The role of paved surfaces in the Urban Heat Island phenomenon: Assessment of fundamental thermal parameters and finite element analysis for UHI mitigation

Nowadays the environmental issues and the climatic change play fundamental roles in the design of urban spaces. Our cities are growing in size, many times only following immediate needs without a long-term vision. Consequently, the sustainable development has become not only an ethical but also a strategic need: we can no longer afford an uncontrolled urban expansion. One serious effect of the territory industrialisation process is the increase of urban air and surfaces temperatures compared to the outlying rural surroundings. This difference in temperature is what constitutes an urban heat island (UHI). The purpose of this study is to provide a clarification on the role of urban surfacing materials in the thermal dynamics of an urban space, resulting in useful indications and advices in mitigating UHI. With this aim, 4 coloured concrete bricks were tested, measuring their emissivity and building up their heat release curves using infrared thermography. Two emissivity evaluation procedures were carried out and subsequently put in comparison. Samples performances were assessed, and the influence of the colour on the thermal behaviour was investigated. In addition, some external pavements were analysed. Albedo and emissivity parameters were evaluated in order to understand their thermal behaviour in different conditions. Surfaces temperatures were recorded in a one-day measurements campaign. ENVI-met software was used to simulate how the tested materials would behave in two typical urban scenarios: a urban canyon and a urban heat basin. Improvements they can carry to the urban microclimate were investigated. Emissivities obtained for the bricks ranged between 0.92 and 0.97, suggesting a limited influence of the colour on this parameter. Nonetheless, white concrete brick showed the best thermal performance, whilst the black one the worst; red and yellow ones performed pretty identical intermediate trends. De facto, colours affected the overall thermal behaviour. Emissivity parameter was measured in the outdoor work, getting (as expected) high values for the asphalts. Albedo measurements, conducted with a sunshine pyranometer, proved the improving effect given by the yellow paint in terms of solar reflection, and the bad influence of haze on the measurement accuracy. ENVI-met simulations gave a demonstration on the effectiveness in thermal improving of some tested materials. In particular, results showed good performances for white bricks and granite in the heat basin scenario, and painted concrete and macadam in the urban canyon scenario. These materials can be considered valuable solutions in UHI mitigation.

Controlled wetting on silica-based nano- and microstructured surfaces

Der Fokus dieser Doktorarbeit liegt auf der kontrollierten Benetzung von festen Oberflächen, die in vielen Bereichen, wie zum Beispiel in der Mikrofluidik, für Beschichtungen und in biologischen Studien von Zellen oder Bakterien, von großer Bedeutung ist.rnDer erste Teil dieser Arbeit widmet sich der Frage, wie Nanorauigkeit das Benetzungsverhalten, d.h. die Kontaktwinkel und die Pinningstärke, von hydrophoben und superhydrophoben Beschichtungen beeinflusst. Hierfür wird eine neue Methode entwickelt, um eine nanoraue Silika-Beschichtung über die Gasphase auf eine superhydrophobe Oberfläche, die aus rauen Polystyrol-Silika-Kern-Schale-Partikeln besteht, aufzubringen. Es wird gezeigt, dass die Topographie und Dichte der Nanorauigkeiten bestimmt, ob sich die Superhydrophobizität verringert oder erhöht, d.h. ob sich ein Flüssigkeitstropfen im Nano-Wenzel- oder Nano-Cassie-Zustand befindet. Das verstärkte Pinning im Nano-Wenzel-Zustand beruht auf dem Eindringen von Flüssigkeitsmolekülen in die Nanoporen der Beschichtung. Im Nano-Cassie-Zustand dagegen sitzt der Tropfen auf den Nanorauigkeiten, was das Pinning vermindert. Die experimentellen Ergebnisse werden mit molekulardynamischen Simulationen in Bezug gesetzt, die den Einfluss der Oberflächenbeschichtungsdichte und der Länge von fluorinierten Silanen auf die Hydrophobizität einer Oberfläche untersuchen. rnEs wurden bereits verschiedenste Techniken zur Herstellung von transparenten superhydrophoben, d.h. extrem flüssigkeitsabweisenden, Oberflächen entwickelt. Eine aktuelle Herausforderung liegt darin, Funktionalitäten einzuführen, ohne die superhydrophoben Eigenschaften einer Oberfläche zu verändern. Dies ist extrem anspruchsvoll, da funktionelle Gruppen in der Regel hydrophil sind. In dieser Arbeit wird eine innovative Methode zur Herstellung von transparenten superhydrophoben Oberflächen aus Janus-Mikrosäulen mit variierenden Dimensionen und Topographien entwickelt. Die Janus-Säulen haben hydrophobe Seitenwände und hydrophile Silika-Oberseiten, die anschließend selektiv und ohne Verlust der superhydrophoben Eigenschaften der Oberfläche funktionalisiert werden können. Diese selektive Oberflächenfunktionalisierung wird mittels konfokaler Mikroskopie und durch das chemische Anbinden von fluoreszenten Molekülen an die Säulenoberseiten sichtbar gemacht. Außerdem wird gezeigt, dass das Benetzungsverhalten durch Wechselwirkungen zwischen Flüssigkeit und Festkörper in der Nähe der Benetzungslinie bestimmt wird. Diese Beobachtung widerlegt das allgemein akzeptierte Modell von Cassie und Baxter und beinhaltet, dass hydrophile Flächen, die durch mechanischen Abrieb freigelegt werden, nicht zu einem Verlust der Superhydrophobizität führen müssen, wie allgemein angenommen.rnBenetzung kann auch durch eine räumliche Beschränkung von Flüssigkeiten kontrolliert werden, z.B. in mikrofluidischen Systemen. Hier wird eine modifizierte Stöber-Synthese verwendet, um künstliche und natürliche Faser-Template mit einer Silika-Schicht zu ummanteln. Nach der thermischen Zersetzung des organischen Templat-Materials entstehen wohldefinierte Silika-Kanäle und Kanalkreuzungen mit gleichmäßigen Durchmessern im Nano- und Mikrometerbereich. Auf Grund ihrer Transparenz, mechanischen Stabilität und des großen Länge-zu-Durchmesser-Verhältnisses sind die Kanäle sehr gut geeignet, um die Füllgeschwindigkeiten von Flüssigkeiten mit variierenden Oberflächenspannungen und Viskositäten zu untersuchen. Konfokale Mikroskopie ermöglicht es hierbei, die Füllgeschwindigkeiten über eine Länge von mehreren Millimetern, sowie direkt am Kanaleingang zu messen. Das späte Füllstadium kann sehr gut mit der Lucas-Washburn-Gleichung beschrieben werden. Die anfänglichen Füllgeschwindigkeiten sind jedoch niedriger als theoretisch vorhergesagt. Wohingegen die vorhergehenden Abschnitte dieser Arbeit sich mit der quasistatischen Benetzung beschäftigen, spielt hier die Dynamik der Benetzung eine wichtige Rolle. Tatsächlich lassen sich die beobachteten Abweichungen durch einen geschwindigkeitsabhängigen Fortschreitkontaktwinkel erklären und durch dynamische Benetzungstheorien modellieren. Somit löst diese Arbeit das seit langem diskutierte Problem der Abweichungen von der Lucas-Washburn-Gleichung bei kleinen Füllgeschwindigkeiten.

The wind profile in the atmospheric stable boundary layer over complex terrain and heterogeneous surfaces: limitations of local similarity theory

L'indagine ha riguardato il profilo del vento nei primi 30 metri dello strato limite atmosferico stabile nell'ambito della teoria di similarità locale. Ad oggi, diversi esperimenti hanno confermato la validità della teoria per strati-limite su terreni livellati e superfici omogenee. Tali condizioni ideali sono però infrequenti nella realtà ed è perciò importante capire quali siano i limiti della similarità locale per strati-limite su terreni complessi e superfici disomogenee. Entrambe le condizioni sono presenti a Ny-Alesund (Svalbard, Norvegia) dove il Consiglio Nazionale delle Ricerche (CNR), nel 2009, ha installato una torre di 30 m, la Amudsen-Nobile Climate Change Tower (CCT), per lo studio dello strato-limite artico. Il lavoro di tesi ha riguardato misure di vento e turbolenza acquisite sulla CCT da maggio 2012 a maggio 2014. Il confronto tra le velocità del vento misurate dagli anemometri installati sulla CCT, ha rivelato criticità nel dato sonico manifestatesi con sovrastime sistematiche e maggiore erraticità rispetto alle misure provenienti dagli anemometri a elica. Un test condotto fra diversi metodi per il calcolo dei gradienti verticali della velocità del vento ha rivelato scarsa sensibilità dei risultati ottenuti al particolare metodo utilizzato. Lo studio ha riguardato i gradienti verticali adimensionali della velocità del vento nei primi 30-m dello strato limite stabile. Deviazioni significative tra i tra le osservazioni e i valori predetti dalla similarità locale sono state osservate in particolare per i livelli più distanti dal suolo e per valori crescenti del parametro di stabilità z/L (L, lunghezza di Obukhov locale). In particolare, si sono osservati gradienti adimensionali inferiori a quelli predetti dalle più usate relazioni di flusso-gradiente. Tali deviazioni, presenti perlopiù per z/L>0.1, sono state associate ad un effetto di accentuazione della turbolenza da parte delle irregolarità del terreno. Per condizioni meno stabili, z/L<0.1, scarti positivi tra i gradienti osservati e quelli attesi sono stati attribuiti alla formazione di strati limite interni in condizioni di vento dal mare verso la costa. Sono stati proposti diversi metodi per la stima dell'effetto della self-correlazione nella derivazione delle relazioni di flusso-gradiente, dovuta alla condivisione della variabile u*. La formula per il coefficiente lineare di self correlazione e le sue distribuzioni di probabilità empiriche sono state derivate e hanno permesso di stimare il livello di self-correlazione presente nel dataset considerato.

In vitro detection of secondary caries associated with composite restorations on approximal surfaces using laser fluorescence

This study evaluated the performance of the DIAGNOdent pen laser fluorescence device (LFpen) in comparison with visual examination (VE), bitewing radiographs (BW) and visual examination combined with bitewing radiographs (VEBW) in detecting secondary approximal caries associated with composite restorations. In total, 60 approximal surfaces from 43 permanent molars with composite restorations were assessed twice by two examiners using the LFpen, VE, BW and VEBW. After histological preparation and hardness measurements, the sample was assigned to either a crown or root caries group, depending on the location of the lesions as the gold standard. For crown caries at D1, the highest values of specificity and sensitivity were observed for the LFpen at a cutoff value of 18 (1.00) and for the VEBW (0.89). At D3 (cutoff of 30), the LFpen showed the highest values of sensitivity and specificity. For root caries, the LFpen and VEBW showed the highest values of specificity (0.54), sensitivity (0.81) and accuracy (0.69). The Spearman rank correlation coefficients for crown/root caries with histology were 0.54/0.37 (LFpen), 0.29/0.10 (BW), 0.29/0.18 (VE) and 0.23/0.37 (VEBW). For the LFpen, the ICC varied from 0.80 (interexaminer) to 0.97 (intraexaminer B); the kappa value was 0.19 for BW and 0.35 for VE (interexaminer). Intraexaminer kappa values for BW were 0.25 (A) and 0.29 (B), and those for VE were 0.31 (A) and 0.32 (B). The LFpen device exhibited a performance comparable to that of conventional methods but with higher interexaminer reproducibility. Therefore, the LFpen should be considered an auxiliary method for the detection of secondary approximal caries associated with composite restorations.

Formation of caries-like lesions in vitro on the root surfaces of human teeth in solutions simulating plaque fluid

Lesion formation on root surfaces of human posterior teeth was studied in acetate/lactate buffers with a background electrolyte composition based on plaque fluid analyses. Lesion depth after 28 days at 37 degrees C was measured in relation to: the presence or absence of cementum; the concentration of undissociated buffer; the presence or absence of magnesium ions at plaque fluid concentration. Each factor was evaluated at several values of -log(ion activity product for hydroxyapatite): pI(HA). Solutions were formulated to minimize variation in pH, which varied by < or =0.03 for a given comparison (individual pI(HA)) and by 0.42-0.82 over the range of pI(HA) within experiments. Lesions on surfaces from which cementum had been ground were significantly deeper than on intact surfaces, but this is considered to be due to subsurface mechanical damage and not to a solubility difference. Neither the concentration of undissociated buffer nor the presence of magnesium ions significantly affected lesion depth. Lesion depth was strongly influenced by the correlated variations in pI(HA) and pH. At pI(HA) 54 and 55, only extremely shallow lesions formed. From pI(HA) 56, lesion depth increased with increasing pI(HA). The results confirm that the solubility of the mineral of root tissues is higher than that of hydroxyapatite, but indicate that it is probably lower than suggested by Hoppenbrouwers et al. [Arch Oral Biol 1987;32:319-322]. For calcium concentrations of 3-12 mM, the critical pH for root tissue mineral was calculated as 5.22-5.66 assuming solubility equivalent to pI(HA) 54 and 5.08-5.51 assuming pI(HA) 55.

A minimally destructive technique for removing the smear layer from dentine surfaces

OBJECTIVES: To develop a minimally destructive technique for removing the smear layer produced by cutting and polishing specimens of dentine prepared for use in experimental studies, e.g. on occlusion of dentinal tubules by oral health products. The aim was to avoid the damage caused by conventional techniques utilising short exposures to solutions with very low pH. METHODS: Two acetate buffers, pH 5.5, containing different concentrations of calcium and phosphate, with -log(ion activity product with respect to hydroxyapatite) (pI(HA)) of 55 or 56, were tested on slices of dentine using scanning electron microscopy (SEM). RESULTS: A solution which, from previous work, was slightly undersaturated with respect to dentine mineral, with a pI(HA) of 56, was found to remove smear layers produced by cutting and/or polishing after 15 min. However, to reliably remove debris occluding the tubules an exposure time of 2h, followed by brief ultrasonication, was necessary. After 2h treatment with this buffer, only a small amount of demineralization of the surface was detectable by SEM, while calcium and phosphorus were detectable by X-ray dispersive spectroscopy. CONCLUSION: It is possible to remove smear layers, and to open dentinal tubules, by a reasonably short exposure to an acidic buffer which is undersaturated with respect to dentine mineral.

Killing of bacteria by copper surfaces involves dissolved copper

Bacteria are rapidly killed on copper surfaces. However, the mechanism of this process remains unclear. Using Enterococcus hirae, the effect of inactivation of copper homeostatic genes and of medium compositions on survival and copper dissolution was tested. The results support a role for dissolved copper ions in killing.

The role of bone debris in early healing adjacent to hydrophilic and hydrophobic implant surfaces in man

To evaluate morphologically and morphometrically the sequential healing and osseointegration events at moderately rough implant surfaces with and without chemical modification. Particularly the role of bone debris in initiating bone formation was emphasized.

Early osseointegration to hydrophilic and hydrophobic implant surfaces in humans

To evaluate the rate and degree of osseointegration at chemically modified moderately rough, hydrophilic (SLActive) and moderately rough, hydrophobic (SLA) implant surfaces during early phases of healing in a human model.

Self-assembly of focal point oligo-catechol ethylene glycol dendrons on titanium oxide surfaces: adsorption kinetics, surface characterization, and nonfouling properties

This work covers the synthesis of second-generation, ethylene glycol dendrons covalently linked to a surface anchor that contains two, three, or four catechol groups, the molecular assembly in aqueous buffer on titanium oxide surfaces, and the evaluation of the resistance of the monomolecular adlayers against nonspecific protein adsorption in contact with full blood serum. The results were compared to those of a linear poly(ethylene glycol) (PEG) analogue with the same molecular weight. The adsorption kinetics as well as resulting surface coverages were monitored by ex situ spectroscopic ellipsometry (VASE), in situ optical waveguide lightmode spectroscopy (OWLS), and quartz crystal microbalance with dissipation (QCM-D) investigations. The expected compositions of the macromolecular films were verified by X-ray photoelectron spectroscopy (XPS). The results of the adsorption study, performed in a high ionic strength ("cloud-point") buffer at room temperature, demonstrate that the adsorption kinetics increase with increasing number of catechol binding moieties and exceed the values found for the linear PEG analogue. This is attributed to the comparatively smaller and more confined molecular volume of the dendritic macromolecules in solution, the improved presentation of the catechol anchor, and/or their much lower cloud-point in the chosen buffer (close to room temperature). Interestingly, in terms of mechanistic aspects of "nonfouling" surface properties, the dendron films were found to be much stiffer and considerably less hydrated in comparison to the linear PEG brush surface, closer in their physicochemical properties to oligo(ethylene glycol) alkanethiol self-assembled monolayers than to conventional brush surfaces. Despite these differences, both types of polymer architectures at saturation coverage proved to be highly resistant toward protein adsorption. Although associated with higher synthesis costs, dendritic macromolecules are considered to be an attractive alternative to linear polymers for surface (bio)functionalization in view of their spontaneous formation of ultrathin, confluent, and nonfouling monolayers at room temperature and their outstanding ability to present functional ligands (coupled to the termini of the dendritic structure) at high surface densities.

AM1 and PM3 Calculations of the Potential Energy Surfaces for CH2OH Reactions with NO and NO2

The AM1 and PM3 molecular orbital methods have been utilized to investigate the reactions of CH20H with NO and NO2 PM3 and AM1 calculated heats of formation differ from experimental values by 8.6 and 18.8 kcal mol-', respectively. The dominant reaction of CH20H with NO is predicted to produce the adduct HOCH2N0, supporting the hypothesis of Pagsberg, Munk, Anastasi, and Simpson. Calculated activation energies for the NO2 system predict the formation of the adducts HOCH2N02 and HOCH20N0. In addition, the PM3 calculations predict that the abstraction reaction producing CH20 and HN02 is more likely than one producing CH20 and HONO from reactions of CH20H with NO2.

Exploration of the Potential Energy Surfaces, Prediction of Atmospheric Concentrations, and Prediction of Vibrational Spectra for the HO2···(H2O)n (n = 1−2) Hydrogen Bonded Complexes

The hydroperoxy radical (HO2) plays a critical role in Earth's atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work, we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concentrations and vibrational spectra of these complexes. We predict that when the HO2 concentration is on the order of 108molecules·cm-3 at 298 K, that the number of HO2···H2O complexes is on the order of 107molecules·cm-3 and the number of HO2···(H2O)2 complexes is on the order of 106molecules·cm-3. Using the computed abundance of HO2···H2O, we predict that, at 298 K, the bimolecular rate constant for HO2···H2O + HO2 is about 10 times that for HO2 + HO2.