Crystallization kinetics of polyamide 11 in the presence of sepiolite and montmorillonite nanofillers

The crystallization kinetics of polyamide 11 (PA 11) in presence of sepiolite and organomodified montmorillonite nanofillers has been studied in a wide range of temperatures and cooling rates by conventional differential scanning calorimetry (DSC) and fast scanning chip calorimetry (FSC). The presence of the nanofillers has a negligible effect on the crystallization temperature of PA 11 at low cooling rates. However, at rapid cooling conditions a distinct nucleating effect of the nanofillers is detected. The critical cooling rate to suppress crystallization increases from 600 K s–1 to about 1000 and 3000 K s–1 in nanocomposites containing sepiolite and montmorillonite, respectively. Regardless the cooling rate applied for solidification the melt, in the nanocomposites the crystallinity of PA 11 is 5 to 10 % higher than in neat PA 11, with the highest values obtained for the montmorillonite-containing system. The nucleating effect of the nanofillers onto the crystallization of the PA 11 is confirmed by analysis of the half-times of isothermal crystallization, and by analysis of the spherulitic superstructure. All measurements proved a saturation of the nucleation efficiency at a loading of the nanofiller of 2.5 m%.Deutsche Forschungsgemeinschaft (DFG) (Grant AN 212/18).http://link.springer.com/journal/3962017-07-31hb2016Chemical Engineerin

Slow-DEET-release mosquito-repellent system based on poly(butylene succinate)

Bio-sourced and biodegradable poly(butylene succinate) (PBS) strands containing up to 40 m% mosquito-repellent N,N-diethyl-3-methylbenzamide (DEET) were obtained by extrusion, for an initial evaluation of the DEET evaporation characteristics and the possible application of such strands as biodegradable slow-release repellent-delivery devices. For DEET concentrations up to 20 m%, DEET is entrapped in the semicrystalline spherulitic superstructure of PBS. In contrast, at higher DEET concentrations, the liquid repellent, at least partially, is not fully incorporated in the PBS spherulites rather than segregates to form an own macrophase. Quantification of the release of DEET to the environment by thermogravimetric analysis at different temperatures between 60 and 100 °C allowed estimation of the evaporation rate at lower service temperatures, suggesting an extremely low release rate with a time constant of the order of magnitude of 1−2 years at 25 °C, independent of the initial concentration.Deutsche Forschungsgemeinschaft (DFG) and Martin Luther University Halle-Wittenberg.http://pubs.acs.org/journal/acsodfChemical Engineerin

Determinants of Deadwood-Inhabiting Fungal Communities in Temperate Forests: Molecular Evidence From a Large Scale Deadwood Decomposition Experiment

Despite the important role of wood-inhabiting fungi (WIF) in deadwood decomposition, our knowledge of the factors shaping the dynamics of their species richness and community composition is scarce. This is due to limitations regarding the resolution of classical methods used for characterizing WIF communities and to a lack of well-replicated long-term experiments with sufficient numbers of tree species. Here, we used a large scale experiment with logs of 11 tree species at an early stage of decomposition, distributed across three regions of Germany, to identify the factors shaping WIF community composition and Operational Taxonomic Unit (OTU) richness using next generation sequencing. We found that tree species identity was the most significant factor, corresponding to (P < 0.001) and explaining 10% (representing 48% of the explainable variance) of the overall WIF community composition. The next important group of variables were wood-physicochemical properties, of which wood pH was the only factor that consistently corresponded to WIF community composition. For overall WIF richness patterns, we found that approximately 20% of the total variance was explained by wood N content, location, tree species identity and wood density. It is noteworthy that the importance of determinants of WIF community composition and richness appeared to depend greatly on tree species group (broadleaved vs. coniferous) and it differed between the fungal phyla Ascomycota and Basidiomycota

Effect of Molar Mass on Critical Specific Work of Flow for Shear-Induced Crystal Nucleation in Poly (l-Lactic Acid)

The concept of specific work of flow has been applied for the analysis of critical shearing conditions for the formation of crystal nuclei in poly (l-lactic acid) (PLLA). Systematic variation in both time and rate of shearing the melt in a parallel-plate rheometer revealed that these parameters are interconvertible regarding the shear-induced formation of crystal nuclei; that is, low shear rate can be compensated for by increasing the shear time and vice versa. This result supports the view that critical shearing conditions can be expressed by a single quantity, providing additional options for tailoring polymer processing routes when enhanced nuclei formation is desired/unwanted. Analysis of PLLA of different mass-average molar masses of 70, 90, 120, and 576 kDa confirmed improved shear-induced crystal nucleation for materials of higher molar mass, with critical specific works of flow, above which shear-induced nuclei formation occurs, of 550, 60, 25, and 5 kPa, respectively

Effect of Molar Mass on Critical Specific Work of Flow for Shear-Induced Crystal Nucleation in Poly (l-Lactic Acid)

The concept of specific work of flow has been applied for the analysis of critical shearing conditions for the formation of crystal nuclei in poly (l-lactic acid) (PLLA). Systematic variation in both time and rate of shearing the melt in a parallel-plate rheometer revealed that these parameters are interconvertible regarding the shear-induced formation of crystal nuclei; that is, low shear rate can be compensated for by increasing the shear time and vice versa. This result supports the view that critical shearing conditions can be expressed by a single quantity, providing additional options for tailoring polymer processing routes when enhanced nuclei formation is desired/unwanted. Analysis of PLLA of different mass-average molar masses of 70, 90, 120, and 576 kDa confirmed improved shear-induced crystal nucleation for materials of higher molar mass, with critical specific works of flow, above which shear-induced nuclei formation occurs, of 550, 60, 25, and 5 kPa, respectively

Crystallization of Random Metallocene-Catalyzed Propylene-Based Copolymers with Ethylene and 1-Hexene on Rapid Cooling

Propylene-based random copolymers with either ethylene or 1-hexene as comonomer, produced using a metallocene catalyst, were studied regarding their crystallization behaviors, with a focus on rapid cooling. To get an impression of processing effects, fast scanning chip calorimetry (FSC) was used in addition to the characterization of the mechanical performance. When comparing the comonomer type and the relation to commercial grades based on Ziegler–Natta-type catalysts, both an interaction with the catalyst-related regio-defects and a significant difference between ethylene and 1-hexene was observed. A soluble-type nucleating agent was found to modify the behavior, but to an increasingly lesser degree at high cooling rates

Crystallization of polyamide 11 during injection molding

The semicrystalline morphology of injection moldings of polyamide 11 (PA 11) prepared using mold temperatures of 25, 50, and 80°C was investigated. Regardless of the mold temperature, position‐resolved X‐ray diffraction (XRD) and polarized‐light optical microscopy (POM) revealed presence of poor/imperfect α‐crystals with an almost hexagonal arrangement of molecular stems in a nonspherulitic superstructure in the skin, and formation of α‐crystals and spherulites in the core. With increasing mold temperature, the thickness of the skin layer decreased, and the perfection of α‐crystals and the spherulite size in the core increased. The experimental observations are discussed in terms of predicted crystallization temperatures, with the prediction based on cooling‐rate simulations for the various parts of the injection moldings using Moldflow® and analysis of crystallization of the relaxed melt using fast scanning chip calorimetry, XRD, and POM. It is shown that the structure gradient in PA 11 injection moldings can be forecast without considering the effects of shear for this particular polymer.Deutsche Forschungsgemeinschaft (DFG); contract grant number: AN 212/18.https://onlinelibrary.wiley.com/journal/154826342019-07-01hj2018Chemical Engineerin

Shear-induced crystallization of polyamide 11

Shear-induced formation of crystal nuclei in polyamide 11 (PA 11) was studied using a conventional parallel-plate rheometer. Crystallization of PA 11 after shearing the melt at different rates for 60 s was followed by the evolution of the complex viscosity. The sheared samples showed in an optical microscope a gradient structure along the radius, due to the increasing shear rate from the center to the edge. The critical shear rate for shear-induced formation of nuclei was identified at the position where a distinct change of the semicrystalline superstructure is observed, being at around 1 to 2 s−1. Below this threshold, a space-filled spherulitic superstructure developed as in quiescent-melt crystallization. Above this value, after shearing at rates between 1 and 5 s−1, an increased number of point-like nuclei was detected, connected with formation of randomly oriented crystals. Shearing the melt at even higher rates led to a further increase of the nuclei number and growth of crystals oriented such that the chain axis is in parallel to the direction of flow. In addition, optical microscopy confirmed formation of long fibrillar structures after shearing at such condition. The critical specific work of flow of PA 11 was calculated to allow a comparison with that of polyamide 66 (PA 66). This comparison showed that in the case of PA 11 more work for shear-induced formation of nuclei is needed than in the case of PA 66, discussed in terms of the chemical structure of the repeat unit in the chains