Study of the surface and interfacial tensions in systems containing a low molar mass liquid crystal

The surface tension of a low molar mass liquid crystal (LMMLC), 4-cyano-4'-n-heptyloxybiphenyl (70CB), was measured as a function of temperature using the pendant drop method, forming drops of different volumes ranging from 5 to 11 mm³. Contact angles formed by drops of 70CB in the nematic and isotropic phases on plates of polystyrene (PS) and of a liquid crystal polymer (LCP), VECTRA A910, were also measured. Only large drops could be used for surface tension analysis. It was shown that in the nematic phase the surface tension of 70CB decreases with increasing temperature, and that in the isotropic phase the surface tension increases with increasing temperature. Using the values of contact angle and of surface tension of 7OCB it was possible to evaluate the interfacial energy between 7OCB and PS and between 7OCB and VECTRA. The interfacial energy between 7OCB and PS, and between 7OCB and VECTRA, decreased with increasing temperature for ranges of temperatures corresponding to both phases of 70CB.     

Study of the surface and interfacial tensions in systems containing a low molar mass liquid crystal

The surface tension of a low molar mass liquid crystal (LMMLC), 4-cyano-4'-n-heptyloxybiphenyl (70CB), was measured as a function of temperature using the pendant drop method, forming drops of different volumes ranging from 5 to 11 mm³. Contact angles formed by drops of 70CB in the nematic and isotropic phases on plates of polystyrene (PS) and of a liquid crystal polymer (LCP), VECTRA A910, were also measured. Only large drops could be used for surface tension analysis. It was shown that in the nematic phase the surface tension of 70CB decreases with increasing temperature, and that in the isotropic phase the surface tension increases with increasing temperature. Using the values of contact angle and of surface tension of 7OCB it was possible to evaluate the interfacial energy between 7OCB and PS and between 7OCB and VECTRA. The interfacial energy between 7OCB and PS, and between 7OCB and VECTRA, decreased with increasing temperature for ranges of temperatures corresponding to both phases of 70CB.     

Experimental observation and prediction of interfacial tension and viscoelastic emulsion model behavior in novel phosphate glass-polymer hybrids

The interfacial tension of hybrids composed of a tin-based phosphate glass (Pglass) and thermoplastic polymers, low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) was investigated using pendant drop and droplet deformation methods. High surface tension values were determined for the pure Pglass and subsequently used to obtain interfacial tension values that were found to be greater than that of most polymer blends reported in the literature. Small amplitude oscillatory shear data were fitted to the Choi-Schowalter and Palierne emulsion models in order to estimate the interfacial tension and to validate the accuracy (or lack thereof) of using a polymer emulsion model on the special Pglass-polymer systems. Although some of the hybrids showed satisfactory agreement with the emulsion models, wide ranges of interfacial tensions were obtained, suggesting that a more complicated theory that explicitly takes the Pglass-polymer interactions, shape factor, and size distributions of the dispersed Pglass phase into account may be necessary for more accurate modeling of these special hybrid systems with enhanced benefits.     

Interfacial Tension of Aqueous Three‐Phase Systems Formed by Triton X‐100/PEG/Dextran

A novel aqueous three‐phase system was formed spontaneously when a nonionic surfactant (Triton X‐100) and two polymers (PEG and dextran) were mixed. The interfacial tension between the phases was measured by the spinning drop method. It was shown that the values of interfacial tension were extremely small. The interfacial tensions of the top/middle phases were much lower than those of the middle/bottom phases. The interfacial tension was affected by component concentrations, temperature, added salts, and the density difference between two phases. Temperature exhibited a special effect on interfacial tension: with the increase of temperature, interfacial tension increases significantly.     

Influence of hyperbranched polymers on the interfacial tension of polypropylene/polyamide‐6 blends

The compatibilizing effect of polypropylene (PP) grafted with hyperbranched polymers (PP–HBP) has been investigated in PP/polyamide‐6 (PA‐6) blends. Because of its high reactivity and diffusitivity, PP–HBP has been shown to be a more effective compatibilizer in decreasing the interfacial tension than the commonly used maleic anhydride–grafted polypropylene (PP–MAH). This article describes the influence of PP–HBP and PP–MAH on the interfacial tension between PP and PA‐6, as measured by the deformed drop‐retraction method (DDRM). Overall, PP–HBP yielded lower interfacial tension values between PP and PA‐6, which resulted in a finer particle size of the secondary phase. The time dependence of the interfacial tension can be monitored by DDRM, enabling evaluation of the diffusitivity and reactivity of the compatibilizer. A model based on particle coarsening has been developed to describe the time dependence of the interfacial tension. This model showed that the diffusitivity and reactivity for PP–HBP was higher than that of PP–MAH. Therefore, PP–HBP has strong potential as a compatibilizer in diffusitivity‐dependant processes such as film coextrusion and fusion bonding. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2069–2077, 1999     

Interfacial tension of blends containing thermotropic liquid crystalline polymers

A method is proposed to determine the interfacial tension of immiscible blends containing a liquid crystalline polymer (LCP) and a flexible-molecule polymer, under flow conditions. The method is based on Taylor's theorem for immiscible fluids, i.e., that a suspended drop of liquid A in liquid matrix B is deformed in shear or elongational flow in proportion to the ratio of interfacial to viscous stresses. Taylor's theorem, as originally derived, applies to low concentrations, Newtonian fluids and small deformations. Thus, the theorem was modified to account for “Power Law” fluids in elongational flow and large deformations, more applicable to the system under investigation. The elongational viscosities of the LCP and the flexible polymer (polycarbonate) as a function of elongational rate were determined using converging type flow. The two polymers exhibited a Power-Law behavior in elongational flow and, hence, the experimental constitutive equations of state were used to quantify the viscous stresses. The interfacial stresses were modified for large deformations by taking into consideration the deformed shape and hence increased surface area of the elongated LCP particle. Using the modified expression, the interfacial tension of LCP and PC was determined to be in the range of 5–6.6 dyne/cm.     

Synthesis of a thermosensitive surface by construction of a thin layer of poly (N-isopropylacrylamide) on maleimide-immobilized polypropylene

Thermosensitive surfaces were developed by the grafting of a thin layer of PNIPAAm through an UV-induced photopolymerization reaction of vinyl monomers with a free radical-activated polypropylene (PP) surface. PNIPAAm layer covering the PP surface corrected, to some extension, both depressions and fissures of the previously modified PP surfaces. The layered surfaces have morphological characteristic different from those of the non-layered surfaces, and their thickness was dependent on irradiation time. Water contact angles of the layered surfaces revealed a transition at approximately 33.5-36.5 °C as a result of a response to the variation of temperature. There was an increase in the values of the contact angles with an increase in temperature from 26 °C to 44 °C, revealing the nature both hydrophilic and hydrophobic of the surfaces due to a conformational rearrangement of PNIPAAm exposing its isopropyl groups to the liquid drop. This work offers a chemically stable thermosensitive surface (because it is covalently structured) with great potential for use as sensors and actuators.     

The relative role of coalescence and interfacial tension in controlling dispersed phase size reduction during the compatibilization of polyethylene terephthalate/polypropylene blends

The breaking thread and the sessile drop methods have been used to evaluate the interfacial tension between a polypropylene (PP) and a polyethylene-terephthalate (PET). An excellent correlation was found between the two. The breaking thread technique was then used to evaluate the interfacial tension of these blends at various levels of a styrene-ethylene butylene-styrene grafted with maleic anhydride (SEBS-g-MA) compatibilizer. In order to evaluate the relative roles of coalescence and interfacial tension in controlling dispersed phase size reduction during compatibilization, the morphology of PP/PET 1/99 and 10/90 blends compatibilized by a SEBS-g-MA were studied and compared. The samples were prepared in a Brabender mixer. For the 10/90 blend, the addition of the compatibilizer leads to a typical emulsification curve, and a decrease in dispersed phase size of 3.4 times is observed. For the 1/99 blend, a 1.7 times reduction in particle size is observed. In the latter case, this decrease can only be attributed to the decrease of the interfacial tension. It is evident from these results that the drop in particle size for the 10/90 PP/PET blend after compatibilization is almost equally due to diminished coalescence and interfacial tension reduction. These results were corroborated with the interfacial tension data in the presence of the copolymer. A direct relationship between the drop in dispersed phase size for the 1/99 PP/PET blend and the interfacial tension reduction was found for this predominantly shear mixing device. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2271–2280, 1997     

Determination of surface tension and contact angle from the shapes of axisymmetric fluid interfaces without use of apex coordinates

Drop shape techniques, such as axisymmetric drop shape analysis, are widely used to measure surface properties, as they are accurate and reliable. Nevertheless, they are not applicable in experimental studies dealing with fluid configurations that do not present an apex. A new methodology is presented for measuring interfacial properties of liquids, such as surface tension and contact angles, by analyzing the shape of an axisymmetric liquid-fluid interface without use of apex coordinates. The theoretical shape of the interface is generated numerically as a function of surface tension and some geometrical parameters at the starting point of the interface, e.g., contact angle and radius of the interface. Then, the numerical shape is fitted to the experimental profile, taking the interfacial properties as adjustable parameters. The best fit identifies the true values of surface tension and contact angle. Comparison between the experimental and the theoretical profiles is performed using the theoretical image fitting analysis (TIFA) strategy. The new method, TIFA-axisymmetric interfaces (TIFA-AI), is applicable to any axisymmetric experimental configuration (with or without apex). The versatility and accuracy of TIFA-AI is shown by considering various configurations: liquid bridges, sessile and pendant drops, and liquid lenses.     

Evidence for the existence of an effective interfacial tension between miscible fluids: isobutyric acid-water and 1-butanol-water in a spinning-drop tensiometer

We report definitive evidence for an effective interfacial tension between two types of miscible fluids using spinning-drop tensiometry (SDT). Isobutyric acid (IBA) and water have an upper critical solution temperature (UCST) of 26.3 degrees C. We created a drop of the IBA-rich phase in the water-rich phase below the UCST and then increased the temperature above it. Long after the fluids have reached thermal equilibrium, the drop persists. By plotting the inverse of the drop radius cubed (r(-)(3)) vs the rotation rate squared (omega(2)), we confirmed that an interfacial tension exists and estimated its value. The transition between the miscible fluids remained sharp instead of becoming more diffuse, and the drop volume decreased with time. We observed droplet breakup via the Rayleigh-Tomotika instability above the UCST when the rotation rate was decreased by 80%, again demonstrating the existence of an effective interfacial tension. When pure IBA was injected into water above the UCST, drops formed inside the main drop even as the main drop decreased in volume with time. We also studied 1-butanol in water below the solubility limit. Effective interfacial tension values measured over time were practically constant, while the interface between the two phases remains sharp as the volume of the drop declines. The effective interfacial tension was found to be insensitive to changes in temperature and always larger than the equilibrium interfacial tension. Although these results may not apply to all miscible fluids, they clearly show that an effective interfacial tension can exist and be measured by SDT for some systems.     

Determination of line tension for systems near wetting

Contact angle measurements for three n-alkanes, heptane, octane, and nonane, on two different self-assembled surfaces (SAM) are reported as a function of drop size. These liquids all formed low contact angles (below 20 degrees ); the measurements were performed using an accurate method for systems with low contact angle, ADSA-D. The observed drop size dependence of the contact angles was interpreted using the modified Young equation. It was concluded that the observed drop size dependence of contact angles was due to line tension. The choice of systems also provided the opportunity to examine the behavior of the line tension for systems near wetting (i.e., low contact angles). It was determined that the line tension is positive and ranges from below 10(-7) to just below 10(-6) J/m for the systems studied; the observations suggested that the line tension decreases as the contact angle decreases and likely vanishes at complete wetting.     

Surface activity of myristic acid in the poly(methyl methacrylate)/supercritical carbon dioxide system

To confirm the surface activity of myristic acid in the dispersion polymerization of vinyl monomers in scCO2, the interfacial tension (IFT) at the polymer/supercritical carbon dioxide (scCO2) interface has been measured. For the IFT measurements, a high-pressure pendant drop apparatus was constructed. The IFT data was obtained by the axisymmetric drop shape analysis of melt polymer droplets formed at the tip of a capillary. The reliability of the apparatus was confirmed by measuring the IFT of polystyrene (PS)/scCO2 and polypropylene (PP)/CO2 systems. The IFT of the poly(methyl methacrylate) (PMMA)/scCO2 system with and without myristic acid was also measured. The IFT decreased on addition of myristic acid. The magnitude of the IFT depression due to the myristic acid was comparable to that of PS/scCO2 systems with the block copolymer surfactant, PS-b-poly(fluorooctyl acrylate). The surface activity of the myristic acid was confirmed by the decrease of IFT.     

Prediction of solid-fluid interfacial tension and contact angle

Two simple equations have been developed using the lattice theory and the regular solution assumption to predict the solid-vapor and solid-liquid interfacial tension. The required parameters are the liquid critical temperature and volume, the solid melting temperature and the molar volume of liquid and solid compounds. To confirm the models, the predicted solid-fluid interfacial tension values have been used to predict the contact angle of the liquid drop on the solid surface applying Young's equation. Agreement of the predicted contact angle with the experimental data reveals the reliability of the developed models.     

Preparation and properties of self-reinforced polypropylene/liquid crystalline polymer composites

A fast and potentially economic method for creating a composite material of polypropylene (PP) with liquid crystalline polymers (LCPs) was explored. The LCPs were dispersed in the PP matrix in a conventional extrusion process and subsequently drawn in order to obtain a highly uniaxially molecular orientation of the LCP fibres. The strongest mechanical properties were found after rapid cooling of the blend, which was optimally exploited in thin filaments where cooling was fast enough to prevent fibre break-up and/or orientation relaxation. To enable the production of extrudates which are thick enough to be cut into self-reinforced pellets, a fused multi-filament technology was developed. In this technology several thin filaments were extruded/drawn and rapidly cooled to a temperature between the crystallisation temperatures of the LCP and the PP. After solidification of the LCP, the single filaments were fused to a multifilament strand and further cooled to room temperature. The thick multifilament LCP reinforced PP strands were cut into pellets and used in injection-and compression-moulding processes. This processing took place between the melting temperature of the PP and the LCP, with retention of the aspect ratio and the molecular orientation of the LCP fibres.     

CFD evaluation of drop retraction methods for the measurement of interfacial tension of surfactant-laden drops

Drop retraction methods are popular means of measuring the interfacial tension between immiscible polymers. Experiments show that two different drop retraction methods, imbedded fiber retraction (IFR) and deformed drop retraction (DDR), give inconsistent results when a surfactant is present on the surface of the drop. These inconsistencies are deemed to be due to dilution of the surfactant and due to gradients in interfacial concentration of surfactant along the drop surface. This physical picture is quantified for the simple case of a Newtonian drop in a Newtonian matrix, with an insoluble, nondiffusive surfactant at the interface. The drop is deformed in computational fluid dynamics simulations by shearing the matrix, and then allowed to retract. Dilution and interfacial tension gradients effects are found to be especially large at the early stages of retraction, making IFR unsuitable for measuring the interfacial tension of surfactant-laden interfaces. The effects of surfactant dilution and gradients are found to persist even at late stages of retraction, causing the DDR method to underestimate the equilibrium interfacial tension significantly. The largest underestimates occur when the drop viscosity is lower than the matrix viscosity.     

Determining the contact angle between liquids and cylindrical surfaces

One of the simplest methods of measuring the quantities for estimating the adhesion properties of materials (i.e., the adhesion work, the surface energy, and the interfacial tension between certain liquids and a surface) requires the determination of the contact angle between the liquid and the surface. In the case of plane surfaces the determination of the drop dimensions makes it possible to calculate the contact angle by the sessile drop method, but in the case of cylindrical surfaces (such as the monofilaments), several methods were developed to improve the accuracy of the contact angle measurements. This paper presents a comprehensive method for precise evaluation of the contact angle between liquid drops and monofilaments by establishing a differential equation describing the drop contour. This equation makes it possible to accurately compute the contact angle using the dimensions of the drop. A comparison of the values of the contact angle calculated by our method and those obtained by other approaches is made. We applied our method in the case of polyamide-6 monofilaments treated using dielectric barrier discharge, knowing their medical applications in surgical sutures.     

Evaluation of the surface tension measurement of axisymmetric drop shape analysis (ADSA) using a shape parameter

A quantitative criterion called “shape parameter” to evaluate the quality of surface tension measurement of Axisymmetric Drop Shape Analysis (ADSA) is presented. ADSA is a powerful technique for the measurement of interfacial tensions and contact angles of pendant drops, sessile drops, and bubbles. Despite the general success of ADSA, deficient results may be obtained for drops close to spherical shape. Therefore, the “shape parameter” was used to determine the range of drop shapes in which ADSA succeeds or fails. The “shape parameter” is a dimensionless parameter that expresses quantitatively the difference in shape between a given experimental profile and an inscribed circle. The surface tension measurements of ADSA were evaluated for both pendant drop and constrained sessile drop configurations using the shape parameter. Different shapes of the pendant drop were studied using different sizes and materials of holders. For each drop configuration, a “critical shape parameter” was defined based on the minimum value of the shape parameter that guarantees an error of less than ±0.1 mJ/m². Furthermore, the effects of the type of liquid and constellation on the “critical shape parameter” were studied.     

Simultaneous measurement of contact angle and surface tension using axisymmetric drop-shape analysis-no apex (ADSA-NA)

Axisymmetric drop-shape analysis-no apex (ADSA-NA) is a recent drop-shape method that allows the simultaneous measurement of contact angles and surface tensions of drop configurations without an apex (i.e., a sessile drop with a capillary protruding into the drop). Although ADSA-NA significantly enhanced the accuracy of contact angle and surface tension measurements compared to that of original ADSA using a drop with an apex, it is still not as accurate as a surface tension measurement using a pendant drop suspended from a holder. In this article, the computational and experimental aspects of ADSA-NA were scrutinized to improve the accuracy of the simultaneous measurement of surface tensions and contact angles. It was found that the results are relatively insensitive to different optimization methods and edge detectors. The precision of contact angle measurement was enhanced by improving the location of the contact points of the liquid meniscus with the solid substrate to subpixel resolution. To optimize the experimental design, the capillary was replaced with an inverted sharp-edged pedestal, or holder, to control the drop height and to ensure the axisymmetry of the drops. It was shown that the drop height is the most important experimental parameter affecting the accuracy of the surface tension measurement, and larger drop heights yield lower surface tension errors. It is suggested that a minimum nondimensional drop height (drop height divided by capillary length) of 1.7 is required to reach an error of less than 0.2 mJ/m(2) for the measured surface tension. As an example, the surface tension of water was measured to be 72.46 ± 0.04 at 24 °C by ADSA-NA, compared to 72.39 ± 0.01 mJ/m(2) obtained with pendant drop experiments.     

Contact angle kinetics of human albumin solutions at solid surfaces

Contact angle kinetics of sessile drops of albumin solution on hydrophilic acetal and hydrophobic FC 721 surfaces were measured using axisymmetric drop shape analysis. Young's equation is used to calculate the solid/liquid interfacial tension from measured contact angles and surface tensions as a function of time. The change in solid/liquid interfacial tension is a result of protein adsorption. It indicates that at the hydrophilic acetal surface the albumin molecules, interact only weakly, whereas the interaction with the hydrophobic FC 721 surface is quite strong.     

Determination of interfacial tension between two immiscible polymers with and without surfactants at the interface

A second-order drop deformation method for inferring interfacial tension between two immiscible polymers is proposed and shown to improve the accuracy of tension estimate appreciably. A small step-strain method, which uses a strong flow (capillary number >1) and short flow time approximately O(0.1s), is successfully developed to avoid complications caused by the surfactants for surfactant-laden drops. This method is demonstrated to give good tension estimates for a range of viscosity ratios and surface coverage.