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Leandra Boucheron
Shpyrko Research Group
July 19, 2012
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Outline
Introduction
How and Why do Coffee Rings Form?
Manipulating Coffee Rings
Reversing the Effect
Particle Shape and Size
Other Factors
Conclusion
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Coffee Ring Effect
What is the coffee ring effect?
Why do we care?
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The Two Sides of the Fence Minimize the effect Enhance the effect
Majumder, M., et al,, “Overcoming the ‘Coffee-Stain’ Effect by Compositional Marangoni-Flow-Assisted Drop-Drying.,” J. Phys. Chem. B, 116 (2012).
What causes the effect, and how can we manipulate it?
Magdassi, S., et al, “Ring Stain Effect at Room Temperature in Silver Nanoparticles Yields High Electrical Conductivity,” Langmuir 21 (2005).
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Formation of Coffee Rings
Why do they form?
What is required?
Contact angle
Pinning
Evaporation
Deegan, R.D., et al., “Capillary flow as the cause of ring stains from dried liquid drops”, Nature 389 (1997).
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Coffee Rings are a Geometrical Effect
Deegan, R.D., et al., “Contact line deposits in an evaporating drop,” Phys. Rev. E 62 (2000).
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What Causes the Pinning?
Surface Irregularities
Deposited Particles
Self-Pinning
Deegan, R.D., et al., “Pattern formation in drying drops,” Phys. Rev. E 61 (2000). Magdassi, S., et al, “Ring Stain Effect at Room Temperature in Silver Nanoparticles Yields High Electrical Conductivity,” Langmuir 21 (2005).
Water Droplet Radius as a Function of Time on an Atomically Flat Mica Surface
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Droplet Size Criteria
Shen, X., et al., “Minimal Size of Coffee Ring Structure,” J. Phys. Chem. B, 114 (2010).
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Reversing the Effect
Hu, H. and R.G. Larson, “Marangoni Effect Reverses Coffee-Ring Depositions”, J. Phys. Chem. B 110 (2006).
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Marangoni Effect
Hu, H. and R.G. Larson, “Marangoni Effect Reverses Coffee-Ring Depositions”, J. Phys. Chem. B 110 (2006). Wikimedia Commons
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Recirculatory Flows
Myspace.com
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What’s so different about water?
theory experiment
“The case of water is a long lasting story.”
Surface contaminants affect water surface tension
Savino, R., et al, “Buoyancy and Marangoni Effects in an Evaporating Drop,” J. Thermophys. Heat Transfer 16 (2002). Majumder, M., et al,, “Overcoming the ‘Coffee-Stain’ Effect by Compositional Marangoni-Flow-Assisted Drop-Drying.,” J. Phys. Chem. B, 116 (2012). Poulard, C., et al, “Diffusion-driven evaporation of sessile drops,” J. Phys.: Condens. Matter, 17 (2005).
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What is required?
Contact angle
Pinning
Evaporation
Minimum Droplet Size
Suppression of Marangoni Effect
How do particles arrange within the ring itself?
And Back to Coffee Ring Formation…
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Order-to-Disorder Transition
Marín, A.G., et al., “Order-to-Disorder Transition in Ring-Shaped Colloidal Stains”, PRL 107 (2011).
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The Rush-Hour or Tetris Analogy
Marín, A.G., et al., “Order-to-Disorder Transition in Ring-Shaped Colloidal Stains”, PRL 107 (2011).
ConsttutA )()(
Radial Particle Velocity as a Function of Evaporation Time
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This isn’t quite the whole story…
Confinement
Voronoi Areas
Marín, A.G., et al., “Order-to-Disorder Transition in Ring-Shaped Colloidal Stains”, PRL 107 (2011). Pieranski, P., et al, “Thin Colloidal Crystals,” PRL 50 (1983).
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Confinement Effects
Munich-touristik.com
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So how can we manipulate coffee rings?
Weon, B.M., and J.H. Je, “Capillary force repels coffee ring effect”, Phys Rev E 82, (2010).
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Geometric Constraints
Weon, B.M., and J.H. Je, “Capillary force repels coffee ring effect”, Phys Rev E 82, (2010).
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Health Care Application
Wong, T.S., et al., “Nanochromatography Driven by the Coffee Ring Effect”, Analytical Chemistry 83, (2011).
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What about the shape of the particles?
Yunker, P.J., et al, “Suppression of the coffee-ring effect by shape-dependent capillary interactions”, Nature 476,(2011).
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…or is it the shape?
+ surfactant
Yunker, P.J., et al, “Suppression of the coffee-ring effect by shape-dependent capillary interactions”, Nature 476,(2011).
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What’s actually going on here?
Yunker, P.J., et al, “Suppression of the coffee-ring effect by shape-dependent capillary interactions”, Nature 476,(2011). Park, B.J., and E.M. Furst, “Attractive interactions between colloids at the oil-water interface,” Soft Matter 7 (2011). Vella, D., and L. Mahadevan, “The ‘Cheerios effect’,” Am. J. Phys. 73 (2005).
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Non-Homogeneous Size/Shape Distribution
Yunker, P.J., et al, “Suppression of the coffee-ring effect by shape-dependent capillary interactions”, Nature 476,(2011).
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Substrate Composition
Dou, R., and B. Derby, “Formation of Coffee Stains on Porous Surfaces,” Langmuir 28,(2012).
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Temperature Control
Soltman, D., and V. Subramanian, “Inkjet-Printed Line Morphologies and Temperature Control of the Coffee Ring Effect,” Langmuir 24,(2008).
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Electrowetting
Eral, H.B., et al, “Suppressing the coffee stain effect: how to control colloidal self-assembly in evaporating drops using electrowetting,” Soft Matter 7,(2011).
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Conclusion Surface tension
Surfactants
Particle size
Particle shape
Solvent
Evaporation rate
Applied electric field
Temperature
Substrate Porosity
pH
Others?
Quantitative Predictive Model?
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Backup Slides
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pH Control
Bhardwaj, R., et al, “Self-Assembly of Colloidal Particles from Evaporating Droplets: Role of DLVO Interactions and Proposition of a Phase Diagram,” Langmuir 26,(2010).
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Silver Nanoparticle Rings
Magdassi, S., et al, “Ring Stain Effect at Room Temperature in Silver Nanoparticles Yields High Electrical Conductivity,” Langmuir 21 (2005).
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Marangoni-Flow-Assisted Drop-Drying
Majumder, M., et al,, “Overcoming the ‘Coffee-Stain’ Effect by Compositional Marangoni-Flow-Assisted Drop-Drying.,” J. Phys. Chem. B, 116 (2012).
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Evaporative Flux
2
10
22
2
J(r)
c
c
c
rR
Deegan, R.D., et al., “Capillary flow as the cause of ring stains from dried liquid drops”, Nature 389 (1997).
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Evaporation Profiles
Deegan, R.D., et al., “Contact line deposits in an evaporating drop,” Phys. Rev. E 62 (2000).
Normal Evaporation
Surrounded by bath of water, water level at base of droplet
Inside chamber with small hole above droplet center
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Minimal Droplet Size
Shen, X., et al., “Minimal Size of Coffee Ring Structure,” J. Phys. Chem. B, 114 (2010).
2
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particle
RC
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Substrate Porosity
Dou, R., and B. Derby, “Formation of Coffee Stains on Porous Surfaces,” Langmuir 28,(2012).
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The Cheerios Effect
Vella, D., and L. Mahadevan, “The ‘Cheerios effect’,” Am. J. Phys. 73 (2005).