Density, conductivity, viscosity, and excess properties of (pyrrolidinium nitrate-based Protic Ionic Liquid + propylene carbonate) binary mixture

Density, ?, viscosity, ?, and conductivity, s, measurements of binary mixtures containing the pyrrolidinium nitrate Protic Ionic Liquid (PIL) and propylene carbonate (PC), are determined at the atmospheric pressure as a function of the temperature from (283.15 to 353.15) K and within the whole composition range. The temperature dependence of both the viscosity and conductivity of each mixture exhibits a non-Arrhenius behaviour, but is correctly fitted by using the Vogel–Tamman–Fulcher (VTF) equation. In each case, the best-fit parameters, such as the pseudo activation energy, View the MathML source and ideal glass transition temperature, T0 are then extracted. The excess molar volumes VE, and viscosity deviations from the ideality, ??, of each investigated mixture were then deduced from the experimental results, as well as, their apparent molar volumes, V?, thermal expansion coefficients ap, and excess Gibbs free energies (?G*E) of activation of viscous flow. The VE, apE, ?? values are negative over the whole composition range for each studied temperature therein. According to the Walden rule, the ionicity of each mixture was then evaluated as a function of the temperature from (283.15 to 353.15) K and of the composition. Results have been then discussed in terms of molecular interactions and molecular structures in this binary mixture.

Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements

We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.

Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile-butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass-transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. Copyright © 2011 Wiley Periodicals, Inc.

On the scaling behavior of electric conductivity in [C(4)mim][NTf2]

In this work we examine, for the first time, the molar conductivity behavior of the deeply supercooled room temperature ionic liquid [C₄mim][NTf₂] in the temperature, pressure and volume thermodynamic space in terms of density scaling (TV^γ)⁻¹ combined with the equation of state (EOS). The exponent γ_σ determined from the Avramov model analysis is compared with the coefficient obtained from the viscosity studies carried out at moderate temperatures. Therefore, the experimental results presented herein provide the answer to the long-standing question regarding the validity of thermodynamic scaling of ionic liquids over a wide temperature range, i.e. from the normal liquid state to the glass transition point. Finally, we investigate the relationship between the dynamic and thermodynamic properties of [C₄mim][NTf₂] represented by scaling exponent γ and Grüneisen constant γ_G, respectively.

Evolution of microstructure and changes of mechanical properties of CLAM steel after long-term aging

The China Low Activation Martensitic (CLAM) steel has been developed as a candidate structural material for future fusion reactors. It is essential to investigate the evolution of microstructure and changes of mechanical properties of CLAM steel during thermal exposure. In this study, the long-term thermal aging of the CLAM steel has been carried out in air at 600 °C and 650 °C for 1100 h, 3000 h and 5000 h. The microstructural evolution with aging time was studied, including characteristics of the growth of M23C6 carbides and the formation of Laves-phase precipitates as well as the evolved subgrains. The microstructural evolution leads to the changes of mechanical properties of the CLAM steel. The Ductile–Brittle Transition Temperature (DBTT) increases significantly during the thermal aging, which is related to the formation of Laves-phase in the steel matrix. The possible mechanism of stabilizing microstructure during the thermal exposure has been analyzed based on the interaction between M23C6 carbides and subgrain boundaries.

Microstructure and Mechanical Propertiesof a Nitride-Strengthened Reduced ActivationFerritic/Martensitic Steel

Nitride-strengthened reduced activation ferritic/martensitic (RAFM) steels are developed taking advantage of the high thermal stability of nitrides. In the current study, the microstructure and mechanical properties of a nitride-strengthened RAFM steel with improved composition were investigated. Fully martensitic microstructure with fine nitrides dispersion was achieved in the steel. In all, 1.4 pct Mn is sufficient to suppress delta ferrite and assure the steel of the full martensitic microstructure. Compared to Eurofer97, the steel showed similar strength at room temperature but higher strength at 873 K (600 °C). The steel exhibited very high impact toughness and a low ductile-to-brittle transition temperature (DBTT) of 243 K (–30 °C), which could be further reduced by purification.

The impact toughness of a nitride-strengthened martensitic heat resistant steel

The nitride-strengthened martensitic heat resistant steel is precipitation strengthened only by nitrides. In the present work, the effect of nitride precipitation behavior on the impact toughness of an experimental steel was investigated. Nitrides could hardly be observed when the steel was tempered at 650°C. When the tempering temperature was increased to 700°C and 750°C, a large amount of nitrides were observed in the matrix. It was surprising to reveal that the impact energy of the half-size samples greatly increased from several Joules to nearly a hundred Joules. The ductile-brittle transition temperature (DBTT) was also discovered to decrease from room temperature to −50°C when the tempering temperature was increased from 650°C to 750°C. The nitride precipitation with increasing tempering temperature was revealed to be responsible for the improved impact toughness.

High Strength Thermoplastic Bonding for Multi-channel, Multi-layer Lab-on-Chip Devices for Ocean and Environmental applications

A solvent-vapour thermoplastic bonding process is reported which provides high strength bonding of PMMA over a large area for multi-channel and multi-layer microfluidic devices with shallow high resolution channel features. The bond process utilises a low temperature vacuum thermal fusion step with prior exposure of the substrate to chloroform (CHCl3) vapour to reduce bond temperature to below the PMMA glass transition temperature. Peak tensile and shear bond strengths greater than 3 MPa were achieved for a typical channel depth reduction of 25 µm. The device-equivalent bond performance was evaluated for multiple layers and high resolution channel features using double-side and single-side exposure of the bonding pieces. A single-sided exposure process was achieved which is suited to multi-layer bonding with channel alignment at the expense of greater depth loss and a reduction in peak bond strength. However, leak and burst tests demonstrate bond integrity up to at least 10 bar channel pressure over the full substrate area of 100 mm x 100 mm. The inclusion of metal tracks within the bond resulted in no loss of performance. The vertical wall integrity between channels was found to be compromised by solvent permeation for wall thicknesses of 100 µm which has implications for high resolution serpentine structures. Bond strength is reduced considerably for multi-layer patterned substrates where features on each layer are not aligned, despite the presence of an intermediate blank substrate. Overall a high performance bond process has been developed that has the potential to meet the stringent specifications for lab-on-chip deployment in harsh environmental conditions for applications such as deep ocean profiling.

Novel Supercritical Carbon Dioxide Impregnation Technique for the Production of Amorphous Solid Drug Dispersions: A Comparison to Hot Melt Extrusion

The formulation of BCS Class II drugs as amorphous solid dispersions has been shown to provide advantages with respect to improving the aqueous solubility of these compounds. While hot melt extrusion (HME) and spray drying (SD) are among the most common methods for the production of amorphous solid dispersions (ASDs), the high temperatures often required for HME can restrict the processing of thermally labile drugs, while the use of toxic organic solvents during SD can impact on end-product toxicity. In this study, we investigated the potential of supercritical fluid impregnation (SFI) using carbon dioxide as an alternative process for ASD production of a model poorly water-soluble drug, indomethacin (INM). In doing so, we produced ASDs without the use of organic solvents and at temperatures considerably lower than those required for HME. Previous studies have concentrated on the characterization of ASDs produced using HME or SFI but have not considered both processes together. Dispersions were manufactured using two different polymers, Soluplus and polyvinylpyrrolidone K15 using both SFI and HME and characterized for drug morphology, homogeneity, presence of drug-polymer interactions, glass transition temperature, amorphous stability of the drug within the formulation, and nonsink drug release to measure the ability of each formulation to create a supersaturated drug solution. Fully amorphous dispersions were successfully produced at 50% w/w drug loading using HME and 30% w/w drug loading using SFI. For both polymers, formulations containing 50% w/w INM, manufactured via SFI, contained the drug in the γ-crystalline form. Interestingly, there were lower levels of crystallinity in PVP dispersions relative to SOL. FTIR was used to probe for the presence of drug-polymer interactions within both polymer systems. For PVP systems, the nature of these interactions depended upon processing method; however, for Soluplus formulations this was not the case. The area under the dissolution curve (AUC) was used as a measure of the time during which a supersaturated concentration could be maintained, and for all systems, SFI formulations performed better than similar HME formulations.

Hydrogel antimicrobial capture coatings for endotracheal tubes; a pharmaceutical strategy designed to prevent ventilator-associated pneumonia.

This paper presents a novel strategy for the prevention of ventilator-associatedpneumonia that involves coating poly(vinyl chloride, PVC) endotracheal tubes (ET) withhydrogels that may be subsequently used to entrap nebulized antimicrobial solutions. Candidatehydrogels were prepared containing a range of ratios of hydroxyethyl methacrylate (HEMA) andmethacrylic acid (MAA) from 100:0 to 70:30 using free radical polymerization and, whenrequired, simultaneous attachment to PVC was performed. The mechanical properties, glasstransition temperatures, swelling kinetics, uptake of gentamicin from an aqueous medium, andgentamicin release were characterized. Increasing the MAA content of the hydrogels significantlydecreased the ultimate tensile strength, % elongation at break, Young’s modulus, and increasedthe glass transition temperature, the swelling ratio, and gentamicin uptake. Microbial(Staphylococcus aureus and Pseudomonas aeruginosa) adherence to control (drug-free) hydrogelswas observed; however, while adherence to gentamicin-containing p(HEMA) occurred, noadherence occurred to gentamicin-containing HEMA:MAA copolymers. Antimicrobialpersistence of gentamicin-containing hydrogels was examined by determining the zone ofinhibition against each microorganism on successive days. Hydrogel composition affected the observed antimicrobial persistence,with the hydrogel composed of 70:30 HEMA:MAA exhibiting >20 days persistence against S. aureus and P. aeruginosa,respectively. To simulate clinical use, the hydrogels (coated onto PVC) were first exposed to a nebulized solution of gentamicin(4 mL, 80 mg for 20 min), and then to nebulized bacteria (4 mL ca. 1 × 109 colony forming units mL−1, 30 min). Viable bacteriawere not observed on the gentamicin-treated p(HEMA: MAA) copolymers, whereas growth was observed on gentamicin-treatedp(HEMA). In light of the excellent antimicrobial activity and physicochemical properties, p(HEMA: MAA) copolymerscomposed of ratios of 80:20 or 70:30 HEMA: MAA were identified as potentially useful coatings of endotracheal tubes to be usedin conjunction with the clinical nebulization of gentamicin and designed for the prevention of ventilator-associated pneumonia

Optimising drug solubilisation in amorphous polymer dispersions: rational selection of hot-melt extrusion processing parameters

The aim of this article was to construct a T–ϕ phase diagram for a model drug (FD) and amorphous polymer (Eudragit® EPO) and to use this information to understand the impact of how temperature–composition coordinates influenced the final properties of the extrudate. Defining process boundaries and understanding drug solubility in polymeric carriers is of utmost importance and will help in the successful manufacture of new delivery platforms for BCS class II drugs. Physically mixed felodipine (FD)–Eudragit® EPO (EPO) binary mixtures with pre-determined weight fractions were analysed using DSC to measure the endset of melting and glass transition temperature. Extrudates of 10 wt% FD–EPO were processed using temperatures (110°C, 126°C, 140°C and 150°C) selected from the temperature–composition (T–ϕ) phase diagrams and processing screw speed of 20, 100 and 200rpm. Extrudates were characterised using powder X-ray diffraction (PXRD), optical, polarised light and Raman microscopy. To ensure formation of a binary amorphous drug dispersion (ADD) at a specific composition, HME processing temperatures should at least be equal to, or exceed, the corresponding temperature value on the liquid–solid curve in a F–H T–ϕ phase diagram. If extruded between the spinodal and liquid–solid curve, the lack of thermodynamic forces to attain complete drug amorphisation may be compensated for through the use of an increased screw speed. Constructing F–H T–ϕ phase diagrams are valuable not only in the understanding drug–polymer miscibility behaviour but also in rationalising the selection of important processing parameters for HME to ensure miscibility of drug and polymer.

Dynamically mechanical and nano-impact (fatigue) analysis of touch screen thin films deposited on polyethylene terephthalate substrate

Nano-scale touch screen thin film have not been thoroughly investigated in terms of dynamic impact analysis under various strain rates. This research is focused on two different thin films, Zinc Oxide (ZnO) film and Indium Tin Oxide (ITO) film, deposited on Polyethylene Terephthalate (PET) substrate for the standard touch screen panels. Dynamic Mechanical Analysis (DMA) was performed on the ZnO film coated PET substrates. Nano-impact (fatigue) testing was performed on ITO film coated PET substrates. Other analysis includes hardness and the elastic modulus measurements, atomic force microscopy (AFM), Fourier Transform Infrared Spectroscopy (FTIR) and the Scanning Electron Microscopy (SEM) of the film surface.
Ten delta of DMA is described as the ratio of loss modulus (viscous properties) and storage modulus (elastic properties) of the material and its peak against time identifies the glass transition temperature (Tg). Thus, in essence the Tg recognizes changes from glassy to rubber state of the material and for our sample ZnO film, Tg was found as 388.3 K. The DMA results also showed that the Ten delta curve for Tg increases monotonically in the viscoelastic state (before Tg) and decreases sharply in the rubber state (after Tg) until recrystallization of ZnO takes place. This led to an interpretation that enhanced ductility can be achieved by negating the strength of the material.
For the nano-impact testing using the ITO coated PET, the damage started with the crack initiation and propagation. The interpretation of the nano-impact results depended on the characteristics of the loading history. Under the nano-impact loading, the surface structure of ITO film suffered from several forms of failure damages that range from deformation to catastrophic failures. It is concluded that in such type of application, the films should have low residual stress to prevent deformation, good adhesive strength, durable and good resistance to wear.