The effects of nanostructure and composition on the hydrophobic properties of solid surfaces

The effects of nanoroughness and chemical composition on the contact and sliding angles on hydrophobic surfaces were studied theoretically and experimentally. A theoretical model based on forces developed at the contact area between a liquid drop and hydrophobic smooth or nanoroughened surface was developed and compared with the existing models, which are based on forces developed at the periphery between the drop and the solid surface. The contact area based model gives rise to an interfacial adhesion strength parameter that better describes the drop-sliding phenomenon. Consequently, relationships were derived describing the dependence between the interfacial adhesion strength of the liquid drop to the surface of a given composition, the mass of the drop, the measured contact angles and the sliding angle. For a given surface chemistry, the sliding angle on a nanometric roughened surface can be predicted based on measurements of contact angles and the sliding angle on the respective smooth surface. Various hydrophobic coatings having different surface nanoroughnesses were prepared and, subsequently, contact angles and sliding angles on them as a function of drop volume were measured. The validity of the proposed model was investigated and compared with the existing models and the proposed model demonstrated good agreement with experimental results.     

Adhesion of solid particles to gas bubbles. Part 2: Experimental

In slurry bubble columns, the adhesion of solid catalyst particles to bubbles may significantly affect the G-L mass transfer and bubble size distribution. This feature may be exploited in design by modifying the hydrophilic or hydrophobic nature of the particles used. Previously we have proposed a generalised model, describing the adhesion of particles to G-L interface under stagnant conditions. In this work, we studied the adhesion of particles characterised by different degree of hydrophobicity and porosity: non-porous polystyrene and glass beads, unmodified and hydrophobised mesoporous silica, and activated carbon particles. Images recorded at high optical magnification show the particles adhering to gas bubbles individually or as aggregates. In aqueous media, higher liquid surface tension and particle surface hydrophobicity increase the adhesion strength and the tendency of particles to agglomerate, in agreement with the model. The adhesion of non-porous rough-surface particles to gas bubbles can be characterised by the receding contact angle. The advancing contact angle represents better the adhesion of the same particles to liquid droplets. We found that the “effective” contact angle of porous particles is much lower than an “intrinsic” contact angle calculated from the heat of immersion in water, or measured by sessile drop method. An equivalent contact angle derived from the Cassie rule explains the wetting behaviour of particles having the pores filled with liquid.     

Contact Angle Hysteresis on Polymer Surfaces: An Experimental Study

In order to characterize a solid surface, the commonly used approach is to measure the advancing and receding contact angles, i.e., the contact angle hysteresis. However, often an estimate of the average wettability of the solid–liquid system is required, which involves both the dry and wetted states of the surface. In this work, we measured advancing and receding contact angles on six polymer surfaces (polystyrene, poly(ethylene terephthalate), poly(methyl methacrylate), polycarbonate, unplasticized poly(vinyl chloride), and poly(tetrafluoroethylene)) with water, ethylene glycol and formamide using the sessile drop and captive bubble methods. We observed a general disagreement between these two methods in the advancing and receding contact angles values and the average contact angle determined separately by each method, although the contact angle hysteresis range mostly agreed. Surface mobility, swelling or liquid penetration might explain this behaviour. However, we found that the 'cross' averages of the advancing and receding angles coincided. This finding suggests that the cross-averaged angle might be a meaningful contact angle for polymer–liquid systems. Hence, we recommend using both the sessile drop and captive bubble methods.     

Adhesion: Comparison Between Physico-chemical Expected and Measured Adhesion of Oxygen-plasma-treated Carbon Fibers and Polycarbonate

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (?)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.     

Adhesion: Comparison Between Physico-chemical Expected and Measured Adhesion of Oxygen-plasma-treated Carbon Fibers and Polycarbonate

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (ς)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.     

Development of a model for thin-film stability and spreading in solid–liquid–liquid systems

The presence of thin aqueous films and their stability has a profound effect on reservoir rock–fluids interactions involved in spreading and adhesion. The stability of thin wetting aqueous films on rock surfaces is governed by several variables including pH, brine and crude oil compositions, and capillary pressure. These variables govern the wetting states in the solid–liquid–liquid systems. The wetting states influence the residual oil saturation and the oil-water relative permeabilities and, consequently, the oil recovery. The objective of this study was to deduce a functional dependence of thin-film stability on the above parameters by considering intermolecular and surface interactions in rock–crude oil–brine systems. The surface forces are manifested as disjoining pressure in thin films. The disjoining pressure isotherms for the selected solid–liquid–liquid systems have been computed in terms of the bulk properties of the media. The equilibrium contact angles have also been computed from the integration of the Young–Laplace equation, which relates contact angle to the capillary pressure and disjoining pressure isotherm of the system. The contact-angle data obtained from sessile-drop experiments have been compared with the calculated results, as well as with other published results. Adhesion maps, which relate the film stability to brine pH and molarity, have been developed. The rock–fluids systems considered for this study consisted of smooth glass, quartz and Yates reservoir fluids. The DLVO theory has been used to model the intermolecular forces. The structural forces are incorporated to overcome the limitations of the DLVO theory. A charge regulation model has been used to analyze the crude oil–brine and glass–brine interfaces. The effects of multivalent ions have been incorporated using an equivalent molarity concept. The overall computational model developed in this study is aimed at providing a priori prediction capability of rock-fluids interactions in petroleum reservoirs for inclusion in reservoir simulators.     

Reactive melt infiltration fabrication of C/C-SiC composite: Wetting and infiltration

Reactive melt infiltration is a fast and economical fabrication process for high performance C/C-SiC composite. In order to help understanding reactive melt infiltration production of C/C-SiC composite by liquid silicon, wetting and infiltration of the porous C/C composite preform by liquid silicon were investigated using a sessile drop technique. The contact angle decreased with the increase of time while the drop base diameter increased. According to the variation of drop base diameter and contact angle as a function of time, four different stages corresponding to the interfacial reaction and infiltration of liquid silicon were identified during wetting of the porous C/C composite preform by the liquid silicon. The infiltration height based on wetting curve linearly increased with time, much smaller than that calculated according to Washburn equation, which strongly indicated the reaction control of silicon infiltration.     

Viscoelasticity and Kinetics of Wetting on Rubber

The kinetics of spreading of a liquid drop is usually controlled by conversion of capillary potential energy into viscous dissipation within the liquid when the solid is rigid. However, if the solid is soft, a “wetting ridge” near the solid/liquid/vapour triple line can also be a dissipative sink as the wetting front moves. As a consequence, the kinetics of wetting of rubber may be controlled essentially by viscoelastic losses in the polymer rather than by viscous losses in the liquid drops. Therefore, a direct analogy between the kinetics of wetting and adhesion, respectively, for a liquid and a solid on an elastomeric substrate has been recently proposed. In this paper, the superposition of viscoelastic braking and moderate rubber swelling in the drop spreading phenomenon is considered.     

Viscoelasticity and Kinetics of Wetting on Rubber

The kinetics of spreading of a liquid drop is usually controlled by conversion of capillary potential energy into viscous dissipation within the liquid when the solid is rigid. However, if the solid is soft, a “wetting ridge” near the solid/liquid/vapour triple line can also be a dissipative sink as the wetting front moves. As a consequence, the kinetics of wetting of rubber may be controlled essentially by viscoelastic losses in the polymer rather than by viscous losses in the liquid drops. Therefore, a direct analogy between the kinetics of wetting and adhesion, respectively, for a liquid and a solid on an elastomeric substrate has been recently proposed. In this paper, the superposition of viscoelastic braking and moderate rubber swelling in the drop spreading phenomenon is considered.     

Determination of dynamic contact angles in solid–liquid–liquid systems using the Wilhelmy plate apparatus

The purpose of this work was to carry out a systematic study of the effects of brine composition and rock mineralogy on rock-oil-brine interactions taking place in petroleum reservoirs. These terms are generally lumped into a single term called wettability in petroleum engineering. The extent of wetting of the rock surface by water or oil depends on the dynamic contact angles measured in such a mode as to enable movements of the three-phase contact line. The Wilhelmy plate technique has been used in this study to measure adhesion tension (which is the product of interfacial tension and cosine of the contact angle) at the solid-liquid interface. The water-advancing and water-receding contact angles have been calculated from the adhesion tensions by making independent measurements of the liquid-liquid interfacial tensions using a du Noüy ring tensiometer. The water-advancing and receding angles have been measured in this study for pure hydrocarbons against synthetic brines of different concentrations. Polished surfaces of glass slides and dolomite have been used to simulate the reservoir rock surfaces. A nonionic surfactant (ethoxy alcohol), which is being used in Yates reservoir in West Texas for enhancing oil recovery, was used to quantify its wettability effects. The results of the systematic experimental investigation of the effects of practical variables on wettability are presented. It is found that interactions between surface-active agents at the interface of two liquids have an effect on wettability alteration. The composition and concentrations of different organic and inorganic chemical species have a major effect in making a reservoir oil-wet or water-wet.     

Analysis and surface energy estimation of various model polymeric surfaces using contact angle hysteresis

Wetting of hydrophobic polymer surfaces commonly employed in electronic coatings and their interaction with surfactant-laden liquids and aqueous polymer solutions are analyzed using a contact angle hysteresis (CAH) approach developed by Chibowski and co-workers. In addition, a number of low surface tension acrylic monomer liquids, as well as common probe liquids are used to estimate solid surface energy of the coatings in order to facilitate a thorough analysis of surfactant effects in adhesion. Extensive literature data on contact angle hysteresis of surfactant-laden liquids on polymeric surfaces are available and are used here to estimate solid surface energy for further understanding and comparisons with the present experimental data. In certain cases, adhesion tension plots are utilized to interpret wetting of surfaces by surfactant and polymer solutions. Wetting of an ultra-hydrophobic surface with surfactant-laden liquids is also analyzed using the contact angle hysteresis method. Finally, a detailed analysis of the effect of probe liquid molecular structure on contact angle hysteresis is given using the detailed experiments of Timmons and Zisman on a hydrophobic self-assembled monolayer (SAM) surface. Hydrophobic surfaces used in the present experiments include an acetal resin [poly(oxymethylene), POM] surface, and silane, siloxane and fluoro-acrylic coatings. Model surfaces relevant to the literature data include paraffin wax, poly(methyl methacrylate) and a nano-textured surface. Based on the results, it is suggested that for practical coating applications in which surfactant-laden and acrylic formulations are considered, a preliminary evaluation and analysis of solid surface energy can be made using surfactant-laden probe liquids to tailor and ascertain the quality of the final coating.     

A new method for the characterisation of the wettability of powders

The wetting characteristics of fine powders play an important role in a variety of processes. The most important way of characterising the wettability of a fluid/fluid/solid system is to measure the contact angle. This paper describes a relatively simple method for the determination of the contact angle on powdery materials. The technique involves the measurement of the dynamic contact angle which is formed when a liquid drop is placed on a horizontal porous surface. On the basis of the measured dynamic contact angle as a function of time an “apparent” static contact angle has been defined, which gives a measure of the wettability of porous solid systems by analogy with the wetting of non-porous solids. Determinations with glass beads and NaCl-powders as the test materials indicate that the measured value depends on the particle size of the powder, the porosity and the temperature. It was concluded that the capillary penetration of the liquid droplet into the porous media itself influences the wetting characteristics.     

Adhesion and Wettability Characteristics of Chemically Modified Banana Fibre for Composite Manufacturing

In this work banana fibre was chemically modified using various chemical agents. The surface energy of the fibre is an important parameter and one which governs the interaction of fibre with polymeric matrices. This paper describes the influence of various chemical treatments on the surface energy of the banana fibre investigated by contact angle measurements, spectroscopic analysis and surface morphology studies. The surface energy, work of adhesion, polarity, spreading coefficient, interfacial energy and interaction parameter were determined in the case of raw and chemically modified fibres. Chemical modification has been found to have a profound effect on the surface energy. The polar and dispersive components of the surface energy were also found to be dependent on the chemical treatment involved. The chemical modifications done in this work were: alkali treatment, silanation, benzoylation, formylation, potassium permanganate treatment and acetylation. Of all the modifications, the relative surface energy was found to be a maximum for alkali treated fibre and minimum for silanated fibre. Contact angle measurements were found to be an effective tool in predicting the possible interaction of the fibres with phenol formaldehyde matrix resin. Atomic force microscopy roughness analysis revealed a significant decrease in surface roughness for the chemically modified fibre. An increase both in fibre/matrix adhesion and interfacial shear strength has been observed for all surface modified fibres except for those modified by benzoylation and acetylation.     

Contact angle measurements and interpretation: wetting behavior and solid surface tensions for poly(alkyl methacrylate) polymers

Low-rate dynamic contact angles of a large number of liquids were measured on a poly(ethyl methacrylate) (PEMA) polymer using an automated axisymmetric drop shape analysis profile (ADSA-P). The results suggested that not all experimental contact angles can be used for the interpretation in terms of solid surface tensions: eight liquids yielded non-constant contact angles and/or dissolved the polymer on contact. From the experimental contact angles of the remaining four liquids, we found that the liquid-vapor surface tension times the cosine of the contact angle changes smoothly with the liquid-vapor surface tension, i.e. γlv cos ζ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is again in harmony with those from other methacrylate polymer surfaces of different compositions and side-chains. The solid-vapor surface tension of PEMA calculated from the equation-of-state approach for solid-liquid interfacial tensions was found to be 33.6 ± 0.5 mJ/m2 from the experimental contact angles of the four liquids. The experimental results also suggested that surface tension component approaches do not reflect physical reality. In particular, experimental contact angles of polar and nonpolar liquids on polar methacrylate polymers were employed to determine solid surface tension and solid surface tension components. Contrary to the results obtained from the equation-of-state approach, we obtained inconsistent values from the Lifshitz-van der Waals/acid-base (van Oss and Good) approach using the same sets of experimental contact angles.     

Characterization of epoxy resin surface energetics

This study has characterized the energetics of both the liquid state and the solid state of two commercially available epoxy resins: a DGEBA- and a TGMDA-based epoxy system. The surface properties of the liquid epoxies were evaluated by wetting measurements using a dynamic contact angle analysis (DCA). The Lifshitz-van der Waals components of the surface tension were found to be similar for both epoxy systems, while the acid-base components were found to be slightly different. Two different techniques were used to characterize the cured epoxy surface properties: wetting measurements and vapor adsorption measurements by means of inverse gas chromatography (IGC). The Lifshitz-van der Waals components of the surface energy were observed to be nearly the same for both epoxies, confirming that both resins have the same potential for non-specific interactions, in both liquid and solid states. Evaluations of the acid-base components of the work of adhesion by DCA and the Gibbs free energy change by IGC suggest that both cured epoxies show non-negligible specific interactions with both acidic and basic probes. However, computations of the accepticity and donicity parameters showed that both cured epoxies are predominantly basic, but also possess non-negligible acidity. It is likely that the presence of water on the solid surface contributes to the acidic character of the cured epoxies. The temperature dependence of the liquid surface tension for both epoxy systems was investigated. The same temperature dependence was observed: the surface tension decreased with temperature, following a linear regression. Corrections for viscous-drag effects on the liquid surface tension measurements were also made.     

Wetting and interfacial phenomena in Ni-Cr-Hf/sapphire systems

The wetting of Ni-Hf and Ni-Cr-Hf alloys on sapphire has been studied in this work. Sapphire represents a “simple” and ideal case adopted for better understanding the basic phenomena involved in liquid/solid contact during casting of Ni-based superalloys. Wettability tests were performed by means of the sessile drop method at 1500 °C; moreover, after a certain time of liquid/solid contact, the liquid drop was pushed out from the substrate in order to open the interface and to investigate what happened at the interface. The characterization was performed by SEM/EDS and confocal microscopy in order to check the final interfacial structure. The results are discussed in terms of chemical interactions and by means of ad-hoc calculated phase diagrams. Hf present in Ni-based melts strongly reacted with sapphire forming HfO₂ layers and inclusions; on the other hand, Cr decreased the contact angles of Ni melts without forming interfacial layers during liquid/solid contact.     

引入液固界面效应的滴状冷凝传热模型

针对液固界面相互作用对滴状冷凝传热的影响,以Rose滴状冷凝传热模型为基础,考虑接触角、脱落直径对冷凝传热的影响,对滴状冷凝过程中液滴空间序列上的构象,作时间序列上的重构,建立了包含液固界面效应的滴状冷凝传热模型.模型计算结果表明液固表面自由能差越大、接触角滞后越小则越有利于冷凝传热.为滴状冷凝文献数据间存在差异的原因提供了一个新的解释,即液固界面效应的影响.模型可计算得到在不同界面条件下的不同传热结果,模型计算结果与Rose实验值以及本文滴状冷凝传热实验较为吻合.     

Influence of composition of sodium aluminoborosilicate melts containing nickel and calcium oxides on the wetting angle on platinum

The influence of the composition of sodium aluminoborosilicate melts containing nickel and calcium oxides on the wetting angle on platinum has been studied by the method of “small drop on thin thread.” It is shown that partial mutual replacement of silicon, aluminum, and boron oxides (up to 4 mol %) does not substantially change the wetting angle. The wetting angle increases after the partial replacement of these oxides by calcium oxide and decreases after their replacement by nickel oxide. Since a change in the surface tension of melts in the composition range studied is insignificant, the work of adhesion and the “glass melt-metallic substrate” interfacial tension are determined by the wetting angle. The maximum work of adhesion and the minimum interfacial tension are characteristic of melts with an increased nickel oxide content, and the minimum work of adhesion and the maximum interfacial tension are observed for melts with an increased calcium oxide content. Deceased.     

Influence of oxide dopants on the wetting of doped graphite by cryolite/alumina melts

In the aluminium smelting industry, the wetting of the electrolyte on the carbon anode is an important property associated with the onset of the anode effect. The effect of dopants on the wettability of the anode was investigated in this study. The carbon material selected was graphite. The composition of the cryolite/alumina melts varied between a very low alumina content and 6 wt.% alumina. The sessile drop approach was adopted to measure the contact angle between the melt and the graphite at 1030 °C. The influence of oxide dopants, chromium III oxide and alumina, in the graphite on the wettability was studied. The wettability on a pure graphite surface depends to a small extent on the liquid surface tension but mostly on the liquid–solid interfacial tension that varies with the concentration of alumina in the liquid. The wettability on an oxide doped graphite surface depends on the dissolution of the oxide in the melt that changes the liquid–solid interfacial tension. The alumina dissolution has a double effect on the liquid–solid interfacial tension: the chemical reaction as well as the change in the oxy-anions concentration at the interface decrease the interfacial tension.     

Influence of composition of sodium aluminoborosilicate melts containing nickel and calcium oxides on the wetting angle on platinum

The influence of the composition of sodium aluminoborosilicate melts containing nickel and calcium oxides on the wetting angle on platinum has been studied by the method of “small drop on thin thread.” It is shown that partial mutual replacement of silicon, aluminum, and boron oxides (up to 4 mol %) does not substantially change the wetting angle. The wetting angle increases after the partial replacement of these oxides by calcium oxide and decreases after their replacement by nickel oxide. Since a change in the surface tension of melts in the composition range studied is insignificant, the work of adhesion and the “glass melt-metallic substrate” interfacial tension are determined by the wetting angle. The maximum work of adhesion and the minimum interfacial tension are characteristic of melts with an increased nickel oxide content, and the minimum work of adhesion and the maximum interfacial tension are observed for melts with an increased calcium oxide content. Deceased.