探针型表面张力测试技术的应用研究进展

表面张力是流体重要的物理性质,测定液体表面张力的方法通常包括毛细管上升法、最大气泡压力法、吊环法/吊片法、滴重法/滴体积法、旋滴法和悬滴法。本文综述了测定界面处表(界)面张力和表面压力的方法,详细介绍了基于最大拉力法(Whilhemy吊片法)改进的表面张力测试技术(Du Noüy-Padday),并且概述了这一技术近些年在生物研究、药物研发以及环境监测等领域方面的最新应用。     

Sum rules for molecular electronic spectra: Application to exact and reflection principle solutions

Sum rules for overlap integrals are presented which give the width and mean frequency of an electronic spectrum as a function of potential curves and internal energy. Exact quantum mechanical results are compared with both the traditional reflection principle and a modification of it which conserves momentum. Applications to real spectra, particularly continuous absorption spectra of small molecules, are discussed.     

Novel route to dendritic structures and their application for surface modification

Monodisperse branched polyurethanes containing long alkyl chains have been prepared by a new convergent synthesis. This synthesis comprises two steps, with hexamethylene diisocyanate uretdione as the starting molecule. The free isocyanate groups of this monomer are reacted with long‐chain alkanols. These diurethane uretdiones are then reacted with amines or amino alcohols under ring opening and the formation of a biuret group. Branching points are not, as usual, part of the monomer but are formed during preparation. The structure of these dendrons has been established with NMR spectroscopy, elemental analysis, mass spectroscopy, and gel permeation chromatography. The dendritic polyurethanes are thermally stable up to 200 °C. Surfaces coated with these materials are hydrophobic. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1372–1386, 2006     

On the relationship between o-Ps lifetime in liquids and their surface tension

It is shown that the Nakanishi-Jean formulae for o-Ps lifetime vs. radius of spherical cavity gives the empirical relationship of Tao which links the o-Ps annihilation rate with macroscopic surface tension.     

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.     

Relationship between surface tension and surface coverage

Surfactant action is caused in part by a dramatic reduction in surface tension. Using surface excess measurements from a radioactive surfactant, it was possible to show that (a) the surface tension declines only slightly when the occupancy of the air/water interface increases from 0 to 60% of the maximum and (b) the steep drop in surface tension in region B (Figure 1 ), frequently observed to be linear, begins at about 80% occupancy. Surfactant continues to enter the interface cooperatively up to and past the critical micelle concentration. Linearity in region B is not indicative of surface saturation despite a seemingly constant surface excess throughout the region. The disparity between interfacial areas determined by surface tension and by other methods is discussed in terms of these results.     

Dynamic surface tension of saliva: General relationships and application in medical diagnostics

Maximum bubble pressure and pendent drop profile analysis tensiometry are used to study the dynamic surface tension and rheological characteristics of saliva samples taken from volunteers of various sexes and age, and children with caries. The tensiometric characteristics of the secretions released by parotid, submandibular and sublingual glands are studied, and age-related and sex-related changes of some tensiometric characteristics of saliva are found. The differences are most essential for the tensiometric characteristics of saliva samples taken from caries-free children as compared with those taken from children with caries. Thus, the dynamic interfacial tensiometry is very sensitive and capable of providing information additional to the biochemical data about the properties of saliva, and could be recommended for the development of new diagnostic methods in dentistry.     

Improved methodology to measure surface tension and its application to polystyrene or poly(methyl methacrylate) in styrene solutions

Several methods to measure surface tension involve some inconveniences when applied to moderate or highly viscous polymer solutions. Therefore, an improved version of the weight drop method (WDM) is proposed here. In addition, a comparative analysis of methods is carried out, including the drop profile (DPM), the selected planes (SPM), the WDM and the one proposed here (WDSM), finding that the WDSM is as easy to apply as the SPM and the WDM, although in practical conditions it is much more accurate than either of them. Moreover, the WDSM allows to reproduce the results that can be obtained using DPM, but, in general, it is much easier to implement and apply than such method. The WDSM was used to determine surface tension in polystyrene or poly(methyl methacrylate) in styrene solutions, where the dependence of such property with polymer average molecular weight and polymer concentration was experimentally evaluated.     

On relativistic surface tension

On the basis of special relativity and classical thermodynamics, the surface tension was shown to be a relativistic invariant.     

Dynamic surface tension and surface rheology of biological liquids

The paper presents results of dynamic and equilibrium surface tension measurements (using a maximum bubble pressure instrument) of serum and urine samples that were obtained from 80 healthy human of various sexes and ages. These data were compared with surface tension measurements of biological liquids obtained from patients suffering from malignant neoplasm of corpus uteri (n=5) and cervix uteri (n=31). In addition, surface dilatational rheology was determined on 32 samples using a drop shape method. The dilatational rheology data were compared with the dynamic surface tension data. Although some trends were found, no significant correlations exist between surface tension and rheology data and any of the disease states or stages. It is difficult to explain these findings in the framework of known mechanisms. However, our studies demonstrate that dynamic interface tensiometry of human biological liquids provide new insight into the biophysical behavior of these liquids, most likely reflecting compositional changes of them during ageing, the course of cancer and as a consequence of therapeutical interventions.     

New approach to defining thermodynamic surface tension of solids

Using either the chemical potential of the immobile component of a solid dissolved in a fluid phase or the corresponding component of the tensor of chemical potential in solid phase, a new concept of the grand thermodynamic potential of solid-fluid two-phase system is proposed. For a planar interfacial surface, this makes it possible to generalize the notion of thermodynamic surface tension σ introduced by Gibbs that has the meaning of the formation work of a unit surface. This tension is determined as the specific surface excess of the grand thermodynamic potential. This definition of the thermodynamic surface tension does not depend on the position of the dividing surface and is common for fluids and solids. It is shown that, at the arbitrary position of dividing surface, the difference between thermodynamic σ and mechanical @[gamma] surface tensions for solid surface is determined by the nonuniformity of the tensor of chemical potential in a solid, as well as by its anisotropy in the bulk of solid phase.     

Polarizable contributions to the surface tension of liquid water

Surface tension, gamma, strongly affects interfacial properties in fluids. The degree to which polarizability affects gamma in water is thus far not well established. To address this situation, we carry out molecular dynamics simulations to study the interfacial forces acting on a slab of liquid water surrounded by vacuum using the Gaussian charge polarizable (GCP) model at 298.15 K. The GCP model incorporates both a fixed dipole due to Gaussian distributed charges and a polarizable dipole. We find a well-defined bulklike region forms with a width of approximately 31 A. The average density of the bulklike region agrees with the experimental value of 0.997 g/cm3. However, we find that the orientation of the molecules in the bulklike region is strongly influenced by the interfaces, even at a distance five molecular diameters from the interface. Specifically, the orientations of both the permanent and induced dipoles show a preferred orientation parallel to the interface. Near the interface, the preferred orientation of the dipoles becomes more pronounced and the average magnitude of the induced dipoles decreases monotonically. To quantify the degree to which molecular orientation affects gamma, we calculate the contributions to gamma from permanent dipolar interactions, induced dipolar interactions, and dispersion forces. We find that the induced dipole interactions and the permanent dipole interactions, as well as the cross interactions, have positive contributions to gamma, and therefore contribute stability to the interface. The repulsive core interactions result in a negative contribution to gamma, which nearly cancels the positive contributions from the dipoles. The large negative core contributions to gamma are the result of small oxygen-oxygen separation between molecules. These small separations occur due to the strong attractions between hydrogen and oxygen atoms. The final predicted value for gamma (68.65 m/Nm) shows a deviation of approximately 4% of the experimental value of 71.972 m/Nm. The inclusion of polarization is critical for this model to produce an accurate value.     

Dynamic surface tension measurements on surface active materials

Surface tension measurements by the Wilhelmy plate method are being done at our laboratory using an automatic balance. Surface-active material (surfactant) is spread as a monolayer on an air-water interface and a Pt plate, suspended from a micro-balance, is brought vertically into contact with the interface. The water is contained in a trough, two opposite sides of which can move independently, one producing a large variation in surface area and the other generating a longitudinal wave in the monolayer. This set-up is a new, asymmetric variant of the Benjamins-De Feyter method. Results of measurements on visco-elastic interfacial properties of model compounds of lung surfactant are reported.     

The interconnection between the surface tension and fluctuations within fine drops, bubbles, and their nuclei

We consider the effect of surface tension upon fluctuations within the core of drops and bubbles. We also investigate the fluctuations of the substance density rho, volume V, and particle number N within the objects under study. It is demonstrated that cores of drops and bubbles are homogeneous when they contain several thousand nanoparticles (molecules, atoms). Fluctuations of particle number are very large within the nucleus core containing only a few nanoparticles. Therefore, the surface tension has a probabilistic character since there is no surface separating the nucleus substance from the surrounding medium, only a transitional zone whose radius fluctuates considerably in time. In this case, it is more correct to consider not the surface tension but a certain quantity that we named the quasi surface tension.     

Empirical equation for predicting the surface tension of some liquid metals at their melting point

A new empirical equation is proposed for predicting the surface tension of some pure metals at their melting point. The investigation has been conducted adopting a statistical approach using some of the most accredited data available in literature. It is found that for Ag, Al, Au, Co, Cu, Fe, Ni, and Pb the surface tension can be conveniently expressed in function of the latent heat of fusion and of the geometrical parameters of an ideal liquid spherical drop. The equation proposed has been compared also with the model proposed by Lu and Jiang giving satisfactory agreement for the metals considered.     

A theory of adsorption kinetics with time delay and its application to overshoot and oscillation in the surface tension of gelatin solution

A theory of adsorption kinetics with time delay [Ohshima et al. (1992) Colloid Polym. Sci. 270:707] is developed and applied to the surface tension of a polymer solution. It is found that the general appearance of the overshoot and oscillation in the time course of the surface tension of aqueous gelatin solution observed by Sato and Ueberreiter [(1979) Makromol. Chem. 180:829, 1107; (1979) Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 20:907) can be explained by the present theory.