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Ostwald ripening

Ostwald ripening in Pd nanoparticles dissolved in


formaldehyde at 6 (a), 24 (b), 48 (c) and 72 hours (d).
The small Pd particles are being consumed as the
larger ones grow bigger.[1]
Play media
Growth of bubbles in a liquid foam via Ostwald
ripening.[2]

Ostwald ripening is an observed


phenomenon in solid solutions or liquid
sols that describes the change of an
inhomogeneous structure over time, i.e.,
small crystals or sol particles dissolve,
and redeposit onto larger crystals or sol
particles.[3]

Dissolution of small crystals or sol


particles and the redeposition of the
dissolved species on the surfaces of
larger crystals or sol particles was first
described by Wilhelm Ostwald in 1896.[4][5]
Ostwald ripening is generally found in
water-in-oil emulsions, while flocculation is
found in oil-in-water emulsions.[6]

Mechanism
This thermodynamically-driven
spontaneous process occurs because
larger particles are more energetically
favored than smaller particles.[7] This
stems from the fact that molecules on the
surface of a particle are energetically less
stable than the ones in the interior.
Cubic crystal structure (sodium chloride)

Consider a cubic crystal of atoms: all the


atoms inside are bonded to 6 neighbors
and are quite stable, but atoms on the
surface are only bonded to 5 neighbors or
fewer, which makes these surface atoms
less stable. Large particles are more
energetically favorable since, continuing
with this example, more atoms are bonded
to 6 neighbors and fewer atoms are at the
unfavorable surface. As the system tries
to lower its overall energy, molecules on
the surface of a small particle
(energetically unfavorable, with only 3 or 4
or 5 bonded neighbors) will tend to detach
from the particle, as per the Kelvin
equation, and diffuse into the solution.
When all small particles do this, it
increases the concentration of free
molecules in solution. When the free
molecules in solution are supersaturated,
the free molecules have a tendency to
condense on the surface of larger
particles.[7] Therefore, all smaller particles
shrink, while larger particles grow, and
overall the average size will increase. As
time tends to infinity, the entire population
of particles becomes one large spherical
particle to minimize the total surface area.

The history of research progress in


quantitatively modeling Ostwald ripening
is long, with many derivations.[8] In 1958,
Lifshitz and Slyozov[9] performed a
mathematical investigation of Ostwald
ripening in the case where diffusion of
material is the slowest process. They
began by stating how a single particle
grows in a solution. This equation
describes where the boundary is between
small, shrinking particles and large,
growing particles. They finally conclude
that the average radius of the particles ⟨R⟩,
grows as follows:

where
=average radius of all the particles
particle surface tension or surface
=
energy
=solubility of the particle material
=molar volume of the particle material
diffusion coefficient of the particle
=
material
=ideal gas constant
=absolute temperature and
=time.

Note that the quantity ⟨R⟩3 is different


from ⟨R3⟩, and only the latter one can be
used to calculate average volume, and that
the statement that ⟨R⟩ goes as t1/3 relies
on ⟨R⟩0 being zero; but because nucleation
is a separate process from growth, this
places ⟨R⟩0 outside the bounds of validity
of the equation. In contexts where the
actual value of ⟨R⟩0 is irrelevant, an
approach that respects the meanings of all
terms is to take the time derivative of the
equation to eliminate ⟨R⟩0 and t. Another
such approach is to change the ⟨R⟩0 to
⟨R⟩i with the initial time i having a positive
value.

Also contained in the Lifshitz and Slyozov


derivation is an equation for the size
distribution function f(R, t) of particles.
For convenience, the radius of particles is
divided by the average radius to form a
new variable, ρ = R(⟨R⟩)−1.

Three years after that Lifshitz and Slyozov


published their findings (in Russian, 1958),
Carl Wagner performed his own
mathematical investigation of Ostwald
ripening,[10] examining both systems
where diffusion was slow and also where
attachment and detachment at the particle
surface was slow. Although his
calculations and approach were different,
Wagner came to the same conclusions as
Lifshitz and Slyozov for slow-diffusion
systems. This duplicate derivation went
unnoticed for years because the two
scientific papers were published on
opposite sides of the Iron Curtain in 1961.
It was not until 1975 that Kahlweit
addressed the fact that the theories were
identical[11] and combined them into the
Lifshitz-Slyozov-Wagner or LSW theory of
Ostwald ripening. Many experiments and
simulations have shown LSW theory to be
robust and accurate. Even some systems
that undergo spinodal decomposition have
been shown to quantitatively obey LSW
theory after initial stages of growth.[12]
Wagner derived that when attachment and
detachment of molecules is slower than
diffusion, then the growth rate becomes

where ks is the reaction rate constant of


attachment with units of length per time.
Since the average radius is usually
something that can be measured in
experiments, it is fairly easy to tell if a
system is obeying the slow-diffusion
equation or the slow-attachment equation.
If the experimental data obeys neither
equation, then it is likely that another
mechanism is taking place and Ostwald
ripening is not occurring.

Although LSW theory and Ostwald ripening


were intended for solids ripening in a fluid,
Ostwald ripening is also observed in liquid-
liquid systems, for example, in an oil-in-
water emulsion polymerization.[6] In this
case, Ostwald ripening causes the
diffusion of monomers (i.e. individual
molecules or atoms) from smaller droplets
to larger droplets due to greater solubility
of the single monomer molecules in the
larger monomer droplets. The rate of this
diffusion process is linked to the solubility
of the monomer in the continuous (water)
phase of the emulsion. This can lead to
the destabilization of emulsions (for
example, by creaming and
sedimentation).[13]

Specific examples

Oil droplets in pastis mixed with water grow by


Ostwald ripening.
An everyday example of Ostwald ripening
is the re-crystallization of water within ice
cream which gives old ice cream a gritty,
crunchy texture. Larger ice crystals grow
at the expense of smaller ones within the
ice cream, creating a coarser texture.[14]

Another gastronomical example is in the


ouzo effect, where the droplets in the
cloudy microemulsion grow by Ostwald
ripening.

In geology, it is the textural coarsening,


aging or growth of phenocrysts and
crystals in solid rock which is below the
solidus temperature. It is often ascribed as
a process in the formation of orthoclase
megacrysts,[15] as an alternative to the
physical processes governing crystal
growth from nucleation and growth rate
thermochemical limitations.

In chemistry, the term refers to the growth


of larger crystals from those of smaller
size which have a higher solubility than the
larger ones. In the process, many small
crystals formed initially slowly disappear,
except for a few that grow larger, at the
expense of the small crystals. The smaller
crystals act as fuel for the growth of
bigger crystals. Limiting Ostwald ripening
is fundamental in modern technology for
the solution synthesis of quantum dots.[16]
Ostwald ripening is also the key process in
the digestion of precipitates, an important
step in gravimetric analysis. The digested
precipitate is generally purer, and easier to
wash and filter.

Ostwald ripening can also occur in


emulsion systems, with molecules
diffusing from small droplets to large ones
through the continuous phase. When a
miniemulsion is desired, an extremely
hydrophobic compound is added to stop
this process from taking place.

See also
Aggregation
Coalescence (chemistry)
Coalescence (physics)
Critical radius
Flocculation
Kelvin equation
Kirkendall effect
Rock microstructure
Solubility equilibrium § Particle size
effect

References
1. Zhang, Zhaorui; Wang, Zhenni; He,
Shengnan; Wang, Chaoqi; Jin, Mingshang;
Yin, Yadong (2015). "Redox reaction
induced Ostwald ripening for size- and
shape-focusing of palladium nanocrystals".
Chem. Sci. 6 (9): 5197.
doi:10.1039/C5SC01787D .
2. Huang, Zhandong; Su, Meng; Yang, Qiang;
Li, Zheng; Chen, Shuoran; Li, Yifan; Zhou,
Xue; Li, Fengyu; Song, Yanlin (2017). "A
general patterning approach by
manipulating the evolution of two-
dimensional liquid foams" . Nature
Communications. 8: 14110.
Bibcode:2017NatCo...814110H .
doi:10.1038/ncomms14110 .
PMC 5290267  . PMID 28134337 .
3. IUPAC, Compendium of Chemical
Terminology, 2nd ed. (the "Gold Book")
(1997). Online corrected version:  (2006–)
"Ostwald ripening ".
4. Ostwald, W. (1896). Lehrbuch der
Allgemeinen Chemie, vol. 2, part 1. Leipzig,
Germany.
5. Ostwald, W. (1897). "Studien über die
Bildung und Umwandlung fester Körper"
[Studies on the formation and
transformation of solid bodies] (PDF).
Zeitschrift für physikalische Chemie. 22:
289–330.
6. Hubbard, Arthur T. (2004). Encyclopedia
of Surface and Colloid Science . CRC Press.
p. 4230. ISBN 0-8247-0759-1. Retrieved
2007-11-13.
7. Ratke, Lorenz; Voorhees, Peter W. (2002).
Growth and Coarsening: Ostwald Ripening
in Material Processing . Springer. pp. 117–
118. ISBN 3-540-42563-2.
8. Baldan, A. (2002). "Review Progress in
Ostwald ripening theories and their
applications to nickel-base superalloys Part
I: Ostwald ripening theories". Journal of
Materials Science. 37 (11): 2171–2202.
Bibcode:2002JMatS..37.2171B .
doi:10.1023/A:1015388912729 .
9. Lifshitz, I.M.; Slyozov, V.V. (1961). "The
Kinetics of Precipitation from
Supersaturated Solid Solutions". Journal of
Physics and Chemistry of Solids. 19 (1–2):
35–50. Bibcode:1961JPCS...19...35L .
doi:10.1016/0022-3697(61)90054-3 .
10. Wagner, C. (1961). "Theorie der Alterung
von Niederschlägen durch Umlösen
(Ostwald-Reifung)" [Theory of the aging of
precipitates by dissolution-reprecipitation
(Ostwald ripening)]. Zeitschrift für
Elektrochemie. 65 (7): 581–591.
doi:10.1002/bbpc.19610650704 (inactive
2017-03-07).
11. Kahlweit, M. (1975). "Ostwald Ripening
of Precipitates". Advances in Colloid and
Interface Science. 5 (1): 1–35.
doi:10.1016/0001-8686(75)85001-9 .
12. Vladimirova, N.; Malagoli, A.; Mauri, R.
(1998). "Diffusion-driven phase separation
of deeply quenched mixtures". Physical
Review E. 58 (6): 7691–7699.
Bibcode:1998PhRvE..58.7691V .
doi:10.1103/PhysRevE.58.7691 .
13. Branen, Alfred Larry (2002). Food
Additives . CRC Press. p. 724. ISBN 0-8247-
9343-9.
14. Clark, Chris (2004). The Science of Ice
Cream . Royal Society of Chemistry. pp. 78–
79. ISBN 0-85404-629-1.
15. Mock, A. (2003). "Using Quantitative
Textural Analysis to Understand the
Emplacement of Shallow-Level Rhyolitic
Laccoliths—a Case Study from the Halle
Volcanic Complex, Germany". Journal of
Petrology. 44 (5): 833–849.
Bibcode:2003JPet...44..833M .
doi:10.1093/petrology/44.5.833 .
16. Vengrenovich, R.D.; Gudyma, Yu. V.;
Yarema, S. V. (December 2001). "Ostwald
ripening of quantum-dot nanostructures".
Semiconductors. 35 (12): 1378–1382.
Bibcode:2001Semic..35.1378V .
doi:10.1134/1.1427975 .

External links
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to Ostwald ripening.

Ostwald Ripening a 3D Kinetic Monte


Carlo simulation
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