Surfaces, Interfaces, and their Applications I

The Liquid Interface

13 Interfaces with Liquids

Interfaces with liquids are central to a huge variety of naturally occurring and technological phenomena. We define a liquid interface as the interface between a liquid and a solid or as the interface between two fluids, either two liquids or a liquid and a gas/vapor. We can summarize the different types of liquid interfaces, their occurrence and their importance in the following table: Interface type Occurrence Any situation where a solid surface is in contact with a liquid Importance/applications Coatings/corrosion Lubrication Wetting Biomaterials (fouling) . Emulsions (food, chemistry, cosmetics, pharma, mining, .) Environment (oil spills,) Biomembranes .

Liquid-Solid

Liquid-Liquid

Contact between two immiscible (or partially miscible) liquids

Liquid-Gas (Vapor)

Foams (food, chemistry, Liquid in direct contact with cosmetics, pharma, mining, .) a gas or in equilibrium with Free liquid surfaces its vapor .

13.1 Solid-Liquid Interfaces

This is the most common and familiar example of a liquid interface. Below a few fundamental concepts of solid-liquid interfaces are reviewed. 13.1.1 Interfacial Energy The interactions between atoms or molecules in the bulk determine the bulk properties of the material (e.g. elastic moduli in the solid, or viscosity in the liquid). At the solid-liquid interface there is a material discontinuity, whose properties are determined by the interactions between the molecules or atoms in the two phases. The sum of these interactions determines the interfacial energy Fint, which is often described through the interfacial tension : !"# = (13.1) defined as the interfacial energy per unit area.

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The key concept worth emphasizing is that each interface has an energy cost and the interfacial tension is a representation of what is the energy cost to increase the area of the interface per unit area.

Figure 13-1 Molecular interactions at the solid-liquid interface determine the interfacial energy Fint. The interfacial tension is defined as Fint per unit area. (Photo from http://www.limmatschwimmen.ch)

13.1.2 Wettability and Contact Angles A liquid is said to wet a surface if a droplet of the liquid deposited on the surface spreads to create a film of uniform thickness. If, instead, the liquid spreading stops at a certain drop size and a finite angle is observed between the tangent to the droplet surface and the solid surface at the contact point, the liquid is said to partially wet the surface. These definitions can be quantified using Youngs equation:

cos =

!! !! (13.2) !"

where s1, s2, 12 are the interfacial tensions of the solid with fluid 1, with fluid 2 (the wetting liquid) and between the two fluid phases, Figure 13-2. Definition of the contact angle of a liquid on a solid surface. respectively, and is the contact angle of fluid 2 on the surface. Youngs equation shows that the equilibrium of the interfacial tensions defines the contact angle of the liquid on the surface. The physical meaning of the equation is directly related to the above-mentioned concept that any interface has an energy cost. In the case depicted in Figure 13.2, the liquid will spread if the energy cost of creating additional interfacial area with the solid and with the other fluid (either a gas or another liquid) is lower than the energy gain of removing interfacial area between the solid and fluid 1 upon spreading. In the case of complete wetting, it is always favorable to create the liquid-solid interface, regardless of the other energy penalties. The liquid keeps spreading and the contact angle goes to zero. From Equation (13.2) it also follows that, if s1 > s2, then the left side of the equation is positive, implying that the contact angle is smaller than 90. For the opposite case, s1< s2, the
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cosine of is negative and thus the contact angle is larger than 90. In the case of water as the wetting fluid, such surfaces are termed hydrophilic and hydrophobic, respectively. In the special case where, s1 = s2, the contact angle is 90 and the surface is said to be neutrally wetting.

Figure 13-3 The contact angle of a liquid on a solid surface can be tuned by changing the interactions between the two phases, e.g. by changing the surface chemistry. In this image the surface displays a continuous change of the wettability from more hydrophobic (left) towards more hydrophilic (right). Image from Morgenthaler, S. et al.. Langmuir 2003, 19(25), 10459.

13.2 Interfaces between Liquids and Other Fluids

Perhaps at first sight the case where an interface exists between two fluids, either two liquids or a liquid and a gas (vapor), is a less familiar situation. In the following sections some examples of such interfaces are described and the concepts introduced before for the solid-liquid interfaces are extended to this case. 13.2.1 Examples of Interfaces between Liquids and Other Fluids Liquid-Liquid Interfaces: Emulsions

The most commonly occurring situation where an interface between two immiscible liquids is found is in the case of emulsions. Emulsions are droplets of one liquid phase dispersed in a second surrounding immiscible liquid phase. They find use in a vast range of practical applications, as for instance shown in Figure 13.4. Liquid-Gas Interfaces: Foams

Liquid-gas (or vapor) interfaces are often encountered at the free surface of liquids (e.g. the surface of a lake), but have a higher practical importance in foams, where a thin liquid film separates and stabilizes two gas bubbles. Foams are vital for many naturally occurring processes and find vast use in industry and technology (see Figure 13.5). Hydrophilic-Hydrophobic Fluid Interfaces: Bio-membranes

Bio-membranes, like the cell membrane, can also be considered fluid interfaces. In fact the cell membrane separates two hydrophilic environments (the inside and the outside of a cell) via a thin hydrophobic layer, as depicted in Figure 13.6. Moreover the lipid molecules that compose the cell wall are free to move around and diffuse along the cell membrane, giving fluidity to the system.

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Figure 13-4 Examples of the practical use of emulsions. From left to right: Milk is an emulsion of fat droplets in water. Butter is instead an emulsion of water droplets in a fat matrix. Many inks or other chemical products are emulsions and emulsions are commonly used in cosmetic or pharmaceutical formulations. Emulsions are also commonly used in mineral processing. Schematic representation of an emulsion. At large length scales emulsions look like a homogeneous fluids, but at smaller length scales, droplets dispersed in a continuous phase are found.

Figure 13-5Examples of naturally occurring or artificial foams. Schematic representation of the microstructure of a foam with gas bubbles separated by a thin liquid film.

Figure 13-6 Schematic of the cell membrane, constituted of a lipid bilayer, which defines two hydrophobichydrophilic interfaces.

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13.2.2 Interfacial Energy Similarly to what was defined above for the solid-liquid interface, liquid-liquid or liquid-gas interfaces are also characterized by an interfacial energy and thus by an interfacial tension. In the case of such fluid interfaces, the definition of the surface tension is much more intuitive and can be rationalized as reported below.

Figure 13-7 Schematics of an experiment to define the interfacial tension.

Imagine having a liquid film freely suspended in a rectangular frame that has a movable barrier. If the barrier is moved to the right by applying a force F, the area of the liquid film is increased by an amount directly proportional to the displacement of the frame. We can thus calculate the energy spent (the work done) in this process as indicated in Figure 13.7. The work can also be written as proportional to the area change, where the surface tension is the proportionality constant. Given such definition, has the units of a force per unit length and it is typically measured in mN/m. 13.2.3 Interfacial Free-Energy Minimization: Coalescence Thermodynamic equilibrium is defined as the configuration of a system in which the systems free energy is minimized. This implies that every thermodynamic system will evolve in time towards the minimization of the free energy. We have just demonstrated that every interface has a free-energy cost proportional to the interface area and the interfacial tension. As a consequence of this, every system where interfaces are present will try to reduce its free energy by reducing the interfacial area. This concept is fundamental to understand the stability of emulsions and foams.

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Figure 13-8 Schematic of the coalescence process in emulsions.

Imagine having an emulsion composed of a collection of monodisperse oil droplets of radius r1. If we now take two of those droplets, the ensemble has a given volume and surface area. If the two droplets merge (or coalesce) into one bigger droplet of radius r2, the total oil volume is conserved, but the surface area of the new droplet is smaller than the sum of the surface areas of the two initial droplets. This implies that by coalescing, the two droplets have reduced the total area of the liquid-liquid interface and thus the free energy of the system. This process proceeds until the interfacial area is minimized, which is achieved by fully de-mixing the system. Thermodynamic instability of emulsions towards coalescence is therefore a direct consequence of the energy cost of an interface. Similar arguments can be made for the coalescence of foams. The kinetics of coalescence can be very fast and some oil/water emulsions de-mix almost instantaneously. Another consequence of free energy minimization is that a free droplet or bubble will always take up the shape that minimizes the surface area, which is a sphere. If the droplet or bubble has some geometrical constraints, e.g. set by the presence of neighboring droplets or hard walls, surface tension will find the shape which minimizes the energy of the system.

Figure 13-9Examples of minimum energy surfaces for 2, 3 and 200 bubbles in two dimensions. Images from Simon Cox (The University of Wales).

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13.3 Adsorption at Interfaces between Liquids and Other Fluids

Most of the emulsions or foams that we encounter in our everyday life are not unstable but appear to maintain their structure over extended periods of time. This is obtained by adding a third component to the system, typically called emulsifier or foamer. Depending on the type of emulsifier, different mechanisms are responsible for the enhanced stability of the emulsion (or foam). 13.3.1 Surfactant Molecules The most common emulsifiers are surfactant molecules. Surfactants are amphiphilic molecules, i.e. molecules whose structure presents a hydrophilic part and a hydrophobic part, which are respectively water-soluble and oil-soluble. A very common example of surfactant is for instance sodium dodecyl sulfate or SDS, which is represented in the figure below.

Figure 13-10 Chemical formula of SDS. The molecule has a charged hydrophilic head and a hydrophobic tail constituted by a carbon chain. SDS molecules arrange themselves at oil-water interfaces by exposing the tail to the oil and the head to the water phase, respectively. Molecules like SDS can adsorb and orient on the surface of emulsion droplets.

Surfactants are responsible for emulsion stabilization through different mechanisms. The often dominating effect is that surfactants reduce the interfacial tension between the two fluid phases. Given the relation between free energy and interfacial tension previously described, this can be understood in terms of the Gibbs adsorption isotherm: =
! !"

!" !"

(13.3)

which relates the concentration of surfactant molecules adsorbed at the interface and their chemical potential to the interfacial tension. Using the definition of the chemical potential, the equation on the left can be made explicit in terms of the surface coverage. The equation on the right directly says that if the surface coverage is positive, then the interfacial tension is reduced. Adsorbing surfactants therefore reduces the surface tension and thus the drive towards surface minimization (which is still there though), slowing coalescence down.

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The other mechanisms by which surfactant molecules delay or prevent coalescence are based on the idea of preventing two droplets from entering into contact by inducing repulsive forces between them. These can be of different nature. The simplest case is to use charged surfactants which induce electrostatic repulsion between droplets. Additionally hydration forces can also be used to prevent contact between droplets; in order for two hydrophilic heads to get closer than a certain distance, the water hydration shells around them need to be removed and this has an energy cost which results into en effective repulsive force. Another very common way to achieve stabilization is through steric interactions; when two layers of surfactant molecules get close to each other, the presence of the other molecules restricts their mobility and their configurational freedom, leading to a reduction of the entropy and thus again to an effective repulsive interaction.

Figure 13-11Schematics of the different stabilization mechanisms for surfactants on the surface of emulsion droplets.

13.3.2 Colloidal Particles Free-energy reduction can also drive the interfacial adsorption of objects that are not amphiphilic in nature. A clear example is given by solid micro- and nanoparticles. At the beginning of the 1900s Ramsden and Pickering observed that oil-water emulsions prepared in the presence of fine powders did not show any de-emulsification and were stable indefinitely.

Figure 0-12. Extract from Pickerings paper in 1906 describing particle-stabilized emulsions.

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Experimental observations showed that droplets in those emulsions were coated by a layer of particles and were therefore termed particle-stabilized emulsions or Pickering emulsions. The extraordinary stability of Pickering emulsions derives from the fact that colloidal particles adsorbed at the liquid interface have very large binding energies, which means that in order for coalescence to occur, they (or some of them) would have to be expelled from the interface, which has a huge energy cost. These arguments can be quantified as follows.

Figure 13-13. Schematics of the free-energy calculations for the adsorption of a spherical colloidal particle at a liquid-liquid interface.

To calculate the free energy difference caused by the adsorption of a spherical micro- or nanoparticle at a liquid interface, we have to consider the free energy of the particle+interface system before and after the adsorption. Starting from a particle dispersed in water, prior to adsorption the interfacial free energy of the system is given by the sum of the energies of the oil-water interface, obtained by multiplying the area of the interface Aow by its interfacial tension ow, and the energy of the particle-water interface, given by pw Apw. After the particle adsorbs at the interface and partly protrudes in the oil, two additional contributions have to be considered: the newly created particle-oil interface of energy po Apo and the contribution stemming from the fact that an area equal to the particle cross-section Ai has been removed from the oil-water interface, which has then an energy contribution of ow Ai. We can then write the full expression for the free energy difference as: F = F1 F0 = pwApw + poApo + owAow owAi pwApw owAow (13.4) The definition of contact angle introduced before for a solid surface can be extended to a solid particle at the liquid-liquid interface. Again the contact angle is defined using Youngs equation where the equilibrium between the interfacial tensions of the three phases determines the equilibrium position of the particle relative to the interface. If the contact angle is lower than 90, the particle is mostly immersed in the water and it is therefore called hydrophilic. If instead

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the contact angle is larger than 90, most of the particle surface is exposed to the oil, and thus the particle is termed hydrophobic. For =90, the particle sits in the middle and it is neutrally wetting. By exploiting the geometrical relations reported in Figure 13.13 between the particle area, the immersion depth h, and the contact angle, the free energy balance in Equation 13.4 can be rewritten as: F = ow r2(1 |cos|)2 (13.5) From this equation we can make three main observations: the free energy difference is always negative for any value of the contact angle. This means that it is always favorable to adsorb a particle at a liquid interface, as the free energy is always reduced. This is true under the conditions that a contact angle can be defined, and thus that | po - pw | ow, following Youngs equation. If this condition is not verified, then it is not energetically favorable for a particle to adsorb at the interface. the free energy of adsorption depends on the square of the particle size. This implies that by increasing the dimensions of the objects adsorbed at the interface, the adsorption energy grows very rapidly. the free energy of adsorption depends on the contact angle, and in particular it vanishes for contact angles approaching 0 and 180, while it is maximized when =90. This is directly related to the fact that for neutrally-wetting conditions, the cross section of the particle at the interface is maximized (see Figure 13.14). The particle contact angle depends on the surface properties and on the two liquid phases. Equation 13.5 indicates that the mechanism driving the adsorption of particles at liquid interfaces is the reduction of the interfacial area between the two fluids. We note that this is the same mechanism that drives emulsion coalescence. If we calculate the typical values of the adsorption free energies for oil-water interfaces and nanoparticles, we can understand why Pickering emulsions are so stable. In fact, taking neutrally wetting silica nanoparticles of 10nm radius at the water-toluene interface (ow = 36 mN/m) we obtain that F -2700 kBT. This means that the energy which traps a 10nm radius particle at the interface greatly exceeds thermal energy and therefore such particle will practically never spontaneously leave the interface. Such energies also increase rapidly if larger particles are used. Therefore, if two particle-stabilized droplets are to coalesce, given that the overall surface has to decrease, then some of the particles have to spontaneously leave the interface, which we have just said is energetically extremely unfavorable. This means that even if the thermodynamic equilibrium situation is the one where the two fluids are de-mixed and the particles are dispersed in one liquid (to minimize interfacial area), the system is kinetically trapped in a situation where spontaneous thermal fluctuations are unable promote particle desorption and thus droplet coalescence. Therefore this is a different kind of stability which is linked the free energy of particle adsorption.

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Figure 13-14. Left: Trapping energy of a 10 nm silica particle at the water-toluene interface as a function of the particle contact angle. Figure from B. P. Binks, and S. O. Lumsdon, Langmuir, 2000, 16 (23), 8622-8631. Right: examples of particle-stabilized emulsions. Images from F.J. Rossier-Miranda et al. , Colloids Surf. A. 2009, 343(1 3), 4349.

The concepts described above for emulsions apply similarly to the case of particle-stabilized gas bubbles in a liquid or to the reversed case of liquid droplets in a gas, often called liquid marbles.

Figure 13-15Left images: examples of particle-stabilized air bubbles in water. Image from U.T. Gonzenbach et al. Angew Chem Int Ed, 2006, 45, 35263530. Right image: liquid marble. A droplet of water is coated by microparticles and stays intact in ambient conditions. Photo from Kim SH et al., Angew.Chem.Int.Ed. 2010, 49, 2535 2538.

The case of foams, can instead be different depending on whether the interface of each bubble is coated by one particle layer, or if particles bridge through the liquid film and are thus meeting two liquid-gas interfaces. In the former case, the stability analysis is analogous to the one for emulsions, while in the latter it presents some differences. In fact, as shown in Figure 13.16 c-d, the condition of =90 for a particle bridging the liquid film corresponds to the rupture of the film itself and therefore to foam coarsening. The optimum angle which maximizes the stability
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of the interface and of the liquid film is therefore at an intermediate value, i.e. around 70 for monodisperse spherical particles.

Figure 13-16. a) Schematic representation of a foam where each liquid interface is stabilized by a particle monolayer, i.e. the liquid film is stabilized by a particle double layer. Image from A. Stocco et al., Physical Chemistry Chemical Physics (2010). b) Schematics of a foam where the particles bridge through the liquid film into two gas bubbles. Image from Prof. Denkov. University of Sofia. c) Geometrical representation of particles stabilizing a liquid film between two gas bubbles and d) corresponding stability curve as a function of particle contact angle. Graphs from Kaptay G. Colloid Surf A, 200, 282, 387-401.

13.3.3 Proteins In biological systems or in food stuff applications, very often interfaces are coated and stabilized by protein layers. Most proteins are amphiphilic macromolecules with dimensions in the few nanometers range, therefore their adsorption at interfaces is similar to both surfactants and solid particles. In addition to those other systems, proteins also have the possibility to change their conformation (denature) when adsorbed at an interface, which often leads to aggregation within the interface and to the formation of solid film. Therefore foams and emulsions coated by protein layers can also benefit from the mechanical stabilization provided by such films.

13.3.4 Examples and Applications - Beer Froth As previously mentioned, many food products present particle-stabilized interfaces. A very clear example is the froth found on the top of a beer glass (also known as head). The froth in a beer head is different from the foam produced by soap solutions. The latter is stabilized by adsorption of surfactant molecules and very often by electrostatic repulsion between neighboring bubbles through the formation of charged monolayers at the interfaces which prevent liquid film drainage or rupture (see Figure 13.11 and the left side of Figure 13.17). Beer froth is instead stabilized by the adsorption of proteins at the gas-liquid interface. In particular a uniform coverage of the interface is important for foam stabilization and it is achieved by the so called Gibbs-Marangoni effect. This mechanism determines a net flow of proteins from regions of low surface tension, to regions of high surface tension within the interface. Recalling that

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high coverage corresponds to low surface tension (see Equation 13.3), this means that proteins will be transported to areas of high concentration towards areas of low concentrations, providing uniform coverage and self-healing of the protein film upon rupture or formation of new interfacial areas. Gibbs-Marangoni flows are extremely sensitive to local values of the surface tension. This is the reason behind the fact that beer glasses need to be very clean for the head to be stable. In fact any addition of other surface-active molecules, such as soap or grease (even from fingertips!) disrupts the Gibbs-Marangoni flow and prevents the formation of a stable protein film. Beers with higher protein contents (e.g. Weizenbier) are able to stabilize denser heads with smaller bubbles.

13-17 Different stabilization mechanisms for soap foams (left) and beer froth (right). In the right case, GibbsMarangoni flow, represented by the arrows, drives the formation of a uniform interfacial protein film. From Physics Today, May 2010, 62.

- Mineral flotation A very old and successful application of particle trapping at liquid interfaces is the so called mineral flotation or froth flotation. In this process, metal-containing minerals are ground into fine powders and then mixed with water into dense slurries. Afterwards, air is bubbled through the slurry and the more hydrophobic species in the slurry are captured by the liquid-gas interface, rising through the slurry and forming a dense froth on top, which can be later removed to collect the refined product (typically metal sulfides). In some cases some surfactants are added in the process to coat the mineral particles and render them more hydrophobic, increasing the efficiency of the separation process. A similar method can be used in waste water treatments, to separate hydrophobic contaminants (e.g. oils) though interfacial capturing.

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13-18Example of the mineral flotation process.

13.4 Additional resources:

For additional reading you can refer to these two books: - for a general introduction to the physics of interfaces: Hans-Jrgen Butt, Karlheinz Graf, Michael Klapp, Physics and Chemistry of Interfaces, 2003, WILEY-VCH, Weinheim - for more details on particles at interfaces: Colloidal Particles at Liquid Interfaces, Edited by Bernard P. Binks and Tommy S. Horozov, Cambridge University Press, 2006, Cambridge

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