Surface/Interfacial Tension + Surface tension: the contracting force per unit length around the perimeter of a surface if the surface separates {gas from liquid or solid phases. + Interfacial tension refers to the Seco en of mae same contracting force if the Son . surface separates two nongaseous phases, e.g. oil droplet in water : Force aX} Goan PSL Perimeter : Tenth fn + Unit: dynesfom or mN/m Sipe ue, oe (Ul dynefem = I mN/m) ‘twaer on aie Surface/Interfacial Tension + More definitions: — Surface tension isthe reversible work required to create a new area ofa liquid. OF Hato enrs a Unit: energy per unit surface area; ie. ergiem, or milf? + Significance: = Transport of molecules from bulk to surface region, across phase boundaries,especially in micro-scale phenomena — Innature and biological systemsSurface/Interfacial tension + Typical values of a === surface tension for pape | pure liquids: peserwos [a ee + Typical values of [** caugsie [Gala interfacial tension peaterbutanol = + a between water and — frmrsicone EDS] 30 ae another liquids: [estas |= ar fnciolSAA) Fa Surface/Interfacial Tension The surface tension depends on the difference in the packing density of the molecules in the bulk and the interfaci Air Interface Bulk Pure liquid Surfactant solution Yo Y o> Yourfactant ial zoon,Temperature Dependence + Surface tension decreases linearly over a wide range of temperature, i.e. the higher temperature, the lower the surface tension + The coefficient, do/d', is approximately ~0.1 dyne/em-K, + The van der Waals ~ Guggenheim correlation: For apolar organic liquids Te [=] K; ve [=] em*/mol Surface Tension Measurements Du Nuoy Ring Wilhelmy Slide To the balance To the balance mz 4 Measure the force required to Measure the force on a dipping detach a ring from the surface slide against which the contact angle is known, © = conection functionYoung-Laplace equation Young-Laplace equation describes the relation ‘c= Localeuvatrof suice between the pressure drop ) across a curved interface, AP, with the surface/interfacial tension ‘yand the local surface curvature x. Special Cases: 1. Sphere, (R,=R,) 2. Circular eylinder, (R,=») Liquid drop under zero-gravity ‘Spherical drops: = Fora given volume, sphere isthe geometrical form that has the smallest surface rea, ie. minimum energy is required to form, The smaller the surface ara, the smaller amount of energy required, and thus energetically favorable. Forces acting on a zero-gravity (levitating) liquid droplet: Infernal pressure fore of uid Exteral pressure force of gus phase Surface tension forses Sfece ion Force balance: Assume isothermal and mechanical equilibrium Consider symmetry about sphere bl plane ~_Pesform force balance on the hemispherical plane = [ Net pressure foree = surface tension force apres force EE ueLiquid drop under zero-gravity + Force balance (cont'd): Net pressure force ~ surface tension force = Net pressure force Intcmal pressure force ~ external pressure foree Pressure force due t liquid inside drop ~ Pressure force due to fluid (gas oF liguid) outside drop ae D, wR? =P, 2? = AP aR? “wce = Surface tension force = 2 Ry = APaRE=2RRy > + NOTE: Internal pressure of liquid is larger than Netprewurforce force environmental pressure cg. fora lym water droplet in air under atmospheric pressure, AP= 3 atm!!! = When outside pressure decreases, the pressure difference increases, ‘an burst when surface tension cannot hold the liquid iaside any moe, the drop Droplet formation in a liqui + First studied by Lord Rayleigh + Liquid forced through a tube or orifice under frequency perturbation in air. + Cylindrical jet is not ‘ili aby na dod dynamically stable, + Droplet volumes tend to assume spherical shape, but other perturbations are also possible. + Applications: ink-jet and eee es electrospray technology.Emulsions + Emulsions are dispersions of one liquid in another (a two- phase system) stabilized by the presence of strong surfactant adsorption at the fluid interface, even though they are thermodynamically unstable. + Droplets size 0.1-100 mm, * eg. (synthetic) cosmetic, hand cream...ete; (biological) milk ae Soybean dit gst in wate emia Solid-liquid interaction c \ ‘ontact angle 0 gas + A quantitative measure of the qui liquid-solid interaction Classification of wetting behavior: S555 Coio=&»- Wetting out ax 0° <0 < 90°, Wetting a 90° < 0 < 180°, Non-weitingYoung’s equation 1, » gas Horizontal force balance: liquid y\ ® ‘1: liquid-gas interfacial tension, ie., surface tension of liquid 41: Solid-liquid interfacial tension so? Solid-gas interfacial tension 6: contact angle Ys, +71, 0080 =} Ysom th eos = Young’s equation Controls of wetting of liquids on solid surfaces To promote wetting: + Roughen (if 8, < 90°) + Reduce y , with surfactants (¢.g., detergent) + Put adsorbate on solid + Chemically modify solid surface (e.g. plasma treatment) To hinder wetting: + Roughen (if @, > 90°) + Put adsorbate on solid + Chemically modify solid surfacePromote wetting of water on surfaces by chemical modifications Plasma treatment of solid surfaces + Plasma is a gas under moderate vacuum subject to radio frequency waves which disrupt the molecules into free radicals which react chemically with the solid surface. + Oxygen or nitrogen containing plasmas will implant those elements in an otherwise low-energy surface and increase the surface energy. ose = substrate Pvaser ‘untreated poly(dimethylsiloxane) (PDMS) ~105° treated PDMS (right after treatment) oe untreated polystyrene (after 20 min) 16° treated polystyrene 33° Promote wetting of water on surfaces by chemical modifications + Silane coupling agent Y-Si-(OR), +H,O—" = "_, y_si- (OH), +3ROH OH si-Y 1 ° OH + (OH),-Si-Y > Si-y + H,0 1 ° OH Si-Y 1 oO Hydrophilic HydrophobicGeneration of water droplets in oil in microfluidic channels Diameter of the droplet ~ 10 um hydrophobic channel walls Generation of water droplets in oil in microfluidic channels To form droplets at a T-junction: Laplace pressure ~ shear stress o . o- interfacial tension —~né R: the radius of the droplet R rt the viscosity of the continuous &: the shear rate The continuous phase has to wet the channel walls better than the disperse phase does.Electrowetting + Surface tension can be altered by application of electric field Y¥glV) = Ya(O) - e/2d * V2 Applied Voltage nal