Study of the fire resistant behavior of unfilled and carbon nanofibers reinforced polybenzimidazole coating for structural applications

With increasing interest in epoxy‐based carbon fiber composites for structural applications, it is important to improve the fire resistant properties of these materials. The fire resistant performance of these materials can be improved either by using high performance epoxy resin for manufacturing carbon fiber composite or by protecting the previously used epoxy‐based composite with some fire resistant coating. In this context, work is carried out to evaluate the fire resistance performance of recently emerged high performance polybenzimidazole (PBI) when used as a coating material. Furthermore, the effect of carbon nanofibers (CNFs) on fire resistant properties of inherently flame retardant PBI coating was studied. Thermogravimetric analysis of carbon/epoxy composite, unfilled PBI and nano‐filled PBI shows that the carbon/epoxy composite maintained its thermal stability up to a temperature of 400°C and afterwards showed a large decrease in mass, while both unfilled PBI and nano‐filled PBI have shown thermal stability up to a temperature of 575°C corresponding to only 11% weight loss. Cone calorimeter test results show that unfilled PBI coating did not improve the fire retardant performance of carbon/epoxy composite. Conversely, nano‐filled PBI coating has shown a significant improvement in fire retardant performance of the carbon/epoxy composite in terms of increased ignition time, reduced average and peak heat release rate and reduced smoke and carbon monoxide emission. These results indicate that addition of carbon nanofibers to inherently flame retardant coating can significantly be helpful for improving the fire resistance performance of composite materials even with low coating thickness. Copyright © 2013 John Wiley & Sons, Ltd.     

Allyl ether of aralkyl phenolic resin with low melt viscosity and its Alder‐ene blends with bismaleimide: synthesis,curing, and laminate properties

This paper outlines the synthesis and characterization of O‐allyl aralkyl phenolic (O‐allyl Xylok, OAX) resins having low melt viscosity and its Alder‐ene blends with 2, 2′‐bis 4‐[(4′‐maleimido phenoxy) phenyl] propane. The blends manifested a three‐stage curing pattern that converged to a two‐stage pattern on enhancing the maleimide content. The polymerization kinetics of typical allyl and maleimide rich resin systems showed apparent activation energy increasing and pre‐exponential factor decreasing from ene to the Diels–Alder step. Increased allyl content improved mechanical and impact properties of the composites at ambient temperature, although it diminished the retention of interlaminar shear strength at elevated temperature. Increased maleimide content of the resin was conducive for the higher rigidity for the composite and its retention at elevated temperature. A substantial increase in T_g (from 153°C to 280°C) and thermal stability was observed with an increase in maleimide content. High allyl content resulted in improved mechanical properties thanks to better resin–reinforcement interaction as revealed from morphological analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Improving the flame retardancy of polyamide 6 by incorporating hexachlorocyclotriphosphazene modified MWNT

A nitrogen‐, phosphorus‐ and chlorine‐containing flame retardant, hexachlorocyclotriphosphazene (HCTP), has been covalently grafted onto the surface of multi‐wall carbon nanotubes (MWNT) to obtain MWNT‐HCTP. Polyamide 6 (PA6)/MWNT composites were then prepared via melt compounding. The flammability of PA6/MWNT composite was characterized by cone calorimetry, limiting oxygen index (LOI) and UL‐94 tests. The results showed that peak heat release rate of samples containing 3 wt% MWNT‐HCTP was only 460 kW/m², which decreased by 35.2% compared with that of a neat PA6 sample. The LOI value was increased from 22.7% to 26.5%, and UL‐94 test performance was also significantly improved by the presence of MWNT‐HCTP. Scanning electron microscope (SEM) and optical microscope analysis showed that modified MWNT had a better dispersion and compatibility in PA6 than unmodified MWNT. The composition of residue chars and volatile products was investigated by SEM/energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric‐FTIR, respectively. It was proposed that grafted HCTP was mainly functioned in the condensed phase, where P, N can synergistically promote char formation and Cl element can catch free radicals to terminate the chain reaction during combustion of the PA6 composite. Copyright © 2014 John Wiley & Sons, Ltd.     

Phenylboronate‐diol crosslinked polymer/SWCNT hybrid gels with reversible sol–gel transition

This work demonstrates the successful incorporation of functionalized single‐walled carbon nanotubes (f‐SWCNTs) into the phenylboronate‐diol crosslinked polymer gel to create a hybrid system with reversible sol–gel transition. The phenylboronic acid‐containing and diol‐containing polymers were first separately prepared by the reversible addition–fragmentation chain transfer polymerization. Covalent functionalization of single‐walled carbon nanotubes (SWCNTs) with an azide‐derivatized, diol‐containing polymer was then accomplished by a nitrene addition reaction. Subsequently, the hybrid gels were prepared by crosslinking the mixture of f‐SWCNTs and diol‐containing polymer with the phenylboronic acid‐containing polymer. The hybrid gel has been characterized by scanning electron microscopy (SEM) and rheological analysis. The SEM measurement demonstrated a homogeneous dispersion of f‐SWCNTs within the gel matrices. Rheological experiments also demonstrated that the hybrid gel exhibited storage moduli significantly higher than those of the native gel obtained from the phenylboronic acid‐containing and diol‐containing polymers. The hybrid gel can be switched into their starting polymer (f‐SWCNTs) solutions by adjusting the pH of the system. Moreover, the hybrid gel revealed a self‐healing property that occurred autonomously without any outside intervention. By employing this dynamic character, it is possible to regenerate the used gel, and thus, it has the potential to perform in a range of dynamic or bioresponsive applications Copyright © 2013 John Wiley & Sons, Ltd.     

Single‐Molecule Sensing of Environmental pH—an STM Break Junction and NEGF‐DFT Approach

Sensors play a significant role in the detection of toxic species and explosives, and in the remote control of chemical processes. In this work, we report a single‐molecule‐based pH switch/sensor that exploits the sensitivity of dye molecules to environmental pH to build metal–molecule–metal (m‐M‐m) devices using the scanning tunneling microscopy (STM) break junction technique. Dyes undergo pH‐induced electronic modulation due to reversible structural transformation between a conjugated and a nonconjugated form, resulting in a change in the HOMO–LUMO gap. The dye‐mediated m‐M‐m devices react to environmental pH with a high on/off ratio (≈100:1) of device conductivity. Density functional theory (DFT) calculations, carried out under the non‐equilibrium Green’s function (NEGF) framework, model charge transport through these molecules in the two possible forms and confirm that the HOMO–LUMO gap of dyes is nearly twice as large in the nonconjugated form as in the conjugated form.     

Supercapacitive Swing Adsorption of Carbon Dioxide

An electrical effect, the supercapacitive swing adsorption (SSA) effect is reported, which allows for reversible adsorption and desorption of carbon dioxide by capacitive charge and discharge of electrically conducting porous carbon materials. The SSA effect can be observed when an electrically conducting, nanoporous carbon material is brought into contact with carbon dioxide gas and an aqueous electrolyte. Charging the supercapacitor electrodes initiates the spontaneous organization of electrolyte ions into an electric double layer at the surface of each porous electrode. The presence of this double layer leads to reversible, selective uptake and release of the CO₂ as the supercapacitor is charged and discharged.     

A Rechargeable Hydrogen Battery Based on Ru Catalysis

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H₂ battery which is based on the principle of the Ru‐catalyzed hydrogenation of CO₂ to formic acid (charging process) and the Ru‐catalyzed decomposition of formic acid to CO₂ and H₂ (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure‐free conditions (discharging process). Up to five charging–discharging cycles were performed without decrease of storage capacity. The resulting CO₂/H₂ mixture is free of CO and can be employed directly in fuel‐cell technology.     

Molecular Parameters and Transmembrane Transport Mechanism of Imidazolium‐Functionalized Binols

We describe the molecular parameters governing the transmembrane activity of imidazolium‐functionalized anion transporters and present a detailed mechanistic study. These ionophores adopt a mobile‐carrier mechanism for short methyl and butyl chains, a combined mobile‐carrier/transmembrane‐pore mechanism for octyl and dodecyl chains, and form transmembrane aggregates for hexadecyl chains.     

Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency

Three new electron‐rich metal–organic frameworks ( MOF‐1 – MOF‐3 ) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3 , on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (K_S) as well as collisional constants (K_C) has revealed that MOF‐1 and MOF‐2 have higher K_S values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.     

Highly Luminescent N‐Doped Carbon Quantum Dots as an Effective Multifunctional Fluorescence Sensing Platform

The doping of carbon quantum dots with nitrogen provides a promising direction to improve fluorescence performance and broaden their applications in sensing systems. Herein we report a one‐pot solvothermal synthesis of N‐doped carbon quantum dots (NCQDs) and the synthesis of a series of NCQDs with different nitrogen contents. The as‐prepared NCQDs were compared with carbon quantum dots (CQDs); the introduction of nitrogen atoms largely increased the quantum yield of NCQDs and highest emission efficiency is up to 36.3 %. The fluorescence enhancement may originate from more polyaromatic structures induced by incorporated nitrogen atoms and protonation of nitrogen atoms on dots. It was found that NCQDs can act as a multifunctional fluorescence sensing platform because they can be used to detect pH values, Ag^I, and Fe^III in aqueous solution. The fluorescence intensity of NCQDs is inversely proportional to pH values across a broad range from 5.0 to 13.5, which indicates that NCQDs can be devised as an effective pH indicator. Selective detection of Ag^I and Fe^III was achieved based on their distinctive fluorescence influence because Ag^I can significantly enhance the fluorescence whereas Fe^III can greatly quench the fluorescence. The quantitative determination of Ag^I can be accomplished with NCQDs by using the linear relationship between fluorescence intensity of NCQDs and concentration of Ag^I. The sensitive detection of H₂O₂ was developed by taking advantage of the distinct quenching ability of Fe^III and Fe^II toward the fluorescence of NCQDs. Cellular toxicity test showed NCQDs still retain low toxicity to cells despite the introduction of a great deal of nitrogen atoms. Moreover, bioimaging experiments demonstrated that NCQDs have stronger resistance to photobleaching than CQDs and more excellent fluorescence labeling performance.