Zur oligomerenbildung bei der thermischen polymerisation von styrol

It is shown that in thermal polymerization of styrene four dimers and six trimers are formed by parallel occurring oligomerization reactions. With increasing temperature the rate of oligomerization increases more rapidly than the rate of polymerization. The relativ yields of the different oligomers depend on temperature, too.     

Struktur und eigenschaften von ABS-polymeren. IX. Quantitative untersuchungen zur morphologie von ABS-polymerisaten

The technological properties of ABS polymers largely depend on the structure of the elastomer phase as well as on the elastomer/thermoplast interface. The morphological structure of such polymers can be determined from electron micrographs of ultramicrotome sections – after selective contrasting of the polybutadiene phase – or of replicas of fracture surfaces after selective chemical degradation. The various ABS polymers are classified by their manufacturing processes and their morphologies and characterized by electron micrographs. The degree and place of grafting are of particular importance. The quantitative determination of the surface- and internal grafting is achieved by combining the determination of the degree of grafting (extraction), the evaluation of the results obtained on particle counting, and a morphometric process. It is demonstrated that the morphometric process can in general be applied for the quantitative determination of the contrastable component in two-phase polymers.     

Das Verhalten organischer Pigmente in Polymeren

The importance of colouring matter is of prime importance in the plastics industry. The individual behaviour of organic pigments in the various polymer materials necessitates, however, on the part of the plastics manufacturer a precise knowledge of ?which pigment for which plastic”?. For example, a well known Thioindigo pigment behaves very differently in various polymer materials : In polystyrene, depending on the concentration used, it is monomolecularly dissolved, in associated solution or present as undissolved particles. In PVC, however, the good migration fastness is indicative of the insolubility of the pigment in this medium and so it is not surprising that PVC is the ideal plastic medium for this pigment. The behaviour of organic pigments in polymers is largely a function of molecular structure, e. g. intermolecular H-bonds can cause a decrease in solubility of a pigment in a polymer material, which in turn results in improved migration fastness. This is demonstrated by the improved migration fastness of variously substituted β-hydroxy naphthoic acid arylamide derivatives. Many phenomena exist however, which as yet can only be explained on the basis of the crystal structure of the pigment particles, i. e. the presence of aggregates or agglomerates. Such a phenomenon is, for example, the dispersibility of pigments in polymers. Here pigment surface, wettability by polymer and intermolecular forces are all of importance. In general, the dispersibility is better the smaller the specific surface area, as is shown for a typical quinacridone pigment. The influence of the rate of wetting on dispersibility is demonstrated using polyethylene wax. A further effect, which demonstrates the intermolecular forces between pigment and polymer, is the way in which certain pigments influence the rate of crystallization of partly crystalline polymers. This itself is connected with the shape and size of the pigment particles embedded in the polymer material. Such effects are demonstrated by measurements on various polyethylene objects. The pigment in this case was a naphthalene tetra carbonic acid derivative in both cis and trans form with widely varying specific surface areas.     

Compatibilisation of PPE/SAN blends by triblock terpolymers: Correlation between block terpolymer composition, morphology and properties

Immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN) with a weight composition of 60/40 were compatibilised by polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymers (SBM) using a two-stage melt-processing approach. In order to investigate the influence of the SBM composition on the compatibilisation efficiency, the block lengths of the triblock terpolymers were systematically varied. The resulting morphological features of the blend systems as function of SBM composition and processing parameters are correlated with the resulting thermal and thermo-mechanical properties. In the ideal case, SBM should be located at the interface as PS is miscible with PPE while PMMA is miscible with SAN. The elastomeric middle block as an immiscible component should remain at the interface. This particular morphological arrangement is known as the ‘raspberry morphology’. A detailed TEM analysis of the blend morphologies following initial extrusion-compounding revealed a high compatibilisation efficiency of the SBM types with equal lengths of the end blocks and, furthermore, the desired raspberry morphology was achieved. In contrast, high PS contents in comparison to the other blocks led to a pronounced micelle formation in the PPE phase. Further evaluation of the blend structures following injection-moulding indicated that the morphologies remain relatively stable during this second melt-processing step. A detailed thermal analysis of all blend systems supports the interpretation of the observed morphological features. The fundamental correlation between SBM composition and blend morphology established in this study opens the door for the controlled development of interfacial properties of such compatibilised PPE/SAN blends during melt-processing.     

Zur Selbstdiffusion von Benzol und Azeton in Polymethylmethacrylat

The selfdiffusion coefficients of acetone and benzene are studied in the systems acetone/poly(methylmethacrylate) and benzene/poly(methylmethacrylate) by means of the spin echo technique as function of concentration and temperature. From the dependence of temperature, the activation energies are calculated as function of concentration. The dependence of concentration of the selfdiffusion coefficients is discussed using the theory of Free Volume according to FUJITA. The Free Volume of the poly(methylmethacrylate) is calculated as function of temperature.     

Intercorrelations among plasma high density lipoprotein,obesity and triglycerides in a normal population

The interrelationships among fatness measures, plasma triglycerides and high density lipoproteins (HDL) were examined in 131 normal adult subjects: 38 men aged 27–46, 40 men aged 47–66, 29 women aged 27–46 and 24 women aged 47–66. None of the women were taking estrogens or oral contraceptive medication. The HDL concentration was subdivided into HDL_2b, HDL_2a and HDL₃ by a computerized fitting of the total schlieren pattern to reference schlieren patterns. Anthropometric measures employed included skinfolds at 3 sites, 2 weight/height indices and 2 girth measurements. A high correlation was found among the various fatness measures. These measures were negatively correlated with total HDL, reflecting the negative correlation between fatness measures and HDL₂ (as the sum of HDL_2a and_2b). Fatness measures showed no relationship to HDL₃. There was also an inverse correlation between triglyceride concentration and HDL₂. No particular fatness measure was better than any other for demonstrating the inverse correlation with HDL but multiple correlations using all of the measures of obesity improved the correlations. Partial correlations controlling for fatness did not reduce any of the significant correlations between triglycerides and HDL₂ to insignificance. The weak correlation between fatness and triglycerides was reduced to insignificance when controlled for HDL₂. Presented (in part) at the Annual Meeting of the Oil Chemists' Society in St. Louis, MO, May 1978.     

Recovery of Phosphoric Acid from Spent Petrochemical Catalysts

Petrochemical catalysts are widely used in the industry. For the production of cumene, zeolite-based catalysts containing phosphoric acid are applied. Over the time, coking deactivates the surface, and the catalyst has to be exchanged and disposed of. Different process approaches for recycling the phosphoric acid-containing catalysts were investigated. Related preliminary investigations have shown that calcination of the used catalyst is necessary prior to reprocessing. By digesting the catalyst with hydrofluoric acid, ∼96 % phosphate was recovered. However, this process is very costly in terms of process technology. More promising is digestion by basic or acidic routes. Several options are possible here, and digestion with H₃PO₄ proved to be particularly suitable. Here, phosphate yields reached up to 98.8 %, with a positive balance of economic efficiency at the same time. The catalyst can be produced and recycled in the same plant with the same reagents, what constitutes a major breakthrough towards sustainability in industrial catalysis.     

Solving linear generalized Nash equilibrium problems numerically

This paper considers the numerical solution of linear generalized Nash equilibrium problems (LGNEPs). Since many methods for nonlinear problems require the nonsingularity of some second-order derivative, standard convergence conditions are not satisfied in our linear case. We provide new convergence criteria for a potential reduction algorithm (PRA) that allow its application to LGNEPs. Furthermore, we discuss a projected subgradient method (PSM) and a penalty method that exploit some known Nikaido–Isoda function-based constrained and unconstrained optimization reformulations of the LGNEP. Moreover, it is shown that normalized Nash equilibria of an LGNEP can be obtained by solving a single linear program. All proposed algorithms are tested on randomly generated instances of economic market models that are introduced and analysed in this paper and that lead to LGNEPs with shared and with non-shared constraints. It is shown that these problems have some favourable properties that can be exploited to obtain their solutions. With the PRA and in particular with the PSM we are able to compute solutions with satisfying precision even for problems with up 10,000 variables.     

Assessment of crowdsourcing and gamification loss in user-assisted object segmentation

There has been a growing interest in applying human computation – particularly crowdsourcing techniques – to assist in the solution of multimedia, image processing, and computer vision problems which are still too difficult to solve using fully automatic algorithms, and yet relatively easy for humans. In this paper we focus on a specific problem – object segmentation within color images – and compare different solutions which combine color image segmentation algorithms with human efforts, either in the form of an explicit interactive segmentation task or through an implicit collection of valuable human traces with a game. We use Click’n’Cut, a friendly, web-based, interactive segmentation tool that allows segmentation tasks to be assigned to many users, and Ask’nSeek, a game with a purpose designed for object detection and segmentation. The two main contributions of this paper are: (i) We use the results of Click’n’Cut campaigns with different groups of users to examine and quantify the crowdsourcing loss incurred when an interactive segmentation task is assigned to paid crowd-workers, comparing their results to the ones obtained when computer vision experts are asked to perform the same tasks. (ii) Since interactive segmentation tasks are inherently tedious and prone to fatigue, we compare the quality of the results obtained with Click’n’Cut with the ones obtained using a (fun, interactive, and potentially less tedious) game designed for the same purpose. We call this contribution the assessment of the gamification loss, since it refers to how much quality of segmentation results may be lost when we switch to a game-based approach to the same task. We demonstrate that the crowdsourcing loss is significant when using all the data points from workers, but decreases substantially (and becomes comparable to the quality of expert users performing similar tasks) after performing a modest amount of data analysis and filtering out of users whose data are clearly not useful. We also show that – on the other hand – the gamification loss is significantly more severe: the quality of the results drops roughly by half when switching from a focused (yet tedious) task to a more fun and relaxed game environment.