Two-degree-of-freedom vortex-induced vibration of circular cylinders with very low aspect ratio and small mass ratio

The investigation of vortex-induced vibration on very short cylinders with two degrees of freedom has drawn the attention of a large number of researchers. Some investigations on such a problem are carried out in order to have a better understanding of the physics involved in vortex-induced motions of floating bodies such as offshore platforms. In this paper, experiments were carried out in a recirculating water channel over the range of Reynolds number 6000of cylinders with two degrees of freedom, three different small mass ratios (m⁎=1.00; 2.62 and 4.36) and very low aspect ratios (0.3≤L/D≤2.0) were shown and the results were discussed in depth. Conversely to what would be expected for cylinders with very low aspect ratio, the results showed large motions in the transverse direction with maximum amplitudes around 1.5 diameters for cylinders with L/D=2.0, despite being smaller when the aspect ratio is reduced. Moreover, the response amplitudes presented high values around 0.4 diameters in the in-line direction. In fact, the large transverse motions were related to a strong coupling with the in-line responses, visibly identified in the plots of nondimensional frequency, as well as by the trajectories in the XY-plane, Lissajous figures, particularly in the case of m⁎=1.00 and L/D=2.0, when 8-shape trajectories were clearly observed. The case of m⁎=1.00 deserves more attention because of its smaller amplitude compared to the cases with the same aspect ratio and a larger mass ratio. This counter-intuitive behavior seems to be related to the energy transferring process from the steady stream to the oscillatory hydroelastic system. Finally, it is noteworthy that the characteristic of the “Strouhal-like” number decreases when the aspect ratio decreases, as also observed in previous works available in the literature, most of them for stationary cylinders.

Determination of degree of ionization of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy‑4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in layer-by-layer films using vacuum photoabsorption spectroscopy

Electrostatic and hydrophobic interactions govern most of the properties of supramolecular systems, which is the reason determining the degree of ionization of macromolecules has become crucial for many applications. In this paper, we show that highresolution ultraviolet spectroscopy (VUV) can be used to determine the degree of ionization and its effect on the electronic excitation energies of layer-by-layer (LbL) films of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy-4 hydroxyphenylazo)- benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). A full assignment of the VUV peaks of these polyelectrolytes in solution and in cast or LbL films could be made, with their pH dependence allowing us to determine the p'K IND. a' using the Henderson-Hasselbach equation. The p'K IND. a' for PAZO increased from ca. 6 in solution to ca. 7.3 in LbL films owing to the charge transfer from PAH. Significantly, even using solutions at a fixed pH for PAH, the amount adsorbed on the LbL films still varied with the pH of the PAZO solutions due to these molecular-level interactions. Therefore, the procedure based on a comparison of VUV spectra from solutions and films obtained under distinct conditions is useful to determine the degree of dissociation of macromolecules, in addition to permitting interrogation of interface effects in multilayer films.

A molecular dynamics study of the influence of chain branching on the properties of polymer systems

Die vorliegende Arbeit beschäftigt sich mit dem Einfluß von Kettenverzweigungen unterschiedlicher Topologien auf die statischen Eigenschaften von Polymeren. Diese Untersuchungen werden mit Hilfe von Monte-Carlo- und Molekular-Dynamik-Simulationen durchgeführt.Zunächst werden einige theoretische Konzepte und Modelle eingeführt, welche die Beschreibung von Polymerketten auf mesoskopischen Längenskalen gestatten. Es werden wichtige Bestimmungsgrößen eingeführt und erläutert, welche zur quantitativen Charakterisierung von Verzweigungsstrukturen bei Polymeren geeignet sind. Es wird ebenso auf die verwendeten Optimierungstechniken eingegangen, die bei der Implementierung des Computerprogrammes Verwendung fanden. Untersucht werden neben linearen Polymerketten unterschiedliche Topolgien -Sternpolymere mit variabler Armzahl, Übergang von Sternpolymeren zu linearen Polymeren, Ketten mit variabler Zahl von Seitenketten, reguläre Dendrimere und hyperverzweigte Strukturen - in Abhängigkeit von der Lösungsmittelqualität. Es wird zunächst eine gründliche Analyse des verwendeten Simulationsmodells an sehr langen linearen Einzelketten vorgenommen. Die Skalierungseigenschaften der linearen Ketten werden untersucht in dem gesamten Lösungsmittelbereich vom guten Lösungsmittel bis hin zu weitgehend kollabierten Ketten im schlechten Lösungsmittel. Ein wichtiges Ergebnis dieser Arbeit ist die Bestätigung der Korrekturen zum Skalenverhalten des hydrodynamischen Radius Rh. Dieses Ergebnis war möglich aufgrund der großen gewählten Kettenlängen und der hohen Qualität der erhaltenen Daten in dieser Arbeit, insbesondere bei den linearen ketten, und es steht im Widerspruch zu vielen bisherigen Simulations-Studien und experimentellen Arbeiten. Diese Korrekturen zum Skalenverhalten wurden nicht nur für die linearen Ketten, sondern auch für Sternpolymere mit unterchiedlicher Armzahl gezeigt. Für lineare Ketten wird der Einfluß von Polydispersität untersucht.Es wird gezeigt, daß eine eindeutige Abbildung von Längenskalen zwischen Simulationsmodell und Experiment nicht möglich ist, da die zu diesem Zweck verwendete dimensionslose Größe eine zu schwache Abhängigkeit von der Polymerisation der Ketten besitzt. Ein Vergleich von Simulationsdaten mit industriellem Low-Density-Polyäthylen(LDPE) zeigt, daß LDPE in Form von stark verzweigten Ketten vorliegt.Für reguläre Dendrimere konnte ein hochgradiges Zurückfalten der Arme in die innere Kernregion nachgewiesen werden.

Synthesis and characterization of novel poly(imino ketone)s via palladium-catalyzed aryl amination

The challenge of the present work was to synthesize and to characterize new classes of N-containing polymers via palladium-catalyzed aryl amination. This work was inspired by a desire to combine the properties of high-performance polymers such as PEKs with those of N-containing conductive polymers such as polyaniline (PANI), poly(aromatic amides) (PAAs), and the ready synthesis of N-containing simple aromatic compound by the Buchwald-Hartwig reaction. Careful investigation of a model reaction was carried out to provide insights into the formation of side products which will have a negative effect upon the molecular weight or upon the materials properties of the desired polymers in the polycondensation reaction. In this thesis, five new different polymer classes namely, poly(imino ketone)s (PIKs), poly(imino acridine)s (PIAcs), poly(imino azobenzene)s (PIAzos), poly(imino fluorenone)s (PIFOs), and poly(imino carbazole)s (PICs) were synthesized and fully characterized by means of 1H-NMR, elemental analysis, UV, FT-IR, X-ray, GPC, TGA, DSC, DMA, and dielectric spectroscopy. To optimize the polycondensation process, the influence of the concentration, temperature, ligands and the reactivity of the halogen containing monomers were investigated. A temperature of 100-165 °C and a concentration of 30-36 % were found to be optimal for the palladium-catalyzed polycondensation to produce polymer with high molecular weight (Mn = 85 900, Mw = 474 500, DP = 126). Four different ligands were used successfully in the Pd-catalyzed process, of which the Pd/BINAP system was found to be the most effective catalyst, producing the highest yield and highest molecular weight polymers. It was found that the reactivity decreases strongly with increasing electronegativity of the halogen atoms, for example better yields, and higher molecular weights were obtained by using dibromo compounds than dichloro compounds while difluoro compounds were totally unreactive. Polymer analogous transformations, such as the protonation reaction of the ring nitrogens in PIAcs, or of the azobenzene groups of PIAzos, the photo and thermal cis-trans-isomerization of PIAzos, and of poly(imino alcohol)s were also studied. The values of the dielectric constants of PIKs at 1 MHz were in the range 2.71-3.08. These low values of the dielectric constant are lower than that of "H Film", a polyimide Kapton film which is one of the most preferred high-performance dielectrics in microelectronic applications having a dielectric constant of 3.5. In addition to the low values of the dielectric constants, PIKs have lower and glass transition temperatures (Tgs) than arimides such as Kapton which may make them more easily processable. Cyclic voltammetry showed that PICs exhibited low oxidation and reduction potentials and their values were shifted to low values with increasing degree of polymerization i.e. with increasing of the carbazole content in backbone of PICs (PIC-7, 0.44, 0.33 V, DP= 37, PIC-5, 0.63, 0.46, DP= 16, respectively).

Expanding the scope of poly(ethylene glycol)s for bioconjugation to squaric acid-mediated PEGylation and pH-sensitivity

Poly(ethylene glycol) (PEG) is used in a broad range of applications due to its unique combination of properties and is approved use in formulations for body-care products, edibles and medicine. This thesis aims at the synthesis and characterization of novel heterofunctional PEG structures and the establishment of diethyl squarate as a suitable linker for the covalent attachment to proteins. Chapter 1 is an introduction on the properties and applications of PEG as well as the fascinating chemistry of squaric acid derivatives. In Chapter 1.1, the synthesis and properties of PEG are described, and the versatile applications of PEG derivatives in everyday products are emphasized with a focus on PEG-based pharmaceuticals and nonionic surfactants. This chapter is written in German, as it was published in the German Journal Chemie in unserer Zeit. Chapter 1.2 deals with PEGs major drawbacks, its non-biodegradability, which impedes parenteral administration of PEG conjugates with polyethers exceeding the renal excretion limit, although these would improve blood circulation times and passive tumor targeting. This section gives a comprehensive overview of the cleavable groups that have been implemented in the polyether backbone to tackle this issue as well as the synthetic strategies employed to accomplish this task. Chapter 1.3 briefly summarizes the chemical properties of alkyl squarates and the advantages in protein conjugation chemistry that can be taken from its use as a coupling agent. In Chapter 2, the application of diethyl squarate as a coupling agent in the PEGylation of proteins is illustrated. Chapter 2.1 describes the straightforward synthesis and characterization of squaric acid ethyl ester amido PEGs with terminal hydroxyl functions or methoxy groups. The reactivity and selectivity of theses activated PEGs are explored in kinetic studies on the reactions with different lysine and other amino acid derivatives, followed by 1H NMR spectroscopy. Further, the efficient attachment of the novel PEGs to a model protein, i.e., bovine serum albumin (BSA), demonstrates the usefulness of the new linker for the PEGylation with heterofunctional PEGs. In Chapter 2.3 initial studies on the biocompatibility of polyether/BSA conjugates synthesized by the squaric acid mediated PEGylation are presented. No cytotoxic effects on human umbilical vein endothelial cells exposed to various concentrations of the conjugates were observed in a WST-1 assay. A cell adhesion molecule - enzyme immunosorbent assay did not reveal the expression of E-selectin or ICAM-1, cell adhesion molecules involved in inflammation processes. The focus of Chapter 3 lies on the syntheses of novel heterofunctional PEG structures which are suitable candidates for the squaric acid mediated PEGylation and exhibit superior features compared to established PEGs applied in bioconjugation. Chapter 3.1 describes the synthetic route to well-defined, linear heterobifunctional PEGs carrying a single acid-sensitive moiety either at the initiation site or at a tunable position in the polyether backbone. A universal concept for the implementation of acetal moieties into initiators for the anionic ring-opening polymerization (AROP) of epoxides is presented and proven to grant access to the degradable PEG structures aimed at. The hydrolysis of the heterofunctional PEG with the acetal moiety at the initiating site is followed by 1H NMR spectroscopy in deuterium oxide at different pH. In an exploratory study, the same polymer is attached to BSA via the squarate acid coupling and subsequently cleaved from the conjugate under acidic conditions. Furthermore, the concept for the generation of acetal-modified AROP initiators is demonstrated to be suitable for cholesterol, and the respective amphiphilic cholesteryl-PEG is cleaved at lowered pH. In Chapter 3.2, the straightforward synthesis of α-amino ω2-dihydroxyl star-shaped three-arm PEGs is described. To assure a symmetric length of the hydroxyl-terminated PEG arms, a novel AROP initiator is presented, who’s primary and secondary hydroxyl groups are separated by an acetal moiety. Upon polymerization of ethylene oxide for these functionalities and subsequent cleavage of the acid-labile unit no difference in the degree of polymerization is seen for both polyether fragments.

The effect of polymerization procedure on Vickers hardness of dual-curing resin cements

To investigate the surface hardness (Vickers hardness, HVN) of one light-curing flowable resin composite and five dual-curing resin cements after different polymerization procedures.

Influence of curing rate on softening in ethanol, degree of conversion, and wear of resin composite

PURPOSE: To investigate the effect of curing rate on softening in ethanol, degree of conversion, and wear of resin composites. METHOD: With a given energy density and for each of two different light-curing units (QTH or LED), the curing rate was reduced by modulating the curing mode. Thus, the irradiation of resin composite specimens (Filtek Z250, Tetric Ceram, Esthet-X) was performed in a continuous curing mode and in a pulse-delay curing mode. Wallace hardness was used to determine the softening of resin composite after storage in ethanol. Degree of conversion was determined by infrared spectroscopy (FTIR). Wear was assessed by a three-body test. Data were submitted to Levene's test, one and three-way ANOVA, and Tukey HSD test (alpha = 0.05). Results: Immersion in ethanol, curing mode, and material all had significant effects on Wallace hardness. After ethanol storage, resin composites exposed to the pulse-delay curing mode were softer than resin composites exposed to continuous cure (P< 0.0001). Tetric Ceram was the softest material followed by Esthet-X and Filtek Z250 (P< 0.001). Only the restorative material had a significant effect on degree of conversion (P< 0.001): Esthet-X had the lowest degree of conversion followed by Filtek Z250 and Tetric Ceram. Curing mode (P= 0.007) and material (P< 0.001) had significant effect on wear. Higher wear resulted from the pulse-delay curing mode when compared to continuous curing, and Filtek Z250 showed the lowest wear followed by Esthet-X and Tetric Ceram.

Deviation from Murray's law is associated with a higher degree of calcification in coronary bifurcations

Murray's law describes the optimal branching anatomy of vascular bifurcations. If Murray's law is obeyed, shear stress is constant over the bifurcation. Associations between Murray's law and intravascular ultrasound (IVUS) assessed plaque composition near coronary bifurcations have not been investigated previously.

Curing capability of halogen and LED light curing units in deep class II cavities in extracted human molars

Class II cavities were prepared in extracted lower molars filled and cured in three 2-mm increments using a metal matrix. Three composites (Spectrum TPH A4, Ceram X mono M7 and Tetric Ceram A4) were cured with both the SmartLite PS LED LCU and the Spectrum 800 continuous cure halogen LCU using curing cycles of 10, 20 and 40 seconds. Each increment was cured before adding the next. After a seven-day incubation period, the composite specimens were removed from the teeth, embedded in self-curing resin and ground to half the orofacial width. Knoop microhardness was determined 100, 200, 500, 1000, 1500, 2500, 3500, 4500 and 5500 microm from the occlusal surface at a distance of 150 microm and 1000 microm from the metal matrix. The total degree of polymerization of a composite specimen for any given curing time and curing light was determined by calculating the area under the hardness curve. Hardness values 150 microm from the metal matrix never reached maximum values and were generally lower than those 1000 microm from the matrix. The hardest composite was usually encountered between 200 microm and 1000 microm from the occlusal surface. For every composite-curing time combination, there was an increase in microhardness at the top of each increment (measurements at 500, 2500 and 4500 microm) and a decrease towards the bottom of each increment (measurements at 1500, 3500 and 5500 microm). Longer curing times were usually combined with harder composite samples. Spectrum TPH composite was the only composite showing a satisfactory degree of polymerization for all three curing times and both LCUs. Multiple linear regression showed that only the curing time (p < 0.001) and composite material (p < 0.001) had a significant association with the degree of polymerization. The degree of polymerization achieved by the LED LCU was not significantly different from that achieved by the halogen LCU (p = 0.54).

Microhardness and marginal adaptation of pre-warmed composites

Objectives: The aim of this study was to examine the effect of pre-warmed composite on the microhardness and marginal adaptation. Methods: Ninety six identical class II cavities were prepared in extracted human molars and filled/cured in three 2 mm increments using a metal matrix. Two composites (Tetric Evo Ceram (IvoclarVivadent) and ELS(Saremco)) were cured with a LED curing unit (Bluephase (IvoclarVivadent)) using curing cycles of 20 and 40 seconds. The composite was used at room temperature or pre-warmed at 54.5ºC (Calset(AdDent)). Twelve teeth were filled for every composite-curing time-composite temperature combination. The teeth were thermocycled (1000 cycles at 5º and 55ºC) and then stored at 37° C for seven days . Dye penetration (basic fuchsine 5% for 8 hours) was measured using a score scale. Knoop microhardness was determined 100, 200, 500, 1000, 1500, 2500, 3500, 4500 and 5500µm from the occlusal surface at a distance of 150 and 1000µm from the metal matrix. The total degree of polymerization of a composite specimen was determined by calculating the area under the hardness curve. Results: Statistical analyses showed no difference in marginal adaptation (p>0.05). Hardness values at 150µm from the matrix were lower than those at 1000µm. There was an increase of the microhardness at the top of each increment and decrease towards the bottom of each increment. Longer curing times resulted in harder composite samples. Multiple linear regression showed that only the curing time (p<0.001) and composite material (p<0.001) had a significant association with the degree of polymerization. The degree of polymerization was not influenced by pre-warming the composite at a temperature of 54.5ºC (p=4.86). Conclusion: Polymerization time can not be reduced by pre-warming the composite on a temperature of 54.5ºC. The marginal adaptation is not compromised by pre-warming the composite.

Estimation of the degree of polarization through computational sensing

The degree of polarization of a refected field from active laser illumination can be used for object identifcation and classifcation. The goal of this study is to investigate methods for estimating the degree of polarization for refected fields with active laser illumination, which involves the measurement and processing of two orthogonal field components (complex amplitudes), two orthogonal intensity components, and the total field intensity. We propose to replace interferometric optical apparatuses with a computational approach for estimating the degree of polarization from two orthogonal intensity data and total intensity data. Cramer-Rao bounds for each of the three sensing modalities with various noise models are computed. Algebraic estimators and maximum-likelihood (ML) estimators are proposed. Active-set algorithm and expectation-maximization (EM) algorithm are used to compute ML estimates. The performances of the estimators are compared with each other and with their corresponding Cramer-Rao bounds. Estimators for four-channel polarimeter (intensity interferometer) sensing have a better performance than orthogonal intensities estimators and total intensity estimators. Processing the four intensities data from polarimeter, however, requires complicated optical devices, alignment, and four CCD detectors. It only requires one or two detectors and a computer to process orthogonal intensities data and total intensity data, and the bounds and estimator performances demonstrate that reasonable estimates may still be obtained from orthogonal intensities or total intensity data. Computational sensing is a promising way to estimate the degree of polarization.

Light curing through glass ceramics with a second- and a third-generation LED curing unit: effect of curing mode on the degree of conversion of dual-curing resin cements

Objectives The aim of this study was to measure the degree of conversion (DC) of five dual-curing resin cements after different curing modes with a second- and a third-generation light-emitting diode (LED) curing unit. Additionally, irradiance of both light curing units was measured at increasing distances and through discs of two glass ceramics for computer-aided design/manufacturing (CAD/CAM). Materials and methods Irradiance and spectra of the Elipar FreeLight 2 (Standard Mode (SM)) and of the VALO light curing unit (High Power Mode (HPM) and Xtra Power Mode (XPM)) were measured with a MARC radiometer. Irradiance was measured at increasing distances (control) and through discs (1.5 to 6 mm thickness) of IPS Empress CAD and IPS e.max CAD. DC of Panavia F2.0, RelyX Unicem 2 Automix, SpeedCEM, BisCem, and BeautiCem SA was measured with an attenuated total reflectance–Fourier transform infrared spectrometer when self-cured (negative control) or light cured in SM for 40 s, HPM for 32 s, or XPM for 18 s. Light curing was performed directly (positive control) or through discs of either 1.5- or 3-mm thickness of IPS Empress CAD or IPS e.max CAD. DC was analysed with Kruskal–Wallis tests followed by pairwise Wilcoxon rank sum tests (α = 0.05). Results Maximum irradiances were 1,545 mW/cm2 (SM), 2,179 mW/cm2 (HPM), and 4,156 mW/cm2 (XPM), and all irradiances decreased by >80 % through discs of 1.5 mm, ≥95 % through 3 mm, and up to >99 % through 6 mm. Generally, self-curing resulted in the lowest DC. For some cements, direct light curing did not result in higher DC compared to when light cured through ceramic discs. For other cements, light curing through ceramic discs of 3 mm generally reduced DC. Conclusions Light curing was favourable for dual-curing cements. Some cements were more susceptible to variations in curing mode than others. Clinical relevance When light curing a given cement, the higher irradiances of the third-generation LED curing unit resulted in similar DC compared to the second-generation one, though at shorter light curing times.