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Poly(vinyl acetate), PVAc, with a degree of polymerization Xn = 10 was prepared by chain-transfer radical polymerization using carbon tetrachloride and used as oligomeric plasticizer for commercial PVAc. However, the chlorinated chain ends cause a low thermal stability requiring mild Cl/H substitution. The product exhibits high thermal stability and excellent melt-compounding properties. Blends of oligomeric and commercial PVAc show single glass transition temperatures which decrease with higher oligomer content and exhibit small negative deviations from Fox' linear additivity rule. This indicates plasticization and miscibility being mainly due to entropic effects. Injection-moulded thick specimens show ductile behaviour at oligomer contents >10 wt %, while sheets with a thickness of 0.2–0.5 mm appear flexible already at 7.5 wt %. The oxygen permeability coefficients are an order of magnitude lower than those of low-density polyethylene. Due to the sum of their properties, the plasticized sheets present a promising alternative in the preparation of barrier materials.
Molecular Modeling Approach to the Prediction of Mechanical Properties of Silica-Reinforced Rubbers
(2014)
Recently, we have suggested a nanomechanical model for dissipative loss in filled elastomer networks in the context of the Payne effect. The mechanism is based on a total interfiller particle force exhibiting an intermittent loop, due to the combination of short-range repulsion and dispersion forces with a long-range elastic attraction. The sum of these forces leads, under external strain, to a spontaneous instability of “bonds” between the aggregates in a filler network and attendant energy dissipation. Here, we use molecular dynamics simulations to obtain chemically realistic forces between surface modified silica particles. The latter are combined with the above model to estimate the loss modulus and the low strain storage modulus in elastomers containing the aforementioned filler-compatibilizer systems. The model is compared to experimental dynamic moduli of silica filled rubbers. We find good agreement between the model predictions and the experiments as function of the compatibilizer's molecular structure and its bulk concentration.
Access to promising radiometals as isotopes for novel molecular imaging agents requires that they are routinely available and inexpensive to obtain. Proximity to a cyclotron center outfitted with solid target hardware, or to an isotope generator for the metal of interest is necessary, both of which can introduce significant hurdles in development of less common isotopes. Herein, we describe the production of ⁴⁴Sc (t₁⸝₂ = 3.97 h, Eavg,β⁺ = 1.47 MeV, branching ratio = 94.27%) in a solution target and an automated loading system which allows a quick turn-around between different radiometallic isotopes and therefore greatly improves their availability for tracer development. Experimental yields are compared to theoretical calculations.
High-intensity discharge lamps can be driven by radio-frequency signals in the ISM frequency band at 2.45 GHz, using a matching network to transform the impedance of the plasma to the source impedance. To achieve an optimal operating condition, a good characterization of the lamp in terms of radio frequency equivalent circuits under operating conditions is necessary, enabling the design of an efficient matching network. This paper presents the characterization technique for such lamps and presents the design of the required matching network. For the characterization, a high-intensity discharge lamp was driven by a monofrequent large signal at 2.45 GHz, whereas a frequency sweep over 300 MHz was performed across this signal to measure so-called small-signal hot S-parameters using a vector network analyzer. These parameters are then used as an equivalent load in a circuit simulator to design an appropriate matching network. Using the measured data as a black-box model in the simulation results in a quick and efficient method to simulate and design efficient matching networks in spite of the complex plasma behavior. Furthermore, photometric analysis of high-intensity discharge lamps are carried out, comparing microwave operation to conventional operation.
High-k perovskite oxide of barium strontium titanate (BST) represents a very attractive multi-functional transducer material for the development of (bio-)chemical sensors for liquids. In this work, BST films have been applied as a sensitive transducer material for a label-free detection of adsorbed charged macromolecules (positively charged polyelectrolytes) and concentration of hydrogen peroxide vapor as well as protection insulator layer for a contactless electrolyte-conductivity sensor. The experimental results of characterization of individual sensors are presented. Special emphasis is devoted towards the development of a capacitively-coupled contactless electrolyte-conductivity sensor.
It is well known that biochemical and biotechnological processes are strongly dependent and affected by a variety of physico-chemical parameters such as pH value, temperature, pressure and electrolyte conductivity. Therefore, these quantities have to be monitored or controlled in order to guarantee a stable process operation, optimization and high yield. In this work, a sensor chip for the multiparameter detection of three physico-chemical parameters such as electrolyte conductivity, pH and temperature is realized using barium strontium titanate (BST) as multipurpose material. The chip integrates a capacitively coupled four-electrode electrolyte-conductivity sensor, a capacitive field-effect pH sensor and a thin-film Pt-temperature sensor. Due to the multifunctional properties of BST, it is utilized as final outermost coating layer of the processed sensor chip and serves as passivation and protection layer as well as pH-sensitive transducer material at the same time. The results of testing of the individual sensors of the developed multiparameter sensor chip are presented. In addition, a quasi-simultaneous multiparameter characterization of the sensor chip in buffer solutions with different pH value and electrolyte conductivity is performed. To study the sensor behavior and the suitability of BST as multifunctional material under harsh environmental conditions, the sensor chip was exemplarily tested in a biogas digestate.
Use of textile structures for reinforcement of pelvic floor structures has to consider mechanical forces to the implant, which are quite different to the tension free conditions of the abdominal wall. Thus, biomechanical analysis of textile devices has to include the impact of strain on stretchability and effective porosity. Prolift® and Prolift + M®, developed for tension free conditions, were tested by measuring stretchability and effective porosity applying mechanical strain. For comparison, we used Dynamesh-PR4®, which was designed for pelvic floor repair to withstand mechanical strain. Prolift® at rest showed moderate porosity with little stretchability but complete loss of effective porosity at strain of 4.9 N/cm. Prolift + M® revealed an increased porosity at rest, but at strain showed high stretchability, with subsequent loss of effective porosity at strain of 2.5 N/cm. Dynamesh PR4® preserved its high porosity even under strain, but as consequence of limited stretchability. Though in tension free conditions Prolift® and Prolift + M® can be considered as large pore class I meshes, application of mechanical strain rapidly lead to collapse of pores. The loss of porosity at mechanical stress can be prevented by constructions with high structural stability. Assessment of porosity under strain was found helpful to define requirements for pelvic floor devices. Clinical studies have to prove whether devices with high porosity as well as high structural stability can improve the patients' outcome.