A relatively simple look at the rather complex crystallization kinetics of PLLA

[Abstract] This work demonstrates that, despite the existence of a significant number of works on PLA crystallization, there is still a relatively simple way, different from those already described, in which its complex kinetics can be observed. The X-ray diffraction (XRD) results presented here confirm that the PLLA under study crystallizes mostly in the α and α′ forms. An interesting observation is that at any temperature in the studied range of the patterns, the X-ray reflections stabilize with a given shape and at a given angle, different for each temperature. That means that both α and α′ forms coexist and are stable at the same temperatures so that the shape of each pattern results from both structures. However, the patterns obtained at each temperature are different because the predominance of one crystal form over the other depends on temperature. Thus, a two-component kinetic model is proposed to account for both crystal forms. The method involves the deconvolution of the exothermic DSC peaks using two logistic derivative functions. The existence of the rigid amorphous fraction (RAF) in addition to the two crystal forms increases the complexity of the whole crystallization process. However, the results presented here show that a two-component kinetic model can reproduce the overall crystallization process fairly well over a broad range of temperatures. The method used here for PLLA may be useful for describing the isothermal crystallization processes of other polymers

Properties of Mosquito Repellent-Plasticized Poly(lactic acid) Strands

This article belongs to the Special Issue Thermal and Rheological Characterization of Polymeric Materials[Abstract] Poly(lactic acid) (PLA) is an attractive candidate for replacing petrochemical polymers because it is fully biodegradable. This study investigated the potential of PLA as a sustainable and environmentally friendly alternative material that can be developed into commercially viable wearable mosquito repellent devices with desirable characteristics. PLA strands containing DEET and IR3535 were prepared by twin screw extrusion compounding and simultaneously functioned as plasticizers for the polymer. The plasticizing effect was investigated by thermal and rheological studies. DSC studies showed that the addition of DEET and IR3535 into PLA strands reduced the glass transition temperature consistent with predictions of the Fox equation, thus proving their efficiency as plasticizers. The rheology of molten samples of neat PLA and PLA/repellents blends, evaluated at 200 °C, was consistent with shear-thinning pseudoplastic behaviour. Raman studies revealed a nonlinear concentration gradient for DEET in the PLA strand, indicating non-Fickian Type II transport controlling the desorption process. Release data obtained at 50 °C showed initial rapid release followed by a slower, near constant rate at longer times. The release rate data were fitted to a novel modification of the Peppas-Sahlin desorption modelThis work was financially supported from the Deutsche Forschungsgemeinschaft (DFG), Germany [Grant number AN 212/22-2] and University of Pretoria (UP) Postdoctoral Fellowship programme. The research has been also supported by Spanish MINECO grant MTM2017-82724-R through the ERDFDeutsche Forschungsgemeinschaft (DFG); AN 212/22-2https://www.mdpi.com/journal/molecules/special_issues/Thermal_Rheological_Polymeric_Material

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

Tribological and mechanical properties of polyamide-11/halloysite nanotube nanocomposites

This article reports some morphological, tribological, and mechanical data on polyamide-11(PA11)/ halloysite nanotube (HNT) nanocomposites prepared by melt-compounding. HNTs extracted from the Djebel Deb- bagh deposit in Algeria were incorporated into the polymer at 1, 3, and 5 wt%. For comparison, commercial HNTs were also used under the same processing conditions. Scanning electron microscopy showed that both HNTs were homogeneously dispersed in the PA11 matrix, despite the presence of few aggregates, in particular at higher filler contents. The tribological properties were significantly improved, resulting in a decrease in the friction coefficient and the wear rate characteristics due to the lubricating effect of HNTs. This is consistent with optical profilometry data, which evidenced the impact of both types of HNTs on the surface topography of the nanocomposite samples, in which the main wear process was plastic deformation. Furthermore, Young’s modulus and tensile strength were observed to increase with the filler content, but to the detriment of elongation at break and impact strength. Regarding the whole data, the raw Algerian halloysite led to interesting results in PA11 nanocomposites, thus reveal- ing its potential in polymer engineering nanotechnology

LSST: from Science Drivers to Reference Design and Anticipated Data Products

(Abridged) We describe here the most ambitious survey currently planned in the optical, the Large Synoptic Survey Telescope (LSST). A vast array of science will be enabled by a single wide-deep-fast sky survey, and LSST will have unique survey capability in the faint time domain. The LSST design is driven by four main science themes: probing dark energy and dark matter, taking an inventory of the Solar System, exploring the transient optical sky, and mapping the Milky Way. LSST will be a wide-field ground-based system sited at Cerro Pach\'{o}n in northern Chile. The telescope will have an 8.4 m (6.5 m effective) primary mirror, a 9.6 deg$^2$ field of view, and a 3.2 Gigapixel camera. The standard observing sequence will consist of pairs of 15-second exposures in a given field, with two such visits in each pointing in a given night. With these repeats, the LSST system is capable of imaging about 10,000 square degrees of sky in a single filter in three nights. The typical 5$\sigma$ point-source depth in a single visit in $r$ will be $\sim 24.5$ (AB). The project is in the construction phase and will begin regular survey operations by 2022. The survey area will be contained within 30,000 deg$^2$ with $\delta<+34.5^\circ$, and will be imaged multiple times in six bands, $ugrizy$, covering the wavelength range 320--1050 nm. About 90\% of the observing time will be devoted to a deep-wide-fast survey mode which will uniformly observe a 18,000 deg$^2$ region about 800 times (summed over all six bands) during the anticipated 10 years of operations, and yield a coadded map to $r\sim27.5$. The remaining 10\% of the observing time will be allocated to projects such as a Very Deep and Fast time domain survey. The goal is to make LSST data products, including a relational database of about 32 trillion observations of 40 billion objects, available to the public and scientists around the world.Comment: 57 pages, 32 color figures, version with high-resolution figures available from https://www.lsst.org/overvie

Geometric effects control isothermal oxidation of graphite flakes

The oxidation, in a neat oxygen atmosphere, of high-purity and highly crystalline natural graphite and synthetic Kish graphite was investigated. The physico-geometric model function of the kinetic rate equation was experimentally determined by isothermal thermogravimetric analysis at 650 °C. Analytic solutions for basic flake shapes indicate that this function strictly decreases with conversion. However, for both samples the experimental data trend was a rapid initial increase followed by the expected decrease to zero. High resolution field emission scanning electron microscopy (FEGSEM), of partially oxidized flakes, provided plausible explanations for this discrepancy. Rapid development of macroscopic surface roughness during the initial stages of oxidation was evident and could be attributed to the presence of catalytic impurities. Large fissures along the planes of the natural graphite and the initiation, growth and coalescence of internal cavities in the Kish graphite were observed. Flake models incorporating the latter two features are difficult to analyse analytically. However, a facile probabilistic approach showed that reasonably good agreement with experimental data was possible.The Skye Foundation, PBMR,The South African Research Chairs Initiative of the Department of Science and Technology and the National Research Foundation.http://www.springerlink.com/content/102948