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MSE 342, ERB

Properties of 3-D Nanomaterials


(Chapter # 4 Part I)

Uwe Erb

Materials Science and Engineering,


University of Toronto, Toronto, Ontario, Canada.

MSE 342, ERB

Properties of 3-D Nanomaterials


Before looking at details of properties you should consider that there are
structurally three different types of 3-D nanomaterials.
1) Consolidated Powder Materials
These materials have been prepared by two-step processes. First
nanopowders are made by techniques such as inert gas condensation, ball
milling or chemical precipitation. In the second step these particles are
consolidated under high pressures and at elevated temperatures. There is
considerable residual porosity in these materials in addition to grain
boundaries and tripe junctions.
2) Fully Dense Equiaxed Materials
These materials are made in one step such as electrodeposition or severe
plastic deformation. The materials are usually fully dense with negligible
porosity. Grain boundaries, triple junctions (and dislocations) are the main
defects.
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MSE 342, ERB

Properties of 3-D Nanomaterials


3) Nanocrystallized Materials

The materials are produced by crystallization of amorphous


precursor material. In addition to grain boundaries and triple
junctions they contain residual amorphous matrix.

The properties of these materials are not always the same and
direct comparisons are sometimes difficult.

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Consolidated Powder Material

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Fully Dense Equiaxed Material

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Nanocrystallized Material

amorphous

crystalline

clusters

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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.

MSE 342, ERB

Grain Growth in Conventional Materials

W.D. Callister, 6th ed., Materials Science and Engineering, Willey, NY, 2003

MSE 342, ERB

Grain Growth in Conventional Materials

Larger grains grow


Smaller grains shrink
L.H. van Vlack, Elements of Materials Science and Engineering, 3rd ed., Addison-Wesley, Reading, MA, 1975

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Driving Force for Grain Growth


Curvature Induced

Higher coordination number in growing grain

L.H. van Vlack, Elements of Materials Science and Engineering, 3rd ed., Addison-Wesley, Reading, MA, 1975

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MSE 342, ERB

Driving and Dragging Forces


Driving Force
Curvature Induced

F~/d

Dragging Forces
Solute Drag

F ~ C0 / r

Zener Drag

F~f /R

interfacial energy
d average grain size
C0 average concentration

r atomic radius of solute


R particle diameter
f particle volume fraction
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MSE 342, ERB

Normal Grain Growth Kinetics

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

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MSE 342, ERB

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.

Y. Zhou, Ph.D. Thesis, University of Toronto, 2006

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MSE 342, ERB

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

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Time Exponents for Grain Growth

Time exponent:
1/n

C. Suryanarayana & C.C. Koch, Hyperfine Interactions 130, (2000) 5

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MSE 342, ERB

Activation Energies
Kissinger Analysis
0.10

DSC @ 5 to 80 0C/min

4200 to 4670

Heat Release (W/g)

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
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heating rate of 50 C/min

Y. Zhou, Ph.D. Thesis, University of Toronto, 2006

MSE 342, ERB

Activation Energy
Modified Kissinger Analysis
ln(b /T p ) Q / kT p C
where

L.C. Chen, F. Spaepen, Appl. Phys., 69 (1991) 679)

b:
Tp:
C:
k:
T:
Q:

heating rate
peak temperature
constant
Boltzmanns constant
Temperature
Activation energy

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MSE 342, ERB

Peak Temperatures
480

Peak temperature (oC)

440
Ni
Ni-20%Fe

400

Ni-1.2%P

360

320

280
0

20

40

60

80

Scanning rate ( C/min)

G.H. Hibbard, U. Erb, K.T. Aust, U. Klement, G. Palumbo, Mat. Sci. Forum, 386-388 (2002) 387

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Kissinger Analysis
Activation Energies
-2

Heating rate (b/Tp )

-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

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MSE 342, ERB

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

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MSE 342, ERB

Youngs Modulus

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Physical Meaning of Youngs Modulus

Youngs modulus ~ slope in force curve at a0


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Grain Boundaries

Very important for many properties of 3-D nanocrystals


W.D. Callister, 6th ed., Materials Science and Engineering, Willey, NY, 2003

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Nanocrystalline Ni and Ni-P

YOUNG'S MODULUS (GPa)

400

300

minor reductions
200

100

100

101

102

103

104

105

GRAIN SIZE (nm)

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MSE 342, ERB

Normalized Youngs Modulus


for Nanocrystals

major reductions

Region II: High Porosity


Region I: Low Porosity
Y. Zhou, U. Erb, K. T. Aust, G. Palumbo, Z. Metallk., 94 (2003) 10

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MSE 342, ERB

Effect of Porosity

Strong Solids (e.g., ceramics)

V. Krstic, U. Erb and G. Palumbo, Scripta Metall. Mater., 29 (1993) 1501

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Effect of Porosity
Elastic Theory

2)
4
V
(
1

E E 1

1 S / R

9
4 5

2(7 5 ) (1 S / R)2 2(7 5 )

V : Pore volume fraction


: Poissons ratio

V. Krstic, U. Erb and G. Palumbo, Scripta Metall. Mater., 29 (1993) 1501

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MSE 342, ERB

Effect of Porosity
Atomistic Modeling: Pore in Single Crystal

R. Zugic, B. Szpunar, V.D. Krstic, U. Erb, Phil. Mag., A75 (1997) 1041

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MSE 342, ERB

Effect of Porosity
Atomistic Modeling: Pore at 5 grain boundary

R. Zugic, B. Szpunar, V.D. Krstic, U. Erb, Phil. Mag., A75 (1997) 1041

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MSE 342, ERB

Effect of Porosity
Atomistic Modeling

R. Zugic, B. Szpunar, V.D. Krstic, U. Erb, Phil. Mag., A75 (1997) 1041

Elastic Theory

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MSE 342, ERB

Effect of Porosity

data from
Region II

V. Krstic, U. Erb and G. Palumbo, Scripta Metall. Mater., 29 (1993) 1501

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MSE 342, ERB

Effect of Grain Size


Fully Dense Nanomaterials

Youngs modulus (normalized with respect to Youngs modulus of


polycrystalline nickel, E0) of nanocrystalline Ni-2.5 wt% P alloys, pure
nanocrystalline nickel and amorphous Ni-15 wt% P.

U. Erb, K. T. Aust, G. Palumbo, Z. Metallk., 94 (2003) 10

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MSE 342, ERB

Composite Model
Em EG f G EGB f GB ETJ fTJ
fs:
Es:
G:
GB:
TJ:

Y. Zhou, U. Erb, K. T. Aust, G. Palumbo, Z. Metallk., 94 (2003) 10

Volume fractions
Modulus values
Grain
Grain boundary
Triple junctions

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MSE 342, ERB

Composite Model
Results for Nano Ni-2.5% P

E 208 GPa
G
E 157 GPa
GB
ETJ 151 GPa

Y. Zhou, U. Erb, K. T. Aust, G. Palumbo, Z. Metallk., 94 (2003) 10

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MSE 342, ERB

Youngs Modulus Summary


1)

2)

3)

Grain boundaries and triple junctions have some


effect on elastic properties. For the case of Ni it was
shown that their Youngs Modulus is reduced by
about 20% at grain sizes of ~ 5nm.
Fully dense 3-D nanomaterials produced by
electrodeposition show some grain size dependence
below 20 nm and virtually no grain size dependence
above 20 nm.
3-D nanomaterials produced from 1-D precursor
material contain considerable porosity. Their Youngs
modulus decreases rapidly with increasing porosity
levels.
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MSE 342, ERB

Hardness, Strength, Ductility

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MSE 342, ERB

Vickers Hardness
Electrodeposited Ni
8

VICKER'S HARDNESS (GPa)

7
6
5
4
3
2
1
0
100

101

102

103

104

105

GRAIN SIZE (nm)

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MSE 342, ERB

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)

E. O. Hall, Proc. Phys. Soc., London, B54 (1951) 747


N. J. Petch, J. Iron Steel Inst., 174 (1953) 25

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Hall-Petch Plot
Electrodeposited Ni

A. M. El-Sherik, U. Erb, G. Palumbo, K. T. Aust, Scripta Metal., 27 (1992) 1185

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Hall-Petch Plot
Electrodeposited Ni-P

G. Palumbo, U. Erb, K. T. Aust, Scripta Metal., 24 (1990) 2347

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Normal Crystalline Cu
Regular Hall-Petch

A. H. Chokshi, A. Rosen, J. Karch, H. Gleiter, Scripta Metal, 23 (1989) 1679

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MSE 342, ERB

Comparison with Gas Condensed Pd, Cu


Inverse Hall-Petch

A. H. Chokshi, A. Rosen, J. Karch, H. Gleiter, Scripta Metal, 23 (1989) 1679

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MSE 342, ERB

Hall-Petch Plot
Various Materials

R. W. Siegel, G. E. Fougere,, Nanostruct. Mat., 6 (1995) 205

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Hall-Petch Plot
Various Materials

R. W. Siegel, G. E. Fougere,, Nanostruct. Mat., 6 (1995) 205

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MSE 342, ERB

Yield Strength
Electrodeposited Ni
1000

YIELD STRENGTH (MPa)

800

600

400

200

100

101

102

103

104

105

GRAIN SIZE (nm)

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MSE 342, ERB

Yield Strength
Electrodeposited Ni

N. Wang, Z. Wang, K. T. Aust, U. Erb, Mat. Sci., A237 (1997) 150

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MSE 342, ERB

Grain Boundaries: Dislocation Barriers

S: source

At small grain size: no longer dominant deformation mechanism


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MSE 342, ERB

Constitutive Equations for Diffusional


Mechanisms
Nabarro-Herring

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

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MSE 342, ERB

Constitutive Equations for Diffusional


Mechanisms
d
: strain rate
dt
: applied stress

d:

grain size

: volume of vacancy

: grain boundary thickness

D1 : lattice diffusion coefficient


D gb : grain boundary diffusion coefficient
: shear modulus

b : Burgers vector
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MSE 342, ERB

Nabarro-Herring Creep, Coble Creep

Nabarro-Herring:
Coble:

lattice diffusion
grain boundary diffusion

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MSE 342, ERB

Grain Boundary Sliding

grain boundary or lattice diffusion controlled


C. R. Barrett, W. D. Nix, A. S. Tetelman, in The Principles of Engineering Materials, Prentice-Hall, Inc., Englewood Cliffs, NJ (1973)

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Ductility
Electrodeposited Ni (early results)

very disappointing

N. Wang, Z. Wang, K. T. Aust, U. Erb, Mat. Sci., A237 (1997) 150

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MSE 342, ERB

Ductility
Electrodeposited Ni (early results)
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TENSILE ELONGATION (%)

50

very disappointing

40

30

20

10

100

101

102

103

104

105

GRAIN SIZE (nm)

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Comparison with Gas Condensed Pd

very disappointing

R. W. Siegel, G. E. Fougere,, Nanostruct. Mat., 6 (1995) 205

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Elongation to Failure
Various Nanomaterials

C. Suryanarayana & C.C. Koch, Hyperfine Interactions 130, (2000) 5

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However: More Recently


Conventional and Nanodeposit Co

good news

A. A. Karimpoor, Ph.D. Thesis, University of Toronto

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Stress Strain Curve


Electrodeposited Ni-Fe

good news

H. Wei, M.A.Sc. Thesis, U of T, 2006

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MSE 342, ERB

Hardness, Strength,Ductility
Summary
1)

All 3-D nanocrystalline materials show significant


increases in hardness, yield strength and tensile
strength, regardless of synthesis method. Depending
on the system, increases by factors of 3-10 are
commonly observed.

2)

All 3-D nanomaterials exhibit regular Hall-Petch


behavior for larger grain sizes. Changes in the HallPetch slope are observed at smaller grain sizes (<100
nm). Some materials show the inverse Hall-Petch
relationships at very small grain sizes(<10 nm).
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MSE 342, ERB

Hardness, Strength,Ductility
Summary
3)

At very small grain sizes dislocation slip is no longer


the dominant deformation mechanism.

4)

The inverse Hall-Petch relationship can be explained


on the basis of diffusional creep (Nabarro-Herring,
Coble) and grain boundary sliding which become
important at very small grain sizes even at room
temperature.

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Hardness, Strength,Ductility
Summary
5)

Early results on the ductility of 3-D nanomaterials were


very disappointing. Most materials showed low ductility
in tension (<5%), regardless of synthesis technique.
However, these results were obtained using very small
tensile samples.

6)

Recent advances in electrodeposition processes have


resulted in better materials and larger sample sizes for
meaningful tensile tests. As a result tensile elongations
in excess of 10% have been observed.
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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.
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MSE 342, ERB

Summary
Changes in Hall-Petch Behavior

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Summary
Low Temperature Deformation Mechanisms
a

1)

Dislocation slip

2)

Twinning

50 m
Polycrystals
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MSE 342, ERB

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

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