Investigation of the postcure reaction and surface energy of epoxy resins using time-of-flight secondary ion mass spectrometry and contact-angle measurements

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate correlations between the molecular changes and postcuring reaction on the surface of a diglycidyl ether of bisphenol A and diglycidylether of bisphenol F based epoxy resin cured with two different amine-based hardeners. The aim of this work was to present a proof of concept that ToF-SIMS has the ability to provide information regarding the reaction steps, path, and mechanism for organic reactions in general and for epoxy resin curing and postcuring reactions in particular. Contact-angle measurements were taken for the cured and postcured epoxy resins to correlate changes in the surface energy with the molecular structure of the surface. Principal components analysis (PCA) of the ToFSIMS positive spectra explained the variance in the molecular information, which was related to the resin curing and postcuring reactions with different hardeners and to the surface energy values. The first principal component captured information related to the chemical phenomena of the curing reaction path, branching, and network density based on changes in the relative ion density of the aliphatic hydrocarbon and the C₇H₇O⁺ positive ions. The second principal component captured information related to the difference in the surface energy, which was correlated to the difference in the relative intensity of the C_xH_yN_z⁺ ions of the samples. PCA of the negative spectra provided insight into the extent of consumption of the hardener molecules in the curing and postcuring reactions of both systems based on the relative ion intensity of the nitrogen-containing negative ions and showed molecular correlations with the sample surface energy.

Real-time surface formation using a network of interconnected programmable actuators

This research has explored methods for developing a large interactive dynamic 3D surface using an array of interconnected pneumatically actuated cylinders. People can control the surface using body movement, sound or pre-programmed sequences. The main contribution is a method for accurately positioning cylinders without the need for position feedback.

Adaptive fast finite-time multiple-surface sliding control for a class of uncertain non-linear systems

This paper concerns the adaptive fast finite-time multiple-surface sliding control (AFFTMSSC) problem for a class of high-order uncertain non-linear systems of which the upper bounds of the system uncertainties are unknown. By using the fast control Lyapunov function and the method of so-called adding a power integrator merging with adaptive technique, a recursive design procedure is provided, which guarantees the fast finite-time stability of the closed-loop system. Further, it is proved that the control input is bounded.

Air velocity and exposure time to ventilation affect body surface and rectal temperature of broiler chickens

Increasing air movement over poultry by using fans (ventilation) has become an accepted means of reducing environmental heat stress over the last several years. The purpose of this study was to evaluate the effect of air velocity and exposure time to ventilation on body surface and rectal temperature of broiler chickens. Male broiler chickens aged 36-42 days were placed in individual wire cages and exposed to five different air velocities (5.7, 4.2, 3.1, 2.4, or 1.8 m/sec). Throughout the experiment head, back, leg, and rectal temperatures were monitored every 10 min during a 30-min period for each air velocity. The data showed that exposure time to the wind affected (P<.05) leg and body temperature, with a rapid reduction being observed during the first 10 min. There was a reduction in leg temperature with air velocity of 2 m/sec; however, air velocity lower than 4.5 m/sec was not effective in decreasing head and back temperature. The results suggest that air velocity of 2 m/sec, in air temperature of 29 degrees C, improves heat loss in the birds. The data also indicate that exposure time to ventilation seems to be a critical point in the maintenance of bird thermal homeostasis.

Influence of surface sealant on the translucency of composite resin: effect of immersion time and immersion media

This study evaluated the effect of surface sealant on the translucency of composite resin immersed in different solutions. The study involved the following materials: Charisma, Fortify and coffee, Coca-Cola®, tea and artificial saliva as solutions. Sixty-four specimens (n = 8) were manufactured and immersed in artificial saliva at 37 ± 1 °C. Samples were immersed in the solutions for three times a day and re-immersed in artificial saliva until the translucency readings. The measurements were carried out at nine times: T1 - 24 hours after specimen preparation, T2 - 24 hours after immersion in the solutions, T3 - 48 hours and T4 to T9 - 7, 14, 21, 30, 60 and 90 days, respectively, after immersion. The translucency values were measured using a JOUAN device. The results were subjected to ANOVA and Tukey's test at 5%. The surface sealant was not able to protect the composite resin against staining, the coffee showed the strongest staining action, followed by tea and regarding immersion time, a significant alteration was noted in the translucency of composite resin after 21 days.

Electron time-of-flight measurements in sulfur interpreted via an extra surface mobility channel

Time-of-flight measurements were carried out in orthorhombic sulfur for various fields, ranging from -2 to -20 kV/cm. No dependence of the mobility with the electric field was found but the current, normalized by the initial current, showed an electric field dependence at small times, decaying faster for larger electric field. After the failure of the usual models in explaining the resultsincluding the assumption of depth-dependent density of trapsa model assuming an extra mobility channel near the surface provided a reasonable set of parameters independent of the electric field. The measurements were carried out at 8.5, 29, 53, 68, and 79°C. © 1988 The American Physical Society.

Microhardness of glass ionomer cements indicated for the ART technique according to surface protection treatment and storage time

The aim of this study was to assess the microhardness of 5 glass ionomer cements (GIC) - Vidrion R (V, SS White), Fuji IX (F, GC Corp.), Magic Glass ART (MG, Vigodent), Maxxion R (MR, FGM) and ChemFlex (CF, Dentsply) - in the presence or absence of a surface protection treatment, and after different storage periods. For each GIC, 36 test specimens were made, divided into 3 groups according to the surface protection treatment applied - no protection, varnish or nail varnish. The specimens were stored in distilled water for 24 h, 7 and 30 days and the microhardness tests were performed at these times. The data obtained were submitted to the ANOVA for repeated measures and Tukey tests (α = 5%). The results revealed that the mean microhardness values of the GICs were, in decreasing order, as follows: F > CF = MR > MG > V; that surface protection was significant for MR, at 24 h, without protection (64.2 ± 3.6a), protected with GIC varnish (59.6 ± 3.4b) and protected with nail varnish (62.7 ± 2.8ab); for F, at 7 days, without protection (97.8 ± 3.7ab), protected with varnish (95.9 ± 3.2b) and protected with nail varnish (100.8 ± 3.4a); and at 30 days, for F, without protection (98.8 ± 2.6b), protected with varnish (103.3 ± 4.4a) and protected with nail varnish (101 ± 4.1ab) and, for V, without protection (46 ± 1.3b), protected with varnish (49.6 ± 1.7ab) and protected with nail varnish (51.1 ± 2.6a). The increase in storage time produced an increase in microhardness. It was concluded that the different GICs, surface protection treatments and storage times could alter the microhardness values.

The effects of exposure time on the surface microhardness of three dual-cured dental resin cements

This study evaluated the exposure time of light-curing of the polymers used for cementation on microhardness test in different storage times. The polymers (specifically called resin cements) were RelyX ARC, RelyX U100, and SET. Five specimens of each group were prepared and photo-polymerized with exposure times of 20 s and 180 s, using a LED polymerization unit with wavelength of 440 ~ 480 nm and light output was consistently 1,500 mW/cm2. The Vickers hardness test was performed in a MMT-3 Microhardness Tester. Data were submitted to ANOVA and Tukey's test (α = 0.05). The values of RelyX ARC showed statistically significant difference to groups with light exposure when considering only chemical cure (p < 0.05). The groups with light exposure (20 s and 180 s) showed no significant difference between them (p > 0.05). The RelyX U100 cured only chemically showed statistically significant difference between 48 h and 7 days (p < 0.05). The SET resin cement showed no significant difference to groups without light exposure for all storage times (p > 0.05). The values of hardening of the dual-cured resin cements improved after setting by light and chemical activation demonstrating the importance of light curing. © 2011 by the authors.

Application of the log-conformation tensor to three-dimensional time-dependent free surface flows

The numerical simulation of flows of highly elastic fluids has been the subject of intense research over the past decades with important industrial applications. Therefore, many efforts have been made to improve the convergence capabilities of the numerical methods employed to simulate viscoelastic fluid flows. An important contribution for the solution of the High-Weissenberg Number Problem has been presented by Fattal and Kupferman [J. Non-Newton. Fluid. Mech. 123 (2004) 281-285] who developed the matrix-logarithm of the conformation tensor technique, henceforth called log-conformation tensor. Its advantage is a better approximation of the large growth of the stress tensor that occur in some regions of the flow and it is doubly beneficial in that it ensures physically correct stress fields, allowing converged computations at high Weissenberg number flows. In this work we investigate the application of the log-conformation tensor to three-dimensional unsteady free surface flows. The log-conformation tensor formulation was applied to solve the Upper-Convected Maxwell (UCM) constitutive equation while the momentum equation was solved using a finite difference Marker-and-Cell type method. The resulting developed code is validated by comparing the log-conformation results with the analytic solution for fully developed pipe flows. To illustrate the stability of the log-conformation tensor approach in solving three-dimensional free surface flows, results from the simulation of the extrudate swell and jet buckling phenomena of UCM fluids at high Weissenberg numbers are presented. (C) 2012 Elsevier B.V. All rights reserved.

Time-resolved surface enhanced resonance Raman spectro-electrochemistry of heme proteins

The membrane protein Cytochrome c Oxidase (CcO) is one of the most important functional bio-molecules. It appears in almost every eukaryotic cell and many bacteria. Although the different species differ in the number of subunits, the functional differences are merely marginal. CcO is the terminal link in the electron transfer pathway of the mitochondrial respiratory chain. Electrons transferred to the catalytic center of the enzyme conduce to the reduction of molecular oxygen to water. Oxygen reduction is coupled to the pumping of protons into the inter-membrane space and hence generates a difference in electrochemical potential of protons across the inner mitochondrial membrane. This potential difference drives the synthesis of adenosine triphosphate (ATP), which is the universal energy carrier within all biological cells. rnrnThe goal of the present work is to contribute to a better understanding of the functional mechanism of CcO by using time-resolved surface enhanced resonance Raman spectroscopy (TR-SERRS). Despite intensive research effort within the last decades, the functional mechanism of CcO is still subject to controversial discussions. It was the primary goal of this dissertation to initiate electron transfer to the redox centers CuA, heme a, heme a3 and CuB electrochemically and to observe the corresponding redox transitions in-situ with a focus on the two heme structures by using SERRS. A measuring cell was developed, which allowed combination of electrochemical excitation with Raman spectroscopy for the purpose of performing the accordant measurements. Cytochrome c was used as a benchmark system to test the new measuring cell and to prove the feasibility of appropriate Raman measurements. In contrast to CcO the heme protein cc contains only a single heme structure. Nevertheless, characteristic Raman bands of the hemes can be observed for both proteins.rnrnIn order to investigate CcO it was immobilized on top of a silver substrate and embedded into an artificial membrane. The catalytic activity of CcO and therefore the complete functional capability of the enzyme within the biomimetic membrane architecture was verified using cyclic voltammetry. Raman spectroscopy was performed using a special nano-structured silver surface, which was developed within the scope of the present work. This new substrate combined two fundamental properties. It facilitated the formation of a protein tethered bilayer lipid membrane (ptBLM) and it allowed obtaining Raman spectra with sufficient high signal-to-noise ratios.rnSpectro-electrochemical investigations showed that at open circuit potential the enzyme exists in a mixed-valence state, with heme a and and heme a3 in the reduced and oxidized state, respectively. This was considered as an intermediate state between the non-activated and the fully activated state of CcO. Time-resolved SERRS measurements revealed that a hampered electron transfer to the redox center heme a3 characterizes this intermediate state.rn

Direct electron transfer to cytochrome c oxidase investigated by electrochemistry and time-resolved surface-enhanced infrared absorption spectroscopy

Cytochrom c Oxidase (CcO), der Komplex IV der Atmungskette, ist eine der Häm-Kupfer enthaltenden Oxidasen und hat eine wichtige Funktion im Zellmetabolismus. Das Enzym enthält vier prosthetische Gruppen und befindet sich in der inneren Membran von Mitochondrien und in der Zellmembran einiger aerober Bakterien. Die CcO katalysiert den Elektronentransfer (ET) von Cytochrom c zu O2, wobei die eigentliche Reaktion am binuklearen Zentrum (CuB-Häm a3) erfolgt. Bei der Reduktion von O2 zu zwei H2O werden vier Protonen verbraucht. Zudem werden vier Protonen über die Membran transportiert, wodurch eine elektrochemische Potentialdifferenz dieser Ionen zwischen Matrix und Intermembranphase entsteht. Trotz ihrer Wichtigkeit sind Membranproteine wie die CcO noch wenig untersucht, weshalb auch der Mechanismus der Atmungskette noch nicht vollständig aufgeklärt ist. Das Ziel dieser Arbeit ist, einen Beitrag zum Verständnis der Funktion der CcO zu leisten. Hierzu wurde die CcO aus Rhodobacter sphaeroides über einen His-Anker, der am C-Terminus der Untereinheit II angebracht wurde, an eine funktionalisierte Metallelektrode in definierter Orientierung gebunden. Der erste Elektronenakzeptor, das CuA, liegt dabei am nächsten zur Metalloberfläche. Dann wurde eine Doppelschicht aus Lipiden insitu zwischen die gebundenen Proteine eingefügt, was zur sog. proteingebundenen Lipid-Doppelschicht Membran (ptBLM) führt. Dabei musste die optimale Oberflächenkonzentration der gebundenen Proteine herausgefunden werden. Elektrochemische Impedanzspektroskopie(EIS), Oberflächenplasmonenresonanzspektroskopie (SPR) und zyklische Voltammetrie (CV) wurden angewandt um die Aktivität der CcO als Funktion der Packungsdichte zu charakterisieren. Der Hauptteil der Arbeit betrifft die Untersuchung des direkten ET zur CcO unter anaeroben Bedingungen. Die Kombination aus zeitaufgelöster oberflächenverstärkter Infrarot-Absorptionsspektroskopie (tr-SEIRAS) und Elektrochemie hat sich dafür als besonders geeignet erwiesen. In einer ersten Studie wurde der ET mit Hilfe von fast scan CV untersucht, wobei CVs von nicht-aktivierter sowie aktivierter CcO mit verschiedenen Vorschubgeschwindigkeiten gemessen wurden. Die aktivierte Form wurde nach dem katalytischen Umsatz des Proteins in Anwesenheit von O2 erhalten. Ein vier-ET-modell wurde entwickelt um die CVs zu analysieren. Die Methode erlaubt zwischen dem Mechanismus des sequentiellen und des unabhängigen ET zu den vier Zentren CuA, Häm a, Häm a3 und CuB zu unterscheiden. Zudem lassen sich die Standardredoxpotentiale und die kinetischen Koeffizienten des ET bestimmen. In einer zweiten Studie wurde tr-SEIRAS im step scan Modus angewandt. Dafür wurden Rechteckpulse an die CcO angelegt und SEIRAS im ART-Modus verwendet um Spektren bei definierten Zeitscheiben aufzunehmen. Aus diesen Spektren wurden einzelne Banden isoliert, die Veränderungen von Vibrationsmoden der Aminosäuren und Peptidgruppen in Abhängigkeit des Redoxzustands der Zentren zeigen. Aufgrund von Zuordnungen aus der Literatur, die durch potentiometrische Titration der CcO ermittelt wurden, konnten die Banden versuchsweise den Redoxzentren zugeordnet werden. Die Bandenflächen gegen die Zeit aufgetragen geben dann die Redox-Kinetik der Zentren wieder und wurden wiederum mit dem vier-ET-Modell ausgewertet. Die Ergebnisse beider Studien erlauben die Schlussfolgerung, dass der ET zur CcO in einer ptBLM mit größter Wahrscheinlichkeit dem sequentiellen Mechanismus folgt, was dem natürlichen ET von Cytochrom c zur CcO entspricht.