Cer103 WS00 Notes Shelby Chapter 2 2-1

Kinetic Theory of Glass Formation

Since most glasses are formed from melts, it is appropriate to first discuss glass
formation in terms of crystallization kinetics.

Any melt will form a glass if cooled fast enough.
Kinetic theory of glass formation is an attempt to define 'fast enough'.


So-- What is 'fast enough'? Why don't all melts form glasses?

Classical Nucleation/Crystallization Theory
Applied to any solutionsolid transformation
Metals, rock candy, snow, etc.
See D. R. Uhlmann, "Kinetics of glass formation and devitrification
behavior," J. de Physique, C9 43 175 (1982).

'Crystallization' is the opposite of 'Glass Formation'.
Avoid crystallization to form a glass.

'Crystallization' refers to two processes:
1. Nucleation: formation of crystal embryos- critical size
2. Crystal growth: beyond the critical size

Most Glasses are Formed by Melt Techniques
Oxides (SiO
2
, B
2
O
3
, P
2
O
5
, etc.)
Halides (F, Cl, Br, I)
Chalcogenides (S, Se, Te, etc.)
Metals
Salts
(see N. J. Kreidl, Glass Forming Systems, Glass
Science and Technology, Vol. 1 (1983).)
All Bond Types: Covalent (SiO
2
, chalcogenides)
Ionic (KNO
3
Ca(NO
3
)
2
)
Metallic (Au
4
Si, Pd
4
Si, Fe-Ni-P-B)
van der Waals (toluene)
Hydrogen (water)
and all combinations (homodesmic and
heterodesmic).
Cer103 WS00 Notes Shelby Chapter 2 2-2
Step 1: Nucleation
Homogeneous: spontaneous formation from the melt; composition of the melt
and crystal are the same.
Heterogeneous: nuclei form on some 'foreign' surface: impurities, crucible wall,
bubbles, seeds, etc.

If you do not first form a nuclei (and there are no heterogeneities), crystallization
can be avoided.

Two contributions to the energetics of
nucleation

Thermodynamics: free energy
changes associated with crystal
formation (W*)
Surface creation barrier
Volume creation driving force

Kinetics: energy barrier associated with
moving material to create/grow nuclei
(G
D
, where 'D' refers to diffusion.)

Nucleation is an activated process- that is, the nucleation rate (I) increases with
temperature, and can be described by an Arrhenius equation:
I is the homogeneous nucleation rate
A is the pre-exponential factor
k is Boltzmann's constant
E
n
e
r
g
y
Meta-
stable
glass
Stable
nuclei
Energy
Barrier
Driving
Force
] ) * ( exp[ kT G W A I
D
+ =
Notes about Activated Processes
P
r
o
p
e
r
t
y
Temperature
Typical behavior for chemical
reactions: rates (slope of property
curve) increase with temperature.
Arrhenius (1889) recognized that this
could be described by an exponential
function
1/Temp. (K)
-1
l
n

P
r
o
p
e
r
t
y
Property = A exp(-E
a
/kT)
A = pre-exponential factor
(intercept)
E
a
= activation energy
(slope)
k = Boltzmanns constant
(sometimes R)
Cer103 WS00 Notes Shelby Chapter 2 2-3
Thermodynamic Considerations:

Consider the Free Energy changes associated with nuclei formation


1. Volume Energy Gain

Above the melting point, the liquid is the thermodynamically favored state (has
the lower free energy). Upon cooling below T
m
, the solid (crystal) state is
favored, but can be avoided during supercooling. The free energy difference (per
volume) between a glass and crystal (or nucleus) is G
V
.

Spherical nuclei, radius 'r'
Free energy reduction for a volume of material to transform from a glass to
the thermodynamically favored crystalline nucleus is given by: G
V
volume
of sphere ([4/3]r
3
)

2. Surface Energy Penalty (Barrier)

Nucleation opposed by energy needed to create a new surface (blowing bubbles,
surface energy minimized with spheres):
Surface tension () surface area (4r
2
)

Nucleation dependent on the balance between surface & volume energies.

W = (4/3)r
3
G
v
+ 4r
2
(eq. 2-4)

Temperature
F
r
e
e

E
n
e
r
g
y

(
G
)
solid
liquid
T
melt
supercooled
liquid
glass
G
v
Cer103 WS00 Notes Shelby Chapter 2 2-4

Small nuclei (r<r*) are dominated by surface energy term and will tend to re-
dissolve because an increase in r causes an increase in W.
If the nucleus reaches a critical size (r*), that nucleus will grow because the
dominance of the volume term causes W to decrease with increasing r.
Thermodynamically stable particles when rr*

Find r* from the first derivative of eq. 2.4:

eq. 2.5: r G r
dr
dW
V
8 4 0
2
+ = =
eq. 2-6: Solve for r:
V
G
r

=
2
*
Note: blowing bubbles? Replace G
V
with P.

In practice, stable nuclei are about 100 molecules in size.

Definition for thermodynamic energy barrier to nucleation (substitute 2-6 into 2-4)

eq. 2-7:
2
3
3
16
*
V
G
W

=


& G
V
are experimentally obtainable. Large better glass forming tendency
reduce promote nucleation

W = (4/3)r
3
G
v
+ 4r
2

W

(
e
n
e
r
g
y
)
r (nucleus radius)
Surface
Energy (+r
2
)
Volume
energy (-r
3
)
W*
r*
Cer103 WS00 Notes Shelby Chapter 2 2-5
Heterogeneous Nucleation: effective reduction of surface energy by the presence
of 'impurity' surfaces- seeds, bubbles, crucible walls, etc. (Don't need to expend
energy to initially create 'homogeneous' surfaces.

From eq. 2-7: reducing
eff
reduces W* and so lowers the energy barrier for
nucleation.


Surfaces that are readily wet by the liquid (defined by the contact angle, ,
between the growing nucleus and the heterogeneous surface) provide better
nucleation sites.

Smaller contact angles lower surface energies greater nucleation rates
E
n
e
r
g
y
Meta-
stable
glass
Stable
nucleus
Surface
Energy
Barrier
Volume
Energy
Gain
Homogeneous
Nucleation
E
n
e
r
g
y
Heterogeneous
Nucleation

Small contact
angle (): good
nucleation

Poor nucleation
Cer103 WS00 Notes Shelby Chapter 2 2-6
Recall:

Thermodynamic estimate for driving energy:

eq. 2-7:
m m m V V
T V T T H G / ) ( (H
V
is the
heat of fusion)

The further below T
m
, the greater the driving
force for nucleation becomes.


So: if G
V
becomes greater and greater with decreasing temperature, why don't
all melts crystallize upon cooling? What keeps the thermodynamics from
controlling glass formation?

I. Kinetic Considerations

G
D
: related to how fast material moves to the surface of a growing nuclei:
expressed as a diffusion coefficient:
eq. 2-13: ) exp( ) (
2
kT
G
h
kT
D
D

=

,
is atomic jump distance, and D is related to viscosity by Stokes-Einstein:

eq. 2-14: )
3
(

kT
D = . Note, high , low diffusion coefficient.
Plug these equations into eq. 2-1 to obtain description of nucleation rate (I):

eq. 2-15: )
*
exp( )
3
(
3
kT
W Ah
I

=



Note: I
-1
: increasing decreases I (counterbalances the increasing G
V
).

So: what does eq. 2-15 look like?

Temperature
F
r
e
e

E
n
e
r
g
y

(
G
)
solid
liquid
T
melt
supercooled
liquid
glass
G
v
Cer103 WS00 Notes Shelby Chapter 2 2-7

Metastable zone of undercooling: no stable nuclei form at these temperatures
just below T
m
: high surface energies of small particles decreases melting
points (small particles melt at T<T
m
). So, nucleation must begin at the
melting point of particles with r*, not at the macroscopic T
m
shown above.

Step 2: Crystal Growth

Growing particles with r>r*.
Surface tension less important; barrier to r* already overcome
Same thermodynamic (G) and kinetic (E) considerations.
Balance crystallization energies against diffusional barriers

Consider atoms jumping back and forth across the liquid/solid interface:
atomic jump frequency

lx
= exp(-E/kT)

xl
= exp((-E-G)/kT)
(more energy needed for xl jump)

the net crystal growth rate is

U=a
0
(
lx
-
xl
), a
0
is interatomic distance

And so:

eq. 2.20: ) / exp( 1 )[ exp(
0
kt G kT E a U = ]
(diffusion barrier) (Xtal. Driving force)
Crystal Growth
E
n
e
r
g
y
liquid
Crystal
Diffusional
Energy
Barrier (E)
Xtal.
Energy
Gain ( G)
N
u
c
l
e
a
t
i
o
n

R
a
t
e

(
I
)

Temperature
T
melt
T
g
Increasing I:
G
V
(T
m
-T) Decreasing I:
kinetics (
-1
)
Metastable zone
of undercooling
Cer103 WS00 Notes Shelby Chapter 2 2-8

again, using Stokes-Einstein (eq. 2.13 & 2.14):

eq. 2.21: ) exp( 1 )[
3
(
2
0
kT
G
a
kT
U

=

]

Shelby Figure 2.1:
a. no metastable undercooling zone
for U; particles are large enough to
melt at T
m
.

b. extent of U-I overlap is an indication
of glass forming tendency. Large
overlap, poor glass forming melt
(nucleation and growth occurring
contemporaneously).


What happens if we rapidly cool from above T
m
to T
1
and hold?
Nothing, no nuclei can form in metastable undercooling zone

What happens if we rapidly cool from above T
m
to T
2
and hold?
Nuclei will form, but will not grow. Reheat to T(U
max
) to crystallize sample
(process cycle for glass-ceramics).

So: to avoid crystallization, must cool below T
g
faster than nucleation and
crystallization rates.

Consider the modified Avrami equation from classical transformation kinetics.
The volume fraction of a melt that has crystallized:

eq. 2.22: ] ' ) ( exp[ 1
0 '
3

=
t t
t
V
x
dt Ud I
V
V

(I is volume, U is linear (so U
3
).

Under isothermal conditions, (2.22) becomes:

eq. 2.23: ]
3
exp[ 1
4 3
t U I
V
V
V
x

=
where t is the time the sample is held at experimental temperature.
By knowing I, U at various temperatures, one can calculate (V
x
/V) in
time/temperature space to produce Time-Temperature-Transformation (TTT)
curves:


Shelby, Figure 2.1
(a)
(b)
T
1 T
2
Cer103 WS00 Notes Shelby Chapter 2 2-9


Note: shape of curves a consequence of the balance between thermodynamic
and kinetic processes:
Crystallization driving force increases with undercooling
Viscosity increases with undercooling.

Most favorable conditions for crystallization (and so least favorable conditions for
glass formation) when temperature is held at nose temperature (T
n
) where the
shortest amount of time (t
n
) is needed for transformation to occur. (Large
viscosity at T
n
means greater t
n
). Note: for smaller transformation volumes, t
n
is
shorter.

Thus, to avoid crystallization, the melt must be cooled at a critical cooling rate:

eq. 2.24:
n n m C
t T T
C
dt dT
T
) ( ) (

If thermal diffusivity (D
T
) is known, the maximum sample thickness is:

eq. 2.25:
n T C
t D L

Examples of C T

for various liquids:

Material
C T

(C/s)
SiO
2
910
-6
Na
2
O 2SiO
2
610
-3

Water 110
7

Silver 110
10

Fun Fact: The glassy state of water is the dominant form in the Universe- slow accumulation of
water molecules from the vapor state onto cold substrates such as dust particles- agglomerate
into larger bodies that form comets. (P. Jenniskens et al., J. Chem Phys., 107 1232 (1997))
In practice, air quenching is 0.1-1.0 C/sec, liquid quenching is 10
2
C/sec, splat
quenching is 10
4
-10
7
C/sec.
time
T
e
m
p
e
r
a
t
u
r
e
T
n
t
n
T
m
(V
x
/V)=10
-6
10
-8
(Glass)
(Crystal)
Cer103 WS00 Notes Shelby Chapter 2 2-10
Heterogeneities can reduce C T

by orders of magnitude


Homo. 100 60 40
SiO2 910
-6
110
-5
810
-3
210
-1


Lower contact angle between nuclei
and heterogeneity, smaller critical
cooling rate.

Glass-Ceramics: Class of material based on controlled crystallization
Nucleation step to get a uniform distribution
Crystallization step: uniform size

Stookey story: nucleated sample (metal colloids for photosensitivity) into furnace
runaway furnace. Stookey expected puddle, got instead a white material with
outstanding mechanical properties. Serendipity (but Stookey was already
prepared to recognize importance of discovery).

Note: minimize U/I overlap for best controlled process
Advantages of glass-processing over typical ceramic powder-processing:
Complex shapes, faster, lower temperatures
Generally stronger, lower CTE, etc. than straight glass

Disadvantages:
Can only use glass-forming melts
Residual glassy phases- some high temperature properties not as good as
'straight' ceramics.
time
T
e
m
p
e
r
a
t
u
r
e
T
m
Homogeneous
Heterogeneous
(Glass)
(Crystal)
Process as a glass, then crystallize to yield ceramic properties
Step 1: melt/form
Step 2: nucleate
Step 3: crystallize
Process Crystallize
Nucleate
time
T
e
m
p
e
r
a
t
u
r
e
Cer103 WS00 Notes Shelby Chapter 2 2-11
Determination of Glass Formability:

Differential Thermal Analysis
Measure the temperature difference between a sample (S) and an inert
reference material (R) as both are heated. The sample will undergo
endothermic (glass transition) and exothermic (crystallization) processes that
change its temperature relative to the reference.

Summarizing the Kinetic Theory for Glass Formation

Glass formation is a kinetic process: any liquid will form a glass if cooled fast
enough. Fast enough is the critical cooling rate C T

.

C T

depends on crystallization and nucleation rates.

These rates depend on competing processes:
Free Energy for Crystallization G
V
: liquidcrystal transformation
Depends on heat of fusion (-H
f
)
Degree of undercooling (T
m
-T)

Surface Tension
Opposes nucleation
Reduced by heterogeneities

Melt Viscosity
Controls transport; prevents transformations at low temperatures

Melts that tend to form glasses:
High viscosity at T
n
(long t
n
), like SiO
2

Large d/dT- like organics
Large nucleation barriers:
High surface tension
No nucleating sites
Differential Thermal Analysis is Used to Characterize
Glassforming Ability and Thermal Stability
T
g
T
x
S is sample
R is inert reference
measure the temperature
difference between the two
Large (T
x
-T
g
): Better
glassforming ability, better
thermal stability