Photophysics of Carbon Nanotubes: from Dispersion to Supramolecular Systems

The aim of this PhD thesis is the investigation of the photophysical properties of materials that can be exploited in solar energy conversion. In this context, my research was mainly focused on carbon nanotube-based materials and ruthenium complexes. The first part of the thesis is devoted to carbon nanotubes (CNT), which have unique physical and chemical properties, whose rational control is of substantial interest to widen their application perspectives in many fields. Our goals were (i) to develop novel procedures for supramolecular dispersion, using amphiphilic block copolymers, (ii) to investigate the photophysics of CNT-based multicomponent hybrids and understand the nature of photoinduced interactions between CNT and selected molecular systems such as porphyrins, fullerenes and oligo (p-phynylenevinylenes). We established a new protocol for the dispersion of SWCNTs in aqueous media via non-covalent interactions and demonstrated that some CNT-based hybrids are suitable for testing in PV devices. The second part of the work is focussed on the study of homoleptic and heteroleptic Ru(II) complexes with bipyridine and extended phenanthroline ligands. Our studies demonstrated that these compounds are potentially useful as light harvesting systems for solar energy conversion. Both CNT materials and Ru(II) complexes have turned out to be remarkable examples of photoactive systems. The morphological and photophysical characterization of CNT-based multicomponent systems allowed a satisfactory rationalization of the photoinduced interactions between the individual units, despite several hurdles related to the intrinsic properties of CNTs that prevent, for instance, the utilization of laser spectroscopic techniques. Overall, this work may prompt the design and development of new functional materials for photovoltaic devices.

The velocity dispersion profile of the globular cluster 47Tucanae

Gli ammassi globulari rappresentano i laboratori ideali nei quali studiare la dinamica di sistemi ad N-corpi ed i suoi effetti sull’evoluzione stellare. Infatti, gli ammassi globulari sono gli unici sistemi astrofisici che, entro il tempo scala dell’età dell’Universo, sperimentano quasi tutti i processi di dinamica stellare noti. Questo lavoro di tesi si inserisce in un progetto a lungo termine volto a fornire una dettagliata caratterizzazione delle proprietà dinamiche degli ammassi globulari galattici. In questa ricerca, strumenti di fondamentale importanza sono il profilo di dispersione di velocità del sistema e la sua curva di rotazione. Per determinare le componenti radiali di questi profili cinematici in ammassi globulari galattici è necessario misurare la velocità lungo la linea di vista di un ampio campione di stelle membre, a differenti distanze dal centro. Seguendo un approccio multi-strumentale, è possibile campionare l’intera estensione radiale dell’ammasso utilizzando spettrografi multi-oggetto ad alta risoluzione spettrale nelle regioni intermedie/esterne, e spettrografi IFU con ottiche adattive per le regioni centrali (pochi secondi d’arco dal centro). Questo lavoro di tesi è volto a determinare il profilo di dispersione di velocità dell’ammasso globulare 47 Tucanae, campionando un’estensione radiale compresa tra circa 20'' e 13' dal centro. Per questo scopo sono state misurate le velocità radiali di circa un migliaio di stelle nella direzione di 47 Tucanae, utilizzando spettri ad alta risoluzione ottenuti con lo spettrografo multi-oggetto FLAMES montato al Very Large Telescope dell’ESO. Le velocità radiali sono state misurate utilizzando la tecnica di cross-correlazione tra gli spettri osservati e appropriati spettri teorici, e sono state ottenute accuratezze inferiori a 0.5km/s. Il campione così ottenuto (complementare a quello raccolto con strumenti IFU nelle regioni centrali) è fondamentale per costruire il profilo di dispersione di velocità dell’ammasso e la sua eventuale curva di rotazione. Questi dati, combinati col profilo di densità dell’ammasso precedentemente determinato, permetteranno di vincolare opportunamente modelli teorici come quelli di King (1966) o di Wilson (1975), e di arrivare così alla prima solida determinazione dei parametri strutturali e dinamici (raggi di core e di metà massa, tempo di rilassamento, parametro collisionale, etc.) e della massa totale e distribuzione di massa del sistema.

Relating the physicochemical characteristics and dispersion of multiwalled carbon nanotubes in different suspension media to their oxidative reactivity in vitro and inflammation in vivo

Reactive oxygen species (ROS) production is important in the toxicity of pathogenic particles such as fibres. We examined the oxidative potential of straight (50 microm and 10 microm) and tangled carbon nanotubes in a cell free assay, in vitro and in vivo using different dispersants. The cell free oxidative potential of tangled nanotubes was higher than for the straight fibres. In cultured macrophages tangled tubes exhibited significantly more ROS at 30 min, while straight tubes increased ROS at 4 h. ROS was significantly higher in bronchoalveolar lavage cells of animals instilled with tangled and 10 mum straight fibres, whereas the number of neutrophils increased only in animals treated with the long tubes. Addition of dispersants in the suspension media lead to enhanced ROS detection by entangled tubes in the cell-free system. Tangled fibres generated more ROS in a cell-free system and in cultured cells, while straight fibres generated a slower but more prolonged effect in animals.

Efficient fabrication of polymer nanocomposites with effective exfoliation and dispersion by solid-state/melt extrusion

In this communication, solid-state/melt extrusion (SSME) is introduced as a novel technique that combines solid-state shear pulverization (SSSP) and conventional twin screw extrusion (TSE) in a single extrusion system. The morphology and property enhancements in a model linear low-density polyethylene/organically modified clay nanocomposite sample fabricated via SSME were compared to those fabricated via SSSP and TSE. The results show that SSME is capable of exfoliating and dispersing the nanofillers similarly to SSSP, while achieving a desirable output rate and producing extrudate similar in form to that from TSE.

PA21, a New Iron-Based Noncalcium Phosphate Binder, Prevents Vascular Calcification in Chronic Renal Failure Rats

Chronic renal failure (CRF) is associated with the development of secondary hyperparathyroidism and vascular calcifications. We evaluated the efficacy of PA21, a new iron-based noncalcium phosphate binder, in controlling phosphocalcic disorders and preventing vascular calcifications in uremic rats. Rats with adenine-diet-induced CRF were randomized to receive either PA21 0.5, 1.5, or 5% or CaCO3 3% in the diet for 4 weeks, and were compared with uremic and nonuremic control groups. After 4 weeks of phosphate binder treatment, serum calcium, creatinine, and body weight were similar between all CRF groups. Serum phosphorus was reduced with CaCO3 3% (2.06 mM; P ≤ 0.001), PA21 1.5% (2.29 mM; P < 0.05), and PA21 5% (2.21 mM; P ≤ 0.001) versus CRF controls (2.91 mM). Intact parathyroid hormone was strongly reduced in the PA21 5% and CaCO3 3% CRF groups to a similar extent (1138 and 1299 pg/ml, respectively) versus CRF controls (3261 pg/ml; both P ≤ 0.001). A lower serum fibroblast growth factor 23 concentration was observed in the PA21 5%, compared with CaCO3 3% and CRF, control groups. PA21 5% CRF rats had a lower vascular calcification score compared with CaCO3 3% CRF rats and CRF controls. In conclusion, PA21 was as effective as CaCO3 at controlling phosphocalcic disorders but superior in preventing the development of vascular calcifications in uremic rats. Thus, PA21 represents a possible alternative to calcium-based phosphate binders in CRF patients.

PERFORMANCE EVALUATION OF LLDPE/CaCO3 MODIFIERS WITH AND WITHOUT TITANATE COUPLING AGENT ON ASPHALT BINDER AND MIXTURE

The complexity and challenge created by asphalt material motivates researchers and engineers to investigate the behavior of this material to develop a better understanding, and improve the performance of asphalt pavement. Over decades, a wide range of modification at macro, meso, micro and nano scales have been conducted to improve the performance of asphalt pavement. This study was initiated to utilize the newly developed asphalt modifier pellets. These pellets consisted of different combinations of calcium carbonate (CaCO3), linear low-density polyethylene (LLDPE) and titanate coupling agent (CA) to improve the asphalt binder as well as pavement performance across a wide range of temperature and loading pace. These materials were used due to their unique characteristics and promising findings from various industries, especially as modifiers in pavement material. The challenge is to make sure the CaCO3 disperses very well in the mixture. The rheological properties of neat asphalt binder PG58-28 and modified asphalt binder (PG58-28/LLDPE, PG58-28/CaCO3, PG58-28/CaCO3/LLDPE, and PG58-28/CaCO3/LLDPE/CA), were determined using rotational viscometer (RV) test, dynamic shear rheometer (DSR) test and bending beam rheometer test. In the DSR test, the specimens were evaluated using frequency sweep and multiple shear creep recovery (MSCR). The asphalt mixtures (aggregate/PG58-28, aggregate/ PG58-28/LLDPE, aggregate/PG58-28/CaCO3, aggregate/PG58-28/LLDPE/CaCO3 and aggregate/PG58-28/LLDPE/CaCO3/CA) were evaluated using the four point beam fatigue test, the dynamic modulus (E*) test, and tensile strength test (to determines tensile strength ratio, TSR). The RV test results show that all modified asphalt binders have a higher viscosity compared to the neat asphalt binder (PG58-28). Based on the Jnr results (using MSCR test), all the modified asphalt binders have a better resistance to rutting compared to the neat asphalt binder. A higher modifier contents have resulted in a better recovery percentage of asphalt binder (higher resistance to rutting), except the specimens prepared using PECC’s modified asphalt binder (PG58-28/CaCO3/LLDPE). The BBR test results show that all the modified asphalt binders have shown comparable performance in term of resistance to low temperature cracking, except the specimen prepared using the LLDPE modifier. Overall, 5 wt% LLDPE modified asphalt binder was found to be the best asphalt binder in terms of resistance to rutting. Meanwhile, 3 wt% PECC-1CA’s modified asphalt binder can be considered as the best (in terms of resistance to thermal cracking) with the lowest mean critical cracking temperature. The appearance of CaCO3 was found useful merely in improving the resistance to fatigue cracking of asphalt mixture. However, application of LLDPE has undermined the fatigue life of asphalt mixtures. Adding LLDPE and coupling agent throughout this study does not sufficiently help in terms of elastic behavior which essential to enhance the resistance to fatigue cracking. In contrast, application of LLDPE has increased the indirect tensile strength values and TSR of asphalt mixtures, indicates a better resistance to moisture damage. The usage of the coupling agent does not change the behavior of the asphalt mixture, which could be due to imbalance effects resulted by combination of LLDPE and CaCO3 in asphalt binder. Further investigations without incorporating CaCO3 should be conducted further. To investigate the feasibility of using LLDPE and coupling agent as modifiers in asphalt pavements, more research should be conducted on different percentages of LLDPE (less than 3 wt%), and at the higher and w wider range of coupling agent content, from 3 wt% to 7 wt% based on the polymer mass.

THE DISPERSION AND SELECTIVE FLOCCULATION OF HEMATITE ORE

Iron ore is one of the most important ores in the world. Over the past century, most mining of iron ore has been focused on magnetite (Fe3O4). As the name suggests, magnetite is magnetic in nature and is easily separated from gangue (unwanted) minerals through magnetic separation processes. Unfortunately, the magnetite ore bodies are diminishing. Because of this, there has been a recent drive to pursue technology that can economically separate hematite (Fe2O3) from its gangue minerals as hematite is a much more abundant source of iron. Most hematite ore has a very small liberation size that is frequently less than 25μm. Beneficiation of any ore with this fine of a liberation size requires advanced processing methods and is seldom pursued. A single process, known as selective flocculation and dispersion, has been successfully implemented at a plant scale for the beneficiation of fine liberation size hematite ore. Very little is known about this process as it was discovered by the U.S. Bureau of Mines by accident. The process is driven by water chemistry and surface chemistry modifications that enhance the separation of the hematite from its gangue minerals. This dissertation focuses on the role of water chemistry and process reagents in this hematite beneficiation process. It has been shown that certain ions, including calcium and magnesium, play a significant role in the process. These ions have a significant effect on the surface chemistry as reported by zeta potential studies. It was shown that magnesium ions within the process water have a more significant impact on surface chemistry than calcium ions due to steric hindrance effects at the hematite surface. It has also been shown that polyacrylic acid dispersants, if used in the process, can increase product quality (increase iron content, decrease phosphorus content, decrease silica content) substantially. Water, surface and reagent chemistry experiments were performed at a laboratory, pilot, and full plant scale during the course of this work. Many of the conclusions developed in the laboratory and pilot scale were found to be true at the full plant scale as well. These studies are the first published in history to develop theories of water chemistry and surface chemistry interactions at a full plant scale.

The Laboratory Evaluation of Bio Oil Derived From Waste Resources as Extender for Asphalt Binder

A shortage of petroleum asphalt is creating opportunities for engineers to utilize alternative pavement materials. Three types of bio oils, original bio oil (OB), dewatered bio oil (DWB) and polymer-modified bio oil (PMB) were used to modify and partially replace petroleum asphalt in this research. The research investigated the procedure of producing bio oil, the rheological properties of asphalt binders modified and partially replaced by bio oil, and the mechanical performances of asphalt mixtures modified by bio oil. The analysis of variance (ANOVA) is conducted on the test results for the significance analysis. The main finding of the study includes: 1) the virgin bioasphalt is softer than the traditional asphalt binder PG 58-28 but stiffer after RTFO aging because bio oil ages much faster than the traditional asphalt binder during mixing and compaction; 2) the binder test showed that the addition of bio oil is expected to improve the rutting performance while reduce the fatigue and low temperature performance; 3) both the mass loss and the oxidation are important reasons for the bio oil aging during RTFO test; the mixture test showed that 1) most of the bio oil modified asphalt mixture had slightly higher rutting depth than the control asphalt mixture, but the difference is not statistically significant; 2) the dynamic modulus of some of the bio oil modified asphalt mixture were slightly lower than the control asphalt mixture, the E* modulus is also not statistically significant; 3) most of the bio oil modified asphalt mixture had higher fatigue lives than the control asphalt mixture; 4) the inconsistence of binder test results and mixture test results may be attributed to that the aging during the mixing and compaction was not as high as that in the RTFO aging simulation. 5) the implementation of Michigan wood bioasphalt is anticipated to reduce the emission but bring irritation on eyes and skins during the mixing and compaction.

Biokompatible Pulver-Binder-Systeme für das 3D-Drucken von ImplantatenBiokompatible Pulver-Binder-Systeme für das 3D-Drucken von Implantaten

Calciumphosphate werden auf Grund ihrer chemischen und strukturellen Ähnlichkeit mit der mineralischen Phase des humanen Knochens und ihrer osteokonduktiven Eigenschaften seit langem als Implantatmaterialien eingesetzt. Auf Basis dieser Stoffklasse war es unser Ziel, patientenspezifische Implantate mit individuell angepasster, komplexer Geometrie und Strukturierung zu entwickeln, die sich möglichst exakt in den Knochendefekt einpassen lassen und damit zu einer Stabilisierung des Knochenlagers beitragen.