Stretching and deformation vibrations of CH2, C(CH3) and O(CH3) groups of poly(methyl methacrylate)

Infrared and Raman spectra of atactic PMMA and infrared spectra of stereoregular PMMA and of its four deuterated derivatives

, were measured. They were used to assign the bands of stretching and deformation vibrations of CH₂, CCH₃ and OCH₃ groups in the infrared and Raman spectra and to discuss the effect of stereoregularity on these bands in the infrared spectra.     

Detailed Molecular Structure Modeling – A Path Forward to Designing Application Properties of ldPE

Summary: This paper describes a step on the ambitious aim to “design” application properties of ldPE by first simulating the detailed molecular structure of a high‐pressure tubular reactor product. The reactor of a certain configuration produces under well‐defined operating conditions. The next step is to correlate the structure with the application properties. Finally, the sequence will be reversed in order to deduce the operating conditions, which lead to the desired product quality. Two‐dimensional distributions, in molecular weight and branching frequency, as well a two compartment models with a core and a shell stream were simulated and compared with experimental results. Therefore, CFD simulations were carried out to discretize the reaction medium. Samples were taken from both pilot and commercial plants. The TREF‐SEC analytical method was successfully applied in order to measure the microscopic structure of the material. The tremendous numerical problems were solved with the help of the software PREDICI .

Detailed MWD for a pilot scale reactor product.     

Iron(II)‐based catalysts for ethene oligomerization

The synthesis of iron(II) complexes with various tridentate di(imino)pyridine ligands and their potential as ethene oligomerization catalysts are described. The ligands are characterized by ¹H‐ and ¹³C‐NMR spectroscopy and the complexes only by mass spectrometry due to their paramagnetism. After activation either with methylalumoxane (MAO) or with a heterogeneous cocatalyst consisting of partially hydrolyzed trimethylaluminum and silica gel, the prepared complexes proved to be good catalysts for the oligomerization of ethene. 1‐Octene, 1‐hexene, and 1‐decene were the major products, formed in very high isomeric purity (99.9 %). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 476–482, 2003     

Mandibular gland allomones ofDasymutilla occidentalis and other mutillid wasps

The mandibular gland secretion of the mutillid wasp,Dasymutilla occidentalis, possesses three short-chained ketones-4-methyl-3-heptanone (4MH), 4,6-dimethyl-3-nonanone (4,6DMN), 4,6-dimethyl-3-octanone (4,6DMO)—and several unidentified compounds. This is the first report of 4,6DMN as a natural product and its synthesis is described. These ketones, which are either known to be ant alarm pheromones or are structurally very similar to ant alarm pheromones, appear to function as allomones against ants, major potential predators of mutillid wasps. The major secretory component, 4-methyl-3-heptanone, which was identified in females and/ or males of the species analyzed within the generaDasymutilla, Timulla, Traumatomutilla, andPappognatha, appears to constitute a chemical character of the defensive secretions of these genera.     

The Resource-Energy Nexus as a Key Factor for Circular Economy

The extraction of raw materials is associated with energy input and CO₂ emissions. What is obvious for extraction from mining, however, also applies to recycling. Mostly, recycling is preferred for reasons of climate protection or because of the geological scarcity of raw materials, which is controversially discussed. While in mining, the declining ore grade is a driver for the energy demand, in case of recycling it is the dissipation of materials into products or waste. As concentration decreases, the effort required also increases disproportionately. The “closing the loop” metaphor of Circular Economy is therefore inappropriate in its stricter meaning. It is rather about optimizing the overall system and finding the optimal recycling rate. However, first, it must be clarified what the political goals for Circular Economy are.     

New developments in cold spray based on higher gas and particle temperatures

In cold spraying, bonding is associated with shear instabilities caused by high strain rate deformation during the impact. It is well known that bonding occurs when the impact velocity of an impacting particle exceeds a critical value. This critical velocity depends not only on the type of spray material, but also on the powder quality, the particle size, and the particle impact temperature. Up to now, optimization of cold spraying mainly focused on increasing the particle velocity. The new approach presented in this contribution demonstrates capabilities to reduce critical velocities by well-tuned powder sizes and particle impact temperatures. A newly designed temperature control unit was implemented to a conventional cold spray system and various spray experiments with different powder size cuts were performed to verify results from calculations. Microstructures and mechanical strength of coatings demonstrate that the coating quality can be significantly improved by using well-tuned powder sizes and higher process gas temperatures. The presented optimization strategy, using copper as an example, can be transferred to a variety of spray materials and thus, should boost the development of the cold spray technology with respect to the coating quality. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Why do fish strand? An analysis of ten years of flow reduction monitoring data from the Columbia and Kootenay rivers,Canada

Stranding of fish due to flow reductions has been documented in the near shore of the Columbia and Kootenay Rivers, Canada, and can result in sub‐lethal or lethal effects on fish. Ten years (1999–2009) of monitoring data have been collected at sites below two hydro‐electric dams (Hugh‐L‐Keenleyside and Brilliant Dam) following flow reductions. A generalized linear mixed effects model analysed the probability of a stranding event in relation to environmental and operational variables including the rate of change in the water levels, the duration of shoreline inundation prior to a reduction (wetted history), the river stage, the magnitude of the reduction, distance downstream from the dam, time of day, day of year (season) and whether a site had been physically altered to mitigate stranding. The results demonstrated statistically significant effects on stranding risk from minimum river stage, day of the year and whether a site had been physically re‐contoured. The combination of investigated factors giving the highest probability of stranding was a large magnitude reduction completed in the afternoon in midsummer, at low water levels when the near shore had been inundated for a long period. This research is significant in its approach to assessing years of ecosystem scale monitoring data and using the modelling results to determine ways for these findings to be applied in regulated river management to minimize fish stranding. It also highlighted data gaps that require addressing and provides ecosystem scale results to compare with stranding studies carried out in mesocosms. © 2014 The Authors. River Research and Applications published by John Wiley & Sons Ltd.     

Backscatter from the data plane – Threats to stability and security in information-centric network infrastructure

Information-centric networking (ICN) raises data objects to first class routable entities in the network and changes the Internet paradigm from host-centric connectivity to data-oriented delivery. However, current approaches to content routing heavily rely on data-driven protocol events and thereby introduce a strong coupling of the control to the data plane in the underlying routing infrastructure. In this paper, threats to the stability and security of the content distribution system are analyzed in theory, simulations, and practical experiments. We derive relations between state resources and the performance of routers, and demonstrate how this coupling can be misused in practice. We further show how state-based forwarding tends to degrade by decorrelating resources. We identify intrinsic attack vectors present in current content-centric routing, as well as possibilities and limitations to mitigate them. Our overall findings suggest that major architectural refinements are required prior to global ICN deployment in the real world.     

Robustness of an aerobic metabolically vinyl chloride degrading bacterial enrichment culture

Degradation of the lower chlorinated ethenes is crucial to the application of natural attenuation or in situ bioremediation on chlorinated ethene contaminated sites. Recently, within mixtures of several chloroethenes as they can occur in contaminated groundwater inhibiting effects on aerobic chloroethene degradation have been shown. The current study demonstrated that metabolic vinyl chloride (VC) degradation by an enrichment culture originating from groundwater was not affected by an equimolar concentration (50 μM) of cis-1,2-dichloroethene (cDCE). Only cDCE concentrations at a ratio of 2.4:1 (initial cDCE to VC concentration) caused minor inhibition of VC degradation. Furthermore, the degradation of VC was not affected by the presence of trans-1,2-dichloroethene (tDCE), 1,1-dichloroethene (1,1-DCE), trichloroethene (TCE), and tetrachloroethene (PCE) in equimolar concentrations (50 μM). Only cDCE and tDCE were cometabolically degraded in small amounts. The VC-degrading culture demonstrated a broad pH tolerance from 5 to 9 with an optimum between 6 and 7. Results also showed that the culture could degrade VC concentrations up to 1,800 μM (110 mg/L).     

Validation of GOES and MODIS active fire detection products using ASTER and ETM+ data

In this study we implemented a comprehensive analysis to validate the MODIS and GOES satellite active fire detection products (MOD14 and WFABBA, respectively) and characterize their major sources of omission and commission errors which have important implications for a large community of fire data users. Our analyses were primarily based on the use of 30 m resolution ASTER and ETM+ imagery as our validation data. We found that at the 50% true positive detection probability mark, WFABBA requires four times more active fire area than is necessary for MOD14 to achieve the same probability of detection, despite the 16× factor separating the nominal spatial resolutions of the two products. Approximately 75% and 95% of all fires sampled were omitted by the MOD14 and WFABBA instantaneous products, respectively; whereas an omission error of 38% was obtained for WFABBA when considering the 30-minute interval of the GOES data. Commission errors for MOD14 and WFABBA were found to be similar and highly dependent on the vegetation conditions of the areas imaged, with the larger commission errors (approximately 35%) estimated over regions of active deforestation. Nonetheless, the vast majority (> 80%) of the commission errors were indeed associated with recent burning activity where scars could be visually confirmed in the higher resolution data. Differences in thermal dynamics of vegetated and non-vegetated areas were found to produce a reduction of approximately 50% in the commission errors estimated towards the hours of maximum fire activity (i.e., early-afternoon hours) which coincided with the MODIS/Aqua overpass. Lastly, we demonstrate the potential use of temporal metrics applied to the mid-infrared bands of MODIS and GOES data to reduce the commission errors found with the validation analyses.