Multiproperty correlation of experimental data of the binaries propyl ethanoate+alkanes (pentane to decane). New experimental information for vapor-liquid equilibrium and mixing properties

[EN]A thermodynamic study is carried out on binary systems composed of propyl ethanoate with six alkanes, from pentane to decane. Vapor pressures of the ester and the isobaric vapor−liquid equilibria of these six mixtures were measured at 101.32 kPa in a small-capacity ebulliometer and also the mixing properties yE = vE,hE over a range of temperatures and at atmospheric pressure. Adequate correlations are drawn for the surfaces yE = yE(x,T) with an interpretation on the behavior of the mixtures and also using cp E data from literature.

An equilibrium approach to modelling social interaction

The aim of this work is to put forward a statistical mechanics theory of social interaction, generalizing econometric discrete choice models. After showing the formal equivalence linking econometric multinomial logit models to equilibrium statical mechanics, a multi- population generalization of the Curie-Weiss model for ferromagnets is considered as a starting point in developing a model capable of describing sudden shifts in aggregate human behaviour. Existence of the thermodynamic limit for the model is shown by an asymptotic sub-additivity method and factorization of correlation functions is proved almost everywhere. The exact solution for the model is provided in the thermodynamical limit by nding converging upper and lower bounds for the system's pressure, and the solution is used to prove an analytic result regarding the number of possible equilibrium states of a two-population system. The work stresses the importance of linking regimes predicted by the model to real phenomena, and to this end it proposes two possible procedures to estimate the model's parameters starting from micro-level data. These are applied to three case studies based on census type data: though these studies are found to be ultimately inconclusive on an empirical level, considerations are drawn that encourage further refinements of the chosen modelling approach, to be considered in future work.

Stability, viscous dissipation and local thermal non-equilibrium in fluid saturated porous media

In this thesis, the field of study related to the stability analysis of fluid saturated porous media is investigated. In particular the contribution of the viscous heating to the onset of convective instability in the flow through ducts is analysed. In order to evaluate the contribution of the viscous dissipation, different geometries, different models describing the balance equations and different boundary conditions are used. Moreover, the local thermal non-equilibrium model is used to study the evolution of the temperature differences between the fluid and the solid matrix in a thermal boundary layer problem. On studying the onset of instability, different techniques for eigenvalue problems has been used. Analytical solutions, asymptotic analyses and numerical solutions by means of original and commercial codes are carried out.

Non-equilibrium molecular dynamics study of an amphiphilic model system

Diese Doktorarbeit untersucht das Verhalten von komplexenFluidenunter Scherung, insbesondere den Einfluss von Scherflüssenauf dieStrukturbildung.Dazu wird ein Modell dieser entworfen, welches imRahmen von Molekulardynamiksimulationen verwendet wird.Zunächst werden Gleichgewichtseigenschaften dieses Modellsuntersucht.Hierbei wird unter anderem die Lage desOrdnungs--Unordnungsübergangs von derisotropen zur lamellaren Phase der Dimere bestimmt.Der Einfluss von Scherflüssen auf diese lamellare Phase wirdnununtersucht und mit analytischen Theorien verglichen. Die Scherung einer parallelen lamellaren Phase ruft eineNeuausrichtung des Direktors in Flussrichtung hervor.Das verursacht eine Verminderung der Schichtdicke mitsteigender Scherrateund führt oberhalb eines Schwellwertes zu Ondulationen.Ein vergleichbares Verhalten wird auch in lamellarenSystemengefunden, an denen in Richtung des Direktors gezogen wird.Allerdings wird festgestellt, dass die Art der Bifurkationenin beidenFällen unterschiedlich ist.Unter Scherung wird ein Übergang von Lamellen parallelerAusrichtung zu senkrechter gefunden.Dabei wird beoachtet, dass die Scherspannung in senkrechterOrientierungniedriger als in der parallelen ist.Dies führt unter bestimmten Bedingungen zum Auftreten vonScherbändern, was auch in Simulationen beobachtet wird. Es ist gelungen mit einem einfachen Modell viele Apsekte desVerhalten vonkomplexen Fluiden wiederzugeben. Die Strukturbildung hängt offensichtlich nurbedingt von lokalen Eigenschaften der Moleküle ab.

Biomedical and industrial applications of atmospheric pressure non-equilibrium plasmas

This dissertation will be focused on the characterization of an atmospheric pressure plasma jet source with an application oriented diagnostic approach and the description of processes supported by this plasma source. The plasma source investigated is a single electrode plasma jet. Schlieren images, optical emission spectra, temperature and heat flux profiles are analyzed to deeply investigate the fluid dynamic, the chemical composition and the thermal output of the plasma generated with a nanosecond-pulsed high voltage generator. The maximum temperature measured is about 45 °C and values close to the room temperature are reached 10 mm down the source outlet, ensuring the possibility to use the plasma jet for the treatment of thermosensitive materials, such as, for example, biological substrate or polymers. Electrospinning of polymeric solution allows the production of nanofibrous non-woven mats and the plasma pre-treatment of the solutions leads to the realization of defect free nanofibers. The use of the plasma jet allows the electrospinnability of a non-spinnable poly(L-lactic acid) (PLLA) solution, suitable for the production of biological scaffold for the wound dressing.

The effect of elastic modulus and equilibrium vapor adsorption on capillary forces

Die Kapillarkraft entsteht durch die Bildung eines Meniskus zwischen zwei Festkörpen. In dieser Doktorarbeit wurden die Auswirkungen von elastischer Verformung und Flϋssigkeitadsorption auf die Kapillarkraft sowohl theoretisch als auch experimentell untersucht. Unter Verwendung eines Rasterkraftmikroskops wurde die Kapillarkraft zwischen eines Siliziumoxid Kolloids von 2 µm Radius und eine weiche Oberfläche wie n.a. Polydimethylsiloxan oder Polyisopren, unter normalen Umgebungsbedingungen sowie in variierende Ethanoldampfdrϋcken gemessen. Diese Ergebnisse wurden mit den Kapillarkräften verglichen, die auf einem harten Substrat (Silizium-Wafer) unter denselben Bedingungen gemessen wurden. Wir beobachteten eine monotone Abnahme der Kapillarkraft mit zunehmendem Ethanoldampfdruck (P) fϋr P/Psat > 0,2, wobei Psat der Sättigungsdampfdruck ist.rnUm die experimentellen Ergebnisse zu erklären, wurde ein zuvor entwickeltes analytisches Modell (Soft Matter 2010, 6, 3930) erweitert, um die Ethanoladsorption zu berϋcksichtigen. Dieses neue analytische Modell zeigte zwei verschiedene Abhängigkeiten der Kapillarkraft von P/Psat auf harten und weichen Oberflächen. Fϋr die harte Oberfläche des Siliziumwafers wird die Abhängigkeit der Kapillarkraft vom Dampfdruck vom Verhältnis der Dicke der adsorbierten Ethanolschicht zum Meniskusradius bestimmt. Auf weichen Polymeroberflächen hingegen hängt die Kapillarkraft von der Oberflächenverformung und des Laplace-Drucks innerhalb des Meniskus ab. Eine Abnahme der Kapillarkraft mit zunehmendem Ethanoldampfdruck hat demnach eine Abnahme des Laplace-Drucks mit zunehmendem Meniskusradius zur folge. rnDie analytischen Berechnungen, fϋr die eine Hertzsche Kontakt-deformation angenommen wurde, wurden mit Finit Element Methode Simulationen verglichen, welche die reale Deformation des elastischen Substrats in der Nähe des Meniskuses explizit berϋcksichtigen. Diese zusätzliche nach oben gerichtete oberflächenverformung im Bereich des Meniskus fϋhrt zu einer weiteren Erhöhung der Kapillarkraft, insbesondere fϋr weiche Oberflächen mit Elastizitätsmodulen < 100 MPa.rn

Relationship between DIAGNOdent values and sealant penetration depth on occlusal fissures

The aim of this in vitro study was to evaluate the relationship between laser fluorescence values and sealant penetration depth on occlusal fissures. One hundred and sixty-six permanent molars were selected and divided into four groups, which were each treated using a different sealant (two clear and two opaque). The teeth were independently measured twice by two experienced dentists using two laser fluorescence devices-DIAGNOdent (LF and LFpen)-before and after sealing, and then thermoclycled. After measuring, the teeth were histologically prepared and assessed for caries extension. Digital photographs of the cut sealed sites were assessed, and the sealant penetration depth was measured. All 166 sites were measured by one of the examiners taking as limits the outer and inner surface of the sealant into the fissure. For each device (LF and LFpen) and each group, the difference between the values at baseline and after sealing was plotted against the sealant penetration depth and scatter plots were provided. It could be observed that most of the points were concentrated around the zero line, for both LF and LFpen in the four groups. In conclusion, there is no relation between changes in DIAGNOdent values and increasing of depth sealant penetration within the occlusal fissures.

Performance of laser fluorescence devices, visual and radiographic examination for the detection of occlusal caries in primary molars

The aim of this in vitro study was to compare the performance of two laser fluorescence devices (LF, LFpen), conventional visual criteria (VE), ICDAS and radiographic examination on occlusal surfaces of primary teeth. Thirty-seven primary human molars were selected from a pool of extracted teeth, which were stored frozen at -20°C until use. Teeth were assessed twice by two experienced examiners using laser fluorescence devices (LF and LFpen), conventional visual criteria, ICDAS and bitewing radiographs, with a 2-week interval between measurements. After measurement, the teeth were histologically prepared and assessed for caries extension. The highest sensitivity was observed for ICDAS at D(1) and D(3) thresholds, with no statistically significant difference when compared to the LF devices, except at the D(3) threshold. Bitewing radiographs presented the lowest values of sensitivity. Specificity at D(1) was higher for LFpen (0.90) and for VE at D(3) (0.94). When VE was combined with LFpen the post-test probabilities were the highest (94.0% and 89.2% at D(1) and D(3) thresholds, respectively). High values were observed for the combination of ICDAS and LFpen (92.0% and 80.0%, respectively). LF and LFpen showed the highest values of ICC for interexaminer reproducibility. However, regarding ICDAS, BW and VE, intraexaminer reproducibility was not the same for the two examiners. After primary visual inspection using ICDAS or not, the use of LFpen may aid in the detection of occlusal caries in primary teeth. Bitewing radiographs may be indicated only for approximal caries detection.

Influence of examiner's clinical experience on the reproducibility and accuracy of radiographic examination in detecting occlusal caries

The aim of this in vitro study was to assess the influence of varying examiner's clinical experience on the reproducibility and accuracy of radiographic examination for occlusal caries detection. Standardized bitewing radiographs were obtained from 166 permanent molars. Radiographic examination was performed by final-year dental students from two universities (A, n = 5; B, n = 5) and by dentists with 5 to 7 years of experience who work in two different countries (C, n = 5; D, n = 5). All examinations were repeated after 1-week interval. The teeth were histologically prepared and assessed for caries extension. For intraexaminer reproducibility, the unweighted kappa values were: A (0.11-0.40), B (0.12-0.33), C (0.47-0.58), and D (0.42-0.71). Interexaminer reproducibility statistics were computed based on means ± SD of unweighted kappa values: A (0.07 ± 0.05), B (0.12 ± 0.09), C (0.24 ± 0.08), and D (0.33 ± 0.10). Sensitivity, specificity, and accuracy were calculated at D(1) and D(3) thresholds and compared by performing McNemar test (p = 0.05). D(1) sensitivity ranged between 0.29 and 0.75 and specificity between 0.24 and 0.85. D(3) specificity was moderate to high (between 0.62 and 0.95) for all groups, with statistically significant difference between the dentists groups (C and D). Sensitivity was low to moderate (between 0.21 and 0.57) with statistically significant difference for groups B and D. Accuracy was similar for all groups (0.55). Spearman's correlations were: A (0.12), B (0.24), C (0.30), and D (0.38). In conclusion, the reproducibility of radiographic examination was influenced by the examiner's clinical experience, training, and dental education as well as the accuracy in detecting occlusal caries.

Light-emitting diode and laser fluorescence-based devices in detecting occlusal caries

The aim of this study was to assess the performance of two light-emitting diode (LED)- and two laser fluorescence-based devices in detecting occlusal caries in vitro. Ninety-seven permanent molars were assessed twice by two examiners using two LED- (Midwest Caries - MID and VistaProof - VP) and two laser fluorescence-based (DIAGNOdent 2095 - LF and DIAGNOdent pen 2190 - LFpen) devices. After measuring, the teeth were histologically prepared and classified according to lesion extension. At D1 the specificities were 0.76 (LF and LFpen), 0.94 (MID), and 0.70 (VP); the sensitivities were 0.70 (LF), 0.62 (LFpen), 0.31 (MID), and 0.75 (VP). At D(3) threshold the specificities were 0.88 (LF), 0.87 (LFpen), 0.90 (MID), and 0.70 (VP); the sensitivities were 0.63 (LF and LFpen), 0.70 (MID), and 0.96 (VP). Spearman's rank correlations with histology were 0.56 (LF), 0.51 (LFpen), 0.55 (MID), and 0.58 (VP). Inter- and intraexaminer ICC values were high and varied from 0.83 to 0.90. Both LF devices seemed to be useful auxiliary tools to the conventional methods, presenting good reproducibility and better accuracy at D(3) threshold. MID was not able to differentiate sound surfaces from enamel caries and VP still needs improvement on the cut-off limits for its use.

Influence of different professional prophylactic methods on fluorescence measurements for detection of occlusal caries

This study aimed to evaluate the influence of professional prophylactic methods on the DIAGNOdent 2095, DIAGNOdent 2190 and VistaProof performance in detecting occlusal caries. Assessments were performed in 110 permanent teeth at baseline and after bicarbonate jet or prophylactic paste and rinsing. Performance in terms of sensitivity improved after rinsing of the occlusal surfaces when the prophylactic paste was used. However, the sodium bicarbonate jet did not significantly influence the performance of the fluorescence-based methods. It can be concluded that different professional prophylactic methods can significantly influence the performance of fluorescence-based methods for occlusal caries detection.

In situ and in vitro comparison of laser fluorescence with visual inspection in detecting occlusal caries lesions

The aim of this study was to compare the in situ and in vitro performances of a laser fluorescence (LF) device (DIAGNOdent 2095) with visual inspection for the detection of occlusal caries in permanent teeth. Sixty-four sites were selected, and visual inspection and LF assessments were carried out, in vitro, three times by two independent examiners, with a 1-week interval between evaluations. Afterwards, the occlusal surfaces were mounted on the palatal portion of removable acrylic orthodontic appliances and placed in six volunteers. Assessments were repeated and validated by histological analysis of the tooth sections under a stereomicroscope. For both examiners, the highest intra-examiner values were observed for the visual inspection when in vitro and in situ evaluations were compared. The inter-examiner reproducibility varied from 0.61 to 0.64, except for the in vitro assessment using LF, which presented a lower value (0.43). The methods showed high specificity at the D(1) threshold (considering enamel and dentin caries as disease). In vitro evaluations showed the highest values of sensitivity for both methods when compared to the in situ evaluations at D(1) and D(2) (considering only dentinal caries as the disease) thresholds. For both methods, the results of sensitivity (at D(1) and D(2)) and accuracy (at D(1)) showed significant differences between in vitro and in situ conditions. However, the sensitivity (at D(1) and D(2)), specificity and accuracy (both at D(1)) of the methods were not significantly different when the same condition was considered. It can be concluded that visual inspection and LF showed better performance in vitro than in situ.

Comparison among gold standard techniques used for the validation of methods for occlusal caries detection

The aim of this in vitro study was to assess the agreement among four techniques used as gold standard for the validation of methods for occlusal caries detection. Sixty-five human permanent molars were selected and one site in each occlusal surface was chosen as the test site. The teeth were cut and prepared according to each technique: stereomicroscopy without coloring (1), dye enhancement with rhodamine B (2) and fuchsine/acetic light green (3), and semi-quantitative microradiography (4). Digital photographs from each prepared tooth were assessed by three examiners for caries extension. Weighted kappa, as well as Friedman's test with multiple comparisons, was performed to compare all techniques and verify statistical significant differences. Results: kappa values varied from 0.62 to 0.78, the latter being found by both dye enhancement methods. Friedman's test showed statistical significant difference (P < 0.001) and multiple comparison identified these differences among all techniques, except between both dye enhancement methods (rhodamine B and fuchsine/acetic light green). Cross-tabulation showed that the stereomicroscopy overscored the lesions. Both dye enhancement methods showed a good agreement, while stereomicroscopy overscored the lesions. Furthermore, the outcome of caries diagnostic tests may be influenced by the validation method applied. Dye enhancement methods seem to be reliable as gold standard methods.