Search results for: nickel doped cobalt sulfide

Authors: Dyah Purwaningsih, Roto Roto, Hari Sutrisno

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Manganese dioxide (MnO₂) and its derivatives are among the most widely used materials for the positive electrode in both primary and rechargeable lithium batteries. The MnO₂ derivative compound of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) is one of the leading candidates for positive electrode materials in lithium batteries as it is abundant, low cost and environmentally friendly. Over the years, synthesis of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) has been carried out using various methods including sol-gel, gas condensation, spray pyrolysis, and ceramics. Problems with these various methods persist including high cost (so commercially inapplicable) and must be done at high temperature (environmentally unfriendly). This research aims to: (1) synthesize LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) by reflux technique; (2) develop microstructure analysis method from XRD Powder LiMₓMn₂₋ₓO₄ data with the two-stage method; (3) study the electrical conductivity of LiMₓMn₂₋ₓO₄. This research developed the synthesis of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) with reflux. The materials consisting of Mn(CH₃COOH)₂. 4H₂O and Na₂S₂O₈ were refluxed for 10 hours at 120°C to form β-MnO₂. The doping of Co, Ni and Cr were carried out using solid-state method with LiOH to form LiMₓMn₂₋ₓO₄. The instruments used included XRD, SEM-EDX, XPS, TEM, SAA, TG/DTA, FTIR, LCR meter and eight-channel battery analyzer. Microstructure analysis of LiMₓMn₂₋ₓO₄ was carried out on XRD powder data by two-stage method using FullProf program integrated into WinPlotR and Oscail Program as well as on binding energy data from XPS. The morphology of LiMₓMn₂₋ₓO₄ was studied with SEM-EDX, TEM, and SAA. The thermal stability test was performed with TG/DTA, the electrical conductivity was studied from the LCR meter data. The specific capacity of LiMₓMn₂₋ₓO₄ as lithium battery cathode was tested using an eight-channel battery analyzer. The results showed that the synthesis of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) was successfully carried out by reflux. The optimal temperature of calcination is 750°C. XRD characterization shows that LiMn₂O₄ has a cubic crystal structure with Fd3m space group. By using the CheckCell in the WinPlotr, the increase of Li/Mn mole ratio does not result in changes in the LiMn₂O₄ crystal structure. The doping of Co, Ni and Cr on LiMₓMn₂₋ₓO₄ (x = 0.02; 0.04; 0; 0.6; 0.08; 0.10) does not change the cubic crystal structure of Fd3m. All the formed crystals are polycrystals with the size of 100-450 nm. Characterization of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) microstructure by two-stage method shows the shrinkage of lattice parameter and cell volume. Based on its range of capacitance, the conductivity obtained at LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) is an ionic conductivity with varying capacitance. The specific battery capacity at a voltage of 4799.7 mV for LiMn₂O₄; Li₁.₀₈Mn₁.₉₂O₄; LiCo₀.₁Mn₁.₉O₄; LiNi₀.₁Mn₁.₉O₄ and LiCr₀.₁Mn₁.₉O₄ are 88.62 mAh/g; 2.73 mAh/g; 89.39 mAh/g; 85.15 mAh/g; and 1.48 mAh/g respectively.

Keywords: LiMₓMn₂₋ₓO₄, solid-state, reflux, two-stage method, ionic conductivity, specific capacity

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Authors: Ahmad Kayvani Fard, Gordon Mckay, Muataz Hussien

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Adsorption/sorption is believed to be one of the optimal processes for the removal of heavy metals from water due to its low operational and capital cost as well as its high removal efficiency. Different materials have been reported in literature as adsorbent for heavy metal removal in waste water such as natural sorbents, organic polymers (synthetic) and mineral materials (inorganic). The selection of adsorbents and development of new functional materials that can achieve good removal of heavy metals from water is an important practice and depends on many factors, such as the availability of the material, cost of material, and material safety and etc. In this study we reported the synthesis of doped Activated carbon and Carbon nanotube (CNT) with different loading of metal oxide nanoparticles such as Fe2O3, Fe3O4, Al2O3, TiO2, SiO2 and Ag nanoparticles and their application in removal of heavy metals, hydrocarbon, and organics from waste water. Commercial AC and CNT with different loadings of mentioned nanoparticle were prepared and effect of pH, adsorbent dosage, sorption kinetic, and concentration effects are studied and optimum condition for removal of heavy metals from water is reported. The prepared composite sorbent is characterized using field emission scanning electron microscopy (FE-SEM), high transmission electron microscopy (HR-TEM), thermogravimetric analysis (TGA), X-ray diffractometer (XRD), the Brunauer, Emmett and Teller (BET) nitrogen adsorption technique, and Zeta potential. The composite materials showed higher removal efficiency and superior adsorption capacity compared to commercially available carbon based adsorbent. The specific surface area of AC increased by 50% reaching up to 2000 m2/g while the CNT specific surface area of CNT increased by more than 8 times reaching value of 890 m2/g. The increased surface area is one of the key parameters along with surface charge of the material determining the removal efficiency and removal efficiency. Moreover, the surface charge density of the impregnated CNT and AC have enhanced significantly where can benefit the adsorption process. The nanoparticles also enhance the catalytic activity of material and reduce the agglomeration and aggregation of material which provides more active site for adsorbing the contaminant from water. Some of the results for treating wastewater includes 100% removal of BTEX, arsenic, strontium, barium, phenolic compounds, and oil from water. The results obtained are promising for the use of AC and CNT loaded with metal oxide nanoparticle in treatment and pretreatment of waste water and produced water before desalination process. Adsorption can be very efficient with low energy consumption and economic feasibility.

Keywords: carbon nanotube, activated carbon, adsorption, heavy metal, water treatment

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Authors: Adrian Niewiadomski, Barbara Surma, Katarzyna Kolodziejak, Dorota A. Pawlak

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Oxide-oxide eutectic is attracting increasing interest of scientific community because of their unique properties and numerous potential applications. Some of the most interesting examples of applications are metamaterials, glucose sensors, photoactive materials, thermoelectric materials, and photocatalysts. Their unique properties result from the fact that composite materials consist of two or more phases. As a result, these materials have additive and product properties. Additive properties originate from particular phases while product properties originate from the interaction between phases. MnTiO3-TiO2 eutectic is one of such materials. TiO2 is a well-known semiconductor, and it is used as a photocatalyst. Moreover, it may be used to produce solar cells, in a gas sensing devices and in electrochemistry. MnTiO3 is a semiconductor and antiferromagnetic. Therefore it has potential application in integrated circuits devices, and as a gas and humidity sensor, in non-linear optics and as a visible-light activated photocatalyst. The above facts indicate that eutectic MnTiO3-TiO2 constitutes an extremely promising material that should be studied. Despite that Raman spectroscopy is a powerful method to characterize materials, to our knowledge Raman studies of eutectics are very limited, and there are no studies of the MnTiO3-TiO2 eutectic. While to our knowledge the papers regarding this material are scarce. The MnTiO3-TiO2 eutectic, as well as TiO2 and MnTiO3 single crystals, were grown by the micro-pulling-down method at the Institute of Electronic Materials Technology in Warsaw, Poland. A nitrogen atmosphere was maintained during whole crystal growth process. The as-grown samples of MnTiO3-TiO2 eutectic, as well as TiO2 and MnTiO3 single crystals, are black and opaque. Samples were cut perpendicular to the growth direction. Cross sections were examined with scanning electron microscopy (SEM) and with Raman spectroscopy. The present studies showed that maintaining nitrogen atmosphere during crystal growth process may result in obtaining black TiO2 crystals. SEM and Raman experiments showed that studied eutectic consists of three distinct regions. Furthermore, two of these regions correspond with MnTiO3, while the third region corresponds with the TiO2-xNx phase. Raman studies pointed out that TiO2-xNx phase crystallizes in rutile structure. The studies show that Raman experiments may be successfully used to characterize eutectic materials. The MnTiO3-TiO2 eutectic was grown by the micro-pulling-down method. SEM and micro-Raman experiments were used to establish phase composition of studied eutectic. The studies revealed that the TiO2 phase had been doped with nitrogen. Therefore the TiO2 phase is, in fact, a solid solution with TiO2-xNx composition. The remaining two phases exhibit Raman lines of both rutile TiO2 and MnTiO3. This points out to some kind of coexistence of these phases in studied eutectic.

Keywords: compound materials, eutectic growth and characterization, Raman spectroscopy, rutile TiO₂

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Authors: S. V. Kuznetsov, M. N. Mayakova, V. Yu. Proydakova, V. V. Pavlov, A. S. Nizamutdinov, O. A. Morozov, V. V. Voronov, P. P. Fedorov

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Increase in the share of electricity received by conversion of solar energy results in the reduction of the industrial impact on the environment from the use of the hydrocarbon energy sources. One way to increase said share is to improve the efficiency of solar energy conversion in silicon-based solar panels. Such efficiency increase can be achieved by transferring energy from sunlight-insensitive areas of work of silicon solar panels to the area of their photoresistivity. To achieve this goal, a transition to new luminescent materials with the high quantum yield of luminescence is necessary. Improvement in the quantum yield can be achieved by quantum cutting, which allows obtaining a quantum yield of down conversion of more than 150% due to the splitting of high-energy photons of the UV spectral range into lower-energy photons of the visible and near infrared spectral ranges. The goal of present work is to test approach of excitation through sensibilization of 4f-4f fluorescence of Yb3+ by various RE ions absorbing in UV and Vis spectral ranges. One of promising materials for quantum cutting luminophores are fluorides. In our investigation we have developed synthesis of nano- and submicron powders of calcium fluoride and strontium doped with rare-earth elements (Yb: Ce, Yb: Pr, Yb: Eu) of controlled dimensions and shape by co-precipitation from water solution technique. We have used Ca(NO3)2*4H2O, Sr(NO3)2, HF, NH4F as precursors. After initial solutions of nitrates were prepared they have been mixed with fluorine containing solution by dropwise manner. According to XRD data, the synthesis resulted in single phase samples with fluorite structure. By means of SEM measurements, we have confirmed spherical morphology and have determined sizes of particles (50-100 nm after synthesis and 150-300 nm after calcination). Temperature of calcination appeared to be 600°C. We have investigated the spectral-kinetic characteristics of above mentioned compounds. Here the diffuse reflection and laser induced fluorescence spectra of Yb3+ ions excited at around 4f-4f and 4f-5d transitions of Pr3+, Eu3+ and Ce3+ ions in the synthesized powders are reported. The investigation of down conversion luminescence capability of synthesized compounds included measurements of fluorescence decays and quantum yield of 2F5/2-2F7/2 fluorescence of Yb3+ ions as function of Yb3+ and sensitizer contents. An optimal chemical composition of CaF2-YbF3- LnF3 (Ln=Ce, Eu, Pr), SrF2-YbF3-LnF3 (Ln=Ce, Eu, Pr) micro- and nano- powders according to criteria of maximal IR fluorescence yield is proposed. We suppose that investigated materials are prospective in solar panels improvement applications. Work was supported by Russian Science Foundation grant #17-73- 20352.

Keywords: solar cell, fluorides, down-conversion luminescence, maximum quantum yield

Procedia PDF Downloads 246

Authors: Tomás Sobrino, Lara García-Varela, Marta Aramburu-Núñez, Mónica Castro, Noemí Gómez-Lado, Mariña Rodríguez-Arrizabalaga, Antía Custodia, Juan Manuel Pías-Peleteiro, José Manuel Aldrey, Daniel Romaus-Sanjurjo, Ángeles Almeida, Pablo Aguiar, Alberto Ouro

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Introduction: Alzheimer’s disease (AD) and other tauopathies are primary causes of dementia, causing progressive cognitive deterioration that entails serious repercussions for the patients' performance of daily tasks. Currently, there is no effective approach for the early diagnosis and treatment of AD and tauopathies. This study suggests a theragnostic approach based on the importance of phosphorylated tau protein (p-Tau) in the early pathophysiological processes of AD. We have developed a novel theragnostic monoclonal antibody (mAb) to provide both diagnostic and therapeutic effects. Methods/Results: We have developed a p-Tau mAb, which was doped with deferoxamine for radiolabeling with Zirconium-89 (89Zr) for PET imaging, as well as fluorescence dies for immunofluorescence assays. The p-Tau mAb was evaluated in vitro for toxicity by MTT assay, LDH activity, propidium iodide/Annexin V assay, caspase-3, and mitochondrial membrane potential (MMP) assay in both mouse endothelial cell line (bEnd.3) and cortical primary neurons cell cultures. Importantly, non-toxic effects (up to concentrations of p-Tau mAb greater than 100 ug/mL) were detected. In vivo experiments in the tauopathy model mice (PS19) show that the 89Zr-pTau-mAb and 89Zr-Fragments-pTau-mAb are stable in circulation for up to 10 days without toxic effects. However, only less than 0.2% reached the brain, so further strategies have to be designed for crossing the Brain-Blood-Barrier (BBB). Moreover, an intraparenchymal treatment strategy was carried out. The PS19 mice were operated to implement osmotic pumps (Alzet 1004) at two different times, at 4 and 7 months, to stimulate the controlled release for one month each of the B6 antibody or the IgG1 control antibody. We demonstrated that B6-treated mice maintained their motor and memory abilities significantly compared with IgG1 treatment. In addition, we observed a significant reduction in p-Tau deposits in the brain. Conclusions /Discussion: A theragnostic pTau-mAb was developed. Moreover, we demonstrated that our p-Tau mAb recognizes very-early pathology forms of p-Tau by non-invasive techniques, such as PET. In addition, p-Tau mAb has non-toxic effects, both in vitro and in vivo. Although the p-Tau mAb is stable in circulation, only 0.2% achieve the brain. However, direct intraventricular treatment significantly reduces cognitive impairment in Alzheimer's animal models, as well as the accumulation of toxic p-Tau species.

Keywords: alzheimer's disease, theragnosis, tau, PET, immunotherapy, tauopathies

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Authors: Mohamed A. Baba, Gazy Rodowan, Brigita Abakevičienė, Sigitas Tamulevičius, Bartlomiej Lemieszek, Sebastian Molin, Tomas Tamulevičius

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Solid oxide fuel cells (SOFC) efficiently convert hydrogen to energy without producing any disturbances or contaminants. The core of the cell is electrolyte. For improving the performance of electrolyte-supported cells, it is desirable to extend the available exchange surface area by micro-structuring of the electrolyte with laser-based micromachining. This study investigated the electrochemical performance of cells micro machined using a femtosecond laser. Commercial ceramic SOFC (Elcogen, AS) with a total thickness of 400 μm was structured by 1030 nm wavelength Yb: KGW fs-laser Pharos (Light Conversion) using 100 kHz repetition frequency and 290 fs pulse length light by scanning with the galvanometer scanner (ScanLab) and focused with a f-Theta telecentric lens (SillOptics). The sample height was positioned using a motorized z-stage. The microstructures were formed using a laser spiral trepanning in Ni/YSZ anode supported membrane at the central part of the ceramic piece of 5.5 mm diameter at active area of the cell. All surface was drilled with 275 µm diameter holes spaced by 275 µm. The machining processes were carried out under ambient conditions. The microstructural effects of the femtosecond laser treatment on the electrolyte surface were investigated prior to the electrochemical characterisation using a scanning electron microscope (SEM) Quanta 200 FEG (FEI). The Novo control Alpha-A was used for electrochemical impedance spectroscopy on a symmetrical cell configuration with an excitation amplitude of 25 mV and a frequency range of 1 MHz to 0.1 Hz. The fuel cell characterization of the cell was examined on open flanges test setup by Fiaxell. Using nickel mesh on the anode side and au mesh on the cathode side, the cell was electrically linked. The cell was placed in a Kittec furnace with a Process IDentifier temperature controller. The wires were connected to a Solartron 1260/1287 frequency analyzer for the impedance and current-voltage characterization. In order to determine the impact of the anode's microstructure on the performance of the commercial cells, the acquired results were compared to cells with unstructured anode. Geometrical studies verified that the depth of the -holes increased linearly according to laser energy and scanning times. On the other hand, it reduced as the scanning speed increased. The electrochemical analysis demonstrates that the open circuit voltage OCV values of the two cells are equal. Further, the modified cell's initial slope reduces to 0.209 from 0.253 of the unmodified cell, revealing that the surface modification considerably decreases energy loss. Plus, the maximum power density for the cell with the microstructure and the reference cell respectively, are 1.45 and 1.16 Wcm⁻².

Keywords: electrochemical performance, electrolyte-supported cells, laser micro-structuring, solid oxide fuel cells

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Authors: Mihail Simion Beldean-Galea, Virginia Coman, Florina Copaciu, Mihaela Vlassa, Radu Mihaiescu, Adina Croitoru, Viorel Arghius, Modest Gertsiuk, Mikola Gertsiuk

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Taking into consideration the huge number of chemicals released into environment compartments a proper environmental risk assessment is difficult to predict due to the gap of legislation and improper toxicological assessment of chemicals compounds. In Romania as well as in many other countries from Europe, the chemical status of the water body is characterized taking into consideration the Water Framework Directive (WFD) and the substances listed in Annex X. This Annex includes 45 substances from different classes of organic compounds and heavy metals for which AA-EQS and MAC-EQS have been established. For other compounds which are not included in Annex X, different methodologies to prioritize chemicals for risk assessment and monitoring has been proposed. These methodologies take into account Predicted No-Effect Concentrations (PNECs) of different classes of chemicals compounds available from existing risk assessments or from read-across models for acute toxicity to the standard test organisms such as Daphnia magna and Selenastrum capricornutum. Our work presents the monitoring results of 30 priority substances including polyaromatic hydrocarbons, pesticides, halogenated compounds, plasticizers and heavy metals and other 34 substances from different classes of pesticides and pharmaceuticals which are not included on the list of priority substances, performed in the Upper Tisza River Watershed from Romania and Ukraine. The obtained monitoring data were used for the establishment of the list of more relevant pollutants in the studied area and to establish the potential river basin specific pollutants. For this purpose, two indicators such as the Frequency of exceedance and Extent of exceedance of Predicted no-Effect Concentration (PNEC) were evaluated. These two indicators are based on maximum environmental concentrations (MECs) of priority substances and for other pollutants is use statistically based averages of obtained measured concentration compared to the lowest PNEC thresholds. From the obtained results it can be concluded that polyaromatic hydrocarbon such as Fluoranthene, Benzo[a]pyrene, Benzo[b]fluorathene, benzo[k]fluoranthene, Benzo(g.h.i)perylene, Indeno(1.2.3-cd)-pyrene, heavy metals such as Cadmium, Lead and Nickel can be considered as river basin specific pollutants, their concentration exceeding the Annual Average EQS concentration. Other compounds such as estrone, estriol, 174-β estradiol, naproxen or some antibiotics (Penicillin G, Tetracycline or Ceftazidime) should be taken into account for a long monitoring, in some cases their concentration exceeding PNEC. Acknowledgements: This work is performed in the frame of NATO SfP Programme, Project no. 984440.

Keywords: prioritization, river basin specific pollutants, Tisza River, water framework directive

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Authors: Bastian Waduge Naveen Harindu Hemasiri, Jae-Kwan Kim, Ji-Myon Lee

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Indium tin oxide (ITO) remains the industrial standard transparent conducting oxides with better performances. Recently, graphene becomes as a strong material with unique properties to replace the ITO. However, graphene/ITO hybrid composite material is a newly born field in the electronic world. In this study, the graphene/ITO composite bi-film was synthesized by a two steps process. 10 wt.% tin-doped, ITO thin films were produced by an environmentally friendly aqueous sol-gel spin coating technique with economical salts of In(NO3)3.H2O and SnCl4 without using organic additives. The wettability and surface free energy (97.6986 mJ/m2) enhanced oxygen plasma treated glass substrates were used to form voids free continuous ITO film. The spin-coated samples were annealed at 600 0C for 1 hour under low vacuum conditions to obtained crystallized, ITO film. The crystal structure and crystalline phases of ITO thin films were analyzed by X-ray diffraction (XRD) technique. The Scherrer equation was used to determine the crystallite size. Detailed information about chemical composition and elemental composition of the ITO film were determined by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) coupled with FE-SEM respectively. Graphene synthesis was done under chemical vapor deposition (CVD) method by using Cu foil at 1000 0C for 1 min. The quality of the synthesized graphene was characterized by Raman spectroscopy (532nm excitation laser beam) and data was collected at room temperature and normal atmosphere. The surface and cross-sectional observation were done by using FE-SEM. The optical transmission and sheet resistance were measured by UV-Vis spectroscopy and four point probe head at room temperature respectively. Electrical properties were also measured by using V-I characteristics. XRD patterns reveal that the films contain the In2O3 phase only and exhibit the polycrystalline nature of the cubic structure with the main peak of (222) plane. The peak positions of In3d5/2 (444.28 eV) and Sn3d5/2 (486.7 eV) in XPS results indicated that indium and tin are in the oxide form only. The UV-visible transmittance shows 91.35 % at 550 nm with 5.88 x 10-3 Ωcm specific resistance. The G and 2D band in Raman spectroscopy of graphene appear at 1582.52 cm-1 and 2690.54 cm-1 respectively when the synthesized CVD graphene on SiO2/Si. The determined intensity ratios of 2D to G (I2D/IG) and D to G (ID/IG) were 1.531 and 0.108 respectively. However, the above-mentioned G and 2D peaks appear at 1573.57 cm-1 and 2668.14 cm-1 respectively when the CVD graphene on the ITO coated glass, the positions of G and 2D peaks were red shifted by 8.948 cm-1 and 22.396 cm-1 respectively. This graphene/ITO bi-film shows modified electrical properties when compares with sol-gel derived ITO film. The reduction of sheet resistance in the bi-film was 12.03 % from the ITO film. Further, the fabricated graphene/ITO bi-film shows 88.66 % transmittance at 550 nm wavelength.

Keywords: chemical vapor deposition, graphene, ITO, Raman Spectroscopy, sol-gel

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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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Authors: Łukasz Mazur, Kamil Domaradzki, Maciej Bik, Tomasz Brylewski, Aleksander Gil

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Interconnects used in solid oxide fuel and electrolyzer cells (SOFCₛ/SOECs) serve several important functions, and therefore interconnect materials must exhibit certain properties. Their thermal expansion coefficient needs to match that of the ceramic components of these devices – the electrolyte, anode and cathode. Interconnects also provide structural rigidity to the entire device, which is why interconnect materials must exhibit sufficient mechanical strength at high temperatures. Gas-tightness is also a prerequisite since they separate gas reagents, and they also must provide very good electrical contact between neighboring cells over the entire operating time. High-chromium ferritic steels meets these requirements to a high degree but are affected by the formation of a Cr₂O₃ scale, which leads to increased electrical resistance. The final criterion for interconnect materials is chemical inertness in relation to the remaining cell components. In the case of ferritic steels, this has proved difficult due to the formation of volatile and reactive oxyhydroxides observed when Cr₂O3 is exposed to oxygen and water vapor. This process is particularly harmful on the cathode side in SOFCs and the anode side in SOECs. To mitigate this, protective-conducting ceramic coatings can be deposited on an interconnect's surface. The area-specific resistance (ASR) of a single interconnect cannot exceed 0.1 m-2 at any point of the device's operation. The rate at which the CrO₃ scale grows on ferritic steels can be reduced significantly via the so-called reactive element effect (REE). Research has shown that the deposition of Gd₂O₃ nanoparticles on the surface of the Crofer 22 APU, already modified using a protective-conducting spinel layer, further improves the oxidation resistance of this steel. However, the deposition of the manganese-cobalt spinel layer is a rather complex process and is performed at high temperatures in reducing and oxidizing atmospheres. There was thus reason to believe that this process may reduce the effectiveness of Gd₂O₃ nanoparticles added as an active element source. The objective of the present study was, therefore, to determine any potential impact by introducing a preoxidation stage after the nanoparticle deposition and before the steel is coated with the spinel. This should have allowed the nanoparticles to incorporate into the interior of the scale formed on the steel. Different samples were oxidized for 7000 h in air at 1073 K under quasi-isothermal conditions. The phase composition, chemical composition, and microstructure of the oxidation products formed on the samples were determined using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. A four-point, two-probe DC method was applied to measure ASR. It was found that coating deposition does indeed reduce the beneficial effect of Gd₂O₃ addition, since the smallest mass gain and the lowest ASR value were determined for the sample for which the additional preoxidation stage had been performed. It can be assumed that during this stage, gadolinium incorporates into and segregates at grain boundaries in the thin Cr₂O₃ that is forming. This allows the Gd₂O₃ nanoparticles to be a more effective source of the active element.

Keywords: interconnects, oxide nanoparticles, reactive element effect, SOEC, SOFC

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Authors: Helen Bartsch, Markus Feldmann

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The dimensioning of steel structures subject to fatigue loads, such as wind turbines, bridges, masts and towers, crane runways and weirs or components in crane construction, is often dominated by fatigue verification. The fatigue details defined by the welded connections, such as butt or cruciform joints, longitudinal welds, welded-on or welded-in stiffeners, etc., are decisive. In Europe, the verification is usually carried out according to EN 1993-1-9 on a nominal stress basis. The basis is the detailed catalog, which specifies the fatigue strength of the various weld and construction details according to fatigue classes. Until now, a relation between fatigue classes and weld imperfection sizes is not included. Quality levels for imperfections in fusion-welded joints in steel, nickel, titanium and their alloys are regulated in EN ISO 5817, which, however, doesn’t contain direct correlations to fatigue resistances. The question arises whether some imperfections might be tolerable to a certain extent since they may be present in the test data used for detail classifications dating back decades ago. Although current standardization requires proof of satisfying limits of imperfection sizes, it would also be possible to tolerate welds with certain irregularities if these can be reliably quantified by non-destructive testing. Fabricators would be prepared to undertake carefully and sustained weld inspection in view of the significant economic consequences of such unfavorable fatigue classes. This paper presents investigations on the fatigue behavior of common welded details containing imperfections. In contrast to the common nominal stress concept, local fatigue concepts were used to consider the true stress increase, i.e., local stresses at the weld toe and root. The actual shape of a weld comprising imperfections, e.g., gaps or undercuts, can be incorporated into the fatigue evaluation, usually on a numerical basis. With the help of the effective notch stress concept, the fatigue resistance of detailed local weld shapes is assessed. Validated numerical models serve to investigate notch factors of fatigue details with different geometries. By utilizing parametrized ABAQUS routines, detailed numerical studies have been performed. Depending on the shape and size of different weld irregularities, fatigue classes can be defined. As well load-carrying welded details, such as the cruciform joint, as non-load carrying welded details, e.g., welded-on or welded-in stiffeners, are regarded. The investigated imperfections include, among others, undercuts, excessive convexity, incorrect weld toe, excessive asymmetry and insufficient or excessive throat thickness. Comparisons of the impact of different imperfections on the different types of fatigue details are made. Moreover, the influence of a combination of crucial weld imperfections on the fatigue resistance is analyzed. With regard to the trend of increasing efficiency in steel construction, the overall aim of the investigations is to include a more economical differentiation of fatigue details with regard to tolerance sizes. In the long term, the harmonization of design standards, execution standards and regulations of weld imperfections is intended.

Keywords: effective notch stress, fatigue, fatigue design, weld imperfections

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Authors: S. M. Giripunje, Mohit Kumar

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Acoustic energy that exists in our everyday life and environment have been overlooked as a green energy that can be extracted, generated, and consumed without any significant negative impact to the environment. The harvested energy can be used to enable new technology like wireless sensor networks. Technological developments in the realization of truly autonomous MEMS devices and energy storage systems have made acoustic energy harvesting (AEH) an increasingly viable technology. AEH is the process of converting high and continuous acoustic waves from the environment into electrical energy by using an acoustic transducer or resonator. AEH is not popular as other types of energy harvesting methods since sound waves have lower energy density and such energy can only be harvested in very noisy environment. However, the energy requirements for certain applications are also correspondingly low and also there is a necessity to observe the noise to reduce noise pollution. So the ability to reclaim acoustic energy and store it in a usable electrical form enables a novel means of supplying power to relatively low power devices. A quarter-wavelength straight-tube acoustic resonator as an acoustic energy harvester is introduced with polyvinylidene fluoride (PVDF) and PVDF doped with ZnO nanoparticles, piezoelectric cantilever beams placed inside the resonator. When the resonator is excited by an incident acoustic wave at its first acoustic eigen frequency, an amplified acoustic resonant standing wave is developed inside the resonator. The acoustic pressure gradient of the amplified standing wave then drives the vibration motion of the PVDF piezoelectric beams, generating electricity due to the direct piezoelectric effect. In order to maximize the amount of the harvested energy, each PVDF and PVDF-ZnO piezoelectric beam has been designed to have the same structural eigen frequency as the acoustic eigen frequency of the resonator. With a single PVDF beam placed inside the resonator, the harvested voltage and power become the maximum near the resonator tube open inlet where the largest acoustic pressure gradient vibrates the PVDF beam. As the beam is moved to the resonator tube closed end, the voltage and power gradually decrease due to the decreased acoustic pressure gradient. Multiple piezoelectric beams PVDF and PVDF-ZnO have been placed inside the resonator with two different configurations: the aligned and zigzag configurations. With the zigzag configuration which has the more open path for acoustic air particle motions, the significant increases in the harvested voltage and power have been observed. Due to the interruption of acoustic air particle motion caused by the beams, it is found that placing PVDF beams near the closed tube end is not beneficial. The total output voltage of the piezoelectric beams increases linearly as the incident sound pressure increases. This study therefore reveals that the proposed technique used to harvest sound wave energy has great potential of converting free energy into useful energy.

Keywords: acoustic energy, acoustic resonator, energy harvester, eigenfrequency, polyvinylidene fluoride (PVDF)

Procedia PDF Downloads 355

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

Procedia PDF Downloads 130

Authors: Glauco M. M. M. Lustosa, João Paulo C. Costa, Sonia M. Zanetti, Mario Cilense, Leinig Antônio Perazolli, Maria Aparecida Zaghete

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The contamination of the environment has been one of the biggest problems of our time, mostly due to developments of many industries. SnO2 is an n-type semiconductor with band gap about 3.5 eV and has its electrical conductivity dependent of type and amount of modifiers agents added into matrix ceramic during synthesis process, allowing applications as sensing of gaseous pollutants on ambient. The chemical synthesis by polymeric precursor method consists in a complexation reaction between tin ion and citric acid at 90 °C/2 hours and subsequently addition of ethyleneglycol for polymerization at 130 °C/2 hours. It also prepared polymeric resin of zinc, cobalt and niobium ions. Stoichiometric amounts of the solutions were mixed to obtain the systems (Zn, Nb)-SnO2 and (Co, Nb) SnO2 . The metal immobilization reduces its segregation during the calcination resulting in a crystalline oxide with high chemical homogeneity. The resin was pre-calcined at 300 °C/1 hour, milled in Atritor Mill at 500 rpm/1 hour, and then calcined at 600 °C/2 hours. X-Ray Diffraction (XDR) indicated formation of SnO2 -rutile phase (JCPDS card nº 41-1445). The characterization by Scanning Electron Microscope of High Resolution showed spherical ceramic powder nanostructured with 10-20 nm of diameter. 20 mg of SnO2 -based powder was kept in 20 ml of isopropyl alcohol and then taken to an electrophoretic deposition (EPD) system. The EPD method allows control the thickness films through the voltage or current applied in the electrophoretic cell and by the time used for deposition of ceramics particles. This procedure obtains films in a short time with low costs, bringing prospects for a new generation of smaller size devices with easy integration technology. In this research, films were obtained in an alumina substrate with interdigital electrodes after applying 2 kV during 5 and 10 minutes in cells containing alcoholic suspension of (Zn, Nb)-SnO2 and (Co, Nb) SnO2 of powders, forming a sensing layer. The substrate has designed integrated micro hotplates that provide an instantaneous and precise temperature control capability when a voltage is applied. The films were sintered at 900 and 1000 °C in a microwave oven of 770 W, adapted by the research group itself with a temperature controller. This sintering is a fast process with homogeneous heating rate which promotes controlled growth of grain size and also the diffusion of modifiers agents, inducing the creation of intrinsic defects which will change the electrical characteristics of SnO2 -based powders. This study has successfully demonstrated a microfabricated system with an integrated micro-hotplate for detection of CO and NO2 gas at different concentrations and temperature, with self-heating SnO2 - based nanoparticles films, being suitable for both industrial process monitoring and detection of low concentrations in buildings/residences in order to safeguard human health. The results indicate the possibility for development of gas sensors devices with low power consumption for integration in portable electronic equipment with fast analysis. Acknowledgments The authors thanks to the LMA-IQ for providing the FEG-SEM images, and the financial support of this project by the Brazilian research funding agencies CNPq, FAPESP 2014/11314-9 and CEPID/CDMF- FAPESP 2013/07296-2.

Keywords: chemical synthesis, electrophoretic deposition, self-heating, gas sensor

Procedia PDF Downloads 254

Authors: Nihad Chakri, Btissam El Amrani, Faouzi Berrada, Halima Jounaid, Fouad Amraoui

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Public baths or hammams play an essential role in the Moroccan urban and peri-urban fabric, constituting part of the cultural heritage. Urbanization in Morocco has led to a significant increase in the number of these traditional hammams: between 6,000 and 15,000 units (to be updated) operate with a traditional heating system. Numerous studies on energy consumption indicate that a hammam consumes between 60 and 120m3 of water and one to two tons of wood per day. On average, one ton of wood costs 650 Moroccan dirhams (approximately 60 Euros), resulting in a daily fuel cost of around 1300 Moroccan dirhams (about 120 Euros). These high consumptions result in significant environmental nuisances generated by: Wastewater: in the case of hammams located on the outskirts of Casablanca, such as our study area, the Municipality of Dar Bouazza, most of these waters are directly discharged into the receiving environment without prior treatment because they are not connected to the sanitation network. Emissions of black smoke and ashes produced by the often incomplete combustion of wood. Reducing the liquid and gas emissions generated by these hammams thus poses an environmental and sustainable development challenge that needs to be addressed. In this context, we initiated the Eco-hammam project with the objective of implementing innovative and locally adapted solutions to limit the negative impacts of hammams on the environment and reduce water and wood energy consumption. This involves treating and reusing wastewater through a compact system with heat recovery and using alternative energy sources to increase and enhance the energy efficiency of these traditional hammams. To achieve this, on-site surveys of hammams in the Dar Bouazza Municipality and the application of statistical approaches to the results of the physico-chemical and bacteriological characterization of incoming and outgoing water from these units were conducted. This allowed us to establish an environmental diagnosis of these entities. In conclusion, the analysis of well water used by Dar Bouazza's hammams revealed the presence of certain parameters that could be hazardous to public health, such as total germs, total coliforms, sulfite-reducing spores, chromium, nickel, and nitrates. Therefore, this work primarily focuses on prospecting upstream of our study area to verify if other sources of pollution influence the quality of well water.

Keywords: public baths, hammams, cultural heritage, urbanization, water consumption, wood consumption, environmental nuisances, wastewater, environmental challenge, sustainable development, Eco-hammam project, innovative solutions, local adaptation, negative impacts, water conservation, wastewater treatment, heat recovery, alternative energy sources, on-site surveys, Dar Bouazza Municipality, statistical approaches, physico-chemical characterization, bacteriological characterization, environmental diagnosis, well water analysis, public health, pollution sources, well water quality

Procedia PDF Downloads 39

Authors: Masood Otarod, Ronald M. Supkowski

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This abstract discusses a method that reduces the general dispersion model in cylindrical coordinates to a second order linear ordinary differential equation with constant coefficients so that it can be utilized to conduct kinetic studies in packed bed tubular catalytic reactors at a broad range of Reynolds numbers. The model was tested by 13CO isotope transient tracing of the CO adsorption of Boudouard reaction in a differential reactor at an average Reynolds number of 0.2 over Pd-Al2O3 catalyst. Detailed experimental results have provided evidence for the validity of the theoretical framing of the model and the estimated parameters are consistent with the literature. The solution of the general dispersion model requires the knowledge of the radial distribution of axial velocity. This is not always known. Hence, up until now, the implementation of the dispersion model has been largely restricted to the plug-flow regime. But, ideal plug-flow is impossible to achieve and flow regimes approximating plug-flow leave much room for debate as to the validity of the results. The reduction of the general dispersion model transpires as a result of the application of a factorization theorem. Factorization theorem is derived from the observation that a cross section of a catalytic bed consists of a solid phase across which the reaction takes place and a void or porous phase across which no significant measure of reaction occurs. The disparity in flow and the heterogeneity of the catalytic bed cause the concentration of reacting compounds to fluctuate radially. These variabilities signify the existence of radial positions at which the radial gradient of concentration is zero. Succinctly, factorization theorem states that a concentration function of axial and radial coordinates in a catalytic bed is factorable as the product of the mean radial cup-mixing function and a contingent dimensionless function. The concentration of adsorbed compounds are also factorable since they are piecewise continuous functions and suffer the same variability but in the reverse order of the concentration of mobile phase compounds. Factorability is a property of packed beds which transforms the general dispersion model to an equation in terms of the measurable mean radial cup-mixing concentration of the mobile phase compounds and mean cross-sectional concentration of adsorbed species. The reduced model does not require the knowledge of the radial distribution of the axial velocity. Instead, it is characterized by new transport parameters so denoted by Ωc, Ωa, Ωc, and which are respectively denominated convection coefficient cofactor, axial dispersion coefficient cofactor, and radial dispersion coefficient cofactor. These cofactors adjust the dispersion equation as compensation for the unavailability of the radial distribution of the axial velocity. Together with the rest of the kinetic parameters they can be determined from experimental data via an optimization procedure. Our data showed that the estimated parameters Ωc, Ωa Ωr, are monotonically correlated with the Reynolds number. This is expected to be the case based on the theoretical construct of the model. Computer generated simulations of methanation reaction on nickel provide additional support for the utility of the newly conceptualized dispersion model.

Keywords: factorization, general dispersion model, isotope transient kinetic, partial differential equations

Procedia PDF Downloads 244

Authors: Katherine Dropiewski, Michael Yakimov, Vadim Tokranov, Allan Minns, Pavel Murat, Serge Oktyabrsky

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InAs Quantum Dots (QDs) in a GaAs matrix is a well-documented luminescent material with high light yield, as well as thermal and ionizing radiation tolerance due to quantum confinement. These benefits can be leveraged for high-efficiency, room temperature scintillation detectors. The proposed scintillator is composed of InAs QDs acting as luminescence centers in a GaAs stopping medium, which also acts as a waveguide. This system has appealing potential properties, including high light yield (~240,000 photons/MeV) and fast capture of photoelectrons (2-5ps), orders of magnitude better than currently used inorganic scintillators, such as LYSO or BaF2. The high refractive index of the GaAs matrix (n=3.4) ensures light emitted by the QDs is waveguided, which can be collected by an integrated photodiode (PD). Scintillation structures were grown using Molecular Beam Epitaxy (MBE) and consist of thick GaAs waveguiding layers with embedded sheets of modulation p-type doped InAs QDs. An AlAs sacrificial layer is grown between the waveguide and the GaAs substrate for epitaxial lift-off to separate the scintillator film and transfer it to a low-index substrate for waveguiding measurements. One consideration when using a low-density material like GaAs (~5.32 g/cm³) as a stopping medium is the matrix thickness in the dimension of radiation collection. Therefore, luminescence properties of very thick (4-20 microns) waveguides with up to 100 QD layers were studied. The optimization of the medium included QD shape, density, doping, and AlGaAs barriers at the waveguide surfaces to prevent non-radiative recombination. To characterize the efficiency of QD luminescence, low temperature photoluminescence (PL) (77-450 K) was measured and fitted using a kinetic model. The PL intensity degrades by only 40% at RT, with an activation energy for electron escape from QDs to the barrier of ~60 meV. Attenuation within the waveguide (WG) is a limiting factor for the lateral size of a scintillation detector, so PL spectroscopy in the waveguiding configuration was studied. Spectra were measured while the laser (630 nm) excitation point was scanned away from the collecting fiber coupled to the edge of the WG. The QD ground state PL peak at 1.04 eV (1190 nm) was inhomogeneously broadened with FWHM of 28 meV (33 nm) and showed a distinct red-shift due to self-absorption in the QDs. Attenuation stabilized after traveling over 1 mm through the WG, at about 3 cm⁻¹. Finally, a scintillator sample was used to test detection and evaluate timing characteristics using 5.5 MeV alpha particles. With a 2D waveguide and a small area of integrated PD, the collected charge averaged 8.4 x10⁴ electrons, corresponding to a collection efficiency of about 7%. The scintillation response had 80 ps noise-limited time resolution and a QD decay time of 0.6 ns. The data confirms unique properties of this scintillation detector which can be potentially much faster than any currently used inorganic scintillator.

Keywords: GaAs, InAs, molecular beam epitaxy, quantum dots, III-V semiconductor

Procedia PDF Downloads 235

Authors: Yazan S. Khaled, Shazana Shamsuddin, Jim Tiernan, Mike McPherson, Thomas Hughes, Paul Millner, David G. Jayne

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Introduction: There is a need for real-time imaging of colorectal cancer (CRC) to allow tailored surgery to the disease stage. Fluorescence guided laparoscopic imaging of primary colorectal cancer and the draining lymphatics would potentially bring stratified surgery into clinical practice and realign future CRC management to the needs of patients. Fluorescent nanoparticles can offer many advantages in terms of intra-operative imaging and therapy (theranostic) in comparison with traditional soluble reagents. Nanoparticles can be functionalised with diverse reagents and then targeted to the correct tissue using an antibody or Affimer (artificial binding protein). We aimed to develop and test fluorescent silica nanoparticles and targeted against CRC using an anti-carcinoembryonic antigen (CEA) Affimer (Aff). Methods: Anti-CEA and control Myoglobin Affimer binders were subcloned into the expressing vector pET11 followed by transformation into BL21 Star™ (DE3) E.coli. The expression of Affimer binders was induced using 0.1 mM isopropyl β-D-1-thiogalactopyranoside (IPTG). Cells were harvested, lysed and purified using nickle chelating affinity chromatography. The photosensitiser Foslip (soluble analogue of 5,10,15,20-Tetra(m-hydroxyphenyl) chlorin) was incorporated into the core of silica nanoparticles using water-in-oil microemulsion technique. Anti-CEA or control Affs were conjugated to silica nanoparticles surface using sulfosuccinimidyl-4-(N-maleimidomethyl) cyclohexane-1-carboxylate (sulfo SMCC) chemical linker. Binding of CEA-Aff or control nanoparticles to colorectal cancer cells (LoVo, LS174T and HC116) was quantified in vitro using confocal microscopy. Results: The molecular weights of the obtained band of Affimers were ~12.5KDa while the diameter of functionalised silica nanoparticles was ~80nm. CEA-Affimer targeted nanoparticles demonstrated 9.4, 5.8 and 2.5 fold greater fluorescence than control in, LoVo, LS174T and HCT116 cells respectively (p < 0.002) for the single slice analysis. A similar pattern of successful CEA-targeted fluorescence was observed in the maximum image projection analysis, with CEA-targeted nanoparticles demonstrating 4.1, 2.9 and 2.4 fold greater fluorescence than control particles in LoVo, LS174T, and HCT116 cells respectively (p < 0.0002). There was no significant difference in fluorescence for CEA-Affimer vs. CEA-Antibody targeted nanoparticles. Conclusion: We are the first to demonstrate that Foslip-doped silica nanoparticles conjugated to anti-CEA Affimers via SMCC allowed tumour cell-specific fluorescent targeting in vitro, and had shown sufficient promise to justify testing in an animal model of colorectal cancer. CEA-Affimer appears to be a suitable targeting molecule to replace CEA-Antibody. Targeted silica nanoparticles loaded with Foslip photosensitiser is now being optimised to drive photodynamic killing, via reactive oxygen generation.

Keywords: colorectal cancer, silica nanoparticles, Affimers, antibodies, imaging

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Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis

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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.

Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals

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Authors: Nonita Sarin, K.J.Singh, Anuj Kumar, Davinder Singh

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Polymeric 3D hydrogels have pivotal role in bone tissue regeneration applications. Hydrogels behave similar to the living tissues because they have large water imbibing capacity in swollen state and adjust their shape according to the tissues during tissue formation after implantation. On the other hand, hydrogels are very soft, fragile and lack mechanical strength. Incorporation of bioceramics can improve mechanical strength. Furthermore, bioceramics synthesized by sol gel technique may enhance the apatite formation and degradation rates which can lead to the increase in faster rates for new bone and tissue regeneration. Simulated body fluid (SBF) induces the poly-condensation of silanol groups which leads to formation of silica matrix and provide active sites for the precipitation of Ca2+ and PO43- ions to form apatite layer which is similar to mineral form of bone. Therefore, authors have synthesized bioceramic incorporated Polyacrylamide-carboxymethylcellulose hydrogels by free radical polymerization and bioceramic compositions of xSrO-(36-x)CaO-45SiO2-ySeO3-(12-y)P2O5-7MgO (where x=0,4 and y=0,2 mol%) were synthesized by sol gel technique. Bioceramics incorporated in polymer matrix induces quicker apatite formation during immersion in SBF by raising the pH with the release of alkaline ions during ion exchange process and the apatite formation takes place in alkaline medium. The behavior of samples PABC-0 (without bioceramics) and PABC-20 (with 20 wt% bioceramics) were evaluated by X-Ray Diffraction and FTIR. In term of bioactivity, it was observed that PABC-20 has shown hydroxyapatite (HA) formation on 1st day of immersion whereas, PABC-0 was shown apatite formation on 7th day of immersion in SBF. The rapid rate of HA growth on 1st day of immersion in SBF signifies easy regeneration of damaged bone tissues. Degradation studies have been undertaken in Phosphate Buffer Saline and PABC-20 exhibited slower degradation rate up to 9%as compared to PABC-0 up to 18%. Slower degradation rate is suitable for new tissue regeneration and cell attachment. Also, Zeta potential studies have been employed to check the surface charge and it has been observed that samples carry negative charge when immersed in SBF. In addition, the swelling test of the samples have been performed and relative swelling ratio % observed for PABC-0 is 607% and PABC-20 is 305%. This indicates that the incorporation of bioceramics leads to the filling up of the voids in between the polymer matrix which in result reduces porosity and increase the mechanical strength by filling the voids. The porosity of PABC-0 is 84% and PABC-20 is 72%. PABC-20 sample demonstrates that bioceramics incorporation reduce the porosity and improves mechanical strength. Also, maximum in vitro cell viability up to 98% with MG63 cell line has been observed which indicate that the bioceramic incorporated hydrogel(PABC-20) provide the alkaline medium which is suitable environment for cell growth.

Keywords: hydrogels, hydroxyapatite, MG63 cell line, zeta potential

Procedia PDF Downloads 115

Authors: Anwar Beg, Sireetorn Kuharat, Rashid Mehmood, Rabil Tabassum, Meisam Babaie

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Nano-polymeric solar paints and sol-gels have emerged as a major new development in solar cell/collector coatings offering significant improvements in durability, anti-corrosion and thermal efficiency. They also exhibit substantial viscosity variation with temperature which can be exploited in solar collector designs. Modern manufacturing processes for such nano-rheological materials frequently employ stagnation flow dynamics under high temperature which invokes radiative heat transfer. Motivated by elaborating in further detail the nanoscale heat, mass and momentum characteristics of such sol gels, the present article presents a mathematical and computational study of the steady, two-dimensional, non-aligned thermo-fluid boundary layer transport of copper metal-doped water-based nano-polymeric sol gels under radiative heat flux. To simulate real nano-polymer boundary interface dynamics, thermal slip is analysed at the wall. A temperature-dependent viscosity is also considered. The Tiwari-Das nanofluid model is deployed which features a volume fraction for the nanoparticle concentration. This approach also features a Maxwell-Garnet model for the nanofluid thermal conductivity. The conservation equations for mass, normal and tangential momentum and energy (heat) are normalized via appropriate transformations to generate a multi-degree, ordinary differential, non-linear, coupled boundary value problem. Numerical solutions are obtained via the stable, efficient Runge-Kutta-Fehlberg scheme with shooting quadrature in MATLAB symbolic software. Validation of solutions is achieved with a Variational Iterative Method (VIM) utilizing Langrangian multipliers. The impact of key emerging dimensionless parameters i.e. obliqueness parameter, radiation-conduction Rosseland number (Rd), thermal slip parameter (α), viscosity parameter (m), nanoparticles volume fraction (ϕ) on non-dimensional normal and tangential velocity components, temperature, wall shear stress, local heat flux and streamline distributions is visualized graphically. Shear stress and temperature are boosted with increasing radiative effect whereas local heat flux is reduced. Increasing wall thermal slip parameter depletes temperatures. With greater volume fraction of copper nanoparticles temperature and thermal boundary layer thickness is elevated. Streamlines are found to be skewed markedly towards the left with positive obliqueness parameter.

Keywords: non-orthogonal stagnation-point heat transfer, solar nano-polymer coating, MATLAB numerical quadrature, Variational Iterative Method (VIM)

Procedia PDF Downloads 109

Authors: Till Fehlauer, Blanche Collin, Bernard Angeletti, Andrea Somogyi, Claire Lallemand, Perrine Chaurand, Cédric Dentant, Clement Levard, Jerome Rose

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Over the last decades, yttrium (Y) has gained importance in high-tech applications. It is an essential part of alloys and compounds used for lasers, displays, or cell phones, for example. Due to its chemical similarities with the lanthanides, Y is often considered a rare earth element (REE). Despite their increased usage, the environmental behavior of REEs remains poorly understood. Especially regarding their interactions with plants, many uncertainties exist. On the one hand, Y is known to have a negative effect on root development and germination, but on the other hand, it appears to promote plant growth at low concentrations. In order to understand these phenomena, a precise knowledge is necessary about how Y is absorbed by the plant and how it is handled once inside the organism. Contradictory studies exist, stating that due to a similar ionic radius, Y and the other REEs might be absorbed through Ca²⁺-channels, while others suspect that Y has a shared pathway with Al³⁺. In this study, laser ablation coupled ICP-MS, and synchrotron-based micro-X-ray fluorescence (µXRF, beamline Nanoscopium, SOLEIL, France) have been used in order to localize Y within the plant tissue and identify associated elements. The plant used in this study is Saxifraga paniculata, a rugged alpine plant that has shown an affinity for Y in previous studies (in prep.). Furthermore, Saxifraga paniculata performs guttation, which means that it possesses phloem sap secreting openings on the leaf surface that serve to regulate root pressure. These so-called hydathodes could provide special insights in elemental transport in plants. The plants have been grown on Y doped soil (500mg/kg DW) for four months. The results showed that Y was mainly concentrated in the roots of Saxifraga paniculata (260 ± 85mg/kg), and only a small amount was translocated to the leaves (10 ± 7.8mg/kg). µXRF analysis indicated that within the root transects, the majority of Y remained in the epidermis and hardly penetrated the stele. Laser ablation coupled ICP-MS confirmed this finding and showed a positive correlation in the roots between Y, Fe, Al, and to a lesser extent Ca. In the stem transect, Y was mainly detected in a hotspot of approximately 40µm in diameter situated in the endodermis area. Within the stem and especially in the hotspot, Y was highly colocalized with Al and Fe. Similar-sized Y hotspots have been detected in/on the leaves. All of them were strongly colocalized with Al and Fe, except for those situated within the hydathodes, which showed no colocalization with any of the measured elements. Accordingly, a relation between Y and Ca during root uptake remains possible, whereas a correlation to Fe and Al appears to be dominant in the aerial parts, suggesting common storage compartments, the formation of complexes, or a shared pathway during translocation.

Keywords: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Phytoaccumulation, Rare earth elements, Saxifraga paniculata, Synchrotron-based micro-X-ray fluorescence, Yttrium

Procedia PDF Downloads 127

Authors: Krzysztof Skiba, Zbigniew Czyz, Ksenia Siadkowska, Piotr Borowiec

Abstract:

The article presents selected concepts of technologies that use intelligent materials in aircraft in order to improve their performance. Most of the research focuses on solutions that improve the performance of fixed wing aircraft due to related to their previously dominant market share. Recently, the development of the rotorcraft has been intensive, so there are not only helicopters but also gyroplanes and unmanned aerial vehicles using rotors and vertical take-off and landing. There are many different technologies to change a shape of the aircraft or its elements. Piezoelectric, deformable actuator systems can be applied in the system of an active control of vibration dampening in the aircraft tail structure. Wires made of shape memory alloys (SMA) could be used instead of hydraulic cylinders in the rear part of the aircraft flap. The aircraft made of intelligent materials (piezoelectrics and SMA) is one of the NASA projects which provide the possibility of changing a wing shape coefficient by 200%, a wing surface by 50%, and wing deflections by 20 degrees. Active surfaces made of shape memory alloys could be used to control swirls in the flowing stream. An intelligent control system for helicopter blades is a method for the active adaptation of blades to flight conditions and the reduction of vibrations caused by the rotor. Shape memory alloys are capable of recovering their pre-programmed shapes. They are divided into three groups: nickel-titanium-based, copper-based, and ferromagnetic. Due to the strongest shape memory effect and the best vibration damping ability, a Ni-Ti alloy is the most commercially important. The subject of this work was to prepare a conceptual design of a rotor blade with SMA actuators. The scope of work included 3D design of the supporting rotor blade, 3D design of beams enabling to change the geometry by changing the angle of rotation and FEM (Finite Element Method) analysis. The FEM analysis was performed using NX 12 software in the Pre/Post module, which includes extended finite element modeling tools and visualizations of the obtained results. Calculations are presented for two versions of the blade girders. For FEM analysis, three types of materials were used for comparison purposes (ABS, aluminium alloy 7057, steel C45). The analysis of internal stresses and extreme displacements of crossbars edges was carried out. The internal stresses in all materials were close to the yield point in the solution of girder no. 1. For girder no. 2 solution, the value of stresses decreased by about 45%. As a result of the displacement analysis, it was found that the best solution was the ABS girder no. 1. The displacement of about 0.5 mm was obtained, which resulted in turning the crossbars (upper and lower) by an angle equal to 3.59 degrees. This is the largest deviation of all the tests. The smallest deviation was obtained for beam no. 2 made of steel. The displacement value of the second girder solution was approximately 30% lower than the first solution. Acknowledgement: This work has been financed by the Polish National Centre for Research and Development under the LIDER program, Grant Agreement No. LIDER/45/0177/L-9/17/NCBR/2018.

Keywords: aircraft, helicopters, shape memory alloy, SMA, smart material, unmanned aerial vehicle, UAV

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Authors: Nadine Raidl, Benjamin Kaufmann, Michael Hofstätter, Peter Supancic

Abstract:

If polycrystalline ZnO is properly doped and sintered under very specific conditions, it shows unique electrical properties, which are indispensable for today’s electronic industries, where it is used as the number one overvoltage protection material. Under a critical voltage, the polycrystalline bulk exhibits high electrical resistance but becomes suddenly up to twelve magnitudes more conductive if this voltage limit is exceeded (i.e., varistor effect). It is known that these peerless properties have their origin in the grain boundaries of the material. Electric charge is accumulated in the boundaries, causing a depletion layer in their vicinity and forming potential barriers (so-called Double Schottky Barriers, or DSB) which are responsible for the highly non-linear conductivity. Since ZnO is a piezoelectric material, mechanical stresses induce polarisation charges that modify the DSB heights and as a result the global electrical characteristics (i.e., piezotronic effect). In this work, a finite element method was used to simulate emerging stresses on individual grains in the bulk. Besides, experimental efforts were made to testify a coherent model that could explain this influence. Electron back scattering diffraction was used to identify grain orientations. With the help of wet chemical etching, grain polarization was determined. Micro lock-in infrared thermography (MLIRT) was applied to detect current paths through the material, and a micro 4-point probes method system (M4PPS) was employed to investigate current-voltage characteristics between single grains. Bulk samples were tested under uniaxial pressure. It was found that the conductivity can increase by up to three orders of magnitude with increasing stress. Through in-situ MLIRT, it could be shown that this effect is caused by the activation of additional current paths in the material. Further, compressive tests were performed on miniaturized samples with grain paths containing solely one or two grain boundaries. The tests evinced both an increase of the conductivity, as observed for the bulk, as well as a decreased conductivity. This phenomenon has been predicted theoretically and can be explained by piezotronically induced surface charges that have an impact on the DSB at the grain boundaries. Depending on grain orientation and stress direction, DSB can be raised or lowered. Also, the experiments revealed that the conductivity within one single specimen can increase and decrease, depending on the current direction. This novel finding indicates the existence of asymmetric Double Schottky Barriers, which was furthermore proved by complementary methods. MLIRT studies showed that the intensity of heat generation within individual current paths is dependent on the direction of the stimulating current. M4PPS was used to study the relationship between the I-V characteristics of single grain boundaries and grain orientation and revealed asymmetric behavior for very specific orientation configurations. A new model for the Double Schottky Barrier, taking into account the natural asymmetry and explaining the experimental results, will be given.

Keywords: Asymmetric Double Schottky Barrier, piezotronic, varistor, zinc oxide

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Authors: Oscar Bareiro, Johannes Sackmann, Thomas Gries

Abstract:

Carbon fiber reinforced polymer composites (CFRP) are used in a wide variety of applications due to its advantageous properties and design versatility. The braiding process enables the manufacture of components with good toughness and fatigue strength. However, failure mechanisms of CFRPs are complex and still present challenges associated with their maintenance and repair. Within the broad scope of structural health monitoring (SHM), strain monitoring can be applied to composite materials to improve reliability, reduce maintenance costs and safely exhaust service life. Traditional SHM systems employ e.g. fiber optics, piezoelectrics as sensors, which are often expensive, time consuming and complicated to implement. A cost-efficient alternative can be the exploitation of the conductive properties of fiber-based sensors such as carbon, copper, or constantan - a copper-nickel alloy – that can be utilized as sensors within composite structures to achieve strain monitoring. This allows the structure to provide feedback via electrical signals to a user which are essential for evaluating the structural condition of the structure. This work presents a strategy for the in-process integration of resistance-based sensors (Elektrisola Feindraht AG, CuNi23Mn, Ø = 0.05 mm) into textile preforms during its manufacture via the braiding process (Herzog RF-64/120) to achieve strain monitoring of braided composites. For this, flat samples of instrumented composite laminates of carbon fibers (Toho Tenax HTS40 F13 24K, 1600 tex) and epoxy resin (Epikote RIMR 426) were manufactured via vacuum-assisted resin infusion. These flat samples were later cut out into test specimens and the integrated sensors were wired to the measurement equipment (National Instruments, VB-8012) for data acquisition during the execution of mechanical tests. Quasi-static tests were performed (tensile, 3-point bending tests) following standard protocols (DIN EN ISO 527-1 & 4, DIN EN ISO 14132); additionally, dynamic tensile tests were executed. These tests were executed to assess the sensor response under different loading conditions and to evaluate the influence of the sensor presence on the mechanical properties of the material. Several orientations of the sensor with regards to the applied loading and sensor placements inside the laminate were tested. Strain measurements from the integrated sensors were made by programming a data acquisition code (LabView) written for the measurement equipment. Strain measurements from the integrated sensors were then correlated to the strain/stress state for the tested samples. From the assessment of the sensor integration approach it can be concluded that it allows for a seamless sensor integration into the textile preform. No damage to the sensor or negative effect on its electrical properties was detected during inspection after integration. From the assessment of the mechanical tests of instrumented samples it can be concluded that the presence of the sensors does not alter significantly the mechanical properties of the material. It was found that there is a good correlation between resistance measurements from the integrated sensors and the applied strain. It can be concluded that the correlation is of sufficient accuracy to determinate the strain state of a composite laminate based solely on the resistance measurements from the integrated sensors.

Keywords: braiding process, in-process sensor integration, instrumented composite material, resistance-based sensor, strain monitoring

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Authors: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

Abstract:

Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of biomass platform, comprising a potential pool of hydrogen energy that stands as a new energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need of in-situ H2 production, which plays a key role in the hydrogenation reactions of biomass into higher value components. It is reported elsewhere in literature that catalytic decomposition of FA is usually performed in poorly designed setup using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. it work suggests an approach that integrates designing a novel catalyst featuring magnetic property with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H2 gas from FA. Using ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under inert medium. Through a novel approach, FA is charged into the reactor via high-pressure positive displacement pump at steady state conditions. The produced gas (H2+CO2) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The novelty of this work lies in designing a very responsive catalyst, pumping consistent amount of FA into a sealed reactor running at steady state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at lower temperature range (35-50°C) yielded more gas while the catalyst loading and Pd doping wt.% were found to be the most significant factors with a P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

Procedia PDF Downloads 23

Authors: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

Abstract:

Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of the biomass platform, comprising a potential pool of hydrogen energy that stands as a distinct energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need for in-situ H₂ production, which plays a key role in the hydrogenation reactions of biomass into higher-value components. It is reported elsewhere in the literature that catalytic decomposition of FA is usually performed in poorly designed setups using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. Our work suggests an approach that integrates designing a distinct catalyst featuring magnetic properties with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for the dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H₂ gas from FA. Using an ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under an inert medium. Through a distinct approach, FA is charged into the reactor via a high-pressure positive displacement pump at steady-state conditions. The produced gas (H₂+CO₂) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The uniqueness of this work lies in designing a very responsive catalyst, pumping a consistent amount of FA into a sealed reactor running at steady-state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at a lower temperature range (35-50°C) yielded more gas, while the catalyst loading and Pd doping wt.% were found to be the most significant factors with P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

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Authors: Utpal Das, Sona Das

Abstract:

InAs/GaSb type-II superlattice (T2SL) Mid-wave infrared (MWIR) focal plane arrays (FPAs) have recently seen rapid development. However, in small pixel size large format FPAs, the occurrence of high mesa sidewall surface leakage current is a major constraint necessitating proper surface passivation. A simple pixel isolation technique in InAs/GaSb T2SL detector arrays without the conventional mesa etching has been proposed to isolate the pixels by forming a more resistive higher band gap material from the SL, in the inter-pixel region. Here, a single step femtosecond (fs) laser anneal of the T2SL structure of the inter-pixel T2SL regions, have been used to increase the band gap between the pixels by QW-intermixing and hence increase isolation between the pixels. The p-i-n photodiode structure used here consists of a 506nm, (10 monolayer {ML}) InAs:Si (1x10¹⁸cm⁻³)/(10ML) GaSb SL as the bottom n-contact layer grown on an n-type GaSb substrate. The undoped absorber layer consists of 1.3µm, (10ML)InAs/(10ML)GaSb SL. The top p-contact layer is a 63nm, (10ML)InAs:Be(1x10¹⁸cm⁻³)/(10ML)GaSb T2SL. In order to improve the carrier transport, a 126nm of graded doped (10ML)InAs/(10ML)GaSb SL layer was added between the absorber and each contact layers. A 775nm 150fs-laser at a fluence of ~6mJ/cm² is used to expose the array where the pixel regions are masked by a Ti(200nm)-Au(300nm) cap. Here, in the inter-pixel regions, the p+ layer have been reactive ion etched (RIE) using CH₄+H₂ chemistry and removed before fs-laser exposure. The fs-laser anneal isolation improvement in 200-400μm pixels due to spatially selective quantum well intermixing for a blue shift of ~70meV in the inter-pixel regions is confirmed by FTIR measurements. Dark currents are measured between two adjacent pixels with the Ti(200nm)-Au(300nm) caps used as contacts. The T2SL quality in the active photodiode regions masked by the Ti-Au cap is hardly affected and retains the original quality of the detector. Although, fs-laser anneal of p+ only etched p-i-n T2SL diodes show a reduction in the reverse dark current, no significant improvement in the full RIE-etched mesa structures is noticeable. Hence for a 128x128 array fabrication of 8μm square pixels and 10µm pitch, SU8 polymer isolation after RIE pixel delineation has been used. X-n+ row contacts and Y-p+ column contacts have been used to measure the optical response of the individual pixels. The photo-response of these 8μm and other 200μm pixels under a 2ns optical pulse excitation from an Optical-Parametric-Oscillator (OPO), shows a peak responsivity of ~0.03A/W and 0.2mA/W, respectively, at λ~3.7μm. Temporal response of this detector array is seen to have a fast response ~10ns followed typical slow decay with ringing, attributed to impedance mismatch of the connecting co-axial cables. In conclusion, response times of a few ns have been measured in 8µm pixels of a 128x128 array. Although fs-laser anneal has been found to be useful in increasing the inter-pixel isolation in InAs/GaSb T2SL arrays by QW inter-mixing, it has not been found to be suitable for passivation of full RIE etched mesa structures with vertical walls on InAs/GaSb T2SL.

Keywords: band-gap blue-shift, fs-laser-anneal, InAs/GaSb T2SL, Inter-pixel isolation, ns-Response, photodiode array

Procedia PDF Downloads 126

Authors: Kamolvara Sirisuksakulchai, Soamwadee Chaianansutcharit, Kazunori Sato

Abstract:

Solid Oxide Fuel Cells (SOFCs) have been considered as one of the most efficient large unit power generators for household and industrial applications. The efficiency of an electronic cell depends mainly on the electrochemical reactions in the anode. The development of anode materials has been intensely studied to achieve higher kinetic rates of redox reactions and lower internal resistance. Recent studies have introduced an efficient cermet (ceramic-metallic) material for its ability in fuel oxidation and oxide conduction. This could expand the reactive site, also known as the triple-phase boundary (TPB), thus increasing the overall performance. In this study, a bimetallic catalyst Ni₀.₇₅Co₀.₂₅Oₓ was combined with Gd₀.₁Ce₀.₉O₁.₉₅ (GDC) to be used as a cermet anode (NiCo-GDC) for an anode-supported type SOFC. The synthesis of Ni₀.₇₅Co₀.₂₅Oₓ was carried out by ball milling NiO and Co3O4 powders in ethanol and calcined at 1000 °C. The Gd₀.₁Ce₀.₉O₁.₉₅ was prepared by a urea co-precipitation method. Precursors of Gd(NO₃)₃·6H₂O and Ce(NO₃)₃·6H₂O were dissolved in distilled water with the addition of urea and were heated subsequently. The heated mixture product was filtered and rinsed thoroughly, then dried and calcined at 800 °C and 1500 °C, respectively. The two powders were combined followed by pelletization and sintering at 1100 °C to form an anode support layer. The fabrications of an electrolyte layer and cathode layer were conducted. The electrochemical performance in H₂ was measured from 800 °C to 600 °C while for CH₄ was from 750 °C to 600 °C. The maximum power density at 750 °C in H₂ was 13% higher than in CH₄. The difference in performance was due to higher polarization resistances confirmed by the impedance spectra. According to the standard enthalpy, the dissociation energy of C-H bonds in CH₄ is slightly higher than the H-H bond H₂. The dissociation of CH₄ could be the cause of resistance within the anode material. The results from lower temperatures showed a descending trend of power density in relevance to the increased polarization resistance. This was due to lowering conductivity when the temperature decreases. The long-term stability was measured at 750 °C in CH₄ monitoring at 12-hour intervals. The maximum power density tends to increase gradually with time while the resistances were maintained. This suggests the enhanced stability from charge transfer activities in doped ceria due to the transition of Ce⁴⁺ ↔ Ce³⁺ at low oxygen partial pressure and high-temperature atmosphere. However, the power density started to drop after 60 h, and the cell potential also dropped from 0.3249 V to 0.2850 V. These phenomena was confirmed by a shifted impedance spectra indicating a higher ohmic resistance. The observation by FESEM and EDX-mapping suggests the degradation due to mass transport of ions in the electrolyte while the anode microstructure was still maintained. In summary, the electrochemical test and stability test for 60 h was achieved by NiCo-GDC cermet anode. Coke deposition was not detected after operation in CH₄, hence this confirms the superior properties of the bimetallic cermet anode over typical Ni-GDC.

Keywords: bimetallic catalyst, ceria-based SOFCs, methane oxidation, solid oxide fuel cell

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Authors: Natia Jalagonia, Tinatin Kuchukhidze

Abstract:

Polymer electrolytes (PE) play an important part in electrochemical devices such as batteries and fuel cells. To achieve optimal performance, the PE must maintain a high ionic conductivity and mechanical stability at both high and low relative humidity. The polymer electrolyte also needs to have excellent chemical stability for long and robustness. According to the prevailing theory, ionic conduction in polymer electrolytes is facilitated by the large-scale segmental motion of the polymer backbone, and primarily occurs in the amorphous regions of the polymer electrolyte. Crystallinity restricts polymer backbone segmental motion and significantly reduces conductivity. Consequently, polymer electrolytes with high conductivity at room temperature have been sought through polymers which have highly flexible backbones and have largely amorphous morphology. The interest in polymer electrolytes was increased also by potential applications of solid polymer electrolytes in high energy density solid state batteries, gas sensors and electrochromic windows. Conductivity of 10-3 S/cm is commonly regarded as a necessary minimum value for practical applications in batteries. At present, polyethylene oxide (PEO)-based systems are most thoroughly investigated, reaching room temperature conductivities of 10-7 S/cm in some cross-linked salt in polymer systems based on amorphous PEO-polypropylene oxide copolymers.. It is widely accepted that amorphous polymers with low glass transition temperatures Tg and a high segmental mobility are important prerequisites for high ionic conductivities. Another necessary condition for high ionic conductivity is a high salt solubility in the polymer, which is most often achieved by donors such as ether oxygen or imide groups on the main chain or on the side groups of the PE. It is well established also that lithium ion coordination takes place predominantly in the amorphous domain, and that the segmental mobility of the polymer is an important factor in determining the ionic mobility. Great attention was pointed to PEO-based amorphous electrolyte obtained by synthesis of comb-like polymers, by attaching short ethylene oxide unit sequences to an existing amorphous polymer backbone. The aim of presented work is to obtain of solid polymer electrolyte membranes using PMHS as a matrix. For this purpose the hydrosilylation reactions of α,ω-bis(trimethylsiloxy)methyl¬hydrosiloxane with allyl triethylene-glycol mo¬nomethyl ether and vinyltriethoxysilane at 1:28:7 ratio of initial com¬pounds in the presence of Karstedt’s catalyst, platinum hydrochloric acid (0.1 M solution in THF) and platinum on the carbon catalyst in 50% solution of anhydrous toluene have been studied. The synthesized olygomers are vitreous liquid products, which are well soluble in organic solvents with specific viscosity ηsp ≈ 0.05 - 0.06. The synthesized olygomers were analysed with FTIR, 1H, 13C, 29Si NMR spectroscopy. Synthesized polysiloxanes were investigated with wide-angle X-ray, gel-permeation chromatography, and DSC analyses. Via sol-gel processes of doped with lithium trifluoromethylsulfonate (triflate) or lithium bis¬(trifluoromethylsulfonyl)¬imide polymer systems solid polymer electrolyte membranes have been obtained. The dependence of ionic conductivity as a function of temperature and salt concentration was investigated and the activation energies of conductivity for all obtained compounds are calculated

Keywords: synthesis, PMHS, membrane, electrolyte

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