Polylactic Acid Nanofiber Membranes Grafted with Carbon Nanotubes with Enhanced Mechanical and Electrical Properties.

Electroconductive materials based on poly(lactic acid) (PLA) electrospinning membranes grafted with carbon nanotubes (CNTs) functionalized with the carboxylic group R-COOH have been obtained. PLA electrospun membranes were modified with sulfuric acid (H2SO4) to oxidize its surface to subsequently graft the CNTs, the treatment time and drying of the membranes before grafting with CNTs being critical, influencing the final properties of the materials. SEM images showed that CNTs presented a uniform distribution on the surface of the PLA nanofibers, while FTIR spectra of PLA-CNTs materials revealed characteristic hydroxyl groups, as evidenced by absorption peaks of CNTs. Thanks to the grafting with CNTs, the resulting PLA-CNTs membranes present an improvement of the mechanical and conductive properties when compared with PLA membranes. On the one hand, grafting with CNTs causes the nanofibers to have greater rigidity, so they are more manipulable and can more easily preserve their conformation when stress is exerted. On the other hand, grafting with CNTs allows elimination of the insulating barrier of the PLA, reducing the resistivity and providing high electrical conductivity to the PLA-CNTs membranes. The incorporation of CNTs into PLA electrospun membranes is expected to offer greater functionalities to electrospun composite nanofibers for medical and industrial applications.

Correction: Free ion diffusivity and charge concentration on cross-linked polymeric ionic liquid iongel films based on sulfonated zwitterionic salts and lithium ions.

Correction for 'Free ion diffusivity and charge concentration on cross-linked polymeric ionic liquid iongel films based on sulfonated zwitterionic salts and lithium ions' by David Valverde et al., Phys. Chem. Chem. Phys., 2019, 21, 17923-17932, DOI: 10.1039/C9CP01903K.

Diffusivity and free anion concentration of ionic liquid composite polybenzimidazole membranes.

In this article, PBI composite membranes containing the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM-NTf2) at 1, 5, 10, 20 and 50 wt% (named PBI-IL-x) have been prepared by a casting method. The internal morphology of the membranes was analyzed by scanning electron microscopy (SEM), revealing that the incorporation of IL promotes the formation of porous channels. Thermal and mechanical stability was confirmed by thermogravimetric analysis (TGA) and tensile test measurements. The ionic transport through membranes was analysed by means of electrochemical impedance spectroscopy (EIS), showing a dependence on the IL loading, reaching a highest conductivity value of 1.8 × 10-2 S cm-1 for the PBI-IL-50 membrane at 160 °C. The experimental results showed a Vogel-Fulcher-Tammann (VFT) type relation for the ionic conductivity with temperature and the calculated activation energies suggest that ionic conduction in the films can occur by both hopping and vehicle-type mechanisms. Eyring's absolute rate theory was also used to obtain activation enthalpy and entropy from the temperature dependence of the conductivity. Diffusivity and free ion number density were obtained by means of electrode polarization analysis to obtain more insight into the conduction in these composite membranes. Finally, the Debye length was calculated and related to both transport parameters.

Effect of metallacarborane salt H[COSANE] doping on the performance properties of polybenzimidazole membranes for high temperature PEMFCs.

In this paper, a series of composite proton exchange membranes comprising a cobaltacarborane protonated H[Co(C2B9H11)2] named (H[COSANE]) and polybenzimidazole (PBI) for a high temperature proton exchange membrane fuel cell (PEMFC) is reported, with the aim of enhancing the proton conductivity of PBI membranes doped with phosphoric acid. The effects of the anion [Co(C2B9H11)2] concentration in three different polymeric matrices based on the PBI structure, poly(2,2'-(m-phenylene)-5,5'-bibenzimidazole) (PBI-1), poly[2,2'-(p-oxydiphenylene)-5,5'-bibenzimidazole] (PBI-2) and poly(2,2'-(p-hexafluoroisopropylidene)-5,5'-bibenzimidazole) (PBI-3), have been investigated. The conductivity, diffusivity and mobility are greater in the composite membrane poly(2,2'-(p-hexafluoroisopropylidene)-5,5'-bibenzimidazole) containing fluorinated groups, reaching a maximum when the amount of H[COSANE] was 15%. In general, all the prepared membranes displayed excellent and tunable properties as conducting materials, with conductivities higher than 0.03 S cm-1 above 140 °C. From an analysis of electrode polarization (EP) the proton diffusion coefficients and mobility have been calculated.

A Deep Insight into Different Acidic Additives as Doping Agents for Enhancing Proton Conductivity on Polybenzimidazole Membranes.

The use of phosphoric acid doped polybenzimidazole (PBI) membranes for fuel cell applications has been extensively studied in the past decades. In this article, we present a systematic study of the physicochemical properties and proton conductivity of PBI membranes doped with the commonly used phosphoric acid at different concentrations (0.1, 1, and 14 M), and with other alternative acids such as phytic acid (0.075 M) and phosphotungstic acid (HPW, 0.1 M). The use of these three acids was reflected in the formation of channels in the polymeric network as observed by cross-section SEM images. The acid doping enhanced proton conductivity of PBI membranes and, after doping, these conducting materials maintained their mechanical properties and thermal stability for their application as proton exchange membrane fuel cells, capable of operating at intermediate or high temperatures. Under doping with similar acidic concentrations, membranes with phytic acid displayed a superior conducting behavior when compared to doping with phosphoric acid or phosphotungstic acid.

Free ion diffusivity and charge concentration on cross-linked polymeric ionic liquid iongel films based on sulfonated zwitterionic salts and lithium ions.

The properties of various mixtures of a zwitterionic ionic liquid (ZIs-1) and LiNTf2, including their conductivity, have been studied showing how they can be adjusted through their molar composition. Conductivity tends to increase with the LiNTf2 content although it presents a minimum at the region close to the eutectic point. These mixtures also provide excellent features as liquid phases for the preparation of composite materials based on crosslinked PILs. The prepared films display excellent and tuneable properties as conducting materials, with conductivities that can be higher than 10-2 S cm-1 above 100 °C. The selected polymeric compositions show very good mechanical properties and thermal stability, even for low crosslinking degrees, along with a suitable flexibility and good transparency. The final properties of the films correlate with the composition of the monomeric mixture used and with that of the ZIs-1:LiNTf2 mixture.

Proton Conductivity through Polybenzimidazole Composite Membranes Containing Silica Nanofiber Mats.

The quest for sustainable and more efficient energy-converting devices has been the focus of researchers' efforts in the past decades. In this study, SiO2 nanofiber mats were fabricated through an electrospinning process and later functionalized using silane chemistry to introduce different polar groups -OH (neutral), -SO3H (acidic) and -NH2 (basic). The modified nanofiber mats were embedded in PBI to fabricate mixed matrix membranes. The incorporation of these nanofiber mats in the PBI matrix showed an improvement in the chemical and thermal stability of the composite membranes. Proton conduction measurements show that PBI composite membranes containing nanofiber mats with basic groups showed higher proton conductivities, reaching values as high as 4 mS·cm-1 at 200 °C.

Ionic Liquid Composite Polybenzimidazol Membranes for High Temperature PEMFC Applications.

A series of proton exchange membranes based on polybenzimidazole (PBI) were prepared using the low cost ionic liquids (ILs) derived from 1-butyl-3-methylimidazolium (BMIM) bearing different anions as conductive fillers in the polymeric matrix with the aim of enhancing the proton conductivity of PBI membranes. The composite membranes prepared by casting method (containing 5 wt. % of IL) exhibited good thermal, dimensional, mechanical, and oxidative stability for fuel cell applications. The effects of anion, temperature on the proton conductivity of phosphoric acid-doped membranes were systematically investigated by electrochemical impedance spectroscopy. The PBI composite membranes containing 1-butyl-3-methylimidazolium-derived ionic liquids exhibited high proton conductivity of 0.098 S·cm-1 at 120 °C when tetrafluoroborate anion was present in the polymeric matrix. This conductivity enhancement might be attributed to the formed hydrogen-bond networks between the IL molecules and the phosphoric acid molecules distributed along the polymeric matrix.

Phosphoric Acid Doped Polybenzimidazole (PBI)/Zeolitic Imidazolate Framework Composite Membranes with Significantly Enhanced Proton Conductivity under Low Humidity Conditions.

The preparation and characterization of composite polybenzimidazole (PBI) membranes containing zeolitic imidazolate framework 8 (ZIF-8) and zeolitic imidazolate framework 67 (ZIF-67) is reported. The phosphoric acid doped composite membranes display proton conductivity values that increase with increasing temperatures, maintaining their conductivity under anhydrous conditions. The addition of ZIF to the polymeric matrix enhances proton transport relative to the values observed for PBI and ZIFs alone. For example, the proton conductivity of PBI@ZIF-8 reaches 3.1 × 10-3 S·cm-1 at 200 °C and higher values were obtained for PBI@ZIF-67 membranes, with proton conductivities of up to 4.1 × 10-2 S·cm-1. Interestingly, a composite membrane containing a 5 wt.% binary mixture of ZIF-8 and ZIF-67 yielded a proton conductivity of 9.2 × 10-2 S·cm-1, showing a synergistic effect on the proton conductivity.

Structural and dielectric properties of cobaltacarborane composite polybenzimidazole membranes as solid polymer electrolytes at high temperature.

The conductivity of a series of composite membranes, based on polybenzimidazole (PBI) containing the metallacarborane salt M[Co(C2B9H11)2], M[COSANE] and tetraphenylborate, M[B(C6H5)4], M[TPB] both anions having the same number of atoms and the same negative charge, has been investigated. Different cations (M = H+, Li+ and Na+) have been studied and the composite membranes have been characterized by water uptake, swelling ratios, ATR FT-IR, thermogravimetric analysis and electrochemical impedance spectroscopy to explore the dielectric response and ion dynamics in composite membranes. Our results show that conductivity increases with increasing temperature and it is higher for H+ than for Li+ and Na+ for all temperatures under study. The mobility of Li+ is greater in [COSANE]- than in [TPB]- composite PBI@membranes while for Na+ it is the opposite. The temperature dependence of the conductivity of the composite was followed by a typical Arrhenius behaviour with two different regions: (1) between 20 and 100 °C, and (2) between 100 and 150 °C. Using the analysis of electrode polarization (EP) based on the Thrukhan theory we have calculated the ionic diffusion coefficients and the density of carriers. From the double logarithmic plot of the imaginary part of the conductivity (σ'') versus frequency in the entire range of temperatures studied we have determined for each sample at each temperature, the frequency values of the onset (fON) and full development of electrode polarization (fMAX), respectively, which permit us to calculate static permittivity.

Size-tunable micron-bubbles based on fluorous-fluorous interactions of perfluorinated dendritic polyglycerols.

This paper describes the behavior of various generations of polyglycerol dendrimers that contain a perfluorinated shell. The aggregation in organic solvents is based on supramolecular fluorous-fluorous interactions, which can be described by means of (19)F NMR spectroscopy. In order to study the interaction and aggregation phenomena of dendrimers with perfluorinated shell and perfluoro-tagged guest molecules we investigated [G3.5]-dendrimer with a perfluorinated shell in the presence of perfluoro-tagged disperse red. Noteworthy, the interaction intensities varied in an unexpected manner depending on the equivalents of perfluoro-tagged guest molecules added to the dendrimers in solution which then formed supramolecular complexes based on fluorous-fluorous interactions. We found that these complexes aggregated around residual air in the solvent to form stable micron-sized bubbles. Their sizes correlated with the interaction intensities measured for certain dendrimer-guest molecule ratios. Degassing of the solutions led to a quasi phase separation between organic and fluorous phase, whereby the dendrimers formed the fluorous phases. Regassing the sample with air afforded bubbles of the initial size again.

Secondary and primary relaxations in hyperbranched polyglycerol: a comparative study in the frequency and time domains.

The non-Debye relaxation behavior of hyperbranched polyglycerol was investigated by broadband dielectric spectroscopy. A thorough study of the relaxations was carried out paying special attention to truncation effects on deconvolutions of overlapping processes. Hyperbranched polyglycerol exhibits two relaxations in the glassy state named in increasing order of frequency beta and gamma processes. The study of the evolution of these two fast processes with temperature in the time retardation spectra shows that the beta absorption is swallowed by the alpha in the glass-liquid transition, the gamma absorption being the only relaxation that remains operative in the liquid state. In heating, a temperature is reached at which the alpha absorption vanishes appearing the alphagamma relaxation. Two characteristics of alpha absorptions, decrease of the dielectric strength with increasing temperature and rather high activation energy, are displayed by the alphagamma process. Williams' ansatz seems to hold for these topologically complex macromolecules.

Syntheses and phase-transfer properties of dendritic nanocarriers that contain perfluorinated shell structures.

Perfect dendrimers that contain perfluorinated shells have recently attracted attention because they have been shown to encapsulate polar molecules in supercritical CO(2) and catalytically active metal nanoparticles in perfluorinated solvents. Moreover, they can then be easily separated after reaction from the biphasic organic/fluorous system. In this paper several dendritic architectures that contain perfluorinated shells were derived by covalent modification of glycerol dendrimers ([G0.5]-[G3.5]), hyperbranched polyglycerol, and polyethyleneimine. These core-shell architectures show interesting physicochemical properties. For example, they are soluble in fluorinated solvents, they are able to transport different guest molecules, and they display thermomorphic behavior. The transport capacity of these molecular nanocarriers increases significantly when amino groups are present in the core. Certain functionalized polyethyleneimines that contain perfluorinated shells show high transport capacities (up to 3 dye molecules per nanocarrier) in perfluorinated solvents. Moreover, these perfluoro-functionalized dendritic polyethyleneimines can act as templates that stabilize nanoparticles; for example, encapsulation and subsequent chemical reduction of Ag(I) ions. Silver nanoparticles with a narrow size distribution (3.9+/-1 nm) have been prepared and characterized by transmission electron microscopy. Furthermore, it has been demonstrated that the encapsulated guest molecules remain accessible to small molecules after transport into the fluorous phase. Therefore, dendritic nanocarriers that contain perfluorinated shells are currently being investigated as polar environments in nonpolar reaction media such as fluorous phases and supercritical CO(2), in particular, for application in homogenous catalysis.