Interfacial Properties of LiTFSI and LiPF6-Based Electrolytes in Binary and Ternary Mixtures of Alkylcarbonates on Graphite Electrodes and Celgard Separator

For a better understanding of the adsorption behavior of alkylcarbonate-based electrolytes on graphite electrodes and Celgard separator for Li-ion batteries applications, the interface parameters are determined by contact angle and surface tension measurements. The correlation between these parameters and chemical compositions made of alkyl carbonate with a varying nature of lithium salts (LiPF6 and LiTFSI) and volume fractions of binary and ternary mixtures containing propylene carbonate (PC), ethylene carbonate (EC), and dimethyl carbonate (DMC) is investigated. From the obtained contact angle and surface tension (?L) values for each liquid, the dispersive and polar components of the surface tension (?Ld and ?Lp) of the electrolyte and interfacial free energy between the solid and liquid (?SL) were then calculated using the Young’s equation. The variation of contact angle (?) and the surface tension, as well as the work of adhesion (WA) of binary PC/DMC mixtures on PP, PE, and PET model surfaces were also measured and commented as function of volume fraction of PC in DMC. Finally, the Zisman’s critical surface tension (?C) for studied surfaces was then obtained showing positives slopes of cos ? versus ?L. This behavior is explained by a relative higher adsorption of alkylcarbonates to the hydrogenated supports or graphite. These results are decisive to understand the performance of electrolyte/electrode material/separator interfaces in lithium-ion battery devices.

Phase Behaviour, Interactions, and Structural Studies of (Amines+Ionic Liquids) Binary Mixtures

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [Cnmim] [NTf2] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory–Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C2mim] [NTf2]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C2mim][NTf2]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents.

The mechanical and rheological characterisation of implantable medical devices formulated from binary mixtures of cellulose derivatives

This study highlights the potential associated with utilising multi-component polymeric gels to formulate materials that possess unique rheological and mechanical properties. The synergistic effect* and interaction between hydroxyethylcellulose (HEC) and sodium carboxymethylcellulose (NaCMC), polymers which are commonly employed as drug delivery platforms for implantable medical devices (1), have been determined using dynamic, continuous shear and texture profile analysis. * The difference between the actual response of a binary mixture and the sum of the two components comprising the mixture Increases in polymer concentration resulted in an increase in G', G? and ?' whereas tan d decreased. Similarly, significant increases were also apparent in continuous shear and texture analysis. All binary mixtures showed positive synergy values which may suggest associative interaction between the two components.

EFFECT OF POWDER COMPOSITION ON THE GRANULATION OF BINARY MIXTURES

In most granulation processes involving processing of a mixture of powders, the powders have comparable densities and similar particle size distributions. Granulation of powders with large variation differences in powder densities is usually avoided due problems such as particle segregation. The granular product being designed in this work required the use of two different powders namely limestone and teawaste; these materials have different bulk and particle densities.The overall aim of the project was to obtain a granular product in
the size range 2 to 4mm. The two powders were granulated in different proportions using carboxymethyl cellose (CMC) as the binder. The effect of amount of binder added, relative composition of the powder, and type of tea wasted on the product yield was studied. The results show that the optimum product yield was a function of both relative powder composition and the amount of binder used; increasing the composition of teawaste in the powder increased the amount of binder required for successful granulation.Increasing the mass fraction of teawaste in the powder mix must be accompanied by an increase in the amount of binder to achieve the desired product yield. It was found that attrition losses decreased with increasing binder content.

Structure and dynamics of dextran in binary mixtures of a good and a bad solvent

The structure and dynamics of the common polysaccharide dextran have been investigated in mixed solvents at two different temperatures using small-angle X-ray scattering (SAXS) and viscosity measurements. More specifically, binary mixtures of a good solvent (water, formamide, dimethylsulfoxide, ethanolamine) and the bad solvent ethanol as the minority component have been considered. The experimentally observed effects on the polymer conformation (intrinsic viscosity, coil radius, and radius of gyration) of the bad solvent addition are discussed in terms of hydrogen bonding density and are correlated with the Hansen solubility parameters and the surface tension of the solvent mixtures. Hydrogen bonding appears to be an important contributor to the solubility of dextran but is not sufficient to capture the dextran coil contraction in the mixtures of good+bad solvents.

Degradable Polymer Networks and Star Polymers Based on Mixtures of Two Cleavable Dimethacrylate Crosslinkers: Synthesis, Characterization, and Degradation

Mixtures of two cleavable dimethacrylate crosslinkers, the hydrolyzable di(methacryloyloxy-1-ethoxy)methane (DMOEM) and the thermolyzable 1,1-ethylene-diol dimethacrylate (EDDMA), were used for the preparation of neat crosslinker polymer networks, randomly crosslinked polymer networks of methyl methacrylate (MMA), and star polymers of MMA, using group transfer polymerization in tetrahydrofuran (THF). All star polymers and randomly crosslinked polymer networks containing mixtures of the hydrolyzable DMOEM and the thermolyzable EDDMA crosslinkers gave THF-soluble final products when subjected to sequential thermolysis and hydrolysis, in this order. When applying sequential hydrolysis and thermolysis, only the star polymers with an EDDMA crosslinker content equal to or higher than 50% gave THF-soluble final products.

High shear granulation of binary mixtures: Effect of powder composition on granule properties: Effect of powder composition on granule properties

The granular product being designed in this work required the use of two different powders namely limestone and teawaste; these materials have different bulk and particle densities. The overall aim of the project was to obtain a granular product in the size range of 2 to 4. mm. The two powders were granulated in different proportions using carboxymethylcellulose (CMC) as the binder. The effect of amount of binder added, relative composition of the powder, and type of teawaste on the product yield was studied. The results show that the optimum product yield was a function of both relative powder composition and the amount of binder used; increasing the composition of teawaste in the powder increased the amount of binder required for successful granulation. An increase in the mass fraction of teawaste in the powder mix must be accompanied by an increase in the amount of binder to maintain the desired product yield.

Evaluation of methodologies to determine vegetable oil species present in oil mixtures: Proposition of an approach to meet the EU legislation demands for correct vegetable oils labelling

Refined vegetable oils are widely used in the food industry as ingredients or components in many processed food products in the form of oil blends. To date, the generic term 'vegetable oil' has been used in the labelling of food containing oil blends. With the introduction of new EU Regulation for Food Information (1169/2011) due to take effect in 2014, the oil species used must be clearly identified on the package and there is a need for development of fit for purpose methodology for industry and regulators alike to verify the oil species present in a product. The available methodologies that may be employed to authenticate the botanical origin of a vegetable oil admixture were reviewed and evaluated. The majority of the sources however, described techniques applied to crude vegetable oils such as olive oil due to the lack of refined vegetable oil focused studies. Nevertheless, DNA based typing methods and stable isotopes procedures were found not suitable for this particular purpose due to several issues. Only a small number of specific chromatographic and spectroscopic fingerprinting methods in either targeted or untargeted mode were found to be applicable in potentially providing a solution to this complex authenticity problem. Applied as a single method in isolation, these techniques would be able to give limited information on the oils identity as signals obtained for various oil types may well be overlapping. Therefore, more complex and combined approaches are likely to be needed to identify the oil species present in oil blends employing a stepwise approach in combination with advanced chemometrics. Options to provide such a methodology are outlined in the current study.

Identification of oil mixtures in extracted and refined vegetable oils

Identification of adulteration in mechanically extracted oils or the botanical origin of refined vegetable oil blends can be effectively achieved through the combination of spectroscopic methods and chemometric techniques. Chromatographic methods remain highly relevant but suffer from various limitations which derive from natural compositional variation. Modern multivariate techniques have demonstrated that it is possible to identify patterns and effectively classify unknown samples in both cases. Development of robust analytical methodologies requires however vigorous validation. Spectroscopic methods combined with chemometric techniques lack established validation protocols and this might hinder their use by law enforcement authorities. 

Cytotoxic assessment of the regulated, co-existing mycotoxins aflatoxin B1, fumonisin B1 and ochratoxin, in single, binary and tertiary mixtures

Aflatoxin B1 (AFB1), ochratoxin A (OTA) and fumonisin B1 (FB1) are contaminants which have been shown to regularly co-occur in a range of foods. However, only a small number of studies have evaluated the interactive effect of binary and tertiary mycotoxins. The present study evaluated the effects of low levels of each mycotoxin in combination at their EU regulatory limits. Toxic effect with respect to cell viability was measured by MTT and neutral red assays, assessing mitochondria and lysosome integrities respectively. Individual toxicity showed that OTA (10 μg/ml) was the most cytotoxic mycotoxin in all three cell lines studied (caco-2, MDBK and raw 264.7). Binary combinations were cytotoxic to the MDBK cell line in the order [OTA/FB1] > [AFB1/FB1] > [AFB1/OTA], whilst all effects observed were classified as being additive. Tertiary combinations of AFB1, FB1 and OTA at the EU regulatory limits were tested and not found to exhibit measurable cytotoxicity in MDBK, caco-2 or raw 264.7 cells. However by increasing these concentrations above the legal limits to OTA (3 μg/ml), FB1 (8 μg/ml) and AFB1 (1.28 μg/ml), cytotoxicity was observed with up to 26% reduction in cell viability and synergistic effects were evident with regard to mitochondrial integrity. © 2014 Elsevier Ltd. All rights reserved.

The solution structure of 1:2 phenol/N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide liquid mixtures

Neutron diffraction has been used to investigate the liquid structure of a 1:2 solution of phenol in the ionic liquid N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide at 60 ◦C, using the empirical potential structure refinement (EPSR) process to model the data obtained from the SANDALS diffractometer at ISIS. Addition of phenol results in suppression of the melting point of the pyridinium salt and formation of a room temperature solution with aromatic phenol–cation and phenol-OH to anion hydrogen-bonding interactions.

Association and liquid structure of pyridine-acetic acid mixtures determined from neutron scattering using a ‘free proton’ EPSR simulation model

The liquid structure of pyridine-acetic acid mixtures have been investigated using neutron scattering at various mole fractions of acetic acid, χHOAc = 0.33, 0.50, and 0.67, and compared to the structures of neat pyridine and acetic acid. Data has been modelled using Empirical Potential Structure Refinement (EPSR) with a ‘free proton’ reference model, which has no prejudicial weighting towards either the existence of molecular or ionised species. Analysis of the neutron scattering results shows the existence of hydrogen-bonded acetic acid chains with pyridine inclusions, rather than the formation of an ionic liquid by proton transfer.

Identifying oil species in oil mixtures

Detection of adulteration of non-processed vegetable oil with lesser value seed oils (classic example is hazelnut in virgin olive oil) has been in the centre of scientific attention for many years and several chemical methods were proposed. The recent EC Regulation 1169/2011, however, introduces necessity for different analytical method in a more complicated matrix. From the end of 2014, food businesses required to declare the composition of the refined oil mixture in the food product label. This creates a gap since there is no analytical method currently available to perform such analysis. In the first phase the work focused on 100% oil blends of various oil species of palm oil (and derivatives), sunflower and rapeseed oil before expanding to foodstuffs. Chromatographic methods remain highly relevant although suffer from various limitations which derive from natural compositional variation. Modern multivariate techniques based on machine learning algorithms, however, when applied in FTIR, Raman spectroscopic data have a strong potential in tackling the problem.

Mixtures of azepanium based ionic liquids and propylene carbonate as high voltage electrolytes for supercapacitors

This work provides a study of mixtures of the azepanium-based ionic liquid (IL) N-methyl, N-butyl-azepanium bis[(trifluoromethane) sulfonyl]imide (Azp₁₄TFSI) and propylene carbonate (PC) as electrolyte components in electrochemical double layer capacitors (EDLCs). The considered mixtures' properties were then compared to the properties of mixtures of N-butyl, N-methylpyrrolidinium bis[(trifluoromethane) sulfonyl]imide (Pyr₁₄TFSI) and PC in terms of viscosity, conductivity and electrochemical behavior. The mixtures' operative potentials were found to be comparable to each other, leading to operative voltages as high as 3.5 V, while retaining the low viscosities and high conductivities of PC based EDLC electrolytes.