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Uwe Erb
The properties of these materials are not always the same and
direct comparisons are sometimes difficult.
Nanocrystallized Material
amorphous
crystalline
clusters
Thermal Stability
Nanomaterials contain very high interface contents
(e.g. surfaces in 0-D nanomaterials, grain
boundaries in 3-D nanomaterials). The associated
interfacial energy gives the nanomaterial a very
high driving force for crystal or grain growth.
Therefore, for any nanomaterial, one of the key
questions is their thermal stability with increasing
temperature.
W.D. Callister, 6th ed., Materials Science and Engineering, Willey, NY, 2003
L.H. van Vlack, Elements of Materials Science and Engineering, 3rd ed., Addison-Wesley, Reading, MA, 1975
10
F~/d
Dragging Forces
Solute Drag
F ~ C0 / r
Zener Drag
F~f /R
interfacial energy
d average grain size
C0 average concentration
dn don = Kt
n = 1.5 8
K = Ko exp (-Q/kBT)
d average grain size after time t
do average starting grain size
K constant
Ko
kB
Q
T
pre-exponential factor
Boltzmanns constant
activation energy
temperature
12
Ex-situ TEM
Normal Grain Growth
100 nm
a)
100 nm
b)
250 nm
c)
Ni 2.5 % P
TEM bright field images of a) as-plated, b) DSC annealed, 50C/min to 4000C, c) annealed to 5000C.
13
Ex-Situ TEM
Abnormal Grain Growth
(a)
(b)
300 nm
(d)
(c)
Ni 800ppm S
U. Klement, U. Erb, A.M. El-Sherik, K.T. Aust,Mat. Sci. Eng., A203 (1995) 177
14
Time exponent:
1/n
15
Activation Energies
Kissinger Analysis
0.10
DSC @ 5 to 80 0C/min
4200 to 4670
0.08
0.06
0.04
d = 6.9 nm
0.02
0.00
TP
0
100
200
300
400
500
600
Temperature ( 0C)
Ni 2.5% P
The curve was obtained for the Ni-P sample with starting grain size
16
heating rate of 50 C/min
Activation Energy
Modified Kissinger Analysis
ln(b /T p ) Q / kT p C
where
b:
Tp:
C:
k:
T:
Q:
heating rate
peak temperature
constant
Boltzmanns constant
Temperature
Activation energy
17
Peak Temperatures
480
440
Ni
Ni-20%Fe
400
Ni-1.2%P
360
320
280
0
20
40
60
80
G.H. Hibbard, U. Erb, K.T. Aust, U. Klement, G. Palumbo, Mat. Sci. Forum, 386-388 (2002) 387
18
Kissinger Analysis
Activation Energies
-2
-2.5
Ni
1.46 eV
-3
-3.5
Ni-1.2%P
2.25 eV
-4
-4.5
Ni-20%Fe
2.53 eV
-5
15
16
17
18
19
20
21
1/k B T p
G.H. Hibbard, U. Erb, K.T. Aust, U. Klement, G. Palumbo, Mat. Sci. Forum, 386-388 (2002) 387
19
Activation Energies
System
Grain size
(nm)
Tp (0C)
Q (eV)
Ni
Ni
Ni
Ni
Ni
Ni-1.2 wt% P
Ni-1.9 wt% P
Ni-2.5 wt% P
Ni-20 wt% Fe
Co
20
26
20
15
20
10
9
7
13
20
290
266
269
293
296
432
412
420
379
355
1.36
1.20
1.22
1.42
1.46
2.25
2.63
2.58
2.53
1.63
G.H. Hibbard, U. Erb, K.T. Aust, U. Klement, G. Palumbo, Mat. Sci. Forum, 386-388 (2002) 387
20
Youngs Modulus
21
Grain Boundaries
23
400
300
minor reductions
200
100
100
101
102
103
104
105
24
major reductions
25
Effect of Porosity
26
Effect of Porosity
Elastic Theory
2)
4
V
(
1
E E 1
1 S / R
9
4 5
27
Effect of Porosity
Atomistic Modeling: Pore in Single Crystal
R. Zugic, B. Szpunar, V.D. Krstic, U. Erb, Phil. Mag., A75 (1997) 1041
28
Effect of Porosity
Atomistic Modeling: Pore at 5 grain boundary
R. Zugic, B. Szpunar, V.D. Krstic, U. Erb, Phil. Mag., A75 (1997) 1041
29
Effect of Porosity
Atomistic Modeling
R. Zugic, B. Szpunar, V.D. Krstic, U. Erb, Phil. Mag., A75 (1997) 1041
Elastic Theory
30
Effect of Porosity
data from
Region II
31
32
Composite Model
Em EG f G EGB f GB ETJ fTJ
fs:
Es:
G:
GB:
TJ:
Volume fractions
Modulus values
Grain
Grain boundary
Triple junctions
33
Composite Model
Results for Nano Ni-2.5% P
E 208 GPa
G
E 157 GPa
GB
ETJ 151 GPa
34
2)
3)
36
Vickers Hardness
Electrodeposited Ni
8
7
6
5
4
3
2
1
0
100
101
102
103
104
105
37
Hall-Petch Relationship
regular
0 k d 1 / 2
strength
regular
H H 0 k d 1 / 2
hardness
where
d: grain size
k, k: constants
since 1989: k, k negative (inverse Hall-Petch)
38
Hall-Petch Plot
Electrodeposited Ni
39
Hall-Petch Plot
Electrodeposited Ni-P
40
Normal Crystalline Cu
Regular Hall-Petch
41
42
Hall-Petch Plot
Various Materials
43
Hall-Petch Plot
Various Materials
44
Yield Strength
Electrodeposited Ni
1000
800
600
400
200
100
101
102
103
104
105
45
Yield Strength
Electrodeposited Ni
46
S: source
d 14 1
D1
2
dt
kT d
Coble creep
d 14
D gb
3
dt
kT d
GB Sliding
d
b b
2x 105 D gb
dt
kT d
GB Sliding
d
b
8x 106 D1
dt
kT
Dislocation Climb
b
d
d
b
3.83x 105 D1
dt
kT
48
d:
grain size
: volume of vacancy
b : Burgers vector
49
Nabarro-Herring:
Coble:
lattice diffusion
grain boundary diffusion
50
51
Ductility
Electrodeposited Ni (early results)
very disappointing
52
Ductility
Electrodeposited Ni (early results)
60
50
very disappointing
40
30
20
10
100
101
102
103
104
105
53
very disappointing
54
Elongation to Failure
Various Nanomaterials
55
good news
56
good news
57
Hardness, Strength,Ductility
Summary
1)
2)
Hardness, Strength,Ductility
Summary
3)
4)
59
Hardness, Strength,Ductility
Summary
5)
6)
Hardness, Strength,Ductility
Summary
7) Recent advances in other synthesis methods have also
resulted in materials with better ductility.
8) Current efforts towards higher ductility include the
synthesis of materials with much broader grain size
distributions or even bimodal distributions. In these
materials a compromise between high strength and
reasonable ductility is achieved, whereby the smaller
grains in the distribution are responsible for
strengthening while the larger grains retain some
ductility in the system.
61
Summary
Changes in Hall-Petch Behavior
62
Summary
Low Temperature Deformation Mechanisms
a
1)
Dislocation slip
2)
Twinning
50 m
Polycrystals
63
Summary
Low Temperature Deformation Mechanisms
b
1)
Dislocation slip
2)
Twinning
3)
Coble
4)
Nabarro-Herring
5)
GB sliding
6)
Grain rotation
50 nm
Nanocrystals
64