distinct electropolymerization methodologies employed. In the optical characterization, differences in the energy band gap (Eg) values and positions of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were observed, attributable to variations in doping levels and structural irregularities introduced during the electropolymerization procedures. To assess the charge transfer properties of the PANI photoelectrodes, electrochemical impedance spectroscopy (EIS) experiments were carried out within a 0.1 M sodium sulfate (Na₂SO₄) electrolyte. The results displayed a substantial decrease in charge transfer resistance with the PANI coatings compared to uncoated substrates, with PANI obtained through cyclic voltammetry (CV) presenting the lowest charge transfer resistance, contrasting PANI obtained via chronoamperometry (CA) and potential pulses (PP). Subsequently, the photoactive response of the PANI photoelectrodes was measured through linear sweep voltammetry (LSV) and chronoamperometry. The photoelectrochemical measurements revealed a discernible photoactivity in all PANI-coated electrodes. However, PANI electropolymerized through CV displayed the highest photocurrent. Interestingly, PANI derived from chronoamperometry (CA) exhibited the highest degree of stable photocurrent over an extended temporal interval.

Keywords: PANI, photocurrent, photoresponse, charge separation, recombination

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167 Theoretical Study on the Visible-Light-Induced Radical Coupling Reactions Mediated by Charge Transfer Complex

Authors: Lishuang Ma

Abstract:

Charge transfer (CT) complex, also known as Electron donor-acceptor (EDA) complex, has received attentions increasingly in the field of synthetic chemistry community, due to the CT complex can absorb the visible light through the intermolecular charge transfer excited states, various of catalyst-free photochemical transformations under mild visible-light conditions. However, a number of fundamental questions are still ambiguous, such as the origin of visible light absorption, the photochemical and photophysical properties of the CT complex, as well as the detailed mechanism of the radical coupling pathways mediated by CT complex. Since these are critical factors for target-specific design and synthesis of more new-type CT complexes. To this end, theoretical investigations were performed in our group to answer these questions based on multiconfigurational perturbation theory. The photo-induced fluoroalkylation reactions are mediated by CT complexes, which are formed by the association of an acceptor of perfluoroalkyl halides RF−X (X = Br, I) and a suitable donor molecule such as β-naphtholate anion, were chosen as a paradigm example in this work. First, spectrum simulations were carried out by both CASPT2//CASSCF/PCM and TD-DFT/PCM methods. The computational results showed that the broadening spectra in visible light range (360-550nm) of the CT complexes originate from the 1(σπ*) excitation, accompanied by an intermolecular electron transfer, which was also found closely related to the aggregate states of the donor and acceptor. Moreover, from charge translocation analysis, the CT complex that showed larger charge transfer in the round state would exhibit smaller charge transfer in excited stated of 1(σπ*), causing blue shift relatively. Then, the excited-state potential energy surface (PES) was calculated at CASPT2//CASSCF(12,10)/ PCM level of theory to explore the photophysical properties of the CT complexes. The photo-induced C-X (X=I, Br) bond cleavage was found to occur in the triplet state, which is accessible through a fast intersystem crossing (ISC) process that is controlled by the strong spin-orbit coupling resulting from the heavy iodine and bromine atoms. Importantly, this rapid fragmentation process can compete and suppress the backward electron transfer (BET) event, facilitating the subsequent effective photochemical transformations. Finally, the reaction pathways of the radical coupling were also inspected, which showed that the radical chain propagation pathway could easy to accomplish with a small energy barrier no more than 3.0 kcal/mol, which is the key factor that promote the efficiency of the photochemical reactions induced by CT complexes. In conclusion, theoretical investigations were performed to explore the photophysical and photochemical properties of the CT complexes, as well as the mechanism of radical coupling reactions mediated by CT complex. The computational results and findings in this work can provide some critical insights into mechanism-based design for more new-type EDA complexes

Keywords: charge transfer complex, electron transfer, multiconfigurational perturbation theory, radical coupling

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166 Light Weight Fly Ash Based Composite Material for Thermal Insulation Applications

Authors: Bharath Kenchappa, Kunigal Shivakumar

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Lightweight, low thermal conductivity and high temperature resistant materials or the system with moderate mechanical properties and capable of taking high heating rates are needed in both commercial and military applications. A single material with these attributes is very difficult to find and one needs to come with innovative ideas to make such material system using what is available. To bring down the cost of the system, one has to be conscious about the cost of basic materials. Such a material system can be called as the thermal barrier system. This paper focuses on developing, testing and characterization of material system for thermal barrier applications. The material developed is porous, low density, low thermal conductivity of 0.1062 W/m C and glass transition temperature about 310 C. Also, the thermal properties of the developed material was measured in both longitudinal and thickness direction to highlight the fact that the material shows isotropic behavior. The material is called modified Eco-Core which uses only less than 9% weight of high-char resin in the composite. The filler (reinforcing material) is a component of fly ash called Cenosphere, they are hollow micro-bubbles made of ceramic materials. Special mixing-technique is used to surface coat the fillers with a thin layer of resin to develop a point-to-point contact of particles. One could use commercial ceramic micro-bubbles instead of Cenospheres, but it is expensive. The bulk density of Cenospheres is about 0.35 g/cc and we could accomplish the composite density of about 0.4 g/cc. One percent filler weight of 3mm length standard drywall grade fibers was used to bring the added toughness. Both thermal and mechanical characterization was performed and properties are documented. For higher temperature applications (up to 1,000 C), a hybrid system was developed using an aerogel mat. Properties of combined material was characterized and documented. Thermal tests were conducted on both the bare modified Eco-Core and hybrid materials to assess the suitability of the material to a thermal barrier application. The hybrid material system was found to meet the requirement of the application.

Keywords: aerogel, fly ash, porous material, thermal barrier

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165 Nanotechnology in Construction as a Building Security

Authors: Hanan Fayez Hussein

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‘Due to increasing environmental challenges and security problems in the world such as global warming, storms, and terrorism’, humans have discovered new technologies and new materials in order to program daily life. As providing physical and psychological security is one of the primary functions of architecture, so in order to provide security, building must prevents unauthorized entry and harm to occupant and reduce the threat of attack by making building less attractive targets by new technologies such as; Nanotechnology, which has emerged as a major science and technology focus of the 21st century and will be the next industrial revolution. Nanotechnology is control of the properties of matter, and it deals with structures of the size 100 nanometers or smaller in at least one dimension and has wide application in various fields. The construction and architecture sectors were among the first to be identified as a promising application area for nanotechnology. The advantages of using nanomaterials in construction are enormous, and promises heighten building security by utilizing the strength of building materials to make our buildings more secure and get smart home. Access barriers such as wall and windows could incorporate stronger materials benefiting from nano-reinforcement utilizing nanotubes and nano composites to act as protective cover. Carbon nanotubes, as one of nanotechnology application, can be designed up to 250 times stronger than steel. Nano-enabled devices and materials offer both enhanced and, in some cases, completely new defence systems. In the addition, the small amount of carbon nanoparticles to the construction materials such as; cement, concrete, wood, glass, gypson, and steel can make these materials act as defence elements. This paper highlights the fact that nanotechnology can impact the future global security and how building’s envelop can act as a defensive cover for the building and can be resistance to any threats can attack it. Then focus on its effect on construction materials such as; Concrete can obtain by nanoadditives excellent mechanical, chemical, and physical properties with less material, which can acts as a precautionary shield to the building.

Keywords: nanomaterial, global warming, building security, smart homes

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164 Determination of Elasticity Constants of Isotropic Thin Films Using Impulse Excitation Technique

Authors: M. F. Slim, A. Alhussein, F. Sanchette, M. François

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Thin films are widely used in various applications to enhance the surface properties and characteristics of materials. They are used in many domains such as: biomedical, automotive, aeronautics, military, electronics and energy. Depending on the elaboration technique, the elastic behavior of thin films may be different from this of bulk materials. This dependence on the elaboration techniques and their parameters makes the control of the elasticity constants of coated components necessary. Our work is focused on the characterization of the elasticity constants of isotropic thin films by means of Impulse Excitation Techniques. The tests rely on the measurement of the sample resonance frequency before and after deposition. In this work, a finite element model was performed with ABAQUS software. This model was then compared with the analytical approaches used to determine the Young’s and shear moduli. The best model to determine the film Young’s modulus was identified and a relation allowing the determination of the shear modulus of thin films of any thickness was developed. In order to confirm the model experimentally, Tungsten films were deposited on glass substrates by DC magnetron sputtering of a 99.99% purity tungsten target. The choice of tungsten was done because it is well known that its elastic behavior at crystal scale is ideally isotropic. The macroscopic elasticity constants, Young’s and shear moduli and Poisson’s ratio of the deposited film were determined by means of Impulse Excitation Technique. The Young’s modulus obtained from IET was compared with measurements by the nano-indentation technique. We did not observe any significant difference and the value is in accordance with the one reported in the literature. This work presents a new methodology on the determination of the elasticity constants of thin films using Impulse Excitation Technique. A formulation allowing the determination of the shear modulus of a coating, whatever the thickness, was developed and used to determine the macroscopic elasticity constants of tungsten films. The developed model was validated numerically and experimentally.

Keywords: characterization, coating, dynamical resonant method, Poisson's ratio, PVD, shear modulus, Young's modulus

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163 Reliability Analysis of Glass Epoxy Composite Plate under Low Velocity

Authors: Shivdayal Patel, Suhail Ahmad

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Safety assurance and failure prediction of composite material component of an offshore structure due to low velocity impact is essential for associated risk assessment. It is important to incorporate uncertainties associated with material properties and load due to an impact. Likelihood of this hazard causing a chain of failure events plays an important role in risk assessment. The material properties of composites mostly exhibit a scatter due to their in-homogeneity and anisotropic characteristics, brittleness of the matrix and fiber and manufacturing defects. In fact, the probability of occurrence of such a scenario is due to large uncertainties arising in the system. Probabilistic finite element analysis of composite plates due to low-velocity impact is carried out considering uncertainties of material properties and initial impact velocity. Impact-induced damage of composite plate is a probabilistic phenomenon due to a wide range of uncertainties arising in material and loading behavior. A typical failure crack initiates and propagates further into the interface causing de-lamination between dissimilar plies. Since individual crack in the ply is difficult to track. The progressive damage model is implemented in the FE code by a user-defined material subroutine (VUMAT) to overcome these problems. The limit state function is accordingly established while the stresses in the lamina are such that the limit state function (g(x)>0). The Gaussian process response surface method is presently adopted to determine the probability of failure. A comparative study is also carried out for different combination of impactor masses and velocities. The sensitivity based probabilistic design optimization procedure is investigated to achieve better strength and lighter weight of composite structures. Chain of failure events due to different modes of failure is considered to estimate the consequences of failure scenario. Frequencies of occurrence of specific impact hazards yield the expected risk due to economic loss.

Keywords: composites, damage propagation, low velocity impact, probability of failure, uncertainty modeling

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