Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

Utilisation of Glass Reinforced Plastics as Cost Effective Alternative to Traditional Materials in Access Panel Design for Waste Water Treatment Plants

Composites are fast becoming a cost effective option when considering the design of engineering structures in a broad range of applications. If the strength to weight benefits of these material systems can be exploited and challenges in developing lower cost manufacturing methods overcome, then the advanced composite systems will play a bigger role in the diverse range of sectors outside the aerospace industry where they have been used for decades.
This paper presents physical testing results that showcase the advantages of GRP (Glass Reinforced Plastics), such as the ability to endure loading with minimal deformation. The testing involved is a cross comparison of GRP grating vs. GRP encapsulated foam core. Resulting data gained within this paper will then be coupled with design optimization (utilising model simulation) to bring forward layup alterations to meet the specified load classifications involved.

Large-Scale Controlled-Condition Experiment to Evaluate Light Weight Deflectometers for Modulus Determination and Compaction Quality Assurance of Unbound Pavement Materials

Compaction control using lightweight deflectometers (LWD) is currently being evaluated in several states and countries and fully implemented for pavement construction quality assurance (QA) by a few. Broader implementation has been hampered by the lack of a widely recognized standard for interpreting the load and deflection data obtained during construction QA testing. More specifically, reliable and practical procedures are required for relating these measurements to the fundamental material property—modulus—used in pavement design. This study presents a unique set of data and analyses for three different LWDs on a large-scale controlled-condition experiment. Three 4.5x4.5 m2 test pits were designed and constructed at target moisture and density conditions simulating acceptable and unacceptable construction quality. LWD testing was performed on the constructed layers along with static plate loading testing, conventional nuclear gauge moisture-density testing, and non-nuclear gravimetric and volumetric water content measurements. Additional material was collected for routine and exploratory tests in the laboratory. These included grain size distributions, soil classification, moisture-density relations, resilient modulus testing at optimum and field conditions, and an advanced experiment of LWD testing on top of the Proctor compaction mold. This unique large-scale controlled-condition experiment provides an excellent high quality resource of data that can be used by future researchers to find a rigorous, theoretically sound, and straightforward technique for standardizing LWD determination of modulus and construction QA for unbound pavement materials.

Backflow prevention certification workshop information and materials

The information enclosed in this booklet consists of memos, policy statements and other pertinent information to guide you in the establishment of a backflow prevention program.

Use of Sludge as Ceramic Materials

Nowadays, with increase amounts of sludge derived from the treatment of domestic sewage put pressure into research on systems for the adequate use of these materials. The aim of the present work is to study the use of sludge ash, from sintering and calcinated process, as a raw material for the ceramic industry. Using the sewage sludge ashes as ceramic raw material there will be no contamination of soil and underground water. Metals and toxic compounds like Al, Fe, Ba, Cr, Cu, Mn and Zn oxides were analyzed and characterized by X-ray fluorescence (XRF), scanning electron microscopy (SEM) and plasma emission spectroscopy (ICP-OES). The leached material was chemically analyzed where the integration of oxides into the ceramic matrix of sludge ash was observed. Residual decomposition was analyzed by TG, DTG and DTA curves.

Transplantation of artificial gelatin-co-bletillastriata gelatin/Salvia miltiorrhiza Corium promotes dermal repair in rats

Purpose: To evaluate the growth of the composite corium (constructed with fibroblast cells and gelatinco- Bletillastriata gelatin/Salvia miltiorrhiza materials) on rats. Methods: The composite artificial corium was constructed by culturing fibroblast cells in gelatin-co- Bletillastriata gelatin/Salvia miltiorrhiza materials. Full-thickness area of skin was excised from the mice and subsequently, the composite corium was transplanted on the wound. Thereafter, the growth difference of the composite artificial corium and natural corium were compared. In addition, real-time fluorogenic reverse transcription polymerase chain reaction (qRT-PCR) and western blot were performed to determine vascular endothelial growth factor (VEGF) expression at gene and protein levels. Results: The composite artificial corium showed significant repair promoting effect on the skin, and the structure of the repaired skin was similar to that of natural corium. Interestingly, PCR and western blot results showed that the expressions of VEGF were higher in composite artificial corium than in natural corium on days 3 and 7 post-transplantation. Conclusion: The composite artificial corium has some clinical prospects for use in the treatment of wounds on large areas of skin.

Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Advanced electrospun nanofibrous mats for hindering delamination, improving damping and for sensing of composite laminates

Carbon Fiber Reinforced Polymers (CFRPs) display high specific mechanical properties, allowing the creation of lightweight components and products by metals replacement. To reach outstanding mechanical performances, the use of stiff thermoset matrices, like epoxy, is preferred. Laminated composites are commonly used for their ease of manipulation during object manufacturing. However, the natural anisotropic structure of laminates makes them vulnerable toward delamination. Moreover, epoxy-based CFRPs are very stiff materials, thus showing low damping capacity, which results in unwanted vibrations and structure-borne noise that may contribute to delamination triggering. Hence, searching for systems able to limit these drawbacks is of primary importance for safety reasons, as well as for economic ones. In this experimental thesis, the production and integration of innovative rubbery nanofibrous mats into CFRP laminates are presented. A smart approach, based on single-needle electrospinning of rubber-containing blends, is proposed for producing dimensionally stable rubbery nanofibers without the need for rubber crosslinking. Nano-modified laminates aim at obtaining structural composites with improved delamination resistance and enhanced damping capacity, without significantly lowering other relevant mechanical properties. The possibility of producing nanofibers nano-reinforced with graphene to be applied for reinforcing composite laminates is also investigated. Moreover, the use of piezoelectric nanofibrous mats in hybrid composite laminates for achieving self-sensing capability is presented too as a different approach to prevent the catastrophic consequences of possible structural laminate failure. Finally, an accurate, systematic, and critical study concerning tensile testing of nonwovens, using electrospun Nylon 66 random nanofibrous mats as a case study, is proposed. Nanofibers diameter and specimen geometry were investigated to thoroughly describe the nanomat tensile behaviour, also considering the polymer thermal properties, and the number of nanofibers crossings as a function of the nanofibers diameter. Stress-strain data were also analysed using a phenomenological data fitting model to interpret the tensile behaviour better.

Advanced numerical modeling of masonry vaulted structures based on BIM parametric geometry generation

Vaults are an architectural element which during construction history have been built with a great variety of different materials, shapes, and sizes. The shape of these structural elements was often dependent by the necessity to cover complex spaces, by the needed loading capacity, or by architectural aesthetics. Within this complex scenario masonry patterns generates also different effects on loading capacity, load percolation and stiffness of the structure. These effects were been extensively investigated, both with empirical observations and with modern numerical methods. While most of them focus on analyzing the load bearing capacity or the texture effect on vaulted structures, the aim of this analysis is to investigate on the effects of the variation of a single structural characteristic on the load percolation in the vault. Moreover, an additional purpose of the work is related to the coding of a parametrical model aiming at generating different masonry vaulted structures. Nevertheless, proposed script can generate different typology of vaulted structure basing on some structural characteristics, such as the span and the length to cover and the dimensions of the blocks.

Development of novel multi-substituted apatite nanophases with advanced functionalities for bone regeneration

In the field of bone substitutes is highly researched an innovative material able to fill gaps with high mechanical performances and able to stimulate cell response, permitting the complete restoration of the bone portion. In this respect, the synthesis of new bioactive materials able to mimic the compositional, morphological and mechanical features of bone is considered as the elective approach for effective tissue regeneration. Hydroxyapatite (HA) is the main component of the inorganic part of bone. Additionally ionic substitution can be performed in the apatite lattice producing different effects, depending from the selected ions. Magnesium, in substitution of calcium, and carbonate, in substitution of phosphate, extensively present in the biological bones, are able to improve properties naturally present in the apatitic phase, (i.e. biomimicry, solubility e osteoinductive properties). Other ions can be used to give new useful properties, like antiresorptive or antimicrobial properties, to the apatitic phase. This thesis focused on the development of hydroxyapatite nanophases with multiple ionic substitutions including gallium, or zinc ions, in association with magnesium and carbonate, with the purpose to provide double synergistic functionality as osteogenic and antibacterial biomaterial. Were developed bioactive materials based on Sr-substituted hydroxyapatite in the form of sintered targets. The obtained targets were treated with Pulsed Plasma Deposition (PED) resulting in the deposition of thin film coatings able to improve the roughness and wettability of PEEK, enhancing its osteointegrability. Were investigated heterogeneous gas-solid reactions, addressed to the biomorphic transformations of natural 3D porous structures into bone scaffolds with biomimetic composition and hierarchical organization, for application in load-bearing sites. The kinetics of the different reactions of the process were optimized to achieve complete and controlled phase transformation, maintaining the original 3-D morphology. Massive porous scaffolds made of ion-substituted hydroxyapatite and bone-mimicking structure were developed and tested in 3-D cell culture models.

Solutions for the conservation and restoration of cement-based materials in XX Century architectural heritage

Among the most representative materials of XX Century architectural heritage, this dissertation focuses on the cement-based ones, investigating some different fields where they were exploited. Primarily, concerning the surface preservation of cement-based materials used with aesthetic intent, new self-cleaning treatments based on titania nanoparticles embedded in inorganic matrices were tested. In order to consider the role of porosity, the treatments were applied to different kinds of materials (cement-based mortar, marble and concrete) and several analyses were conducted to investigate the morphology of the coatings, their photocatalytic effectiveness, their durability and the interaction between the coating and the substrate material. The outcomes showed that several parameters influence the treatment’s performances, in particular, the presence and nature of the matrix, the concentration and dispersion of nanoparticles and, in some cases, the amount of substrate material which interacts with the coatings. Secondly, this dissertation deals with the historic “Terranova” render, a colored dry-mix mortar largely widespread in Europe in the first half of XX Century, whose formulation is still basically unknown. Some original samples of supposedly Terranova renders were subjected to several characterization analyses and the results were compared to those of the original “Terranova” render of the Engineering Faculty in Bologna. Despite the recurrence of some features, defining a common formulation seemed to be challenging. Finally, the repair and conservation of structural reinforced concrete in heritage buildings were investigated, adopting the former “Casa del Fascio” in Predappio (FC, Italy) as case study. Three different materials and solutions were tested on a slab of the building, making its repair only from the intrados. Then several analyses were conducted both on site and in laboratory. Aside from the specific features characterizing every product, the results highlighted that the application method played a fundamental role in the effectiveness of the retrofit strategies.

Fluorogenic hyaluronan-based probe: characterization and use in advanced microscopy

Among all, the application of nanomaterials in biomedical research and most recently in the environmental one has opened the fields of nanomedicine and nanoremediation. Sensing methods based on fluorescence optical probe are generally requested for their selectivity, sensitivity. However, most imaging methods in literature rely on a fluorescent covalent labelling of the system. Therefore, the main aim of this project was to synthetise a biocompatible fluorogenic hyaluronan probe (HA) polymer functionalised with a rhomadine B (RB) moieties and study its behaviour as an optical probe with different materials with microscopy techniques. A derivatization of HA with RB (HA-RB) was successfully obtained providing a photophysical characterization showing a particular fluorescence mechanism of the probe. Firstly, we tested the interaction with different lab-grade micro and nanoplastics in water. Thanks to the peculiar photophysical behaviour of the probe nanoplastics can be detected with confocal microscopy and more interestingly their nature can be discriminated based on the fluorescence lifetime decay with FLIM microscopy. After, the interaction of a model plant derived metabolic enzyme GAPC1 undergoing oxidative-triggered aggregation was explored with the HA-RB. We highlighted the probe interaction with the protein even at early stage of the kinetic. Moreover, nanoparticle tracking analysis (NTA) experiment demonstrates that the probe is in fact able to interact with the small pre-aggregates in the early stage of the aggregation kinetic. Ultimately, we focused on the possibility to apply the probe in a super resolution microscopy technique, PALM, exploiting its aspecific interaction to characterize the surface topography of PTFE polydisperse microplastics. Optimal conditions were reached at high concentration of the probe (70 nM) where 0.5-5 nM is always advisable for this technique. Thanks to the polymeric nature and fluorescence mechanism of the probe, this technique was able to reveal features of PTFE surface under the diffraction limit (< 250 nm).