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Polypropylene/Layered Double Hydroxide Nanocomposites: Influence of LDH Intralayer Metal Constituents on the Properties of Polypropylene
Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.
Electrical and melt rheological characterization of PC and co-continuous PC/SAN blends filled with CNTs: Relationship between melt-mixing parameters, filler dispersion, and filler aspect ratio
Electrical and melt rheological properties of melt-mixed polycarbonate (PC) and co-continuous PC/poly(styrene–acrylonitrile) (SAN) blends with carbon nanotubes (CNTs) are investigated. Using two sets of mixing parameters, different states of filler dispersion are obtained. With increasing CNT dispersion, an increase in electrical resistivity near the percolation threshold of PC–CNT composites and (PC + CNT)/SAN blends is observed. This suggests that the higher mixing energies required for better dispersion also result in a more severe reduction of the CNT aspect ratio; this effect was proven by CNT length measurements. Melt rheological studies show higher reinforcing effects for composites with worse dispersion. The Eilers equation, describing the melt viscosity as function of filler content, was used to fit the data and to obtain information about an apparent aspect ratio change, which was in accordance with measured CNT length reduction. Such fitting could be also transferred to the blends and serves for a qualitatively based discussion. © 2017 Wiley Periodicals
Adaptive responses of animals to climate change are most likely insufficient
Biological responses to climate change have been widely documented across taxa and regions, but it remains unclear whether species are maintaining a good match between phenotype and environment, i.e. whether observed trait changes are adaptive. Here we reviewed 10,090 abstracts and extracted data from 71 studies reported in 58 relevant publications, to assess quantitatively whether phenotypic trait changes associated with climate change are adaptive in animals. A meta-analysis focussing on birds, the taxon best represented in our dataset, suggests that global warming has not systematically affected morphological traits, but has advanced phenological traits. We demonstrate that these advances are adaptive for some species, but imperfect as evidenced by the observed consistent selection for earlier timing. Application of a theoretical model indicates that the evolutionary load imposed by incomplete adaptive responses to ongoing climate change may already be threatening the persistence of species. © 2019, The Author(s).
Does the Processing Method Resulting in Different States of an Interconnected Network of Multiwalled Carbon Nanotubes in Polymeric Blend Nanocomposites Affect EMI Shielding Properties?
Electromagnetic interference (EMI), an unwanted phenomenon, often affects the reliability of precise electronic circuitry. To prevent this, an effective shielding is prerequisite to protect the electronic devices. In this study, an attempt was made to understand how processing of polymeric blend nanocomposites involving multiwalled carbon nanotubes (MWCNTs) affects the evolving interconnected network structure of MWCNTs and eventually their EMI shielding properties. Thereby, the overall blend morphology and especially the connectivity of the polycarbonate (PC) component, in which the MWCNTs tend to migrate, as well as the perfectness of their migration, and the state of nanotube dispersion are considered. For this purpose, blends of varying composition of PC and poly(methyl methacrylate) were chosen as a model system as they show a phase diagram with lower critical solution temperature type of characteristic. Such blends were processed in two different ways: solution mixing (from the homogeneous state) and melt mixing (in the biphasic state). In both the processes, MWCNTs (3 wt %) were mixed into the blends, and the evolved structures (after phase separation induced by annealing in solution-mixed blends) and the quenched structures (as the blends exit the extruder) were systematically studied using transmission electron microscopy (TEM). Both the set of blends were subjected to the same thermal history, however, under different conditions such as under quiescent conditions (in the case of solution mixing) and under shear (in the case of melt mixing). The electrical volume conductivity and the evolved morphologies of these blend nanocomposites were evaluated and correlated with the measured EMI shielding behavior. The results indicated that irrespective of the type of processing, the MWCNTs localized in the PC component; driven by thermodynamic factors and depending on the blend composition, sea-island, cocontinuous, and phase-inverted structures evolved. Interestingly, the better interconnected network structures of MWCNTs observed using TEM in the solution-mixed samples together with larger nanotube lengths resulted in higher EMI shielding properties (-27 dB at 18 GHz) even if slightly higher electrical volume conductivities were observed in melt-mixed samples. Moreover, the shielding was absorption-driven, facilitated by the dense network of MWCNTs in the PC component of the blends, at any given concentration of nanotubes. Taken together, this study highlights the effects of different blend nanocomposite preparation methods (solution and melt) and the developed morphology and nanotube network structure in MWCNT filled blend nanocomposites on the EMI shielding behavior.
Measuring the morphology and density of internally mixed black carbon with SP2 and VTDMA: New insight into the absorption enhancement of black carbon in the atmosphere
The morphology and density of black carbon (BC) cores in internally mixed BC (In-BC) particles affect their mixing state and absorption enhancement. In this work, we developed a new method to measure the morphology and effective density of the BC cores of ambient In-BC particles using a single-particle soot photometer (SP2) and a volatility tandem differential mobility analyzer (VTDMA) during the CAREBeijing-2013 campaign from 8 to 27 July 2013 at Xianghe Observatory. This new measurement system can select size-resolved ambient In-BC particles and measure the mobility diameter and mass of the In-BC cores. The morphology and effective density of the ambient In-BC cores are then calculated. For the In-BC cores in the atmosphere, changes in their dynamic shape factor (χ) and effective density (ρeff) can be characterized as a function of the aging process (Dp∕Dc) measured by SP2 and VTDMA. During an intensive field study, the ambient In-BC cores had an average shape factor χ of ∼ 1.2 and an average density of ∼ 1.2 g cm−3, indicating that ambient In-BC cores have a near-spherical shape with an internal void of ∼ 30 %. From the measured morphology and density, the average shell ∕ core ratio and absorption enhancement (Eab) of ambient BC were estimated to be 2.1–2.7 and 1.6–1.9, respectively, for In-BC particles with sizes of 200–350 nm. When the In-BC cores were assumed to have a void-free BC sphere with a density of 1.8 g cm−3, the shell ∕ core ratio and Eab were overestimated by ∼ 13 and ∼ 17 %, respectively. The new approach developed in this work improves the calculations of the mixing state and optical properties of ambient In-BC particles by quantifying the changes in the morphology and density of ambient In-BC cores during aging.
Promoting abnormal grain growth in Fe-based shape memory alloys through compositional adjustments
Iron-based shape memory alloys are promising candidates for large-scale structural applications due to their cost efficiency and the possibility of using conventional processing routes from the steel industry. However, recently developed alloy systems like Fe–Mn–Al–Ni suffer from low recoverability if the grains do not completely cover the sample cross-section. To overcome this issue, here we show that small amounts of titanium added to Fe–Mn–Al–Ni significantly enhance abnormal grain growth due to a considerable refinement of the subgrain sizes, whereas small amounts of chromium lead to a strong inhibition of abnormal grain growth. By tailoring and promoting abnormal grain growth it is possible to obtain very large single crystalline bars. We expect that the findings of the present study regarding the elementary mechanisms of abnormal grain growth and the role of chemical composition can be applied to tailor other alloy systems with similar microstructural features.
Physico-Chemical Properties and Deposition Potential of PM2.5 during Severe Smog Event in Delhi, India
The present work studies a severe smog event that occurred in Delhi (India) in 2017, targeting the characterization of PM2.5 and its deposition potential in human respiratory tract of different population groups in which the PM2.5 levels raised from 124.0 µg/m3 (pre-smog period) to 717.2 µg/m3 (during smog period). Higher concentration of elements such as C, N, O, Na, Mg, Al, Si, S, Fe, Cl, Ca, Ti, Cr, Pb, Fe, K, Cu, Cl, P, and F were observed during the smog along with dominant organic functional groups (aldehyde, ketones, alkyl halides (R-F; R-Br; R-Cl), ether, etc.), which supported potential contribution from transboundary biomass-burning activities along with local pollution sources and favorable meteorological conditions. The morphology of individual particles were found mostly as non-spherical, including carbon fractals, aggregates, sharp-edged, rod-shaped, and flaky structures. A multiple path particle dosimetry (MPPD) model showed significant deposition potential of PM2.5 in terms of deposition fraction, mass rate, and mass flux during smog conditions in all age groups. The highest PM2.5 deposition fraction and mass rate were found for the head region followed by the alveolar region of the human respiratory tract. The highest mass flux was reported for 21-month-old (4.7 × 102 µg/min/m2), followed by 3-month-old (49.2 µg/min/m2) children, whereas it was lowest for 21-year-old adults (6.8 µg/min/m2), indicating babies and children were more vulnerable to PM2.5 pollution than adults during smog. Deposition doses of toxic elements such as Cr, Fe, Zn, Pb, Cu, Mn, and Ni were also found to be higher (up to 1 × 10−7 µg/kg/day) for children than adults.
Crystalline Carbosilane-Based Block Copolymers: Synthesis by Anionic Polymerization and Morphology Evaluation in the Bulk State
Block copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains.
Reversibly growing crosslinked polymers with programmable sizes and properties
Growth constitutes a powerful method to post-modulate materials’ structures and functions without compromising their mechanical performance for sustainable use, but the process is irreversible. To address this issue, we here report a growing-degrowing strategy that enables thermosetting materials to either absorb or release components for continuously changing their sizes, shapes, compositions, and a set of properties simultaneously. The strategy is based on the monomer-polymer equilibrium of networks in which supplying or removing small polymerizable components would drive the networks toward expansion or contraction. Using acid-catalyzed equilibration of siloxane as an example, we demonstrate that the size and mechanical properties of the resulting silicone materials can be significantly or finely tuned in both directions of growth and decomposition. The equilibration can be turned off to yield stable products or reactivated again. During the degrowing-growing circle, material structures are selectively varied either uniformly or heterogeneously, by the availability of fillers. Our strategy endows the materials with many appealing capabilities including environment adaptivity, self-healing, and switchability of surface morphologies, shapes, and optical properties. Since monomer-polymer equilibration exists in many polymers, we envision the expansion of the presented strategy to various systems for many applications.
Determinants of barley grain yield in drought-prone Mediterranean environments
The determinants of barley grain yield in drought-prone Mediterranean environments have been studied in the Nure x Tremois (NT) population. A large set of yield and other morpho-physiological data were recorded in 118 doubled haploid (DH) lines of the population, in multi-environment field trials (18 site-year combination). Agrometeorological variables have been recorded and calculated at each site too. Four main periods of barley development were considered, vegetative, reproductive early and late grain filling phases, to dissect the effect on yield traits of the growth phases. Relationships between agrometeorological variables, grain yield (GY) and its main components (GN and GW) were also investigated by correlation. Results firstly gave a clear indication of the involvement of water consumption in determining GY and GW (r2=0.616, P=0.007 and r2=0.703, P=0.005, respectively) calculated from sowing to the early grain filling period, while GN showed its highest correlation with the total photothermal quotient (PQ) calculated for the same period (r2=0.646, P=0.013). With the only exception of total PQ calculated during the vegetative period, all significant correlations with GY were associated to water-dependent agrometeorological parameters. As a second result, the NT segregating population allowed us to weight the amount of interaction due to genotypes over environments or to environments in relation to genotypes by a GGE analysis; 47.67% of G+GE sum of squares was explained by the first two principal components. Then, the introduction of genomic information at major barley genes regulating the length of growth cycle allowed us to explain patterns of adaptation of different groups of NT lines according to the variants (alleles) harbored at venalization (Vrn-H1) in combination with earliness (Eam6) genes. The superiority of the lines carrying the Nure allele at Eam6 was confirmed by factorial ANOVA testing the four possible haplotypes obtained combining alternative alleles at Eam6 and Vrn-H1. Maximum yield potential and differentials among the NT genotypes was finally explored through Finlay-Wilkinson model to interpret grain yield of NT genotypes together with yield adaptability (Ya), as the regression coefficient bi; Ya ranged from 0.71 for NT77 to 1.20 for NT19. Lines simply harboring the Nure variants at the two genes behaved as highest yielding (3.04 t ha-1), and showed the highest yield adaptability (bi=1.05). The present study constitutes a starting point towards the introduction of genomic variables in agronomic models for barley grain yield in Mediterranean environments.