丁醛等离子体处理云母粉对其表面特性及与聚合物界面特性的影响

用电容耦合式等离子体聚合方法对云母粉进行丁醛等离子体处理,通过测定各种液体对密堆积云母粉的渗透速度,确定了液体在云母粉表面的接触角,估算了云母粉的表面张力及与典型线形聚合物的界面张力。结果表明,极性液体在云母粉表面的浸润性因处理而削弱,非极性液体的浸润性基本来变;云母粉表面张力由处理前的41.34(N·m~(-1)·10~(-3))下降到处理5min时的31.51和处理30min时的25.59(N·m~(-1)·10~(-3));处理对云母粉与线形聚合物界面张力的影响因聚合物而不同,但该界面张力的极性分量均因处理而减小。     

Interface between ionic and nonionic liquids: theoretical study

We use a Flory-Huggins type approach to calculate the structure and the surface tension coefficient of the boundary between ionic and nonionic liquids. The mixture of ionic and nonionic liquids is treated as a "three-component" system including anions, cations, and neutral molecules. We show that if the affinities of the cations and the anions to the neutral molecules are different, the interface comprises an electric double layer. The presence of this layer (uncompensated electric field) stabilizes the interface: the field inhibits the ions segregation at the interface and increases the surface tension. On the other hand, the short-range volume interactions promote the segregation and decrease the surface tension. Furthermore, the surface tension coefficient can be negative, if the difference of the affinities is high enough. It implies a possibility of microphase separation of the system.     

Surface tension and scaling of critical nuclei in diatomic and triatomic fluids

Density functional theory has been used to investigate surface tension and scaling of critical clusters in fluids consisting of diatomic and rigid triatomic molecules. The atomic sites are hard spheres with attractive interactions obtained from the tail part of the Lennard-Jones potential. Asymmetry in attractive interactions between the atomic sites has been introduced to cause molecular orientation and oscillatory density profiles at liquid-vapor interfaces. The radial dependence of cluster surface tension in fluids showing modest orientation in unimolecular layer at the interface or no orientation at all resembles the surface tension behavior of clusters in simple monoatomic fluids, although the surface tension maximum becomes more pronounced with increasing chain length of the molecule. Surface tension of clusters having multiple oscillatory layers at the interface shows a prominent maximum at small cluster sizes; however, the surface tension of large clusters is lower than the planar value. The scaling relation for the number of molecules in the critical cluster and the nucleation barrier height developed by McGraw and Laaksonen [Phys. Rev. Lett. 76, 2754 (1996)] are well obeyed for fluids with little structure at liquid-vapor interface. However, fluids having enhanced interfacial structure show some deviation from the particle number scaling, and the barrier height scaling breaks up seriously.     

等离子体处理云母粉对其表面特性及对其与聚合物界面特性的影响

In this work mica powder was treated with n-butyl aldehyde plasma of radio frequency. Then the apparent contact angle of different liquids on the powder was determined by measuring the penetration rate of the liquid through the packed powder. The surface tension of mica powder and interface tension between the powder and typical linear macromolecules were calculated from the data of contact angle obtained under Fowkes' assumption. Rationalized conclusions were as follows: (i) For polar liquids, wetting of treated mica is more difficult than the untreated one and for nonpolar liquids, no difference has been observed. (ii) The surface tension of mica powder drops from 41.34 (N·m~(-1)·10~(-3)) to 31.51 after 5 min plasma treatment and to 25.59 (N·m~(-1)·10~(-3)) after 30 min plasma treatment. (iii) The polar component of interface tension between the mica powder and any linear macromolecule monotonically decreases with the time of plasma treating. However, the whole interface tension changes after plasma treatment, depending on the polymer used.     

Molecular dynamics study of the surface tension of a binary immiscible fluid

The planar interface between two liquids having two degrees of affinity to mix has been studied by molecular dynamics simulations. The surface tension is calculated from the normal, PN, and transverse, PT, components of the pressure tensor P for a wide range of temperatures. An unusual increase in surface tension with increasing temperature is attributed to a pressure induced void transfer mechanism that is justified by basic thermodynamic arguments. This effect is diminished on the addition of a modest attractive potential between the two species, and there is a turnover point at higher temperatures beyond which the surface tension decreases with increasing temperature. An order parameter is identified as the gradient of the mole fraction distribution through the interfacial region. An additional effect is the dramatic inversion of the kinetic and potential contributions to the PN profile as the temperature is varied. It is found that a commonly used approximation for P, the Irving-Kirkwood 1 or IK1 method, results in a relatively modest unphysical variability in PN that weakly violates the condition of local mechanical stability. However, this artifact does not prevent the IK1 method from producing an interfacial tension which is nearly identical to that derived from the complete IK formula with no additional approximations.     

Deep eutectic solvents formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids

Deep Eutectic Solvents (DES) can be formed between a variety of quaternary ammonium salts and carboxylic acids. The physical properties are significantly affected by the structure of the carboxylic acid but the phase behavior of the mixtures can be simply modeled by taking account of the mole fraction of carboxylic acid in the mixture. The physical properties such as viscosity, conductivity, and surface tension of these DES are similar to ambient temperature ionic liquids and insight into the cause of these properties is gained using hole-theory. It is shown that the conductivity and viscosity of these liquids is controlled by ion mobility and the availability of voids of suitable dimensions, and this is consistent with the fluidity of other ionic liquids and molten salts. The DES are also shown to be good solvents for metal oxides, which could have potential application for metal extraction.     

Molecular dynamics simulations of ionic liquid-vapour interfaces: effect of cation symmetry on structure at the interface

The influence of alkyl chain symmetry of the imidazolium cation on the structure and properties of the ionic liquid-vapour interface has been addressed through molecular dynamics simulations. The anion chosen is bis(trifluoromethylsulfonyl)imide (NTf(2)). Profiles of number densities, orientation of cations, charge density, electrostatic potential, and surface tension have been obtained. At the interface, both cations and anions were present, and the alkyl chains of the former preferred to orient out into the vapour phase. A large fraction of cations preferred to be oriented with their ring-normal parallel to the surface and alkyl chains perpendicular to it. These orientational preferences are reduced in ionic liquids with symmetric cations. Although the charge densities at the interface were largely negative, an additional small positive charge density has been observed for systems with longer alkyl chains. The electrostatic potential difference developed between the liquid and the vapour phases were positive and decreased with increasing length of the alkyl group. The calculated surface tension of the liquids also decreased with increasing alkyl chain length, in agreement with experiment. The surface tension of an ionic liquid with symmetric cation was marginally higher than that of one with an asymmetric, isomeric cation.     

Oscillatory surface tension due to finite-size effects

The simulation results of surface tension at the liquid-vapor interface are presented for fluids interacting with Lennard Jones and square-well potentials. From the simulation of liquids we have reported [M. González-Melchor et al., J. Chem. Phys. 122, 4503 (2005)] that the components of pressure tensor in parallelepiped boxes are not the same when periodic boundary conditions and small transversal areas are used. This fact creates an artificial oscillatory stress anisotropy in the system with even negative values. By doing direct simulations of interfaces we show in this work that surface tension has also an oscillatory decay at small surface areas; this behavior is opposite to the monotonic decay reported previously for the Lennard Jones fluid. It is shown that for small surface areas, the surface tension of the square-well potential artificially takes negative values and even increases with temperature. The calculated surface tension using a direct simulation of interfaces might have two contributions: one from finite-size effects of interfacial areas due to box geometry and another from the interface. Thus, it is difficult to evaluate the true surface tension of an interface when small surface areas are used. Care has to be taken to use the direct simulation method of interfaces to evaluate the predicted surface tension as a function of interfacial area from capillary-wave theory. The oscillations of surface tension decay faster at temperatures close to the critical point. It is also discussed that a surface area does not show any important effect on coexisting densities, making this method reliable to calculate bulk coexisting properties using small systems.     

Rheological parameters of protein interfacial layers as a criterion of the transition from stable emulsions to microemulsions

Proteins are considered as surface active substances. On the basis of experimentally measured rheological parameters of interfacial layers, protein accumulation at an interface between two immiscible liquids, isotherms of interfacial tension, accounting theoretical ideas elaborated for multicomponent systems, the formation of interfacial layers was referred to phase transition. The property of proteins to stabilise emulsions supposedly is connected with the formation of middle phases of lamellar structure. The correlation between elastic properties of interfacial layers and a phase transition of the middle phase upon addition of salts or lipids has been shown. Lipids being added as cosurfactants lead to the transition from lamellar to other structures, which does not provide emulsion stabilisation.     

Instability of the Contact Line between Three Fluid Phases during Mass Transfer Processes

The movable contact line between two liquids and a gas phase sensitively reacts to small disturbances in the force equilibrium. The shape of the contact line and the adjoining interfaces is determined by the interface and surface tensions, the contact angles, the density differences (hydrostatic pressure), and the Laplace capillary pressure. When these change, the three-phase contact line can deform and even become unstable. Interface and surface tension depend on the concentration and temperature. During mass transport processes (concentration changes) various forms of the instability of the contact line can be observed: -Oscillations of a circular contact line (regular expansion and reduction); -Single deformations (bulges) which quickly disappear again; -Deformations (bulges) which run along the boundary line; -Periodically generated and damped deformations with different modes. The behavior of the three-phase contact line is of practical importance for coalescence processes and for spontaneous emulsification on liquid surfaces. Copyright 2000 Academic Press.     

Molecular dynamics simulations of the surface tension of ionic liquids

We report molecular dynamics computer simulations of the surface tension and interfacial thickness of ionic liquid-vapor interfaces modeled with a soft core primitive model potential. We find that the surface tension shows an anomalous oscillatory behavior with interfacial area. This observation is discussed in terms of finite size effects introduced by the periodic boundary conditions employed in computer simulations. Otherwise we show that the thickness of the liquid-vapor interface increases with surface area as predicted by the capillary wave theory. Data on the surface tension of size-asymmetric ionic liquids are reported and compared with experimental data of molten salts. Our data suggest that the surface tensions of size-asymmetric ionic liquids do not follow a corresponding states law.     

Wettability conversion from superoleophobic to superhydrophilic on titania/single-walled carbon nanotube composite coatings

Superoleophobic surfaces were demonstrated on perfluorosilane-rendered titania (TiO(2))/single-walled carbon nanotube (SWNT) composite coatings. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that SWNTs play a key role in the formation of overhanging structures and the nanoscale roughness on the coating surface, which compose the two critical morphologic factors for a superoleophobic surface. The wettability conversion from superoleophobic to superhydrophilic of the composite coatings was realized by the gradual decomposition of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) on the coating surface using UV irradiation. Contact angle measurement on both smooth TiO(2) surface and rough composite coating surface under different UV irradiation time revealed that the wetting behavior of the liquids on the composite coating surface passes from the Cassie to the Wenzel and finally to the inversed-Cassie regime. Different liquids show different irradiation time for the wetting state change. By controlling the UV irradiation dose, liquids with surface tension difference smaller than 5 mN/m can exist in completely converse wetting states on the same coating surface, that is, superphobic for one liquid while superphilic for another with lower surface tension. Mixed organic liquids with different surface tension can be completely separated through a coated grid using this wettability tuning technique.     

Imidazolium-based ionic liquids formed with dicyanamide anion: influence of cationic structure on ionic conductivity

Ionic liquids composed of dicyanamide anion and various imidazolium-based cations were prepared, and the influence of structural variations such as substituting a hydrogen at 2-position and changing the sort of alkyl group at 1-position of imidazolium cations on their thermal behavior, density, solvatochromic effects, viscosity, ionic conductivity, and surface tension was characterized. The substitution of the 2-hydrogen for methyl group or N-methylimidazole decreases the fluidity and ionic conductivity, mainly caused by the increased cohesive energy associated with the increasing cation size. Chain branching at 1-position also gives rise to the pronounced depression of the fluidity and ionic conductivity, presumably as a consequence of the increased pi-pi interactions between imidazolium rings. We found that the surface tension of the present ionic liquids is in inverse proportion to the molar concentration, which can be originally rationalized on the basis of the hole theory.     

More Convenient and Suitable Methods for Sphere Tensiometry

Two new convenient and suitable gravimetric methods of measuring surface and interfacial tensions of liquids and contact angles of liquids on a spherical surface by pulling a sphere through the interface were examined. First, the accuracy of numerical integration was increased. Second, two methods which treat the experimental data were presented and compared. Both methods can be used for determination of the contact angle and interfacial tension at the same time.     

Facile fabrication of a superamphiphobic surface on the copper substrate

A simple solution-immersion technique was developed for the fabrication of a superamphiphobic surface on the copper sheet. Hierarchical structure composed of nanorod arrays and microflowers was formed on the copper surface by an alkali assistant oxidation process; after fluorination, the surface became super-repellent toward water and several organic liquids possessing much lower surface tension than that of water, such as hexadecane. Such superamphiphobicity is attributed to the synergistic effect of their special surface chemicals and microscopic structures, which allows for the formation of a composite interface with all probing liquids tested. We also discuss the effects of surface chemical constituent and geometrical structure on hydrophobicity and oleophobicity; such information allows us to engineer surfaces with specific oleophobic behavior. Additionally, the stability of the composite interface on the created superamphiphobic surface is studied by the compression and immersion test.     

How surface tension of surfactant solutions influences the characteristics of sprays produced by hydraulic nozzles used for pesticide application

The sprays produced by hydraulic agricultural nozzles are influenced by the surface tension of the spray liquid, but models of spray formation relate only to pure liquids with constant surface tension. The way surfactant solutions affect spray formation is studied by investigating sprays of pure liquids compared with a range of surfactant solutions. Some surfactants caused changes in the appearance of the liquid sheet produced by the nozzles, which did not occur with pure liquids, and smaller spray drop sizes than pure liquids, suggesting that other surface properties may also be important.     

The surface tension of polymer liquids

A brief review of the surface tension of polymer liquids is presented. A strong emphasis is placed on recent measurements of surface tensions of homologous liquid series up to high-molecular-weight polymers, and the thermodynamic liquid properties of these same homologous series obtained from sources such as pressure-volume-temperature (PVT) data. The accuracy and limitations of the thermodynamic information which are used as input to many of the theories applied to the surface properties of polymer molecules are discussed. By scaling the surface tension data using a true measure of the cohesive energy density of the liquid state, we can clearly observe the entropic contribution to the surface tension caused by the conformational restriction of a large molecule at the liquid-vapor interface. The scaling implies the existence of a corresponding states principle for both polymer liquids and for low-molecular-weight liquids. The ramifications of the existence of a corresponding states principle for the surface tension of polymer melts are discussed. One consequence of the corresponding states principle is that it allows us to use surface tension measurements to compute the cohesive energy density of polymer melts using PVT data.     

Effect of alkyl chain length and hydroxyl group functionalization on the surface properties of imidazolium ionic liquids

Properties of the surface of ionic liquids, such as surface tension, ordering, and charge and density profiles, were studied using molecular simulation. Two types of modification in the molecular structure of imidazolium cations were studied: the length of the alkyl side chain and the presence of a polar hydroxyl group at the end of the side chain. Four ionic liquids were considered: 1-ethyl-3-methylimidazolium tetrafluoroborate, [C(2)C(1)im][BF(4)]; 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate, [C(2)OHC(1)im][BF(4)]; 1-octyl-3-methylimidazolium tetrafluoroborate, [C(8)C(1)im][BF(4)] and 1-(8-hydroxyoctyl)-3-methylimidazolium tetrafluoroborate, [C(8)OHC(1)im][BF(4)]. The surface tension was calculated using both mechanical and thermodynamic definitions, with consistent treatment of the long-range corrections. The simulations reproduce the available experimental values of surface tension with a maximum deviation of ±10%. This energetic characterization of the interface is completed by microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface. The presence of the hydroxyl group modifies the local structure at the interface, leading to a less organized liquid phase. The results allow us to relate the surface tension to the structural ordering at the liquid-vacuum interface.     

Dynamic surface tension of polyelectrolyte/surfactant systems with opposite charges: two states for the surfactant at the interface

The molecular reorientation model of Fainerman et al. is conceptually adapted to explain the dynamic surface tension behavior in polyelectrolyte/surfactant systems with opposite charges. The equilibrium surface tension curves and the adsorption dynamics may be explained by assuming that there are two different states for surfactant molecules at the interface. One of these states corresponds to the adsorption of the surfactant as monomers, and the other to the formation of a mixed complex at the surface. The model also explains the plateaus that appear in the dynamic surface tension curves and gives a picture of the adsorption process.     

Nanoscale structure and morphology of thin films of poly(2-chloroxylylene) synthesized by the CVD method on different liquids

Poly(2-chloroxylylene) (PCX) thin films are obtained on the surface of liquids with different density and surface tension values. Morphology of these films is different showing increasing roughness and hydrophobicity in correlation with aforementioned physical parameters. A detailed study by means of vibrational spectroscopy, XRD and TEM of the structure of PCX at the interface with the liquid is reported. The results here obtained prove the possibility to tailor the surface of thin solid films of PCX changing the liquid substrate thus addressing the surface functionalities.