Continuous polyacrylonitrile nanofiber yarns: Preparation and dry-drawing treatment for carbon nanofiber production

Precursor fibers with diameters in nanometer scale and highly aligned polymer chains in fibers are highly promising for the preparation of high-performance carbon nanofibers, but are challenging to make. In this study, we demonstrate for the first time that a carbon nanofiber precursor can be prepared by the electrospinning of polyacrylonitrile into a nanofiber yarn and by the subsequent drawing treatment of the yarn in dry conditions. The yarn shows excellent drawing performance, which can be drawn evenly up to 6 times of its original length without breaking. The drawing treatment improves the yarn and fiber uniformity, polymer chain orientation within the fibers, as well as yarn tension and modules, but shows decreased yarn and fiber diameter and elongation at break. The drawing temperature and force show influences on the drawing behavior. The highest strength and modules (362 ± 37 MPa and 9.2 ± 1.4 GPa, respectively) are found on the yarn drawn by 5 times its length, which increased by 800% and 1800% when compared to the as-spun yarn. Through un-optimized stabilization and carbonization treatments, we further demonstrate that the carbonized nanofiber yarn shows comparable tensile properties as the commercial carbon fibers. Electrospun nanofiber yarns may form next generation precursors for making high performance carbon fibers. This journal is

A superamphiphobic coating with an ammonia-triggered transition to superhydrophilic and superoleophobic for oil-water separation

Superhydrophilic and superoleophobic materials are very attractive for efficient and cost-effective oil-water separation, but also very challenging to prepare. Reported herein is a new superamphiphobic coating that turns superhydrophilic and superoleophobic upon ammonia exposure. The coating is prepared from a mixture of silica nanoparticles and heptadecafluorononanoic acid-modified TiO2 sol by a facile dip-coating method. Commonly used materials, including polyester fabric and polyurethane sponge, modified with this coating show unusual capabilities for controllable filtration of an oil-water mixture and selective removal of water from bulk oil. We anticipate that this novel coating may lead to the development of advanced oil-water separation techniques.

The Influence of water and metal salt on the transport and structural properties of 1-Octyl-3-methylimidazolium Chloride

The addition of diluents to ionic liquids (ILs) has recently been shown to enhance the transport properties of ILs. In the context of electrolyte design, this enhancement allows the realisation of IL-based electrolytes for metal-air batteries and other storage devices. It is likely that diluent addition not only impacts the viscosity of the IL, but also the ion-ion interactions and structure. Here, we investigate the nano-structured 1-methyl-3-octylimidazolium chloride (OMImCl) with varying water concentrations in the presence of two metal salts, zinc chloride and magnesium chloride. We find that the choice of metal salt has a significant impact on the structure and transport properties of the system; this is explained by the water structuring and destructing properties of the metal salt.

Tristearin bilayers: structure of the aqueous interface and stability in the presence of surfactants

We report results of atomistic molecular dynamics simulations of an industrially-relevant, exemplar triacylglycerol (TAG), namely tristearin (TS), under aqueous conditions, at different temperatures and in the presence of an anionic surfactant, sodium dodecylbenzene sulphonate (SDBS). We predict the TS bilayers to be stable and in a gel phase at temperatures of 350 K and below. At 370 K the lipid bilayer was able to melt, but does not feature a stable liquid-crystalline phase bilayer at this elevated temperature. We also predict the structural characteristics of TS bilayers in the presence of SDBS molecules under aqueous conditions, where surfactant molecules are found to spontaneously insert into the TS bilayers. We model TS bilayers containing different amounts of SDBS, with the presence of SDBS imparting only a moderate effect on the structure of the system. Our study represents the first step in applying atomistic molecular dynamics simulations to the investigation of TAG-aqueous interfaces. Our results suggest that the CHARMM36 force-field appears suitable for the simulation of such systems, although the phase behaviour of the system may be shifted to lower temperatures than is the case for the actual system. Our findings provide a foundation for further simulation studies of the TS-aqueous interface.

In situ synthesis of natural rubber latex-supported gold nanoparticles for flexible SERS substrates

Natural rubber latex (NRL) from Hevea brasiliensis was used as a matrix to synthesize gold nanoparticles (AuNPs), leading to an organic-inorganic hybrid latex of NRL-supported AuNPs (AuNPs@NRL). The in situ and environmentally friendly preparation of AuNPs in an NRL matrix was developed by thermal treatment without using any other reducing agents or stabilizers because natural rubber particles and non-rubber components present in serum can serve as supporters for the synthesized AuNPs. As a result, the nanosized and well-dispersed AuNPs not only are decorated on the surface of natural rubber particles, but also can be found in the serum of NRL. The size of the AuNPs presented in NRL matrix can be controlled by adjusting the concentration of NRL. Furthermore, the flexible surface-enhanced Raman scattering (SERS) substrates made from the AuNPs@NRL through vacuum filtration presented good enhancement of the Raman probe molecule of 4-mercaptopyridine and outstanding SERS reproducibility. The capability of synthesizing the bio-supported nanohybrid latex provides a novel green and simple approach for the fabrication of flexible and effective SERS substrates.

Hydrotelluration of acetylenic esters: structural characterization of stereoisomers of methyl/ethyl beta-(aryltelluro)acrylates

Synthesis and complete characterization of some ester functionalized vinylic tellurides bearing an aryl ligand with varying steric and electronic effects bound to tellurium is described. Hydrotelluration of methyl propiolate using Ar2Te2/NaBH4 in methanol results in a mixture of stereoisomers of methyl β-(aryltelluro)acrylates, ArTeCH[double bond, length as m-dash]CHCOOMe (Ar = 4-MeOC6H4, 1A; 1-C10H7, 2A; 2,4,6-Me3C6H2, 3A; C5H5FeC5H4, 4A; 4-Me2NC6H4, 5A; and 2-C4H3S, 6A). The same reaction in ethanol provides isomeric mixtures of the ethyl esters ArTeCH[double bond, length as m-dash]CHCOOEt (1B–6B). However, in the reactions between methyl propiolate and Ar2Te2 (Ar = 2,4,6-Me3C6H2, 4-Me2NC6H4) in isopropanol or t-butanol, no exchange of alkyl groups between the parent ester and the solvent is observed, instead detelluration of the Ar2Te2 to Ar2Te is a competing reaction along with almost exclusive formation of the (Z)-isomers (3Aa, 5Aa). The geometry of the separated stereoisomers is established in solution, with the help of 1H, 13C and 125Te NMR spectrometry. Of particular interest is the observation that 125Te chemical shifts {deshielded in (Z) compared to (E); Δδ = 106–136 ppm} and the geminal heteronuclear coupling constants {2J(1H–125Te) values for (E) are more than seven times that of the corresponding (Z) isomer} can be used to distinguish between liquid isomers. Structural characterization in the solid state by single-crystal X-ray diffraction for the 2Ba, 3Aa, 3Ba, 5Aa, 8 (Z)-isomers as well as for both stereoisomers of 4-Me2NC6H4TeCH[double bond, length as m-dash]CHCOOEt (5Ba and 5Bb) is also presented. The carbonyl O atom of the ester group is invariably involved, at least in the solid state, in a secondary bonding interaction with the Te(II) atom. While an intermolecular Te⋯O interaction gives rise to one-dimensional supramolecular arrays in the crystal lattice of 5Bb with (E) configuration, it is realized intramolecularly in the case of the (Z)-isomers due to the cis position of the chalcogen atoms.

Enhanced thermal stability and lifetime of epoxy nanocomposites using covalently functionalized clay: Experimental and modelling

The present work aims at finding a relationship between kinetic models of thermal degradation process with the physiochemical structure of epoxy-clay nanocomposites in order to understand its service temperature. In this work, two different types of modified clays, including clay modified with (3-aminopropyl)triethoxysilane (APTES) and a commercial organoclay, were covalently and non-covalently incorporated into epoxy matrix, respectively. The effect of different concentrations of silanized clay on thermal behaviour of epoxy nanocomposites were first investigated in order to choose the optimum clay concentration. Afterwards, thermal characteristics of the degradation process of epoxy nanocomposites were obtained by TGA analysis and the results were employed to determine the kinetic parameters using model-free isoconversional and model-fitting methods. The obtained kinetic parameters were used to model the entire degradation process. The results showed that the incorporation of the different modified clay into epoxy matrix change the mathematical model of the degradation process, associating with different orientations of clay into epoxy matrix confirming by XRD results. The obtained models for each epoxy nanocomposite systems were used to investigate the dependence of degradation rate and degradation time on temperature and conversion degree. Our results provide an explanation as to how the life time of epoxy and its nanocomposites change in a wide range of operating temperatures as a result of their structural changes.

Effect of electrospinning parameters and polymer concentrations on mechanical-to-electrical energy conversion of randomly-oriented electrospun poly(vinylidene fluoride) nanofiber mats

Poly(vinylidene fluoride) (PVDF) nanofiber mats prepared by an electrospinning technique were used as an active layer for making mechanical-to-electric energy conversion devices. The effects of PVDF concentration and electrospinning parameters (e.g. applied voltage, spinning distance), as well as nanofiber mat thickness on the fiber diameter, PVDF β crystal phase content, and mechanical-to-electrical energy conversion properties of the electrospun PVDF nanofiber mats were examined. It was interesting to find that finer uniform PVDF fibers showed higher β crystal phase content and hence, the energy harvesting devices had higher electrical outputs, regardless of changing the electrospinning parameters and PVDF concentration. The voltage output always changed in the same trend to the change of current output whatever the change trend was caused by the operating parameters or polymer concentration. Both voltage and current output changes followed a similar trend to the change of the β crystal phase content in the nanofibers. The nanofiber mat thickness influenced the device electrical output, and the maximum output was found on the 70 μm thick nanofiber mat. These results suggest that uniform PVDF nanofibers with smaller diameters and high β crystal phase content facilitate mechanical-to-electric energy conversion. The understanding obtained from this study may benefit the development of novel piezoelectric nanofibrous materials and devices for various energy uses.

Synthesis of norbornane bisether antibiotics via silver-mediated alkylation

A small series of norbornane bisether diguanidines have been synthesized and evaluated as antibacterial agents. The key transformation-bisalkylation of norbornane diol 6-was not successful using Williamson methodology but has been accomplished using Ag2O mediated alkylation. Further functionalization to incorporate two guanidinium groups gave rise to a series of structurally rigid cationic amphiphiles; several of which (16d, 16g and 16h) exhibited antibiotic activity. For example, compound 16d was active against a broad range of bacteria including Pseudomonas aeruginosa (MIC = 8 µg/mL), Escherichia coli (MIC = 8 µg/mL) and methicillin-resistant Staphylococcus aureus (MIC = 8 µg/mL).

Organogelators based on the norbornane scaffold

Using the rigid norbornane scaffold, a series of low-molecular-weight organogelators has been synthesised and evaluated. Three separate compounds (16, 19 and 20) were identified as organogelators in three aromatic organic solvents (PhMe, anisole and o-xylene). The formation of fibrillar assemblies at nanometre level was confirmed using atomic force microscopy and transmission electron microscopy.

Thermally flexible epoxy/cellulose blends mediated by an ionic liquid

Blends between the widely used thermoset resin, epoxy, and the most abundant organic material, natural cellulose are demonstrated for the first time. The blending modification induced by charge transfer complexes using a room temperature ionic liquid, leads to the formation of thermally flexible thermoset materials. The blend materials containing low concentrations of cellulose were optically transparent which indicates the miscibility at these compositions. We observed the existence of intermolecular hydrogen bonding between epoxy and cellulose in the presence of the ionic liquid, leading to partial miscibility between these two polymers. The addition of cellulose improves the tensile mechanical properties of epoxy. This study reveals the use of ionic liquids as a compatible processing medium to prepare epoxy thermosets modified with natural polymers.

Ductile thermoset polymers via controlling network flexibility

We report the design and synthesis of a polymer structure from a cross-linkable epoxy-ionic liquid system which behaves like a hard and brittle epoxy thermoset, perfectly ductile thermoplastic and an elastomer, all depending on controllable network compositions.