Marangoni

Coffee Rings: Cultivating a healthy respect for bacteria

coffee ring, ink jet printing, organic electronics

Why does it form a ring?

It is twenty years since Sidney Nagel and colleagues at the University of Chicago started to work on the “Coffee Ring” problem. When spilled coffee dries, it forms rings rather than blobs of dried coffee. Why does it do that? Why doesn’t it just form into a homogeneous mass of brown dried coffee? Surely someone knew the answer to these questions?

Well, it turns out that until 1997 no one had asked these questions. Did we all assume that someone somewhere knew? A bit like those ubiquitous white mists that form on hot drinks, surely someone knew what they were? (They didn’t, the paper looking at those only came out two years ago and is here). Unlike the white mists though, coffee rings are of enormous technological importance. Many of our electronic devices are now printed with electrically conducting ink. As anyone who still writes with a fountain pen may be aware, it is not just coffee that forms ‘coffee rings’. Ink too can form rings as it dries. This is true whether the ink is from a pen or a specially made electrically conducting ink. We need to know how coffee rings form so that we can know how to stop them forming when we print our latest gadgets. This probably helps to explain why Nagel’s paper suggesting a mechanism for coffee ring formation has been cited thousands (>2000) of times since it was published.

More information on the formation of coffee rings (and some experiments that you can do with them on your work top) can be found here. Instead, for today’s Daily Grind, I’d like to focus on how to avoid the coffee ring effect and the fact that bacteria beat us to it. By many years.

There is a bacteria called Pseudomonas aeruginosa (P. aeruginosa for short) that has been subverting the coffee ring effect in order to survive. Although P. aeruginosa is fairly harmless for healthy individuals, it can affect people with compromised immune systems (such as some patients in hospitals). Often water borne, if P. aeruginosa had not found a way around the coffee ring effect, as the water hosting it dried, it would, like the coffee, be forced into a ring on the edge of the drop. Instead, drying water droplets that contain P. aeruginosa deposit the bacteria uniformly across the drop’s footprint, maximising the bacteria’s survival and, unfortunately for us, infection potential.

The bacteria can do this because they produce a surfactant that they inject into the water surrounding them. A surfactant is any substance that reduces the surface tension of a liquid. Soap is a surfactant and can be used to illustrate what the bacteria are doing (but with coffee). At the core of the bacteria’s survival mechanism is something called the Marangoni effect. This is the liquid flow that is caused by a gradient in surface tension; there is a flow of water from a region of lower surface tension to a region of higher surface tension. If we float a coffee bean on a dish of water and then drop some soap behind it, the bean accelerates away from the dripped drop (see video). The soap lowers the surface tension in the area around it causing a flow of water (that carries the bean) away from the soap drop.

If now you can imagine thousands of bacteria in a liquid drop ejecting tiny amounts of surfactant into the drop, you can hopefully see in your mind’s eye that the water flow in the drying droplet is going to get quite turbulent. Lots of little eddies will form as the water flows from areas of high surface tension to areas of low surface tension. These eddies will carry the bacteria with them counteracting the more linear flow from the top of the droplet to the edges (caused by the evaporation of the droplet) that drives the normal coffee ring formation. Consequently, rather than get carried to the edge of the drop, the bacteria are constantly moved around it and so when the drop finally dries, they will be more uniformly spread over the circle of the drop’s footprint.

Incidentally, the addition of a surfactant is one way that electronics can now be printed so as to avoid coffee ring staining effects. However, it is amusing and somewhat thought provoking to consider that the experimentalist bacteria had discovered this long before us.

Levitating water

V60 from Leyas

Time to look more closely at the surface of your black coffee.

Have you ever sat watching the steam that forms above a hot Americano? Beneath the swirling steam clouds you can occasionally see patterns of a white mist that seem to hover just above the dark brew. Bean Thinking is about taking time to notice what occurs in a coffee cup and yet I admit, I had seen these mists and thought that it was something that was just associated with the evaporation of the water and that “someone”, “somewhere” had probably explained it. So it was entirely right that I was recently taken to task (collectively with others who have observed this phenomenon and taken the same attitude) for this assumption by the authors of this paper who wrote “The phenomenon that we studied here can be observed everyday and should have been noticed by many scientists, yet very few people appear to have imagined such fascinating phenomena happening in a teacup.

ineedcoffee.com, espresso grind

The water particles in the white mist are a similar size to the smallest particles in an espresso grind. Photo courtesy of ineedcoffee.com, (CC Attribution, No Derivs). The coin shown is a US nickel of diameter 21.21 mm

The authors of the study show that the white mists (these “fascinating phenomena”) are, in fact, layers of water drops that have a typical diameter of around 10 μm (which is roughly the size of the smallest particles in an espresso grind). Although the white mists exist above tea and even hot water as well as coffee, they are probably easiest to see against the black surface of the Americano.

More surprising than the fairly uniform distribution of water droplet size though is the fact that the authors of this study showed that the droplets were levitating above the coffee. Each water droplet was somehow literally hovering above the surface of the coffee at a height of between 10 – 100 μm (which is, coincidentally, roughly the particle size distribution in an espresso grind).

white mists, slow science

You can (just about) see the white mists over the surface of this cup of tea (which is a still from the video below)

One of the questions that the authors of the paper have not yet managed to answer is what is causing this levitation? Could it be the pressure of the hot coffee evaporating that keeps these particles held aloft? This would explain the observation that the mists form patterns similar to those caused by (heat) convection currents. Alternatively perhaps the droplets are charged and are kept away from the coffee by electrostatic repulsion, an explanation that is suggested by the behaviour of the droplets when near a statically charged object (eg. hair comb, balloon, try it). Perhaps the levitation is caused by the droplets spinning and inducing an air cushion under them? Why not design some experiments and try to find out. It would be great if we can drink hot black coffee in the name of science. Let me know the results of your observations in the comments section below. In the meanwhile, here is a video of the white mists in tea, enjoy your coffee:

You can read the study at: Umeki et al., Scientific Reports, 5, 8046, (2015)