Search results for: adiabatic absorption

Authors: C. Fornacelli, P. Colomban, E. Mugnaioli, I. Memmi Turbanti

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When semiconductor particles are reduced in scale to nanometer dimension, their optical and electro-optical properties strongly differ from those of bulk crystals of the same composition. Since sampling is often not allowed concerning cultural heritage artefacts, the potentialities of two non-invasive techniques, such as Raman and Fiber Optic Reflectance Spectroscopy (FORS), have been investigated and the results of the analysis on some original glasses of different colours (from yellow to orange and deep red) and periods (from the second decade of the 20th century to present days) are reported in the present study. In order to evaluate the potentialities of the application of non-invasive techniques to the investigation of the structure and distribution of nanoparticles dispersed in a glass matrix, Scanning Electron Microscopy (SEM) and energy-disperse spectroscopy (EDS) mapping, together with Transmission Electron Microscopy (TEM) and Electron Diffraction Tomography (EDT) have also been used. Raman spectroscopy allows a fast and non-destructive measure of the quantum dots composition and size, thanks to the evaluation of the frequencies and the broadening/asymmetry of the LO phonons bands, respectively, though the important role of the compressive strain arising from the glass matrix and the possible diffusion of zinc from the matrix to the nanocrystals should be taken into account when considering the optical-phonons frequency values. The incorporation of Zn has been assumed by an upward shifting of the LO band related to the most abundant anion (S or Se), while the role of the surface phonons as well as the confinement-induced scattering by phonons with a non-zero wavevectors on the Raman peaks broadening has been verified. The optical band gap varies from 2.42 eV (pure CdS) to 1.70 eV (CdSe). For the compositional range between 0.5≤x≤0.2, the presence of two absorption edges has been related to the contribution of both pure CdS and the CdSxSe1-x solid solution; this particular feature is probably due to the presence of unaltered cubic zinc blende structures of CdS that is not taking part to the formation of the solid solution occurring only between hexagonal CdS and CdSe. Moreover, the band edge tailing originating from the disorder due to the formation of weak bonds and characterized by the Urbach edge energy has been studied and, together with the FWHM of the Raman signal, has been assumed as a good parameter to evaluate the degree of topological disorder. SEM-EDS mapping showed a peculiar distribution of the major constituents of the glass matrix (fluxes and stabilizers), especially concerning those samples where a layered structure has been assumed thanks to the spectroscopic study. Finally, TEM-EDS and EDT were used to get high-resolution information about nanocrystals (NCs) and heterogeneous glass layers. The presence of ZnO NCs (< 4 nm) dispersed in the matrix has been verified for most of the samples, while, for those samples where a disorder due to a more complex distribution of the size and/or composition of the NCs has been assumed, the TEM clearly verified most of the assumption made by the spectroscopic techniques.

Keywords: CdSxSe1-x, EDT, glass, spectroscopy, TEM-EDS

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Authors: Erik Vassøy Olsen, Hirpa G. Lemu

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Inspired by the Formula-1 competition, IMechE (Institute of Mechanical Engineers) and Formula SAE (Society of Mechanical Engineers) organize annual competitions for University and College students worldwide to compete with a single-seat race car they have designed and built. The design of the chassis or the frame is a key component of the competition because the weight and stiffness properties are directly related with the performance of the car and the safety of the driver. In addition, a reduced weight of the chassis has a direct influence on the design of other components in the car. Among others, it improves the power to weight ratio and the aerodynamic performance. As the power output of the engine or the battery installed in the car is limited to 80 kW, increasing the power to weight ratio demands reduction of the weight of the chassis, which represents the major part of the weight of the car. In order to reduce the weight of the car, ION Racing team from the University of Stavanger, Norway, opted for a monocoque design. To ensure fulfilment of the above-mentioned requirements of the chassis, the monocoque design should provide sufficient torsional stiffness and absorb the impact energy in case of a possible collision. The study reported in this article is based on the requirements for Formula Student competition. As part of this study, diverse mechanical tests were conducted to determine the mechanical properties and performances of the monocoque design. Upon a comprehensive theoretical study of the mechanical properties of sandwich composite materials and the requirements of monocoque design in the competition rules, diverse tests were conducted including 3-point bending test, perimeter shear test and test for absorbed energy. The test panels were homemade and prepared with an equivalent size of the side impact zone of the monocoque, i.e. 275 mm x 500 mm so that the obtained results from the tests can be representative. Different layups of the test panels with identical core material and the same number of layers of carbon fibre were tested and compared. Influence of the core material thickness was also studied. Furthermore, analytical calculations and numerical analysis were conducted to check compliance to the stated rules for Structural Equivalency with steel grade SAE/AISI 1010. The test results were also compared with calculated results with respect to bending and torsional stiffness, energy absorption, buckling, etc. The obtained results demonstrate that the material composition and strength of the composite material selected for the monocoque design has equivalent structural properties as a welded frame and thus comply with the competition requirements. The developed analytical calculation algorithms and relations will be useful for future monocoque designs with different lay-ups and compositions.

Keywords: composite material, Formula student, ION racing, monocoque design, structural equivalence

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Authors: M. Soleimani, D. Cree, C. Chafe, L. Bates

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The accidental release of petroleum products into the environment could have harmful consequences to our ecosystem. Different techniques such as mechanical separation, membrane filtration, incineration, treatment processes using enzymes and dispersants, bioremediation, and sorption process using sorbents have been applied for oil spill remediation. Most of the techniques investigated are too costly or do not have high enough efficiency. This study was conducted to determine the sorption performance of hemp byproducts (cellulosic materials) in terms of sorption capacity and kinetics for hydrophobic and hydrophilic fluids. In this study, heavy oil, light oil, diesel fuel, and water/water vapor were used as sorbate fluids. Hemp stalk in different forms, including loose material (hammer milled (HM) and shredded (Sh) with low bulk densities) and densified forms (pellet form (P) and crumbled pellets (CP)) with high bulk densities, were used as sorbents. The sorption/retention tests were conducted according to ASTM 726 standard. For a quick-purpose application of the sorbents, the sorption tests were conducted for 15 min, and for an ideal sorption capacity of the materials, the tests were carried out for 24 h. During the test, the sorbent material was exposed to the fluid by immersion, followed by filtration through a stainless-steel wire screen. Water vapor adsorption was carried out in a controlled environment chamber with the capability of controlling relative humidity (RH) and temperature. To determine the kinetics of sorption for each fluid and sorbent, the retention capacity also was determined intervalley for up to 24 h. To analyze the kinetics of sorption, pseudo-first-order, pseudo-second order and intraparticle diffusion models were employed with the objective of minimal deviation of the experimental results from the models. The results indicated that HM and Sh materials had the highest sorption capacity for the hydrophobic fluids with approximately 6 times compared to P and CP materials. For example, average retention values of heavy oil on HM and Sh was 560% and 470% of the mass of the sorbents, respectively. Whereas, the retention of heavy oil on P and CP was up to 85% of the mass of the sorbents. This lower sorption capacity for P and CP can be due to the less exposed surface area of these materials and compacted voids or capillary tubes in the structures. For water uptake application, HM and Sh resulted in at least 40% higher sorption capacity compared to those obtained for P and CP. On average, the performance of sorbate uptake from high to low was as follows: water, heavy oil, light oil, diesel fuel. The kinetic analysis indicated that the second-pseudo order model can describe the sorption process of the oil and diesel better than other models. However, the kinetics of water absorption was better described by the pseudo-first-order model. Acetylation of HM materials could improve its oil and diesel sorption to some extent. Water vapor adsorption of hemp fiber was a function of temperature and RH, and among the models studied, the modified Oswin model was the best model in describing this phenomenon.

Keywords: environment, fiber, petroleum, sorption

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Authors: Josef Uher, Jana Boháčová, Richard Kadeřábek

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In this paper, we present a multi-robot imaging and irradiation research platform referred to as Irradion, with full capabilities of portable arbitrary path computed tomography (CT). Irradion is an imaging and irradiation unit entirely based on robotic arms for research on cancer treatment with ion beams on small animals (mice or rats). The platform comprises two subsystems that combine several imaging modalities, such as 2D X-ray imaging, CT, and particle tracking, with precise positioning of a small animal for imaging and irradiation. Computed Tomography: The CT subsystem of the Irradion platform is equipped with two 6-joint robotic arms that position a photon counting detector and an X-ray tube independently and freely around the scanned specimen and allow image acquisition utilizing computed tomography. Irradiation measures nearly all conventional 2D and 3D trajectories of X-ray imaging with precisely calibrated and repeatable geometrical accuracy leading to a spatial resolution of up to 50 µm. In addition, the photon counting detectors allow X-ray photon energy discrimination, which can suppress scattered radiation, thus improving image contrast. It can also measure absorption spectra and recognize different materials (tissue) types. X-ray video recording and real-time imaging options can be applied for studies of dynamic processes, including in vivo specimens. Moreover, Irradion opens the door to exploring new 2D and 3D X-ray imaging approaches. We demonstrate in this publication various novel scan trajectories and their benefits. Proton Imaging and Particle Tracking: The Irradion platform allows combining several imaging modules with any required number of robots. The proton tracking module comprises another two robots, each holding particle tracking detectors with position, energy, and time-sensitive sensors Timepix3. Timepix3 detectors can track particles entering and exiting the specimen and allow accurate guiding of photon/ion beams for irradiation. In addition, quantifying the energy losses before and after the specimen brings essential information for precise irradiation planning and verification. Work on the small animal research platform Irradion involved advanced software and hardware development that will offer researchers a novel way to investigate new approaches in (i) radiotherapy, (ii) spectral CT, (iii) arbitrary path CT, (iv) particle tracking. The robotic platform for imaging and radiation research developed for the project is an entirely new product on the market. Preclinical research systems with precision robotic irradiation with photon/ion beams combined with multimodality high-resolution imaging do not exist currently. The researched technology can potentially cause a significant leap forward compared to the current, first-generation primary devices.

Keywords: arbitrary path CT, robotic CT, modular, multi-robot, small animal imaging

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Authors: Katarzyna Zięba, Hajnalka Szentgyörgyi, Paweł Miśkowiec, Agnieszka Moos-Matysik

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Bees are effective pollinators of plants using by humans. However, there is a concern about the fate different species due to their recently decline. Pollution of the environment is described in the literature as one of the causes of this phenomenon. Due to human activities, heavy metals and aromatic hydrocarbons can occur in bee organisms in high concentrations. The presented study aims to provide information on how pollution affects bee quality, taking into account, also the biological differences between various groups of bees. Understanding the consequences of environmental pollution on bees can help to create and promote bee friendly habitats and actions. The analyses were carried out using two contamination gradients with 5 sites on each. The first, mainly heavy metal polluted gradient is stretching approx. 30km from the Bukowno Zinc smelter near Olkusz in the Lesser Poland Voivodship, to the north. The second cuts through the agglomeration of Kraków up to the southern borders of the Ojców National Park. The gradient near Olkusz is a well-described pollution gradient contaminated mainly by zinc, lead, and cadmium. The second gradient cut through the agglomeration of Kraków and end below the Ojców National Park. On each gradient, two bee species were installed: red mason bees (Osmia bicornis) and honey bees (Apis mellifera). Red mason bee is a polylectic, solitary bee species, widely distributed in Poland. Honey bees are a highly social species of bees, with clearly defined casts and roles in the colony. Before installing the bees in the field, samples of imagos of red mason bees and samples of pollen and imagos from each honey bee colony were analysed for zinc, lead cadmium, polycyclic and monocyclic hydrocarbons levels. After collecting the bees from the field, samples of bees and pollen samples for each site were prepared for heavy metal, monocyclic hydrocarbon, and polycyclic hydrocarbon analysis. Analyses of aromatic hydrocarbons were performed with gas chromatography coupled with a headspace sampler (HP 7694E) and mass spectrometer (MS) as detector. Monocyclic compounds were injected into column with headspace sampler while polycyclic ones with manual injector (after solid-liquid extraction with hexane). The heavy metal content (zinc, lead and cadmium) was assessed with flame atomic absorption spectroscopy (FAAS AAnalyst 300 Perkin Elmer spectrometer) according to the methods for honey and bee products described in the literature. Pollution levels found in bee bodies and imago body masses in both species, and proportion of sex in case of red mason bees were correlated with pollution levels found in pollen for each site and colony or trap nest. An attempt to pinpoint the most important form of contamination regarding bee health was also be undertaken based on the achieved results.

Keywords: heavy metals, aromatic hydrocarbons, bees, pollution

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Authors: S.V. Kleyn, S.Yu. Zagorodnov, А.А. Kokoulina

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Technogenic emissions of the mining and processing complex are characterized by a high content of chemical components and solid dust particles. However, each industrial enterprise and the surrounding area have features that require refinement and parameterization. Numerous studies have shown the negative impact of fine dust PM10 and PM2.5 on the health, as well as the possibility of toxic components absorption, including heavy metals by dust particles. The target of the study was the quantitative assessment of the fractional and particle size composition of ambient air dust in the area of impact by primary magnesium production complex. Also, we tried to describe the morphology features of dust particles. Study methods. To identify the dust emission sources, the analysis of the production process has been carried out. The particulate composition of the emissions was measured using laser particle analyzer Microtrac S3500 (covered range of particle size is 20 nm to 2000 km). Particle morphology and the component composition were established by electron microscopy by scanning microscope of high resolution (magnification rate - 5 to 300 000 times) with X-ray fluorescence device S3400N ‘HITACHI’. The chemical composition was identified by X-ray analysis of the samples using an X-ray diffractometer XRD-700 ‘Shimadzu’. Determination of the dust pollution level was carried out using model calculations of emissions in the atmosphere dispersion. The calculations were verified by instrumental studies. Results of the study. The results demonstrated that the dust emissions of different technical processes are heterogeneous and fractional structure is complicated. The percentage of particle sizes up to 2.5 micrometres inclusive was ranged from 0.00 to 56.70%; particle sizes less than 10 microns inclusive – 0.00 - 85.60%; particle sizes greater than 10 microns - 14.40% -100.00%. During microscopy, the presence of nanoscale size particles has been detected. Studied dust particles are round, irregular, cubic and integral shapes. The composition of the dust includes magnesium, sodium, potassium, calcium, iron, chlorine. On the base of obtained results, it was performed the model calculations of dust emissions dispersion and establishment of the areas of fine dust РМ 10 and РМ 2.5 distribution. It was found that the dust emissions of fine powder fractions PM10 and PM2.5 are dispersed over large distances and beyond the border of the industrial site of the enterprise. The population living near the enterprise is exposed to the risk of diseases associated with dust exposure. Data are transferred to the economic entity to make decisions on the measures to minimize the risks. Exposure and risks indicators on the health are used to provide named patient health and preventive care to the citizens living in the area of negative impact of the facility.

Keywords: dust emissions, еxposure assessment, PM 10, PM 2.5

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Authors: Zélia Maria Da Costa Ludwig, Maria José Valenzuela Bell, Geraldo Henriques Da Silva, Thales Alves Faraco, Victor Rocha Da Silva, Daniel Rotmeister Teixeira, Vírgilio De Carvalho Dos Anjos, Valdemir Ludwig

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Advances in telecommunications grow with the development of optical amplifiers based on rare earth ions. The focus has been concentrated in silicate glasses although their amplified spontaneous emission is limited to a few tens of nanometers (~ 40nm). Recently, phosphate glasses have received great attention due to their potential application in optical data transmission, detection, sensors and laser detector, waveguide and optical fibers, besides its excellent physical properties such as high thermal expansion coefficients and low melting temperature. Compared with the silica glasses, phosphate glasses provide different optical properties such as, large transmission window of infrared, and good density. Research on the improvement of physical and chemical durability of phosphate glass by addition of heavy metals oxides in P2O5 has been performed. The addition of Na2O further improves the solubility of rare earths, while increasing the Al2O3 links in the P2O5 tetrahedral results in increased durability and aqueous transition temperature and a decrease of the coefficient of thermal expansion. This work describes the structural and spectroscopic characterization of a phosphate glass matrix doped with different Er (Erbium) concentrations. The phosphate glasses containing Er3+ ions have been prepared by melt technique. A study of the optical absorption, luminescence and lifetime was conducted in order to characterize the infrared emission of Er3+ ions at 1540 nm, due to the radiative transition 4I13/2 → 4I15/2. Our results indicate that the present glass is a quite good matrix for Er3+ ions, and the quantum efficiency of the 1540 nm emission was high. A quenching mechanism for the mentioned luminescence was not observed up to 2,0 mol% of Er concentration. The Judd-Ofelt parameters, radiative lifetime and quantum efficiency have been determined in order to evaluate the potential of Er3+ ions in new phosphate glass. The parameters follow the trend as Ω2 > Ω4 > Ω6. It is well known that the parameter Ω2 is an indication of the dominant covalent nature and/or structural changes in the vicinity of the ion (short range effects), while Ω4 and Ω6 intensity parameters are long range parameters that can be related to the bulk properties such as viscosity and rigidity of the glass. From the PL measurements, no red or green upconversion was measured when pumping the samples with laser excitation at 980 nm. As future prospects: Synthesize this glass system with silver in order to determine the influence of silver nanoparticles on the Er3+ ions.

Keywords: phosphate glass, erbium, luminescence, glass system

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Authors: Md. Hafezur Rahaman, Mohd. Maniruzzaman, Md. Shadiqul Islam, Md. Masud Rana

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With the growth of environmental awareness, enormous researches are running to develop the next generation materials based on sustainability, eco-competence, and green chemistry to preserve and protect the environment. Due to biodegradability and biocompatibility, poly (L-lactic acid) (PLLA) has a great interest in ecological and medical applications. Also, cellulose is one of the most abundant biodegradable, renewable polymers found in nature. It has several advantages such as low cost, high mechanical strength, biodegradability and so on. Recently, an immense deal of attention has been paid for the scientific and technological development of α-cellulose based composite material. PLLA could be used for grafting of cellulose to improve the compatibility prior to the composite preparation. Here it is quite difficult to form a bond between lower hydrophilic molecules like PLLA and α-cellulose. Dimmers and oligomers can easily be grafted onto the surface of the cellulose by ring opening or polycondensation method due to their low molecular weight. In this research, α-cellulose extracted from jute fiber is grafted with oligo(D-lactic acid) (ODLA) via graft polycondensation reaction in presence of para-toluene sulphonic acid and potassium persulphate in toluene at 130°C for 9 hours under 380 mmHg. Here ODLA is synthesized by ring opening polymerization of D-lactides in the presence of stannous octoate (0.03 wt% of lactide) and D-lactic acids at 140°C for 10 hours. Composites of PLLA with ODLA grafted α-cellulose are prepared by solution mixing and film casting method. Confirmation of grafting was carried out through FTIR spectroscopy and SEM analysis. A strongest carbonyl peak of FTIR spectroscopy at 1728 cm⁻¹ of ODLA grafted α-cellulose confirms the grafting of ODLA onto α-cellulose which is absent in α-cellulose. It is also observed from SEM photographs that there are some white areas (spot) on ODLA grafted α-cellulose as compared to α-cellulose may indicate the grafting of ODLA and consistent with FTIR results. Analysis of the composites is carried out by FTIR, SEM, WAXD and thermal gravimetric analyzer. Most of the FTIR characteristic absorption peak of the composites shifted to higher wave number with increasing peak area may provide a confirmation that PLLA and grafted cellulose have better compatibility in composites via intermolecular hydrogen bonding and this supports previously published results. Grafted α-cellulose distributions in composites are uniform which is observed by SEM analysis. WAXD studied show that only homo-crystalline structures of PLLA present in the composites. Thermal stability of the composites is enhanced with increasing the percentages of ODLA grafted α-cellulose in composites. As a consequence, the resultant composites have a resistance toward the thermal degradation. The effects of length of the grafted chain and biodegradability of the composites will be studied in further research.

Keywords: α-cellulose, composite, graft polycondensation, oligo(D-lactic acid), poly(L-lactic acid)

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Authors: Christine Böckmann, Julia Rosemann

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We present an inversion algorithm that is used in the European Aerosol Lidar Network for the inversion of data collected with multi-wavelength Raman lidar. These instruments measure backscatter coefficients at 355, 532, and 1064 nm, and extinction coefficients at 355 and 532 nm. The algorithm is based on manually controlled inversion of optical data which allows for detailed sensitivity studies and thus provides us with comparably high quality of the derived data products. The algorithm allows us to derive particle effective radius, volume, surface-area concentration with comparably high confidence. The retrieval of the real and imaginary parts of the complex refractive index still is a challenge in view of the accuracy required for these parameters in climate change studies in which light-absorption needs to be known with high accuracy. Single-scattering albedo (SSA) can be computed from the retrieve microphysical parameters and allows us to categorize aerosols into high and low absorbing aerosols. From mathematical point of view the algorithm is based on the concept of using truncated singular value decomposition as regularization method. This method was adapted to work for the retrieval of the particle size distribution function (PSD) and is called hybrid regularization technique since it is using a triple of regularization parameters. The inversion of an ill-posed problem, such as the retrieval of the PSD, is always a challenging task because very small measurement errors will be amplified most often hugely during the solution process unless an appropriate regularization method is used. Even using a regularization method is difficult since appropriate regularization parameters have to be determined. Therefore, in a next stage of our work we decided to use two regularization techniques in parallel for comparison purpose. The second method is an iterative regularization method based on Pade iteration. Here, the number of iteration steps serves as the regularization parameter. We successfully developed a semi-automated software for spherical particles which is able to run even on a parallel processor machine. From a mathematical point of view, it is also very important (as selection criteria for an appropriate regularization method) to investigate the degree of ill-posedness of the problem which we found is a moderate ill-posedness. We computed the optical data from mono-modal logarithmic PSD and investigated particles of spherical shape in our simulations. We considered particle radii as large as 6 nm which does not only cover the size range of particles in the fine-mode fraction of naturally occurring PSD but also covers a part of the coarse-mode fraction of PSD. We considered errors of 15% in the simulation studies. For the SSA, 100% of all cases achieve relative errors below 12%. In more detail, 87% of all cases for 355 nm and 88% of all cases for 532 nm are well below 6%. With respect to the absolute error for non- and weak-absorbing particles with real parts 1.5 and 1.6 in all modes the accuracy limit +/- 0.03 is achieved. In sum, 70% of all cases stay below +/-0.03 which is sufficient for climate change studies.

Keywords: aerosol particles, inverse problem, microphysical particle properties, regularization

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Authors: Mariana-Dana Damaceanu

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Electrochemical oxidation is one of the most convenient ways to obtain conjugated polymer films as polypyrrole, polyaniline, polythiophene or polycarbazole. The research in the field has been mainly directed to the study of electrical conduction properties of the materials obtained by electropolymerization, often the main reason being their use as electroconducting electrodes, and very little attention has been paid to the morphological and optical quality of the films electrodeposited on flat surfaces. Electropolymerization of the monomer solution was scarcely used in the past to manufacture polymer-based light-emitting diodes (PLED), most probably due to the difficulty of obtaining defectless polymer films with good mechanical and optical properties, or conductive polymers with well controlled molecular weights. Here we report our attempts in using electrochemical deposition as appropriate method for preparing ultrathin films of fluorene-based polymers for PLED applications. The properties of these films were evaluated in terms of structural morphology, optical properties, and electrochemical conduction. Thus, electropolymerization of 4,4'-(9-fluorenylidene)-dianiline was performed in dichloromethane solution, at a concentration of 10-2 M, using 0.1 M tetrabutylammonium tetrafluoroborate as electrolyte salt. The potential was scanned between 0 and 1.3 V on the one hand, and 0 - 2 V on the other hand, when polymer films with different structures and properties were obtained. Indium tin oxide-coated glass substrate of different size was used as working electrode, platinum wire as counter electrode and calomel electrode as reference. For each potential range 100 cycles were recorded at a scan rate of 100 mV/s. The film obtained in the potential range from 0 to 1.3 V, namely poly(FDA-NH), is visible to the naked eye, being light brown, transparent and fluorescent, and displays an amorphous morphology. Instead, the electrogrowth poly(FDA) film in the potential range of 0 - 2 V is yellowish-brown and opaque, presenting a self-assembled structure in aggregates of irregular shape and size. The polymers structure was identified by FTIR spectroscopy, which shows the presence of broad bands specific to a polymer, the band centered at approx. 3443 cm-1 being ascribed to the secondary amine. The two polymer films display two absorption maxima, at 434-436 nm assigned to π-π* transitions of polymers, and another at 832 and 880 nm assigned to polaron transitions. The fluorescence spectra indicated the presence of emission bands in the blue domain, with two peaks at 422 and 488 nm for poly (FDA-NH), and four narrow peaks at 422, 447, 460 and 484 nm for poly(FDA), peaks originating from fluorene-containing segments of varying degrees of conjugation. Poly(FDA-NH) exhibited two oxidation peaks in the anodic region and the HOMO energy value of 5.41 eV, whereas poly(FDA) showed only one oxidation peak and the HOMO level localized at 5.29 eV. The electrochemical data are discussed in close correlation with the proposed chemical structure of the electrogrowth films. Further research will be carried out to study their use and performance in light-emitting devices.

Keywords: electrogrowth polymer films, fluorene, morphology, optical properties

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

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

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

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Authors: Adeleke G. E., Bello M. A., Abdulateef R. B., Olasinde T. T., Oriaje K. O., AransiI A., Elaigwu K. O., Omidoyin O. S., Shoyinka E. D., Awoyomi M. B., Akano M., Adaramoye O. A.

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Hymenocardia acidatul belongs to the genus, Hymenocardiaceae, which is widely distributed in Africa. Both the leaf and stem bark of the plant have been used in the treatment of several diseases. The present study examined the chemical constituents of the H. acida stem bark extract (HASBE) and its effects on some antioxidant indices and esterase enzymes in female Wistar rats. The HASBE was obtained by Soxhlet extraction using methanol and then subjected to Atomic Absorption Spectroscopy (AAS) for elemental analysis, and Fourier-Transform Infrared (FT-IR) spectroscopy, ultraviolet (UV) spectroscopy, for functional group analysis, while High-performance liquid chromatography (HPLC), and Gas Chromatography-Flame ionization detection (GC-FID) were carried out for compound identification. Forty-eight female Wistar rats were assigned into eight groups of six rats each and separately administered orally with normal saline (Control), 50, 100, 150, 200, 250, 300, 350 mg/kg of HASBE twice per week for eight weeks. The rats were sacrificed under chloroform anesthesia, and kidneys and heart were excised and processed to obtain homogenates. The levels of superoxide dismutase (SOD), catalase, Malondialdehyde (MDA), glutathione peroxidase (GPx), acetylcholinesterase (AChE), and carboxylesterase (CE) were determined spectrophotometrically. The AAS of HASBE shows the presence of eight elements, including Cobalt (0.303), Copper (0.222), Zinc (0.137), Iron (2.027), Nickel (1.304), Chromium (0.313), Manganese (0.213), and Magnesium (0.337 ppm). The FT-IR result of HASBE shows four peaks at 2961.4, 2926.0, 1056.7, and 1034.3 cm-1, while UV analysis shows a maximum absorbance (0.522) at 205 nm. The HPLC spectrum of HASBE indicates the presence of four major compounds, including orientin (77%), β-sitosterol (6.58%), rutin (5.02%), and betulinic acid (3.33%), while GC-FID result shows five major compounds, including rutin (53.27%), orientin (13.06%) and stigmasterol (11.73%), hymenocardine (6.43%) and homopterocarpin (5.29%). The SOD activity was significantly (p < 0.05) lowered in the kidney but elevated in the heart, while catalase was elevated in both organs relative to control rats. The GPx activity was significantly elevated only in the kidney, while MDA was not significantly (p > 0.05) affected in the two organs compared with controls. The activity of AChE was significantly elevated in both organs, while CE activity was elevated only in the kidney relative to control rats. The present study reveals that Hymenocardia acida stem bark extract majorly contains orientin, rutin, stigmasterol, hymenocardine, β-sitosterol, homopterocarpin, and betulinic acid. In addition, these compounds could possibly enhance redox status and esterase activities in the kidney and heart of Wistar rats.

Keywords: hymenocardia acida, elemental analysis, compounds identification, redox status, organs

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Authors: Krzysztof Gwozdzinski, Janusz Mazur

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Bory Tucholskie (Tucholskie Forest) is one of the largest pine forest complexes in Poland. It occupies approx. 3,000 square kilometers of Sandr in the Brda and Wda basin and the Tuchola Plain and the Charzykowskie Plain. Since 2010 it has transformed into The Bory Tucholskie Biosphere Reserve, according to the UNESCO decision. The area of the Bory Tucholskie National Park (BTNP), the park area, has been designated in 1996. There is little data on the presence of heavy metals in the Park's lakes. Concentration of heavy metals in the water of 19 lakes in the BTNP was examined. The lakes were divided into two groups: subglacial channel lakes of Struga Siedmiu Jezior (the Seven Lakes Stream) and other lakes. Heavy metals (transition metals) belong to d-block of elements. The part of these metals plays an important role in the function of living organisms as metalloproteins (enzymes, hemoproteins, vitamins, etc.). However, heavy metals are also typical; heavy metals are typical anthropogenic pollutants. Water samples were collected at the deepest points of lakes during spring and during summer stagnation. The analysis of metals was performed in an atomic absorption spectrophotometer Varian Spectra A300/400 in electric atomizer (GTA 96) in graphite cuvette. In the waters of the Seven Lakes Stream (Ostrowite, Zielone, Jelen, Belczak, Glowka, Plesno, Skrzynka, Mielnica) the increase in the concentration of the manganese and iron from outflow to inflow of Charzykowskie lake was found, while the concentration of copper (approx. 4 μg dm⁻³) and cadmium ( < 0.5 μg dm⁻³) was similar in all lakes. The concentration of the lead also varied within 2.1-3.6 μg dm⁻³. The concentration of nickel was approx. 3-fold higher in Ostrowite lake than other lakes of Struga. In turn the waters of the lakes Ostrowite, Jelen and Belczak were rich in zinc. The lowest level of heavy metals was observed in Zielone lake. In the second group of lakes, i.e., Krzywce Wielkie and Krzywce Male the heavy metal concentrations were lower than in the waters of Struga but higher than in oligotrophic lakes, i.e., Nierybno, Gluche, Kociol, Gacno Wielkie, Gacno Mae, Dlugie, Zabionek, and Sosnowek. The concentration of cadmium was below 0.5 μg dm⁻³ in all the studied lakes from this group. In the group of oligotrophic lakes the highest concentrations of metals such as manganese, iron, zinc and nickel in Gacno Male and Gacno Wielkie were observed. The high level of manganese in Sosnowek and Gacno Wielkie lakes was found. The lead level was also high in Nierybno lake and nickel in Gacno Wielkie lake. The lower level of heavy metals was in oligotrophic lakes such as Kociol, Dlugie, Zabionek and α-mesotrophic lake, Krzywce Wielkie. Generally, the level of heavy metals in studied lakes situated in Bory Tucholskie National Park was lower than in other lakes of Bory Tucholskie Biosphere Reserve.

Keywords: Bory Tucholskie Biosphere Reserve, Bory Tucholskie National Park, heavy metals, lakes

Procedia PDF Downloads 98

Authors: Yakup Ulusu, Faruk Ozel, Numan Eczacioglu, Abdurrahman Ozen, Sabriye Acikgoz

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GFP discovered in the mid-1970s, has been used as a marker after replicated genetic study by scientists. In biotechnology, cell, molecular biology, the GFP gene is frequently used as a reporter of expression. In modified forms, it has been used to make biosensors. Many animals have been created that express GFP as an evidence that a gene can be expressed throughout a given organism. Proteins labeled with GFP identified locations are determined. And so, cell connections can be monitored, gene expression can be reported, protein-protein interactions can be observed and signals that create events can be detected. Additionally, monitoring GFP is noninvasive; it can be detected by under UV-light because of simply generating fluorescence. Moreover, GFP is a relatively small and inert molecule, that does not seem to treat any biological processes of interest. The synthesis of GFP has some steps like, to construct the plasmid system, transformation in E. coli, production and purification of protein. GFP carrying plasmid vector pBAD–GFPuv was digested using two different restriction endonuclease enzymes (NheI and Eco RI) and DNA fragment of GFP was gel purified before cloning. The GFP-encoding DNA fragment was ligated into pET28a plasmid using NheI and Eco RI restriction sites. The final plasmid was named pETGFP and DNA sequencing of this plasmid indicated that the hexa histidine-tagged GFP was correctly inserted. Histidine-tagged GFP was expressed in an Escherichia coli BL21 DE3 (pLysE) strain. The strain was transformed with pETGFP plasmid and grown on LuiraBertoni (LB) plates with kanamycin and chloramphenicol selection. E. coli cells were grown up to an optical density (OD 600) of 0.8 and induced by the addition of a final concentration of 1mM isopropyl-thiogalactopyranoside (IPTG) and then grown for additional 4 h. The amino-terminal hexa-histidine-tag facilitated purification of the GFP by using a His Bind affinity chromatography resin (Novagen). Purity of GFP protein was analyzed by a 12 % sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE). The concentration of protein was determined by UV absorption at 280 nm (Varian Cary 50 Scan UV/VIS spectrophotometer). Synthesis of GFP-Polymer composite nanofibers was produced by using GFP solution (10mg/mL) and polymer precursor Polyvinylpyrrolidone, (PVP, Mw=1300000) as starting materials and template, respectively. For the fabrication of nanofibers with the different fiber diameter; a sol–gel solution comprising of 0.40, 0.60 and 0.80 g PVP (depending upon the desired fiber diameter) and 100 mg GFP in 10 mL water: ethanol (3:2) mixtures were prepared and then the solution was covered on collecting plate via electro spinning at 10 kV with a feed-rate of 0.25 mL h-1 using Spellman electro spinning system. Results show that GFP-based nano-fiber can be used plenty of biomedical applications such as bio-imaging, bio-mechanic, bio-material and tissue engineering.

Keywords: biomaterial, GFP, nano-fibers, protein expression

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Authors: Tomohiko Utsuki, Kyoka Sato

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In emergency medicine, it is recognized that brain resuscitation is very important for the reduction of mortality rate and neurological sequelae. Especially, the control of brain temperature (BT), intracranial pressure (ICP), and cerebral blood flow (CBF) are most required for stabilizing brain’s physiological state in the treatment for such as brain injury, stroke, and encephalopathy. However, the manual control of BT, ICP, and CBF frequently requires the decision and operation of medical staff, relevant to medication and the setting of therapeutic apparatus. Thus, the integration and the automation of the control of those is very effective for not only improving therapeutic effect but also reducing staff burden and medical cost. For realizing such integration and automation, a mathematical model of brain physiological state is necessary as the controlled object in simulations, because the performance test of a prototype of the control system using patients is not ethically allowed. A model of cerebral blood circulation has already been constructed, which is the most basic part of brain physiological state. Also, a migration model of extracellular fluid in brain has been constructed, however the condition that the total volume of intracranial cavity is almost changeless due to the hardness of cranial bone has not been considered in that model. Therefore, in this research, the dynamic migration model of extracellular fluid in brain was constructed on the consideration of the changelessness of intracranial cavity’s total volume. This model is connectable to the cerebral blood circulation model. The constructed model consists of fourteen compartments, twelve of which corresponds to perfused area of bilateral anterior, middle and posterior cerebral arteries, the others corresponds to cerebral ventricles and subarachnoid space. This model enable to calculate the migration of tissue fluid from capillaries to gray matter and white matter, the flow of tissue fluid between compartments, the production and absorption of cerebrospinal fluid at choroid plexus and arachnoid granulation, and the production of metabolic water. Further, the volume, the colloid concentration, and the tissue pressure of/in each compartment are also calculable by solving 40-dimensional non-linear simultaneous differential equations. In this research, the obtained model was analyzed for its validation under the four condition of a normal adult, an adult with higher cerebral capillary pressure, an adult with lower cerebral capillary pressure, and an adult with lower colloid concentration in cerebral capillary. In the result, calculated fluid flow, tissue volume, colloid concentration, and tissue pressure were all converged to suitable value for the set condition within 60 minutes at a maximum. Also, because these results were not conflict with prior knowledge, it is certain that the model can enough represent physiological state of brain under such limited conditions at least. One of next challenges is to integrate this model and the already constructed cerebral blood circulation model. This modification enable to simulate CBF and ICP more precisely due to calculating the effect of blood pressure change to extracellular fluid migration and that of ICP change to CBF.

Keywords: dynamic model, cerebral extracellular migration, brain resuscitation, automatic control

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Authors: Sundaram Chandrasekaran, Seung Hyun Hur

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Exploring strategies for oxygen vacancy engineering under mild conditions and understanding the relationship between dislocations and photoelectrochemical (PEC) cell performance are challenging issues for designing high performance PEC devices. Therefore, it is very important to understand that how the oxygen vacancies (VO) or other defect states affect the performance of the photocatalyst in photoelectric transfer. So far, it has been found that defects in nano or micro crystals can have two possible significances on the PEC performance. Firstly, an electron-hole pair produced at the interface of photoelectrode and electrolyte can recombine at the defect centers under illumination of light, thereby reducing the PEC performances. On the other hand, the defects could lead to a higher light absorption in the longer wavelength region and may act as energy centers for the water splitting reaction that can improve the PEC performances. Even if the dislocation growth of ZnO has been verified by the full density functional theory (DFT) calculations and local density approximation calculations (LDA), it requires further studies to correlate the structures of ZnO and PEC performances. Exploring the hybrid structures composed of graphene oxide (GO) and ZnO nanostructures offer not only the vision of how the complex structure form from a simple starting materials but also the tools to improve PEC performances by understanding the underlying mechanisms of mutual interactions. As there are few studies for the ZnO growth with other materials and the growth mechanism in those cases has not been clearly explored yet, it is very important to understand the fundamental growth process of nanomaterials with the specific materials, so that rational and controllable syntheses of efficient ZnO-based hybrid materials can be designed to prepare nanostructures that can exhibit significant PEC performances. Herein, we fabricated various ZnO nanostructures such as hollow sphere, bucky bowl, nanorod and triangle, investigated their pH dependent growth mechanism, and correlated the PEC performances with them. Especially, the origin of well-controlled dislocation-driven growth and its transformation mechanism of ZnO nanorods to triangles on the GO surface were discussed in detail. Surprisingly, the addition of GO during the synthesis process not only tunes the morphology of ZnO nanocrystals and also creates more oxygen vacancies (oxygen defects) in the lattice of ZnO, which obviously suggest that the oxygen vacancies be created by the redox reaction between GO and ZnO in which the surface oxygen is extracted from the surface of ZnO by the functional groups of GO. On the basis of our experimental and theoretical analysis, the detailed mechanism for the formation of specific structural shapes and oxygen vacancies via dislocation, and its impact in PEC performances are explored. In water splitting performance, the maximum photocurrent density of GO-ZnO triangles was 1.517mA/cm-2 (under UV light ~ 360 nm) vs. RHE with high incident photon to current conversion Efficiency (IPCE) of 10.41%, which is the highest among all samples fabricated in this study and also one of the highest IPCE reported so far obtained from GO-ZnO triangular shaped photocatalyst.

Keywords: dislocation driven growth, zinc oxide, graphene oxide, water splitting

Procedia PDF Downloads 267

Authors: Abayomi O. Adetuyi, Jamiu M. Jabar, Samuel O. Afolabi

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Vegetable fibres are classes of fibres of low density, biodegradable and non-abrasive that are largely abundant fibre materials with specific properties and mostly found/ obtained in plants on earth surface. They are classified into three categories, depending on the part of the plant from which they are gotten from namely: fruit, Blast and Leaf fibre. Ever since four/five millennium B.C, attention has been focussing on the commonest and highly utilized cotton fibre obtained from the fruit of cotton plants (Gossypium spp), for the production of cotton fabric used in every home today. The present study, therefore, focused on the ability of three underutilized vegetable (fruit) fibres namely: coir fiber (Eleas coniferus), palm kernel fiber and empty fruit bunch fiber (Elias guinensis) through chemical modifications for better composite value addition performance to polyurethane form and dye adsorption. These fibres were sourced from their parents’ plants, identified and cleansed with 2% hot detergent solution 1:100, rinsed in distilled water and oven-dried to constant weight, before been chemically modified through alkali bleaching, mercerization and acetylation. The alkali bleaching involves treating 0.5g of each fiber material with 100 mL of 2% H2O2 in 25 % NaOH solution with refluxing for 2 h. While that of mercerization and acetylation involves the use of 5% sodium hydroxide NaOH solution for 2 h and 10% acetic acid- acetic anhydride 1:1 (v/v) (CH3COOH) / (CH3CO)2O solution with conc. H2SO4 as catalyst for 1 h, respectively on the fibres. All were subsequently washed thoroughly with distilled water and oven dried at 105 0C for 1 h. These modified fibres were incorporated as composite into polyurethane form and used in dye adsorption study of indigo. The first two treatments led to fiber weight reduction, while the acidified acetic anhydride treatment gave the fibers weight increment. All the treated fibers were found to be of less hydrophilic nature, better mechanical properties, higher thermal stabilities as well as better adsorption surfaces/capacities than the untreated ones. These were confirmed by gravimetric analysis, Instron Universal Testing Machine, Thermogravimetric Analyser and the Scanning Electron Microscope (SEM) respectively. The fiber morphology of the modified fibers showed smoother surfaces than unmodified fibres.The empty fruit bunch fibre and the coconut coir fibre are better than the palm kernel fibres as reinforcers for composites or as adsorbents for waste-water treatment. Acetylation and alkaline bleaching treatment improve the potentials of the fibres more than mercerization treatment. Conclusively, vegetable fibres, especially empty fruit bunch fibre and the coconut coir fibre, which are cheap, abundant and underutilized, can replace the very costly powdered activated carbon in wastewater treatment and as reinforcer in foam.

Keywords: chemical modification, industrial application, value addition, vegetable fibre

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Authors: Quentin C.P. Bourgogne, Vanessa Bouchart, Pierre Chevrier, Emmanuel Dattoli

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This study presents an experimental and theoretical work conducted on a PolyPhenylene Sulfide reinforced with 40%wt of short glass fibers (PPS GF40) and its matrix. Thermoplastics are widely used in the automotive industry to lightweight automotive parts. The replacement of metallic parts by thermoplastics is reaching under-the-hood parts, near the engine. In this area, the parts are subjected to high temperatures and are immersed in cooling liquid. This liquid is composed of water and glycol and can affect the mechanical properties of the composite. The aim of this work was thus to quantify the evolution of mechanical properties of the thermoplastic composite, as a function of temperature and liquid aging effects, in order to develop a reliable design of parts. An experimental campaign in the tensile mode was carried out at different temperatures and for various glycol proportions in the cooling liquid, for monotonic and cyclic loadings on a neat and a reinforced PPS. The results of these tests allowed to highlight some of the main physical phenomena occurring during these solicitations under tough hydro-thermal conditions. Indeed, the performed tests showed that temperature and liquid cooling aging can affect the mechanical behavior of the material in several ways. The more the cooling liquid contains water, the more the mechanical behavior is affected. It was observed that PPS showed a higher sensitivity to absorption than to chemical aggressiveness of the cooling liquid, explaining this dominant sensitivity. Two kinds of behaviors were noted: an elasto-plastic type under the glass transition temperature and a visco-pseudo-plastic one above it. It was also shown that viscosity is the leading phenomenon above the glass transition temperature for the PPS and could also be important under this temperature, mostly under cyclic conditions and when the stress rate is low. Finally, it was observed that soliciting this composite at high temperatures is decreasing the advantages of the presence of fibers. A new phenomenological model was then built to take into account these experimental observations. This new model allowed the prediction of the evolution of mechanical properties as a function of the loading environment, with a reduced number of parameters compared to precedent studies. It was also shown that the presented approach enables the description and the prediction of the mechanical response with very good accuracy (2% of average error at worst), over a wide range of hydrothermal conditions. A temperature-humidity equivalence principle was underlined for the PPS, allowing the consideration of aging effects within the proposed model. Then, a limit of improvement of the reachable accuracy was determinate for all models using this set of data by the application of an artificial intelligence-based model allowing a comparison between artificial intelligence-based models and phenomenological based ones.

Keywords: aging, analytical modeling, mechanical testing, polymer matrix composites, sequential model, thermomechanical

Procedia PDF Downloads 92

Authors: P. Dubcek, B. Pivac, J. Dasovic, V. Janicki, S. Bernstorff

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When grown only to nanometric sizes, metallic particles (e.g. Ag, Au and Cu) exhibit specific optical properties caused by the presence of plasmon band. The plasmon band represents collective oscillation of the conduction electrons, and causes a narrow band absorption of light in the visible range. When the nanoparticles are embedded in a dielectric, they also cause modifications of dielectrics optical properties. This can be fine-tuned by tuning the particle size. We investigated Cu nanoparticle growth with and without surrounding dielectric (SiO2 capping layer). The morphology and crystallinity were investigated by GISAXS and GIWAXS, respectively. Samples were produced by high vacuum thermal evaporation of Cu onto monocrystalline silicon substrate held at room temperature, 100°C or 180°C. One series was in situ capped by 10nm SiO2 layer. Additionally, samples were annealed at different temperatures up to 550°C, also in high vacuum. The room temperature deposited samples annealed at lower temperatures exhibit continuous film structure: strong oscillations in the GISAXS intensity are present especially in the capped samples. At higher temperatures enhanced surface dewetting and Cu nanoparticles (nanoislands) formation partially destroy the flatness of the interface. Therefore the particle type of scattering is enhanced, while the film fringes are depleted. However, capping layer hinders particle formation, and continuous film structure is preserved up to higher annealing temperatures (visible as strong and persistent fringes in GISAXS), compared to the non- capped samples. According to GISAXS, lateral particle sizes are reduced at higher temperatures, while particle height is increasing. This is ascribed to close packing of the formed particles at lower temperatures, and GISAXS deduced sizes are partially the result of the particle agglomerate dimensions. Lateral maxima in GISAXS are an indication of good positional correlation, and the particle to particle distance is increased as the particles grow with temperature elevation. This coordination is much stronger in the capped and lower temperature deposited samples. The dewetting is much more vigorous in the non-capped sample, and since nanoparticles are formed in a range of sizes, correlation is receding both with deposition and annealing temperature. Surface topology was checked by atomic force microscopy (AFM). Capped sample's surfaces were smoother and lateral size of the surface features were larger compared to the non-capped samples. Altogether, AFM results suggest somewhat larger particles and wider size distribution, and this can be attributed to the difference in probe size. Finally, the plasmonic effect was monitored by UV-Vis reflectance spectroscopy, and relative weak plasmonic effect could be explained by uncomplete dewetting or partial interconnection of the formed particles.

Keywords: coper, GISAXS, nanoparticles, plasmonics

Procedia PDF Downloads 102

Authors: Lishuang Ma

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

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

Procedia PDF Downloads 115

Authors: Xuechun Kan, Dongdong Li, Fan Li, Peidang Liu

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Triple-negative breast cancer (TNBC) is the most malignant subtype of breast cancer with a poor prognosis, and radiotherapy is one of the main treatment methods. However, due to the obvious resistance of tumor cells to radiotherapy, high dose of ionizing radiation is required during radiotherapy, which causes serious damage to normal tissues near the tumor. Therefore, how to improve radiotherapy resistance and enhance the specific killing of tumor cells by radiation is a hot issue that needs to be solved in clinic. Recent studies have shown that silver-based nanoparticles have strong radiosensitization, and silver nanoclusters (AgNCs) also provide a broad prospect for tumor targeted radiosensitization therapy due to their ultra-small size, low toxicity or non-toxicity, self-fluorescence and strong photostability. Aptamer 5TR1 is a 25-base oligonucleotide aptamer that can specifically bind to mucin-1 highly expressed on the membrane surface of TNBC 4T1 cells, and can be used as a highly efficient tumor targeting molecule. In this study, AgNCs were synthesized by DNA template based on 5TR1 aptamer (NC-T5-5TR1), and its role as a targeted radiosensitizer in TNBC radiotherapy was investigated. The optimal DNA template was first screened by fluorescence emission spectroscopy, and NC-T5-5TR1 was prepared. NC-T5-5TR1 was characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and dynamic light scattering. The inhibitory effect of NC-T5-5TR1 on cell activity was evaluated using the MTT method. Laser confocal microscopy was employed to observe NC-T5-5TR1 targeting 4T1 cells and verify its self-fluorescence characteristics. The uptake of NC-T5-5TR1 by 4T1 cells was observed by dark-field imaging, and the uptake peak was evaluated by inductively coupled plasma mass spectrometry. The radiation sensitization effect of NC-T5-5TR1 was evaluated through cell cloning and in vivo anti-tumor experiments. Annexin V-FITC/PI double staining flow cytometry was utilized to detect the impact of nanomaterials combined with radiotherapy on apoptosis. The results demonstrated that the particle size of NC-T5-5TR1 is about 2 nm, and the UV-visible absorption spectrum detection verifies the successful construction of NC-T5-5TR1, and it shows good dispersion. NC-T5-5TR1 significantly inhibited the activity of 4T1 cells and effectively targeted and fluoresced within 4T1 cells. The uptake of NC-T5-5TR1 reached its peak at 3 h in the tumor area. Compared with AgNCs without aptamer modification, NC-T5-5TR1 exhibited superior radiation sensitization, and combined radiotherapy significantly inhibited the activity of 4T1 cells and tumor growth in 4T1-bearing mice. The apoptosis level of NC-T5-5TR1 combined with radiation was significantly increased. These findings provide important theoretical and experimental support for NC-T5-5TR1 as a radiation sensitizer for TNBC.

Keywords: 5TR1 aptamer, silver nanoclusters, radio sensitization, triple-negative breast cancer

Procedia PDF Downloads 24

Authors: Laura C. Loaiza, Elodie Salager, Nicolas Louvain, Athmane Boulaoued, Antonella Iadecola, Patrik Johansson, Lorenzo Stievano, Vincent Seznec, Laure Monconduit

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Lithium-ion batteries (LIBs) have an important place among energy storage devices due to their high capacity and good cyclability. However, the advancements in portable and transportation applications have extended the research towards new horizons, and today the development is hampered, e.g., by the capacity of the electrodes employed. Silicon and germanium are among the considered modern anode materials as they can undergo alloying reactions with lithium while delivering high capacities. It has been demonstrated that silicon in its highest lithiated state can deliver up to ten times more capacity than graphite (372 mAh/g): 4200 mAh/g for Li₂₂Si₅ and 3579 mAh/g for Li₁₅Si₄, respectively. On the other hand, germanium presents a capacity of 1384 mAh/g for Li₁₅Ge₄, and a better electronic conductivity and Li ion diffusivity as compared to Si. Nonetheless, the commercialization potential of Ge is limited by its cost. The synergetic effect of Si₁₋ₓGeₓ alloys has been proven, the capacity is increased compared to Ge-rich electrodes and the capacity retention is increased compared to Si-rich electrodes, but the exact performance of this type of electrodes will depend on factors like specific capacity, C-rates, cost, etc. There are several reports on various formulations of Si₁₋ₓGeₓ alloys with promising LIB anode performance with most work performed on complex nanostructures resulting from synthesis efforts implying high cost. In the present work, we studied the electrochemical mechanism of the Si₀.₅Ge₀.₅ alloy as a realistic micron-sized electrode formulation using carboxymethyl cellulose (CMC) as the binder. A combination of a large set of in situ and operando techniques were employed to investigate the structural evolution of Si₀.₅Ge₀.₅ during lithiation and delithiation processes: powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Raman spectroscopy, and 7Li solid state nuclear magnetic resonance spectroscopy (NMR). The results have presented a whole view of the structural modifications induced by the lithiation/delithiation processes. The Si₀.₅Ge₀.₅ amorphization was observed at the beginning of discharge. Further lithiation induces the formation of a-Liₓ(Si/Ge) intermediates and the crystallization of Li₁₅(Si₀.₅Ge₀.₅)₄ at the end of the discharge. At really low voltages a reversible process of overlithiation and formation of Li₁₅₊δ(Si₀.₅Ge₀.₅)₄ was identified and related with a structural evolution of Li₁₅(Si₀.₅Ge₀.₅)₄. Upon charge, the c-Li₁₅(Si₀.₅Ge₀.₅)₄ was transformed into a-Liₓ(Si/Ge) intermediates. At the end of the process an amorphous phase assigned to a-SiₓGey was recovered. Thereby, it was demonstrated that Si and Ge are collectively active along the cycling process, upon discharge with the formation of a ternary Li₁₅(Si₀.₅Ge₀.₅)₄ phase (with a step of overlithiation) and upon charge with the rebuilding of the a-Si-Ge phase. This process is undoubtedly behind the enhanced performance of Si₀.₅Ge₀.₅ compared to a physical mixture of Si and Ge.

Keywords: lithium ion battery, silicon germanium anode, in situ characterization, X-Ray diffraction

Procedia PDF Downloads 254

Authors: C. Mazilu, D. P. Georgescu, A. Apostu, R. Deju

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Cement mortars and concretes are some of the most used construction materials in the world, global cement production being expected to grow to approx. 5 billion tons, until 2030. But, cement is an energy intensive material, the cement industry being responsible for cca. 7% of the world's CO2 emissions. Also, natural aggregates represent non-renewable resources, exhaustible, which must be used efficiently. A way to reduce the negative impact on the environment is the use of additional hydraulically active materials, as a partial substitute for cement in mortars and concretes and/or the use of recycled concrete aggregates (RCA) for the recovery of construction waste, according to EU Directive 2018/851. One of the most effective active hydraulic admixtures is microsilica and more recently, with the technological development on a nanometric scale, nanosilica. Studies carried out in recent years have shown that the introduction of SiO2 nanoparticles into cement matrix improves the properties, even compared to microsilica. This is due to the very small size of the nanosilica particles (<100nm) and the very large specific surface, which helps to accelerate cement hydration and acts as a nucleating agent to generate even more calcium hydrosilicate which densifies and compacts the structure. The cementitious compositions containing recycled concrete aggregates (RCA) present, in generally, inferior properties compared to those obtained with natural aggregates. Depending on the degree of replacement of natural aggregate, decreases the workability of mortars and concretes with RAC, decrease mechanical resistances and increase drying shrinkage; all being determined, in particular, by the presence to the old mortar attached to the original aggregate from the RAC, which makes its porosity high and the mixture of components to require more water for preparation. The present study aims to use micro and nanosilica for increase the performance of some mortars and concretes obtained with RCA. The research focused on two types of cementitious systems: a special mortar composition used for encapsulating Low Level radioactive Waste (LLW); a composition of structural concrete, class C30/37, with the combination of exposure classes XC4+XF1 and settlement class S4. The mortar was made with 100% recycled aggregate, 0-5 mm sort and in the case of concrete, 30% recycled aggregate was used for 4-8 and 8-16 sorts, according to EN 206, Annex E. The recycled aggregate was obtained from a specially made concrete for this study, which after 28 days was crushed with the help of a Retsch jaw crusher and further separated by sieving on granulometric sorters. The partial replacement of cement was done progressively, in the case of the mortar composition, with microsilica (3, 6, 9, 12, 15% wt.), nanosilica (0.75, 1.5, 2.25% wt.), respectively mixtures of micro and nanosilica. The optimal combination of silica, from the point of view of mechanical resistance, was later used also in the case of the concrete composition. For the chosen cementitious compositions, the influence of micro and/or nanosilica on the properties in the fresh state (workability, rheological characteristics) and hardened state (mechanical resistance, water absorption, freeze-thaw resistance, etc.) is highlighted.

Keywords: cement, recycled concrete aggregates, micro/nanosilica, durability

Procedia PDF Downloads 35

Authors: Claudiu Mazilu, Ion Robu, Radu Deju

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At the end of 2011 worldwide there were 124 power reactors shut down, from which: 16 fully decommissioned, 50 power reactors in a decommissioning process, 49 reactors in “safe enclosure mode”, 3 reactors “entombed”, for other 6 reactors it was not yet have specified the decommissioning strategy. The concrete radioactive waste that will be generated from dismantled structures of VVR-S nuclear research reactor from Magurele (e.g.: biological shield of the reactor core and hot cells) represents an estimated amount of about 70 tons. Until now the solid low activity radioactive waste (LLW) was pre-placed in containers and cementation with mortar made from cement and natural fine aggregates, providing a fill ratio of the container of approximately 50 vol. % for concrete. In this paper is presented an innovative technology in which radioactive concrete is crushed and the mortar made from recycled radioactive sand, cement, water and superplasticizer agent is poured in container with radioactive rubble (that is pre-placed in container) for cimentation. Is achieved a radioactive waste package in which the degree of filling of radioactive waste increases substantially. The tests were carried out on non-radioactive material because the radioactive concrete was not available in a good time. Waste concrete with maximum size of 350 mm were crushed in the first stage with a Liebhher type jaw crusher, adjusted to nominal size of 50 mm. Crushed concrete less than 50 mm was sieved in order to obtain useful sort for preplacement, 10 to 50 mm. The rest of the screening > 50 mm obtained from primary crushing of concrete was crushed in the second stage, with different working principles crushers at size < 2.5 mm, in order to produce recycled fine aggregate (sand) for the filler mortar and which fulfills the technical specifications proposed: –jaw crusher, Retsch type, model BB 100; –hammer crusher, Buffalo Shuttle model WA-12-H; presented a series of characteristics of recycled concrete aggregates by predefined class (the granulosity, the granule shape, the absorption of water, behavior to the Los Angeles test, the content of attached mortar etc.), most in comparison with characteristics of natural aggregates. Various mortar recipes were used in order to identify those that meet the proposed specification (flow-rate: 16-50s, no bleeding, min. 30N/mm2 compressive strength of the mortar after 28 days, the proportion of recycled sand used in mortar: min. 900kg/m3) and allow obtaining of the highest fill ratio for mortar. In order to optimize the mortars following compositional factors were varied: aggregate nature, water/cement (W/C) ratio, sand/cement (S/C) ratio, nature and proportion of additive. To confirm the results obtained on a small scale, it made an attempt to fill the mortar in a container that simulates the final storage drums. Was measured the mortar fill ratio (98.9%) compared with the results of laboratory tests and targets set out in the proposed specification. Although fill ratio obtained on the mock-up is lower by 0.8 vol. % compared to that obtained in the laboratory tests (99.7%), the result meets the specification criteria.

Keywords: characteristics, radioactive recycled concrete aggregate, mortars, fill ratio

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Authors: O. Sauperl, L. Fras Zemljic

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The textile industry is gaining increasing importance in the field of medical materials. Therefore, presented research is focused on textile materials for external (out-of-body) use. Such materials could be various hygienic textile products (diapers, tampons, sanitary napkins, incontinence products, etc.), protective textiles and various hospital linens (surgical covers, masks, gowns, cloths, bed linens, etc.) wound pillows, bandages, orthopedic socks, etc. Function of tampons and sanitary napkins is not only to provide protection during the menstrual cycle, but their function can be also to take care of physiological or pathological vaginal discharge. In general, women's intimate areas are against infection protected by a low pH value of the vaginal flora. High pH inhibits the development of harmful microorganisms, as it is difficult to be reproduced in an acidic environment. The normal vaginal flora in healthy women is highly colonized by lactobacilli. The lactic acid produced by these organisms maintains the constant acidity of the vagina. If the balance of natural protection breaks, infections can occur. In the market, there exist probiotic tampons as a medical product supplying the vagina with beneficial probiotic lactobacilli. But, many users have concerns about the use of tampons due to the possible dry-out of the vagina as well as the possible toxic shock syndrome, which is the reason that they use mainly sanitary napkins during the menstrual cycle. Functionalization of sanitary napkins with probiotics is, therefore, interesting in regard to maintain a healthy vaginal flora and to offer to users added value of the sanitary napkins in the sense of health- and environmentally-friendly products. For this reason, the presented research is oriented in functionalization of the sanitary napkins with the probiotic paste in order to activate the lactic acid bacteria presented in the core of the functionalized sanitary napkin at the time of the contact with the menstrual fluid. In this way, lactobacilli could penetrate into vagina and by maintaining healthy vaginal flora to reduce the risk of vaginal disorders. In regard to the targeted research problem, the influence of probiotic paste applied onto cotton hygienic napkins on selected properties was studied. The aim of the research was to determine whether the sanitary napkins with the applied probiotic paste may assure suitable vaginal pH to maintain a healthy vaginal flora during the use of this product. Together with this, sorption properties of probiotic functionalized sanitary napkins were evaluated and compared to the untreated one. The research itself was carried out on the basis of tracking and controlling the input parameters, currently defined by Slovenian producer (Tosama d.o.o.) as the most important. Successful functionalization of sanitary pads with the probiotic paste was confirmed by ATR-FTIR spectroscopy. Results of the methods used within the presented research show that the absorption of the pads treated with probiotic paste deteriorates compared to non-treated ones. The coating shows a 6-month stability. Functionalization of sanitary pads with probiotic paste is believed to have a commercial potential for lowering the probability of infection during the menstrual cycle.

Keywords: functionalization, probiotic paste, sanitary pads, textile materials

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Authors: Sibele A. F. Leite, Bernno S. Leite, José Vicente H. D´Angelo, Ana Teresa P. Dell’Isola, Julio CéSar Souza

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The generation of bioenergy is one of the oldest and simplest biomass applications and is one of the safest options for minimizing emissions of greenhouse gasses and replace the use of fossil fuels. In addition, the increasing development of technologies for energy biomass conversion parallel to the advancement of research in biotechnology and engineering has enabled new opportunities for exploitation of biomass. Agricultural residues offer great potential for energy use, and Brazil is in a prominent position in the production and export of agricultural products such as banana and rice. Despite the economic importance of the growth prospects of these activities and the increasing of the agricultural waste, they are rarely explored for energy and production of new materials. Brazil products almost 10.5 million tons/year of rice husk and 26.8 million tons/year of banana stem. Thereby, the aim of this study was to analysis the potential of biomass residues for energy production and applications in new materials. Rice husk (specify the type) and banana stem (specify the type) were characterized by physicochemical analyses using the following parameters: organic carbon, nitrogen (NTK), proximate analyses, FT-IR spectroscopy, thermogravimetric analyses (TG), calorific values and silica content. Rice husk and banana stem presented attractive superior calorific (from 11.5 to 13.7MJ/kg), and they may be compared to vegetal coal (21.25 MJ/kg). These results are due to the high organic matter content. According to the proximate analysis, biomass has high carbon content (fixed and volatile) and low moisture and ash content. In addition, data obtained by Walkley–Black method point out that most of the carbon present in the rice husk (50.5 wt%) and in banana stalk (35.5 wt%) should be understood as organic carbon (readily oxidizable). Organic matter was also detected by Kjeldahl method which gives the values of nitrogen (especially on the organic form) for both residues: 3.8 and 4.7 g/kg of rice husk and banana stem respectively. TG and DSC analyses support the previous results, as they can provide information about the thermal stability of the samples allowing a correlation between thermal behavior and chemical composition. According to the thermogravimetric curves, there were two main stages of mass-losses. The first and smaller one occurred below 100 °C, which was suitable for water losses and the second event occurred between 200 and 500 °C which indicates decomposition of the organic matter. At this broad peak, the main loss was between 250-350 °C, and it is because of sugar decomposition (components readily oxidizable). Above 350 °C, mass loss of the biomass may be associated with lignin decomposition. Spectroscopic characterization just provided qualitative information about the organic matter, but spectra have shown absorption bands around 1030 cm-1 which may be identified as species containing silicon. This result is expected for the rice husk and deserves further investigation to the stalk of banana, as it can bring a different perspective for this biomass residue.

Keywords: rice husk, banana stem, bioenergy, renewable feedstock

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Authors: Federico Capra, Emanuele Martelli, Matteo Gazzani, Marco Mazzotti, Maurizio Notaro

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Natural gas is a major energy source in the current global economy, contributing to roughly 21% of the total primary energy consumption. Production of natural gas starting from renewable energy sources is key to limit the related CO2 emissions, especially for those sectors that heavily rely on natural gas use. In this context, biomethane produced via biogas upgrading represents a good candidate for partial substitution of fossil natural gas. The upgrading process of biogas to biomethane consists in (i) the removal of pollutants and impurities (e.g. H2S, siloxanes, ammonia, water), and (ii) the separation of carbon dioxide from methane. Focusing on the CO2 removal process, several technologies can be considered: chemical or physical absorption with solvents (e.g. water, amines), membranes, adsorption-based systems (PSA). However, none emerged as the leading technology, because of (i) the heterogeneity in plant size, ii) the heterogeneity in biogas composition, which is strongly related to the feedstock type (animal manure, sewage treatment, landfill products), (iii) the case-sensitive optimal tradeoff between purity and recovery of biomethane, and iv) the destination of the produced biomethane (grid injection, CHP applications, transportation sector). With this contribution, we explore the use of a technology for biogas upgrading and we compare the resulting performance with benchmark technologies. The proposed technology makes use of a chemical sorbent, which is engineered by RSE and consists of Di-Ethanol-Amine deposited on a solid support made of γ-Alumina, to chemically adsorb the CO2 contained in the gas. The material is packed into fixed beds that cyclically undergo adsorption and regeneration steps. CO2 is adsorbed at low temperature and ambient pressure (or slightly above) while the regeneration is carried out by pulling vacuum and increasing the temperature of the bed (vacuum-temperature swing adsorption - VTSA). Dynamic adsorption tests were performed by RSE and were used to tune the mathematical model of the process, including material and transport parameters (i.e. Langmuir isotherms data and heat and mass transport). Based on this set of data, an optimal VTSA cycle was designed. The results enabled a better understanding of the interplay between material and cycle tuning. As exemplary application, the upgrading of biogas for grid injection, produced by an anaerobic digester (60-70% CO2, 30-40% CH4), for an equivalent size of 1 MWel was selected. A plant configuration is proposed to maximize heat recovery and minimize the energy consumption of the process. The resulting performances are very promising compared to benchmark solutions, which make the VTSA configuration a valuable alternative for biomethane production starting from biogas.

Keywords: biogas upgrading, biogas upgrading energetic cost, CO2 adsorption, VTSA process modelling

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Authors: Malek Mahmoudi, Jonas Keruckas, Dmytro Volyniuk, Jurate Simokaitiene, Juozas V. Grazulevicius

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Host materials have been discovered as one of the most appealing methods for harvesting triplet states in organic materials for application in organic light-emitting diodes (OLEDs). The ideal host-guest system for emission in thermally delayed fluorescence OLEDs with 20% guest concentration for efficient energy transfer has been demonstrated in the present investigation. In this work, 3,3'-bis[9-(4-fluorophenyl) carbazole] (bFPC) has been used as the host, which induces balanced charge carrier transport for high-efficiency OLEDs.For providing a complete characterization of the synthesized compound, photophysical, photoelectrical, charge-transporting, and electrochemical properties of the compound have been examined. Excited-state lifetimes and singlet-triplet energy gaps were measured for characterization of photophysical properties, while thermogravimetric analysis, as well as differential scanning calorimetry measurements, were performed for probing of electrochemical and thermal properties of the compound. The electrochemical properties of this compound were investigated by cyclic voltammetry (CV) method, and ionization potential (IPCV) value of 5.68 eV was observed. UV–Vis absorption and photoluminescence spectrum of a solution of the compound in toluene (10-5 M) showed maxima at 302 and 405 nm, respectively. Photoelectron emission spectrometry was used for the characterization of charge-injection properties of the studied compound in solid. The ionization potential of this material was found to be 5.78 eV, and time-of-flight measurement was used for testing charge-transporting properties and hole mobility estimated using this technique in a vacuum-deposited layer reached 4×10-4 cm2 V-1s-1. Since the compound with high charge mobilities was tested as a host in an organic light-emitting diode. The device was fabricated by successive deposition onto a pre-cleaned indium tin oxide (ITO) coated glass substrate under a vacuum of 10-6 Torr and consisting of an indium-tin-oxide anode, hole injection and transporting layer(MoO3, NPB), emitting layer with bFPC as a host and 4CzIPN (2,4,5,6-tetra(9-carbazolyl)isophthalonitrile) which is a new highly efficient green thermally activated delayed fluorescence (TADF) material as an emitter, an electron transporting layer(TPBi) and lithium fluoride layer topped with aluminum layer as a cathode exhibited the highest maximum current efficiency and power efficiency of 33.9 cd/A and 23.5 lm/W, respectively and the electroluminescence spectrum showed only a peak at 512nm. Furthermore, the new bicarbazole-based compound was tested as a host in thermally activated delayed fluorescence organic light-emitting diodes are reaching luminance of 25300 cd m-2 and external quantum efficiency of 10.1%. Interestingly, the turn-on voltage was low enough (3.8 V), and such a device can be used for highly efficient light sources.

Keywords: thermally-activated delayed fluorescence, host material, ionization energy, charge mobility, electroluminescence

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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

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Authors: Kanchan Mondal, Adam Sims, Madhav Soti, Jitendra Gautam, David Carron

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Fischer-Tropsch (FT) synthesis is a complex series of heterogeneous reactions between CO and H2 molecules (present in the syngas) on the surface of an active catalyst (Co, Fe, Ru, Ni, etc.) to produce gaseous, liquid, and waxy hydrocarbons. This product is composed of paraffins, olefins, and oxygenated compounds. The key challenge in applying the Fischer-Tropsch process to produce transportation fuels is to make the capital and production costs economically feasible relative to the comparative cost of existing petroleum resources. To meet this challenge, it is imperative to enhance the CO conversion while maximizing carbon selectivity towards the desired liquid hydrocarbon ranges (i.e. reduction in CH4 and CO2 selectivities) at high throughputs. At the same time, it is equally essential to increase the catalyst robustness and longevity without sacrificing catalyst activity. This paper focuses on process development to achieve the above. The paper describes the influence of operating parameters on Fischer Tropsch synthesis (FTS) from coal derived syngas in supercritical carbon dioxide (ScCO2). In addition, the unreacted gas and solvent recycle was incorporated and the effect of unreacted feed recycle was evaluated. It was expected that with the recycle, the feed rate can be increased. The increase in conversion and liquid selectivity accompanied by the production of narrower carbon number distribution in the product suggest that higher flow rates can and should be used when incorporating exit gas recycle. It was observed that this process was capable of enhancing the hydrocarbon selectivity (nearly 98 % CO conversion), reducing improving the carbon efficiency from 17 % to 51 % in a once through process and further converting 16 % CO2 to liquid with integrated recycle of the product gas stream and increasing the life of the catalyst. Catalyst robustness enhancement has been attributed to the absorption of heat of reaction by the compressed CO2 which reduced the formation of hotspots and the dissolution of waxes by the CO2 solvent which reduced the blinding of active sites. In addition, the recycling the product gas stream reduced the reactor footprint to one-fourth of the once through size and product fractionation utilizing the solvent effects of supercritical CO2 were realized. In addition to the negative CO2 selectivities, methane production was also inhibited and was limited to less than 1.5%. The effect of the process conditions on the life of the catalysts will also be presented. Fe based catalysts are known to have a high proclivity for producing CO2 during FTS. The data of the product spectrum and selectivity on Co and Fe-Co based catalysts as well as those obtained from commercial sources will also be presented. The measurable decision criteria were the increase in CO conversion at H2:CO ratio of 1:1 (as commonly found in coal gasification product stream) in supercritical phase as compared to gas phase reaction, decrease in CO2 and CH4 selectivity, overall liquid product distribution, and finally an increase in the life of the catalysts.

Keywords: carbon efficiency, Fischer Tropsch synthesis, low GHG, pressure tunable fractionation

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