Influence of Metal Salts Addition on Physical and Electrochemical Properties of Ethyl and Propylammonium Nitrate.

In this work, we deepen in the characterization of two protic ionic liquids (PILs), ethylammonium nitrate (EAN) and propylammonium nitrate (PAN). With this aim, we determined the influence of inorganic nitrate salts addition on their physical properties and their electrochemical potential window (EPW). Thus, experimental measurements of electrical conductivity, density, viscosity, refractive index and surface tension of mixtures of {EAN or PAN + LiNO3, Ca(NO3)2, Mg(NO3)2 or Al(NO3)3} at a temperature range between 5 and 95 °C are presented first, except for the last two properties which were measured at 25 °C. In the second part, the corresponding EPWs were determined at 25 °C by linear sweep voltammetry using three different electrochemical cells. Effect of the salt addition was associated mainly with the metal cation characteristics, so, generally, LiNO3 showed the lower influence, followed by Ca(NO3)2, Mg(NO3)2 or Al(NO3)3. The results obtained for the EAN + LiNO3 mixtures, along with those from a previous work, allowed us to develop novel predictive equations for most of the presented physical properties as functions of the lithium salt concentration, the temperature and the water content. Electrochemical results showed that a general order of EPW can be established for both PILs, although exceptions related to measurement conditions and the properties of the mixtures were found.

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance.

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.

Bubble Solution Description by Non-Extensive Thermodynamics: Pressure Effect.

We showed in this study that nanobubble solutions should not be considered as the simple juxtaposition of autonomous phases (a solution and bubbles) but as particular entities, that is, "supersaturated solutions" where gas is simultaneously in two forms in permanent exchange. Gibbs' extensive thermodynamics cannot claim to describe legitimately their behavior. In this work, we showed how the use of the non-extensive thermodynamics allows describing the physicochemical properties of such media, some of which are counter-intuitive. Thus, an increase in pressure can result in an increase in the bubble size, contrary to what is provided by Boyle-Mariotte's law. The theoretical relationships proposed in this work constitute another approach to bubble solutions, which considers the non-autonomous nature of the components of supersaturated gas solutions and their "non-extensive" nature.

Wettability of zinc oxide nanorod surfaces.

In this work, we have studied the wettability of zinc oxide (ZnO) nanorods grown on fluorine-doped tin oxide (FTO) by highlighting the effect of polar and non-polar ZnO facets on contact angle (CA) results. The variation in the wettability behaviors of the synthesized surfaces is mainly related to physical and chemical surface texturing which influenced the liquid drop penetration. Indeed, three main penetration states can be deduced: total, partial, and null-penetration. Where, low CA (100.9°) with high contact angle hysteresis (CAH) (13°) is observed for total penetration of the liquid drop. While, high CA (139.6°) with low CAH (7°) is observed for null-penetration. Moreover, we have found that the chemical texturing of ZnO, especially the hydrophilicity of ZnO tips, responsible for liquid drop sticking, prevents the liquid slipping over the surface. In order to promote the liquid rolling on the ZnO surface, we reported the physical modification of the ZnO structures. Therefore, the rolling of the liquid drop on the inclined surface of ZnO is achieved by using a new structure based on double scale roughness. This surface exhibits superhydrophobic behavior with a CA of 153° and CAH of 3°.

The effect of alkyl chain length on the structure and thermodynamics of protic-aprotic ionic liquid mixtures: a molecular dynamics study.

Mixtures of alkylammonium based protic ionic liquids and alkylmethylimidazolium based aprotic ionic liquids were studied by means of molecular dynamics simulations. Close to ideal mixing is observed in most studied magnitudes; however, the effect of increasing alkyl chain length in each of the cations is markedly different, with longer protic cations showing larger deviations, especially with regards to mixing enthalpy, which exhibits a strong compound forming tendency. The compound forming nature of these protic ionic liquids is shown to induce sharp changes in their local environment upon mixing.

Why Drops Bounce on Smooth Surfaces.

It is shown that introducing gravity in the energy minimization of drops on surfaces results in different expressions when minimized with respect to volume or with respect to contact angle. This phenomenon correlates with the probability of drops to bounce on smooth surfaces on which they otherwise form a very small contact angle or wet them completely. Theoretically, none of the two minima is stable: the drop should oscillate from one minimum to the other as long as no other force or friction will dissipate the energy. Experimentally, smooth surfaces indeed show drops that bounce on them. In some cases, they bounce after touching the solid surface, and in some cases they bounce from a nanometric air, or vacuum film. The bouncing energy can be stored in the interfaces: liquid-air, liquid-solid, and solid-air. The lack of a single energy minimum prevents a simple convergence of the drop's shape on the solid surface, and supports its bouncing back to the air. Therefore, the lack of a simple minimum described here supports drop bouncing on hydrophilic surfaces such as that reported by Kolinski et al. Our calculation shows that the smaller the surface tension, the bigger the difference between the contact angles calculated based on the two minima. This agrees with experimental finding where reducing the surface tension, for example, by adding surfactants, increases the probability for bouncing of the drops on smooth surfaces.

Electrochemical Impedance Spectroscopy in a Droplet of Solution for the Investigation of Liquid/Solid Interface.

The local electrochemical behavior of a solid-liquid interface can be studied by electrochemical impedance spectroscopy (EIS). The investigated surface area can be delimited by adding a drop of solution, which forms an interface between the liquid drop and the working electrode, and performing the measurements inside. The size of the drop must be sufficiently small for a simultaneous wettability characterization (from the contact angle measurement) and appropriately large so that wettability is not influenced by the presence of the working and the counter electrode inserted in the droplet. In this work, we showed that EIS measurements can be performed in a solution droplet of 2 to 4 µL, although the electrochemical cell lacks the usual geometry. For our measurements, we studied a model system consisting of a KCl aqueous solution of [Fe(CN)6]3-/4- redox couple at a Pt electrode. All the results were compared with those obtained for a bulk configuration. The sessile drop configuration and the EIS response were modeled using finite element method for different electrode sizes and configurations to account for electrochemical kinetics and both current and potential distributions.

Non-applicability of the Gibbs-Duhem relation in nonextensive thermodynamics. Case of micellar solutions.

This work is a discussion on the applicability of the Gibbs-Duhem relationship. We show that it does not exist in the nonextensive thermodynamic approaches. To illustrate this, we have chosen to present the properties of three surfactants (dodecyltrimethylammonium bromide (DTABr), sodium dodecyl sulfate (SDS), sodium decanoate (NaDec) in aqueous solutions at 298 K) whose behavior after the micellization threshold can be described by the rules of the nonextensive thermodynamics. We show that the Gibbs-Duhem relationship does not apply to these systems and we propose to formalize the deviation from this law. The consequences of this study are discussed for the different approaches that involve the use of Gibbs-Duhem relation in the case of micellized solutions. In particular, the applicability of the Gibbs relation which links surface tension and the chemical potentials of solutes is considered. More generally, this study warns against the blind application of the Gibbs-Duhem (or Gibbs) relation, to any system.

In situ probing calcium carbonate formation by combining fast controlled precipitation method and small-angle X-ray scattering.

The initial stage of calcium carbonate nucleation and growth, found usually in "natural" precipitation conditions, is still not well understood. The calcium carbonate formation for moderate supersaturation level could be achieved by an original method called the fast controlled precipitation (FCP) method. FCP was coupled with SAXS (small-angle X-ray scattering) measurements to get insight into the nucleation and growth mechanisms of calcium carbonate particles in Ca(HCO3)2 aqueous solutions. Two size distributions of particles were observed. The particle size evolutions of these two distributions were obtained by analyzing the SAXS data. A nice agreement was obtained between the total volume fractions of CaCO3 obtained by SAXS analysis and by pH-resistivity curve modeling (from FCP tests).

Solubility of gas in confined systems. Nonextensive thermodynamics approach.

The use of the concepts of the nonextensive thermodynamics allows reconsidering the equilibrium of bubble solubilization and more commonly of gaseous aggregates in supersaturated solutions of gas. The introduced relations are general and include as particular cases the equations usually used to describe these phenomena. These equations are discussed. Especially, we specified the domain of application of Kelvin's relation which was illustrated by the solubility of gases in fogs and clouds. Various possibilities of thoughts on the behavior of the gaseous aggregates and nano-systems are proposed. Thus, the introduced relations permit to consider the presence of gaseous aggregates in equilibrium with the solution even for under-saturated solution. Nonextensive thermodynamics admits the notion of negative pressure at the inner of confined phases (solid or liquid).

Highly hydrophilic surfaces from polyglycidol grafts with dual antifouling and specific protein recognition properties.

Homopolymer grafts from α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGL) were prepared on gold and stainless steel (SS) substrates modified by 4-benzoyl-phenyl (BP) moieties derived from the electroreduction of the parent salt 4-benzoyl benzene diazonium tetrafluoroborate. The grafted BP aryl groups efficiently served to surface-initiate photopolymerization (SIPP) of PGL. In similar conditions, SIPP of hydroxyethyl methacrylate (HEMA) permitted the production of PHEMA grafts as model surfaces. Water contact angles were found to be 66°, 15°, and 0° for SS-BP, SS-PHEMA, and SS-PPGL, respectively. The spontaneous spreading of water drops on SS-PPGL was invariably observed with 1.5 µL water drops. PPGL thus appears as a superhydrophilic polymer. Resistance to nonspecific adsorption of proteins of PPGL and PHEMA grafts on gold was evaluated by surface plasmon resonance (SPR) using antibovine serum albumin (anti-BSA). The results conclusively show that PPGL-grafts exhibit enhanced resistance to anti-BSA adsorption compared to the well-known hydrophilic PHEMA. PPGL grafts were further modified with BSA through the carbonyldiimidazole activation of the OH groups providing immunosensing surfaces. The so-prepared PPGL-grafted BSA hybrids specifically interacted with anti-BSA in PBS as compared to antimyoglobin. It is clear that the superhydrophilic character of PPGL grafts opens new avenues for biomedical applications where surfaces with dual functionality, namely, specific protein grafting together with resistance to biofouling, are required.

Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.

Thoughts on the ideal behavior of mixed micelles and the appropriate application of regular solution theory (RST).

Solutions of mixed surfactants are often considered as solvent mixtures. Usually, mixed micellar aggregates are considered as a homogeneous mixture of solvents dispersed in a solution. But the transposition of the usual thermodynamic models of solvent mixtures to mixed micelles is not always so obvious. We discussed this point in this paper by considering several cases of surfactant mixtures. A major problem is to define the molar fraction of each surfactant in the aggregate especially when a charged surfactant is employed in the mixture, because possible dissociation of the components of the mixture must be considered in the bulk as well in the micelle. This definition is crucial especially for the characterization of the ideal behavior which is usually described by the Clint relation, as well as for the application of regular solution theory (RST) which is the most frequently applied model for interpreting the behavior of surfactant mixtures. We show in this paper how the definition of the molar fraction can change the equations and the interpretations.

Electrografted aryl diazonium initiators for surface-confined photopolymerization: a new approach to designing functional polymer coatings.

This article reports on the preparation of polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(2-hydroxyethyl methacrylate) (PHEMA) ultrathin grafts on gold substrates modified by 4-benzoylphenyl (BP) moieties derived from the electroreduction of the parent diazonium salt BF(4)(-), (+)N(2)-C(6)H(4)-CO-C(6)H(5) (DS). The grafted organic species -C(6)H(4)-CO-C(6)H(5) was found to be very effective in the surface-initiating photopolymerization (SIPP) of vinylic monomers in the presence of an aromatic tertiary amine co-initiator acting as a hydrogen donor. This novel tandem diazonium salt electroreduction/SIPP was found to be effective in grafting PS, PMMA, and PHEMA from the surface of gold-coated silicon wafers. The polymer films were characterized in terms of chemical structure and wettability by infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy, and contact angle measurements, respectively. The polymer grafts were further evaluated as adsorbents for bovine serum albumin (BSA) used as a model protein. It was found gold/PHEMA resisted BSA adsorption because of its hydrophilic character, whereas PS and PMMA grafts adsorbed BSA via interfacial hydrophobic interaction. The XPS-determined extent of adsorbed BSA was found to increase linearly with the hydrophobic character of the polymer grafts as measured by water contact angles. This work shows that this novel tandem diazonium salt electroreduction/SIPP is a facile, ultrafast, efficient protocol for grafting polymer chains to surfaces. It broadens the enormous possibilities offered by aryl diazonium salts to generate functional organic coatings.

Stepwise aggregation of dimethyl-di-n-octylammonium chloride in aqueous solutions: from dimers to vesicles.

The self-aggregation of dimethyl-di-n-octylammonium chloride, in diluted aqueous solutions, was studied with various experimental and theoretical techniques: zetametry, conductimetry, dimethyl-di-n-octylammonium and chloride-selective electrodes, tensiometry, NMR spectroscopy ((1)H and DOSY), and molecular modeling (PM3 and molecular dynamic). The combination of the data obtained by these techniques led us to propose a stepwise aggregation process with increasing concentration: dimers (0.2-10 mM), bilayers (10-30 mM), and finally vesicles (>30 mM).

Mixing behaviour of charged and non-charged surfactants described by BET isotherms.

We analysed various sets of published results concerning the mixing behaviour of charged and non-charged surfactants, beyond their aggregation threshold, by means of the BET model modified by Stokes and Robinson. This approach, which is mainly used to account for properties of concentrated aqueous salt solutions, provides a good description of the properties of mixed micelles across the complete scale of compositions between the two pure surfactants. We use analyses of the behaviour of several systems reported in the literature for illustration. We consider the significance of the parameters C and r introduced in the BET model. For mixed micelle solutions in the presence of a support electrolyte, the value of the solvation enthalpy of the charged amphiphile by the non-ionic surfactant is small (C close to one). This model is compared to the regular solution theory (RST).

Synthesis and micellar properties of 1-decyl-2,3-dimethylimidazolium bromide surfactant in water and water-ethanolamine mixtures at 298.15 K.

1-Decyl-2,3-dimethylimidazolium bromide (ddmimBr) has been synthesized by the reaction of 1,2-dimethylimidazole and 1-bromodecane. Micellization of ddmimBr surfactant in water (W) and water-ethanolamine (W-EA) with the weight percent of EA changing within the range 0-39.79%, has been investigated at 298.15 K. Information about the influence of the added EA on the critical micelle concentration (CMC) was obtained through density and surface tension measurements. This last provides information about the dependence of the surface excess concentration, the minimum area per surfactant molecule and the surface pressure at the CMC on the added weight percentage of organic solvent. The effect of binary aqueous mixtures of W-EA on the apparent molar volume (phi V) of the ddmimBr has been investigated. The apparent molar volume upon aggregation (Delta phi V) shows a maximum at about 15 wt% of EA, this behavior is discussed in terms of the changes of the solvent structure. Partial specific volume data, obtained by density measurements, indicate that the fraction of solvent molecules interact with the surfactant remained roughly constant.

Thermodynamics of mixed micelles: Determination of the aggregate composition.

In most studies concerning surfactant mixtures, the determination of the composition of mixed micelles is often tricky. This composition can be obtained by different ways. One of them, undoubtedly the most used, supposes, a priori, that the surfactant in the micelle follows the regular solution model. This poses a problem on the thermodynamic point of view because in these studies, a model of behavior is first admitted for deducing a composition. In a correct thermodynamic approach, a composition should first be determined and then, a model of behavior which accounts for the observed physicochemical properties can be found. This approach is all the more questionable since the application of the Gibbs-Duhem relationship to the pseudo-phase allows aggregate composition to be determined simply, without using a solution model, because the composition of the bulk at the threshold of aggregation is known. In this article, we describe and validate a simple procedure, which supplements that proposed by Rodenas et al. [E. Rodenas, M. Valiente, M.D. Villafruela, J. Phys. Chem. B 103 (1999) 4549], and which allows determination of the activities of the components of the micellar aggregate and its composition. The results are compared to those obtained with other approaches such as molecular-thermodynamic model.

Micellar aggregation for ionic surfactant in pure solvent and electrolyte solution: nonextensive thermodynamics approach.

We show in this study that the concepts of nonextensive thermodynamics introduced and applied in a series of previous studies can be used to describe the behaviour of ionic surfactant solutions at concentrations higher than the critical micelle concentration (cmc) in pure solvents and in the presence of electrolytes. We supposed that the aggregated amphiphiles and their counter ions form two interpenetrated nonextensive phases of the same thermodynamic dimension, m, characterised by two parameters A(am) and A(CI) related to the aggregated amphiphile and the counter ion, respectively. Our experimental results and those published in the literature indicate that logarithms of the activities of the amphiphile and of its counterion vary with the quantity of aggregated monomer according to a power law. Thus, we demonstrate a linear relation between the logarithms of the activities of the two ions beyond the cmc in pure solvents ("micellization product"). An original relation, different from the Corrin-Harkins relation, can thus be established to describe the effects of salt on the cmc of ionic surfactants. According to this relation the cmc of charged surfactant in some systems can increase in the presence of an electrolyte with a common ion.

Effects of nanorod structure and conformation of fatty acid self-assembled layers on superhydrophobicity of zinc oxide surface.

Superhydrophobic surfaces have been prepared from nanostructured zinc oxide layers by a treatment with fatty acid molecules. The layers are electrochemically deposited from an oxygenated aqueous zinc chloride solution. The effects of the layer's structure, from a dense film to that of a nanorod array, as well as that of the properties of the fatty acid molecules based on C18 chains are described. A contact angle (CA) as high as 167 degrees is obtained with the nanorod structure and the linear saturated molecule (stearic acid). Lower values are found with molecules having an unsaturated bond on C9, in particular with a cis conformation (140 degrees ). These results, supplemented by infrared spectroscopy, indicate an enhancement of the sensitivity to the properties of the fatty acid molecules (conformation, flexibility, saturated or not) when moving from the flat surface to the nanostructured surface. This is attributed to a specific influence of the structure of the tops of the rods and lateral wall properties on the adsorption and organization of the molecules. CA measurements show a very good stability of the surface in time if stored in an environment protected from UV radiations.