Correlation between structure and electrochemistry of LiMO2 cathode materials (M = Ni, Co)

Technical diversity and various knowledge is required for the understanding of undoubtedly complex system such as a Lithium-ion battery. The peculiarity is to combine different techniques that allow a complete investigation while the battery is working. Nowadays, research on Li-ion batteries (LIBs) is experiencing an exponential growth in the development of new cathode materials. Accordingly, Li-rich and Ni-rich NMCs, which have similar layered structure of LiMO2 oxides, have been recently proposed. Despite the promising performance on them, still a lot of issues have to be resolved and the materials need a more in depth characterisation for further commercial applications. In this study LiMO2 material, in particular M = Co and Ni, will be presented. We have focused on the synthesis of pure LiCoO2 and LiNiO2 at first, followed by the mixed LiNi0.5Co0.5O2. Different ways of synthesis were investigated for LCO but the sol-gel-water method showed the best performances. An accurate and systematic structural characterization followed by the appropriate electrochemical tests were done. Moreover, the in situ techniques (in-situ XRD and in situ OEMS) allowed a deep investigation in the structural change and gas evolution upon the electrochemically driven processes.

Materiali ceramici a struttura Aurivillius per la produzione di solar fuels

Solar fuels from CO2 is a topic of current large scientific and industrial interest. In particular, photo-electrochemical cells (PECs) represent today one of the most promising technology for storing sun energy as chemical bonds exploiting carbon dioxide as starting reagent. In this thesis, the possibility of using Aurivillius-type compounds for the production of solar fuels was deeply investigated. Aurivillius-type perovskites, with general formula Bi(n+1)Fe(n-3)Ti3O(3n+3), were synthesized and fully characterized to study the influence of the number of perovskite layers as well as of the synthesis parameters onto their final properties. In particular, 8 different systems were considered increasing the amount of iron and, as a consequence, the number of perovskite layers. These compounds were synthesized through a standard solid-state reaction method as well as via a sol-gel technique and characterized by XRD, SEM and BET analyses. The band gap value and the photocatalytic activity towards Rhodamine B decomposition were assessed as well. For each system, a screen-printing ink was formulated to be deposited as photo-electrodes onto transparent conducting supports. The photo-electrodes were morphologically characterized by XRD and SEM analysis, and their electrochemical properties (cyclic and linear voltammetry, EIS, Mott-Schottky analysis) were determined. Finally, the most promising materials were tested as photo-cathode inside PEC cell under different illumination conditions, to quantify their ability to convert CO2. The obtained results show the potentiality of Aurivillius-type compounds as innovative material for carbon dioxide photo-electrochemical reduction.

Nanostructured smart materials as functional components of medical devices

The field of medical devices has experienced, more than others, technological advances, developments and innovations, thanks to the rapidly expanding scientific knowledge and collaboration between different disciplines such as biology, engineering and materials science. The design of functional components can be achieved by exploiting composite materials based on nanostructured smart materials, that due to the inherent characteristics of single constituents develop unique properties that make them suitable for different applications preserving excellent mechanical proprieties. For instance, recent developments have focused on the fabrication of piezoelectric devices with multiple biomedical functions, as actuation and sensing functions in one component for monitoring pressure signals. The present Ph.D. Thesis aims at investigating nanostructured smart materials embedded into a polymeric matrix to obtain a composite material that can be used as a functional component for medical devices. (i) Nanostructured piezoelectric material with self-sensing capability was successfully manufactured by using ceramic (i.e. lead zirconate titanate (PZT)) and (ii) polymeric (i.e. poly(vinylidene fluoride-trifluoro ethylene (PVDF-TRFE)) piezoelectric materials. PZT nanofibers were obtained by sol-gel electrospinning starting from synthetized PZT precursor solution. Synthesis, sol-gel electrospinning process, and thermal treatment were accurately controlled to obtain PZT nanofibers dimensionally stable with densely packed grains in the perovskite phase. To guarantee the impact resistance of the laminate, the morphology and size of the hosting filler were accurately designed by increasing the surface area to volume ratio. Moreover, to solve the issue relative to the mechanical discrepancy between rigid electronic materials/soft human tissues/different material of the device (iii) a nanostructured flexible composite material based on a network of Poly-L-lactic acid (PLLA) made of curled nanofibers that present a tuneable mechanical response as a function of the applied stress was successful fabricated.

Sviluppo ed ingegnerizzazione di nuovi sistemi ibridi a base di nanoparticelle inorganiche e bio-tensioattivi

In questo lavoro di tesi è stata investigata la sintesi di compositi a base di nano particelle di biossido di titanio rivestite da un bio-tensioattivo naturale. Il noto fotocatalizzatore (Nano-TiO2) è stato accoppiato ad un bio-tensioattivo dalle riconosciute proprietà antibatteriche, antivirali e anti-tumorali per ottenere un materiale composito multifunzionale. Diverse opzioni di design sono state investigate e la sintesi ottimizzata attraverso una caratterizzazione sistematica dei materiali prodotti, sia sulle sospensioni (DLS, ELS, TEM) sia sui prodotti granulati e calcinati (XRD, FT-IR, SEM, UV-Vis., BET). Per comprendere il ruolo del bio-tensioattivo e i potenziali effetti sinergici che il materiale composito potesse generare, si sono effettuate diverse caratterizzazioni funzionali testando il materiale per la realizzazione di nano-fasi fotocatalitiche da impiegare in processi di adsorbimento/degradazione di inquinanti acquosi, per la realizzazione di rivestimenti tessili antibatterici e come composito utile per l’assorbimento di metalli pesanti.

Niobium-based heterogeneous catalysts synthesised in supercritical carbon dioxide for selective olefin epoxidation

In this work, two different protocols for the synthesis of Nb2O5-SiO2 with a sol-gel route in which supercritical carbon dioxide was used as solvent have been developed. The tailored design of the reactor allowed the reactants to come into contact only when supercritical CO2 is present, and the high-throughput experimentation scCO2 unit allowed the screening of synthetic parameters, that led to a Nb2O5 incorporation into the silica matrix of 2.5 wt%. N2-physisorption revealed high surface areas and the presence of meso- and micropores. XRD allowed to demonstrate the amorphous character of these materials. SEM-EDX proved the excellent dispersion of Nb2O5 into the silica matrix. These materials were tested in the epoxidation of cyclooctene with hydrogen peroxide, which is considered an environmentally friendly oxidant. The catalysts were virtually inactive in an organic, polar, aprotic solvent (1,4-dioxane). However, the most active scCO2 Nb2O5-SiO2 catalyst achieved a cyclooctene conversion of 44% with a selectivity of 88% towards the epoxide when tested in ethanol. Catalytic tests on cyclohexene revealed the presence of the epoxide, which is remarkable, considering that this substrate is easily oxidised to the diol. The behaviour in protic and aprotic solvents is compared to that of TS-1.

Structural characterization of a tin oxyhydroxide gel and its precursor sol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

From sol to aerogel: a study of the nanostructural characteristics of TEOS derived sonogels

The nanostructural characteristics of acid-catalyzed sonogels are studied along the aging process at 60 degreesC in saturated conditions and after the CO, supercritical extraction (aerogel). The structural evolution was studied by means of small-angle X-ray scattering (SAXS) and UV-Visible absorption techniques. The sonogel exhibits a mass fractal structure in a length scale between zeta - 1/q(0) similar to 5.3 and a(1) similar to 1/q(m) similar to 0.22 nm, as the length scale probed by SAXS. The apparent mass fractal dimension lightly increases from 2.0 for fresh gel until 2.2 for 14 days aging in wet conditions. The UV absorption also increases with the aging time in wet conditions. Both observations are consistent with the syneresis process accompanying the polycondensation progress during aging in saturated conditions. For long aging times, the wet sonogels show a light transition from a mass to a surface fractal. in a very small interval of the length scale, developing an extremely rough surface with fractal dimension D-S similar to 2.9, the fractal characteristics of the sonogels practically do not change with the alcohol exchange. With the CO2 supercritical extraction (aerogel). The interval in the length scale in which the surface fractal is defined increases, while the surface fractal dimension diminishes to D-S similar to 2.5. The mass fractal characteristics are less apparent in the aerogels. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Determination of cadmium in river water samples by flame AAS after on-line preconcentration in mini-column packed with 2-aminothiazole-modified silica gel

A rapid and sensitive method was developed to determine trace levels of Cd2+ ions in an aqueous medium by flame atomic absorption spectrometry, using on-line preconcentration in a mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT). The Cd2+ ions were sorbed at pH 5.0. The preconcentrated Cd2+ ions were directly eluted from the column to the spectrometer's nebulizer-burner system using 100 μL of 2 mol L-1 hydrochloric acid. A retention efficiency of over 95% was achieved. The enrichment factor (calculated as the ratio of slopes of the calibration graphs) obtained with preconcentrations in a mini-column packed with SiAT (A = -1.3 × 10-3 + 1.8 × 10-3 [Cd2+]) and without preconcentrations (A = 4 × 10-5 + 3.5 × 10-3[Cd2+]), was 51 and the detection limit calculated was 0.38 μg L-1. The preconcentration procedure was applied to determine trace levels of Cd in river water samples. The optimum preconcentration conditions are discussed herein.

Technical note: Comparison of automated ribosomal intergenic spacer analysis (ARISA) and denaturing gradient gel electrophoresis (DGGE) to assess bacterial diversity in the rumen of sheep

The aim of this study was to compare automated ribosomal intergenic spacer analysis (ARISA) and denaturing gradient gel electrophoresis (DGGE) techniques to assess bacterial diversity in the rumen of sheep. Sheep were fed 2 diets with 70% of either alfalfa hay or grass hay, and the solid (SOL) and liquid (LIQ) phases of the rumen were sampled immediately before feeding (0 h) and at 4 and 8 h postfeeding. Both techniques detected similar differences between forages, with alfalfa hay promoting greater (P < 0.05) bacterial diversity than grass hay. In contrast, whereas ARISA analysis showed a decrease (P < 0.05) of bacterial diversity in SOL at 4 h postfeeding compared with 0 and 8 h samplings, no variations (P > 0.05) over the postfeeding period were detected by DGGE. The ARISA technique showed lower (P < 0.05) bacterial diversity in SOL than in LIQ samples at 4 h postfeeding, but no differences (P > 0.05) in bacterial diversity between both rumen phases were detected by DGGE. Under the conditions of this study, the DGGE was not sensitive enough to detect some changes in ruminal bacterial communities, and therefore ARISA was considered more accurate for assessing bacterial diversity of ruminal samples. The results highlight the influence of the fingerprinting technique used to draw conclusions on factors affecting ruminal bacterial diversity.

Mise au point d'essais simples pour estimer les propriétés mécaniques et la sensibilité au gel des sols et des matériaux de chaussées

La conception de la structure d’une chaussée dépend en grande partie des caractéristiques du sol qui constituera l’infrastructure, telles que ses propriétés mécaniques réversibles et sa sensibilité à l’eau et au gel. Ces paramètres peuvent être mesurés en laboratoire grâce à l’exécution d’essais très fiables, mais laborieux et dispendieux comme par exemple les essais en cellule triaxiale et celui du potentiel de ségrégation en cellule de gel. L’utilisation des équipements portatifs, comme le déflectomètre LWD et le Percomètre®, permet d’effectuer une évaluation des propriétés du sol. Dix types de sols d’infrastructure ont été testés en laboratoire; les résultats ont été validés avec des essais in situ et corrélés avec les modules réversibles et les potentiels de ségrégation obtenus en laboratoire. Des modèles mathématiques ont été développés permettant une quantification adéquate du module réversible et du potentiel de ségrégation en fonction des propriétés géotechniques du sol.

Analyse de profils de chaussées: Effet du gel saisonnier et de la dégradation du pergélisol

Des techniques adaptées aux contextes routiers sont nécessaires pour maintenir et réhabiliter des chaussées construites sur pergélisol ou en contexte de gel saisonnier. Plusieurs problématiques peuvent engendrer une augmentation des coûts de réparation et entretien, une diminution de la durée de vie des chaussées et des problèmes reliés à la sécurité des usagers de la route. L’objectif du projet consiste donc à élaborer un outil d’aide à la décision, qui contribuerait à localiser les zones sensibles au gel saisonnier et à la dégradation du pergélisol, à discerner les causes de dégradation des chaussées dues au gel saisonnier et à sélectionner les meilleures stratégies d’atténuation et de réfection à moindre coût. Le projet de recherche est divisé en deux volets distincts. Le premier volet traite des problématiques de gel de chaussées en contexte de gel saisonnier. Actuellement, il existe des méthodes de diagnostic qui permettent de détecter les endroits où un problème de gélivité est susceptible d’être présent. Par contre, ces méthodes ne permettent pas de discerner si le problème de gel est en profondeur ou en surface de la chaussée; en d’autres mots si le problème est lié à un soulèvement différentiel du sol ou à un soulèvement de fissures. De plus, les méthodes utilisées ne sont pas adaptées aux chaussées en contexte municipal. Selon les problématiques connues de certains sites, il a été possible de développer un abaque permettant de différencier si la problématique de gel se situe en surface ou en profondeur dans une chaussée. Puis, une analyse d’imagerie 3D a été réalisée pour complémenter l’abaque créé. À l’aide de cette technologie, une nouvelle méthode sera mise au point pour détecter des problématiques de gel grâce aux profils transversaux. Le deuxième volet porte sur les chaussées construites sur pergélisol. Les méthodes actuelles de détection de la dégradation du pergélisol sous les chaussées manquent de précision et ont besoin d’être raffinées, surtout dans le contexte actuel de réchauffement climatique. Pour ce faire, trois sites d’essais ont été étudiés sur l’Alaska Highway au Yukon. En fonction de différentes analyses telles que des analyses de profils longitudinaux, de la densité spectrale et de longueurs d’onde, des tendances ont été décelées pour caractériser l’instabilité du pergélisol.

Autologous Platelet Gel: Five Cases Illustrating Use On Sickle Cell Disease Ulcers.

Leg ulcers represent a particularly disabling complication in patients with sickle cell disease (SCD). Platelet gel (PG) is a novel therapeutic strategy used for accelerating wound healing of a wide range of tissues through the continuous release of platelet growth factors. Here, we describe the use of PG preparation according to Anitua's PRGF (preparations rich in growth factors) protocol for treating chronic nonhealing ulcers in patients with SCD. A positive response occurred in 3 patients with an area reduction of 85.7% to 100%, which occurred within 7 to 10 weeks, and a 35.2% and 20.5% of area reduction in 2 other patients, who however, had large ulcers. After calcium chloride addition, the platelet-rich plasmas demonstrated enhanced platelet-derived growth factors-BB (P < .001), transforming growth factor-β1 (P = .015), vascular endothelial growth factors (P = .03), and hepatocyte growth factors (nonsignificant) secretion. Furthermore, calcium chloride addition induced a significant decrease in platelet number (P = .0134) and there was no leukocyte detection in the PG product. These results demonstrate that PG treatment might impact the healing of leg ulcers in sickle cell disease, especially in patients with small ulcers.

Microbial Evaluation Of Traumatized Teeth Treated With Triple Antibiotic Paste Or Calcium Hydroxide With 2% Chlorhexidine Gel In Pulp Revascularization.

Revascularization outcome depends on microbial elimination because apical repair will not happen in the presence of infected tissues. This study evaluated the microbial composition of traumatized immature teeth and assessed their reduction during different stages of the revascularization procedures performed with 2 intracanal medicaments. Fifteen patients (7-17 years old) with immature teeth were submitted to the revascularization procedures; they were divided into 2 groups according to the intracanal medicament used: TAP group (n = 7), medicated with a triple antibiotic paste, and CHP group (n = 8), dressed with calcium hydroxide + 2% chlorhexidine gel. Samples were taken before any treatment (S1), after irrigation with 6% NaOCl (S2), after irrigation with 2% chlorhexidine (S3), after intracanal dressing (S4), and after 17% EDTA irrigation (S5). Cultivable bacteria recovered from the 5 stages were counted and identified by means of polymerase chain reaction assay (16S rRNA). Both groups had colony-forming unit counts significantly reduced after S2 (P < .05); however, no significant difference was found between the irrigants (S2 and S3, P = .99). No difference in bacteria counts was found between the intracanal medicaments used (P = .95). The most prevalent bacteria detected were Actinomyces naeslundii (66.67%), followed by Porphyromonas endodontalis, Parvimonas micra, and Fusobacterium nucleatum, which were detected in 33.34% of the root canals. An average of 2.13 species per canal was found, and no statistical correlation was observed between bacterial species and clinical/radiographic features. The microbial profile of infected immature teeth is similar to that of primarily infected permanent teeth. The greatest bacterial reduction was promoted by the irrigation solutions. The revascularization protocols that used the tested intracanal medicaments were efficient in reducing viable bacteria in necrotic immature teeth.

Recolonization Of Mutans Streptococci After Application Of Chlorhexidine Gel.

Streptococcus mutans is specifically suppressed by intensive treatment with chlorhexidine gel, but the time for recolonization and the effect on other oral bacteria are not totally clear. In this study, recolonization of mutans streptococci was evaluated in nine healthy adult volunteers, who were highly colonized with this microorganism. Stimulated saliva was collected before (baseline) and at 1, 7, 14, 21 and 28 days after application of 1% chlorhexidine gel on volunteers' teeth for two consecutive days. On each day, the gel was applied using disposable trays for 3 x 5 min with intervals of 5 min between each application. Saliva was plated on blood agar to determine total microorganisms (TM); on mitis salivarius agar to determine total streptococci (TS) and on mitis salivarius agar plus bacitracin to determine mutans streptococci (MS). Chlorhexidine was capable of reducing the counts of MS and the proportion of MS with regard to total microorganisms (%MS/TM) (p<0.05), but these values did not differ statistically from baseline (p>0.05) after 14 days for MS and 21 days for %MS/TM. The counts of TM and TS and the proportion of MS to total streptococci did not differ statistically from baseline (p>0.05) after chlorhexidine treatment. The results suggest that the effect of chlorhexidine gel treatment on suppression of mutans streptococci is limited to less than a month in highly colonized individuals.

Liposomal Lidocaine Gel For Topical Use At The Oral Mucosa: Characterization, In Vitro Assays And In Vivo Anesthetic Efficacy In Humans.

To characterize liposomal-lidocaine formulations for topical use on oral mucosa and to compare their in vitro permeation and in vivo anesthetic efficacy with commercially available lidocaine formulations. Large unilamellar liposomes (400 nm) containing lidocaine were prepared using phosphatidylcholine, cholesterol, and α-tocoferol (4:3:0.07, w:w:w) and were characterized in terms of membrane/water partition coefficient, encapsulation efficiency, size, polydispersity, zeta potential, and in vitro release. In vitro permeation across pig palatal mucosa and in vivo topical anesthetic efficacy on the palatal mucosa in healthy volunteers (double-blinded cross-over, placebo controlled study) were performed. The following formulations were tested: liposome-encapsulated 5% lidocaine (Liposome-Lido5); liposome-encapsulated 2.5% lidocaine (Liposome-Lido2.5); 5% lidocaine ointment (Xylocaina®), and eutectic mixture of lidocaine and prilocaine 2.5% (EMLA®). The Liposome-Lido5 and EMLA showed the best in vitro permeation parameters (flux and permeability coefficient) in comparison with Xylocaina and placebo groups, as well as the best in vivo topical anesthetic efficacy. We successfully developed and characterized a liposome encapsulated 5% lidocaine gel. It could be considered an option to other topical anesthetic agents for oral mucosa.