Nucleation and Growth of

Crystals
Nucleation and Growth Rates
Control R
c

Nucleation, the first step
First process is for microscopic clusters (nuclei)
of atoms or ions to form
Nuclei possess the beginnings of the structure of the
crystal
Only limited diffusion is necessary
Thermodynamic driving force for crystallization must
be present
NUCLEATION
water as example

initiation of freezing
formation of small nuclei -center of
crystals
homogeneous or heterogeneous
homogeneous -water -random
accumulation of water molecules
heterogeneous -small particles present in
the solution act as nuclei



Crystal Growth
water as example

can only occur after nuclei are formed
exceed the crystal size
function of :

rate at which the water molecules reacts
at the crystal surface
diffusion rate of water molecules from the
unfrozen solution to the crystal surface
rate heat is removed


Growth of crystals from nuclei
Growth processes then enlarge existing
nuclei
Smallest nuclei often redissolve
Larger nuclei can get larger
Thermodynamics favors the
formation of larger nuclei
Nucleation and Growth Rates
Poor Glass Formers
T
m

T
Strong overlap of growth
and nucleation rates
Nucleation rate is high
Growth rate is high
Both are high at the same
temperature
Rate
Growth Rate
Nucleation Rate
Nucleation and Growth Rates
Good Glass Formers
T
m

T
No overlap of growth
and nucleation rates
Nucleation rate is small
Growth rate is small
At any one temperature one
of the two is zero
Rate
Growth Rate
Nucleation Rate
Fluid Processing
Molten glass is processed to maximize
clarity or durability.
Pure raw materials are often produced to
exacting sizes through precipitation from
aqueous solutions.
Large single crystals are grown from pure
molten solids for specialty applications.
Liquid
Critical Cooling Rate
Rapidly cooled liquids skip crystallization
and form random amorphous solids.
Calculating this rate involves minimizing
both nucleation and grain growth.
Glass
What This Means
Clear glasses are processed to reduce the
number and size of crystals.
Crystalline ceramics are processed so that
properties are optimized.
Nucleation Rate
Thermodynamic barrier W
*

At r
*
, (cW(r)/ cr)
r=r*
= 0

r
*
= -2o/ AG
cryst
(T)
W(r
*
) W
*
= 16t o
3
/3(AG
cryst
(T))
2

r
W
S
= 4tr
2
o,
o is the surface energy
W
B
= 4/3tr
3
AG
crsyt
(T),
the Gibbs Free-Energy of
Crystallization
W
tot
= W
S
+ W
B

W
*

r
*
+
-
0
Nucleation Rate I(T)
I = nvexp(-N 16t o
3
/3(AG
crsyt
(T))
2
/RT)exp(-AE
D
/RT)
AG
cryst
(T) = AH
cryst
(T
m
)(1 T/T
m
)
AG
cryst
(T)
0
+
-
T
m

Approx. for o:
o ~ 1/3AH
cryst
/N
1/3
V
m
2/3
)
`

|
|
.
|

\
|
A
A
|
|
.
|

\
|
=
RT
E
T
T H
RT V
n I
D
m cryst
m
exp
81
16
exp
2
2
t
v
Liquid is Stable

Crystal is Stable

Growth Rates -
Crystal Growth requires diffusion to the nuclei surface
Crystallization onto the exposed crystal lattice
AG
cryst

AE
D

v
lc
= vexp(-AE
D
/RT)
v
cl
= vexp(-(AE
D
- AG
cryst
) /RT)
v
net
= v
lc
- v
cl
=
vexp(-AE
D
/RT) -
vexp(-(AE
D
- AG
cryst
) /RT)

= a v
net
= a v exp(-AE
D
/RT) x
(1 exp(AG
cryst
) /RT)
Growth Rates -
Diffusion coefficient, D
D = a
2
vexp(-AE
D
/RT) = fRT/3Ntaq(T)
Hence:
= fRT/3Nta
2
q(T)(1 exp(AH
m
/RT(AT/T
m
)
where q(T) = q
0
exp(AE
D
/RT)

Precipitation

The objective of precipitation is to
remove salts, metals, or other
contaminants present in liquid waste
streams. Most often, this deals with the
removal of metals at varying pH levels.
Generally, the size of a precipitated
particle increases if the reaction is
allowed to occur with previously
precipitated particle.
1. Process Description

Precipitation has generally been shown to occur in three
steps: (a) nucleation; (b) crystal growth; and (3)
agglomeration and the ripening of the solids.


(a) Nucleation
:a nucleus is a fine particle on which the spontaneous
formation or precipitation of a solid phase can take place
in a supersaturated solution.

Homogeneous nucleation occurs when the nuclei is
formed from component ions of the precipitate; if
foreign particles are the nuclei, heterogeneous nucleation
occurs.
PRECIPITATION
(b) Crystal growth
: crystals form by the deposition of the precipitate constituent ions onto nuclei.

Crystal growth rate can be expressed as:




where
C* = saturation concentration (mole/L)
C = actual concentration of limiting ion (mole/L)
k = rate constant (L
n
/ time mg)
S = surface area available for precipitation (mg/L of a given particle size)
n = constant

When the diffusion rate of ions to the surface of the crystal controls the crystal
growth rate, the exponent n has a value of unity; when other processes such as the
reaction rate at the crystal surface are rate limiting, n may have a value other than
unity.
dC
dt
kS C C
n
= ( *)
PRECIPITATION
Protein Crystals

day 6 day 10

Day 13
Day 16
(c) Agglomeration and ripening

: conversion of small particles into larger
particles is enhance by agglomeration of
particles to form larger particles, which is the
continual growth until equilibrium is reached.
The changes in crystal structure that take
place over time are often called aging.

A phenomenon called ripening may also take
place whereby the crystal size of the
precipitate increases.

PRECIPITATION
Definition of Ostwald ripening

Many small crystals form in a system
initially but slowly disappear except for
a few that grow larger, at the expense
of the small crystals. The smaller
crystals act as "nutrients" for the
bigger crystals. As the larger crystals
grow, the area around them is depleted
of smaller crystals.
LEEM (Low-energy electron microscopy) images of ripening of
single atomic layer height islands on Si(001) at various times after
the temperature was increased to 670 C: (a) 10 s, (b) 50 s, (c) 400
s, and (d) 1300 s.
Explanation for the occurrence
of Ostwald ripening

This is a spontaneous process that occurs because larger
crystals are more energetically favored than smaller crystals.
(This might be hard to believe seeing as how it seems far more
common to get many small crystals than a few large ones, but
there is a believable explanation.) . While the formation of many
small crystals is kinetically favored, (i.e. they nucleate more
easily) large crystals are thermodynamically favored. Thus,
from a standpoint of kinetics, it is easier to nucleate many
small crystals. However, small crystals have a larger surface
area to volume ratio than large crystals. Molecules on the
surface are energetically less stable than the ones already well
ordered and packed in the interior. (Think of packing your
vacation clothes in a suitcase. Which ones are more energetic?
The ones in the middle or the ones you are packing in on top,
trying to get them to fit?) Large crystals, with their greater
volume to surface area ratio, represent a lower energy state.
Thus, many small crystals will attain a lower energy state if
transformed into large crystals and this is what we see in
Ostwald ripening.
So why doesn't Ostwald ripening
happen all the time? One reason
is that the nucleation of many
small crystals reduces the amount
of supersaturation and thus, the
thermodynamically favored large
crystals never get a chance to
appear.