In physics, a "coffee ring" is a pattern left by a puddle of particle-laden liquid after it evaporates. The phenomenon is named for the characteristic ring-like deposit along the perimeter of a spill of coffee. It is also commonly seen after spilling red wine. The mechanism behind the formation of these and similar rings is known as the coffee ring effect or in some instances, the coffee stain effect, or simply ring stain.
The coffee-ring pattern originates from the capillary flow induced by the evaporation of the drop: liquid evaporating from the edge is replenished by liquid from the interior. [1] The resulting current can carry nearly all the dispersed material to the edge. As a function of time, this process exhibits a "rush-hour" effect, that is, a rapid acceleration of the flow towards the edge at the final stage of the drying process. [2]
Evaporation induces a Marangoni flow inside a droplet. The flow, if strong, redistributes particles back to the center of the droplet. Thus, for particles to accumulate at the edges, the liquid must have a weak Marangoni flow, or something must occur to disrupt the flow. [3] For example, surfactants can be added to reduce the liquid's surface tension gradient, disrupting the induced flow. Water has a weak Marangoni flow to begin with, which is then reduced significantly by natural surfactants. [4]
Interaction of the particles suspended in a droplet with the free surface of the droplet is important in creating a coffee ring. [5] "When the drop evaporates, the free surface collapses and traps the suspended particles ... eventually all the particles are captured by the free surface and stay there for the rest of their trip towards the edge of the drop." [6] This result means that surfactants can be used to manipulate the motion of the solute particles by changing the surface tension of the drop, rather than trying to control the bulk flow inside the drop. A number of interesting morphologies of the deposited particles can result. For example, an enantiopure poly (isocyanate) derivative has been shown to form ordered arrays of squashed donut structures. [7]
The coffee-ring pattern is detrimental when uniform application of a dried deposit is required, such as in printed electronics. It can be suppressed by adding elongated particles, such as cellulose fibers, to the spherical particles that cause the coffee-ring effect. The size and weight fraction of added particles may be smaller than those of the primary ones. [2]
It is also reported that controlling flow inside a droplet is a powerful way to generate a uniform film; for example, by harnessing solutal Marangoni flows occurring during evaporation. [8]
Mixtures of low boiling point and high boiling point solvents were shown to suppress the coffee ring effect, changing the shape of a deposited solute from a ring-like to a dot-like shape. [9]
Control of the substrate temperature was shown to be an effective way to suppress the coffee ring formed by droplets of water-based PEDOT:PSS solution. [10] On a heated hydrophilic or hydrophobic substrate, a thinner ring with an inner deposit forms, which is attributed to Marangoni convection. [11]
Control of the substrate wetting properties on slippery surfaces can prevent the pinning of the drop contact line, which will, therefore, suppress the coffee ring effect by reducing the number of particles deposited at the contact line. Drops on superhydrophobic or liquid impregnated surfaces are less likely to have a pinned contact line and will suppress ring formation. [12] Drops with an oil ring formed at the drop contact line have high mobility and can avoid the ring formation on hydrophobic surfaces. [13]
Alternating voltage electrowetting may suppress coffee stains without the need to add surface-active materials. [14] Reverse particle motion may also reduce the coffee-ring effect because of the capillary force near the contact line. [15] The reversal takes place when the capillary force prevails over the outward coffee-ring flow by the geometric constraints.
The lower-limit size of a coffee ring depends on the time scale competition between the liquid evaporation and the movement of suspended particles. [16] When the liquid evaporates much faster than the particle movement near a three-phase contact line, coffee ring cannot be formed successfully. Instead, these particles will disperse uniformly on a surface upon complete liquid evaporation. For suspended particles of size 100 nm, the minimum diameter of the coffee ring structure is found to be 10 μm, or about 10 times smaller than the width of human hair. The shape of particles in the liquid is responsible for coffee ring effect. [17] [18] On porous substrates, the competition among infiltration, particle motion and evaporation of the solvent governs the final deposition morphology. [19]
The pH of the solution of the drop influences the final deposit pattern. [20] The transition between these patterns is explained by considering how DLVO interactions such as the electrostatic and Van der Waals forces modify the particle deposition process.
The coffee ring effect is utilized in convective deposition by researchers wanting to order particles on a substrate using capillary-driven assembly, replacing a stationary droplet with an advancing meniscus drawn across the substrate. [21] [22] [23] This process differs from dip-coating in that evaporation drives flow along the substrate as opposed to gravity.
Convective deposition can control particle orientation, resulting in the formation of crystalline monolayer films from nonspherical particles such as hemispherical, [24] dimer, [25] and dumbbell [26] shaped particles. Orientation is afforded by the system trying to reach a state of maximum packing of the particles in the thin meniscus layer over which evaporation occurs. They showed that tuning the volume fraction of particles in solution will control the specific location along the varying meniscus thickness at which assembly occurs. Particles will align with their long axis in- or out-of-plane depending on whether or not their longer dimension of the particle was equal to the thickness of the wetting layer at the meniscus location. [26] Such thickness transitions were established with spherical particles as well. [27] It was later shown that convective assembly could control particle orientation in assembling multi-layers, resulting in long-range 3D colloidal crystals from dumbbell shaped particles. [28] These finds were attractive for the self-assembled of colloidal crystal films for applications such as photonics. [28] Recent advances have increased the application of coffee-ring assembly from colloidal particles to organized patterns of inorganic crystals. [12]
In chemistry, hydrophobicity is the physical property of a molecule that is seemingly repelled from a mass of water. In contrast, hydrophiles are attracted to water.
The Leidenfrost effect is a physical phenomenon in which a liquid, close to a surface that is significantly hotter than the liquid's boiling point, produces an insulating vapor layer that keeps the liquid from boiling rapidly. Because of this repulsive force, a droplet hovers over the surface, rather than making physical contact with it. The effect is named after the German doctor Johann Gottlob Leidenfrost, who described it in A Tract About Some Qualities of Common Water.
An ion source is a device that creates atomic and molecular ions. Ion sources are used to form ions for mass spectrometers, optical emission spectrometers, particle accelerators, ion implanters and ion engines.
Self-assembly is a process in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. When the constitutive components are molecules, the process is termed molecular self-assembly.
Electrospray ionization (ESI) is a technique used in mass spectrometry to produce ions using an electrospray in which a high voltage is applied to a liquid to create an aerosol. It is especially useful in producing ions from macromolecules because it overcomes the propensity of these molecules to fragment when ionized. ESI is different from other ionization processes since it may produce multiple-charged ions, effectively extending the mass range of the analyser to accommodate the kDa-MDa orders of magnitude observed in proteins and their associated polypeptide fragments.
A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films is a fundamental step in many applications. A familiar example is the household mirror, which typically has a thin metal coating on the back of a sheet of glass to form a reflective interface. The process of silvering was once commonly used to produce mirrors, while more recently the metal layer is deposited using techniques such as sputtering. Advances in thin film deposition techniques during the 20th century have enabled a wide range of technological breakthroughs in areas such as magnetic recording media, electronic semiconductor devices, integrated passive devices, LEDs, optical coatings, hard coatings on cutting tools, and for both energy generation and storage. It is also being applied to pharmaceuticals, via thin-film drug delivery. A stack of thin films is called a multilayer.
The Marangoni effect is the mass transfer along an interface between two phases due to a gradient of the surface tension. In the case of temperature dependence, this phenomenon may be called thermo-capillary convection.
The name electrospray is used for an apparatus that employs electricity to disperse a liquid or for the fine aerosol resulting from this process. High voltage is applied to a liquid supplied through an emitter. Ideally the liquid reaching the emitter tip forms a Taylor cone, which emits a liquid jet through its apex. Varicose waves on the surface of the jet lead to the formation of small and highly charged liquid droplets, which are radially dispersed due to Coulomb repulsion.
The phenomenon called tears of wine is manifested as a ring of clear liquid, near the top of a glass of wine, from which droplets continuously form and drop back into the wine. It is most readily observed in a wine which has a high alcohol content. It is also referred to as wine legs, fingers, curtains, church windows, or feet.
In chemistry and materials science, ultrahydrophobic surfaces are highly hydrophobic, i.e., extremely difficult to wet. The contact angles of a water droplet on an ultrahydrophobic material exceed 150°. This is also referred to as the lotus effect, after the superhydrophobic leaves of the lotus plant. A droplet striking these kinds of surfaces can fully rebound like an elastic ball. Interactions of bouncing drops can be further reduced using special superhydrophobic surfaces that promote symmetry breaking, pancake bouncing or waterbowl bouncing.
Janus particles are special types of nanoparticles or microparticles whose surfaces have two or more distinct physical properties. This unique surface of Janus particles allows two different types of chemistry to occur on the same particle. The simplest case of a Janus particle is achieved by dividing the particle into two distinct parts, each of them either made of a different material, or bearing different functional groups. For example, a Janus particle may have one-half of its surface composed of hydrophilic groups and the other half hydrophobic groups, the particles might have two surfaces of different color, fluorescence, or magnetic properties. This gives these particles unique properties related to their asymmetric structure and/or functionalization.
Particle deposition is the spontaneous attachment of particles to surfaces. The particles in question are normally colloidal particles, while the surfaces involved may be planar, curved, or may represent particles much larger in size than the depositing ones. Deposition processes may be triggered by appropriate hydrodynamic flow conditions and favorable particle-surface interactions. Depositing particles may just form a monolayer which further inhibits additional particle deposition, and thereby one refers to surface blocking. Initially attached particles may also serve as seeds for further particle deposition, which leads to the formation of thicker particle deposits, and this process is termed as surface ripening or fouling. While deposition processes are normally irreversible, initially deposited particles may also detach. The latter process is known as particle release and is often triggered by the addition of appropriate chemicals or a modification in flow conditions.
Edward Bormashenko is a professor of Materials Science and the Head of the Laboratory of Interface Science of the Ariel University in Israel. He was born in 1962 in Kharkiv, Ukraine and lives in Israel since 1997. He studied in the V. N. Karazin Kharkiv National University. His research is in the polymer science and surface science. He accomplished his PhD in Moscow Institute of Plastics in 1990.
Nanosphere lithography (NSL) is an economical technique for generating single-layer hexagonally close packed or similar patterns of nanoscale features. Generally, NSL applies planar ordered arrays of nanometer-sized latex or silica spheres as lithography masks to fabricate nanoparticle arrays. NSL uses self-assembled monolayers of spheres as evaporation masks. These spheres can be deposited using multiple methods including Langmuir-Blodgett, Dip Coating, Spin Coating, solvent evaporation, force-assembly, and air-water interface. This method has been used to fabricate arrays of various nanopatterns, including gold nanodots with precisely controlled spacings.
Self-cleaning surfaces are a class of materials with the inherent ability to remove any debris or bacteria from their surfaces in a variety of ways. The self-cleaning functionality of these surfaces are commonly inspired by natural phenomena observed in lotus leaves, gecko feet, and water striders to name a few. The majority of self-cleaning surfaces can be placed into three categories:
Droplet-based microfluidics manipulate discrete volumes of fluids in immiscible phases with low Reynolds number and laminar flow regimes. Interest in droplet-based microfluidics systems has been growing substantially in past decades. Microdroplets offer the feasibility of handling miniature volumes of fluids conveniently, provide better mixing, encapsulation, sorting, sensing and are suitable for high throughput experiments. Two immiscible phases used for the droplet based systems are referred to as the continuous phase and dispersed phase.
Nanoparticle deposition refers to the process of attaching nanoparticles to solid surfaces called substrates to create coatings of nanoparticles. The coatings can have a monolayer or a multilayer and organized or unorganized structure based on the coating method used. Nanoparticles are typically difficult to deposit due to their physical properties.
Liquid marbles are non-stick droplets wrapped by micro- or nano-metrically scaled hydrophobic, colloidal particles ; representing a platform for a diversity of chemical and biological applications. Liquid marbles are also found naturally; aphids convert honeydew droplets into marbles. A variety of non-organic and organic liquids may be converted into liquid marbles. Liquid marbles demonstrate elastic properties and do not coalesce when bounced or pressed lightly. Liquid marbles demonstrate a potential as micro-reactors, micro-containers for growing micro-organisms and cells, micro-fluidics devices, and have even been used in unconventional computing. Liquid marbles remain stable on solid and liquid surfaces. Statics and dynamics of rolling and bouncing of liquid marbles were reported. Liquid marbles coated with poly-disperse and mono-disperse particles have been reported. Liquid marbles are not hermetically coated by solid particles but connected to the gaseous phase. Kinetics of the evaporation of liquid marbles has been investigated.
Droplet cluster is a self-assembled levitating monolayer of microdroplets usually arranged into a hexagonally ordered structure over a locally heated thin layer of water. The droplet cluster is typologically similar to colloidal crystals. The phenomenon was observed for the first time in 2004, and it has been extensively studied after that.
Self-propulsion is the autonomous displacement of nano-, micro- and macroscopic natural and artificial objects, containing their own means of motion. Self-propulsion is driven mainly by interfacial phenomena. Various mechanisms of self-propelling have been introduced and investigated, which exploited phoretic effects, gradient surfaces, breaking the wetting symmetry of a droplet on a surface, the Leidenfrost effect, the self-generated hydrodynamic and chemical fields originating from the geometrical confinements, and soluto- and thermo-capillary Marangoni flows. Self-propelled system demonstrate a potential as micro-fluidics devices and micro-mixers. Self-propelled liquid marbles have been demonstrated.
