Thermodynamics of Tri- and Tetraepoxyimidazolium NTf2 Amine Polyaddition: A Theoretical Perspective.

The thermodynamics of newly designed tri- and tetraepoxyimidazolium NTf2 monomers reacting with several diamines used as curing agents to form epoxy/amine thermosets was studied. The ability of each epoxy/amine combination to induce cross-linking both through the substitution of multiple epoxy groups and through multiple additions to a single amine was investigated. Through an increased understanding of the thermodynamics of epoxy-amine polymerization in complex polyepoxy-ILs, it is possible to more thoroughly understand the factors affecting the reactivity in these complex systems. These calculations showed that while each possible epoxy-amine combination was exergonic to both forms of cross-linking, the degree to which both amines-induced cross-linking and epoxy-induced cross-linking was favored varied between epoxy-amine combinations. Thermodynamic results obtained using density functional theory were experimentally validated through differential scanning calorimetry results, wherein similar trends were noted between theory and experiment. Among the trends noted in amines-epoxy combinations tested, tetraepoxyimidazolium NTf2/PACM (i.e., a cycloaliphatic diamine) was found to be a prime candidate for amine cross-linking, with the addition of a second epoxy to a single amine group being notably the most negative of all epoxy-amine combinations at -77.6 kJ mol-1. While in the case of epoxy cross-linking, the aliphatic polyetheramine denoted Jeffamine-D230-containing systems were found to be the most exergonic, with additions of primary amines to triepoxyimidazolium and tetraepoxyimidazolium NTf2 averaging -86.9 kJ mol-1. Interaction energy analysis indicated that the aromatic amine named sulfanilamide is the most favorable to engage in reactions due to having the most negative interaction energies with already highly substituted epoxy monomers. These results can be used to adjust the cross-linking possibilities of tri- and tetraepoxyimidazolium NTf2/amine polymerization and give insight into the predominant cross-linking reactions in these unique systems.

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.

Theoretical Analysis of Physical and Chemical CO2 Absorption by Tri- and Tetraepoxidized Imidazolium Ionic Liquids.

The efficient capture of CO2 from flue gas or directly from the atmosphere is a key subject to mitigate global warming, with several chemical and physical absorption methods previously reported. Through polarizable molecular dynamics (MD) simulations and high-level quantum chemical (QC) calculations, the physical and chemical absorption of CO2 by ionic liquids based on imidazolium cations bearing oxirane groups was investigated. The ability of the imidazolium group to absorb CO2 was found to be prevalent in both the tri- and tetraepoxidized imidazolium ionic liquids (ILs) with coordination numbers over 2 for CO2 within the first solvation shell in both systems. Thermodynamic analysis of the addition of CO2 to convert epoxy groups to cyclic carbonates also indicated that the overall reaction is exergonic for all systems tested, allowing for chemical absorption of CO2 to also be favored. The rate-determining step of the chemical absorption involved the initial opening of the epoxy ring through addition of the chloride anion and was seen to vary greatly between the epoxy groups tested. Among the groups tested, the less sterically hindered monoepoxy side of the triepoxidized imidazolium was shown to be uniquely capable of undergoing intramolecular hydrogen bonding and thus lowering the barrier required for the intermediate structure to form during the reaction. Overall, this theoretical investigation highlights the potential for epoxidized imidazolium chloride ionic liquids for simultaneous chemical and physical absorption of CO2.

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.

Synthesis of Carbon Nanodots from Sugarcane Syrup, and Their Incorporation into a Hydrogel-Based Composite to Fabricate Innovative Fluorescent Microstructured Polymer Optical Fibers.

Carbon nanodots (CNDs) are interesting materials due to their intrinsic fluorescence, electron-transfer properties, and low toxicity. Here, we report a sustainable, cheap, and scalable methodology to obtain CNDs from sugarcane syrup using a domestic microwave oven. The CNDs were characterized by infrared spectroscopy, dynamic light scattering, atomic force microscopy, absorption, and emission spectroscopies. The CNDs have 3 nm in diameter with low polydispersity and are fluorescent. A fluorescent hydrogel-CNDs composite was obtained using gelatin polypeptide as the polymeric matrix. The new hydrogel-CNDs composite was incorporated in the cavities of a double-clad optical fiber using an innovative approach that resulted in a microstructured polymer optical fiber with intrinsic fluorescence. This work shows a promising alternative for the fabrication of fluorescent materials since the CNDs synthesis is sustainable and environmentally friendly. These CNDs might substitute the rare-earth and other heavy metals of high cost and toxicity, which are usually incorporated in double-clad fibers for applications on lasers, amplifiers, and spectroscopy.

Recent Advances in the Interfacial Shear and Dilational Rheology of Polymer Systems: From Fundamentals to Applications.

The study of the viscoelastic properties of polymer systems containing huge internal two-dimensional interfacial areas, such as blends, foams and multilayer films, is of growing interest and plays a significant role in a variety of industrial fields. Hence, interfacial rheology can represent a powerful tool to directly investigate these complex polymer-polymer interfaces. First, the current review summarizes the theoretical basics and fundamentals of interfacial shear rheology. Particular attention has been devoted to the double-wall ring (DWR), bicone, Du Noüy ring and oscillating needle (ISR) systems. The measurement of surface and interfacial rheological properties requires a consideration of the relative contributions of the surface stress arising from the bulk sub-phases. Here, the experimental procedures and methodologies used to correct the numerical data are described considering the viscoelastic nature of the interface. Second, the interfacial dilational rheology is discussed, starting with the theory and underlying principles. In particular, the Langmuir trough method, the oscillating spinning drop technique and the oscillating pendant drop technique are investigated. The major pioneering studies and latest innovations dedicated to interfacial rheology in both shear and dilatation-compression are highlighted. Finally, the major challenges and limits related to the development of high-temperature interfacial rheology at the molten state are presented. The latter shows great potential for assessing the interfaces of polymer systems encountered in many high-value applications.

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.

Molecular-Level Investigation of Cycloaliphatic Epoxidised Ionic Liquids as a New Generation of Monomers for Versatile Poly(Ionic Liquids).

Recently, a new generation of polymerised ionic liquids with high thermal stability and good mechanical performances has been designed through novel and versatile cycloaliphatic epoxy-functionalised ionic liquids (CEILs). From these first promising results and unexplored chemical structures in terms of final properties of the PILs, a computational approach based on molecular dynamics simulations has been developed to generate polymer models and predict the thermo-mechanical properties (e.g., glass transition temperature and Young's modulus) of experimentally investigated CEILs for producing multi-functional polymer materials. Here, a completely reproducible and reliable computational protocol is provided to design, test and tune poly(ionic liquids) based on epoxidised ionic liquid monomers for future multi-functional thermoset polymers.

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 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.

The Role of Fluorinated IL as an Interfacial Agent in P(VDF-CTFE)/Graphene Composite Films.

The incorporation of graphene into a polymer matrix can endow composites with extended functions. However, it is difficult to well disperse pristine graphene into a polymer matrix in order to obtain polymer nanocomposites due to the lack of functional groups on the surface for bonding with a polymer matrix. Herein, we investigated the role of fluorinated ionic liquid (IL) as a new interfacial agent in poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-CTFE))/graphene composite films. First, a task-specific IL, perfluorooctyltriphenylphosphonium iodide (IL-C8F13), was synthesized and adsorbed on the surface of graphene oxide (GO) and reduced graphene oxide (rGO) for making functional nanofillers which were capable of being incorporated into the P(VDF-CTFE) matrix. The cation structure of IL combined three phenyls (potential π-π interactions with graphene) and a short fluorinated chain (enhanced miscibility with fluorinated matrix via dipolar interactions) to make a compatible graphene filler and P(VDF-CTFE) matrix at the interface among them. Second, two series of P(VDF-CTFE)/GO-IL and P(VDF-CTFE)/rGO-IL composites with different loading contents were prepared with the goal of providing an understanding of the mechanism of interfacial interactions. This paper investigated the difference in the interaction model between GO with IL and rGO with IL. Subsequently, the interfacial effect of IL on the properties of P(VDF-CTFE)/graphene composites, such as crystallization, chain segmental relaxation behavior, dispersion, and the final dielectric properties will be further studied.

Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries.

In this work, new gelled electrolytes were prepared based on a mixture containing phosphonium ionic liquid (IL) composed of trihexyl(tetradecyl)phosphonium cation combined with bis(trifluoromethane)sulfonimide [TFSI] counter anions and lithium salt, confined in a host network made from an epoxy prepolymer and amine hardener. We have demonstrated that the addition of electrolyte plays a key role on the kinetics of polymerization but also on the final properties of epoxy networks, especially thermal, thermo-mechanical, transport, and electrochemical properties. Thus, polymer electrolytes with excellent thermal stability (>300 °C) combined with good thermo-mechanical properties have been prepared. In addition, an ionic conductivity of 0.13 Ms·cm−1 at 100 °C was reached. Its electrochemical stability was 3.95 V vs. Li°/Li⁺ and the assembled cell consisting in Li|LiFePO4 exhibited stable cycle properties even after 30 cycles. These results highlight a promising gelled electrolyte for future lithium ion batteries.

PeakForce QNM AFM study of chitin-silica hybrid films.

Chitin-silica hybrid thin films, prepared through the colloidal self-assembly of chitin nanorods and siloxane oligomers, have been studied for the first time by PeakForce QNM AFM mode to explore their structure and mechanical behaviour. The change in structure and mechanical properties of chitin-silica hybrids is mainly driven by the relative quantities in chitin nanorods and silica, expressed as the chitin volume fraction ϕchi. The coating of the chitin polysaccharide by silica leads to an increase of the nanorods diameter and films surface roughness at small ϕchi values. The DMT (Derjaguin-Muller-Toporov) modulus increased both at small ϕchi due to a large amount of silica and at very high ϕchi→1 due to an incomplete tip penetration between nanorods. The local parallel orientation of nanorods observed at different ϕchi values resulted in a modulus increase due to an enhancement of the cohesion between nanorods.

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.

1,2,3-Triazolium-Based Epoxy-Amine Networks: Ion-Conducting Polymer Electrolytes.

A diepoxy-functionalized 1,2,3-triazolium ionic liquid is synthesized in three steps and used in combination with a poly(propylene glycol) diamine to obtain ion-conducting epoxy-amine networks (EANs). The curing kinetics are followed by Fourier transform infrared spectroscopy, while the physical, mechanical, and ion-conducting properties of the resulting networks are studied by swelling experiments, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis, and broadband dielectric spectroscopy. The curing kinetics and thermomechanical properties of this system are relatively similar to those of conventional DGEBA- (bisphenol A diglycidyl ether)-based EANs with low glass transition temperature (Tg = -44 and -52 °C, respectively) characteristic of rubbery polymer networks. The anhydrous ionic conductivity of the pure network at 30 °C reaches a remarkably high value of 2 × 10(-7) S cm(-1) that could be further increased to 10(-6) S cm(-1) by the addition of 10 wt% LiTFSI.

Synthesis and physical properties of new layered double hydroxides based on ionic liquids: application to a polylactide matrix.

Ionic liquids based on tetraalkylphosphonium salts combined with different anions (decanoate and dodecylsulfonate) have been used as intercalating agents of layered double hydroxides (LDHs) by ion exchange. The synthesized phosphonium-treated LDHs display a dramatically improved thermal degradation and a significant increase in the interlayer distance as confirmed by thermogravimetric analysis (TGA) and X-ray Diffraction (XRD), respectively. To highlight the effect of thermostable ionic liquids, a very low amount of LDHs has been introduced within a polylactide (PLA) matrix and PLA/LDHs nanocomposites have been processed in melt by twin-screw extrusion. Then, transmission electron microscopy (TEM) analysis has been used to investigate the influence of ILs on the different morphologies of these nanocomposites. Even though the thermal stability of PLA matrix decreased, an excellent stiffness-toughness compromise has been obtained.

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.

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.