Search results for: melting/solidification
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 514

Search results for: melting/solidification

94 Study of the Hysteretic I-V Characteristics in a Polystyrene/ZnO-Nanorods Stack Layer

Authors: You-Lin Wu, Yi-Hsing Sung, Shih-Hung Lin, Jing-Jenn Lin

Abstract:

Performance improvement in optoelectronic devices such as solar cells and photodetectors has been reported when a polymer/ZnO nanorods stack is used. Resistance switching of polymer/ZnO nanocrystals (or nanorods) hybrid has also gained a lot of research interests recently. It has been reported that high- and low-resistance states of a metal/insulator/metal (MIM) structure diode with a polystyrene (PS) and ZnO hybrid as the insulator layer can be switched by applied bias after a high-voltage forming process, while the same device structure merely with a PS layer does not show any forming behavior. In this work, we investigated the current-voltage (I-V) characteristics of an MIM device with a PS/ZnO nanorods stack deposited on fluorine-doped tin oxide (FTO) glass substrate. The ZnO nanorods were grown by a hydrothermal method using a mixture of zinc nitrate, hexamethylenetetramine, and DI water. Following that, a PS layer was deposited by spin coating. Finally, the device with a structure of Ti/ PS/ZnO nanorods/FTO was completed by e-gun evaporated Ti layer on top of the PS layer. Semiconductor parameters analyzer Agilent 4156C was then used to measure the I-V characteristics of the device by applying linear ramp sweep voltage with sweep sequence of 0V → 4V → 0V → 3V → 0V → 2V → 0V → 1V → 0V in both positive and negative directions. It is interesting to find that the I-V characteristics are bias dependent and hysteretic, indicating that the device Ti/PS/ZnO nanorods/FTO structure has ferroelectricity. Our results also show that the maximum hysteresis loop height of the I-V characteristics as well as the voltage at which the maximum hysteresis loop height of each scan occurs increase with increasing maximum sweep voltage. It should be noticed that, although ferroelectricity has been found in ZnO at its melting temperature (1975℃) and in Li- or Co-doped ZnO, neither PS nor ZnO has ferroelectricity at room temperature. Using the same structure but with a PS or ZnO layer only as the insulator does not give and hysteretic I-V characteristics. It is believed that a charge polarization layer is induced near the PS/ZnO nanorods stack interface and thus causes the ferroelectricity in the device with Ti/PS/ZnO nanorods/FTO structure. Our results show that the PS/ZnO stack can find a potential application in a resistive switching memory device with MIM structure.

Keywords: ferroelectricity, hysteresis, polystyrene, resistance switching, ZnO nanorods

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93 Effect of Citric Acid on Hydrogen-Bond Interactions and Tensile Retention Properties of Citric Acid Modified Thermoplastic Starch Biocomposites

Authors: Da-Wei Wang, Liang Yang, Xuan-Long Peng, Mei-Chuan Kuo, Jen-Taut Yeh

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The tensile retention and waterproof properties of thermoplastic starch (TPS) resins were significantly enhanced by modifying with proper amounts of citric acid (CA) and by melt-blending with poly(lactic acid) (PLA), although no distinguished chemical reaction occurred between CA and starch molecules. As evidenced by Fourier transform infrared spectroscopy and Solid-state 13C Nuclear Magnetic Resonance analyses, disruption of intra and interhydrogen-bondings within starch molecules did occur during the modification processes of CA modified TPS (i.e. TPS100CAx) specimens. The tensile strength (σf) retention values of TPS specimens reduced rapidly from 27.8 to 20.5 and 0.4 MPa, respectively, as the conditioning time at 20°C/50% relative humidity (RH) increased from 0 to 7 and 70 days, respectively. While the elongation at break (εf) retention values of TPS specimens increased rapidly from 5.9 to 6.5 and 34.8%, respectively, as the conditioning time increased from 0 to 7 and 70 days. After conditioning at 20°C/50% RH for 70 days, the σf and εf retention values of the best prepared (TPS100CA0.1)30PLA70 specimen are equivalent to 85% and 167% of its initial σf and εf values, respectively, and are more than 105 times higher but 48% lower than those of TPS specimens conditioned at 20°C/50% RH for the same amount of time. Demarcated diffraction peaks, new melting endotherms of recrystallized starch crystals and distinguished ductile characteristics with drawn debris were found for many conditioned TPS specimens, however, only slight retrogradation effect and much less drawn debris was found for most conditioned TPS100CAx and/or (TPS100CA0.1)xPLAy specimens. The significantly improved water proof, tensile retention properties and relatively unchanged in retrogradation effect found for most conditioned TPS100CAx and/or (TPS100CA0.1)xPLAy specimens are apparently due to the efficient blocking of the moisture-absorbing hydroxyl groups (free or hydrogen bonded) by hydrogen-bonding CA with starch molecules during their modification processes.

Keywords: thermoplastic starch, hydrogen-bonding, water proof, strength retention

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92 Thorium-Doped PbS Thin Films for Radiation Damage Studies

Authors: Michael Shandalov, Tzvi Templeman, Michael Schmidt, Itzhak Kelson, Eyal Yahel

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We present a new method to produce a model system for the study of radiation damage in non-radioactive materials. The method is based on homogeneously incorporating 228Th ions in PbS thin films using a small volume chemical bath deposition (CBD) technique. The common way to alloy metals with radioactive elements is by melting pure elements, which requires considerable amounts of radioactive material with its safety consequences such as high sample activity. Controlled doping of the thin films with (very) small amounts (100-200ppm) of radioactive elements such as thorium is expected to provide a unique path for studying radiation damage in materials due to decay processes without the need of sealed enclosure. As a first stage, we developed CBD process for controlled doping of PbS thin films (~100 nm thick) with the stable isotope (t1/2~106 years), 232Th. Next, we developed CBD process for controlled doping of PbS thin films with active 228Th isotope. This was achieved by altering deposition parameters such as temperature, pH, reagent concentrations and time. The 228Th-doped films were characterized using X-ray diffraction, which indicated a single phase material. Film morphology and thickness were determined using scanning electron microscopy (SEM). Energy dispersive spectroscopy (EDS) mapping in the analytical transmission electron microscope (A-TEM), X-ray photoelectron spectroscopy (XPS) depth profiles and autoradiography indicated that the Th ions were homogeneously distributed throughout the films, suggesting Pb substitution by Th ions in the crystal lattice. The properties of the PbS (228Th) film activity were investigated by using alpha-spectroscopy and gamma spectroscopy. The resulting films are applicable for isochronal annealing of resistivity measurements and currently under investigation. This work shows promise as a model system for the analysis of dilute defect systems in semiconductor thin films.

Keywords: thin films, doping, radiation damage, chemical bath deposition

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91 Development of Solid Electrolytes Based on Networked Cellulose

Authors: Boor Singh Lalia, Yarjan Abdul Samad, Raed Hashaikeh

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Three different kinds of solid polymer electrolytes were prepared using polyethylene oxide (PEO) as a base polymer, networked cellulose (NC) as a physical support and LiClO4 as a conductive salt for the electrolytes. Networked cellulose, a modified form of cellulose, is a biodegradable and environmentally friendly additive which provides a strong fibrous networked support for structural stability of the electrolytes. Although the PEO/NC/LiClO4 electrolyte retains its structural integrity and mechanical properties at 100oC as compared to pristine PEO-based polymer electrolytes, it suffers from poor ionic conductivity. To improve the room temperature conductivity of the electrolyte, PEO is replaced by the polyethylene glycol (PEG) which is a liquid phase that provides high mobility for Li+ ions transport in the electrolyte. PEG/NC/LiClO4 shows improvement in ionic conductivity compared to PEO/NC/LiClO4 at room temperature, but it is brittle and tends to form cracks during processing. An advanced solid polymer electrolyte with optimum ionic conductivity and mechanical properties is developed by using a ternary system: TEGDME/PEO/NC+LiClO4. At room temperature, this electrolyte exhibits an ionic conductivity to the order of 10-5 S/cm, which is very high compared to that of the PEO/LiClO4 electrolyte. Pristine PEO electrolytes start melting at 65 °C and completely lose its mechanical strength. Dynamic mechanical analysis of TEGDME: PEO: NC (70:20:10 wt%) showed an improvement of storage modulus as compared to the pristine PEO in the 60–120 °C temperature range. Also, with an addition of NC, the electrolyte retains its mechanical integrity at 100 oC which is beneficial for Li-ion battery operation at high temperatures. Differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA) studies revealed that the ternary polymer electrolyte is thermally stable in the lithium ion battery operational temperature range. As-prepared polymer electrolyte was used to assemble LiFePO4/ TEGDME/PEO/NC+LiClO4/Li half cells and their electrochemical performance was studied via cyclic voltammetry and charge-discharge cycling.

Keywords: solid polymer electrolyte, ionic conductivity, mechanical properties, lithium ion batteries, cyclic voltammetry

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90 Dynamic Mechanical Analysis of Supercooled Water in Nanoporous Confinement and Biological Systems

Authors: Viktor Soprunyuk, Wilfried Schranz, Patrick Huber

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In the present work, we show that Dynamic Mechanical Analysis (DMA) with a measurement frequency range f= 0.2 - 100 Hz is a rather powerful technique for the study of phase transitions (freezing and melting) and glass transitions of water in geometrical confinement. Inserting water into nanoporous host matrices, like e.g. Gelsil (size of pores 2.6 nm and 5 nm) or Vycor (size of pores 10 nm) allows one to study size effects occurring at the nanoscale conveniently in macroscopic bulk samples. One obtains valuable insight concerning confinement induced changes of the dynamics by measuring the temperature and frequency dependencies of the complex Young's modulus Y* for various pore sizes. Solid-liquid transitions or glass-liquid transitions show up in a softening or the real part Y' of the complex Young's modulus, yet with completely different frequency dependencies. Analysing the frequency dependent imaginary part of the Young´s modulus in the glass transition regions for different pore sizes we find a clear-cut 1/d-dependence of the calculated glass transition temperatures which extrapolates to Tg(1/d=0)=136 K, in agreement with the traditional value of water. The results indicate that the main role of the pore diameter is the relative amount of water molecules that are near an interface within a length scale of the order of the dynamic correlation length x. Thus we argue that the observed strong pore size dependence of Tg is an interfacial effect, rather than a finite size effect. We obtained similar signatures of Y* near glass transitions in different biological objects (fruits, vegetables, and bread). The values of the activation energies for these biological materials in the region of glass transition are quite similar to the values of the activation energies of supercooled water in the nanoporous confinement in this region. The present work was supported by the Austrian Science Fund (FWF, project Nr. P 28672 – N36).

Keywords: biological systems, liquids, glasses, amorphous systems, nanoporous materials, phase transition

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89 Copolymers of Epsilon-Caprolactam Received via Anionic Polymerization in the Presence of Polypropylene Glycol Based Polymeric Activators

Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

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88 Thermal Stability and Electrical Conductivity of Ca₅Mg₄₋ₓMₓ(VO₄)₆ (0 ≤ x ≤ 4) where M = Zn, Ni Measured by Impedance Spectroscopy

Authors: Anna S. Tolkacheva, Sergey N. Shkerin, Kirill G. Zemlyanoi, Olga G. Reznitskikh, Pavel D. Khavlyuk

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Calcium oxovanadates with garnet related structure are multifunctional oxides in various fields like photoluminescence, microwave dielectrics, and magneto-dielectrics. For example, vanadate garnets are self-luminescent compounds. They attract attention as RE-free broadband excitation and emission phosphors and are candidate materials for UV-based white light-emitting diodes (WLEDs). Ca₅M₄(VO₄)₆ (M = Mg, Zn, Co, Ni, Mn) compounds are also considered promising for application in microwave devices as substrate materials. However, the relation between their structure, composition and physical/chemical properties remains unclear. Given the above-listed observations, goals of this study are to synthesise Ca₅M₄(VO₄)₆ (M = Mg, Zn, Ni) and to study their thermal and electrical properties. Solid solutions Ca₅Mg₄₋ₓMₓ(VO₄)₆ (0 ≤ x ≤ 4) where M is Zn and Ni have been synthesized by sol-gel method. The single-phase character of the final products was checked by powder X-ray diffraction on a Rigaku D/MAX-2200 X-ray diffractometer using Cu Kα radiation in the 2θ range from 15° to 70°. The dependence of thermal properties on chemical composition of solid solutions was studied using simultaneous thermal analyses (DSC and TG). Thermal analyses were conducted in a Netzch simultaneous analyser STA 449C Jupiter, in Ar atmosphere, in temperature range from 25 to 1100°C heat rate was 10 K·min⁻¹. Coefficients of thermal expansion (CTE) were obtained by dilatometry measurements in air up to 800°C using a Netzsch 402PC dilatometer; heat rate was 1 K·min⁻¹. Impedance spectra were obtained via the two-probe technique with an impedance meter Parstat 2273 in air up to 700°C with the variation of pH₂O from 0.04 to 3.35 kPa. Cation deficiency in Ca and Mg sublattice under the substitution of MgO with ZnO up to 1/6 was observed using Rietveld refinement of the crystal structure. Melting point was found to decrease with x changing from 0 to 4 in Ca₅Mg₄₋ₓMₓ(VO₄)₆ where M is Zn and Ni. It was observed that electrical conductivity does not depend on air humidity. The reported study was funded by the RFBR Grant No. 17–03–01280. Sample attestation was carried out in the Shared Access Centers at the IHTE UB RAS.

Keywords: garnet structure, electrical conductivity, thermal expansion, thermal properties

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87 Hybrid Nanostructures of Acrylonitrile Copolymers

Authors: A. Sezai Sarac

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Acrylonitrile (AN) copolymers with typical comonomers of vinyl acetate (VAc) or methyl acrylate (MA) exhibit better mechanical behaviors than its homopolymer. To increase processability of conjugated polymer, and to obtain a hybrid nano-structure multi-stepped emulsion polymerization was applied. Such products could be used in, i.e., drug-delivery systems, biosensors, gas-sensors, electronic compounds, etc. Incorporation of a number of flexible comonomers weakens the dipolar interactions among CN and thereby decreases melting point or increases decomposition temperatures of the PAN based copolymers. Hence, it is important to consider the effect of comonomer on the properties of PAN-based copolymers. Acrylonitrile vinylacetate (AN–VAc ) copolymers have the significant effect to their thermal behavior and are also of interest as precursors in the production of high strength carbon fibers. AN is copolymerized with one or two comonomers, particularly with vinyl acetate The copolymer of AN and VAc can be used either as a plastic (VAc > 15 wt %) or as microfibers (VAc < 15 wt %). AN provides the copolymer with good processability, electrochemical and thermal stability; VAc provides the mechanical stability. The free radical copolymerization of AN and VAc copolymer and core Shell structure of polyprrole composites,and nanofibers of poly(m-anthranilic acid)/polyacrylonitrile blends were recently studied. Free radical copolymerization of acrylonitrile (AN) – with different comonomers, i.e. acrylates, and styrene was realized using ammonium persulfate (APS) in the presence of a surfactant and in-situ polymerization of conjugated polymers was performed in this reaction medium to obtain core-shell nano particles. Nanofibers of such nanoparticles were obtained by electrospinning. Morphological properties of nanofibers are investigated by scanning electron microscopy (SEM) and atomic force spectroscopy (AFM). Nanofibers are characterized using Fourier Transform Infrared - Attenuated Total Reflectance spectrometer (FTIR-ATR), Nuclear Magnetic Resonance Spectroscopy (1H-NMR), differential scanning calorimeter (DSC), thermal gravimetric analysis (TGA), and Electrochemical Impedance Spectroscopy. The electrochemical Impedance results of the nanofibers were fitted to an equivalent curcuit by modelling (ECM).

Keywords: core shell nanoparticles, nanofibers, ascrylonitile copolymers, hybrid nanostructures

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86 Investigation on the Effect of Titanium (Ti) Plus Boron (B) Addition to the Mg-AZ31 Alloy in the as Cast and After Extrusion on Its Metallurgical and Mechanical Characteristics

Authors: Adnan I. O. Zaid, Raghad S. Hemeimat

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Magnesium - aluminum alloys are versatile materials which are used in manufacturing a number of engineering and industrial parts in the automobile and aircraft industries due to their strength – to –weight -ratio. Against these preferable characteristics, magnesium is difficult to deform at room temperature therefore it is alloyed with other elements mainly Aluminum and Zinc to add some required properties particularly for their high strength - to -weight ratio. Mg and its alloys oxidize rapidly therefore care should be taken during melting or machining them; but they are not fire hazardous. Grain refinement is an important technology to improve the mechanical properties and the micro structure uniformity of the alloys. Grain refinement has been introduced in early fifties; when Cibula showed that the presence of Ti, and Ti+ B, produced a great refining effect in Al. since then it became an industrial practice to grain refine Al. Most of the published work on grain refinement was directed toward grain refining Al and Zinc alloys; however, the effect of the addition of rare earth material on the grain size or the mechanical behavior of Mg alloys has not been previously investigated. This forms the main objective of the research work; where, the effect of Ti addition on the grain size, mechanical behavior, ductility, and the extrusion force & energy consumed in forward extrusion of Mg-AZ31 alloy is investigated and discussed in two conditions, first in the as cast condition and the second after extrusion. It was found that addition of Ti to Mg- AZ31 alloy has resulted in reduction of its grain size by 14%; the reduction in grain size after extrusion was much higher. However the increase in Vicker’s hardness was 3% after the addition of Ti in the as cast condition, and higher values for Vicker’s hardness were achieved after extrusion. Furthermore, an increase in the strength coefficient by 36% was achieved with the addition of Ti to Mg-AZ31 alloy in the as cast condition. Similarly, the work hardening index was also increased indicating an enhancement of the ductility and formability. As for the extrusion process, it was found that the force and energy required for the extrusion were both reduced by 57% and 59% with the addition of Ti.

Keywords: cast condition, direct extrusion, ductility, MgAZ31 alloy, super - plasticity

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85 Study of the Montmorillonite Effect on PET/Clay and PEN/Clay Nanocomposites

Authors: F. Zouai, F. Z. Benabid, S. Bouhelal, D. Benachour

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Nanocomposite polymer / clay are relatively important area of research. These reinforced plastics have attracted considerable attention in scientific and industrial fields because a very small amount of clay can significantly improve the properties of the polymer. The polymeric matrices used in this work are two saturated polyesters ie polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).The success of processing compatible blends, based on poly(ethylene terephthalate) (PET)/ poly(ethylene naphthalene) (PEN)/clay nanocomposites in one step by reactive melt extrusion is described. Untreated clay was first purified and functionalized ‘in situ’ with a compound based on an organic peroxide/ sulfur mixture and (tetramethylthiuram disulfide) as the activator for sulfur. The PET and PEN materials were first separately mixed in the molten state with functionalized clay. The PET/4 wt% clay and PEN/7.5 wt% clay compositions showed total exfoliation. These compositions, denoted nPET and nPEN, respectively, were used to prepare new n(PET/PEN) nanoblends in the same mixing batch. The n(PET/PEN) nanoblends were compared to neat PET/PEN blends. The blends and nanocomposites were characterized using various techniques. Microstructural and nanostructural properties were investigated. Fourier transform infrared spectroscopy (FTIR) results showed that the exfoliation of tetrahedral clay nanolayers is complete and the octahedral structure totally disappears. It was shown that total exfoliation, confirmed by wide angle X-ray scattering (WAXS) measurements, contributes to the enhancement of impact strength and tensile modulus. In addition, WAXS results indicated that all samples are amorphous. The differential scanning calorimetry (DSC) study indicated the occurrence of one glass transition temperature Tg, one crystallization temperature Tc and one melting temperature Tm for every composition. This was evidence that both PET/PEN and nPET/nPEN blends are compatible in the entire range of compositions. In addition, the nPET/nPEN blends showed lower Tc and higher Tm values than the corresponding neat PET/PEN blends. In conclusion, the results obtained indicate that n(PET/PEN) blends are different from the pure ones in nanostructure and physical behavior.

Keywords: blends, exfoliation, DRX, DSC, montmorillonite, nanocomposites, PEN, PET, plastograph, reactive melt-mixing

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84 Observation of a Phase Transition in Adsorbed Hydrogen at 101 Kelvin

Authors: Raina J. Olsen, Andrew K. Gillespie, John W. Taylor, Cristian I. Contescu, Peter Pfeifer, James R. Morris

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While adsorbent surfaces such as graphite are known to increase the melting temperature of solid H2, this effect is normally rather small, increasing to 20 Kelvin (K) relative to 14 K in the bulk. An as-yet unidentified phase transition has been observed in a system of H2 adsorbed in a porous, locally graphitic, Saran carbon with sub-nanometer sized pores at temperatures (74-101 K) and pressures ( > 76 bar) well above the critical point of bulk H2 using hydrogen adsorption and neutron scattering experiments. Adsorption data shows a discontinuous pressure jump in the kinetics at 76 bar after nearly an hour of equilibration time, which is identified as an exothermic phase transition. This discontinuity is observed in the 87 K isotherm, but not the 77 K isotherm. At higher pressures, the measured isotherms show greater excess adsorption at 87 K than 77 K. Inelastic neutron scattering measurements also show a striking phase transition, with the amount of high angle scattering (corresponding to large momentum transfer/ large effective mass) increasing by up to a factor of 5 in the novel phase. During the course of the neutron scattering experiment, three of these reversible spectral phase transitions were observed to occur in response to only changes in sample temperature. The novel phase was observed by neutron scattering only at high H2 pressure (123 bar and 187 bar) and temperatures between 74-101 K in the sample of interest, but not at low pressure (30 bar), or in a control activated carbon at 186 bar of H2 pressure. Based on several of the more unusual observations, such as the slow equilibration and the presence of both an upper and lower temperature bound, a reasonable hypothesis is that this phase forms only in the presence of a high concentration of ortho-H2 (nuclear spin S=1). The increase in adsorption with temperature, temperatures which cross the lower temperature bound observed by neutron scattering, indicates that this novel phase is denser. Structural characterization data on the adsorbent shows that it may support a commensurate solid phase denser than those known to exist on graphite at much lower temperatures. Whatever this phase is eventually proven to be, these results show that surfaces can have a more striking effect on hydrogen phases than previously thought.

Keywords: adsorbed phases, hydrogen, neutron scattering, nuclear spin

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83 Promoter Methylation of RASSF1A and MGMT Genes in Head and Neck Squamous Cell Carcinoma

Authors: Vitor Rafael Regiani, Carlos Henrique Viesi Do Nascimento Filho, Patricia Matos Biselli-Chicote, Claudia Aparecida Rainho, Luiz Sergio Raposo, José Victor Maniglia, Eny Maria Goloni-Bertollo, Erika Cristina Pavarino

Abstract:

Promoter hypermethylation of tumor-related genes has been associated with prognosis in early-stage head-and-neck cancers, providing strong evidence that these hypermethylated genes are valuable biomarkers for prognostic evaluation. Hence, we selected the MGMT and RASSF1A genes to examine the methylation status in head and neck squamous cell carcinomas (HNSCC) samples matched with non-tumor tissues (tumor-surrounding tissues or peripheral blood samples). DNA methylation analysis was based on Methylation-Sensitive High Resolution Melting, and the methylation status was correlated with clinic-pathological characteristics of the patients. RASSF1A and MGMT promoter methylation was detected in 43.24% (16/37) and in 44.44% (16/36) of the tumors, respectively. RASSF1A and MGMT methylation was significantly more frequent in tumor tissue than non-tumor tissues, as well as, simultaneous methylation of RASSF1A and MGMT also was higher in tumor tissue than non-tumor tissues. In relation to anatomic site, larynx cancer presented significant methylation of MGMT gene compared to tumor-surrounding tissue. The frequency of RASSF1A and MGMT promoter methylated was higher in tumor tissues in relation to peripheral blood from the same patient. No association was found between methylation and the variables analyzed, including gender, age, smoking or alcohol drinking habits. Clinic-pathological characteristics also showed no association in the presence of methylation. The Kaplan–Meier's method showed no association of methylation and both disease-free and overall survival. In conclusion, the presence of epigenetic abnormalities in normal-appearing tissue corroborates the hypothesis of the ‘field cancerization', or it can reflect preneoplastic and/or preinvasive. Moreover, MGMT methylation may serve as an important laryngeal cancer biomarker because it showed significant difference between laryngeal cancer and surrounding tumor tissues.

Keywords: head and neck cancer, DNA methylation, MGMT promoter methylation, RASSF1A promoter methylation

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82 Development of Beeswax-Discharge Writing Material for Visually Impaired Persons

Authors: K. Doi, T. Nishimura, H. Fujimoto, T. Tanaka

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It has been known that visually impaired persons have some problems in getting visual information. Therefore, information accessibility for the visually impaired persons is very important in a current information society. Some application software with read-aloud function for using personal computer and smartphone are getting more and more popular among visually impaired persons in the world. On the other hand, it is also very important for being able to learn how to read and write characters such as Braille and Visual character. Braille typewriter has been widely used in learning Braille. And also raised-line drawing kits as writing material has been used for decades for especially acquired visually impaired persons. However, there are some drawbacks such as the drawn line cannot be erased. Moreover, visibility of drawing lines is not so good for visually impaired with low vision. We had significant number of requests for developing new writing material for especially acquired visually impaired persons instead of raised-line drawing kits. For conducting development research of novel writing material, we could receive a research grant from ministry of health, labor and welfare in Japanese government. In this research, we developed writing material typed pens and pencils with Beeswax-discharge instead of conventional raised-line drawing kits. This writing material was equipped with cartridge heater for melting beeswax and its heat controller. When this pen users held down the pen tip on the regular paper such as fine paper and so on, the melted beeswax could be discharged from pen tip with valve structure. The beeswax was discharged at 100 gf of holding down force based on results of our previous trial study. The shape of pen tip was semispherical for becoming low friction between pen tip and surface of paper. We conducted one basic experiment to evaluate influence of the curvature of pen tip on ease to write. Concretely, the conditions of curvature was 0.15, 0.35, 0.50, 1.00 mm. The following four interval scales were used as indexes of subjective assessment during writing such as feeling of smooth motion of pen, feeling of comfortable writing, sense of security and feeling of writing fatigue. Ten subjects were asked to participate in this experiment. The results reveal that subjects could draw easily when the radius of the pen tip was 1.00 mm, and lines drawn with beeswax-discharge writing material were easy to perceive.

Keywords: beeswax-discharge writing material, raised-line drawing kits, visually impaired persons, pen tip

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81 Molecular Detection of Leishmania from the Phlebotomus Genus: Tendency towards Leishmaniasis Regression in Constantine, North-East of Algeria

Authors: K. Frahtia, I. Mihoubi, S. Picot

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Leishmaniasis is a group of parasitic disease with a varied clinical expression caused by flagellate protozoa of the Leishmania genus. These diseases are transmitted to humans and animals by the sting of a vector insect, the female sandfly. Among the groups of dipteral disease vectors, Phlebotominae occupy a prime position and play a significant role in human pathology, such as leishmaniasis that affects nearly 350 million people worldwide. The vector control operation launched by health services throughout the country proves to be effective since despite the prevalence of the disease remains high especially in rural areas, leishmaniasis appears to be declining in Algeria. In this context, this study mainly concerns molecular detection of Leishmania from the vector. Furthermore, a molecular diagnosis has also been made on skin samples taken from patients in the region of Constantine, located in the North-East of Algeria. Concerning the vector, 5858 sandflies were captured, including 4360 males and 1498 females. Male specimens were identified based on their morphological. The morphological identification highlighted the presence of the Phlebotomus genus with a prevalence of 93% against 7% represented by the Sergentomyia genus. About the identified species, P. perniciosus is the most abundant with 59.4% of the male identified population followed by P. longicuspis with 24.7% of the workforce. P. perfiliewi is poorly represented by 6.7% of specimens followed by P. papatasi with 2.2% and 1.5% S. dreyfussi. Concerning skin samples, 45/79 (56.96%) collected samples were found positive by real-time PCR. This rate appears to be in sharp decline compared to previous years (alert peak of 30,227 cases in 2005). Concerning the detection of Leishmania from sandflies by RT-PCR, the results show that 3/60 PCR performed genus are positive with melting temperatures corresponding to that of the reference strain (84.1 +/- 0.4 ° C for L. infantum). This proves that the vectors were parasitized. On the other side, identification by RT-PCR species did not give any results. This could be explained by the presence of an insufficient amount of leishmanian DNA in the vector, and therefore support the hypothesis of the regression of leishmaniasis in Constantine.

Keywords: Algeria, molecular diagnostic, phlebotomus, real time PCR

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80 Synthesis of Microencapsulated Phase Change Material for Adhesives with Thermoregulating Properties

Authors: Christin Koch, Andreas Winkel, Martin Kahlmeyer, Stefan Böhm

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Due to environmental regulations on greenhouse gas emissions and the depletion of fossil fuels, there is an increasing interest in electric vehicles.To maximize their driving range, batteries with high storage capacities are needed. In most electric cars, rechargeable lithium-ion batteries are used because of their high energy density. However, it has to be taken into account that these batteries generate a large amount of heat during the charge and discharge processes. This leads to a decrease in a lifetime and damage to the battery cells when the temperature exceeds the defined operating range. To ensure an efficient performance of the battery cells, reliable thermal management is required. Currently, the cooling is achieved by heat sinks (e.g., cooling plates) bonded to the battery cells with a thermally conductive adhesive (TCA) that directs the heat away from the components. Especially when large amounts of heat have to be dissipated spontaneously due to peak loads, the principle of heat conduction is not sufficient, so attention must be paid to the mechanism of heat storage. An efficient method to store thermal energy is the use of phase change materials (PCM). Through an isothermal phase change, PCM can briefly absorb or release thermal energy at a constant temperature. If the phase change takes place in the transition from solid to liquid, heat is stored during melting and is released to the ambient during the freezing process upon cooling. The presented work displays the great potential of thermally conductive adhesives filled with microencapsulated PCM to limit peak temperatures in battery systems. The encapsulation of the PCM avoids the effects of aging (e.g., migration) and chemical reactions between the PCM and the adhesive matrix components. In this study, microencapsulation has been carried out by in situ polymerization. The microencapsulated PCM was characterized by FT-IR spectroscopy, and the thermal properties were measured by DSC and laser flash method. The mechanical properties, electrical and thermal conductivity, and adhesive toughness of the TCA/PCM composite were also investigated.

Keywords: phase change material, microencapsulation, adhesive bonding, thermal management

Procedia PDF Downloads 72
79 Feasibility of Washing/Extraction Treatment for the Remediation of Deep-Sea Mining Trailings

Authors: Kyoungrean Kim

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Importance of deep-sea mineral resources is dramatically increasing due to the depletion of land mineral resources corresponding to increasing human’s economic activities. Korea has acquired exclusive exploration licenses at four areas which are the Clarion-Clipperton Fracture Zone in the Pacific Ocean (2002), Tonga (2008), Fiji (2011) and Indian Ocean (2014). The preparation for commercial mining of Nautilus minerals (Canada) and Lockheed martin minerals (USA) is expected by 2020. The London Protocol 1996 (LP) under International Maritime Organization (IMO) and International Seabed Authority (ISA) will set environmental guidelines for deep-sea mining until 2020, to protect marine environment. In this research, the applicability of washing/extraction treatment for the remediation of deep-sea mining tailings was mainly evaluated in order to present preliminary data to develop practical remediation technology in near future. Polymetallic nodule samples were collected at the Clarion-Clipperton Fracture Zone in the Pacific Ocean, then stored at room temperature. Samples were pulverized by using jaw crusher and ball mill then, classified into 3 particle sizes (> 63 µm, 63-20 µm, < 20 µm) by using vibratory sieve shakers (Analysette 3 Pro, Fritsch, Germany) with 63 µm and 20 µm sieve. Only the particle size 63-20 µm was used as the samples for investigation considering the lower limit of ore dressing process which is tens to 100 µm. Rhamnolipid and sodium alginate as biosurfactant and aluminum sulfate which are mainly used as flocculant were used as environmentally friendly additives. Samples were adjusted to 2% liquid with deionized water then mixed with various concentrations of additives. The mixture was stirred with a magnetic bar during specific reaction times and then the liquid phase was separated by a centrifugal separator (Thermo Fisher Scientific, USA) under 4,000 rpm for 1 h. The separated liquid was filtered with a syringe and acrylic-based filter (0.45 µm). The extracted heavy metals in the filtered liquid were then determined using a UV-Vis spectrometer (DR-5000, Hach, USA) and a heat block (DBR 200, Hach, USA) followed by US EPA methods (8506, 8009, 10217 and 10220). Polymetallic nodule was mainly composed of manganese (27%), iron (8%), nickel (1.4%), cupper (1.3 %), cobalt (1.3%) and molybdenum (0.04%). Based on remediation standards of various countries, Nickel (Ni), Copper (Cu), Cadmium (Cd) and Zinc (Zn) were selected as primary target materials. Throughout this research, the use of rhamnolipid was shown to be an effective approach for removing heavy metals in samples originated from manganese nodules. Sodium alginate might also be one of the effective additives for the remediation of deep-sea mining tailings such as polymetallic nodules. Compare to the use of rhamnolipid and sodium alginate, aluminum sulfate was more effective additive at short reaction time within 4 h. Based on these results, sequencing particle separation, selective extraction/washing, advanced filtration of liquid phase, water treatment without dewatering and solidification/stabilization may be considered as candidate technologies for the remediation of deep-sea mining tailings.

Keywords: deep-sea mining tailings, heavy metals, remediation, extraction, additives

Procedia PDF Downloads 155
78 Experimental and Numerical Investigation of Micro-Welding Process and Applications in Digital Manufacturing

Authors: Khaled Al-Badani, Andrew Norbury, Essam Elmshawet, Glynn Rotwell, Ian Jenkinson , James Ren

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Micro welding procedures are widely used for joining materials, developing duplex components or functional surfaces, through various methods such as Micro Discharge Welding or Spot Welding process, which can be found in the engineering, aerospace, automotive, biochemical, biomedical and numerous other industries. The relationship between the material properties, structure and processing is very important to improve the structural integrity and the final performance of the welded joints. This includes controlling the shape and the size of the welding nugget, state of the heat affected zone, residual stress, etc. Nowadays, modern high volume productions require the welding of much versatile shapes/sizes and material systems that are suitable for various applications. Hence, an improved understanding of the micro welding process and the digital tools, which are based on computational numerical modelling linking key welding parameters, dimensional attributes and functional performance of the weldment, would directly benefit the industry in developing products that meet current and future market demands. This paper will introduce recent work on developing an integrated experimental and numerical modelling code for micro welding techniques. This includes similar and dissimilar materials for both ferrous and non-ferrous metals, at different scales. The paper will also produce a comparative study, concerning the differences between the micro discharge welding process and the spot welding technique, in regards to the size effect of the welding zone and the changes in the material structure. Numerical modelling method for the micro welding processes and its effects on the material properties, during melting and cooling progression at different scales, will also be presented. Finally, the applications of the integrated numerical modelling and the material development for the digital manufacturing of welding, is discussed with references to typical application cases such as sensors (thermocouples), energy (heat exchanger) and automotive structures (duplex steel structures).

Keywords: computer modelling, droplet formation, material distortion, materials forming, welding

Procedia PDF Downloads 255
77 Formulation of Suppositories Using Allanblackia Floribunda Butter as a Base

Authors: Mary Konadu

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The rectal route for drug administration is becoming attractive to drug formulators because it can avoid hepatic first-pass effects, decrease gastrointestinal side effects and avoid undesirable effects of meals on drug absorption. Suppositories have been recognized as an alternative to the oral route in situations such as when the patient is comatose, unable to swallow, or when the drug produces nausea or vomiting. Effective drug delivery with appropriate pharmaceutical excipient is key in the production of clinically useful preparations. The high cost of available excipients coupled with other disadvantages have led to the exploration of potential excipients from natural sources. Allanblackia floribunda butter, a naturally occurring lipid, is used for medicinal, culinary, and cosmetic purposes. Different extraction methods (solvent (hexane) extraction, traditional/hot water extraction, and cold/screw press extraction) were employed to extract the oil. The different extracts of A. floribunda oil were analyzed for their physicochemical properties and mineral content. The oil was used as a base to formulate Paracetamol and Diclofenac suppositories. Quality control test were carried out on the formulated suppositories. The %age oil yield for hexane extract, hot water extract, and cold press extract were 50.40 ±0.00, 37.36±0.00, and 20.48±0.00, respectively. The acid value, saponification value, iodine value and free fatty acid were 1.159 ± 0.065, 208.51 ± 8.450, 49.877 ± 0.690 and 0.583 ± 0.032 respectively for hexane extract; 3.480 ± 0.055, 204.672±2.863, 49.04 ± 0.76 and 1.747 ± 0.028 respectively for hot water/traditional extract; 4.43 ± 0.055, 192.05±1.56, 49.96 ± 0.29 and 2.23 ± 0.03 respectively for cold press extract. Calcium, sodium, magnesium, potassium, and iron were minerals found to be present in the A. floribunda butter extracts. The uniformity of weight, hardness, disintegration time, and uniformity of content were found to be within the acceptable range. The melting point ranges for all the suppositories were found to be satisfactory. The cumulative drug release (%) of the suppositories at 45 minutes was 90.19±0.00 (Hot water extract), 93.75±0.00 (Cold Pres Extract), and 98.16±0.00 (Hexane Extract) for Paracetamol suppositories. Diclofenac sodium suppositories had a cumulative %age release of 81.60±0.00 (Hot water Extract), 95.33±0.00 (Cold Press Extract), and 99.20±0.00 (Hexane Extract). The physicochemical parameters obtained from this study shows that Allanblackia floribunda seed oil is edible and can be used as a suppository base. The suppository formulation was successful, and the quality control tests conformed to Pharmacopoeia standard.

Keywords: allanblackia foribunda, paracetamol, diclofenac, suppositories

Procedia PDF Downloads 122
76 Enhanced Kinetic Solubility Profile of Epiisopiloturine Solid Solution in Hipromellose Phthalate

Authors: Amanda C. Q. M. Vieira, Cybelly M. Melo, Camila B. M. Figueirêdo, Giovanna C. R. M. Schver, Salvana P. M. Costa, Magaly A. M. de Lyra, Ping I. Lee, José L. Soares-Sobrinho, Pedro J. Rolim-Neto, Mônica F. R. Soares

Abstract:

Epiisopiloturine (EPI) is a drug candidate that is extracted from Pilocarpus microphyllus and isolated from the waste of Pilocarpine. EPI has demonstrated promising schistosomicidal, leishmanicide, anti-inflammatory and antinociceptive activities, according to in vitro studies that have been carried out since 2009. However, this molecule shows poor aqueous solubility, which represents a problem for the release of the drug candidate and its absorption by the organism. The purpose of the present study is to investigate the extent of enhancement of kinetic solubility of a solid solution (SS) of EPI in hipromellose phthalate HP-55 (HPMCP), an enteric polymer carrier. SS was obtained by the solvent evaporation methodology, using acetone/methanol (60:40) as solvent system. Both EPI and polymer (drug loading 10%) were dissolved in this solvent until a clear solution was obtained, and then dried in oven at 60ºC during 12 hours, followed by drying in a vacuum oven for 4 h. The results show a considerable modification in the crystalline structure of the drug candidate. For instance, X-ray diffraction (XRD) shows a crystalline behavior for the EPI, which becomes amorphous for the SS. Polarized light microscopy, a more sensitive technique than XRD, also shows completely absence of crystals in SS sample. Differential Scanning Calorimetric (DSC) curves show no signal of EPI melting point in SS curve, indicating, once more, no presence of crystal in this system. Interaction between the drug candidate and the polymer were found in Infrared microscopy, which shows a carbonyl 43.3 cm-1 band shift, indicating a moderate-strong interaction between them, probably one of the reasons to the SS formation. Under sink conditions (pH 6.8), EPI SS had its dissolution performance increased in 2.8 times when compared with the isolated drug candidate. EPI SS sample provided a release of more than 95% of the drug candidate in 15 min, whereas only 45% of EPI (alone) could be dissolved in 15 min and 70% in 90 min. Thus, HPMCP demonstrates to have a good potential to enhance the kinetic solubility profile of EPI. Future studies to evaluate the stability of SS are required to conclude the benefits of this system.

Keywords: epiisopiloturine, hipromellose phthalate HP-55, pharmaceuticaltechnology, solubility

Procedia PDF Downloads 607
75 Development of a Wound Dressing Material Based on Microbial Polyhydroxybutyrate Electrospun Microfibers Containing Curcumin

Authors: Ariel Vilchez, Francisca Acevedo, Rodrigo Navia

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The wound healing process can be accelerated and improved by the action of antioxidants such as curcumin (Cur) over the tissues; however, the efficacy of curcumin used through the digestive system is not enough to exploit its benefits. Electrospinning presents an alternative to carry curcumin directly to the wounds, and polyhydroxybutyrate (PHB) is proposed as the matrix to load curcumin owing to its biodegradable and biocompatible properties. PHB is among 150 types of Polyhydroxyalkanoates (PHAs) identified, it is a natural thermoplastic polyester produced by microbial fermentation obtained from microorganisms. The proposed objective is to develop electrospun bacterial PHB-based microfibers containing curcumin for possible biomedical applications. Commercial PHB was solved in Chloroform: Dimethylformamide (4:1) to a final concentration of 7% m/V. Curcumin was added to the polymeric solution at 1%, and 7% m/m regarding PHB. The electrospinning equipment (NEU-BM, China) with a rotary collector was used to obtain Cur-PHB fibers at different voltages and flow rate of the polymeric solution considering a distance of 20 cm from the needle to the collector. Scanning electron microscopy (SEM) was used to determine the diameter and morphology of the obtained fibers. Thermal stability was obtained from Thermogravimetric (TGA) analysis, and Fourier Transform Infrared Spectroscopy (FT-IR) was carried out in order to study the chemical bonds and interactions. A preliminary curcumin release to Phosphate Buffer Saline (PBS) pH = 7.4 was obtained in vitro and measured by spectrophotometry. PHB fibers presented an intact chemical composition regarding the original condition (dust) according to FTIR spectra, the diameter fluctuates between 0.761 ± 0.123 and 2.157 ± 0.882 μm, with different qualities according to their morphology. The best fibers in terms of quality and diameter resulted in sample 2 and sample 6, obtained at 0-10kV and 0.5 mL/hr, and 0-10kV and 1.5 mL/hr, respectively. The melting temperature resulted near 178 °C, according to the bibliography. The crystallinity of fibers decreases while curcumin concentration increases for the studied interval. The curcumin release reaches near 14% at 37 °C at 54h in PBS adjusted to a quasi-Fickian Diffusion. We conclude that it is possible to load curcumin in PHB to obtain continuous, homogeneous, and solvent-free microfibers by electrospinning. Between 0% and 7% of curcumin, the crystallinity of fibers decreases as the concentration of curcumin increases. Thus, curcumin enhances the flexibility of the obtained material. HPLC should be used in further analysis of curcumin release.

Keywords: antioxidant, curcumin, polyhydroxybutyrate, wound healing

Procedia PDF Downloads 131
74 Identification of the Best Blend Composition of Natural Rubber-High Density Polyethylene Blends for Roofing Applications

Authors: W. V. W. H. Wickramaarachchi, S. Walpalage, S. M. Egodage

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Thermoplastic elastomer (TPE) is a multifunctional polymeric material which possesses a combination of excellent properties of parent materials. Basically, TPE has a rubber phase and a thermoplastic phase which gives processability as thermoplastics. When the rubber phase is partially or fully crosslinked in the thermoplastic matrix, TPE is called as thermoplastic elastomer vulcanizate (TPV). If the rubber phase is non-crosslinked, it is called as thermoplastic elastomer olefin (TPO). Nowadays TPEs are introduced into the commercial market with different products. However, the application of TPE as a roofing material is limited. Out of the commercially available roofing products from different materials, only single ply roofing membranes and plastic roofing sheets are produced from rubbers and plastics. Natural rubber (NR) and high density polyethylene (HDPE) are used in various industrial applications individually with some drawbacks. Therefore, this study was focused to develop both TPO and TPV blends from NR and HDPE at different compositions and then to identify the best blend composition to use as a roofing material. A series of blends by varying NR loading from 10 wt% to 50 wt%, at 10 wt% intervals, were prepared using a twin screw extruder. Dicumyl peroxide was used as a crosslinker for TPV. The standard properties for a roofing material like tensile properties tear strength, hardness, impact strength, water absorption, swell/gel analysis and thermal characteristics of the blends were investigated. Change of tensile strength after exposing to UV radiation was also studied. Tensile strength, hardness, tear strength, melting temperature and gel content of TPVs show higher values compared to TPOs at every loading studied, while water absorption and swelling index show lower values, suggesting TPVs are more suitable than TPOs for roofing applications. Most of the optimum properties were shown at 10/90 (NR/HDPE) composition. However, high impact strength and gel content were shown at 20/80 (NR/HDPE) composition. Impact strength, as being an energy absorbing property, is the most important for a roofing material in order to resist impact loads. Therefore, 20/80 (NR/HDPE) is identified as the best blend composition. UV resistance and other properties required for a roofing material could be achieved by incorporating suitable additives to TPVs.

Keywords: thermoplastic elastomer, natural rubber, high density polyethylene, roofing material

Procedia PDF Downloads 126
73 A PHREEQC Reactive Transport Simulation for Simply Determining Scaling during Desalination

Authors: Andrew Freiburger, Sergi Molins

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Freshwater is a vital resource; yet, the supply of clean freshwater is diminishing as the consequence of melting snow and ice from global warming, pollution from industry, and an increasing demand from human population growth. The unsustainable trajectory of diminishing water resources is projected to jeopardize water security for billions of people in the 21st century. Membrane desalination technologies may resolve the growing discrepancy between supply and demand by filtering arbitrary feed water into a fraction of renewable, clean water and a fraction of highly concentrated brine. The leading hindrance of membrane desalination is fouling, whereby the highly concentrated brine solution encourages micro-organismal colonization and/or the precipitation of occlusive minerals (i.e. scale) upon the membrane surface. Thus, an understanding of brine formation is necessary to mitigate membrane fouling and to develop efficacious desalination technologies that can bolster the supply of available freshwater. This study presents a reactive transport simulation of brine formation and scale deposition during reverse osmosis (RO) desalination. The simulation conceptually represents the RO module as a one-dimensional domain, where feed water directionally enters the domain with a prescribed fluid velocity and is iteratively concentrated in the immobile layer of a dual porosity model. Geochemical PHREEQC code numerically evaluated the conceptual model with parameters for the BW30-400 RO module and for real water feed sources – e.g. the Red and Mediterranean seas, and produced waters from American oil-wells, based upon peer-review data. The presented simulation is computationally simpler, and hence less resource intensive, than the existent and more rigorous simulations of desalination phenomena, like TOUGHREACT. The end-user may readily prepare input files and execute simulations on a personal computer with open source software. The graphical results of fouling-potential and brine characteristics may therefore be particularly useful as the initial tool for screening candidate feed water sources and/or informing the selection of an RO module.

Keywords: desalination, PHREEQC, reactive transport, scaling

Procedia PDF Downloads 136
72 Petrogenesis and Tectonic Implication of the Oligocene Na-Rich Granites from the North Sulawesi Arc, Indonesia

Authors: Xianghong Lu, Yuejun Wang, Chengshi Gan, Xin Qian

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The North Sulawesi Arc, located on the east of Indonesia and to the south of the Celebes Sea, is the north part of the K-shape of Sulawesi Island and has a complex tectonic history since the Cenozoic due to the convergence of three plates (Eurasia, India-Australia and Pacific plates). Published rock records contain less precise chronology, mostly using K-Ar dating, and rare geochemistry data, which limit the understanding of the regional tectonic setting. This study presents detailed zircon U-Pb geochronological and Hf-O isotope and whole-rock geochemical analyses for the Na-rich granites from the North Sulawesi Arc. Zircon U-Pb geochronological analyses of three representative samples yield weighted mean ages of 30.4 ± 0.4 Ma, 29.5 ± 0.2 Ma, and 27.3 ± 0.4 Ma, respectively, revealing the Oligocene magmatism in the North Sulawesi Arc. The samples have high Na₂O and low K₂O contents with high Na₂O/K₂O ratios, belonging to Low-K tholeiitic Na-rich granites. The Na-rich granites are characterized by high SiO₂ contents (75.05-79.38 wt.%) and low MgO contents (0.07-0.91 wt.%) and show arc-like trace elemental signatures. They have low (⁸⁷Sr/⁸⁶Sr)i ratios (0.7044-0.7046), high εNd(t) values (from +5.1 to +6.6), high zircon εHf(t) values (from +10.1 to +18.8) and low zircon δ18O values (3.65-5.02). They show an Indian-Ocean affinity of Pb isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb ratio of 18.16-18.37, ²⁰⁷Pb/²⁰⁴Pb ratio of 15.56-15.62, and ²⁰⁸Pb/²⁰⁴Pb ratio of 38.20-38.66. These geochemical signatures suggest that the Oligocene Na-rich granites from the North Sulawesi Arc formed by partial melting of the juvenile oceanic crust with sediment-derived fluid-related metasomatism in a subducting setting and support an intra-oceanic arc origin. Combined with the published study, the emergence of extensive calc-alkaline felsic arc magmatism can be traced back to the Early Oligocene period, subsequent to the Eocene back-arc basalts (BAB) that share similarity with the Celebes Sea basement. Since the opening of the Celebes Sea started from the Eocene (42~47 Ma) and stopped by the Early Oligocene (~32 Ma), the geodynamical mechanism of the formation of the Na-rich granites from the North Sulawesi Arc during the Oligocene might relate to the subduction of the Indian Ocean.

Keywords: North Sulawesi Arc, oligocene, Na-rich granites, in-situ zircon Hf–O analysis, intra-oceanic origin

Procedia PDF Downloads 76
71 Mechanical, Thermal and Biodegradable Properties of Bioplast-Spruce Green Wood Polymer Composites

Authors: A. Atli, K. Candelier, J. Alteyrac

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Environmental and sustainability concerns push the industries to manufacture alternative materials having less environmental impact. The Wood Plastic Composites (WPCs) produced by blending the biopolymers and natural fillers permit not only to tailor the desired properties of materials but also are the solution to meet the environmental and sustainability requirements. This work presents the elaboration and characterization of the fully green WPCs prepared by blending a biopolymer, BIOPLAST® GS 2189 and spruce sawdust used as filler with different amounts. Since both components are bio-based, the resulting material is entirely environmentally friendly. The mechanical, thermal, structural properties of these WPCs were characterized by different analytical methods like tensile, flexural and impact tests, Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and X-ray Diffraction (XRD). Their water absorption properties and resistance to the termite and fungal attacks were determined in relation with different wood filler content. The tensile and flexural moduli of WPCs increased with increasing amount of wood fillers into the biopolymer, but WPCs became more brittle compared to the neat polymer. Incorporation of spruce sawdust modified the thermal properties of polymer: The degradation, cold crystallization, and melting temperatures shifted to higher temperatures when spruce sawdust was added into polymer. The termite, fungal and water absorption resistance of WPCs decreased with increasing wood amount in WPCs, but remained in durability class 1 (durable) concerning fungal resistance and quoted 1 (attempted attack) in visual rating regarding to the termites resistance except that the WPC with the highest wood content (30 wt%) rated 2 (slight attack) indicating a long term durability. All the results showed the possibility to elaborate the easy injectable composite materials with adjustable properties by incorporation of BIOPLAST® GS 2189 and spruce sawdust. Therefore, lightweight WPCs allow both to recycle wood industry byproducts and to produce a full ecologic material.

Keywords: biodegradability, color measurements, durability, mechanical properties, melt flow index, MFI, structural properties, thermal properties, wood-plastic composites, WPCs

Procedia PDF Downloads 137
70 Mechanism of Action of New Sustainable Flame Retardant Additives in Polyamide 6,6

Authors: I. Belyamani, M. K. Hassan, J. U. Otaigbe, W. R. Fielding, K. A. Mauritz, J. S. Wiggins, W. L. Jarrett

Abstract:

We have investigated the flame-retardant efficiency of special new phosphate glass (P-glass) compositions having different glass transition temperatures (Tg) on the processing conditions of polyamide 6,6 (PA6,6) and the final hybrid flame retardancy (FR). We have showed that the low Tg P glass composition (i.e., ILT 1) is a promising flame retardant for PA6,6 at a concentration of up to 15 wt. % compared to intermediate (IIT 3) and high (IHT 1) Tg P glasses. Cone calorimetry data showed that the ILT 1 decreased both the peak heat release rate and the total heat amount released from the PA6,6/ILT 1 hybrids, resulting in an efficient formation of a glassy char layer. These intriguing findings prompted to address several questions concerning the mechanism of action of the different P glasses studied. The general mechanism of action of phosphorous based FR additives occurs during the combustion stage by enhancing the morphology of the char and the thermal shielding effect. However, the present work shows that P glass based FR additives act during melt processing of PA6,6/P glass hybrids. Dynamic mechanical analysis (DMA) revealed that the Tg of PA6,6/ILT 1 was significantly shifted to a lower Tg (~65 oC) and another transition appeared at high temperature (~ 166 oC), thus indicating a strong interaction between PA6,6 and ILT 1. This was supported by a drop in the melting point and crystallinity of the PA6,6/ILT 1 hybrid material as detected by differential scanning calorimetry (DSC). The dielectric spectroscopic investigation of the networks’ molecular level structural variations (i.e. hybrids chain motion, Tg and sub-Tg relaxations) agreed very well with the DMA and DSC findings; it was found that the three different P glass compositions did not show any effect on the PA6,6 sub-Tg relaxations (related to the NH2 and OH chain end groups motions). Nevertheless, contrary to IIT 3 and IHT 1 based hybrids, the PA6,6/ILT 1 hybrid material showed an evidence of splitting the PA6,6 Tg relaxations into two peaks. Finally, the CPMAS 31P-NMR data confirmed the miscibility between ILT 1 and PA6,6 at the molecular level, as a much larger enhancement in cross-polarization for the PA6,6/15%ILT 1 hybrids was observed. It can be concluded that compounding low Tg P-glass (i.e. ILT 1) with PA6,6 facilitates hydrolytic chain scission of the PA6,6 macromolecules through a potential chemical interaction between phosphate and the alpha-Carbon of the amide bonds of the PA6,6, leading to better flame retardant properties.

Keywords: broadband dielectric spectroscopy, composites, flame retardant, polyamide, phosphate glass, sustainable

Procedia PDF Downloads 236
69 The Microstructure and Corrosion Behavior of High Entropy Metallic Layers Electrodeposited by Low and High-Temperature Methods

Authors: Zbigniew Szklarz, Aldona Garbacz-Klempka, Magdalena Bisztyga-Szklarz

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Typical metallic alloys bases on one major alloying component, where the addition of other elements is intended to improve or modify certain properties, most of all the mechanical properties. However, in 1995 a new concept of metallic alloys was described and defined. High Entropy Alloys (HEA) contains at least five alloying elements in an amount from 5 to 20 at.%. A common feature this type of alloys is an absence of intermetallic phases, high homogeneity of the microstructure and unique chemical composition, what leads to obtaining materials with very high strength indicators, stable structures (also at high temperatures) and excellent corrosion resistance. Hence, HEA can be successfully used as a substitutes for typical metallic alloys in various applications where a sufficiently high properties are desirable. For fabricating HEA, a few ways are applied: 1/ from liquid phase i.e. casting (usually arc melting); 2/ from solid phase i.e. powder metallurgy (sintering methods preceded by mechanical synthesis) and 3/ from gas phase e.g. sputtering or 4/ other deposition methods like electrodeposition from liquids. Application of different production methods creates different microstructures of HEA, which can entail differences in their properties. The last two methods also allows to obtain coatings with HEA structures, hereinafter referred to as High Entropy Films (HEF). With reference to above, the crucial aim of this work was the optimization of the manufacturing process of the multi-component metallic layers (HEF) by the low- and high temperature electrochemical deposition ( ED). The low-temperature deposition process was crried out at ambient or elevated temperature (up to 100 ᵒC) in organic electrolyte. The high-temperature electrodeposition (several hundred Celcius degrees), in turn, allowed to form the HEF layer by electrochemical reduction of metals from molten salts. The basic chemical composition of the coatings was CoCrFeMnNi (known as Cantor’s alloy). However, it was modified by other, selected elements like Al or Cu. The optimization of the parameters that allow to obtain as far as it possible homogeneous and equimolar composition of HEF is the main result of presented studies. In order to analyse and compare the microstructure, SEM/EBSD, TEM and XRD techniques were employed. Morover, the determination of corrosion resistance of the CoCrFeMnNi(Cu or Al) layers in selected electrolytes (i.e. organic and non-organic liquids) was no less important than the above mentioned objectives.

Keywords: high entropy alloys, electrodeposition, corrosion behavior, microstructure

Procedia PDF Downloads 80
68 Crisis In/Out, Emergent, and Adaptive Urban Organisms

Authors: Alessandra Swiny, Michalis Georgiou, Yiorgos Hadjichristou

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This paper focuses on the questions raised through the work of Unit 5: ‘In/Out of crisis, emergent and adaptive’; an architectural research-based studio at the University of Nicosia. It focusses on sustainable architectural and urban explorations tackling with the ever growing crises in its various types, phases and locations. ‘Great crisis situations’ are seen as ‘great chances’ that trigger investigations for further development and evolution of the built environment in an ultimate sustainable approach. The crisis is taken as an opportunity to rethink the urban and architectural directions as new forces for inventions leading to emergent and adaptive built environments. The Unit 5’s identity and environment facilitates the students to respond optimistically, alternatively and creatively towards the global current crisis. Mark Wigley’s notion that “crises are ultimately productive” and “They force invention” intrigued and defined the premises of the Unit. ‘Weather and nature are coauthors of the built environment’ Jonathan Hill states in his ‘weather architecture’ discourse. The weather is constantly changing and new environments, the subnatures are created which derived from the human activities David Gissen explains. The above set of premises triggered innovative responses by the Unit’s students. They thoroughly investigated the various kinds of crisis and their causes in relation to their various types of Terrains. The tools used for the research and investigation were chosen in contradictive pairs to generate further crisis situations: The re-used/salvaged competed with the new, the handmade rivalling with the fabrication, the analogue juxtaposed with digital. Students were asked to delve into state of art technologies in order to propose sustainable emergent and adaptive architectures and Urbanities, having though always in mind that the human and the social aspects of the community should be the core of the investigation. The resulting unprecedented spatial conditions and atmospheres of the emergent new ways of living are deemed to be the ultimate aim of the investigation. Students explored a variety of sites and crisis conditions such as: The vague terrain of the Green Line in Nicosia, the lost footprints of the sinking Venice, the endangered Australian coral reefs, the earthquake torn town of Crevalcore, and the decaying concrete urbanscape of Athens. Among other projects, ‘the plume project’ proposes a cloud-like, floating and almost dream-like living environment with unprecedented spatial conditions to the inhabitants of the coal mine of Centralia, USA, not just to enable them to survive but even to prosper in this unbearable environment due to the process of the captured plumes of smoke and heat. Existing water wells inspire inversed vertical structures creating a new living underground network, protecting the nomads from catastrophic sand storms in the Araoune of Mali. “Inverted utopia: Lost things in the sand”, weaves a series of tea-houses and a library holding lost artifacts and transcripts into a complex underground labyrinth by the utilization of the sand solidification technology. Within this methodology, crisis is seen as a mechanism for allowing an emergence of new and fascinating ultimate sustainable future cultures and cities.

Keywords: adaptive built environments, crisis as opportunity, emergent urbanities, forces for inventions

Procedia PDF Downloads 429
67 Performance Improvement of Solar Thermal Cooling Systems Integrated with Encapsulated PCM

Authors: Lana Migla

Abstract:

Phase change materials (PCMs) have an important role in improving the efficiency of thermal heat storage. As these materials are characterized by low thermal conductivity, it is necessary to develop heat transfer techniques to improve their thermophysical properties. This scientific article focuses on the geometrical configurations of encapsulated PCM containers and the impact of designs to improve the performance of the solar thermal cooling system. The literature review showed that in-depth research is being conducted on different methods of improving the efficiency of PCM heat transfer, which is the main design task for the containers. Techniques such as microencapsulated PCMs, adding fins and different combinations of fins and nanoparticles are used. The use of graphite, metal foam and doping of high photothermal materials is also being studied. To determine most efficient container configuration, the article looks at different designs of PCM containers with fins for the storage tank. This paper experimentally investigates the effect of the encapsulation design on the performance of a lab-scale thermal energy storage tank. The development of optimized energy storage with integrated phase change material containers reduces auxiliary heater energy consumption, increases the COP of the solar cooling system, and reduces the environmental impact of the cooling system. The review shows that in the cylindrical construction, the ratio between the radius of shell and tube is significant, which means this ratio is the main issue to enhance transfer efficiency and to increase the value of stored heat. Therefore, three cylindrical tube containers with different radiuses 20mm, 35mm, 50mm filled with commercial phase change material were tested. The results show that using a smaller radius achieved a higher power, leading to a reduction in the charging and discharging time. The three fins were added to the selected cylindrical tube to determine their effects on heat exchanging efficiency. The observed optimized performance given by the fin’s arrangement achieved a 40% reduction of PCM's melting time compared to the heat exchanging without fins. The exact dimensions of the PCM containers and fins placements will be presented on-site.

Keywords: energy performance, PCM containers, solar thermal cooling, storage tank

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66 Structural Property and Mechanical Behavior of Polypropylene–Elemental Sulfur (S8) Composites: Effect of Sulfur Loading

Authors: S. Vijay Kumar, Kishore K. Jena, Saeed M. Alhassan

Abstract:

Elemental sulfur is currently produced on the level of 70 million tons annually by petroleum refining, majority of which is used in the production of sulfuric acid, fertilizer and other chemicals. Still, over 6 million tons of elemental sulfur is generated in excess, which creates exciting opportunities to develop new chemistry to utilize sulfur as a feedstock for polymers. Development of new polymer composite materials using sulfur is not widely explored and remains an important challenge in the field. Polymer nanocomposites prepared by carbon nanotube, graphene, silica and other nanomaterials were well established. However, utilization of sulfur as filler in the polymer matrix could be an interesting study. This work is to presents the possibility of utilizing elemental sulfur as reinforcing fillers in the polymer matrix. In this study we attempted to prepare polypropylene/sulfur nanocomposite. The physical, mechanical and morphological properties of the newly developed composites were studied according to the sulfur loading. In the sample preparation, four levels of elemental sulfur loading (5, 10, 20 and 30 wt. %) were designed. Composites were prepared by the melt mixing process by using laboratory scale mini twin screw extruder at 180°C for 15 min. The reaction time and temperature were maintained constant for all prepared composites. The structure and crystallization behavior of composites was investigated by Raman, FTIR, XRD and DSC analysis. It was observed that sulfur interfere with the crystalline arrangement of polypropylene and depresses the crystallization, which affects the melting point, mechanical and thermal stability. In the tensile test, one level of test temperature (room temperature) and crosshead speed (10 mm/min) was designed. Tensile strengths and tensile modulus of the composites were slightly decreased with increasing in filler loading, however, percentage of elongation improved by more than 350% compared to neat polypropylene. The effect of sulfur on the morphology of polypropylene was studied with TEM and SEM techniques. Microscope analysis revels that sulfur is homogeneously dispersed in polymer matrix and behaves as single phase arrangement in the polymer. The maximum elongation for the polypropylene can be achieved by adjusting the sulfur loading in the polymer. This study reviles the possibility of using elemental sulfur as a solid plasticizer in the polypropylene matrix.

Keywords: crystallization, elemental sulfur, morphology, thermo-mechanical properties, polypropylene, polymer nanocomposites

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65 QSAR Study on Diverse Compounds for Effects on Thermal Stability of a Monoclonal Antibody

Authors: Olubukayo-Opeyemi Oyetayo, Oscar Mendez-Lucio, Andreas Bender, Hans Kiefer

Abstract:

The thermal melting curve of a protein provides information on its conformational stability and could provide cues on its aggregation behavior. Naturally-occurring osmolytes have been shown to improve the thermal stability of most proteins in a concentration-dependent manner. They are therefore commonly employed as additives in therapeutic protein purification and formulation. A number of intertwined and seemingly conflicting mechanisms have been put forward to explain the observed stabilizing effects, the most prominent being the preferential exclusion mechanism. We attempted to probe and summarize molecular mechanisms for thermal stabilization of a monoclonal antibody (mAb) by developing quantitative structure-activity relationships using a rationally-selected library of 120 osmolyte-like compounds in the polyhydric alcohols, amino acids and methylamines classes. Thermal stabilization potencies were experimentally determined by thermal shift assays based on differential scanning fluorimetry. The cross-validated QSAR model was developed by partial least squares regression using descriptors generated from Molecular Operating Environment software. Careful evaluation of the results with the use of variable importance in projection parameter (VIP) and regression coefficients guided the selection of the most relevant descriptors influencing mAb thermal stability. For the mAb studied and at pH 7, the thermal stabilization effects of tested compounds correlated positively with their fractional polar surface area and inversely with their fractional hydrophobic surface area. We cannot claim that the observed trends are universal for osmolyte-protein interactions because of protein-specific effects, however this approach should guide the quick selection of (de)stabilizing compounds for a protein from a chemical library. Further work with a large variety of proteins and at different pH values would help the derivation of a solid explanation as to the nature of favorable osmolyte-protein interactions for improved thermal stability. This approach may be beneficial in the design of novel protein stabilizers with optimal property values, especially when the influence of solution conditions like the pH and buffer species and the protein properties are factored in.

Keywords: thermal stability, monoclonal antibodies, quantitative structure-activity relationships, osmolytes

Procedia PDF Downloads 331