Toughness Optimization of SBR Elastomers – Use of Fracture Mechanics Methods for Characterization

Elastomer materials are used in a wide application range and subjected to different loading from which failure of the material results. Because this failure is caused by initiation and propagation of cracks, the application of fracture mechanics methods for the assessment of the material is obvious. A short summary of the methods of technical fracture mechanics including possibilities of determination of crack resistance curves is given. Vulcanizates on the basis of SBR 1500 with various sulfur and carbon black contents were investigated. For describing the crack initiation and crack propagation behavior, several fracture mechanics examination methods were applied. Tear‐analyzer results were used to assess the crack propagation behavior under fatigue‐like loading conditions. Furthermore, for the characterization of the crack resistance of the materials under impact‐like loading conditions, instrumented tensile‐impact tests were performed. To obtain information about the initiation and propagation of a stable crack, quasi‐static fracture mechanics tests were applied. The results of the several tests are discussed in dependence on sulfur and carbon black contents. We found a non‐monotonous behavior of the toughness as a function of carbon black loading. An explanation is given in connection with a percolation‐like transition in filler morphology on larger length scales.

Schematic crack propagation curve for characterizing the fatigue behavior of the vulcanizates recorded in a TFA test.     

Oxidative stability of structured lipids produced from sunflower oil and caprylic acid

Traditional sunflower oil (SO), randomized lipid (RL) and specific structured lipid (SL), both produced from SO and tricaprylin/caprylic acid, respectively, were stored for up to 12 wk to compare their oxidative stabilities by chemical and sensory analyses. Furthermore, the effect of adding a commercial antioxidant blend Grindox 117 (propyl gallate/ citric acid/ascorbyl palmitate) or gallic acid to the SL was investigated. The lipid type affected the oxidative stability: SL was less stable than SO and RL. The reduced stability was most likely caused by both the structure of the lipid and differences in production/ purification, which caused lower tocopherol content and higher initial levels of primary and secondary oxidation products in SL compared with RL and SO. Grindox 117 and gallic acid did not exert a distinct antioxidative effect in the SL oil samples during storage.     

Oxidative stability of milk drinks containing structured lipids produced from sunflower oil and caprylic acid

Milk drinks containing 5% traditional sunflower oil (SO), randomized lipid (RL) or specific structured lipid (SL) (both produced from SO and tricaprylin/caprylic acid) were compared with respect to their particle size, viscosity and oxidative stability during storage. Furthermore, the effect of adding potential antioxidants EDTA or gallic acid to the milk drink based on SL was investigated. The lipid type significantly affected the oxidative stability of the milk drinks: Milk drink based on SL oxidized faster than milk drink based on RL or SO. The reduced oxidative stability in the SL milk drink could not be ascribed to a single factor, but was most likely influenced by the structure of the lipid and differences in the process applied to produce and purify the lipids. EDTA was a strong antioxidant, while gallic acid did not exert a distinct antioxidative effect in the milk drink based on SL.     

Phase Transformation of Mechanically Milled Nano-Sized γ-Alumina

The phase transformation of mechanically milled nano-sized γ-alumina particles was investigated. The structures and phase presentation of the powders before and after milling were characterized using X-ray diffraction, transmission electron microscopy, and photoluminescence measurement. The phase transformation kinetics was investigated using differential scanning calorimetry. It was found that significant amounts of defects were generated by milling. These defects dramatically lowered the temperatures and activation energies of the transformation by promoting the nucleation and diffusion. The accumulation of the defects appears to show a logarithmic dependence of milling time.     

Filler Wetting in Miscible ESBR/SSBR Blends and Its Effect on Mechanical Properties

The selective wetting behavior of silica in emulsion styrene butadiene rubber (ESBR)/solution styrene butadiene rubber (SSBR) blends is characterized by the wetting concept, which is further developed for filled blends based on miscible rubbers. It is found that not only the chemical rubber–filler affinity but also the topology of the filler surface significantly influences the selective filler wetting in rubber blends. The nanopore structure of the silica surface has been recognized as the main reason for the difference in the wetting behavior of the branched ESBR molecules and linear SSBR molecules. However, the effect of nanopore structure becomes more significant in the presence of silane. It is discussed that the adsorption of silane on silica surface constricts the nanopore to some extent that hinders effectively the space filling of the nanopores by the branched ESBR molecules but not by the linear SSBR molecules. As a result, in silanized ESBR/SSBR blends the dominant wetting of silica surface by the tightly bonded layer of SSBR molecules causes a low‐energy dissipation in the rubber–filler interphase. That imparts the low rolling resistance to the blends similar to that of a silica‐filled SSBR compound, while the ESBR‐rich matrix warrants the good tensile behavior, i.e., good abrasion and wear resistance of the blends.

     

Melt spun matrix fibers of toughened polypropylene copolymers modified by high energy electrons

Binary blends of polypropylene (PP) and ethylene‐octene copolymer (EOC) are prepared by continuous electron‐induced reactive processing at various mass ratios of the blend components and various doses without adding of any grafting agents. The influence of mass ratio and dose is investigated in order to get the optimum processing behavior of toughened PP as well as optimum properties of resulting fibers. It is found that toughened PP with a PP/EOC blend ratio of 97.5–2.5  mass % can be used advantageously as a matrix component for the process of online spinning of glass fiber/toughened PP hybrid yarns. Such hybrid yarns belong to one of the most advanced production methods for the manufacturing of fiber reinforced thermoplastic composites with an increased mechanical performance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44011.     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part II: Influences of extrusion rate on morphological changes of a PLA/PVA blend through a capillary die

The effects of the extrusion rate on the morphological changes of poly(lactic acid) (PLA)/poly(vinyl alcohol) (PVA) blend through a capillary die were investigated. In this study, the extrusion rate or mass flow rate is altered from 0.5 g min^?1 to 2 g min^?1 with an increment of 0.5 g min^?1. The PLA/PVA blend with a composition of 30/70 (wt %) exhibits a particle matrix morphology with dispersed PLA droplets within the PVA matrix. It is found that, the spherical or ellipsoidal dispersed PLA droplets are elongated and coalesced into rod‐like or longer ellipsoidal droplets when they pass through the capillary die. When the extrusion rate increases, the coalescence between the large PLA droplets occurs more intense. However, the changes of the extrusion rate have no strong effect on the coalescence of small droplets having diameter less than about 150 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44257.     

4‐Biphenylalanine‐ and 3‐Phenyltyrosine‐Derived Hydroxamic Acids as Inhibitors of the JumonjiC‐Domain‐Containing Histone Demethylase KDM4A

Overexpression of the histone lysine demethylase KDM4A, which regulates H3K9 and H3K36 methylation states, has been related to the pathology of several human cancers. We found that a previously reported hydroxamate‐based histone deacetylase (HDAC) inhibitor (SW55) was also able to weakly inhibit this demethylase with an IC₅₀ value of 25.4 μm . Herein we report the synthesis and biochemical evaluations, with two orthogonal in vitro assays, of a series of derivatives of this lead structure. With extensive chemical modifications on the lead structure, also by exploiting the versatility of the radical arylation with aryldiazonium salts, we were able to increase the potency of the derivatives against KDM4A to the low‐micromolar range and, more importantly, to obtain demethylase selectivity with respect to HDACs. Cell‐permeable derivatives clearly showed a demethylase‐inhibition‐dependent antiproliferative effect against HL‐60 human promyelocytic leukemia cells.     

Biotransformation of glycidol by the unspecific wax ester synthase/acyl‐CoA:diacylglycerol acyltransferase of Acinetobacter baylyi ADP1

Glycidol was biologically derivatized by the unspecific wax ester synthase/acyl coenzyme A (acyl‐CoA): diacylglycerol acyltransferase (WS/DGAT) from Acinetobacter baylyi ADP1 into glycidyl acyl ester. Catalysis of in vitro conversion of glycidol to glycidyl acyl ester by the WS/DGAT from A. baylyi was verified by (i) a radiometric assay, (ii) thin‐layer chromatography and (iii) also by ESI‐MS. A specific activity of 50 nmol·mg^–1·min^–1 was obtained when 10 mM glycidol and 5 µM palmitoyl‐CoA were used. In vivo synthesized glycidyl acyl esters in recombinant E. coli were detected and quantified by staining with the epoxide‐specific reagent 4‐(4‐nitrobenzyl)‐pyridine. Of glycidyl acyl esters, 1.5 mg/L was obtained from the culture in the presence of 10 mM glycidol and 10 mM oleate.     

An efficient numerical technique for solving population balance equation involving aggregation, breakage, growth and nucleation

A new discretization for simultaneous aggregation, breakage, growth and nucleation is presented. The new discretization is an extension of the cell average technique developed by the authors [J. Kumar, M. Peglow, G. Warnecke, S. Heinrich, and L. Mörl. Improved accuracy and convergence of discretized population balance for aggregation: The cell average technique. Chemical Engineering Science 61 (2006) 3327-3342.]. It is shown that the cell average scheme enjoys the major advantage of simplicity for solving combined problems over other existing schemes. This is done by a special coupling of the different processes that treats all processes in a similar fashion as it handles the individual process. It is demonstrated that the new coupling makes the technique more useful by being not only more accurate but also computationally less expensive. At first, the coupling is performed for combined aggregation and breakage problems. Furthermore, a new idea that considers the growth process as aggregation of existing particle with new small nuclei is presented. In that way the resulting discretization of the growth process becomes very simple and consistent with first two moments. Additionally, it becomes easy to combine the growth discretization with other processes. The new discretization of pure growth is a little diffusive but it predicts the first two moments exactly without any computational difficulties like appearance of negative values or instability etc. The numerical scheme proposed in this work is consistent only with the first two moments but it can easily be extended to the consistency with any two or more than two moments. Finally, the discretization of pure and coupled problems is tasted on several analytically solvable problems.