Effect of two types of graphene nanoplatelets on the physico–mechanical properties of linear low–density polyethylene composites

The influence of two types of graphene nanoplatelets (GNPs) on the physico-mechanical properties of linear low-density polyethylene (LLDPE) was investigated. The addition of these two types of GNPs – designated as grades C and M – enhanced the thermal conductivity of the LLDPE, with a more pronounced improvement resulting from the M-GNPs compared to C-GNPs. Improvement in electrical conductivity and decomposition temperature was also noticed with the addition of GNPs. In contrast to the thermal conductivity, C-GNPs resulted in greater improvements in the electrical conductivity and thermal decomposition temperature. These differences can be attributed to differences in the surface area and dispersion of the two types of GNPs.

Development of Metal–Organic Frameworks for Catalysis : Designing Functional and Porous Crystals

Metal–organic frameworks, or MOFs, have emerged as a new class of porous materials made by linking metal and organic units. The easy preparation, structural and functional tunability, ultrahigh porosity, and enormous surface areas of MOFs have led to them becoming one of the fastest growing fields in chemistry. MOFs have potential applications in numerous areas such as clean energy, adsorption and separation processes, biomedicine, and sensing. One of the most promising areas of research with MOFs is heterogeneous catalysis. This thesis describes the design and synthesis of new, carboxylate-based MOFs for use as catalysts. These materials have been characterized using diffraction, spectroscopy, adsorption, and imaging techniques. The thesis has focused on preparing highly-stable MOFs for catalysis, using post-synthetic methods to modify the properties of these crystals, and applying a combination of characterization techniques to probe these complex materials. In the first part of this thesis, several new vanadium MOFs have been presented. The synthesis of MIL-88B(V), MIL-101(V), and MIL-47 were studied using ex situ techniques to gain insight into the synthesis–structure relationships. The properties of these materials have also been studied. In the second part, the use of MOFs as supports for metallic nanoparticles has been investigated. These materials, Pd@MIL-101–NH2(Cr) and Pd@MIL-88B–NH2(Cr), were used as catalysts for Suzuki–Miyaura and oxidation reactions, respectively. The effect of the base on the catalytic activity, crystallinity, porosity, and palladium distribution of Pd@MIL-101–NH2(Cr) was studied. In the final part, the introduction of transition-metal complexes into MOFs through different synthesis routes has been described. A ruthenium complex was grafted onto an aluminium MOF, MOF-253, and an iridium metallolinker was introduced into a zirconium MOF, UiO-68–2CH3. These materials were used as catalysts for alcohol oxidation and allylic alcohol isomerization, respectively.

Multiphase flow in porous media: meta-modeling techniques for sensitivity analysis and risk assessment

One of the biggest challenges that contaminant hydrogeology is facing, is how to adequately address the uncertainty associated with model predictions. Uncertainty arise from multiple sources, such as: interpretative error, calibration accuracy, parameter sensitivity and variability. This critical issue needs to be properly addressed in order to support environmental decision-making processes. In this study, we perform Global Sensitivity Analysis (GSA) on a contaminant transport model for the assessment of hydrocarbon concentration in groundwater. We provide a quantification of the environmental impact and, given the incomplete knowledge of hydrogeological parameters, we evaluate which are the most influential, requiring greater accuracy in the calibration process. Parameters are treated as random variables and a variance-based GSA is performed in a optimized numerical Monte Carlo framework. The Sobol indices are adopted as sensitivity measures and they are computed by employing meta-models to characterize the migration process, while reducing the computational cost of the analysis. The proposed methodology allows us to: extend the number of Monte Carlo iterations, identify the influence of uncertain parameters and lead to considerable saving computational time obtaining an acceptable accuracy.

Survivorship and Clinical Outcome of the Minimally Invasive Uniglide Medial Fixed Bearing, All-polyethylene Tibia, Unicompartmental Knee Arthroplasty at a Mean Follow-up of 7.3 Years

Background: Medial UKA performed in England and Wales represents 7 to 11% of all knee arthroplasty procedures, and is most commonly performed using mobile-bearing designs. Fixed bearing eliminates the risk of bearing dislocation, however some studies have shown higher revision rates for all-polyethylene tibial components compared to those that utilize metal-backed implants. The aim of the study is to analyse survivorship and maximum 8-year clinical outcome of medial fixed bearing, Uniglide unicompartmental knee arthroplasty performed using an all-polyethylene tibial component with a minimal invasive approach. Methods: Between 2002 and 2009, 270 medial fixed UKAs were performed in our unit. Patients were reviewed pre-operatively, 5 and 8 years post-operatively. Clinical and radiographic reviews were carried out. Patients’ outcome scores (Oxford, WOMAC and American Knee Score) were documented in our database and analysed. Results: Survival and clinical outcome data of 236 knees with a mean 7.3 years follow-up are reported. Every patient with less than 4.93 years follow-up underwent a revision. The patients’ average age at the time of surgery was 69.5 years. The American Knee Society Pain and Function scores, the Oxford Knee Score and the WOMAC score all improved significantly. The 5 years survival rate was 94.1% with implant revision surgery as an end point. The estimated 10 years survival rate is 91.3%. 14 patients were revised before the 5 year follow-up. Conclusion: Fixed bearing Uniglide UKA with an all-polyethylene tibial component is a valuable tool in the management of a medial compartment osteoarthritis, affording good short term survivorship.

Hydrothermal carbonization in the synthesis of sustainable porous carbon materials

Carbon materials are found versatile and applicable in wide range of applications. During the recent years research of carbon materials has focussed on the search of environmentally friendly, sustainable, renewable and low-cost starting material sources as well as simple cost-efficient synthesis techniques. As an alternative synthesis technique in the production of carbon materials hydrothermal carbonization (HTC) has shown a great potential. Depending on the application HTC can be performed as such or as a pretreatment technique. This technique allows synthesis of carbon materials i.e. hydrochars in closed vessel in the presence of water and self-generated pressure at relatively low temperatures (180-250 ˚C). As in many applications well developed porosity and heteroatom distribution are in a key role. Therefore in this study different techniques e.g. varying feedstock, templating and post-treatment in order to introduce these properties to the hydrochars structure were performed. Simple monosaccharides i.e. fructose or glucose and more complex compounds such as cellulose and sludge were performed as starting materials. Addition of secondary precursor e.g. thiophenecarboxaldehyde and ovalbumin was successfully exploited in order to alter heteroatom content. It was shown that well-developed porosity (SBET 550 m2/g) can be achieved via one-pot approach (i.e. exploitation of salt mixture) without conventionally used post-carbonization step. Nitrogen-enriched hydrochars indicated significant Pb(II) and Cr(VI) removal efficiency of 240 mg/g and 68 mg/g respectively. Sulphur addition into carbon network was not found to have enhancing effect on the adsorption of methylene blue or change acidity of the carbon material. However, these hydrochars were found to remove 99.9 % methylene blue and adsorption efficiency of these hydrochars remained over 90 % even after regeneration. In addition to water treatment application N-rich high temperature treated carbon materials were proven applicable as electrocatalyst and electrocatalyst support. Hydrothermal carbonization was shown to be workable technique for the production of carbon materials with variable physico-chemical properties and therefore hydrochars could be applied in several different applications e.g. as alternative low-cost adsorbent for pollutant removal from water.

PIV measurements combined with the motion tracking technique to analyze flow around a moving porous structure

To gain a better understanding of the fluid–structure interaction and especially when dealing with a flow around an arbitrarily moving body, it is essential to develop measurement tools enabling the instantaneous detection of moving deformable interface during the flow measurements. A particularly useful application is the determination of unsteady turbulent flow velocity field around a moving porous fishing net structure which is of great interest for selectivity and also for the numerical code validation which needs a realistic database. To do this, a representative piece of fishing net structure is used to investigate both the Turbulent Boundary Layer (TBL) developing over the horizontal porous moving fishing net structure and the turbulent flow passing through the moving porous structure. For such an investigation, Time Resolved PIV measurements are carried out and combined with a motion tracking technique allowing the measurement of the instantaneous motion of the deformable fishing net during PIV measurements. Once the two-dimensional motion of the porous structure is accessed, PIV velocity measurements are analyzed in connection with the detected motion. Finally, the TBL is characterized and the effect of the structure motion on the volumetric flow rate passing though the moving porous structure is clearly demonstrated.

Evaluation of the impact of polyethylene microbeads ingestion in European sea bass (Dicentrarchus labrax) larvae

Microplastics are present in marine habitats worldwide and may be ingested by low trophic organisms such as fish larvae, with uncertain physiological consequences. The present study aims at assessing the impact of polyethylene (PE 10-45µM) microbeads ingestion in European sea bass (Dicentrarchus labrax) larvae. Fish were fed an inert diet including 0, 104 and 105 fluorescent microbeads per gram from 7 until 43 days post-hatching (dph). Microbeads were detected in the gastrointestinal tract in all fish fed diet incorporating PE. Our data revealed an efficient elimination of PE beads from the gut since no fluorescent was observed in the larvae after 48h depuration. While the mortality rate increased significantly with the amount of microbeads scored per larvae at 14 and 20 dph, only ingestion of the highest concentration slightly impacted mortality rates. Larval growth and inflammatory response through Interleukine-1-beta (IL-1) gene expression were not found to be affected while cytochrome-P450-1A1 (cyp1a1) expression level was significantly positively correlated with the number of microbeads scored per larva at 20 dph. Overall, these results suggest that ingestion of PE microbeads had limited impact on sea bass larvae possibly due to their high potential of egestion