Dispersion of Cellulose Nanofibers in Methacrylate-Based Nanocomposites.

Poly(methylmethacrylate-co-methacrylic acid) (PMMA-co-MAA) polymers were prepared via cobalt-mediated free radical copolymerization and were characterized after synthesis. The synthesis led to a 98.5% conversion and a final ratio between the two units, MMA/MAA, was equal to 63:37 mol%. PMMA-co-MAA was then used as a matrix for cellulose-based nanocomposites to tailor filler compatibility, thanks to the presence of carboxylic groups capable of generating strong H-bonds with the cellulose surface. Cellulose nanofibers (CNFs) were dispersed using a solution with a mixture of two solvents to tailor compatibility of both the components. For this purpose, CNFs were successfully re-dispersed in methanol using the solvent exchange method and tetrahydrofuran/methanol mixtures at different ratios were used for the preparation of the films. Fully transparent films of PMMA-co-MAA + CNF were prepared up to 15 wt% of CNF with a good dispersion in the matrix. This dispersion state leads to the reinforcement of the polymethacrylate matrix, increasing its tensile strength whilst preserving optical transparency.

LIonomers-New Generation of Ionomer: Understanding of Their Interaction and Structuration as a Function of the Tunability of Cation and Anion.

In this work, by combining maleic anhydride-grafted polypropylene (PPgMA) and three different ionic liquids (ILs), i.e., tributyl (ethyl) phosphonium diethyl phosphate (denoted P+DEP), 1-ethyl-3-methylimidazolium diethyl phosphate (denoted EMIM DEP), and 1-ethyl-3-methylimidazolium acetate (denoted EMIM Ac), new ionic PP/IL polymer materials are generated and denoted as LIonomers. The structuration of ILs in LIonomers occurs from a nano/microphase separation process proved by TEM. NMR analyses reveal the existence of ionic-ionic and ionic-dipolar interactions between PPgMA and ILs within LIonomers. The rheological behavior of such IL/polymer combinations interpret the existence of interactions between maleic anhydride group and cation or anion composing the ionic liquid. These interactions can be tuned by the nature of cation (P+DEP vs. EMIM DEP) and anion (EMIM DEP vs. EMIM Ac) but also depend on the IL content. Thermal analyses demonstrate that IL could affect the crystallization process according to different pathways. Thanks to the maleic anhydride/IL interactions, an excellent compromise between stiffness and stretchability is obtained paving the way for processing new polyolefin-based materials.

Research on the Dynamic Response Properties of Nonlethal Projectiles for Injury Risk Assessment.

Based on the models already on the market, we have manufactured six types of nonlethal projectiles. We have made convex heads out of polyurethane foam (PUR) filled with mineral fillers like alumina (Al2O3) and montmorillonite (MMT). We chose a suitable holder for nonlethal projectiles. Also, we made a custom industrial model and used CAD modeling in SolidWorks to simulate the deformation of the nonlethal projectiles. The polymeric nonlethal projectile holders were then 3D-printed. We performed a dynamic mechanical analysis (DMA) and discussed the results. Likewise, we conducted ballistic impact experiments on nonlethal projectiles (XM1006) and nonlethal projectiles manufactured that were evaluated using a rigid wall and a pneumatic launcher. Furthermore, we looked at cell structure, the spread of the mean pore diameter, and the particle size distributions of the mineral fillers using scanning electron microscopy (SEM). We evaluated and discussed injury risks from nonlethal impacts. Data on nonlethal projectile lethality and safe impact speed are collected. This study explains how lab studies and real-world practice coexist through nonlethal projectile properties.

Imidazolium Salt for Enhanced Interfacial Shear Strength in Polyphenylene Sulfide/Ex-PAN Carbon Fiber Composites.

Processing structural or semi-structural thermoplastic-based composites is a promising solution to solve the environmental issues of the aeronautic industry. However, these composites must withstand high standard specification to ensure safety during transportation. For this reason, there is a real need to develop strong interactions between thermoplastic polymers and reinforcement fibers. This paper investigates relationships between the surface chemistry, microstructure and micromechanical properties between polyphenylene sulfide and ex-PAN carbon fibers. The incorporation of ionic salt such as 1,3-Bis(4-carboxyphenyl)imidazolium chloride into neat polyphenylene sulfide was able to significantly increase the interfacial shear strength measured by microbond micromechanical test combined with different carbon fiber surfaces treatment.

New Epoxy Thermosets Organic-Inorganic Hybrid Nanomaterials Derived from Imidazolium Ionic Liquid Monomers and POSS®Ph.

New epoxy-amine networks issue from epoxydized imidazolium ionic liquid monomers (ILMs) and isophorone diamine (IPD) were modified for the first time by incorporating unmodified trisilanol phenyl POSS® (POSS®Ph-triol) and two ionic liquid-modified POSS®Ph (IL-g-POSS®Ph) having chloride (Cl-) and bis-trifluoromethanesulfonimidate (NTf2-) counter anions. Then, 5 wt.% of unmodified and IL-modified POSS®Ph were introduced in order to develop new solid electrolytes. First, a homogeneous dispersion of the POSS®Ph aggregates (diameters from 80 to 400 nm) into epoxy networks was observed. As a consequence, ILM/IPD networks with glass transition temperatures between 45 and 71 °C combined with an enhancement of the thermal stability (>380 °C) were prepared. Moreover, a significant increase of the hydrophobic character and high oil repellency of the network surfaces were obtained by using IL-g-POSS®Ph (19-20 mJ.m-2), opening up promising prospects for surface coating applications. Finally, these new epoxy networks exhibited outstanding high ionic conductivities (from 3.4 × 10-8 to 6.8 × 10-2 S.m-1) combined with an increase in permitivity.

Year-round sexual segregation in the Pyrenean chamois, a nearly monomorphic polygynous herbivore.

Adult females and males live apart outside the mating period in many social vertebrates, but the causes of this phenomenon remain a matter of debate. Current prevailing hypotheses predict no sexual segregation outside the early period of maternal care in nearly monomorphic species such as the Pyrenean chamois (Rupicapra pyrenaica). We examined sexual segregation in a population of the species, using data collected over 143 consecutive months on groups' location and composition, and extending statistical procedures introduced by Conradt (1998b) and Bonenfant et al. (2007). In addition, we analysed the social interactions recorded between group members. As expected, habitat segregation was low throughout the year, with a maximum during the early lactation period. However, social and spatial segregation was consistently high, contradicting the predictions of the current prevailing hypotheses, while suggesting social causes were predominant. The scarcity of social interactions outside the mating season makes unlikely the hypothesis that males segregate to improve their reproductive success. We rather suspect that higher social affinities within than between the two sexes are at work. However, this hypothesis alone is probably insufficient to account for spatial segregation. Our results should revive the debate regarding the causes of sexual segregation.

Key Role of the Dispersion of Carbon Nanotubes (CNTs) within Epoxy Networks on their Ability to Release.

Carbon nanotube (CNT)-reinforced nanocomposites represent a unique opportunity in terms of designing advanced materials with mechanical reinforcement and improvements in the electrical and thermal conductivities. However, the toxic effects of these composites on human health have been studied, and very soon, some regulations on CNTs and on composites based on CNTs will be enacted. That is why the release of CNTs during the nanocomposite lifecycle must be controlled. As the releasing depends on the interfacial strength that is stronger between CNTs and polymers compared to CNTs in a CNT agglomerate, two dispersion states-one poorly dispersed versus another well dispersed-are generated and finely described. So, the main aim of this study is to check if the CNT dispersion state has an influence on the CNT releasing potential in the nanocomposite. To well tailor and characterize the CNT dispersion state in the polymer matrix, electronic microscopies (SEM and TEM) and also rheological analysis are carried out to identify whether CNTs are isolated, in bundles, or in agglomerates. When the dispersion state is known and controlled, its influence on the polymerization kinetic and on mechanical properties is discussed. It appears clearly that in the case of a good dispersion state, strong interfaces are generated, linking the isolated nanotubes with the polymer, whereas the CNT cohesion in an agglomerate seems much more weak, and it does not provide any improvement to the polymer matrix. Raman spectroscopy is relevant to analyze the interfacial properties and allows the relationship with the releasing ability of nanocomposites; i.e., CNTs poorly dispersed in the matrix are more readily released when compared to well-dispersed nanocomposites. The tribological tests confirm from released particles granulometry and observations that a CNT dispersion state sufficiently achieved in the nanocomposite avoids single CNT releasing under those solicitations.

Ionic Liquids-Containing Silica Microcapsules: A Potential Tunable Platform for Shaping-Up Epoxy-Based Composite Materials?

In this work, silica microcapsules containing phosphonium ionic liquid (IL), denoted SiO2@IL, were successfully synthesized for the first time using the one step sol-gel method in IL/H20 emulsion. The morphologies of the obtained micron-size microcapsules, including their diameter distribution, were characterized using dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The thermal behavior of these microcapsules and the mass fraction of the encapsulated IL in the silica microcapsules were determined using thermogravimetric analysis, showing an excellent thermal stability (up to 220 °C) and highlighting that an amount of 20 wt.% of IL is contained in the silica microcapsules. In a second step, SiO2@IL microcapsules (1 wt.%) were dispersed into epoxy-amine networks to provide proof of concept of the ability of such microcapsules to act as healing agents as microcracks propagate into the epoxy networks.

Ionic Liquid-Nanostructured Poly(Methyl Methacrylate).

Here, ionic liquids (ILs) based on imidazolium and ammonium cations were used as modifying agents for poly(methyl methacrylate) (PMMA) by extrusion. The effects of the chemical nature of the cation and/or counter anion on the resulting properties of IL-modified PMMA blends were analyzed. It was found that the use of low amounts of ILs (2 wt.%) improved the thermal stability. A plasticizing effect of ILs is evidenced by a decrease in glass transition temperature Tg of the modified PMMA, allowing to get large strains at break (i.e., up to 280% or 400%) compared to neat PMMA. The deformation and fracture mechanisms of PMMA under uniaxial tensile stress (i.e., crazing) reveal that the presence of IL delayed the strain during the initiation step of crazing.

ß-Myrcene/isobornyl methacrylate SG1 nitroxide-mediated controlled radical polymerization: synthesis and characterization of gradient, diblock and triblock copolymers.

ß-Myrcene (My), a natural 1,3-diene, and isobornyl methacrylate (IBOMA), from partially bio-based raw materials sources, were copolymerized by nitroxide-mediated polymerization (NMP) in bulk using the SG1-based BlocBuilder™ alkoxyamine functionalized with an N-succinimidyl ester group, NHS-BlocBuilder, at T = 100 °C with initial IBOMA molar feed compositions f IBOMA,0 = 0.10-0.90. Copolymer reactivity ratios were r My = 1.90-2.16 and r IBOMA = 0.02-0.07 using Fineman-Ross, Kelen-Tudos and non-linear least-squares fitting to the Mayo-Lewis terminal model and indicated the possibility of gradient My/IBOMA copolymers. A linear increase in molecular weight versus conversion and a low dispersity (D ≤ 1.41) were exhibited by My/IBOMA copolymerization with f IBOMA,0 ≤ 0.80. My-rich and IBOMA-rich copolymers were shown to have a high degree of chain-end fidelity by performing subsequent chain-extensions with IBOMA and/or My, and by 31P NMR analysis. The preparation by NMP of My/IBOMA thermoplastic elastomers (TPEs), mostly bio-sourced, was then attempted. IBOMA-My-IBOMA triblock copolymers containing a minor fraction of My or styrene (S) units in the outer hard segments (M n = 51-95 kg mol-1, D = 1.91-2.23 and F IBOMA = 0.28-0.36) were synthesized using SG1-terminated poly(ethylene-stat-butylene) dialkoxyamine. The micro-phase separation was suggested by the detection of two distinct T gs at about -60 °C and +180 °C and confirmed by atomic force microscopy (AFM). A plastic stress-strain behavior (stress at break σ B = 3.90 ± 0.22 MPa, elongation at break ε B = 490 ± 31%) associated to an upper service temperature of about 140 °C were also highlighted for these triblock polymers.

Polyether Sulfone-Based Epoxy Toughening: From Micro- to Nano-Phase Separation via PES End-Chain Modification and Process Engineering.

The toughness of a high-performance thermosetting epoxy network can be greatly improved by generating polyether sulfone-based macro- to nano-scale morphologies. Two polyethersulfones (PES) which only differ by their chain-end nature have been successively investigated as potential tougheners of a high-Tg thermoset matrix based on a mixture of trifunctional and difunctional aromatic epoxies and an aromatic diamine. For a given PES content, morphologies and toughness of the resulting matrices have been tuned by changing curing conditions and put into perspective with PES chain-end nature.

Cross-Linking Induced Self-Organization of Polymers into Degradable Assemblies.

Covalently stabilized polymer assemblies are normally fabricated from the self-assembly of polymer chains followed by a cross-linking reaction. In this report, we show that a cross-linking-induced self-assembly approach, in which boronate cross-linking sites are formed by the condensation reaction between boronic and catechol groups, can organize polymer networks into uniform assemblies. Self-assembly of these boronate cross-linked polymer networks adopts two different driving forces in water and methanol solutions. Hydrophobic aggregation of polymer networks in water solution affords spherical assemblies, while B-N dative bond formed between boronate and imine functionalities in methanol solution organizes the polymer networks into bundle-like assemblies. We not only demonstrate the intrinsic stimuli-responsive degradability of these cross-linked assemblies but also show that their degradation can cause a controllable release of guest molecules. Moreover, bundle-like assemblies with rough surface and exposed boronate functionalities exhibit dramatically higher cell penetration capability than the spherical assemblies with smooth surface and embedded boronate functionalities.

Effect of polyvinylidene fluoride electrospun fiber orientation on neural stem cell differentiation.

Electrospun polymer piezoelectric fibers can be used in neural tissue engineering (NTE) to mimic the physical, biological, and material properties of the native extracellular matrix. In this work, we have developed scaffolds based on polymer fiber architectures for application in NTE. To study the role of such three-dimensional scaffolds, a rotating drum collector was used for electrospinning poly(vinylidene) fluoride (PVDF) polymer at various rotation speeds. The morphology, orientation, polymorphism, as well as the mechanical behavior of the nonaligned and aligned fiber-based architectures were characterized. We have demonstrated that the jet flow and the electrostatic forces generated by electrospinning of PVDF induced local conformation changes which promote the generation of the ß-phase. Fiber anisotropy could be a critical feature for the design of suitable scaffolds for NTEs. We thus assessed the impact of PVDF fiber alignment on the behavior of monkey neural stem cells (NSCs). NSCs were seeded on nonaligned and aligned scaffolds and their morphology, adhesion, and differentiation capacities into the neuronal and glial pathways were studied using microscopic techniques. Significant changes in the growth and differentiation capacities of NSCs into neuronal and glial cells as a function of the fiber alignment were evidenced. These results demonstrate that PVDF scaffolds may serve as instructive scaffolds for NSC survival and differentiation, and may be valuable tools for the development of cell- and scaffold-based strategies for neural repair. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2376-2393, 2017.

Development of Bioresorbable Hydrophilic-Hydrophobic Electrospun Scaffolds for Neural Tissue Engineering.

In this study, electrospun fiber scaffolds based on biodegradable and bioabsorbable polymers and showing a similar structure to that of the extracellular matrix (ECM) present in the neural tissues were prepared. The effects of electrospun-based scaffolds processed from poly(lactic acid) (PLA)/poly(lactide-b-ethylene glycol-b-lactide) block copolymer (PELA) and PLA/polyethylene glycol (PEG) (50:50 by wt) blends on the morphology, wettability, and mechanical properties, as well as on neural stem cell (NSC) behavior, were investigated. Thus, PLA/PELA and PLA/PEG fiber mats composed of PEG with different chain lengths were evaluated for optimal use as tissue engineering scaffolds. In both cases, the hydrophilic character of the scaffold surface was increased from the introduction of PEG homopolymer or PEG-based block copolymer compared with neat PLA. A microphase separation and a surface erosion of PLA/PEG blend-based electrospun fibers were highlighted, whereas PLA/PELA blend-based fibers displayed a moderate hydrophilic surface and a tunable balance between surface erosion and bulk degradation. Even if the mechanical properties of PLA fibers containing PEG or PELA decreased slightly, an excellent compromise between stiffness and the ability to sustain large deformation was found for PLA/PELA(2k), which displayed a significant increase in strain at break, that is, up to 500%. Our results suggest that both neat PLA and PLA/PELA blends supplemented with growth factors may mimic neural-like constructs and provide structural stability. Nonetheless, electrospun PLA/PELA blends have a suitable surface property, which may act synergistically in the modulation of biopotential for implantable scaffolding in neural tissue engineering.

Space-Use Patterns of the Asiatic Wild Ass (Equus hemionus): Complementary Insights from Displacement, Recursion Movement and Habitat Selection Analyses.

The way in which animals move and use the landscape is influenced by the spatial distribution of resources, and is of importance when considering species conservation. We aimed at exploring how landscape-related factors affect a large herbivore's space-use patterns by using a combined approach, integrating movement (displacement and recursions) and habitat selection analyses. We studied the endangered Asiatic wild ass (Equus hemionus) in the Negev Desert, Israel, using GPS monitoring and direct observation. We found that the main landscape-related factors affecting the species' space-use patterns, on a daily and seasonal basis, were vegetation cover, water sources and topography. Two main habitat types were selected: high-elevation sites during the day (specific microclimate: windy on warm summer days) and streambed surroundings during the night (coupled with high vegetation when the animals were active in summer). Distribution of recursion times (duration between visits) revealed a 24-hour periodicity, a pattern that could be widespread among large herbivores. Characterizing frequently revisited sites suggested that recursion movements were mainly driven by a few landscape features (water sources, vegetation patches, high-elevation points), but also by social factors, such as territoriality, which should be further explored. This study provided complementary insights into the space-use patterns of E. hemionus. Understanding of the species' space-use patterns, at both large and fine spatial scale, is required for developing appropriate conservation protocols. Our approach could be further applied for studying the space-use patterns of other species in heterogeneous landscapes.

Nanofluidics Approach to Separate between Static and Kinetic Nanoconfinement Effects on the Crystallization of Polymers.

Here we report a nanofluidics approach that allows one to discriminate, for the first time, between static and kinetic effects on the crystallization of polymers in 2-dimensional nanoconfinement. Nanofluidics cells designed to monitor in real time, via permittivity measurements, the flow process of polymers into cylindrical nanopores were employed to investigate the crystallization of poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) under static and under kinetic confinement conditions. A significant separation between static confinement effects and flow effects in confinement is reported. A characteristic time is deduced, to quantify the impact of flow on the crystallization process of polymers taking place under conditions of 2D geometrical nanoconfinement.

Ranging behaviour of roe deer in an experimental high-density population: are females territorial?

We studied the ranging behaviour and spatial relationships between seven roe deer during more than 4 years in a partly wooded 14.2-ha enclosure. The animals (three young males, four adult females) were monitored with GPS telemetry collars. As expected, the surface area and overlap of the males' bimonthly ranges decreased, and the distance between their arithmetic centres increased, as they became adult and, for two of them, territorial. Unexpectedly, females also tended to space out, the surface area and overlap of their bimonthly ranges being minimal in May to June, i.e. during the birth period. The distance between their arithmetic centres reached its maximum at the same time. Overlap between females' ranges was consistently lower than those between males and females' ranges, or between 1-year old males' ranges. Our results raise the questions of female seasonal territoriality and of independence of the spacing systems of the two sexes in roe deer.

Application of supercritical CO2 and ionic liquids for the preparation of fluorinated nanocomposites.

This work is focused on the tailoring of dispersions of layered silicates, such as MICA SOMASIF (ME-100) within a fluoride matrix (polytetrafluoroethylene) through two strategies: the physicochemical interactions between filler and matrix and the processing of materials. The interactions in these complex systems are modified by new environmentally friendly thermally stable surfactants. The ionic liquids used are based on alkyltriphenyl phosphonium and perfluorinated alkylpyridinium cations. The influences of the cation-anion combination and functionalization were investigated. The use of the supercritical carbon dioxide (ScCO(2)) as a solvent is relevant to generate structuring within the material based on ionic liquid phase separation. The tunability of ionic liquids and their combination with the supercritical carbon dioxide enables to design materials with optimized thermal and mechanical properties.

Synthesis of cross-linked epoxy microparticles: effect of the synthesis parameters.

Epoxy crosslinked microparticles were synthesized from the reaction between diglycidyl ether of bisphenol A and a diamino hardener, through precipitation polymerization in a polypropylene glycol solvent. The influence of the monomer concentration, the amine/epoxy stoichiometric ratio, the reaction temperature and the structure of the diamine (aromatic or cycloaliphatic) were investigated, since these parameters may affect the structure and properties of the particles. Morphological analysis revealed that, in all cases, spherical particles were obtained with diameters ranging from 1 to 6 µm. The glass transition temperatures of the particles was found to vary between 130 and 160 °C using the aromatic diamine and between 116 and 141 °C using the cycloaliphatic diamine. It was also found that the effective stoichiometry of the particles was different from the initial stoichiometry in the feed solution.

Ionic liquids: structuration agents in a fluorinated matrix.

The use of ionic liquids as functional building blocks based on pyridinium, imidazolium and phosphonium cations to achieve materials combining a structuration at nanoscale with the dramatic mechanical properties of the resulting ionomers has been successfully demonstrated for the first time in a fluorinated matrix.