Deidrofluorurazione di copolimeri di VDF/HFP in presenza di alcali

In questo lavoro di tesi, si cerca di studiare una reazione in grado di generare doppi legami sulla catena polimerica di un fluoroelastomero e analizzare le caratteristiche del polimero così ottenuto. I siti di insaturazione generati potranno essere sfruttati per successive reazioni di funzionalizzazione del polimero o per un eventuale processo di vulcanizzazione radicalico. La reazione utilizzata consiste in una deidrofluorurazione in ambiente alcalino di un copolimero VDF/HFP di produzione industriale. Essa è stata condotta sia in un sistema bifasico, sia in una fase omogenea, a 24 tempi e temperature diversi. La formazione dei doppi legami è stata analizzata tramite spettroscopia di risonanza magnetica al nucleo di fluoro (19F-NMR) e spettroscopia infrarossa. La possibilità di poter sfruttare le insaturazioni generate è stata studiata mediante prove di reticolazione via perossido indotta da radiazione UV, radiazione visibile ed energia termica. Nei primi due casi, il fenomeno è stato monitorato con spettri IR e UV-Vis, nel secondo caso la reazione è stata seguita per via reometrica (ODR: Oscillating Disk Reometer). Il lavoro è stato svolto in collaborazione con Elastomers Union srl, azienda con stabilimento di produzione a Castel Guelfo, specializzata nella preparazione di compound a base fluoroelastomerica e fluorosiliconica.

Localizzazione e tracking tramite filtri statistici in sistemi multi antenna

Uno dei temi più recenti nel campo delle telecomunicazioni è l'IoT. Tale termine viene utilizzato per rappresentare uno scenario nel quale non solo le persone, con i propri dispositivi personali, ma anche gli oggetti che le circondano saranno connessi alla rete con lo scopo di scambiarsi informazioni di diversa natura. Il numero sempre più crescente di dispositivi connessi in rete, porterà ad una richiesta maggiore in termini di capacità di canale e velocità di trasmissione. La risposta tecnologica a tali esigenze sarà data dall’avvento del 5G, le cui tecnologie chiave saranno: massive MIMO, small cells e l'utilizzo di onde millimetriche. Nel corso del tempo la crescita delle vendite di smartphone e di dispositivi mobili in grado di sfruttare la localizzazione per ottenere servizi, ha fatto sì che la ricerca in questo campo aumentasse esponenzialmente. L'informazione sulla posizione viene utilizzata infatti in differenti ambiti, si passa dalla tradizionale navigazione verso la meta desiderata al geomarketing, dai servizi legati alle chiamate di emergenza a quelli di logistica indoor per industrie. Data quindi l'importanza del processo di positioning, l'obiettivo di questa tesi è quello di ottenere la stima sulla posizione e sulla traiettoria percorsa da un utente che si muove in un ambiente indoor, sfruttando l'infrastruttura dedicata alla comunicazione che verrà a crearsi con l'avvento del 5G, permettendo quindi un abbattimento dei costi. Per fare ciò è stato implementato un algoritmo basato sui filtri EKF, nel quale il sistema analizzato presenta in ricezione un array di antenne, mentre in trasmissione è stato effettuato un confronto tra due casi: singola antenna ed array. Lo studio di entrambe le situazioni permette di evidenziare, quindi, i vantaggi ottenuti dall’utilizzo di sistemi multi antenna. Inoltre sono stati analizzati altri elementi chiave che determinano la precisione, quali geometria del sistema, posizionamento del ricevitore e frequenza operativa.

Processing-structure-property relationships in solid-state shear pulverization: Parametric study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Processing-Structure-Property Relationships in Solid-State Shear Pulverization: Parametric Study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Lateral ridge augmentation using a PCL-TCP scaffold in a clinically relevant but challenging micropig model

In implant dentistry, there is a need for synthetic bone substitute blocks to support ridge augmentation in situations where large bone volumes are missing. Polycaprolactone-based scaffolds demonstrated excellent results in bone tissue engineering applications. The use of customized polycaprolactone-tricalcium phosphate (PCL-TCP) displayed promising results from recent rat femur and rabbit calvaria studies. However, data from clinically representative models in larger animals do not exist.

Scale Up of PLA Nanoparticle Synthesis by Solvent Displacement and Functionalization of the Particles with a Silica Shell for Targeted Drug Delivery Applications

Biodegradable polymer nanoparticles have the properties necessary to address many of the issues associated with current drug delivery techniques including targeted and controlled delivery. A novel drug delivery vehicle is proposed consisting of a poly(lactic acid) nanoparticle core, with a functionalized, mesoporous silica shell. In this study, the production of PLA nanoparticles is investigated using solvent displacement in both a batch and continuous manner, and the effects of various system parameters are examined. Using Pluronic F-127 as the stabilization agent throughout the study, PLA nanoparticles are produced through solvent displacement with diameters ranging from 200 to 250 nm using two different methods: dropwise addition and in an impinging jet mixer. The impinging jet mixer allows for easy scale-up of particle production. The concentration of surfactant and volume of quench solution is found to have minimal impact on particle diameter; however, the concentration of PLA is found to significantly impact the diameter mean and polydispersity. In addition, the stability of the PLA nanoparticles is observed to increase as residual THF is evaporated. Lastly, the isolated PLA nanoparticles are coated with a silica shell using the Stöber Process. It is found that functionalizing the silica with a phosphonic silane in the presence of excess Pluronic F-127 decreases coalescence of the particles during the coating process. Future work should be conducted to fine-tune the PLA nanoparticle synthesis process by understanding the effect of other system parameters and in synthesizing mesoporous silica shells.

Solid-State Compatibilization of Immiscible Polymer Blends: Cryogenic Milling and Solid-State Shear Pulverization

The blending of common polymers allows for the rapid and facile synthesis of new materials with highly tunable properties at a fraction of the costs of new monomer development and synthesis. Most blends of polymers, however, are completely immiscible and separate into distinct phases with minimal phase interaction, severelydegrading the performance of the material. Cross-phase interactions and property enhancement can be achieved with these blends through reactive processing or compatibilizer addition. A new class of blend compatibilization relies on the mechanochemical reactions between polymer chains via solid-state, high energy processing. Two contrasting mechanochemical processing techniques are explored in this thesis: cryogenic milling and solid-state shear pulverization (SSSP). Cryogenic milling is a batch process where a milling rod rapidly impacts the blend sample while submerged within a bath of liquid nitrogen. In contrast, SSSP is a continuous process where blend components are subjected to high shear and compressive forces while progressing down a chilled twin-screw barrel. In the cryogenic milling study, through the application of a synthesized labeledpolymer, in situ formation of copolymers was observed for the first time. The microstructures of polystyrene/high-density polyethylene (PS/HDPE) blends fabricated via cryomilling followed by intimate melt-state mixing and static annealing were found to be morphologically stable over time. PS/HDPE blends fabricated via SSSP also showed compatibilization by way of ideal blend morphology through growth mechanisms with slightly different behavior compared to the cryomilled blends. The new Bucknell University SSSP instrument was carefully analyzed and optimized to produce compatibilized polymer blends through a full-factorial experiment. Finally, blends of varying levels of compatibilization were subjected to common material tests to determine alternative means of measuring and quantifying compatibilization,

Characterization of Biodegradable Polymer Nanocomposites Fabricated via Solid-State Processing

Biodegradable polymer/clay nanocomposites were prepared withpristine and organically modified montmorillonite in polylactic acid (PLA) and polycaprolactone (PCL) polymer matrices. Nanocomposites were fabricated using extrusion and SSSP to compare the effects of melt-state and solid-state processing on the morphology of the final nanocomposite. Characterization of various material properties was performed on prepared biodegradable polymer/clay nanocomposites to evaluate property enhancements from different clays and/or processing methods.

The Crystallization Kinetics of Polylactic Acid (Pla) Processed Through Solid-State/Melt Extrusion

Polylactic acid (PLA) is a bio-derived, biodegradable polymer with a number of similar mechanical properties to commodity plastics like polyethylene (PE) and polyethylene terephthalate (PETE). There has recently been a great interest in using PLA to replace these typical petroleum-derived polymers because of the developing trend to use more sustainable materials and technologies. However, PLA¿s inherent slow crystallization behavior is not compatible with prototypical polymer processing techniques such as molding and extrusion, and in turn inhibits its widespread use in industrial applications. In order to make PLA into a commercially-viable material, there is a need to process the material in such a way that its tendency to form crystals is enhanced. The industry standard for producing PLA products is via twin screw extrusion (TSE), where polymer pellets are fed into a heated extruder, mixed at a temperature above its melting temperature, and molded into a desired shape. A relatively novel processing technique called solid-state shear pulverization (SSSP) processes the polymer in the solid state so that nucleation sites can develop and fast crystallization can occur. SSSP has also been found to enhance the mechanical properties of a material, but its powder output form is undesirable in industry. A new process called solid-state/melt extrusion (SSME), developed at Bucknell University, combines the TSE and SSSP processes in one instrument. This technique has proven to produce moldable polymer products with increased mechanical strength. This thesis first investigated the effects of the TSE, SSSP, and SSME polymer processing techniques on PLA. The study seeks to determine the process that yields products with the most enhanced thermal and mechanical properties. For characterization, percent crystallinity, crystallization half time, storage modulus, softening temperature, degradation temperature and molecular weight were analyzed for all samples. Through these characterization techniques, it was observed that SSME-processed PLA had enhanced properties relative to TSE- and SSSP-processed PLA. Because of the previous findings, an optimization study for SSME-processed PLA was conducted where throughput and screw design were varied. The optimization study determined PLA processed with a low flow rate and a moderate screw design in an SSME process produced a polymer product with the largest increase in thermal properties and a high retention of polymer structure relative to TSE-, SSSP-, and all other SSME-processed PLA. It was concluded that the SSSP part of processing scissions polymer chains, creating defects within the material, while the TSE part of processing allows these defects to be mixed thoroughly throughout the sample. The study showed that a proper SSME setup allows for both the increase in nucleation sites within the polymer and sufficient mixing, which in turn leads to the development of a large amount of crystals in a short period of time.

Aging and Social Policy: Contrasting Western Europe and the United States

In this essay, three generic issues that underlie our implicit social policy toward older adults and their families are considered: What is the proper division of responsibility for impaired elderly between family members and the state? Is age a morally relevant variable when allocating the resources of society? What should be the balance of competing demands between and among different generations? These issues are considered by contrasting the implicit and explicit policies of the United States with those of several Western European nations (Sweden, West Germany, Austria, and the Netherlands). Suggestions for a family-centered policy on aging are offered. In addition, indications for the appropriate blend of age and need as entitlement criteria are presented.

The Redistribution of Property Rights, Corporate Governance and Company Restructuring after Privatisation"

The project covered the main issues of privatisation, corporate governance and company restructuring after privatisation in Hungary and in the Russian Republic, together with a summary of the broader picture of company-level changes in Central and Eastern Europe, discussing the issues of micro-financial restructuring in the Czech Republic, Hungary, Poland and Slovakia. The two countries selected as the focus of research can be regarded as the two most widely differing cases of the economic transformation in Central and Eastern Europe. Hungary began its transition very early in 1989, while Russia was very late in doing so. Hungary first implemented a series of institutional and systemic reforms before stabilising its public finances, while Russia has struggled with financial stabilisation for years without great success. Company restructuring and the introduction of new forms of governance only began in Russia in the mid-1990s. Hungary opted for "traditional" western methods of privatisation and invited a large amount of foreign direct investment (FDI) while in Russia the bulk of state-owned property was privatised either by free distribution or by a strange blend of ESOP-MBO schemes. FDI in Russia remained modest because of the high risk and uncertainty surrounding economic transactions there. Hungary was a forerunner in privatising public utilities, while Russia has moved cautiously in this area. The group's studies show that the Hungarian economy is now over the "transformation recession" and its economic success is largely due to its successful privatisation and to the dominant participation of foreign investors in company take-overs and in the restructuring process. The study of Russia provides a comprehensive account of the main factors in the so-far modest results in Russian privatisation and economic transformation.

Performance and emissions testing of a small two stroke engine using mid-level ethanol blends

With the introduction of the mid-level ethanol blend gasoline fuel for commercial sale, the compatibility of different off-road engines is needed. This report details the test study of using one mid-level ethanol fuel in a two stroke hand held gasoline engine used to power line trimmers. The study sponsored by E3 is to test the effectiveness of an aftermarket spark plug from E3 Spark Plug when using a mid-level ethanol blend gasoline. A 15% ethanol by volume (E15) is the test mid-level ethanol used and the 10% ethanol by volume (E10) was used as the baseline fuel. The testing comprises running the engine at different load points and throttle positions to evaluate the cylinder head temperature, exhaust temperature and engine speed. Raw gas emissions were also measured to determine the impact of the performance spark plug. The low calorific value of the E15 fuel decreased the speed of the engine along with reduction in the fuel consumption and exhaust gas temperature. The HC emissions for E15 fuel and E3 spark plug increased when compared to the base line in most of the cases and NO formation was dependent on the cylinder head temperature. The E3 spark plug had a tendency to increase the temperature of the cylinder head irrespective of fuel type while reducing engine speed.

Electrospun chitosan nanofibers for virus removal

Electrospinning uses electrostatic forces to create nanofibers that are far smaller than conventional fiber spinning process. Nanofibers made with chitosan were created and techniques to control fibers diameter and were well developed. However, the adsorption of porcine parvovirus (PPV) was low. PPV is a small, nonenveloped virus that is difficult to remove due to its size, 18-26 nm in diameter, and its chemical stability. To improve virus adsorption, we functionalized the nanofibers with a quaternized amine, forming N-[(2-hydroxy-3-trimethylammonium) propyl] chitosan chloride (HTCC). This was blended with additives to increase the ability to form HTCC nanofibers. The additives changed the viscosity and conductivity of the electrospinning solution. We have successfully synthesized and functionalized HTCC nanofibers that absorb PPV. HTCC blend with graphene have the ability to remove a minimum of 99% of PPV present in solution.

Technique to measure heats of reaction of Ti-B, Al-Ti-B, and Al-Ti-B4C powder blends

In this research, a modification to initiation aid ignition in bomb calorimetry that involves systemically blending levels of boron and potassium nitrate initiation aids with a bulk structural energetic elemental power blend is developed. A regression is used to estimate the nominal heat of reaction for the primary reaction. The technique is first applied to the synthesis of TiB2 as a validation study to see if close proximity to literature values can be achieved. The technique is then applied to two systems of interest, Al-Ti-B, and Al-Ti-B4C. In all three investigations, x-ray diffraction is used to characterize the product phases of the reactions to determine the extent and identity of the product phases and any by-products that may have formed as a result of adding the initiation aid. The experimental data indicates the technique approximates the heat of reaction value for the synthesis of TiB2 from Ti-B powder blends and the formation of TiB2 is supported by volume fraction analysis by x-ray diffraction. Application to the Al-Ti-B and Al-Ti-B4C blends show some correlation with variation of the initiation aid, with x-ray diffraction showing the formation of equilibrium products. However, these blends require further investigation to resolve more complex interactions and rule out extraneous variables.