Influence of polymeric flame retardants based on phosphorus‐containing polyesters on morphology and material characteristics of poly(butylene terephthalate)

Flame retarded poly(butylene terephthalate) (PBT) is required for electronic applications and is mostly achieved by low molar mass additives so far. Three phosphorus‐containing polyesters are suggested as halogen‐free and polymeric flame retardants for PBT. Flame retardancy was achieved according to cone calorimeter experiments showing that the peak heat release rate and total heat evolved were reduced because of flame inhibition and condensed‐phase activity. The presented polymers containing derivatives of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide form immiscible blend systems with PBT. Shear‐rheology shows an increase in storage moduli at low frequencies. This is proposed as quantitative measure for the degree of phase interaction. The phase structure of the blends depends on the chemical structure of the phosphorus polyester and was quite different, depending also on the viscosity ratio between matrix and second phase. A lower viscosity ratio leads to two types of phases with spherical and additionally continuous droplets. Addition of the flame retardants showed no influence on the dielectric properties but on the mechanical behavior. The polymeric flame retardants significantly diminish the impact strength because of several reasons: (1) high brittleness of the phosphorus polyesters themselves, (2) thermodynamic immiscibility, and (3) weak phase adhesion. By adding a copolymer consisting of the two base polymers to the blend, an improvement of impact strength was obtained. The copolymer particularly acts as compatibilizer between the phases and therefore leads to a smaller phase size and to a stronger phase adhesion due to the formation of fibrils. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Production of 1‐Octanol from n‐Octane by Pseudomonas putida KT2440

A two‐phase biotransformation process for selective hydroxylation of n‐octane to 1‐octanol via Pseudomonas putida KT2440 harboring heterologously expressed P450 monooxygenase from Mycobacterium marinum is presented. Maximum cell‐specific conversion rates of 12.7 mg_octanol g_CDWh^–1 were observed not only in shaking flasks but also in 3.7‐L‐bioreactor studies. The bioreactor experiments were performed avoiding explosive gas mixtures by lowering volumetric power input, aeration rates and substrate concentrations. Based on a stoichiometric network of P. putida KT2440 topological studies were carried out. As a conclusion, potential limitations of NAD(P)H and/or ATP supply at production conditions can be excluded. Hence, the great potential of the host for further increasing conversion is outlined.     

Validation of a numerical approach to model pyrolysis of biomass and assessment of kinetic data

The objective of this contribution is to introduce a numerical approach that predicts pyrolysis of various biomasses under various boundary conditions such as particle geometry and heating rate. Hence, the approach is applicable to numerical tools that help exploiting further the potential of biomass as an energy resource. Furthermore, it is intended to represent the general trend of state of the art in model developments. The presented model itself is based on one-dimensional and transient differential conservation equations for mass, momentum, species and energy. In order to account for a variety of reaction schemes a formulation based on the Arrhenius equation including intrinsic modelling is chosen. It is believed to represent the majority of kinetic pyrolysis data derived from experiments. Applying this single numerical approach to predict pyrolysis under varying experimental conditions for different materials always revealed good agreement with measurements.     

Stereoisomeric flavour compounds

The enantiomeric distribution of 3-mercaptohexanol (1) and 3-methylthiohexanol (2) in yellow and purple passion fruits was determined by capillary gas chromatography (GC) using two different chiral stationary phases and a flame photometric detector. The results were confirmed by enantioselective capillary GC combined with mass spectrometric detection.1 shows an enrichment of the (S)-enantiomer, but the enantiomeric purity varies in a wide range. Irrespective from the enantiomeric distribution of1, 2 was detected with high enantiomeric purity in favour of the (S)-enantiomer. Using the method presented the addition of synthetic, racemic2 is easily detected.     

Surface reactions on inverse model catalysts: CO adsorption and CO hydrogenation on vanadia- and ceria-modified surfaces of rhodium and palladium

Reducible transition metal oxides are well-known promoters of the hydrogenation of CO on noble metal surfaces. In this study the promotional effect of vanadia and ceria adlayers on Rh and Pd surfaces was investigated with emphasis on the effect of the oxidation state on CO adsorption and catalytic activity. Inverse supported catalysts were prepared by UHV deposition of V and Ce on the noble metal surface (Rh(111), Pd(111) or Rh foil). After oxidation and specified reduction, the reaction kinetics on polycrystalline Rh was measured at atmospheric pressure, and the molecular and dissociative chemisorption of CO on Rh(111) and Pd(111) and the methanation kinetics on Rh(111) were investigated by molecular beam techniques. On Rh(111), the probability of CO dissociation and the reaction rate are enhanced by submonolayer VO _x deposits. Local pressures between 10^-2 and 1 mbar are sufficient to drive the methanation at 573 K with measurable amounts of products, accompanied by significant restructuring of the catalyst surface. Although the reaction on Rh is generally promoted by small quantities of vanadia and ceria, the reaction rates depend strongly on the extent and temperature of hydrogen reduction. The observed increase of the reaction rate by reduction up to 673 K can be correlated to concomitant changes of the structure and composition of the VO _x deposits. If the reduction temperature is raised above 673 K, metallic V is partially dissolved in the bulk, and the resulting V/Rh subsurface alloy exhibits a particularly high activity. Contrary to vanadia, ceria islands on Rh promote the initial reaction only after a low-temperature reduction, but the activity decreases after reduction above 573 K.     

Magnetic penetration depth of Tl2Ba2CuO6+δ:Tc～σ0 in the overdoped region

We report transverse-field muon-spin-rotation experiments carried out on Tl₂Ba₂CuO₆₊ . This system spans the whole overdoped regime, andT _c is reduced by excess oxygen doping, which increases the normal-state carrier concentration. In the heavily overdoped regime(0) is found to scale linearly with the superconducting critical temperatureT _c , similar to the behavior previously observed for other cuprates in the underdoped regime. However, for the overdoped region one has to explain the reduction of ₀, thus the increase of the magnetic penetration depth, in spite of an increasing normal-state carrier concentration. We discuss some possible explanations for this behavior.     

Noise characteristics in line-narrowed semiconductor lasers with optical feedback

Effects of optical-feedback-induced line-narrowing on low-frequency amplitude and phase noise of semiconductor lasers are reported. Free-running laser noise is compared with that of lasers operating with external mirror feedback. While less than 1 dB difference in the amplitude noise with and without feedback is observed, line-narrowed lasers exhibit 15?20 dB reduction in low-frequency wavelength instability, or phase noise.     

On-line fermentation monitoring by mid-infrared spectroscopy

A new method for on-line monitoring of fermentations using mid-infrared (MIR) spectroscopy has been developed. The method has been used to predict the concentrations of glucose and ethanol during a baker's yeast fermentations. A completely automated flow system was employed as an interface between the bioprocess under study and the Fourier transform infrared (FT-IR) spectrometer, which was equipped with a flow cell housing a diamond attenuated total reflection (ATR) element. By using the automated flow system, experimental problems related to adherence of CO(2) bubbles to the ATR surface, as well as formation of biofilms on the ATR surface, could be efficiently eliminated. Gas bubbles were removed during sampling, and by using rinsing steps any biofilm could be removed from the ATR surface. In this way, constant measuring conditions could be guaranteed throughout prolonged fermentation times (approximately 8 h). As a reference method, high-performance liquid chromatography (HPLC) with refractive index detection was used. The recorded data from different fermentations were modeled by partial least-squares (PLS) regression comparing two different strategies for the calibration. On the one hand, calibration sets were constructed from spectra recorded from either synthetic standards or from samples drawn during fermentation. On the other hand, spectra from fermentation samples and synthetic standards were combined to form a calibration set. Differences in the kinetics of the studied fermentation processes used for calibration and prediction, as well as the precision of the HPLC reference method, were identified as the main chemometric sources of error. The optimal PLS regression method was obtained using the mixed calibration set of samples from fermentations and synthetic standards. The root mean square errors of prediction in this case were 0.267 and 0.336 g/L for glucose and ethanol concentration, respectively.