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.     

Rather the Rule than the Exception: Non-Convex Pareto Sets and their Navigation in Distillation Processes

Novel algorithms for adaptive approximation and interactive navigation of Pareto sets are applied to various homogeneous distillation processes with recycle streams within an industrial flowsheet simulator. The adaptive approximation scheme shows that the Pareto set consists of both convex and non-convex regions when the product purities are maximised while minimising the total heat duties. It is illustrated how such Pareto sets can be navigated interactively using a ray tracing technique. Our results suggest that the occurrence of non-convex regions in the Pareto sets is due to recycle streams in the flowsheets and is therefore the rule rather than the exception in multi-objective optimisation of flowsheet simulations in chemical engineering.     

Enzymatic hydrolysis of polyester based coatings

The potential of two hydrolytic enzymes, namely a lipase from Thermomyces lanuginosus (TlL) and a cutinase from Humicola insolens (HiC) for hydrolysis of the phthalic acid backbone based polyester coatings was assessed. Two phthalic acid/trimethylolpropane based model substrates resembling the structure of the polyester backbone of coatings were synthesized. Out of both enzymes, only the cutinase was able to hydrolyze both model substrates while the larger substrate was hydrolyzed at a lower rate. The cutinase was also able to hydrolyze a coating (alkyd resin) both in suspension and as dried film. LC–MS analysis of the hydrolysis products released from the coating revealed the presence of oleic acid, its monoglyceride, phthalic acid and 2-((3-((2-((2,3-dihydroxypropoxy)carbonyl)benzoyl)oxy)-2-hydroxypropoxy)carbonyl)benzoic acid. These results indicate that the enzyme was able to hydrolyze the polyester backbone as well as to release fatty acid side chains. Consequently, enzymatic hydrolysis has a potential for the removal of coatings, their recycling or their functionalization.     

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.

     

Heterodera schachtii Nematodes Interfere with Aphid-Plant Relations on Brassica oleracea

Aboveground and belowground herbivore species modify plant defense responses differently. Simultaneous attack can lead to non-additive effects on primary and secondary metabolite composition in roots and shoots. We previously found that aphid (Brevicoryne brassicae) population growth on Brassica oleracea was reduced on plants that were infested with nematodes (Heterodera schachtii) prior (4 weeks) to aphid infestation. Here, we examined how infection with root-feeding nematodes affected primary and secondary metabolites in the host plant and whether this could explain the increase in aphid doubling time from 3.8 to 6.7 days. We hypothesized that the effects of herbivores on plant metabolites would depend on the presence of the other herbivore and that nematode-induced changes in primary metabolites would correlate with reduced aphid performance. Total glucosinolate concentration in the leaves was not affected by nematode presence, but the composition of glucosinolates shifted, as gluconapin concentrations were reduced, while gluconapoleiferin concentrations increased in plants exposed to nematodes. Aphid presence increased 4-methoxyglucobrassicin concentrations in leaves, which correlated positively with the number of aphids per plant. Nematodes decreased amino acid and sugar concentrations in the phloem. Aphid population doubling time correlated negatively with amino acids and glucosinolate levels in leaves, whereas these correlations were non-significant when nematodes were present. In conclusion, the effects of an herbivore on plant metabolites were independent of the presence of another herbivore. Nematode presence reduced aphid population growth and disturbed feeding relations between plants and aphids.     

Malic acid production from renewables: a review

Malic acid derived from fossil resources is currently applied in the food and beverage industries with a medium global production capacity. However, in the transition from a fossil-based to a bio-based economy, biotechnologically produced l -malic acid may become an important platform chemical with many new applications, especially in the field of biopolymers. In this review, currently used petrochemical production routes to dl -malic acid are outlined and insights into possible bio-based alternatives for microbial l -malic acid production are provided. Besides ecological reasons, the possibility to produce enantiopure l -malic acid by microbial fermentation is the biggest advantage over chemical synthesis. State-of-the-art and open challenges concerning production host engineering, substrate choice and downstream processing are addressed. With regard to production hosts, a literature overview is given covering the leading natural production strains of Aspergillus, Ustilago and Aureobasidium, as well as Escherichia coli as the most important engineered recombinant host. The utilization of renewable substrates as an alternative to glucose is emphasized in particular as a key aspect for a competitive bio-based production. Out of the alternative substrates discussed in this review, the industrial side-streams crude glycerol and molasses seem to be most promising for large-scale l -malic acid production. © 2019 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

New insights into the crystallization process of sol-gel–derived 45S5 bioactive glass

In this work the influence of thermal treatment conditions on crystallization of a sol-gel-derived 45S5 bioactive glass was evaluated using DSC, XRD, TEM, EDX, and X-ray nanocomputed tomography (nano-CT). Temperature and time of the thermal treatment strongly influence the composition of the crystalline phases. At the onset of the glass transition temperature (600°C), combeite crystallizes as the main phase along with a calcium silicate-phosphate phase, which decomposes into rhenanite from 2 hours of thermal treatment at this temperature. At the crystallization temperature (700°C), combeite remains as the main crystalline phase. Additionally, Na₂Ca₂Si₂O₇ crystalline phase is formed. Our results provide a basic platform for tailoring the crystalline phases by controlling the nucleation and growth of crystalline phases via thermal treatments. Different morphologies (round particles, stacked layers, toothpick-like, and long features) were discerned by TEM as a function of temperature and time of treatment. It is the first time that bioactive glass is investigated by nano-CT at laboratory scale. This novel technique enables the 3D visualization of features in the nanometer range, giving clear information about the volumetric distribution of phases in the sample.     

Potenziale und Grenzen der Sekundärrohstoffgewinnung – Ergebnisse der r4-Begleitforschung

The socio-economic and ecological impacts of selected projects of the BMBF funding program “r⁴ – Innovative Technologies for Resource Efficiency – Research for the Provision of Raw Materials of Strategic Economic Importance” are presented. Many, but not all, research projects indicate a potential improvement of the supply situation in Germany. In some cases, the provision of secondary raw materials is unprofitable or ecologically detrimental. These cases require a balancing between security of supply and other economic and ecological objectives.     

Adaptive Immune Responses in a Multiple Sclerosis Patient with Acute Varicella-Zoster Virus Reactivation during Treatment with Fingolimod

Fingolimod, an oral sphingosine 1-phosphate (S1P) receptor modulator, is approved for the treatment of relapsing forms of multiple sclerosis (MS). The interference with S1P signaling leads to retention particularly of chemokine receptor-7 (CCR7) expressing T cells in lymph nodes. The immunological basis of varicella zoster virus (VZV) infections during fingolimod treatment is unclear. Here, we studied the dynamics of systemic and intrathecal immune responses associated with symptomatic VZV reactivation including cessation of fingolimod and initiation of antiviral therapy. Key features in peripheral blood were an about two-fold increase of VZV-specific IgG at diagnosis of VZV reactivation as compared to the previous months, a relative enrichment of effector CD4+ T cells (36% versus mean 12% in controls), and an accelerated reconstitution of absolute lymphocytes counts including a normalized CD4+/CD8+ ratio and reappearance of CCR7+ T cells. In cerebrospinal fluid (CSF) the lymphocytic pleocytosis and CD4+/CD8+ ratios at diagnosis of reactivation and after nine days of fingolimod discontinuation remained unchanged. During this time CCR7+ T cells were not observed in CSF. Further research into fingolimod-associated VZV reactivation and immune reconstitution is mandatory to prevent morbidity and mortality associated with this potentially life-threatening condition.