Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical Termination The photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides ( 1 – 4 ) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the S S bond, which was determined by spin trapping experiments with phenyl tert-butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.     

Influence of different wood flour fractions on the mechanical properties of injection molded WPC with cellulose propionate

This research investigated the effect of different fractions of commercial wood flour (Type c100 from JRS, Germany) on mechanical and physical properties of wood-polymer composites (WPC). The fractions were named regarding the mean lengths of their particles in µm; 80, 130, 255, 405 and 485. The composite samples were manufactured with 30 wt% of wood flour fractions of all five groups as well as the not fractionated flour, and 70 wt% of cellulose propionate (CP). The melt mass-flow rate (MFR) of the different granules, tensile strength, and modulus of elasticity, flexural strength, flexural modulus and the impact strength of the injection molded specimens as well as the water uptake were determined in this study. WPCs with the specific size range used in this investigation exhibited improved strength and modulus of elasticity in tensile and flexural tests, compared to pure CP. Using fraction 255, the mechanical properties increased the most. Tensile strength rose by 28 and 13% compared to CP and to WPC with the not fractioned wood powder, respectively. Fraction 255 increased flexural strength by 33 and 5% compared to CP and WPC with the not fractioned flour. The MFR (tested at 190 °C with 7.16 kg) of WPC_255 is the lowest with 2.3 g/10 min. Composites with the smallest particles showed the least water uptake.     

Thermophysical and Microstructural Studies on Thermally Sprayed Tungsten Carbide-Cobalt Coatings

The development of new hardmetal coating applications such as fatigue-loaded parts, structural components, and tools for metal forming is connected with improvement of their performance and reliability. For modelling purposes, the knowledge of thermophysical, mechanical, and other material data is required. However, this information is still missing today. In this study, the thermophysical data of a WC-17Co coating sprayed with a liquid-fuelled HVOF-process from a commercial agglomerated and sintered feedstock powder from room temperature up to 700 °C was determined as an example. The dependence of the heat conductivity on temperature was obtained through measurement of the coefficient of thermal expansion, the specific heat capacity, and the thermal diffusivity. Heat conductivities ranging from 29.2 W/(mK) at 50 °C to 35.4 W/(mK) at 700 °C were determined. All measurements were performed twice (as-sprayed and after the first thermal cycle) to take into account the structural and compositional changes. Extensive XRD and FESEM studies were performed to characterize the phase compositions and microstructures in the as-sprayed and heat-treated states. Bulk samples obtained by spark plasma sintering from the feedstock powder were studied for comparison.     

Investigations of ductile damage during the process chains of toothed functional components manufactured by sheet-bulk metal forming

Sheet-bulk metal forming processes combine conventional sheet forming processes with bulk forming of sheet semi-finished parts. In these processes the sheets undergo complex forming histories. Due to in- and out-of-plane material flow and large accumulated plastic strains, the conventional failure prediction methods for sheet metal forming such as forming limit curve fall short. As a remedy, damage models can be applied to model damage evolution during those processes. In this study, damage evolution during the production of two different toothed components from DC04 steel is investigated. In both setups, a deep drawn cup is upset to form a circumferential gearing. However, the two final products have different dimensions and forming histories. Due to combined deep drawing and upsetting processes, the material flow on the cup walls is three-dimensional and non-proportional. In this study, the numerical and experimental investigations for those parts are presented and compared. Damage evolution in the process chains is simulated with a Lemaitre damage criterion. Microstructural analysis by scanning electron microscopy is performed in the regions with high mechanical loading. It is observed that the evolution of voids in terms of void volume fraction is strongly dependent on the deformation path. The comparison of simulation results with microstructural data shows that the void volume fraction decreases in the upsetting stage after an initial increase in the drawing stage. Moreover, the concurrent numerical and microstructural analysis provides evidence that the void volume fraction decreases during compression in sheet-bulk metal forming.     

Identification of the Sex Pheromone of the Currant Shoot Borer Lampronia capitella

Under an artificial light:dark cycle, females of Lampronia capitella were observed calling, with extended terminal abdominal segments, during the first 2 hr of the photoperiod. Extracts of terminal abdominal segments from females elicited large electroantennographic responses from male antennae. Gas chromatography with electroantennographic detection revealed three active peaks. Based on comparison of retention times and mass spectra of synthetic standards, these compounds were identified as (Z,Z)-9,11-tetradecadienol and the corresponding acetate and aldehyde. The electroantennographic activity of the four geometric isomers of all three compounds was investigated, and the respective (Z,Z)-isomer was found to be the most active in all cases. Aldehydes generally elicited larger antennal responses than alcohols, whereas acetates were the least active compounds. A subtractive trapping assay in the field, based on a 13:26:100 micrograms mixture of (Z,Z)-9,11-tetradecadienal, (Z,Z)-9,11-tetradecadienyl acetate, and (Z,Z)-9,11-tetradecadienol confirmed that all three compounds are pheromone components. Subtraction of (Z,Z)-9,11-tetradecadienol from the blend completely eliminated its attractiveness, whereas the other two-component blends showed reduced activity. This is the first pheromone identification from the monotrysian superfamily Incurvarioidea, confirming that the common pheromones among ditrysian moths (long-chain fatty acid derivatives comprising alcohols, acetates, and aldehydes with one or more double bonds) is not an autapomorphy of Ditrysia, but a synapomorphy of the more advanced heteroneuran lineages.     

Nitrous oxide emission as affected by liming an acidic mineral soil used for arable agriculture

The effect of liming an acidic mineral soil (Dystric Nitosol from southern China), used for arable agriculture, on N₂O emission was studied in an incubation experiment. After the soil pH had been raised from pH 4.4 to 5.2, 6.7 and 8.1, soil samples were either amended with NH₄ ⁺ and incubated aerobically, favoring nitrification or, after application of NO₃ ^–, the incubation took place under anaerobic conditions, favoring denitrification. Gas sampling for N₂O determination and soil analyses were performed at regular intervals up to 13 days. Under nitrification conditions only small N₂O emission rates were observed (max. 6 g N kg^–1 d^–1) with significant differences between high and low pH values during the first 2 days of incubation. The nitrifying activity was low, even with high pH, and this, together with good aeration conditions, could partly explain the small N₂O evolution. During denitrification, however, cumulative N₂O emissions reached much higher values (1600 g N kg^–1 in comparison to 40 g N kg^–1 under nitrification conditions). N₂O emission during denitrification was significantly enhanced by increasing soil pH. Under alkaline conditions (pH 8.1) a large nitrite accumulation occurred, which was in line with the highest nitrate reductase activity determined in this treatment. The limited availability of organic carbon is probably the main reason for the absence of further reduction of NO₂ ^– to N₂O or N₂. At pH 6.7 the total N₂O emission was slightly higher than at pH 8.1, although the start of pronounced emissions was retarded and only small amounts of NO₂ ^– accumulated. Acid soil conditions caused either negligible (pH 4.4) or only small (pH 5.2) N₂O emissions. It can be concluded that these kinds of soil, used alternatively for production of upland crops or paddy rice, are prone to high N₂O emissions after flooding, particularly under neutral to alkaline conditions. In order to avoid major N₂O evolution and accumulation of nitrite, which can be leached into groundwater, the pH should not be raised to values above 5.5–6.     

Studies on the Effect of Physico‐Chemical Soot Properties and Feed Gas Composition on the Kinetics of Soot Oxidation on Fe2O3 Catalyst

Three commercial carbon black samples as well as self‐made C₃H₆ soot were investigated for their reactivity in the oxidation on an α‐Fe₂O₃ catalyst. These studies were performed by temperature programmed oxidation (TPO) using a packed bed. For reference purposes, TPO studies in the absence of the catalyst were made as well. The carbon black samples were characterized towards the content of C, H, N and O as well as higher heating value, specific surface area, moisture and volatile matter and were deemed to be suitable model substances for diesel soot of different maturity. The correlation of these physico‐chemical properties with the kinetics in catalytic TPO indicated that the soot oxidation on Fe₂O₃ is significantly affected by the initial number of surface oxygen compounds of the soot. The decomposition of these surface species causes the formation of active carbon sites, which are supposed to accelerate the soot oxidation.     

Influence of processing on morphology in short aramid fiber reinforced elastomer compounds

The rubber industry is nowadays facing the general increase of raw materials as the customers are confronted with rising prices for energy. Therefore there is a need for higher durability of elastomer applications. Short fiber reinforced elastomers can contribute to the improvement of dynamic and wear properties. To determine structure–property relationships in short fiber reinforced elastomer compounds it is of crucial interest to know the contributions of fiber aspect ratio, volume content, orientation and fiber–elastomer interaction. Therefore the influence of different processing conditions and fiber contents on the resulting morphology and macroscopic properties was investigated in this article by the help of fluorescence and confocal laser microscopy using a transparent ethylene‐propylene‐diene rubber (EPDM) matrix. It was found that the processing induced fiber breakage was the key factor in determining the composite morphology and subsequent physical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1682–1690, 2013     

Application of PSRK for Process Design

A survey about the current status and potential of the predictive Soave-Redlich-Kwong (PSRK) group contribution equation of state (EoS) is given. The PSRK method combines the SRK EoS with the UNIFAC group contribution model by the PSRK mixing rule. The availability of a large number of interaction parameters between UNIFAC and new PSRK main groups allows calculating the phase equilibrium behavior and other thermodynamic quantities for various kinds of systems even with strong electrolytes. Different fields of application are discussed: the prediction of gas solubilities in asymmetric systems, the air solubility calculated for mixed solvents, the removal of H₂S from natural gas by predicting the physical absorption, and the calculation of the enthalpy effects of absorption processes with pressure and temperature.     

An ARL-unbiased thinning-based EWMA chart to monitor counts

Abstract

Shewhart control charts are known to be somewhat insensitive to shifts of small and moderate size. Expectedly, alternative control schemes such as the exponentially weighted moving average (EWMA) charts have been proposed to speed up the detection of such shifts. Unfortunately, applying the ordinary EWMA recursion to count data leads to a control statistic no longer with a fixed discrete range. Therefore, we propose a novel chart which relies on a EWMA control statistic where the usual scalar product is replaced by a thinning operation. Actually, we use the new fractional binomial thinning to avoid the typical over-smoothing ascribable to ceiling, rounding, and flooring operations. The properties of this discrete statistic are similar to the ones of its continuous EWMA counterpart and the run length (RL) performance of the associated chart can be computed exactly using the Markov chain approach for independent and identically distributed (i.i.d.) counts. Moreover, this chart is set in such way that: the average run length (ARL) curve attains a maximum in the in-control situation, i.e., the chart is ARL-unbiased; and the in-control ARL is equal to a pre-specified value. We use the R statistical software to provide compelling illustrations of this unconventional EWMA chart and to compare its RL performance with the ones of a few competing control charts for the mean of i.i.d. Poisson counts.