Dielectric relaxation of polar aromatics in unoriented and oriented linear low‐density polyethylene

The dielectric behavior of some polar aromatics dissolved in nonpolar unoriented and stretched linear low‐density polyethylene was investigated within the temperature region between 150 and 350 K. The measurements were carried out in the frequency range 1 kHz to 10 MHz. The maximum temperatures and the half widths of the loss tangent peaks depend upon the shape and the polar structure of guest molecules. Stretching the samples induced a shift of the loss tangent to higher temperatures, decreased the height, and increased the width of tan δ peak. The activation energy is also influenced by the type of guest molecules and orientation of polymer matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1278–1282, 2001     

TEMPO‐controlled radical suspension polymerization of poly(styrene)‐block‐poly(styrene‐co‐acrylonitrile) and poly(styrene)‐block‐poly(styrene‐co‐butyl methacrylate)

Suspension polymerization expands the study of controlled radical polymerization to high conversions and is known as a method to synthesize polymers with high molecular weights. The radical block copolymerizations of styrene (S) and acrylonitrile (AN) or butyl methacrylate (BUMA) controlled by 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) was performed in an oil/water pressure reactor system at a temperature of 125°C. TEMPO‐terminated styrene homopolymer was employed as macroinitiator. The systems were examined by varying the composition of the monomer mixture at a constant reaction time, as well as by varying the reaction time for a characteristic monomer composition to get all of the possible conversion range. The solubility effects of acrylonitrile in the suspension medium were considered. Furthermore, the yield of the reaction was improved through initiator addition by taking control of the reaction. The polymerizations could proceed under control up to a conversion of 80–90%. By using the copolymerization equations, the solubility of pure acrylonitrile in the suspension medium could be calculated and was found to be 8 wt.‐%.     

Studium der lebenden radikalischen Polymerisation mit der Differential Scanning Calorimetry (DSC)

The living radical polymerization of styrene, some styrene-analogous vinyl monomers as well as methyl methacrylate (MMA) and butyl methacrylate (BuMA) was investigated with a differential scanning calorimeter. The ability to polymerize was estimated by dynamic measurements, showing that p-methylstyrene, p-chlorostyrene, 3,4-dimethoxystyrene and 4-vinylpyridine polymerize in the presence of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) while MMA and BuMA do not. Isothermal measurements revealed an activation energy of E_A = 81 kJ mol^–1 for thermal bulk polymerization of styrene and values of E_A = 78–94 kJ mol^–1 were measured with different iniferter systems. These polymerizations have induction times which depend on the reaction temperature and the initial concentration of the iniferter systems. An influence of the kind of nitroxyl radical on the induction times was not observed.     

Aluminum Production in the Times of Climate Change: The Global Challenge to Reduce the Carbon Footprint and Prevent Carbon Leakage

JOM - This paper addresses the global challenge of greenhouse gas emissions facing the aluminum industry. The demand, production and use of aluminum are increasing and so are the emissions. From...     

High conversion study of “living” radical polymerization of styrene using DSC

The influence of temperature on nitroxide-controlled living radical polymerization of styrene was examined. It has been established that only in a temperature range of 110°C to 150°C nitroxides are able to control radical polymerization. At temperatures above 160°C the reaction was of rather a free radical character. The results were similar for all the various nitroxides used as capping agents: TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-TEMPO, 4-oxo-TEMPO and 4-acetamido-TEMPO. Differences were found only in the induction times of polymerization and were probably due to side reactions with the initiator (benzoyl peroxide). Living radical polymerization can be best controlled with these nitroxides at temperatures between 120°C and 140°C.     

Influence of N-oxyls on the free radical autopolymerization of styrene

Through comparative studies on the controlled thermally initiated radical polymerization of styrene in the presence of N-oxyls, the effect of the type of the N-oxyls (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (OH-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (oxo-TEMPO) and 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl (acetamido-TEMPO)), as well as the concentration of the N-oxyls (3–20 mmol L^–1) are discussed. The radical formation proceeds exclusively through the thermal initiation of styrene, i.e. without using any initiator. It is observed, that the thermal self-initiation of styrene increases the radical yield remarkably with the N-oxyls concentration, independent of the type of the N-oxyl. The concentration-dependent side reactions of substituted N-oxyls are remarkably more pronounced than those of unsubstituted N-oxyl. This leads to the reduction of the overall rate of polymerization (v_br) as compared to TEMPO (v_br = v_br (thermal polymerization)) with respect to the concentration, but independent of the type of substituents.     

Untersuchungen zur Naßvernetzung von Lyocell-Fasern

The high wet fibrillation tendency of Lyocell fibres forms the background to this investigation. The wet abrasion behaviour can be improved by crosslinking reactions. Substances containing sulfato ethyl sulfonyl groups but different bridging groups were synthesised and optimised regarding to their application. The wet fibrillation tendency can be reduced clearly with these selected substances. If the concentration of the crosslinking agent on the fibre is the basis of comparisons the different structures have a similar effect on the fibrillation tendency. So the swollen Lyocell fibre permits a crosslinking reaction with curing agents of different size.     

Alloy Design,Combinatorial Synthesis,and Microstructure–Property Relations for Low-Density Fe-Mn-Al-C Austenitic Steels

We present recent developments in the field of austenitic steels with up to 18% reduced mass density. The alloys are based on the Fe-Mn-Al-C system. Here, two steel types are addressed. The first one is a class of low-density twinning-induced plasticity or single phase austenitic TWIP (SIMPLEX) steels with 25–30 wt.% Mn and <4–5 wt.% Al or even <8 wt.% Al when naturally aged. The second one is a class of κ-carbide strengthened austenitic steels with even higher Al content. Here, κ-carbides form either at 500–600°C or even during quenching for >10 wt.% Al. Three topics are addressed in more detail, namely, the combinatorial bulk high-throughput design of a wide range of corresponding alloy variants, the development of microstructure–property relations for such steels, and their susceptibility to hydrogen embrittlement.