Search results for: cobalt oxide nano balls
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 2575

Search results for: cobalt oxide nano balls

85 Controlled Synthesis of Pt₃Sn-SnOx/C Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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84 Composition and Catalytic Behaviour of Biogenic Iron Containing Materials Obtained by Leptothrix Bacteria Cultivation in Different Growth Media

Authors: M. Shopska, D. Paneva, G. Kadinov, Z. Cherkezova-Zheleva, I. Mitov

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The iron containing materials are used as catalysts in different processes. The chemical methods of their synthesis use toxic and expensive chemicals; sophisticated devices; energy consumption processes that raise their cost. Besides, dangerous waste products are formed. At present time such syntheses are out of date and wasteless technologies are indispensable. The bioinspired technologies are consistent with the ecological requirements. Different microorganisms participate in the biomineralization of the iron and some phytochemicals are involved, too. The methods for biogenic production of iron containing materials are clean, simple, nontoxic, realized at ambient temperature and pressure, cheaper. The biogenic iron materials embrace different iron compounds. Due to their origin these substances are nanosized, amorphous or poorly crystalline, porous and have number of useful properties like SPM, high magnetism, low toxicity, biocompatibility, absorption of microwaves, high surface area/volume ratio, active sites on the surface with unusual coordination that distinguish them from the bulk materials. The biogenic iron materials are applied in the heterogeneous catalysis in different roles - precursor, active component, support, immobilizer. The application of biogenic iron oxide materials gives rise to increased catalytic activity in comparison with those of abiotic origin. In our study we investigated the catalytic behavior of biomasses obtained by cultivation of Leptothrix bacteria in three nutrition media – Adler, Fedorov, and Lieske. The biomass composition was studied by Moessbauer spectroscopy and transmission IRS. Catalytic experiments on CO oxidation were carried out using in situ DRIFTS. Our results showed that: i) the used biomasses contain α-FeOOH, γ-FeOOH, γ-Fe2O3 in different ratios; ii) the biomass formed in Adler medium contains γ-FeOOH as main phase. The CO conversion was about 50% as evaluated by decreased integrated band intensity in the gas mixture spectra during the reaction. The main phase in the spent sample is γ-Fe2O3; iii) the biomass formed in Lieske medium contains α-FeOOH. The CO conversion was about 20%. The main phase in the spent sample is α-Fe2O3; iv) the biomass formed in Fedorov medium contains γ-Fe2O3 as main phase. CO conversion in the test reaction was about 19%. The results showed that the catalytic activity up to 200°C resulted predominantly from α-FeOOH and γ-FeOOH. The catalytic activity at temperatures higher than 200°C was due to the formation of γ-Fe2O3. The oxyhydroxides, which are the principal compounds in the biomass, have low catalytic activity in the used reaction; the maghemite has relatively good catalytic activity; the hematite has activity commensurate with that of the oxyhydroxides. Moreover it can be affirmed that catalytic activity is inherent in maghemite, which is obtained by transformation of the biogenic lepidocrocite, i.e. it has biogenic precursor.

Keywords: nanosized biogenic iron compounds, catalytic behavior in reaction of CO oxidation, in situ DRIFTS, Moessbauer spectroscopy

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83 The Effect of the Precursor Powder Size on the Electrical and Sensor Characteristics of Fully Stabilized Zirconia-Based Solid Electrolytes

Authors: Olga Yu Kurapova, Alexander V. Shorokhov, Vladimir G. Konakov

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Nowadays, due to their exceptional anion conductivity at high temperatures cubic zirconia solid solutions, stabilized by rare-earth and alkaline-earth metal oxides, are widely used as a solid electrolyte (SE) materials in different electrochemical devices such as gas sensors, oxygen pumps, solid oxide fuel cells (SOFC), etc. Nowadays the intensive studies are carried out in a field of novel fully stabilized zirconia based SE development. The use of precursor powders for SE manufacturing allows predetermining the microstructure, electrical and sensor characteristics of zirconia based ceramics used as SE. Thus the goal of the present work was the investigation of the effect of precursor powder size on the electrical and sensor characteristics of fully stabilized zirconia-based solid electrolytes with compositions of 0,08Y2O3∙0,92ZrO2 (YSZ), 0,06Ce2O3∙ 0,06Y2O3∙0,88ZrO2 and 0,09Ce2O3∙0,06Y2O3-0,85ZrO2. The synthesis of precursors powders with different mean particle size was performed by sol-gel synthesis in the form of reversed co-precipitation from aqueous solutions. The cakes were washed until the neutral pH and pan-dried at 110 °С. Also, YSZ ceramics was obtained by conventional solid state synthesis including milling into a planetary mill. Then the powder was cold pressed into the pellets with a diameter of 7.2 and ~4 mm thickness at P ~16 kg/cm2 and then hydrostatically pressed. The pellets were annealed at 1600 °С for 2 hours. The phase composition of as-synthesized SE was investigated by X-Ray photoelectron spectroscopy ESCA (spectrometer ESCA-5400, PHI) X-ray diffraction analysis - XRD (Shimadzu XRD-6000). Following galvanic cell О2 (РО2(1)), Pt | SE | Pt, (РО2(2) = 0.21 atm) was used for SE sensor properties investigation. The value of РО2(1) was set by mixing of O2 and N2 in the defined proportions with the accuracy of  5%. The temperature was measured by Pt/Pt-10% Rh thermocouple, The cell electromotive force (EMF) measurement was carried out with ± 0.1 mV accuracy. During the operation at the constant temperature, reproducibility was better than 5 mV. Asymmetric potential measured for all SE appeared to be negligible. It was shown that the resistivity of YSZ ceramics decreases in about two times upon the mean agglomerates decrease from 200-250 to 40 nm. It is likely due to the both surface and bulk resistivity decrease in grains. So the overall decrease of grain size in ceramic SE results in the significant decrease of the total ceramics resistivity allowing sensor operation at lower temperatures. For the SE manufactured the estimation of oxygen ion transfer number tion was carried out in the range 600-800 °С. YSZ ceramics manufactured from powders with the mean particle size 40-140 nm, shows the highest values i.e. 0.97-0.98. SE manufactured from precursors with the mean particle size 40-140 nm shows higher sensor characteristic i.e. temperature and oxygen concentration EMF dependencies, EMF (ENernst - Ereal), tion, response time, then ceramics, manufactured by conventional solid state synthesis.

Keywords: oxygen sensors, precursor powders, sol-gel synthesis, stabilized zirconia ceramics

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82 Low-Temperature Poly-Si Nanowire Junctionless Thin Film Transistors with Nickel Silicide

Authors: Yu-Hsien Lin, Yu-Ru Lin, Yung-Chun Wu

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This work demonstrates the ultra-thin poly-Si (polycrystalline Silicon) nanowire junctionless thin film transistors (NWs JL-TFT) with nickel silicide contact. For nickel silicide film, this work designs to use two-step annealing to form ultra-thin, uniform and low sheet resistance (Rs) Ni silicide film. The NWs JL-TFT with nickel silicide contact exhibits the good electrical properties, including high driving current (>10⁷ Å), subthreshold slope (186 mV/dec.), and low parasitic resistance. In addition, this work also compares the electrical characteristics of NWs JL-TFT with nickel silicide and non-silicide contact. Nickel silicide techniques are widely used for high-performance devices as the device scaling due to the source/drain sheet resistance issue. Therefore, the self-aligned silicide (salicide) technique is presented to reduce the series resistance of the device. Nickel silicide has several advantages including low-temperature process, low silicon consumption, no bridging failure property, smaller mechanical stress, and smaller contact resistance. The junctionless thin-film transistor (JL-TFT) is fabricated simply by heavily doping the channel and source/drain (S/D) regions simultaneously. Owing to the special doping profile, JL-TFT has some advantages such as lower thermal the budget which can integrate with high-k/metal-gate easier than conventional MOSFETs (Metal Oxide Semiconductor Field-Effect Transistors), longer effective channel length than conventional MOSFETs, and avoidance of complicated source/drain engineering. To solve JL-TFT has turn-off problem, JL-TFT needs ultra-thin body (UTB) structure to reach fully depleted channel region in off-state. On the other hand, the drive current (Iᴅ) is declined as transistor features are scaled. Therefore, this work demonstrates ultra thin poly-Si nanowire junctionless thin film transistors with nickel silicide contact. This work investigates the low-temperature formation of nickel silicide layer by physical-chemical deposition (PVD) of a 15nm Ni layer on the poly-Si substrate. Notably, this work designs to use two-step annealing to form ultrathin, uniform and low sheet resistance (Rs) Ni silicide film. The first step was promoted Ni diffusion through a thin interfacial amorphous layer. Then, the unreacted metal was lifted off after the first step. The second step was annealing for lower sheet resistance and firmly merged the phase.The ultra-thin poly-Si nanowire junctionless thin film transistors NWs JL-TFT with nickel silicide contact is demonstrated, which reveals high driving current (>10⁷ Å), subthreshold slope (186 mV/dec.), and low parasitic resistance. In silicide film analysis, the second step of annealing was applied to form lower sheet resistance and firmly merge the phase silicide film. In short, the NWs JL-TFT with nickel silicide contact has exhibited a competitive short-channel behavior and improved drive current.

Keywords: poly-Si, nanowire, junctionless, thin-film transistors, nickel silicide

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81 Production of Nanocomposite Electrical Contact Materials Ag-SnO2, W-Cu and Cu-C in Thermal Plasma

Authors: A. V. Samokhin, A. A. Fadeev, M. A. Sinaiskii, N. V. Alekseev, A. V. Kolesnikov

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Composite materials where metal matrix is reinforced by ceramic or metal particles are of great interest for use in the manufacturing of electrical contacts. Significant improvement of the composite physical and mechanical properties as well as increase of the performance parameters of composite-based products can be achieved if the nanoscale structure in the composite materials is obtained by using nanosized powders as starting components. The results of nanosized composite powders synthesis (Ag-SnO2, W-Cu and Cu-C) in the DC thermal plasma flows are presented in this paper. The investigations included the following processes: - Recondensation of micron powder mixture Ag + SnO2 in a nitrogen plasma; - The reduction of the oxide powders mixture (WO3 + CuO) in a hydrogen-nitrogen plasma; - Decomposition of the copper formate and copper acetate powders in nitrogen plasma. The calculations of equilibrium compositions of multicomponent systems Ag-Sn-O-N, W-Cu-O-H-N and Cu-O-C-H-N in the temperature range of 400-5000 K were carried to estimate basic process characteristics. Experimental studies of the processes were performed using a plasma reactor with a confined jet flow. The plasma jet net power was in the range of 2 - 13 kW, and the feedstock flow rate was up to 0.35 kg/h. The obtained powders were characterized by TEM, HR-TEM, SEM, EDS, ED-XRF, XRD, BET and QEA methods. Nanocomposite Ag-SnO2 (12 wt. %). Processing of the initial powder mixture (Ag-SnO2) in nitrogen thermal plasma stream allowed to produce nanopowders with a specific surface area up to 24 m2/g, consisting predominantly of particles with size less than 100 nm. According to XRD results, tin was present in the obtained products as SnO2 phase, and also as intermetallic phases AgxSn. Nanocomposite W-Cu (20 wt .%). Reduction of (WO3+CuO) mixture in the hydrogen-nitrogen plasma provides W-Cu nanopowder with particle sizes in the range of 10-150 nm. The particles have mainly spherical shape and structure tungsten core - copper shell. The thickness of the shell is about several nanometers, the shell is composed of copper and its oxides (Cu2O, CuO). The nanopowders had 1.5 wt. % oxygen impurity. Heat treatment in a hydrogen atmosphere allows to reduce the oxygen content to less than 0.1 wt. %. Nanocomposite Cu-C. Copper nanopowders were found as products of the starting copper compounds decomposition. The nanopowders primarily had a spherical shape with a particle size of less than 100 nm. The main phase was copper, with small amount of Cu2O and CuO oxides. Copper formate decomposition products had a specific surface area 2.5-7 m2/g and contained 0.15 - 4 wt. % carbon; and copper acetate decomposition products had the specific surface area 5-35 m2/g, and carbon content of 0.3 - 5 wt. %. Compacting of nanocomposites (sintering in hydrogen for Ag-SnO2 and electric spark sintering (SPS) for W-Cu) showed that the samples having a relative density of 97-98 % can be obtained with a submicron structure. The studies indicate the possibility of using high-intensity plasma processes to create new technologies to produce nanocomposite materials for electric contacts.

Keywords: electrical contact, material, nanocomposite, plasma, synthesis

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80 Interdigitated Flexible Li-Ion Battery by Aerosol Jet Printing

Authors: Yohann R. J. Thomas, Sébastien Solan

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Conventional battery technology includes the assembly of electrode/separator/electrode by standard techniques such as stacking or winding, depending on the format size. In that type of batteries, coating or pasting techniques are only used for the electrode process. The processes are suited for large scale production of batteries and perfectly adapted to plenty of application requirements. Nevertheless, as the demand for both easier and cost-efficient production modes, flexible, custom-shaped and efficient small sized batteries is rising. Thin-film, printable batteries are one of the key areas for printed electronics. In the frame of European BASMATI project, we are investigating the feasibility of a new design of lithium-ion battery: interdigitated planar core design. Polymer substrate is used to produce bendable and flexible rechargeable accumulators. Direct fully printed batteries lead to interconnect the accumulator with other electronic functions for example organic solar cells (harvesting function), printed sensors (autonomous sensors) or RFID (communication function) on a common substrate to produce fully integrated, thin and flexible new devices. To fulfill those specifications, a high resolution printing process have been selected: Aerosol jet printing. In order to fit with this process parameters, we worked on nanomaterials formulation for current collectors and electrodes. In addition, an advanced printed polymer-electrolyte is developed to be implemented directly in the printing process in order to avoid the liquid electrolyte filling step and to improve safety and flexibility. Results: Three different current collectors has been studied and printed successfully. An ink of commercial copper nanoparticles has been formulated and printed, then a flash sintering was applied to the interdigitated design. A gold ink was also printed, the resulting material was partially self-sintered and did not require any high temperature post treatment. Finally, carbon nanotubes were also printed with a high resolution and well defined patterns. Different electrode materials were formulated and printed according to the interdigitated design. For cathodes, NMC and LFP were efficaciously printed. For anodes, LTO and graphite have shown to be good candidates for the fully printed battery. The electrochemical performances of those materials have been evaluated in a standard coin cell with lithium-metal counter electrode and the results are similar with those of a traditional ink formulation and process. A jellified plastic crystal solid state electrolyte has been developed and showed comparable performances to classical liquid carbonate electrolytes with two different materials. In our future developments, focus will be put on several tasks. In a first place, we will synthesize and formulate new specific nano-materials based on metal-oxyde. Then a fully printed device will be produced and its electrochemical performance will be evaluated.

Keywords: high resolution digital printing, lithium-ion battery, nanomaterials, solid-state electrolytes

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79 The Product Innovation Using Nutraceutical Delivery System on Improving Growth Performance of Broiler

Authors: Kitti Supchukun, Kris Angkanaporn, Teerapong Yata

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The product innovation using a nutraceutical delivery system on improving the growth performance of broilers is the product planning and development to solve the antibiotics banning policy incurred in the local and global livestock production system. Restricting the use of antibiotics can reduce the quality of chicken meat and increase pathogenic bacterial contamination. Although other alternatives were used to replace antibiotics, the efficacy was inconsistent, reflecting on low chicken growth performance and contaminated products. The product innovation aims to effectively deliver the selected active ingredients into the body. This product is tested on the pharmaceutical lab scale and on the farm-scale for market feasibility in order to create product innovation using the nutraceutical delivery system model. The model establishes the product standardization and traceable quality control process for farmers. The study is performed using mixed methods. Starting with a qualitative method to find the farmers' (consumers) demands and the product standard, then the researcher used the quantitative research method to develop and conclude the findings regarding the acceptance of the technology and product performance. The survey has been sent to different organizations by random sampling among the entrepreneur’s population including integrated broiler farm, broiler farm, and other related organizations. The mixed-method results, both qualitative and quantitative, verify the user and lead users' demands since they provide information about the industry standard, technology preference, developing the right product according to the market, and solutions for the industry problems. The product innovation selected nutraceutical ingredients that can solve the following problems in livestock; bactericidal, anti-inflammation, gut health, antioxidant. The combinations of the selected nutraceutical and nanostructured lipid carriers (NLC) technology aim to improve chemical and pharmaceutical components by changing the structure of active ingredients into nanoparticle, which will be released in the targeted location with accurate concentration. The active ingredients in nanoparticle form are more stable, elicit antibacterial activity against pathogenic Salmonella spp and E.coli, balance gut health, have antioxidant and anti-inflammation activity. The experiment results have proven that the nutraceuticals have an antioxidant and antibacterial activity which also increases the average daily gain (ADG), reduces feed conversion ratio (FCR). The results also show a significant impact on the higher European Performance Index that can increase the farmers' profit when exporting. The product innovation will be tested in technology acceptance management methods from farmers and industry. The production of broiler and commercialization analyses are useful to reduce the importation of animal supplements. Most importantly, product innovation is protected by intellectual property.

Keywords: nutraceutical, nano structure lipid carrier, anti-microbial drug resistance, broiler, Salmonella

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78 Human Dental Pulp Stem Cells Attenuate Streptozotocin-Induced Parotid Gland Injury in Rats

Authors: Gehan ElAkabawy

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Background: Diabetes mellitus causes severe deteriorations of almost all the organs and systems of the body, as well as significant damage to the oral cavity. The oral changes are mainly related to salivary glands dysfunction characterized by hyposalivation and xerostomia, which significantly reduce diabetic patients’ quality of life. Human dental pulp stem cells represent a promising source for cell-based therapies, owing to their easy, minimally invasive surgical access, and high proliferative capacity. It was reported that the trophic support mediated by dental pulp stem cells can rescue the functional and structural alterations of damaged salivary glands. However, potential differentiation and paracrine effects of human dental pulp stem cells in diabetic-induced parotid gland damage have not been previously investigated. Our study aimed to investigate the therapeutic effects of intravenous transplantation of human dental pulp stem cells (hDPSCs) on parotid gland injury in a rat model of streptozotocin (STZ)-induced type 1 diabetes. Methods: Thirty Sprague-Dawley male rats were randomly categorised into three groups: control, diabetic (STZ), and transplanted (STZ+hDPSCs). hDPSCs or vehicle was injected into the tail vein 7 days after STZ injection. The fasting blood glucose levels were monitored weekly. A glucose tolerance test was performed, and the parotid gland weight, salivary flow rate, oxidative stress indices, parotid gland histology, and caspase-3, vascular endothelial growth factor (VEGF), and proliferating cell nuclear antigen (PCNA) expression in parotid tissues were assessed 28 days post-transplantation. Results: Transplantation of hDPSCs downregulated blood glucose, improved the salivary flow rate, and reduced oxidative stress. The cells migrated to, survived, and differentiated into acinar, ductal, and myoepithelial cells in the STZ-injured parotid gland. Moreover, they downregulated the expression of caspase-3 and upregulated the expression of VEGF and PCNA, likely exerting pro-angiogenetic and antiapoptotic effects and promoting endogenous regeneration. In addition, the transplanted cells enhanced the parotid nitric oxide (NO) -tetrahydrobiopterin (BH4) pathway. Conclusions: Our results show that hDPSCs can migrate to and survive within the STZ-injured parotid gland, where they prevent its functional and morphological damage by restoring normal glucose levels, differentiating into parotid cell populations, and stimulating paracrine-mediated regeneration. Thus, hDPSCs may have therapeutic potential in the treatment of diabetes-induced parotid gland injury.

Keywords: dental pulp stem cells, diabetes, streptozotocin, parotid gland

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77 Development and application of Humidity-Responsive Controlled Release Active Packaging Based on Electrospinning Nanofibers and In Situ Growth Polymeric Film in Food preservation

Authors: Jin Yue

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Fresh produces especially fruits, vegetables, meats and aquatic products have limited shelf life and are highly susceptible to deterioration. Essential oils (EOs) extracted from plants have excellent antioxidant and broad-spectrum antibacterial activities, and they can play as natural food preservatives. But EOs are volatile, water insoluble, pungent, and easily decomposing under light and heat. Many approaches have been developed to improve the solubility and stability of EOs such as polymeric film, coating, nanoparticles, nano-emulsions and nanofibers. Construction of active packaging film which can incorporate EOs with high loading efficiency and controlled release of EOs has received great attention. It is still difficult to achieve accurate release of antibacterial compounds at specific target locations in active packaging. In this research, a relative humidity-responsive packaging material was designed, employing the electrospinning technique to fabricate a nanofibrous film loaded with a 4-terpineol/β-cyclodextrin inclusion complexes (4-TA/β-CD ICs). Functioning as an innovative food packaging material, the film demonstrated commendable attributes including pleasing appearance, thermal stability, mechanical properties, and effective barrier properties. The incorporation of inclusion complexes greatly enhanced the antioxidant and antibacterial activity of the film, particularly against Shewanella putrefaciens, with an inhibitory efficiency of up to 65%. Crucially, the film realized controlled release of 4-TA under 98% high relative humidity conditions by inducing the plasticization of polymers caused by water molecules, swelling of polymer chains, and destruction of hydrogen bonds within the cyclodextrin inclusion complex. This film with a long-term antimicrobial effect successfully extended the shelf life of Litopenaeus vannamei shrimp to 7 days at 4 °C. To further improve the loading efficiency and long-acting release of EOs, we synthesized the γ-cyclodextrin-metal organic frameworks (γ-CD-MOFs), and then efficiently anchored γ-CD-MOFs on chitosan-cellulose (CS-CEL) composite film by in situ growth method for controlled releasing of carvacrol (CAR). We found that the growth efficiency of γ-CD-MOFs was the highest when the concentration of CEL dispersion was 5%. The anchoring of γ-CD-MOFs on CS-CEL film significantly improved the surface area of CS-CEL film from 1.0294 m2/g to 43.3458 m2/g. The molecular docking and 1H NMR spectra indicated that γ-CD-MOF has better complexing and stabilizing ability for CAR molecules than γ-CD. In addition, the release of CAR reached 99.71±0.22% on the 10th day, while under 22% RH, the release pattern of CAR was a plateau with 14.71 ± 4.46%. The inhibition rate of this film against E. coli, S. aureus and B. cinerea was more than 99%, and extended the shelf life of strawberries to 7 days. By incorporating the merits of natural biopolymers and MOFs, this active packaging offers great potential as a substitute for traditional packaging materials.

Keywords: active packaging, antibacterial activity, controlled release, essential oils, food quality control

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76 Carbon-Foam Supported Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Authors: Albert Mufundirwa, Satoru Yoshioka, K. Ogi, Takeharu Sugiyama, George F. Harrington, Bretislav Smid, Benjamin Cunning, Kazunari Sasaki, Akari Hayashi, Stephen M. Lyth

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Polymer electrolyte membrane fuel cells (PEMFCs) are electrochemical energy conversion devices used for portable, residential and vehicular applications due to their low emissions, high efficiency, and quick start-up characteristics. However, PEMFCs generally use expensive, Pt-based electrocatalysts as electrode catalysts. Due to the high cost and limited availability of platinum, research and development to either drastically reduce platinum loading, or replace platinum with alternative catalysts is of paramount importance. A combination of high surface area supports and nano-structured active sites is essential for effective operation of catalysts. We synthesize carbon foam supports by thermal decomposition of sodium ethoxide, using a template-free, gram scale, cheap, and scalable pyrolysis method. This carbon foam has a high surface area, highly porous, three-dimensional framework which is ideal for electrochemical applications. These carbon foams can have surface area larger than 2500 m²/g, and electron microscopy reveals that they have micron-scale cells, separated by few-layer graphene-like carbon walls. We applied this carbon foam as a platinum catalyst support, resulting in the improved electrochemical surface area and mass activity for the oxygen reduction reaction (ORR), compared to carbon black. Similarly, silver-decorated carbon foams showed higher activity and efficiency for electrochemical carbon dioxide conversion than silver-decorated carbon black. A promising alternative to Pt-catalysts for the ORR is iron-impregnated nitrogen-doped carbon catalysts (Fe-N-C). Doping carbon with nitrogen alters the chemical structure and modulates the electronic properties, allowing a degree of control over the catalytic properties. We have adapted our synthesis method to produce nitrogen-doped carbon foams with large surface area, using triethanolamine as a nitrogen feedstock, in a novel bottom-up protocol. These foams are then infiltrated with iron acetate (FeAc) and pyrolysed to form Fe-N-C foams. The resulting Fe-N-C foam catalysts have high initial activity (half-wave potential of 0.68 VRHE), comparable to that of commercially available Pt-free catalysts (e.g., NPC-2000, Pajarito Powder) in acid solution. In alkaline solution, the Fe-N-C carbon foam catalysts have a half-wave potential of 0.89 VRHE, which is higher than that of NPC-2000 by almost 10 mVRHE, and far out-performing platinum. However, the durability is still a problem at present. The lessons learned from X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements will be used to carefully design Fe-N-C catalysts for higher performance PEMFCs.

Keywords: carbon-foam, polymer electrolyte membrane fuel cells, platinum, Pt-free, Fe-N-C, ORR

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75 Development of Mesoporous Gel Based Nonwoven Structure for Thermal Barrier Application

Authors: R. P. Naik, A. K. Rakshit

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In recent years, with the rapid development in science and technology, people have increasing requirements on uses of clothing for new functions, which contributes to opportunities for further development and incorporation of new technologies along with novel materials. In this context, textiles are of fast decalescence or fast heat radiation media as per as comfort accountability of textile articles are concern. The microstructure and texture of textiles play a vital role in determining the heat-moisture comfort level of the human body because clothing serves as a barrier to the outside environment and a transporter of heat and moisture from the body to the surrounding environment to keep thermal balance between body heat produced and body heat loss. The main bottleneck which is associated with textile materials to be successful as thermal insulation materials can be enumerated as; firstly, high loft or bulkiness of material so as to provide predetermined amount of insulation by ensuring sufficient trapping of air. Secondly, the insulation depends on forced convection; such convective heat loss cannot be prevented by textile material. Third is that the textile alone cannot reach the level of thermal conductivity lower than 0.025 W/ m.k of air. Perhaps, nano-fibers can do so, but still, mass production and cost-effectiveness is a problem. Finally, such high loft materials for thermal insulation becomes heavier and uneasy to manage especially when required to carry over a body. The proposed works aim at developing lightweight effective thermal insulation textiles in combination with nanoporous silica-gel which provides the fundamental basis for the optimization of material properties to achieve good performance of the clothing system. This flexible nonwoven silica-gel composites fabric in intact monolith was successfully developed by reinforcing SiO2-gel in thermal bonded nonwoven fabric via sol-gel processing. Ambient Pressure Drying method is opted for silica gel preparation for cost-effective manufacturing. The formed structure of the nonwoven / SiO₂ -gel composites were analyzed, and the transfer properties were measured. The effects of structure and fibre on the thermal properties of the SiO₂-gel composites were evaluated. Samples are then tested against untreated samples of same GSM in order to study the effect of SiO₂-gel application on various properties of nonwoven fabric. The nonwoven fabric composites reinforced with aerogel showed intact monolith structure were also analyzed for their surface structure, functional group present, microscopic images. Developed product reveals a significant reduction in pores' size and air permeability than the conventional nonwoven fabric. Composite made from polyester fibre with lower GSM shows lowest thermal conductivity. Results obtained were statistically analyzed by using STATISTICA-6 software for their level of significance. Univariate tests of significance for various parameters are practiced which gives the P value for analyzing significance level along with that regression summary for dependent variable are also studied to obtain correlation coefficient.

Keywords: silica-gel, heat insulation, nonwoven fabric, thermal barrier clothing

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74 Evaluation of Nanoparticle Application to Control Formation Damage in Porous Media: Laboratory and Mathematical Modelling

Authors: Gabriel Malgaresi, Sara Borazjani, Hadi Madani, Pavel Bedrikovetsky

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Suspension-Colloidal flow in porous media occurs in numerous engineering fields, such as industrial water treatment, the disposal of industrial wastes into aquifers with the propagation of contaminants and low salinity water injection into petroleum reservoirs. The main effects are particle mobilization and captured by the porous rock, which can cause pore plugging and permeability reduction which is known as formation damage. Various factors such as fluid salinity, pH, temperature, and rock properties affect particle detachment. Formation damage is unfavorable specifically near injection and production wells. One way to control formation damage is pre-treatment of the rock with nanoparticles. Adsorption of nanoparticles on fines and rock surfaces alters zeta-potential of the surfaces and enhances the attachment force between the rock and fine particles. The main objective of this study is to develop a two-stage mathematical model for (1) flow and adsorption of nanoparticles on the rock in the pre-treatment stage and (2) fines migration and permeability reduction during the water production after the pre-treatment. The model accounts for adsorption and desorption of nanoparticles, fines migration, and kinetics of particle capture. The system of equations allows for the exact solution. The non-self-similar wave-interaction problem was solved by the Method of Characteristics. The analytical model is new in two ways: First, it accounts for the specific boundary and initial condition describing the injection of nanoparticle and production from the pre-treated porous media; second, it contains the effect of nanoparticle sorption hysteresis. The derived analytical model contains explicit formulae for the concentration fronts along with pressure drop. The solution is used to determine the optimal injection concentration of nanoparticle to avoid formation damage. The mathematical model was validated via an innovative laboratory program. The laboratory study includes two sets of core-flood experiments: (1) production of water without nanoparticle pre-treatment; (2) pre-treatment of a similar core with nanoparticles followed by water production. Positively-charged Alumina nanoparticles with the average particle size of 100 nm were used for the rock pre-treatment. The core was saturated with the nanoparticles and then flushed with low salinity water; pressure drop across the core and the outlet fine concentration was monitored and used for model validation. The results of the analytical modeling showed a significant reduction in the fine outlet concentration and formation damage. This observation was in great agreement with the results of core-flood data. The exact solution accurately describes fines particle breakthroughs and evaluates the positive effect of nanoparticles in formation damage. We show that the adsorbed concentration of nanoparticle highly affects the permeability of the porous media. For the laboratory case presented, the reduction of permeability after 1 PVI production in the pre-treated scenario is 50% lower than the reference case. The main outcome of this study is to provide a validated mathematical model to evaluate the effect of nanoparticles on formation damage.

Keywords: nano-particles, formation damage, permeability, fines migration

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73 Pt Decorated Functionalized Acetylene Black as Efficient Cathode Material for Li Air Battery and Fuel Cell Applications

Authors: Rajashekar Badam, Vedarajan Raman, Noriyoshi Matsumi

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Efficiency of energy converting and storage systems like fuel cells and Li-Air battery principally depended on oxygen reduction reaction (ORR) which occurs at cathode. As the kinetics of the ORR is very slow, it becomes the rate determining step. Exploring carbon substrates for enhancing the dispersion and activity of the metal catalyst and commercially viable simple preparation method is a very crucial area of research in the field of energy materials. Hence, many researchers made large number of carbon-based ORR materials today. But, there are hardly few studies on the effect of interaction between Pt-carbon and carbon-electrolyte on activity. In this work, we have prepared functionalized carbon-based Pt catalyst (Pt-FAB) with enhanced interfacial properties that lead to efficient ORR catalysis. The present work deals with a single-pot method to exfoliate and functionalized acetylene black with enhanced interaction with Pt as well as electrolyte. Acetylene black was functionalized and exfoliated using a facile single pot acid treatment method. The resulted FAB was further decorated with Pt-nano particles (Pt-np). The TEM images of Pt-FAB with uniformly decorated Pt-np of ~3 nm. Further, XPS studies of Pt 4f peak revealed that Pt0 peak was shifted by 0.4 eV in Pt-FAB compared to binding energy of typical Pt⁰ found in Pt/C. The shift can be ascribed to the modulation of electronic state and strong electronic interaction of Pt with carbon. Modulated electronic structure of Pt and strong electronic interaction of Pt with FAB enhances the catalytic activity and durability respectively. To understand the electrode electrolyte interface, electrochemical impedance spectroscopy was carried out. These measurements revealed that the charge transfer resistance of electrode to electrolyte for Pt-FAB is 10 times smaller than that of conventional Pt/C. The interaction with electrolyte helps reduce the interface boundaries, which in turn affects the overall catalytic performance of the electrode. Cyclic voltammetric measurements in 0.1M HClO₄ aq. at a potential scan rate of 50 mVs-1 was employed to evaluate electrochemical surface area (ECSA) of Pt. ECSA of Pt-FAB was found to be as high as 67.2 m²g⁻¹. The three-electrode system showed very high ORR catalytic activity. Mass activity at 0.9 V vs. RHE showed 460 A/g which is much higher than the DOE target values for the year 2020. Further, it showed enhanced performance by showing 723 mW/cm² of highest power density and 1006 mA/cm² of current density at 0.6 V in fuel cell single cell type configuration and 1030 mAhg⁻¹ of rechargeable capacity in Li air battery application. The higher catalytic activity can be ascribed to the improved interaction of FAB with Pt and electrolyte. The aforementioned results evince that Pt-FAB will be a promising cathode material for efficient ORR with significant cyclability for its application in fuel cells and Li-Air batteries. In conclusion, a disordered material was prepared from AB and was systematically characterized. The extremely high ORR activity and ease of preparation make it competent for replacing commercially available ORR materials.

Keywords: functionalized acetylene black, oxygen reduction reaction, fuel cells, Functionalized battery

Procedia PDF Downloads 89
72 Nanoparticle Supported, Magnetically Separable Metalloporphyrin as an Efficient Retrievable Heterogeneous Nanocatalyst in Oxidation Reactions

Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

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Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

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71 Detection of Triclosan in Water Based on Nanostructured Thin Films

Authors: G. Magalhães-Mota, C. Magro, S. Sério, E. Mateus, P. A. Ribeiro, A. B. Ribeiro, M. Raposo

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Triclosan [5-chloro-2-(2,4-dichlorophenoxy) phenol], belonging to the class of Pharmaceuticals and Personal Care Products (PPCPs), is a broad-spectrum antimicrobial agent and bactericide. Because of its antimicrobial efficacy, it is widely used in personal health and skin care products, such as soaps, detergents, hand cleansers, cosmetics, toothpastes, etc. However, it has been considered to disrupt the endocrine system, for instance, thyroid hormone homeostasis and possibly the reproductive system. Considering the widespread use of triclosan, it is expected that environmental and food safety problems regarding triclosan will increase dramatically. Triclosan has been found in river water samples in both North America and Europe and is likely widely distributed wherever triclosan-containing products are used. Although significant amounts are removed in sewage plants, considerable quantities remain in the sewage effluent, initiating widespread environmental contamination. Triclosan undergoes bioconversion to methyl-triclosan, which has been demonstrated to bio accumulate in fish. In addition, triclosan has been found in human urine samples from persons with no known industrial exposure and in significant amounts in samples of mother's milk, demonstrating its presence in humans. The action of sunlight in river water is known to turn triclosan into dioxin derivatives and raises the possibility of pharmacological dangers not envisioned when the compound was originally utilized. The aim of this work is to detect low concentrations of triclosan in an aqueous complex matrix through the use of a sensor array system, following the electronic tongue concept based on impedance spectroscopy. To achieve this goal, we selected the appropriate molecules to the sensor so that there is a high affinity for triclosan and whose sensitivity ensures the detection of concentrations of at least nano-molar. Thin films of organic molecules and oxides have been produced by the layer-by-layer (LbL) technique and sputtered onto glass solid supports already covered by gold interdigitated electrodes. By submerging the films in complex aqueous solutions with different concentrations of triclosan, resistance and capacitance values were obtained at different frequencies. The preliminary results showed that an array of interdigitated electrodes sensor coated or uncoated with different LbL and films, can be used to detect TCS traces in aqueous solutions in a wide range concentration, from 10⁻¹² to 10⁻⁶ M. The PCA method was applied to the measured data, in order to differentiate the solutions with different concentrations of TCS. Moreover, was also possible to trace a curve, the plot of the logarithm of resistance versus the logarithm of concentration, which allowed us to fit the plotted data points with a decreasing straight line with a slope of 0.022 ± 0.006 which corresponds to the best sensitivity of our sensor. To find the sensor resolution near of the smallest concentration (Cs) used, 1pM, the minimum measured value which can be measured with resolution is 0.006, so the ∆logC =0.006/0.022=0.273, and, therefore, C-Cs~0.9 pM. This leads to a sensor resolution of 0.9 pM for the smallest concentration used, 1pM. This attained detection limit is lower than the values obtained in the literature.

Keywords: triclosan, layer-by-layer, impedance spectroscopy, electronic tongue

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70 A Hybrid Film: NiFe₂O₄ Nanoparticles in Poly-3-Hydroxybutyrate as an Antibacterial Agent

Authors: Karen L. Rincon-Granados, América R. Vázquez-Olmos, Adriana-Patricia Rodríguez-Hernández, Gina Prado-Prone, Margarita Rivera, Roberto Y. Sato-Berrú

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In this work, a hybrid film based on poly-3-hydroxybutyrate (P3HB) and nickel ferrite (NiFe₂O₄) nanoparticles (NPs) was obtained by a simple and reproducible methodology in order to study its antibacterial and cytotoxic properties. The motivation for this research is the current antimicrobial resistance (RAM). This is a threat to human health and development worldwide. RAM is caused by the emergence of bacterial strains resistant to traditional antibiotics that were used as treatment. Due to this, the need to investigate new alternatives for preventing and treating bacterial infections emerges. In this sense, metal oxide NPs have aroused great interest due to their unique physicochemical properties. However, their use is limited by the nanostructured nature, commonly obtained by chemical and physical synthesis methods, as powders or colloidal dispersions. Therefore, the incorporation of nanostructured materials in polymer matrices to obtain hybrid materials that allow disinfecting and preventing the spread of bacteria on various surfaces. Accordingly, this work presents the synthesis and study of the antibacterial properties of the P3HB@NiFe₂O₄ hybrid film as a potential material to inhibit bacterial growth. The NiFe₂O₄ NPs were previously synthesized by a mechanochemical method. The P3HB and P3HB@NiFe₂O₄ films were obtained by the solvent casting method. The films were characterized by X-ray diffraction (XRD), Raman scattering, and scanning electron microscopy (SEM). The XRD pattern showed that the NiFe₂O₄ NPs were incorporated into the P3HB polymer matrix and retained their nanometric sizes. By energy dispersive X-ray spectroscopy (EDS), it was observed that the NPs are homogeneously distributed in the film. The bactericidal effect of the films obtained was evaluated in vitro using the broth surface method against two opportunistic and nosocomial pathogens, Staphylococcus aureus and Pseudomonas aeruginosa. The bacterial growth results showed that the P3HB@NiFe₂O₄ hybrid film was inhibited by 97% and 96% for S. aureus and P. aeruginosa, respectively. Surprisingly, the P3HB film inhibited both bacterial strains by around 90%. The cytotoxicity of the NiFe₂O₄ NPs, P3HB@NiFe₂O₄ hybrid film, and the P3HB film was evaluated using human skin cells, keratinocytes, and fibroblasts, finding that the NPs are biocompatible. The P3HB film and hybrids are cytotoxic, which demonstrated that although P3HB is known and reported as a biocompatible polymer, under our work conditions, P3HB was cytotoxic. Its bactericidal effect could be related to this activity. Its films are bactericidal and cytotoxic to keratinocytes and fibroblasts, the first barrier of human skin. Despite this, the hybrid film of P3HB@NiFe₂O₄ presents synergy with the bactericidal effect between P3HB and NPs, increasing bacterial inhibition. In addition, NPs decrease the cytotoxicity of P3HB to keratinocytes. The methodology used in this work was successful in producing hybrid films with antibacterial activity. However, future challenges are generated to find relationships between NPs and P3HB that allow taking advantage of their bactericidal properties and do not compromise biocompatibility.

Keywords: poly-3-hydroxybutyrate, nanoparticles, hybrid film, antibacterial

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69 Synthesis of Smart Materials Based on Polyaniline Coated Fibers

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

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

Keywords: electrospinning, fibers, smart materials, polyaniline

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68 Moringa olifera Curate The Toxic Potential of CuO Nanoparticles in Oreochromis mossambicus

Authors: Farhat Jabeen, Muhammad Asad

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The study assessed the curative potential of Moringa olifera seeds against copper oxide nanoparticles induced toxicity in Oreochromis mossambicus. In order to investigate the curative potential of M. olifera seeds, firstly we examine its chemical composition, secondary metabolites, and bioactive compounds including hydroxyl-cinnamic acids, flavanols and hydroxybenzoic acids through standard methods and high performance liquid chromatography. In current study, the potential sub-lethal toxic dose of CuO-NPs (0.12 mg/l) was investigated through pilot experiment and three non-lethal doses (low=32, medium=48 and high=96 mg/l) of M. olifera were selected on the basis of its LC50 value for O. mossambicus. The experimental fish, O. mossambicus (n=100 of approximately 20 g each) were procured from Manawan Fisheries Complex, Lahore, and acclimatized for two weeks in glass aquaria. Experiment was conducted in accordance with the guidelines of Institutional Animal Ethics Committee, Government College University Faisalabad, Pakistan. During acclimatization and experimental period, fish received the commercial fish feed at 2.5% body weight daily. In order to assess the curative effect of M. olifera against CuO NPs induced toxicity, O. mossambicus were randomly divided into five groups and were designated as control (C) without any treatment, positive control (G*) exposed to potential toxic dose of CuO-NPs at 0.12 mg/l, and three treated groups namely G1, G2, and G3 co-treated with 0.12 mg/l of CuO-NPs plus different doses of M. olifera seed extract at 32, 48, and 96 mg/l, respectively for 56 days. Fish were exposed to waterborne CuO NPs and M. olifera seed extract. CuO-NPs treatment was ceased after 28 days but the doses of M. olifera were continued for 56 days. Blood was taken after 28 and 56 days through caudal venipuncture. Liver and intestine were taken for oxidative stress and histological studies after 56 days. In M. olifera seeds, moisture contents, crude protein, lipids, carbohydrates and ash were recorded as 3.8, 37.83, 32.52, 46.12, and 7.75%, respectively on dry weight basis. Total energy was recorded as 627.36 kcal/100g. Qualitative analysis of M. olifera seeds showed the presence of terpenoids, saponins, flavonoids, alkaloids and phenolics, while its quantitative analysis showed the considerable amount of total phenolics, flavonoids, saponins, and alkaloids as 134.75, 170.15, 1.57, and 0.4 µg/mg, respectively. Analysis of bioactive compounds in M. olifera seeds showed the presence of hydroxy-cinnamic acids (6.07 µg/ml), flavanols (71.72 µg/ml), and hydroxyl benzoic acids (97.82 µg/ml). The results showed that M. oliefera seed extract at 48 and 56 mg/l was able to cure against the toxic effects of CuO-NPs. The significant changes were observed in G* and G1 for sero-hepatic enzymes, anti-oxidants and histological profile. The investigations of this study showed that M. olifera is a good curative agent against potential induced toxicity of CuO-NPs in O. mossambicus. The curative effect of M. olifera is attributed to the presence of higher amount of secondary metabolites and bioactive compounds. This study suggested the use of M. olifera to curate different ailments in fish and other organisms.

Keywords: CuO nanoparticles, curative, Moringa olifera, Oreochromis mossambicus

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67 Antioxidant Activity of Some Important Indigenous Plant Foods of the North Eastern Region of India

Authors: L. Bidyalakshmi, R. Ananthan, T. Longvah

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Antioxidants are substances that can prevent or delay oxidative damage of lipids, proteins and nucleic acids by reactive oxygen species. These help in lowering incidence of degenerative diseases such as cancer, arthritis, atherosclerosis, heart disease, inflammation, brain dysfunction and acceleration of the ageing process. The north eastern part of India falls among the global hotspots of biodiversity. Over the years, the local communities in the region have developed ingenious uses of many wild plants within their environment as food sources. Many of these less familiar foods form an integral part of the diet of these communities, and some are traditionally valued for its therapeutic effects. So the study was carried to estimate the antioxidant activity of some of these indigenous foods. Twenty-eight indigenous plant foods were studied for their antioxidant activity. Antioxidant activities were determined by using DPPH (2, 2-diphenyl-1-picrylhydrazyl) assay, FRAP (Ferric Reducing Antioxidant Power) assay and SOSA (Super Oxide Scavenging Assay). Out of the twenty-eight plant foods, there were thirteen leafy vegetables, four fruits, five roots and tubers, four spices and two mushrooms. Water extract and methanol extract of the samples were used for the analysis. The leafy vegetable samples exhibited antioxidant capacity with IC50 ranging from 8-1414 mg/ml for lipid extract and 34-37878 mg/ml for aqueous extract in DPPH assay. Total FRAP value ranging from 58-1005 mmol FeSO4 Eq/100g of the sample, which is comparatively higher than the antioxidant capacity of some commonly consumed leafy vegetables. In SOSA, water extract of leafy vegetables show a range of 0.05-193.68 µmol ascorbic acid equivalent/g of the samples. While the methanol extract of the samples show 0.20-21.94 µmol Trolox equivalent/g of the samples. Polygonum barbatum, Wendlandia glabrata and Polygonum posumbu have higher antioxidant activity among the leafy vegetables analysed. Among the fruits, Rhus hookerii showed the highest antioxidant activities in both FRAP and SOSA methods while Spondias magnifera exhibited higher antioxidant activity in DPPH method. Alocasia cucullata exhibited higher antioxidant activity in DPPH and FRAP assays while Alpinia galanga showed higher antioxidant activity in SOSA assay when compared to the other samples of roots and tubers. Elsholtzia communis showed high antioxidant activity in all the three parameters among the spices. For the mushrooms, Pleurotus ostreatus exhibited higher antioxidant activity than Auricularia delicate in DPPH and SOSA. The samples analysed exhibited antioxidant activity at varying levels and some exhibited higher antioxidant activity than the commonly consumed foods. So consumption of these less familiar foods may play a role in preventing human disease in which free radicals are involved. Further studies on these food samples on phytonutrients and its contribution to the antioxidant activities are required.

Keywords: antioxidant activity, DPPH, FRAP, SOSA

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66 Sensitivity Improvement of Optical Ring Resonator for Strain Analysis with the Direction of Strain Recognition Possibility

Authors: Tayebeh Sahraeibelverdi, Ahmad Shirazi Hadi Veladi, Mazdak Radmalekshah

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Optical sensors became attractive due to preciseness, low power consumption, and intrinsic electromagnetic interference-free characteristic. Among the waveguide optical sensors, cavity-based ones attended for the high Q-factor. Micro ring resonators as a potential platform have been investigated for various applications as biosensors to pressure sensors thanks to their sensitive ring structure responding to any small change in the refractive index. Furthermore, these small micron size structures can come in an array, bringing the opportunity to have any of the resonance in a specific wavelength and be addressed in this way. Another exciting application is applying a strain to the ring and making them an optical strain gauge where the traditional ones are based on the piezoelectric material. Making them in arrays needs electrical wiring and about fifty times bigger in size. Any physical element that impacts the waveguide cross-section, Waveguide elastic-optic property change, or ring circumference can play a role. In comparison, ring size change has a larger effect than others. Here an engineered ring structure is investigated to study the strain effect on the ring resonance wavelength shift and its potential for more sensitive strain devices. At the same time, these devices can measure any strain by mounting on the surface of interest. The idea is to change the" O" shape ring to a "C" shape ring with a small opening starting from 2π/360 or one degree. We used the Mode solution of Lumbrical software to investigate the effect of changing the ring's opening and the shift induced by applied strain. The designed ring radius is a three Micron silicon on isolator ring which can be fabricated by standard complementary metal-oxide-semiconductor (CMOS) micromachining. The measured wavelength shifts from1-degree opening of the ring to a 6-degree opening have been investigated. Opening the ring for 1-degree affects the ring's quality factor from 3000 to 300, showing an order of magnitude Q-factor reduction. Assuming a strain making the ring-opening from 1 degree to 6 degrees, our simulation results showing negligible Q-factor reduction from 300 to 280. A ring resonator quality factor can reach up to 108 where an order of magnitude reduction is negligible. The resonance wavelength shift showed a blue shift and was obtained to be 1581, 1579,1578,1575nm for 1-, 2-, 4- and 6-degree ring-opening, respectively. This design can find the direction of the strain-induced by applying the opening on different parts of the ring. Moreover, by addressing the specified wavelength, we can precisely find the direction. We can open a significant opportunity to find cracks and any surface mechanical property very specifically and precisely. This idea can be implemented on polymer ring resonators while they can come with a flexible substrate and can be very sensitive to any strain making the two ends of the ring in the slit part come closer or further.

Keywords: optical ring resonator, strain gauge, strain sensor, surface mechanical property analysis

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65 Caged Compounds as Light-Dependent Initiators for Enzyme Catalysis Reactions

Authors: Emma Castiglioni, Nigel Scrutton, Derren Heyes, Alistair Fielding

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By using light as trigger, it is possible to study many biological processes, such as the activity of genes, proteins, and other molecules, with precise spatiotemporal control. Caged compounds, where biologically active molecules are generated from an inert precursor upon laser photolysis, offer the potential to initiate such biological reactions with high temporal resolution. As light acts as the trigger for cleaving the protecting group, the ‘caging’ technique provides a number of advantages as it can be intracellular, rapid and controlled in a quantitative manner. We are developing caging strategies to study the catalytic cycle of a number of enzyme systems, such as nitric oxide synthase and ethanolamine ammonia lyase. These include the use of caged substrates, caged electrons and the possibility of caging the enzyme itself. In addition, we are developing a novel freeze-quench instrument to study these reactions, which combines rapid mixing and flashing capabilities. Reaction intermediates will be trapped at low temperatures and will be analysed by using electron paramagnetic resonance (EPR) spectroscopy to identify the involvement of any radical species during catalysis. EPR techniques typically require relatively long measurement times and very often, low temperatures to fully characterise these short-lived species. Therefore, common rapid mixing techniques, such as stopped-flow or quench-flow are not directly suitable. However, the combination of rapid freeze-quench (RFQ) followed by EPR analysis provides the ideal approach to kinetically trap and spectroscopically characterise these transient radical species. In a typical RFQ experiment, two reagent solutions are delivered to the mixer via two syringes driven by a pneumatic actuator or stepper motor. The new mixed solution is then sprayed into a cryogenic liquid or surface, and the frozen sample is then collected and packed into an EPR tube for analysis. The earliest RFQ instrument consisted of a hydraulic ram unit as a drive unit with direct spraying of the sample into a cryogenic liquid (nitrogen, isopentane or petroleum). Improvements to the RFQ technique have arisen from the design of new mixers in order to reduce both the volume and the mixing time. In addition, the cryogenic isopentane bath has been coupled to a filtering system or replaced by spraying the solution onto a surface that is frozen via thermal conductivity with a cryogenic liquid. In our work, we are developing a novel RFQ instrument which combines the freeze-quench technology with flashing capabilities to enable the studies of both thermally-activated and light-activated biological reactions. This instrument also uses a new rotating plate design based on magnetic couplings and removes the need for mechanical motorised rotation, which can otherwise be problematic at cryogenic temperatures.

Keywords: caged compounds, freeze-quench apparatus, photolysis, radicals

Procedia PDF Downloads 190
64 Lean Comic GAN (LC-GAN): a Light-Weight GAN Architecture Leveraging Factorized Convolution and Teacher Forcing Distillation Style Loss Aimed to Capture Two Dimensional Animated Filtered Still Shots Using Mobile Phone Camera and Edge Devices

Authors: Kaustav Mukherjee

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In this paper we propose a Neural Style Transfer solution whereby we have created a Lightweight Separable Convolution Kernel Based GAN Architecture (SC-GAN) which will very useful for designing filter for Mobile Phone Cameras and also Edge Devices which will convert any image to its 2D ANIMATED COMIC STYLE Movies like HEMAN, SUPERMAN, JUNGLE-BOOK. This will help the 2D animation artist by relieving to create new characters from real life person's images without having to go for endless hours of manual labour drawing each and every pose of a cartoon. It can even be used to create scenes from real life images.This will reduce a huge amount of turn around time to make 2D animated movies and decrease cost in terms of manpower and time. In addition to that being extreme light-weight it can be used as camera filters capable of taking Comic Style Shots using mobile phone camera or edge device cameras like Raspberry Pi 4,NVIDIA Jetson NANO etc. Existing Methods like CartoonGAN with the model size close to 170 MB is too heavy weight for mobile phones and edge devices due to their scarcity in resources. Compared to the current state of the art our proposed method which has a total model size of 31 MB which clearly makes it ideal and ultra-efficient for designing of camera filters on low resource devices like mobile phones, tablets and edge devices running OS or RTOS. .Owing to use of high resolution input and usage of bigger convolution kernel size it produces richer resolution Comic-Style Pictures implementation with 6 times lesser number of parameters and with just 25 extra epoch trained on a dataset of less than 1000 which breaks the myth that all GAN need mammoth amount of data. Our network reduces the density of the Gan architecture by using Depthwise Separable Convolution which does the convolution operation on each of the RGB channels separately then we use a Point-Wise Convolution to bring back the network into required channel number using 1 by 1 kernel.This reduces the number of parameters substantially and makes it extreme light-weight and suitable for mobile phones and edge devices. The architecture mentioned in the present paper make use of Parameterised Batch Normalization Goodfellow etc al. (Deep Learning OPTIMIZATION FOR TRAINING DEEP MODELS page 320) which makes the network to use the advantage of Batch Norm for easier training while maintaining the non-linear feature capture by inducing the learnable parameters

Keywords: comic stylisation from camera image using GAN, creating 2D animated movie style custom stickers from images, depth-wise separable convolutional neural network for light-weight GAN architecture for EDGE devices, GAN architecture for 2D animated cartoonizing neural style, neural style transfer for edge, model distilation, perceptual loss

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63 Bio-Functionalized Silk Nanofibers for Peripheral Nerve Regeneration

Authors: Kayla Belanger, Pascale Vigneron, Guy Schlatter, Bernard Devauchelle, Christophe Egles

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A severe injury to a peripheral nerve leads to its degeneration and the loss of sensory and motor function. To this day, there still lacks a more effective alternative to the autograft which has long been considered the gold standard for nerve repair. In order to overcome the numerous drawbacks of the autograft, tissue engineered biomaterials may be effective alternatives. Silk fibroin is a favorable biomaterial due to its many advantageous properties such as its biocompatibility, its biodegradability, and its robust mechanical properties. In this study, bio-mimicking multi-channeled nerve guidance conduits made of aligned nanofibers achieved by electrospinning were functionalized with signaling biomolecules and were tested in vitro and in vivo for nerve regeneration support. Silk fibroin (SF) extracted directly from silkworm cocoons was put in solution at a concentration of 10wt%. Poly(ethylene oxide) (PEO) was added to the resulting SF solution to increase solution viscosity and the following three electrospinning solutions were made: (1) SF/PEO solution, (2) SF/PEO solution with nerve growth factor and ciliary neurotrophic factor, and (3) SF/PEO solution with nerve growth factor and neurotrophin-3. Each of these solutions was electrospun into a multi-layer architecture to obtain mechanically optimized aligned nanofibrous mats. For in vitro studies, aligned fibers were treated to induce β-sheet formation and thoroughly rinsed to eliminate presence of PEO. Each material was tested using rat embryo neuron cultures to evaluate neurite extension and the interaction with bio-functionalized or non-functionalized aligned fibers. For in vivo studies, the mats were rolled into 5mm long multi-, micro-channeled conduits then treated and thoroughly rinsed. The conduits were each subsequently implanted between a severed rat sciatic nerve. The effectiveness of nerve repair over a period of 8 months was extensively evaluated by cross-referencing electrophysiological, histological, and movement analysis results to comprehensively evaluate the progression of nerve repair. In vitro results show a more favorable interaction between growing neurons and bio-functionalized silk fibers compared to pure silk fibers. Neurites can also be seen having extended unidirectionally along the alignment of the nanofibers which confirms a guidance factor for the electrospun material. The in vivo study has produced positive results for the regeneration of the sciatic nerve over the length of the study, showing contrasts between the bio-functionalized material and the non-functionalized material along with comparisons to the experimental control. Nerve regeneration has been evaluated not only by histological analysis, but also by electrophysiological assessment and motion analysis of two separate natural movements. By studying these three components in parallel, the most comprehensive evaluation of nerve repair for the conduit designs can be made which can, therefore, more accurately depict their overall effectiveness. This work was supported by La Région Picardie and FEDER.

Keywords: electrospinning, nerve guidance conduit, peripheral nerve regeneration, silk fibroin

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62 Mechanical Response Investigation of Wafer Probing Test with Vertical Cobra Probe via the Experiment and Transient Dynamic Simulation

Authors: De-Shin Liu, Po-Chun Wen, Zhen-Wei Zhuang, Hsueh-Chih Liu, Pei-Chen Huang

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Wafer probing tests play an important role in semiconductor manufacturing procedures in accordance with the yield and reliability requirement of the wafer after the backend-of-the-line process. Accordingly, the stable physical and electrical contact between the probe and the tested wafer during wafer probing is regarded as an essential issue in identifying the known good die. The probe card can be integrated with multiple probe needles, which are classified as vertical, cantilever and micro-electro-mechanical systems type probe selections. Among all potential probe types, the vertical probe has several advantages as compared with other probe types, including maintainability, high probe density and feasibility for high-speed wafer testing. In the present study, the mechanical response of the wafer probing test with the vertical cobra probe on 720 μm thick silicon (Si) substrate with a 1.4 μm thick aluminum (Al) pad is investigated by the experiment and transient dynamic simulation approach. Because the deformation mechanism of the vertical cobra probe is determined by both bending and buckling mechanisms, the stable correlation between contact forces and overdrive (OD) length must be carefully verified. Moreover, the decent OD length with corresponding contact force contributed to piercing the native oxide layer of the Al pad and preventing the probing test-induced damage on the interconnect system. Accordingly, the scratch depth of the Al pad under various OD lengths is estimated by the atomic force microscope (AFM) and simulation work. In the wafer probing test configuration, the contact phenomenon between the probe needle and the tested object introduced large deformation and twisting of mesh gridding, causing the subsequent numerical divergence issue. For this reason, the arbitrary Lagrangian-Eulerian method is utilized in the present simulation work to conquer the aforementioned issue. The analytic results revealed a slight difference when the OD is considered as 40 μm, and the simulated is almost identical to the measured scratch depths of the Al pad under higher OD lengths up to 70 μm. This phenomenon can be attributed to the unstable contact of the probe at low OD length with the scratch depth below 30% of Al pad thickness, and the contact status will be being stable when the scratch depth over 30% of pad thickness. The splash of the Al pad is observed by the AFM, and the splashed Al debris accumulates on a specific side; this phenomenon is successfully simulated in the transient dynamic simulation. Thus, the preferred testing OD lengths are found as 45 μm to 70 μm, and the corresponding scratch depths on the Al pad are represented as 31.4% and 47.1% of Al pad thickness, respectively. The investigation approach demonstrated in this study contributed to analyzing the mechanical response of wafer probing test configuration under large strain conditions and assessed the geometric designs and material selections of probe needles to meet the requirement of high resolution and high-speed wafer-level probing test for thinned wafer application.

Keywords: wafer probing test, vertical probe, probe mark, mechanical response, FEA simulation

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61 Radiofrequency and Near-Infrared Responsive Core-Shell Multifunctional Nanostructures Using Lipid Templates for Cancer Theranostics

Authors: Animesh Pan, Geoffrey D. Bothun

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With the development of nanotechnology, research in multifunctional delivery systems has a new pace and dimension. An incipient challenge is to design an all-in-one delivery system that can be used for multiple purposes, including tumor targeting therapy, radio-frequency (RF-), near-infrared (NIR-), light-, or pH-induced controlled release, photothermal therapy (PTT), photodynamic therapy (PDT), and medical diagnosis. In this regard, various inorganic nanoparticles (NPs) are known to show great potential as the 'functional components' because of their fascinating and tunable physicochemical properties and the possibility of multiple theranostic modalities from individual NPs. Magnetic, luminescent, and plasmonic properties are the three most extensively studied and, more importantly biomedically exploitable properties of inorganic NPs. Although successful attempts of combining any two of them above mentioned functionalities have been made, integrating them in one system has remained challenge. Keeping those in mind, controlled designs of complex colloidal nanoparticle system are one of the most significant challenges in nanoscience and nanotechnology. Therefore, systematic and planned studies providing better revelation are demanded. We report a multifunctional delivery platform-based liposome loaded with drug, iron-oxide magnetic nanoparticles (MNPs), and a gold shell on the surface of liposomes, were synthesized using a lipid with polyelectrolyte (layersomes) templating technique. MNPs and the anti-cancer drug doxorubicin (DOX) were co-encapsulated inside liposomes composed by zwitterionic phophatidylcholine and anionic phosphatidylglycerol using reverse phase evaporation (REV) method. The liposomes were coated with positively charge polyelectrolyte (poly-L-lysine) to enrich the interface with gold anion, exposed to a reducing agent to form a gold nanoshell, and then capped with thio-terminated polyethylene glycol (SH-PEG2000). The core-shell nanostructures were characterized by different techniques like; UV-Vis/NIR scanning spectrophotometer, dynamic light scattering (DLS), transmission electron microscope (TEM). This multifunctional system achieves a variety of functions, such as radiofrequency (RF)-triggered release, chemo-hyperthermia, and NIR laser-triggered for photothermal therapy. Herein, we highlight some of the remaining major design challenges in combination with preliminary studies assessing therapeutic objectives. We demonstrate an efficient loading and delivery system to significant cell death of human cancer cells (A549) with therapeutic capabilities. Coupled with RF and NIR excitation to the doxorubicin-loaded core-shell nanostructure helped in securing targeted and controlled drug release to the cancer cells. The present core-shell multifunctional system with their multimodal imaging and therapeutic capabilities would be eminent candidates for cancer theranostics.

Keywords: cancer thernostics, multifunctional nanostructure, photothermal therapy, radiofrequency targeting

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60 Electrochemical Properties of Li-Ion Batteries Anode Material: Li₃.₈Cu₀.₁Ni₀.₁Ti₅O₁₂

Authors: D. Olszewska, J. Niewiedzial

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In some types of Li-ion batteries carbon in the form of graphite is used. Unfortunately, carbon materials, in particular graphite, have very good electrochemical properties, but increase their volume during charge/discharge cycles, which may even lead to an explosion of the cell. The cell element may be replaced by a composite material consisting of lithium-titanium oxide Li4Ti5O12 (LTO) modified with copper and nickel ions and carbon derived from sucrose. This way you can improve the conductivity of the material. LTO is appropriate only for applications which do not require high energy density because of its high operating voltage (ca. 1.5 V vs. Li/Li+). Specific capacity of Li4Ti5O12 is high enough for utilization in Li-ion batteries (theoretical capacity 175 mAh·g-1) but it is lower than capacity of graphite anodes. Materials based on Li4Ti5O12 do not change their volume during charging/discharging cycles, however, LTO has low conductivity. Another positive aspect of the use of sucrose in the carbon composite material is to eliminate the addition of carbon black from the anode of the battery. Therefore, the proposed materials contribute significantly to environmental protection and safety of selected lithium cells. New anode materials in order to obtain Li3.8Cu0.1Ni0.1Ti5O12 have been prepared by solid state synthesis using three-way: i) stoichiometric composition of Li2CO3, TiO2, CuO, NiO (A- Li3.8Cu0.1Ni0.1Ti5O12); ii) stoichiometric composition of Li2CO3, TiO2, Cu(NO3)2, Ni(NO3)2 (B-Li3.8Cu0.1Ni0.1Ti5O12); and iii) stoichiometric composition of Li2CO3, TiO2, CuO, NiO calcined with 10% of saccharose (Li3.8Cu0.1Ni0.1Ti5O12-C). Structure of materials was studied by X-ray diffraction (XRD). The electrochemical properties were performed using appropriately prepared cell Li|Li+|Li3.8Cu0.1Ni0.1Ti5O12 for cyclic voltammetry and discharge/charge measurements. The cells were periodically charged and discharged in the voltage range from 1.3 to 2.0 V applying constant charge/discharge current in order to determine the specific capacity of each electrode. Measurements at various values of the charge/discharge current (from C/10 to 5C) were carried out. Cyclic voltammetry investigation was carried out by applying to the cells a voltage linearly changing over time at a rate of 0.1 mV·s-1 (in the range from 2.0 to 1.3 V and from 1.3 to 2.0 V). The XRD method analyzes show that composite powders were obtained containing, in addition to the main phase, 4.78% and 4% TiO2 in A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12, respectively. However, Li3.8Cu0.1Ni0.1O12-C material is three-phase: 63.84% of the main phase, 17.49 TiO2 and 18.67 Li2TiO3. Voltammograms of electrodes containing materials A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12 are correct and repeatable. Peak cathode occurs for both samples at a potential approx. 1.52±0.01 V relative to a lithium electrode, while the anodic peak at potential approx. 1.65±0.05 V relative to a lithium electrode. Voltammogram of Li3.8Cu0.1Ni0.1Ti5O12-C (especially for the first measurement cycle) is not correct. There are large variations in values of specific current, which are not characteristic for materials LTO. From the point of view of safety and environmentally friendly production of Li-ion cells eliminating soot and applying Li3.8Cu0.1Ni0.1Ti5O12-C as an active material of an anode in lithium-ion batteries seems to be a good alternative to currently used materials.

Keywords: anode, Li-ion batteries, Li₄O₅O₁₂, spinel

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59 Enhancing the Structural and Electrochemical Performance of Li-Rich Layered Metal Oxides Cathodes for Li-Ion Battery by Coating with the Active Material

Authors: Cyril O. Ehi-Eromosele, Ajayi Kayode

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The Li-rich layered metal oxides (LLO) are the most promising candidates for promising electrodes of high energy Li-ion battery (LIB). In literature, these electrode system has either been designed as a hetero-structure of the primary components (composite) or as a core-shell structure with improved electrochemistry reported for both configurations when compared with its primary components. With the on-going efforts to improve on the electrochemical performance of the LIB, it is important to investigate comparatively the structural and electrochemical characteristics of the core-shell like and ‘composite’ forms of these materials with the same compositions and synthesis conditions which could influence future engineering of these materials. Therefore, this study concerns the structural and electrochemical properties of the ‘composite’ and core-shell like LLO cathode materials with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₂O₂ (LiNi₀.₅Mn₀.₃Co₀.₂O₂ as core and Li₂MnO₃ as the shell). The results show that the core-shell sample (–CS) gave better electrochemical performance than the ‘composite’ sample (–C). Both samples gave the same initial charge capacity of ~300 mAh/g when cycled at 10 mA/g and comparable charge capacity (246 mAh/g for the –CS sample and 240 mAh/g for the –C sample) when cycled at 200 mA/g. However, the –CS sample gave a higher initial discharge capacity at both current densities. The discharge capacity of the –CS sample was 232 mAh/g and 164 mAh/g while the –C sample is 208 mAh/g and 143 mAh/g at the current densities of 10 mA/g and 200 mA/g, respectively. Electrochemical impedance spectroscopy (EIS) results show that the –CS sample generally exhibited a smaller resistance than the –C sample both for the uncycled and after 50th cycle. Detailed structural analysis is on-going, but preliminary results show that the –CS sample had bigger unit cell volume and a higher degree of cation mixing. The thermal stability of the –CS sample was higher than the –C sample. XPS investigation also showed that the pristine –C sample gave a more reactive surface (showing formation of carbonate species to a greater degree) which could result in the greater resistance seen in the EIS result. To reinforce the results obtained for the 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₃O₂ composition, the same investigations were extended to another ‘composite’ and core-shell like LLO cathode materials also with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂. In this case, the aim was to determine the electrochemical performance of the material using a low Ni content (LiNi₀.₃Mn₀.₃Co₀.₃O₂) as the core to clarify the contributions of the core-shell configuration to the electrochemical performance of these materials. Ni-rich layered oxides show active catalytic surface leading to electrolyte oxidation resulting in poor thermal stability and cycle life. Here, the core-shell sample also gave better electrochemical performance than the ‘composite’ sample with 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂ composition. Furthermore, superior electrochemical performance was also recorded for the core-shell like spinel modified LLO (0.5Li₂MnO₃-0.45LiNi₀.₅Mn₀.₃Co₀.₂O₂-0.05LiNi₀.₅Mn₁.₅O₄) when compared to the composite system. These results show that the core-shell configuration can generally be used to improve the structural and electrochemical properties of the LLO and spinel modified LLO materials.

Keywords: lithium-ion battery, lithium rich oxide cathode, core-shell structure, composite structure

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58 Influence Study of the Molar Ratio between Solvent and Initiator on the Reaction Rate of Polyether Polyols Synthesis

Authors: María José Carrero, Ana M. Borreguero, Juan F. Rodríguez, María M. Velencoso, Ángel Serrano, María Jesús Ramos

Abstract:

Flame-retardants are incorporated in different materials in order to reduce the risk of fire, either by providing increased resistance to ignition, or by acting to slow down combustion and thereby delay the spread of flames. In this work, polyether polyols with fire retardant properties were synthesized due to their wide application in the polyurethanes formulation. The combustion of polyurethanes is primarily dependent on the thermal properties of the polymer, the presence of impurities and formulation residue in the polymer as well as the supply of oxygen. There are many types of flame retardants, most of them are phosphorous compounds of different nature and functionality. The addition of these compounds is the most common method for the incorporation of flame retardant properties. The employment of glycerol phosphate sodium salt as initiator for the polyol synthesis allows obtaining polyols with phosphate groups in their structure. However, some of the critical points of the use of glycerol phosphate salt are: the lower reactivity of the salt and the necessity of a solvent (dimethyl sulfoxide, DMSO). Thus, the main aim in the present work was to determine the amount of the solvent needed to get a good solubility of the initiator salt. Although the anionic polymerization mechanism of polyether formation is well known, it seems convenient to clarify the role that DMSO plays at the starting point of the polymerization process. Regarding the fact that the catalyst deprotonizes the hydroxyl groups of the initiator and as a result of this, two water molecules and glycerol phosphate alkoxide are formed. This alkoxide, together with DMSO, has to form a homogeneous mixture where the initiator (solid) and the propylene oxide (PO) are soluble enough to mutually interact. The addition rate of PO increased when the solvent/initiator ratios studied were increased, observing that it also made the initiation step shorter. Furthermore, the molecular weight of the polyol decreased when higher solvent/initiator ratios were used, what revealed that more amount of salt was activated, initiating more chains of lower length but allowing to react more phosphate molecules and to increase the percentage of phosphorous in the final polyol. However, the final phosphorous content was lower than the theoretical one because only a percentage of salt was activated. On the other hand, glycerol phosphate disodium salt was still partially insoluble in DMSO studied proportions, thus, the recovery and reuse of this part of the salt for the synthesis of new flame retardant polyols was evaluated. In the recovered salt case, the rate of addition of PO remained the same than in the commercial salt but a shorter induction period was observed, this is because the recovered salt presents a higher amount of deprotonated hydroxyl groups. Besides, according to molecular weight, polydispersity index, FT-IR spectrum and thermal stability, there were no differences between both synthesized polyols. Thus, it is possible to use the recovered glycerol phosphate disodium salt in the same way that the commercial one.

Keywords: DMSO, fire retardants, glycerol phosphate disodium salt, recovered initiator, solvent

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57 Fly-Ash/Borosilicate Glass Based Geopolymers: A Mechanical and Microstructural Investigation

Authors: Gianmarco Taveri, Ivo Dlouhy

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Geopolymers are well-suited materials to abate CO2 emission coming from the Portland cement production, and then replace them, in the near future, in building and other applications. The cost of production of geopolymers may be seen the only weakness, but the use of wastes as raw materials could provide a valid solution to this problem, as demonstrated by the successful incorporation of fly-ash, a by-product of thermal power plants, and waste glasses. Recycled glass in waste-derived geopolymers was lately employed as a further silica source. In this work we present, for the first time, the introduction of recycled borosilicate glass (BSG). BSG is actually a waste glass, since it derives from dismantled pharmaceutical vials and cannot be reused in the manufacturing of the original articles. Owing to the specific chemical composition (BSG is an ‘alumino-boro-silicate’), it was conceived to provide the key components of zeolitic networks, such as amorphous silica and alumina, as well as boria (B2O3), which may replace Al2O3 and contribute to the polycondensation process. The solid–state MAS NMR spectroscopy was used to assess the extent of boron oxide incorporation in the structure of geopolymers, and to define the degree of networking. FTIR spectroscopy was utilized to define the degree of polymerization and to detect boron bond vibration into the structure. Mechanical performance was tested by means of 3 point bending (flexural strength), chevron notch test (fracture toughness), compression test (compressive strength), micro-indentation test (Vicker’s hardness). Spectroscopy (SEM and Confocal spectroscopy) was performed on the specimens conducted to failure. FTIR showed a characteristic absorption band attributed to the stretching modes of tetrahedral boron ions, whose tetrahedral configuration is compatible to the reaction product of geopolymerization. 27Al NMR and 29Si NMR spectra were instrumental in understanding the extent of the reaction. 11B NMR spectroscopies evidenced a change of the trigonal boron (BO3) inside the BSG in favor of a quasi-total tetrahedral boron configuration (BO4). Thanks to these results, it was inferred that boron is part of the geopolymeric structure, replacing the Si in the network, similarly to the aluminum, and therefore improving the quality of the microstructure, in favor of a more cross-linked network. As expected, the material gained as much as 25% in compressive strength (45 MPa) compared to the literature, whereas no improvements were detected in flexural strength (~ 5 MPa) and superficial hardness (~ 78 HV). The material also exhibited a low fracture toughness (0.35 MPa*m1/2), with a tangible brittleness. SEM micrographies corroborated this behavior, showing a ragged surface, along with several cracks, due to the high presence of porosity and impurities, acting as preferential points for crack initiation. The 3D pattern of the surface fracture, following the confocal spectroscopy, evidenced an irregular crack propagation, whose proclivity was mainly, but not always, to follow the porosity. Hence, the crack initiation and propagation are largely unpredictable.

Keywords: borosilicate glass, characterization, fly-ash, geopolymerization

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56 Biomaterials Solutions to Medical Problems: A Technical Review

Authors: Ashish Thakur

Abstract:

This technical paper was written in view of focusing the biomaterials and its various applications in modern industries. Author tires to elaborate not only the medical, infect plenty of application in other industries. The scope of the research area covers the wide range of physical, biological and chemical sciences that underpin the design of biomaterials and the clinical disciplines in which they are used. A biomaterial is now defined as a substance that has been engineered to take a form which, alone or as part of a complex system, is used to direct, by control of interactions with components of living systems, the course of any therapeutic or diagnostic procedure. Biomaterials are invariably in contact with living tissues. Thus, interactions between the surface of a synthetic material and biological environment must be well understood. This paper reviews the benefits and challenges associated with surface modification of the metals in biomedical applications. The paper also elaborates how the surface characteristics of metallic biomaterials, such as surface chemistry, topography, surface charge, and wettability, influence the protein adsorption and subsequent cell behavior in terms of adhesion, proliferation, and differentiation at the biomaterial–tissue interface. The chapter also highlights various techniques required for surface modification and coating of metallic biomaterials, including physicochemical and biochemical surface treatments and calcium phosphate and oxide coatings. In this review, the attention is focused on the biomaterial-associated infections, from which the need for anti-infective biomaterials originates. Biomaterial-associated infections differ markedly for epidemiology, aetiology and severity, depending mainly on the anatomic site, on the time of biomaterial application, and on the depth of the tissues harbouring the prosthesis. Here, the diversity and complexity of the different scenarios where medical devices are currently utilised are explored, providing an overview of the emblematic applicative fields and of the requirements for anti-infective biomaterials. In addition to this, chapter introduces nanomedicine and the use of both natural and synthetic polymeric biomaterials, focuses on specific current polymeric nanomedicine applications and research, and concludes with the challenges of nanomedicine research. Infection is currently regarded as the most severe and devastating complication associated to the use of biomaterials. Osteoporosis is a worldwide disease with a very high prevalence in humans older than 50. The main clinical consequences are bone fractures, which often lead to patient disability or even death. A number of commercial biomaterials are currently used to treat osteoporotic bone fractures, but most of these have not been specifically designed for that purpose. Many drug- or cell-loaded biomaterials have been proposed in research laboratories, but very few have received approval for commercial use. Polymeric nanomaterial-based therapeutics plays a key role in the field of medicine in treatment areas such as drug delivery, tissue engineering, cancer, diabetes, and neurodegenerative diseases. Advantages in the use of polymers over other materials for nanomedicine include increased functionality, design flexibility, improved processability, and, in some cases, biocompatibility.

Keywords: nanomedicine, tissue, infections, biomaterials

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