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Gibbs-Thomson effects November 2014

Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

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Page 1: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Gibbs-Thomson effects

November 2014

Page 2: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Gibbs-Thomson effects

Small crystals melt at a lower temperature, which is the reason why ice cream gets crunchier with time.

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Page 3: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Melting of metal nanoparticles

Thermochimica Acta 463 (2007) 32–40 Phys. Rev. A 13, 2287–2298 (1976)

Au Al

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Page 4: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

A related but simpler problem

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Page 5: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Gibbs-Thomson

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Page 6: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Gibbs, Thomson and Thomson

Josiah Willard Gibbs 1839-1903

Chemical potential

(1st PhD in Eng. in the US)

Joseph John « J.J. » Thomson 1856-1940

One of the fathers of

atomic physics (discoverer of the electron)

William Thomson (1st baron Kelvin) 1824-1907

The Joules-Thomson effect

etc. etc. etc. 6

Page 7: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Lamellar crystals in polymers

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Page 8: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Gibbs-Thomson for lamellar crystals

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Page 9: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Melting in nanopores

J. Chem. Phys. 93, 9002 (1990); The melting behavior of organic materials confined in

porous solids 9

Page 10: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

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Page 11: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

As an exercise…

11 Appl. Phys. Lett. 85, 5337 (2004)

Derive the Gibbs-Thomson relation in the case of a cylindrical nanowire

Page 12: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Liquid-vapor equilibria

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William Thomson (1st baron Kelvin) 1824-1907

Page 13: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

What if there is no wetting layer?

A small and a large droplets lie on a fiber.

How does the system evolve?

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Page 14: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940
Page 15: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Ostwald ripening of metal nanoparticles: case of Ni in presence of CO

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Page 16: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

16 Supported catalysts with monodispersed particles are more stable in time

Page 17: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Effect of size on solubility

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Page 18: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Stress generationby salt crystallization

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Laplace pressure 2γ/R

Laplace pressure γ/R + compressive stress σr

Page 19: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

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Wheathering by salt crystallization

Page 20: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Honeycomb weathering (tafoni)

20 http://en.wikipedia.org/wiki/Weathering#Salt-crystal_growth

The mechanism is still unclear…

Page 21: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Capillary condensation in nanopores: Kelvin’s equation with a negative curvature

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Surface phenomena

Pore-filling phenomena

Chemical potential

Page 22: Gibbs-Thomson effects - ULiege · Gibbs, Thomson and Thomson Josiah Willard Gibbs 1839-1903 Chemical potential (1st PhD in Eng. in the US) Joseph John « J.J. » Thomson 1856-1940

Adsorption and desorption

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Adsorption

Desorption

Richard Adolf Zsigmondy 1865-1929

Nobel Prize in Chemistry 1925