Lecture2 Martin

Advanced Vitreous State: The Structure of Glass
Optimizing t
internal
for glass formation Structural approach to glass formation
Understand and be able to apply the relationships between atomic level
structure and ease at which a system will form glass
Understand and be able to apply Zacharaisens Rules for glass formation
Be able to apply understanding of the three different types of additives,
modifiers, intermediates, and glass formers, to multi-component systems to
predict whether a particular composition will be glass forming or not.
Estimating t
external
for glass formation Kinetic approach to glass formation
Understand and be able to use nucleation and growth theory
Understand and be able to use TTT curves
Understand and be able to calculate critical cooling rates
Section 1: Lecture 2 Fundamentals of Glass Formation: Structural and
Kinetic Approaches

Glass formation results when the internal structural timescale of the liquid
becomes or is forced to become significantly longer than the external time
scale of the surroundings near the melting or liquidus temperature of the
liquid
Advance Vitreous State: The Structure of Glass Section 1: Lecture 2 - Fundamentals of Glass Formation: Structural and Kintic Approaches SWMartin
2
Structural Approach to Glass Formation
Crystalline materials exhibit a
periodic array of atoms and/or ions
Each atom/ion in the material has a
specific location that is periodic in
the crystalline structure
Each location can be exactly
specified once the crystalline
structure is defined
Defects in the structure occur when
the position and atom/ion type do
not agree with that prescribed by the
crystal structure
A
2
O
3
(B
2
O
3
)
3
Amorphous materials lack this long range order
There is no prescription for which atoms/ions
are located at which locations
However, the energetics of bond formation are
very strong
Atoms will align themselves chemically to:
Balance charge in ionic materials
Minimize bond energies by filling
appropriate bonding orbitals
Hence, local structure is disordered, but there
are still many similarities to the crystalline phase
Coordination numbers are ~ same
Bond lengths are ~ same
Bond Angles are ~ same
A
2
O
3
(B
2
O
3
)
4
Glass Formation results when
Liquids are cooled to below T
M
(T
L
) sufficiently fast to avoid
crystallization
Nucleation of crystalline seeds are avoided
Growth of Nuclei into crystallites (crystals) is avoided
Liquid is frustrated by internal structure that hinders both events

What internal structures promote glass formation?
How can structures be developed that increase the viscosity and
frustrate crystallization processes?

5
Using structure to promote glass formation
Develop atomic bonding structures in the system that produce large
viscosity near the melting point
Silicate liquids and glasses
SiO
2
, Na
2
O + CaO + SiO
2

Develop large molecular structures that due to their size prevent and/or
frustrate the organization into the crystalline structure
Polymeric liquids with large polymer chains
-(CH
2
)
n
-
Develop complex local and variable structures in the liquid that on
cooling have a large number of possible structural motifs to follow
and as a result no one structure is favored over another
Molten salt liquids with a number of components
Ca(NO
3
)
2
+ KNO
3

6
Zacharaisens Rules for Glass Formation
Glass formation requires long range continuous bonding in the liquid to
produce:
High viscosity
3 - Dimensional bonding
Strong individual bond strength
Open structure that is not efficiently packed
Corners of polyhedra are shared to increase connectivity
Bonds for bridges between corner sharing polyhedra
7
Oxygen atoms are linked (bonded) to no more than two atoms
Oxygen coordination around glass forming cations is small, 3, 4
Cation polyhedra share corners and not edges or faces
At least three corners are shared
William H. Zachariasen, Journal of the American Chemical Society
54 (1932) 3841-3851
8
Apply these rules to the following:
SiO
4/2

B
2
O
3
or BO
3/2

Apply these rules to the following:
CaO
Na
2
O
9
SiO
4/2

10
B
2
O
3
or BO
3/2

11
Zacharaisens Rules for Modifiers
Ca
1
O
1
(CaO) Closed-packed cubic
Ca occupying all octahedral
sites
Octahedral sites = Ca = O
12
Zacharaisens Rules for Modifiers M
2
O
Na
2
O
1
(Na
2
O) Closed-packed cubic
Na occupying tetrahedral sites
Tetrahedral sites = 2 x O = Na
13
Suns Bond Strength Model
Glass formation is brought about by both:
Connectivity of bridge bonds
Strong Bonds between atoms (ions)
Sun classified oxide according to their bond strengths
Glass formers form strong bonds to oxygen rigid network,
high viscosity
Modifiers from weak bonds to oxygen Disrupt, modify,
network
Intermediates form intermediate bonds to oxygen cant form
glasses on their own, but aid with other oxides to form glasses

14
Suns Bond Strength Model
Glass formers
Greater than 80 kcal/mole bond strength with oxygen
B
2
O
3
, SiO
2
, Geo
2
, P
2
O
5
, Al
2
O
5
.
Intermediates
Between 60 to 80 kcal/mol bond strength with oxygen
TiO
2
, ZnO, PbO.
Modifiers
Less than 60 kcal/mole bond strength with oxygen
Li
2
O, Na
2
O, K
2
O, MgO, CaO.

15
Glass Formers (Oxides) form glasses on their own
16
Intermediates (Oxides) assist in glass formation
17
Modifiers (Oxides) degrade glass formation
18
Classifying Oxides
How would each of the following be classified?
SiO
2
, B
2
O
3
, P
2
O
5

TiO
2
, PbO
Na
2
O, CaO, ZnO
19
Dietzels Field Strength Criteria
Sun classifies Al as both a glass former and an intermediate
Al
2
O
3
does not form glass at normal quenching rates
More factors are important than just bond strength
Small cations with high charge glass formers
Large cations with small charge modifiers
Medium sized cations with medium charge - intermediates

20
Dietzels Field Strength Model
21
Intermediates assist in glass formation
22
Glass forming oxides form glass on their own
23
Glass forming compositions
How would you classify the following compositions? Glassforming or not?
0.15Na
2
O + 0.35Al
2
O
3
+ 0.50SiO
2

0.35Na
2
O + 0.15CaO + 0.25Al
2
O
3
+ 0.25SiO
2

Advanced Vitreous State: The Structure of Glass
Kinetic Theory of Glass Formation
Understand and be able to use nucleation and
growth theory
Understand and be able to use TTT curves
Understand and be able to calculate critical
cooling rates
Section 1: Lecture 2 Fundamentals of Glass Formation: Structural and
Kinetic Approaches

Glass formation results when the internal structural timescale of the liquid
becomes or is forced to become significantly longer than the external
time scale of the surroundings near the melting or liquidus temperature of
the liquid
25
Kinetic Approach to Glass Formation
Glass formation requires the by-passing of the crystallization events
at T
m
Structural approach is to create high viscosity to frustrate
nucleation and growth processes
SiO
4/2
easily supercools due to the high connectivity of the liquid
through strong O-Si-O- bonding
Kinetic approach to glass formation asserts:
All liquids can be made into the glassy state
The question is how fast must the liquid be cooled?
Fast quenching, >> 100
o
C/sec, implies marginal glass forming
ability
Slow cooling,<< 1
o
C/min, implies strong glass forming ability
The critical cooling rate, R
c
, measures how fast a liquid must be
cooled to avoid crystallization and render the liquid into the
glassy state
26
Critical Cooling Rates for Various Liquids
27
Calculating the Critical Cooling Rate
The kinetic approach to glass formation then becomes:
What is the R
c
value for a particular liquid?
If R
c
>> 100
o
C/sec, then the liquid is a poor glass former
If R
c
is << 1
o
C/min, the the liquid is a good glass former
How can R
c
be calculated?
What are the factors that control R
c
?
28
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
29
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
30
Nucleation and Growth Control R
c

Poor glass formers:
Liquids which quickly form large numbers of nuclei close to
T
m

That grow very quickly

Good glass formers
Liquids that are sluggish to form nuclei even far below T
m

That grow very slowly

31
Nucleation and Growth Rates Poor Glass Formers
Strong overlap of
growth
and nucleation rates
Nucleation rate is high
Growth rate is high
Both are high at the
same
temperature
T
m

T
Rate
Growth Rate (m/sec)
Nucleation Rate (#/cm
3
-sec)
32
Nucleation and Growth Rates Good Glass Formers
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
T
m

T
Rate
Growth Rate (m/sec)
Nucleation Rate (#/cm
3
-sec)
33
Nucleation Rate Theory
Rate at which atoms or ions in the liquid organize into
microscopic crystals, nuclei
I = number of nuclei formed per unit time per unit volume of
liquid
Nucleation Rate (I) number density of atoms x
fastest motion possible x
thermodynamic probability of
formation x
diffusion probability
34
Nucleation Rate Theory
I = nvexp(-NW
*
/RT)exp(-AE
D
/RT)

n = number density of atoms, molecules, or
formula units per unit volume
= p N/Atomic, molecular, formula weight
v = vibration frequency ~ 10
13
sec
-1

N = Avogadros number
= 6.023 x 10
23
atoms/mole
W
*
= thermodynamic energy barrier to form
nuclei
AE
D
= diffusion energy barrier to form nuclei
~ viscosity activation energy
Number density Fastest motion Thermodynamic probability Diffusion probability
35
A word about the f(x,T) = exp(-x/T) function
This function is bounded
between 0 and 1
As x >> 0, f >> 1
As x >> , f >> 0
As T >> 0, f >> 0
As T >> , f >> 1
Sketch a series of curves
for T dependence on
linear f and log f
Linear T and 1/T
36
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, surface
o is the surface energy
W
B
= 4/3tr
3
AG
crsyt
(T), bulk
AG
crsyt
(T),

the Gibbs Free-Energy
of Cryst. per unit volume, V
m
W
tot
= W
S
+ W
B

W
*

r
*
+
-
0
37
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
)/V
m
AH
cryst
(T
m
)(AT
m
/T
m
)

AG
cryst
(T)
0
+
-
T
m

Approx. for o:
o~ 1/3AH
melt
/N
1/3
V
m
2/3

note AH
melt
= - AH
cryst
)
`
|
.
|
\
|
A
|
|
.
|
\
|
A
=
RT
E
T
T
RT
H
n I
D m
cryst
exp
81
16
exp
2
t
v
Liquid is Stable

Crystal is Stable

Liquid and Crystal are in equilibrium
38
Growth Rates u(T)
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)

u = a v
net
= a v exp(-AE
D
/RT) x
(1 exp(AG
cryst
) /RT)
39
Growth Rates - u(T)
Diffusion coefficient, D

Stokes-Einstein relation between D and n

Hence:
|
|
.
|
\
|
|
|
.
|
\
|
A
|
.
|
\
|
A
|
|
.
|
\
|
=
m
m
T
T
RT
H
T a N
fRT
T exp 1
) ( 3
) (
2
n t
u
|
|
.
|
\
|
=
A
=
) ( 3
exp ) (
2
T a N
fRT
RT
E
a T D
D
n t
v
40
Nucleation and Growth Rates
Nucleation and Growth Rates for Water
0
5E+22
1E+23
1.5E+23
2E+23
2.5E+23
3E+23
3.5E+23
4E+23
4.5E+23
100 150 200 250 300
Temperature (K)
N
u
c
l
e
a
t
i
o
n

r
a
t
e

(
s
e
c
-
1
)
0.E+00
2.E-09
4.E-09
6.E-09
8.E-09
1.E-08
1.E-08
1.E-08
G
r
o
w
t
h

r
a
t
e

(
m
-
s
e
c
-
1
)
Nucleation
rate(sec-1)
Growth rate
(m/sec)
41
Nucleation and Growth Rates
Nulceation and Growth for Silica
0.E+00
2.E+07
4.E+07
6.E+07
8.E+07
1.E+08
1.E+08
1.E+08
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100
Temperature (K)
N
u
c
l
e
a
t
i
o
n

R
a
t
e

(
s
e
c
-
1
)
0
5E-26
1E-25
1.5E-25
2E-25
2.5E-25
G
r
o
w
t
h

R
a
t
e

(
m
-
s
e
c
-
1
)
Nucleation rate (sec-1)
Growth rate (m/sec)
42
Time Temperature Transformation Curves (TTT)
How much time does it take at any one temperature for a
given fraction of the liquid to transform (nucleate and grow)
into a crystal?
X(t,T) ~tI(T)u(T)
3
t
4
/3
where X is the fractional volume of crystals formed, typically
taken to be 10
-6
, a barely observable crystal volume
43
TTT curves and the critical cooling rate, R
c

T
T
m

time
R
c
very fast
R
c
much slower
Poor glass former
Better glass former
44
Time Transformation Curves for Water
T-T-T Curve for water
100
150
200
250
0 1 2 3 4 5 6 7 8 9 10
Time (sec)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
45
Time Transformation Curves for Silica
T-T-T Curve for Silica
200
400
600
800
1000
1200
1400
1600
1800
2000
1 1E+13 1E+26 1E+39 1E+52 1E+65 1E+78
Time (sec)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
46
Summary
Glass formation results when the internal structural timescale of
the liquid becomes or is forced to become significantly
longer than the external time scale of the surroundings near
the melting or liquidus temperature of the liquid
Create high viscosity of the liquid near the melting point of the
liquid that frustrates crystallization
Network bonding favorable for high viscosity
Configurational complexity that frustrates crystallization
pathways
Suppress the melting point through compositional
complexity to slow crystallization process
Surpass crystallization processes by limiting available to
system for them to occur
Exceed critical cooling rate in region near and below the
fusion point of the liquid

Lecture2 Martin

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Advanced Vitreous State: The Structure of Glass

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