Search results for: quantile dispersion graphs

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

Abstract:

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

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

Procedia PDF Downloads 57

Authors: Meron Zenaselase Rata, Euridice Leyequien Abarca

Abstract:

The production of major crops in Northern Ethiopia, especially the Tigray Region, is at subsistence level due to drought, erratic rainfall, and poor soil fertility. Since cactus pear is a drought-resistant plant, it is considered as a lifesaver fruit and a strategy for poverty reduction in a drought-affected area of the region. Despite its contribution to household income and food security in the area, the cactus pear sub-sector is experiencing many constraints with limited attention given to its post-harvest loss management. Therefore, this research was carried out to identify opportunities for reducing post-harvest losses and recommend possible strategies to reduce post-harvest losses, thereby improving production and smallholder’s income. Both probability and non-probability sampling techniques were employed to collect the data. Ganta Afeshum district was selected from Eastern Tigray, and two peasant associations (Buket and Golea) were also selected from the district purposively for being potential in cactus pear production. Simple random sampling techniques were employed to survey 30 households from each of the two peasant associations, and a semi-structured questionnaire was used as a tool for data collection. Moreover, in this research 2 collectors, 2 wholesalers, 1 processor, 3 retailers, 2 consumers were interviewed; and two focus group discussion was also done with 14 key farmers using semi-structured checklist; and key informant interview with governmental and non-governmental organizations were interviewed to gather more information about the cactus pear production, post-harvest losses, the strategies used to reduce the post-harvest losses and suggestions to improve the post-harvest management. To enter and analyze the quantitative data, SPSS version 20 was used, whereas MS-word were used to transcribe the qualitative data. The data were presented using frequency and descriptive tables and graphs. The data analysis was also done using a chain map, correlations, stakeholder matrix, and gross margin. Mean comparisons like ANOVA and t-test between variables were used. The analysis result shows that the present cactus pear value chain involves main actors and supporters. However, there is inadequate information flow and informal market linkages among actors in the cactus pear value chain. The farmer's gross margin is higher when they sell to the processor than sell to collectors. The significant postharvest loss in the cactus pear value chain is at the producer level, followed by wholesalers and retailers. The maximum and minimum volume of post-harvest losses at the producer level is 4212 and 240 kgs per season. The post-harvest loss was caused by limited farmers skill on-farm management and harvesting, low market price, limited market information, absence of producer organization, poor post-harvest handling, absence of cold storage, absence of collection centers, poor infrastructure, inadequate credit access, using traditional transportation system, absence of quality control, illegal traders, inadequate research and extension services and using inappropriate packaging material. Therefore, some of the recommendations were providing adequate practical training, forming producer organizations, and constructing collection centers.

Keywords: cactus pear, post-harvest losses, profit margin, value-chain

Procedia PDF Downloads 132

Authors: Roshanak Afrakhteh, Abdolrasoul Salman Mahini, Mahdi Motagh, Hamidreza Kamyab

Abstract:

Urban Heat Islands (UHIs) are distinctive urban areas characterized by densely populated central cores surrounded by less densely populated peripheral lands. These areas experience elevated temperatures, primarily due to impermeable surfaces and specific land use patterns. The consequences of these temperature variations are far-reaching, impacting the environment and society negatively, leading to increased energy consumption, air pollution, and public health concerns. This paper emphasizes the need for simplified approaches to comprehend UHI temperature dynamics and explains how urban development patterns contribute to land surface temperature variation. To illustrate this relationship, the study focuses on the Guilan Plain, utilizing techniques like principal component analysis and generalized additive models. The research centered on mapping land use and land surface temperature in the low-lying area of Guilan province. Satellite data from Landsat sensors for three different time periods (2002, 2012, and 2021) were employed. Using eCognition software, a spatial unit known as a "city block" was utilized through object-based analysis. The study also applied the normalized difference vegetation index (NDVI) method to estimate land surface radiance. Predictive variables for urban land surface temperature within residential city blocks were identified categorized as intrinsic (related to the block's structure) and neighboring (related to adjacent blocks) variables. Principal Component Analysis (PCA) was used to select significant variables, and a Generalized Additive Model (GAM) approach, implemented using R's mgcv package, modeled the relationship between urban land surface temperature and predictor variables.Notable findings included variations in urban temperature across different years attributed to environmental and climatic factors. Block size, shared boundary, mother polygon area, and perimeter-to-area ratio were identified as main variables for the generalized additive regression model. This model showed non-linear relationships, with block size, shared boundary, and mother polygon area positively correlated with temperature, while the perimeter-to-area ratio displayed a negative trend. The discussion highlights the challenges of predicting urban surface temperature and the significance of block size in determining urban temperature patterns. It also underscores the importance of spatial configuration and unit structure in shaping urban temperature patterns. In conclusion, this study contributes to the growing body of research on the connection between land use patterns and urban surface temperature. Block size, along with block dispersion and aggregation, emerged as key factors influencing urban surface temperature in residential areas. The proposed methodology enhances our understanding of parameter significance in shaping urban temperature patterns across various regions, particularly in Iran.

Keywords: urban heat island, land surface temperature, LST modeling, GAM, Gilan province

Procedia PDF Downloads 76

Authors: Inês Amorim Leitão, Loes van Shaick, António Dinis Ferreira, Violette Geissen

Abstract:

Plastic pollution is a growing concern worldwide: plastics are commercialized in large quantities and it takes a long time for them to degrade. When in the environment, plastic is fragmented into microplastics (<5mm), which have been found in all environmental compartments at different locations. Microplastics contribute to the environmental pollution in water, air and soil and are linked to human health problems. The progressive increase of population living in cities led to the aggravation of the pollution problem worldwide, especially in urban environments. Urban areas represent a strong source of pollution, through the roads, industrial production, wastewater, landfills, etc. It is expected that pollutants such as microplastics are transported diffusely from the sources through different pathways such as wind and rain. Therefore, it is very complex to quantify, control and treat these pollutants, designated current problematic issues by the European Commission. Green areas are pointed out by experts as natural filters for contaminants in cities, through their capacity of retention by vegetation. These spaces have thus the capacity to control the load of pollutants transported. This study investigates the spatial distribution of microplastics in urban soils of different land uses, their transport through atmospheric deposition, wind erosion, runoff and streams, as well as their deposition in vegetation like grass and tree leaves in urban environment. Coimbra, a medium large city located in the central Portugal, is the case-study. All the soil, sediments, water and vegetation samples were collected in Coimbra and were later analyzed in the Wageningen University & Research laboratory. Microplastics were extracted through the density separation using Sodium Phosphate as solution (~1.4 g cm−3) and filtration methods, visualized under a stereo microscope and identified using the u-FTIR method. Microplastic particles were found in all the different samples. In terms of soils, higher concentrations of microplastics were found in green parks, followed by landfills and industrial places, and the lowest concentrations in forests and pasture land-uses. Atmospheric deposition and streams after rainfall events seems to represent the strongest pathways of microplastics. Tree leaves can retain microplastics on their surfaces. Small leaves such as needle leaves seem to present higher amounts of microplastics per leaf area than bigger leaves. Rainfall episodes seem to reduce the concentration of microplastics on leaves surface, which suggests the wash of microplastics down to lower levels of the tree or to the soil. When in soil, different types of microplastics could be transported to the atmosphere through wind erosion. Grass seems to present high concentrations of microplastics, and the enlargement of the grass cover leads to a reduction of the amount of microplastics in soil, but also of the microplastics moved from the ground to the atmosphere by wind erosion. This study proof that vegetation can help to control the transport and dispersion of microplastics. In order to control the entry and the concentration of microplastics in the environment, especially in cities, it is essential to defining and evaluating nature-based land-use scenarios, considering the role of green urban areas in filtering small particles.

Keywords: microplastics, cities, sources, pathways, vegetation

Procedia PDF Downloads 60

Authors: Renata Gerhardt, Detlev Belder

Abstract:

Raman spectroscopy has attracted much attention as a structurally descriptive and label-free detection method. It is particularly suited for chemical analysis given as it is non-destructive and molecules can be identified via the fingerprint region of the spectra. In this work possibilities are investigated how to integrate Raman spectroscopy as a detection method for chip-based chromatography, making use of a droplet interface. A demanding task in lab-on-a-chip applications is the specific and sensitive detection of low concentrated analytes in small volumes. Fluorescence detection is frequently utilized but restricted to fluorescent molecules. Furthermore, no structural information is provided. Another often applied technique is mass spectrometry which enables the identification of molecules based on their mass to charge ratio. Additionally, the obtained fragmentation pattern gives insight into the chemical structure. However, it is only applicable as an end-of-the-line detection because analytes are destroyed during measurements. In contrast to mass spectrometry, Raman spectroscopy can be applied on-chip and substances can be processed further downstream after detection. A major drawback of Raman spectroscopy is the inherent weakness of the Raman signal, which is due to the small cross-sections associated with the scattering process. Enhancement techniques, such as surface enhanced Raman spectroscopy (SERS), are employed to overcome the poor sensitivity even allowing detection on a single molecule level. In SERS measurements, Raman signal intensity is improved by several orders of magnitude if the analyte is in close proximity to nanostructured metal surfaces or nanoparticles. The main gain of lab-on-a-chip technology is the building block-like ability to seamlessly integrate different functionalities, such as synthesis, separation, derivatization and detection on a single device. We intend to utilize this powerful toolbox to realize Raman detection in chip-based chromatography. By interfacing on-chip separations with a droplet generator, the separated analytes are encapsulated into numerous discrete containers. These droplets can then be injected with a silver nanoparticle solution and investigated via Raman spectroscopy. Droplet microfluidics is a sub-discipline of microfluidics which instead of a continuous flow operates with the segmented flow. Segmented flow is created by merging two immiscible phases (usually an aqueous phase and oil) thus forming small discrete volumes of one phase in the carrier phase. The study surveys different chip designs to realize coupling of chip-based chromatography with droplet microfluidics. With regards to maintaining a sufficient flow rate for chromatographic separation and ensuring stable eluent flow over the column different flow rates of eluent and oil phase are tested. Furthermore, the detection of analytes in droplets with surface enhanced Raman spectroscopy is examined. The compartmentalization of separated compounds preserves the analytical resolution since the continuous phase restricts dispersion between the droplets. The droplets are ideal vessels for the insertion of silver colloids thus making use of the surface enhancement effect and improving the sensitivity of the detection. The long-term goal of this work is the first realization of coupling chip based chromatography with droplets microfluidics to employ surface enhanced Raman spectroscopy as means of detection.

Keywords: chip-based separation, chip LC, droplets, Raman spectroscopy, SERS

Procedia PDF Downloads 246

Authors: Shlomit Paz, Meir Broza

Abstract:

Cholera is an acute intestinal infection caused by ingestion of food or water contaminated with the bacterium Vibrio cholerae. It has a short incubation period and produces an enterotoxin that causes copious, painless, watery diarrhoea that can quickly lead to severe dehydration and death if treatment is not promptly given. In an epidemic, the source of the contamination is usually the feces of an infected person. The disease can spread rapidly in areas with poor treatment of sewage and drinking water. Cholera remains a global threat and is one of the key indicators of social development. An estimated 3-5 million cases and over 100,000 deaths occur each year around the world. The relevance of climatic events as causative factors for cholera epidemics is well known. However, the examination of the involvement of winds in intra-continental disease distribution is new. The study explore the hypothesis that the spreading of cholera epidemics may be related to the dominant wind direction over land by presenting the influence of the wind direction on windborn dissemination by flying insects, which may serve as vectors. Chironomids ("non-biting midges“) exist in the majority of freshwater aquatic habitats, especially in estuarine and organic-rich water bodies typical to Vibrio cholerae. Chironomid adults emerge into the air for mating and dispersion. They are highly mobile, huge in number and found frequently in the air at various elevations. The huge number of chironomid egg masses attached to hard substrate on the water surface, serve as a reservoir for the free-living Vibrio bacteria. Both male and female, while emerging from the water, may carry the cholera bacteria. In experimental simulation, it was demonstrated that the cholera-bearing adult midges are carried by the wind, and transmit the bacteria from one body of water to another. In our previous study, the geographic diffusions of three cholera outbreaks were examined through their linkage with the wind direction: a) the progress of Vibrio cholerae O1 biotype El Tor in Africa during 1970–1971 and b) again in 2005–2006; and c) the rapid spread of Vibrio cholerae O139 over India during 1992–1993. Using data and map of cholera dissemination (WHO database) and mean monthly SLP and geopotential data (NOAA NCEP-NCAR database), analysis of air pressure data at sea level and at several altitudes over Africa, India and Bangladesh show a correspondence between the dominant wind direction and the intra-continental spread of cholera. The results support the hypothesis that aeroplankton (the tiny life forms that float in the air and that may be caught and carried upward by the wind, landing far from their origin) carry the cholera bacteria from one body of water to an adjacent one. In addition to these findings, the current follow-up study will present new results regarding the possible involvement of winds in the spreading of cholera in recent outbreaks (2010-2013). The findings may improve the understanding of how climatic factors are involved in the rapid distribution of new strains throughout a vast continental area. Awareness of the aerial transfer of Vibrio cholerae may assist health authorities by improving the prediction of the disease’s geographic dissemination.

Keywords: cholera, Vibrio cholerae, wind direction, Vibrio cholerae dissemination

Procedia PDF Downloads 367

Authors: Vladimir A. Basiuk, Laura J. Flores-Sanchez, Victor Meza-Laguna, Jose O. Flores-Flores, Lauro Bucio-Galindo, Elena V. Basiuk

Abstract:

Noncovalent nanohybrid materials combining carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of increasing research effort, with a particular emphasis on the design of new heterogeneous catalysts, efficient organic photovoltaic cells, lithium batteries, gas sensors, field effect transistors, among other possible applications. The possibility of using unsubstituted Pcs for CNT functionalization is very attractive due to their very moderate cost and easy commercial availability. However, unfortunately, the deposition of unsubstituted Pcs onto nanotube sidewalls through the traditional liquid-phase protocols turns to be very problematic due to extremely poor solubility of Pcs. On the other hand, unsubstituted free-base H₂Pc phthalocyanine ligand, as well as many of its transition metal complexes, exhibit very high thermal stability and considerable volatility under reduced pressure, which opens the possibility for their physical vapor deposition onto solid surfaces, including nanotube sidewalls. In the present work, we show the possibility of simple, fast and efficient noncovalent functionalization of single-walled carbon nanotubes (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me= Co, Ni, Cu, and Zn. The functionalization can be performed in a temperature range of 400-500 °C under moderate vacuum and requires about 2-3 h only. The functionalized materials obtained were characterized by means of Fourier-transform infrared (FTIR), Raman, UV-visible and energy-dispersive X-ray spectroscopy (EDS), scanning and transmission electron microscopy (SEM and TEM, respectively) and thermogravimetric analysis (TGA). TGA suggested that Me(II)Pc weight content is 30%, 17% and 35% for NiPc, CuPc, and ZnPc, respectively (CoPc exhibited anomalous thermal decomposition behavior). The above values are consistent with those estimated from EDS spectra, namely, of 24-39%, 27-36% and 27-44% for CoPc, CuPc, and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Me(II)Pc hybrids, as compared to that of pristine nanotubes, implies very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) distribution patterns, calculated with density functional theory by using Perdew-Burke-Ernzerhof general gradient approximation correlation functional in combination with the Grimme’s empirical dispersion correction (PBE-D) and the double numerical basis set (DNP), also suggested that the interactions between Me(II) phthalocyanines and nanotube sidewalls are very strong. The authors thank the National Autonomous University of Mexico (grant DGAPA-IN200516) and the National Council of Science and Technology of Mexico (CONACYT, grant 250655) for financial support. The authors are also grateful to Dr. Natalia Alzate-Carvajal (CCADET of UNAM), Eréndira Martínez (IF of UNAM) and Iván Puente-Lee (Faculty of Chemistry of UNAM) for technical assistance with FTIR, TGA measurements, and TEM imaging, respectively.

Keywords: carbon nanotubes, functionalization, gas-phase, metal(II) phthalocyanines

Procedia PDF Downloads 132

Authors: B. Voucko, M. Benkovic, N. Cukelj, S. Drakula, D. Novotni, S. Balbino, D. Curic

Abstract:

Oxidative stress is considered as one of the causes leading to metabolic disorders in humans. Therefore, the ability of antioxidants to inhibit free radical production is their primary role in the human organism. Antioxidants originating from cereals, especially flavonoids and polyphenols, are mostly bound and indigestible. Micronization damages the cell wall which consecutively results in bioactive material to be more accessible in vivo. In order to ensure complete fragmentation, micronization is often combined with high temperatures (e.g., for bran 200°C) which can lead to degradation of bioactive compounds. The innovative non-thermal technology of cryo-milling is an ultra-fine micronization method that uses liquid nitrogen (LN2) at a temperature of 195°C to freeze and cool the sample during milling. Freezing at such low temperatures causes the material to become brittle which ensures the generation of fine particles while preserving the bioactive content of the material. The aim of this research was to determine if production of ultra-fine material with cryo-milling will result in the augmentation of available bioactive compounds of buckwheat and pumpkin seed cake. For that reason, buckwheat and pumpkin seed cake were ground in a ball mill (CryoMill, Retch, Germany) with and without the use of LN2 for 8 minutes, in a 50 mL stainless steel jar containing one grinding ball (Ø 25 mm) at an oscillation frequency of 30 Hz. The cryo-milled samples were cooled with LN2 for 2 minutes prior to milling, followed by the first cycle of milling (4 minutes), intermediary cooling (2 minutes), and finally the second cycle of milling (further 4 minutes). A continuous process of milling was applied to the samples ground without freezing with LN2. Particle size distribution was determined using the Scirocco 2000 dry dispersion unit (Malvern Instruments, UK). Antioxidant activity was determined by 2,2-Diphenyl-1-picrylhydrazyl (DPPH) test and ferric reducing antioxidant power (FRAP) assay, while the total phenol content was determined using the Folin Ciocalteu method, using the ultraviolet-visible spectrophotometer (Specord 50 Plus, Germany). The content of the free phenolic acids, rutin in buckwheat, tyrosol in pumpkin seed cake, was determined with an HPLC-PDA method (Agilent 1200 series, Germany). Cryo-milling resulted in 11 times smaller size of buckwheat particles, and 3 times smaller size of pumpkin seed particles than milling without the use of LN2, but also, a lower uniformity of the particle size distribution. Lack of freezing during milling of pumpkin seed cake caused a formation of agglomerates due to its high-fat content (21 %). Cryo-milling caused augmentation of buckwheat flour antioxidant activity measured by DPPH test (23,9%) and an increase in available rutin content (14,5%). Also, it resulted in an augmentation of the total phenol content (36,9%) and available tyrosol content (12,5%) of pumpkin seed cake. Antioxidant activity measured with the FRAP test, as well as the content of phenolic acids remained unchanged independent of the milling process. The results of this study showed the potential of cryo-milling for complete raw material utilization in the food industry, as well as a tool for extraction of aimed bioactive components.

Keywords: bioactive, ball-mill, buckwheat, cryo-milling, pumpkin seed cake

Procedia PDF Downloads 133

Authors: Miguel A. Figueroa, José A. Lara-Ramos, Miguel A. Mueses

Abstract:

Pharmaceutical residues are a section of emerging contaminants of anthropogenic origin that are present in a myriad of waters with which human beings interact daily and are starting to affect the ecosystem directly. Conventional waste-water treatment systems are not capable of degrading these pharmaceutical effluents because their designs cannot handle the intermediate products and biological effects occurring during its treatment. That is why it is necessary to hybridize conventional waste-water systems with non-conventional processes. In the specific case of an ozonation process, its efficiency highly depends on a perfect dispersion of ozone, long times of interaction of the gas-liquid phases and the size of the ozone bubbles formed through-out the reaction system. In order to increase the efficiency of these parameters, the use of a modified flotation cell has been proposed recently as a reactive system, which is used at an industrial level to facilitate the suspension of particles and spreading gas bubbles through the reactor volume at a high rate. The objective of the present work is the development of a mathematical model that can closely predict the kinetic rates of reactions taking place in the flotation cell at an experimental scale by means of identifying proper reaction mechanisms that take into account the modified chemical and hydrodynamic factors in the FeO-catalyzed Ozonation of Diclofenac aqueous solutions in a flotation cell. The methodology is comprised of three steps: an experimental phase where a modified flotation cell reactor is used to analyze the effects of ozone concentration and loading catalyst over the degradation of Diclofenac aqueous solutions. The performance is evaluated through an index of utilized ozone, which relates the amount of ozone supplied to the system per milligram of degraded pollutant. Next, a theoretical phase where the reaction mechanisms taking place during the experiments must be identified and proposed that details the multiple direct and indirect reactions the system goes through. Finally, a kinetic model is obtained that can mathematically represent the reaction mechanisms with adjustable parameters that can be fitted to the experimental results and give the model a proper physical meaning. The expected results are a robust reaction rate law that can simulate the improved results of Diclofenac mineralization on water using the modified flotation cell reactor. By means of this methodology, the following results were obtained: A robust reaction pathways mechanism showcasing the intermediates, free-radicals and products of the reaction, Optimal values of reaction rate constants that simulated Hatta numbers lower than 3 for the system modeled, degradation percentages of 100%, TOC (Total organic carbon) removal percentage of 69.9 only requiring an optimal value of FeO catalyst of 0.3 g/L. These results showed that a flotation cell could be used as a reactor in ozonation, catalytic ozonation and photocatalytic ozonation processes, since it produces high reaction rate constants and reduces mass transfer limitations (Ha > 3) by producing microbubbles and maintaining a good catalyst distribution.

Keywords: advanced oxidation technologies, iron oxide, emergent contaminants, AOTS intensification

Procedia PDF Downloads 113

Authors: Anita Conti, Riccardo Ossanna, Lindsey A. Quintero, Giamaica Conti, Andrea Sbarbati

Abstract:

Ischemia/reperfusion (IR) injury induces muscle fiber atrophy and skeletal muscle fiber death with subsequently functionality loss. The heterogeneous pool of cells, especially mesenchymal stem cells, contained in the stromal vascular fraction (SVF) of adipose tissue could promote muscle fiber regeneration. To prevent SVF dispersion, it has been proposed the use of injectable biopolymers that work as cells carrier. A significant element of the extracellular matrix is hyaluronic acid (HA), which has been widely used in regenerative medicine as a cell scaffold given its biocompatibility, degradability, and the possibility of chemical functionalization. Connective tissue micro-fragments enriched with SVF obtained from mechanical disaggregation of adipose tissue were evaluated for IR muscle injury regeneration using low molecular weight HA as a scaffold. IR induction. Hindlimb ischemia was induced in 9 athymic nude mice through the clamping of the right quadriceps using a plastic band. Reperfusion was induced by cutting the plastic band after 3 hours of ischemic period. Contralateral (left) muscular tissue was used as healthy control. Treatment. Twenty-four hours after the IR induction, animals (n=3) were intramuscularly injected with 100 µl of SVF mixed with HA (SVF-HA). Animals treated with 100 µl of HA (n=3) and 100 µl saline solution (n=3) were used as control. Treatment monitoring. All animals were in vivo monitored by magnetic resonance imaging (MRI) at 5, 7, 14 and 18 days post-injury (dpi). High-resolution morphological T2 weighed, quantitative T2 map and Dynamic Contrast-Enhanced (DCE) images were acquired in order to assess the regenerative potential of SVF-HA treatment. Ex vivo evaluation. After 18 days from IR induction, animals were sacrificed, and the muscles were harvested for histological examination. At 5 dpi T2 high-resolution MR images clearly reveal the presence of an extensive edematous area due to IR damage for all groups identifiable as an increase of signal intensity (SI) of muscular and surrounding tissue. At 7 dpi, animals of the SVF-HA group showed a reduction of SI, and the T2relaxation time of muscle tissue of the HA-SVF group was 29±0.5ms, comparable with the T2relaxation time of contralateral muscular tissue (30±0.7ms). These suggest a reduction of edematous overflow and swelling. The T2relaxation time at 7dpi of HA and saline groups were 84±2ms and 90±5ms, respectively, which remained elevated during the rest of the study. The evaluation of vascular regeneration showed similar results. Indeed, DCE-MRI analysis revealed a complete recovery of muscular tissue perfusion after 14 dpi for the SVF-HA group, while for the saline and HA group, controls remained in a damaged state. Finally, the histological examination of SVF-HA treated animals exhibited well-defined and organized fibers morphology with a lateralized nucleus, similar to contralateral healthy muscular tissue. On the contrary, HA and saline-treated animals presented inflammatory infiltrates, with HA slightly improving the diameter of the fibers and less degenerated tissue. Our findings show that connective tissue micro-fragments enriched with SVF induce higher muscle homeostasis and perfusion restoration in contrast to control groups.

Keywords: ischemia/reperfusion injury, regenerative medicine, resonance imaging, stromal vascular fraction

Procedia PDF Downloads 127

Authors: Lacramioara Ochiuz, Aurelia Vasile, Iulian Stoleriu, Cristina Ghiciuc, Maria Ignat

Abstract:

Topical administration of chemotherapeutic agents (eg. carmustine, bexarotene, mechlorethamine etc.) in local treatment of cutaneous T-cell lymphoma (CTCL) is accompanied by multiple side effects, such as contact hypersensitivity, pruritus, skin atrophy or even secondary malignancies. A known method of reducing the side effects of anticancer agent is the development of modified drug release systems using drug incapsulation in biocompatible nanoporous inorganic matrices, such as mesoporous MCM-41 silica. Mesoporous MCM-41 silica is characterized by large specific surface, high pore volume, uniform porosity, and stable dispersion in aqueous medium, excellent biocompatibility, in vivo biodegradability and capacity to be functionalized with different organic groups. Therefore, MCM-41 is an attractive candidate for a wide range of biomedical applications, such as controlled drug release, bone regeneration, protein immobilization, enzymes, etc. The main advantage of this material lies in its ability to host a large amount of the active substance in uniform pore system with adjustable size in a mesoscopic range. Silanol groups allow surface controlled functionalization leading to control of drug loading and release. This study shows (I) the amino-grafting optimization of mesoporous MCM-41 silica matrix by means of co-condensation during synthesis and post-synthesis using APTES (3-aminopropyltriethoxysilane); (ii) loading the therapeutic agent (carmustine) obtaining a modified drug release systems; (iii) determining the profile of in vitro carmustine release from these systems; (iv) assessment of carmustine release kinetics by fitting on four mathematical models. Obtained powders have been described in terms of structure, texture, morphology thermogravimetric analysis. The concentration of the therapeutic agent in the dissolution medium has been determined by HPLC method. In vitro dissolution tests have been done using cell Enhancer in a 12 hours interval. Analysis of carmustine release kinetics from mesoporous systems was made by fitting to zero-order model, first-order model Higuchi model and Korsmeyer-Peppas model, respectively. Results showed that both types of highly ordered mesoporous silica (amino grafted by co-condensation process or post-synthesis) are thermally stable in aqueous medium. In what regards the degree of loading and efficiency of loading with the therapeutic agent, there has been noticed an increase of around 10% in case of co-condensation method application. This result shows that direct co-condensation leads to even distribution of amino groups on the pore walls while in case of post-synthesis grafting many amino groups are concentrated near the pore opening and/or on external surface. In vitro dissolution tests showed an extended carmustine release (more than 86% m/m) both from systems based on silica functionalized directly by co-condensation and after synthesis. Assessment of carmustine release kinetics revealed a release through diffusion from all studied systems as a result of fitting to Higuchi model. The results of this study proved that amino-functionalized mesoporous silica may be used as a matrix for optimizing the anti-cancer topical therapy by loading carmustine and developing prolonged-release systems.

Keywords: carmustine, silica, controlled, release

Procedia PDF Downloads 264

Authors: Oksana G. Cherednichenko, Anastasia L. Pilyugina, Sergey N.Lukashenko, Elena G. Gubitskaya

Abstract:

The estimation of accumulated radiation doses in people professionally exposed to ionizing radiation was performed using methods of biological (chromosomal aberrations frequency in lymphocytes) and physical (radionuclides analysis in urine, whole-body radiation meter, individual thermoluminescent dosimeters) dosimetry. A group of 84 "A" category employees after their work in the territory of former Semipalatinsk test site (Kazakhstan) was investigated. The dose rate in some funnels exceeds 40 μSv/h. After radionuclides determination in urine using radiochemical and WBC methods, it was shown that the total effective dose of personnel internal exposure did not exceed 0.2 mSv/year, while an acceptable dose limit for staff is 20 mSv/year. The range of external radiation doses measured with individual thermo-luminescent dosimeters was 0.3-1.406 µSv. The cytogenetic examination showed that chromosomal aberrations frequency in staff was 4.27±0.22%, which is significantly higher than at the people from non-polluting settlement Tausugur (0.87±0.1%) (р ≤ 0.01) and citizens of Almaty (1.6±0.12%) (р≤ 0.01). Chromosomal type aberrations accounted for 2.32±0.16%, 0.27±0.06% of which were dicentrics and centric rings. The cytogenetic analysis of different types group radiosensitivity among «professionals» (age, sex, ethnic group, epidemiological data) revealed no significant differences between the compared values. Using various techniques by frequency of dicentrics and centric rings, the average cumulative radiation dose for group was calculated, and that was 0.084-0.143 Gy. To perform comparative individual dosimetry using physical and biological methods of dose assessment, calibration curves (including own ones) and regression equations based on general frequency of chromosomal aberrations obtained after irradiation of blood samples by gamma-radiation with the dose rate of 0,1 Gy/min were used. Herewith, on the assumption of individual variation of chromosomal aberrations frequency (1–10%), the accumulated dose of radiation varied 0-0.3 Gy. The main problem in the interpretation of individual dosimetry results is reduced to different reaction of the objects to irradiation - radiosensitivity, which dictates the need of quantitative definition of this individual reaction and its consideration in the calculation of the received radiation dose. The entire examined contingent was assigned to a group based on the received dose and detected cytogenetic aberrations. Radiosensitive individuals, at the lowest received dose in a year, showed the highest frequency of chromosomal aberrations (5.72%). In opposite, radioresistant individuals showed the lowest frequency of chromosomal aberrations (2.8%). The cohort correlation according to the criterion of radio-sensitivity in our research was distributed as follows: radio-sensitive (26.2%) — medium radio-sensitivity (57.1%), radioresistant (16.7%). Herewith, the dispersion for radioresistant individuals is 2.3; for the group with medium radio-sensitivity — 3.3; and for radio-sensitive group — 9. These data indicate the highest variation of characteristic (reactions to radiation effect) in the group of radio-sensitive individuals. People with medium radio-sensitivity show significant long-term correlation (0.66; n=48, β ≥ 0.999) between the values of doses defined according to the results of cytogenetic analysis and dose of external radiation obtained with the help of thermoluminescent dosimeters. Mathematical models based on the type of violation of the radiation dose according to the professionals radiosensitivity level were offered.

Keywords: biodosimetry, chromosomal aberrations, ionizing radiation, radiosensitivity

Procedia PDF Downloads 185

Authors: Sundaram Arulmozhiraja, Kanade Shimizu, Yuta Yamamoto, Satoshi Ichikawa, Maenaka Katsumi, Hiroaki Tokiwa

Abstract:

Drug discovery is shifting from small molecule based drugs targeting local active site to middle molecules (MM) targeting large, flat, and groove-shaped binding sites, for example, protein-protein interface because at least half of all targets assumed to be involved in human disease have been classified as “difficult to drug” with traditional small molecules. Hence, MMs such as peptides, natural products, glycans, nucleic acids with various high potent bioactivities become important targets for drug discovery programs in the recent years as they could be used for ‘undruggable” intracellular targets. Cell membrane permeability is one of the key properties of pharmacodynamically active MM drug compounds and so evaluating this property for the potential MMs is crucial. Computational prediction for cell membrane permeability of molecules is very challenging; however, recent advancement in the molecular dynamics simulations help to solve this issue partially. It is expected that MMs with high membrane permeability will enable drug discovery research to expand its borders towards intracellular targets. Further to understand the chemistry behind the permeability of MMs, it is necessary to investigate their conformational changes during the permeation through membrane and for that their interactions with the membrane field should be studied reliably because these interactions involve various non-bonding interactions such as hydrogen bonding, -stacking, charge-transfer, polarization dispersion, and non-classical weak hydrogen bonding. Therefore, parameters-based classical mechanics calculations are hardly sufficient to investigate these interactions rather, quantum mechanical (QM) calculations are essential. Fragment molecular orbital (FMO) method could be used for such purpose as it performs ab initio QM calculations by dividing the system into fragments. The present work is aimed to study the cell permeability of middle molecules using molecular dynamics simulations and FMO-QM calculations. For this purpose, a natural compound syringolin and its analogues were considered in this study. Molecular simulations were performed using NAMD and Gromacs programs with CHARMM force field. FMO calculations were performed using the PAICS program at the correlated Resolution-of-Identity second-order Moller Plesset (RI-MP2) level with the cc-pVDZ basis set. The simulations clearly show that while syringolin could not permeate the membrane, its selected analogues go through the medium in nano second scale. These correlates well with the existing experimental evidences that these syringolin analogues are membrane-permeable compounds. Further analyses indicate that intramolecular -stacking interactions in the syringolin analogues influenced their permeability positively. These intramolecular interactions reduce the polarity of these analogues so that they could permeate the lipophilic cell membrane. Conclusively, the cell membrane permeability of various middle molecules with potent bioactivities is efficiently studied using molecular dynamics simulations. Insight of this behavior is thoroughly investigated using FMO-QM calculations. Results obtained in the present study indicate that non-bonding intramolecular interactions such as hydrogen-bonding and -stacking along with the conformational flexibility of MMs are essential for amicable membrane permeation. These results are interesting and are nice example for this theoretical calculation approach that could be used to study the permeability of other middle molecules. This work was supported by Japan Agency for Medical Research and Development (AMED) under Grant Number 18ae0101047.

Keywords: fragment molecular orbital theory, membrane permeability, middle molecules, molecular dynamics simulation

Procedia PDF Downloads 189

Authors: Francisco J. Ortega, Claudia Roman, Moisés García-Morales, Francisco J. Navarro

Abstract:

Asphaltic bitumen has been largely used in both industrial and civil engineering, mostly in pavement construction and roofing membrane manufacture. However, bitumen as such is greatly susceptible to temperature variations, and dramatically changes its in-service behavior from a viscoelastic liquid, at medium-high temperatures, to a brittle solid at low temperatures. Bitumen modification prevents these problems and imparts improved performance. Isocyanates like polymeric MDI (mixture of 4,4′-diphenylmethane di-isocyanate, 2,4’ and 2,2’ isomers, and higher homologues) have shown to remarkably enhance bitumen properties at the highest in-service temperatures expected. This comes from the reaction between the –NCO pendant groups of the oligomer and the most polar groups of asphaltenes and resins in bitumen. In addition, oxygen diffusion and/or UV radiation may provoke bitumen hardening and ageing. With the purpose of minimizing these effects, nano-layered-silicates (nanoclays) are increasingly being added to bitumen formulations. Montmorillonites, a type of naturally occurring mineral, may produce a nanometer scale dispersion which improves bitumen thermal, mechanical and barrier properties. In order to increase their lipophilicity, these nanoclays are normally treated so that organic cations substitute the inorganic cations located in their intergallery spacing. In the present work, the combined effect of polymeric MDI and the commercial montmorillonite Cloisite® 20A was evaluated. A selected bitumen with penetration within the range 160/220 was modified with 10 wt.% Cloisite® 20A and 2 wt.% polymeric MDI, and the resulting ternary composites were characterized by linear rheology, X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The rheological tests evidenced a notable solid-like behavior at the highest temperatures studied when bitumen was just loaded with 10 wt.% Cloisite® 20A and high-shear blended for 20 minutes. However, if polymeric MDI was involved, the sequence of addition exerted a decisive control on the linear rheology of the final ternary composites. Hence, in bitumen/Cloisite® 20A/polymeric MDI formulations, the previous solid-like behavior disappeared. By contrast, an inversion in the order of addition (bitumen/polymeric MDI/ Cloisite® 20A) enhanced further the solid-like behavior imparted by the nanoclay. In order to gain a better understanding of the factors that govern the linear rheology of these ternary composites, a morphological and microstructural characterization based on XRD and AFM was conducted. XRD demonstrated the existence of clay stacks intercalated by bitumen molecules to some degree. However, the XRD technique cannot provide detailed information on the extent of nanoclay delamination, unless the entire fraction has effectively been fully delaminated (situation in which no peak is observed). Furthermore, XRD was unable to provide precise knowledge neither about the spatial distribution of the intercalated/exfoliated platelets nor about the presence of other structures at larger length scales. In contrast, AFM proved its power at providing conclusive information on the morphology of the composites at the nanometer scale and at revealing the structural modification that yielded the rheological properties observed. It was concluded that high-shear blending brought about a nanoclay-reinforced network. As for the bitumen/Cloisite® 20A/polymeric MDI formulations, the solid-like behavior was destroyed as a result of the agglomeration of the nanoclay platelets promoted by chemical reactions.

Keywords: Atomic Force Microscopy, bitumen, composite, isocyanate, montmorillonite.

Procedia PDF Downloads 261

Authors: Alberto Fina, Samuele Colonna, Maria del Mar Bernal, Orietta Monticelli, Mauro Tortello, Renato Gonnelli, Julio Gomez, Chiara Novara, Guido Saracco

Abstract:

Thermally conductive polymer nanocomposites are of high interest for several applications including low-temperature heat recovery, heat exchangers in a corrosive environment and heat management in electronics and flexible electronics. In this paper, the preparation of thermally conductive nanocomposites exploiting graphene-related materials is addressed, along with their thermal characterization. In particular, correlations between 1- chemical and physical features of the nanoflakes and 2- processing conditions with the heat conduction properties of nanocomposites is studied. Polymers are heat insulators; therefore, the inclusion of conductive particles is the typical solution to obtain a sufficient thermal conductivity. In addition to traditional microparticles such as graphite and ceramics, several nanoparticles have been proposed, including carbon nanotubes and graphene, for the use in polymer nanocomposites. Indeed, thermal conductivities for both carbon nanotubes and graphenes were reported in the wide range of about 1500 to 6000 W/mK, despite such property may decrease dramatically as a function of the size, number of layers, the density of topological defects, re-hybridization defects as well as on the presence of impurities. Different synthetic techniques have been developed, including mechanical cleavage of graphite, epitaxial growth on SiC, chemical vapor deposition, and liquid phase exfoliation. However, the industrial scale-up of graphene, defined as an individual, single-atom-thick sheet of hexagonally arranged sp2-bonded carbons still remains very challenging. For large scale bulk applications in polymer nanocomposites, some graphene-related materials such as multilayer graphenes (MLG), reduced graphene oxide (rGO) or graphite nanoplatelets (GNP) are currently the most interesting graphene-based materials. In this paper, different types of graphene-related materials were characterized for their chemical/physical as well as for thermal properties of individual flakes. Two selected rGOs were annealed at 1700°C in vacuum for 1 h to reduce defectiveness of the carbon structure. Thermal conductivity increase of individual GNP with annealing was assessed via scanning thermal microscopy. Graphene nano papers were prepared from both conventional RGO and annealed RGO flakes. Characterization of the nanopapers evidenced a five-fold increase in the thermal diffusivity on the nano paper plane for annealed nanoflakes, compared to pristine ones, demonstrating the importance of structural defectiveness reduction to maximize the heat dissipation performance. Both pristine and annealed RGO were used to prepare polymer nanocomposites, by melt reactive extrusion. Thermal conductivity showed two- to three-fold increase in the thermal conductivity of the nanocomposite was observed for high temperature treated RGO compared to untreated RGO, evidencing the importance of using low defectivity nanoflakes. Furthermore, the study of different processing paremeters (time, temperature, shear rate) during the preparation of poly (butylene terephthalate) nanocomposites evidenced a clear correlation with the dispersion and fragmentation of the GNP nanoflakes; which in turn affected the thermal conductivity performance. Thermal conductivity of about 1.7 W/mK, i.e. one order of magnitude higher than for pristine polymer, was obtained with 10%wt of annealed GNPs, which is in line with state of the art nanocomposites prepared by more complex and less upscalable in situ polymerization processes.

Keywords: graphene, graphene-related materials, scanning thermal microscopy, thermally conductive polymer nanocomposites

Procedia PDF Downloads 268

Authors: Nadja Ylvestedt

Abstract:

Uppsala University Library is a geographically dispersed research library consisting of nine subject libraries located in different campus areas throughout the city of Uppsala. Despite the geographical dispersion, it is the library's ambition to be perceived as a cohesive library with consistently high service and quality. A key factor to being one cohesive library is the library's online services, especially the virtual reference service. E-mail, chat and phone are answered by a team of specially trained staff under the supervision of a team leader. When covid-19 hit, well-established routines and processes to provide an infrastructure for students and researchers at the university changed radically. The strong connection between services provided at the library locations as well as at the VRS has been one of the key components of the library’s success in providing patrons with the help they need. With radically minimized availability at the physical locations, the infrastructure was at risk of collapsing. Objectives:- The objective of this project has been to evaluate the consequences of the sudden change in the organization of the library. The focus of this evaluation is the library’s VRS as an important space for learning, interaction and communication between the library and the community when other traditional spaces were not available. The goal of this evaluation is to capture the lessons learned from providing infrastructure for learning and research in times of crisis both on a practical, user-centered level but also to stress the importance of leadership in ever-changing environments that supports and creates agile, flexible services and teams instead of rigid processes adhering to obsolete goals. Results:- Reduced availability at the physical library locations was one of the strategies to prevent the spread of the covid-19 virus. The library staff was encouraged to work from home, so student workers staffed the library’s physical locations during that time, leaving the VRS to be the only place where patrons could get expert help. The VRS had an increase of 65% of questions asked between spring term 2019 and spring term 2020. The VRS team had to navigate often complicated and fast-changing new routines depending on national guidelines. The VRS team has a strong emphasis on agility in their approach to the challenges and opportunities, with methods to evaluate decisions regularly with user experience in mind. Fast decision-making, collecting feedback, an open-minded approach to reviewing rules and processes with both a short-term and a long-term focus and providing a healthy work environment have been key factors in managing this crisis and learn from it. This was resting on a strong sense of ownership regarding the VRS, well-working communication tools and agile and active communication between team members, as well as between the team and the rest of the organization who served as a second-line support system to aid the VRS team. Moving forward, the VRS has become an important space for communication, interaction and provider of infrastructure, implementing new routines and more extensive availability due to the lessons learned during crisis. The evaluation shows that the virtual environment has become an important addition to the physical spaces, existing in its own right but always in connection with and in relationship with the library structure as a whole. Thereby showing that the basis of human interaction stays the same while its form morphs and adapts to changes, thus leaving the virtual environment as a space of communication and infrastructure with unique opportunities for outreach and the potential to become a staple in patron’s education and learning.

Keywords: virtual reference service, leadership, digital infrastructure, research library

Procedia PDF Downloads 171

Authors: Danielle Slomberg, Jerome Labille, Riccardo Catalano, Jean-Claude Hubaud, Alexandra Lopes, Alice Tagliati, Teresa Fernandes

Abstract:

In the assessment and management of cosmetics and personal care products, sunscreens are of emerging concern regarding both human and environmental health. Organic UV blockers in many sunscreens have been evidenced to undergo rapid photodegradation, induce dermal allergic reactions due to skin penetration, and to cause adverse effects on marine systems. While mineral UV-blockers may offer a safer alternative, their fate and impact and resulting regulation are still under consideration, largely related to the potential influence of nanotechnology-based products on both consumers and the environment. Nanometric titanium dioxide (TiO₂) UV-blockers have many advantages in terms of sun protection and asthetics (i.e., transparency). These UV-blockers typically consist of rutile nanoparticles coated with a primary mineral layer (silica or alumina) aimed at blocking the nanomaterial photoactivity and can include a secondary organic coating (e.g., stearic acid, methicone) aimed at favouring dispersion of the nanomaterial in the sunscreen formulation. The nanomaterials contained in the sunscreen can leave the skin either through a bathing of everyday usage, with subsequent release into rivers, lakes, seashores, and/or sewage treatment plants. The nanomaterial behaviour, fate and impact in these different systems is largely determined by its surface properties, (e.g. the nanomaterial coating type) and lifetime. The present work aims to develop the eco-design of sunscreens through the minimisation of risks associated with nanomaterials incorporated into the formulation. All stages of the sunscreen’s life cycle must be considered in this aspect, from its manufacture to its end-of-life, through its use by the consumer to its impact on the exposed environment. Reducing the potential release and/or toxicity of the nanomaterial from the sunscreen is a decisive criterion for its eco-design. TiO₂ UV-blockers of varied size and surface coating (e.g., stearic acid and silica) have been selected for this study. Hydrophobic TiO₂ UV-blockers (i.e., stearic acid-coated) were incorporated into a typical water-in-oil (w/o) formulation while hydrophilic, silica-coated TiO₂ UV-blockers were dispersed into an oil-in-water (o/w) formulation. The resulting sunscreens were characterised in terms of nanomaterial localisation, sun protection factor, and photo-passivation. The risk to the direct aquatic environment was assessed by evaluating the release of nanomaterials from the sunscreen through a simulated laboratory aging procedure. The size distribution, surface charge, and degradation state of the nano-composite by-products, as well as their nanomaterial concentration and colloidal behaviour were determined in a variety of aqueous environments (e.g., seawater and freshwater). Release of the hydrophobic nanocomposites into the aqueous environment was driven by oil droplet formation while hydrophilic nano-composites were readily dispersed. Ecotoxicity of the sunscreen by-products (from both w/o and o/w formulations) and their risk to marine organisms were assessed using coral symbiotes and tropical corals, evaluating both lethal and sublethal toxicities. The data dissemination and provided risk knowledge from the present work will help guide regulation related to nanomaterials in sunscreen, provide better information for consumers, and allow for easier decision-making for manufacturers.

Keywords: alteration, environmental fate, sunscreens, titanium dioxide nanoparticles

Procedia PDF Downloads 263

Authors: Keivan Davami, Michael Munther, Lloyd Hackel

Abstract:

The control of properties and material behavior by implementing thermal-mechanical processes is based on mechanical deformation and annealing according to a precise schedule that will produce a unique and stable combination of grain structure, dislocation substructure, texture, and dispersion of precipitated phases. The authors recently developed a thermal-mechanical technique to stabilize the microstructure of additively manufactured nickel-based superalloys even after exposure to high temperatures. However, the mechanism(s) that controls this stability is still under investigation. Laser peening (LP), also called laser shock peening (LSP), is a shock based (50 ns duration) post-processing technique used for extending performance levels and improving service life of critical components by developing deep levels of plastic deformation, thereby generating high density of dislocations and inducing compressive residual stresses in the surface and deep subsurface of components. These compressive residual stresses are usually accompanied with an increase in hardness and enhance the material’s resistance to surface-related failures such as creep, fatigue, contact damage, and stress corrosion cracking. While the LP process enhances the life span and durability of the material, the induced compressive residual stresses relax at high temperatures (>0.5Tm, where Tm is the absolute melting temperature), limiting the applicability of the technology. At temperatures above 0.5Tm, the compressive residual stresses relax, and yield strength begins to drop dramatically. The principal reason is the increasing rate of solid-state diffusion, which affects both the dislocations and the microstructural barriers. Dislocation configurations commonly recover by mechanisms such as climbing and recombining rapidly at high temperatures. Furthermore, precipitates coarsen, and grains grow; virtually all of the available microstructural barriers become ineffective.Our results indicate that by using “cyclic” treatments with sequential LP and annealing steps, the compressive stresses survive, and the microstructure is stable after exposure to temperatures exceeding 0.5Tm for a long period of time. When the laser peening process is combined with annealing, dislocations formed as a result of LPand precipitates formed during annealing have a complex interaction that provides further stability at high temperatures. From a scientific point of view, this research lays the groundwork for studying a variety of physical, materials science, and mechanical engineering concepts. This research could lead to metals operating at higher sustained temperatures enabling improved system efficiencies. The strengthening of metals by a variety of means (alloying, work hardening, and other processes) has been of interest for a wide range of applications. However, the mechanistic understanding of the often complex processes of interactionsbetween dislocations with solute atoms and with precipitates during plastic deformation have largely remained scattered in the literature. In this research, the elucidation of the actual mechanisms involved in the novel cyclic LP/annealing processes as a scientific pursuit is investigated through parallel studies of dislocation theory and the implementation of advanced experimental tools. The results of this research help with the validation of a novel laser processing technique for high temperature applications. This will greatly expand the applications of the laser peening technology originally devised only for temperatures lower than half of the melting temperature.

Keywords: laser shock peening, mechanical properties, indentation, high temperature stability

Procedia PDF Downloads 151

Authors: Joanna Szymanska, Paulina Wawulska-Marek, Jaroslaw Mizera

Abstract:

Nowadays, the rapid growth of global energy consumption and uncontrolled depletion of natural resources become a serious problem. Shale rocks are the largest and potential global basins containing hydrocarbons, trapped in closed pores of the shale matrix. Regardless of the shales origin, mining conditions are extremely unfavourable due to high reservoir pressure, great depths, increased clay minerals content and limited permeability (nanoDarcy) of the rocks. Taking into consideration such geomechanical barriers, effective extraction of natural gas from shales with plastic zones demands effective operations. Actually, hydraulic fracturing is the most developed technique based on the injection of pressurized fluid into a wellbore, to initiate fractures propagation. However, a rapid drop of pressure after fluid suction to the ground induces a fracture closure and conductivity reduction. In order to minimize this risk, proppants should be applied. They are solid granules transported with hydraulic fluids to locate inside the rock. Proppants act as a prop for the closing fracture, thus gas migration to a borehole is effective. Quartz sands are commonly applied proppants only at shallow deposits (USA). Whereas, ceramic proppants are designed to meet rigorous downhole conditions to intensify output. Ceramic granules predominate with higher mechanical strength, stability in strong acidic environment, spherical shape and homogeneity as well. Quality of ceramic proppants is conditioned by raw materials selection. Aim of this study was to obtain the proppants from aluminosilicates (the kaolinite subgroup) and mix of minerals with a high alumina content. These loamy minerals contain a tubular and platy morphology that improves mechanical properties and reduces their specific weight. Moreover, they are distinguished by well-developed surface area, high porosity, fine particle size, superb dispersion and nontoxic properties - very crucial for particles consolidation into spherical and crush-resistant granules in mechanical granulation process. The aluminosilicates were mixed with water and natural organic binder to improve liquid-bridges and pores formation between particles. Afterward, the green proppants were subjected to sintering at high temperatures. Evaluation of the minerals utility was based on their particle size distribution (laser diffraction study) and thermal stability (thermogravimetry). Scanning Electron Microscopy was useful for morphology and shape identification combined with specific surface area measurement (BET). Chemical composition was verified by Energy Dispersive Spectroscopy and X-ray Fluorescence. Moreover, bulk density and specific weight were measured. Such comprehensive characterization of loamy materials confirmed their favourable impact on the proppants granulation. The sintered granules were analyzed by SEM to verify the surface topography and phase transitions after sintering. Pores distribution was identified by X-Ray Tomography. This method enabled also the simulation of proppants settlement in a fracture, while measurement of bulk density was essential to predict their amount to fill a well. Roundness coefficient was also evaluated, whereas impact on mining environment was identified by turbidity and solubility in acid - to indicate risk of the material decay in a well. The obtained outcomes confirmed a positive influence of the loamy minerals on ceramic proppants properties with respect to the strict norms. This research is perspective for higher quality proppants production with costs reduction.

Keywords: aluminosilicates, ceramic proppants, mechanical granulation, shale gas

Procedia PDF Downloads 163

Authors: Guilherme Giacomini, Ana Luiza Menegatti Pavan, Allan Felipe Fattori Alves, Marcela de Oliveira, Fernando Antonio Bacchim Neto, José Ricardo de Arruda Miranda, Seizo Yamashita, Diana Rodrigues de Pina

Abstract:

The maxillary sinus (MS), part of the paranasal sinus complex, is one of the most enigmatic structures in modern humans. The literature has suggested that MSs function as olfaction accessories, to heat or humidify inspired air, for thermoregulation, to impart resonance to the voice and others. Thus, the real function of the MS is still uncertain. Furthermore, the MS anatomy is complex and varies from person to person. Many diseases may affect the development process of sinuses. The incidence of rhinosinusitis and other pathoses in the MS is comparatively high, so, volume analysis has clinical value. Providing volume values for MS could be helpful in evaluating the presence of any abnormality and could be used for treatment planning and evaluation of the outcome. The computed tomography (CT) has allowed a more exact assessment of this structure, which enables a quantitative analysis. However, this is not always possible in the clinical routine, and if possible, it involves much effort and/or time. Therefore, it is necessary to have a convenient, robust, and practical tool correlated with the MS volume, allowing clinical applicability. Nowadays, the available methods for MS segmentation are manual or semi-automatic. Additionally, manual methods present inter and intraindividual variability. Thus, the aim of this study was to develop an automatic tool to quantity the MS volume in CT scans of paranasal sinuses. This study was developed with ethical approval from the authors’ institutions and national review panels. The research involved 30 retrospective exams of University Hospital, Botucatu Medical School, São Paulo State University, Brazil. The tool for automatic MS quantification, developed in Matlab®, uses a hybrid method, combining different image processing techniques. For MS detection, the algorithm uses a Support Vector Machine (SVM), by features such as pixel value, spatial distribution, shape and others. The detected pixels are used as seed point for a region growing (RG) segmentation. Then, morphological operators are applied to reduce false-positive pixels, improving the segmentation accuracy. These steps are applied in all slices of CT exam, obtaining the MS volume. To evaluate the accuracy of the developed tool, the automatic method was compared with manual segmentation realized by an experienced radiologist. For comparison, we used Bland-Altman statistics, linear regression, and Jaccard similarity coefficient. From the statistical analyses for the comparison between both methods, the linear regression showed a strong association and low dispersion between variables. The Bland–Altman analyses showed no significant differences between the analyzed methods. The Jaccard similarity coefficient was > 0.90 in all exams. In conclusion, the developed tool to quantify MS volume proved to be robust, fast, and efficient, when compared with manual segmentation. Furthermore, it avoids the intra and inter-observer variations caused by manual and semi-automatic methods. As future work, the tool will be applied in clinical practice. Thus, it may be useful in the diagnosis and treatment determination of MS diseases. Providing volume values for MS could be helpful in evaluating the presence of any abnormality and could be used for treatment planning and evaluation of the outcome. The computed tomography (CT) has allowed a more exact assessment of this structure which enables a quantitative analysis. However, this is not always possible in the clinical routine, and if possible, it involves much effort and/or time. Therefore, it is necessary to have a convenient, robust and practical tool correlated with the MS volume, allowing clinical applicability. Nowadays, the available methods for MS segmentation are manual or semi-automatic. Additionally, manual methods present inter and intraindividual variability. Thus, the aim of this study was to develop an automatic tool to quantity the MS volume in CT scans of paranasal sinuses. This study was developed with ethical approval from the authors’ institutions and national review panels. The research involved 30 retrospective exams of University Hospital, Botucatu Medical School, São Paulo State University, Brazil. The tool for automatic MS quantification, developed in Matlab®, uses a hybrid method, combining different image processing techniques. For MS detection, the algorithm uses a Support Vector Machine (SVM), by features such as pixel value, spatial distribution, shape and others. The detected pixels are used as seed point for a region growing (RG) segmentation. Then, morphological operators are applied to reduce false-positive pixels, improving the segmentation accuracy. These steps are applied in all slices of CT exam, obtaining the MS volume. To evaluate the accuracy of the developed tool, the automatic method was compared with manual segmentation realized by an experienced radiologist. For comparison, we used Bland-Altman statistics, linear regression and Jaccard similarity coefficient. From the statistical analyses for the comparison between both methods, the linear regression showed a strong association and low dispersion between variables. The Bland–Altman analyses showed no significant differences between the analyzed methods. The Jaccard similarity coefficient was > 0.90 in all exams. In conclusion, the developed tool to automatically quantify MS volume proved to be robust, fast and efficient, when compared with manual segmentation. Furthermore, it avoids the intra and inter-observer variations caused by manual and semi-automatic methods. As future work, the tool will be applied in clinical practice. Thus, it may be useful in the diagnosis and treatment determination of MS diseases.

Keywords: maxillary sinus, support vector machine, region growing, volume quantification

Procedia PDF Downloads 504