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071
Amorphous Materials
3: Glass Forming Theories
Juejun (JJ) Hu
1
After-class reading list
2
Glass formation from liquid
V, H Supercooled
liquid
Liquid
? Supercooling of liquid
Glass
and suppression of
transition crystallization
? Glass transition: from
Glass supercooled liquid to
the glassy state
? Glass forming ability:
the structural origin
Crystal
Tf Tm T
3
Glass forming theories
4
Crystallization is the opposite of glass formation
Crystallized Amorphous
Gl s Gs Gl 0
V Tm T S
Heterogeneous
G Gl s GS nucleation
W
Size
Surface energy contribution
GS S
Gl s V Tm T S Energy barrier for nucleation
7
Kinetics of nucleation
G Nucleation rate:
GS S W
Rn D exp
k B T
G Gl s GS ED
W D D exp
k B T
Size
ED W
Rn D exp
k B T
T Tm : W , Rn 0
Gl s V Tm T S
T 0: Rn 0
8
Kinetics of growth
Flux into the nucleus:
Nucleus
E
Atom F exp
k B T
Flux out of the nucleus:
E G
F exp
k B T
9
Kinetics of growth
Net diffusion flux:
Nucleus
Atom Rg F F
E G
exp
1 exp
k BT k BT
E G
~ exp
k BT k BT
T Tm : G 0, Rg 0
T 0: Rn 0
10
Crystal nucleation and growth
Metastable
zone of
supercooling
Driving force:
supercooling
Both processes
are thermally
activated
Tm
11
Time-temperature-transformation diagram
Driving force
T (supercooling)
limited
Diffusion
limited
Critical
cooling rate Rc
T
Maximum glass sample thickness: d max ~ : thermal diffusivity
Rc
13
Glass formation from liquid
V, H Supercooled
liquid
Liquid
Increasing
cooling rate
Glasses obtained at
different cooling rates
3 have different structures
With infinitely slow
2
cooling, the ideal glass
1 state is obtained
Tm T
14
Potential energy landscape (PEL)
E Metastable Thermodynamically
glassy state stable crystalline state
Structure
15
Potential energy landscape (PEL)
PE
Laboratory
Ideal glass glass states Crystal
17
Glass former: high valence
state, covalent bonding with O
Modifier: low valence state,
ionic bonding with O
18
Zachariasen’s rules
Rules for glass formation in an oxide AmOn
An oxygen atom is linked to no more than two atoms of A
The oxygen coordination around A is small, say 3 or 4
Open structures with covalent bonds
Small energy difference between glassy and crystalline states
The cation polyhedra share corners, not edges, not faces
Maximize structure geometric flexibility
At least three corners are shared
Formation of 3-D network structures
19
Classification of glass network topology
PE PE PE
r
r 2
r
nr 2
21
Isostatic condition / rigidity percolation threshold
Examples:
GexSe1-x r x 4 1 x 2 2 2 x
AsxS1-x r x 3 1 x 2 2 x
SixO1-x r x 4 1 x 2 2 2 x
22
Temperature-dependent constraints
Normalized distribution
Bond stretching
rSi r
nSi O nO
2 2
O-Si-O bond angle
2rSi 3 nSi
Isostatic condition
x 1 3 SiO2
Si-O-Si bond angle in silica glass
23
Temperature-dependent constraints
24
Enumeration of constraint number
Bond stretching constraints (coordination number):
8-N rule: applies to most covalently bonded nonmetals (O, S, Se,
P, B, As, Si, etc.)
Exceptions: heavy elements (e.g. Te, Sb)
25
Property dependence on network rigidity
26
Measuring glass forming ability
CP
Tg is dependent on
measurement method
and thermal history
Alternative FOM:
Tx Tg Tm Tx
T Hruby coefficient
Tg
27
Summary
Kinetic theory of glass formation
Driving force and energy barrier for nucleation and growth
Temperature dependence of nucleation and growth rates
T-T-T diagram and critical cooling rate
Laboratory glass transition
Potential energy landscape
Ergodicity breakdown: laboratory glass transition
Path dependence of glass structure
Glass network topology theories
Zachariasen’s rules
Topological constraint theory
Parameters characterizing glass forming ability (GFA)
28
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