2007 International Conference on

Nanotechnology for the Forest Products Industry

Knoxville Convention Center, June 13-15, 2007

Siqun Wang, Seung-Hwan Lee, Cheng Xing,
George M. Pharr

University of Tennessee


Nano-Mechanical Properties of Cellulose Fibers
by Nanoindentation
Introductions
Siqun Wang
Wood-plastic composite is a very promising material
to achieve durability without using toxic chemicals.
Deck and fence
Pool and docks
Door panel (Audi A2)
Source from Nexwood website
Introductions
Siqun Wang
To design fiber reinforced polymer composites, we
need to know

Matrix

Fiber

Interphase
Research Goals and Materials
Objectives:
To investigate nano mechanical properties of cellulose fibers by nanoindentation;

To compare data between nanoindentation and conventional tensile test;

To understand what could happen if fiber diameter is too small or fiber cell wall is too
narrow.
Siqun Wang
Materials:
Two types of Lyocell fiber






Refined wood fibers under different
refining steam pressure


The image of refining fiber a) juvenile wood at 2 MPa, b) mature wood
at 2 MPa, c) juvenile wood at 18 MPa, and d) mature at 18 MPa.
Research Goals and Materials
Siqun Wang
Materials:

Refined wood fibers under different refining steam pressure


2 Bars 12 Bars 18 Bars

Experimental Method
Siqun Wang
Lyocell fiber:
Tensile test (Tensile modulus)
Nanoindentation (hardness, elastic modulus,
creep)
X-ray diffraction (crystallinity)
AFM


Refined wood fibers under different refining
steam pressure:
Nanoindentation (hardness, elastic modulus,
creep)
AFM


Nanoindentation influenced by neighboring
materials via finite element analysis


Single fiber nano-
mechanical testing system
Nanoindentation Instrument and Indentation
Procedure
Schematic of the NANO II
Indenter
Indent
marks
s
L
e
30
L
f
L
f
L
e
h
63.5
77
S = 2 Le/tan30
H = Lf + Le
S = 2h (tan65.3 )/(tan30 )
Lf = h (tan77 ) Le = h(tan65.3 )
H = h (tan77 + tan 65.3 )
Geometry of nano-indenter
(Berkovich diamond tip)
Nanoindentation Instrument and Indentation
Procedure
2
max
5 . 24
c
h
P
A
P
H = =
Hardness (H):
I
n
d
e
n
t
a
t
i
o
n

f
o
r
c
e
,

P

Displacement, h
dP/dh
Loading
Unloading
h
c
Typical load-displacement curve
A
dh
dP
E
r
t
2
1
=
( )
1
2
2
1 1
1

|
|
.
|

\
|

=
i
i
r
s s
E E
E
v
v
Elastic modulus (E
s
):
(Oliver and Pharr)
Vs and Vi (0.07) are the Poissons ratios of
the specimen and indenter, respectively.
E
i
is the modulus of the indenter (1141 GPa).
E
r
is reduced elastic modulus, which accounts
for the fact that elastic deformation occurs in
both the sample and the indenter.
Nanoindentation Instrument and Indentation
Procedure
L
o
a
d
,

P
Displacement, h
With single experiment, cycles of
indentation, each of which consists
of incremental loading and partial
unloading, are performed until a
final desired depth is attained.


Each loading-and-partial unloading
cycle provides a series of values of
hardness and elastic modulus.
Continuous stiffness measurement : One of the significant
improvements in nanoindentation test
Results Lyocell fiber
Siqun Wang
Tensile modulus of Lyocell fibers by single fiber tensile test and
sample codes for specimens
Sample Code Fiber direction Tensile modulus
(GPa)
Index of crystallinity
(%)
Lyo13 (L) Longitudinal
12.64 (2.94) 67.5
Lyo13 (T) Transverse
- -
Lyo10 (L) Longitudinal
10.36 (1.88) 65.4
Lyo10 (T) Transverse
- -
The value in parenthesis is the standard deviation (SD)
Results Lyocell fiber
Siqun Wang
Hardness and elastic modulus of Lyocell fibers measured by
continuous nanoindentation
Sample Mean value from 150
to 300 nm depth (GPa)
Unloading value at final
indentation depth (GPa)
H
mean
E
mean
H
u
E
u

Lyo13 (L)
0.44
(0.06)
13.19
(0.10)
0.43
(0.05)
13.10
(0.10)
Lyo13 (T)
0.32
(0.02)
6.77
(0.28)
0.33
(0.02)
6.69
(0.25)
Lyo10 (L)
0.33
(0.05)
11.51
(1.27)
0.32
(0.06)
11.42
(1.25)
Lyo10 (T)
0. 30
(0.01)
6.09
(0.14)
0. 30
(0.01)
6.01
(0.13)
Each is the average value from 5 indents. The value
in parenthesis is the standard deviation (SD).
Results Lyocell fiber
Siqun Wang
Hardness and elastic modulus of Lyocell fibers measured by continuous
nanoindentation
Sample Mean value from
150 to 300 nm depth
(GPa)
Unloading value at final
indentation depth (GPa)
H
mean
E
mean
H
u
E
u

Lyo13 (L)
0.44
(0.06)
13.19
(0.10)
0.43
(0.05)
13.10
(0.10)
Lyo13 (T)
0.32
(0.02)
6.77
(0.28)
0.33
(0.02)
6.69
(0.25)
Lyo10 (L)
0.33
(0.05)
11.51
(1.27)
0.32
(0.06)
11.42
(1.25)
Lyo10 (T)
0. 30
(0.01)
6.09
(0.14)
0. 30
(0.01)
6.01
(0.13)
Each is the average value from 5 indents. The
value in parenthesis is the standard deviation
(SD).
Sample
Code
Fiber direction Tensile
modulus
(GPa)
Index of
crystallinity
(%)
Lyo13 (L) Longitudinal
12.64
(2.94)
67.5
Lyo13 (T) Transverse
- -
Lyo10 (L) Longitudinal
10.36
(1.88)
65.4
Lyo10 (T) Transverse
- -
Results Lyocell fiber
Siqun Wang
Creep behaviors of Lyocell fibers
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300
Holding time (s)
L
o
a
d

(
m
N
)

a
a
a
200s
Hold segment
Loading
Experimental scheme for creep
test by nanoindentation.
-3.45
-3.35
-3.25
-3.15
-0.7 -0.6 -0.5
Log () (GPa)
L
o
g

(

)

(
s
e
c
-
1
)
Lyo8 (T)
Lyo8 (L)
Lyo15 (T)
Lyo15 (L)
Lyo10 (T)
Lyo13 (T)
Lyo10 (L)
Lyo13 (L)
-3.45
-3.35
-3.25
-3.15
-0.7 -0.6 -0.5
Log () (GPa)
L
o
g

(

)

(
s
e
c
-
1
)
Lyo8 (T)
Lyo8 (L)
Lyo15 (T)
Lyo15 (L)
Lyo10 (T)
Lyo13 (T)
Lyo10 (L)
Lyo13 (L)
The plot of indentation strain rate () and contact
stress (hardness, ) obtained from data
corresponding to the holding segment. Load:
1000 N, Loading rate: 20 N/s, Holding time
200 s.
Results Refined wood fibers
Siqun Wang
Summary of nanoindentation results of fiber cell wall
Note: Stdev: standard deviation; CV: coefficients of variation; Ci: indention creeps; n: the number of indents.

Property/pressure 2 bars 4 bars 6 bars 8 bars 10 bars 12 bars 14 bars 18 bars
Es
GPa

H
GPa

Ci
%
n
Mean
Stdev
CV
Mean
Stdev
CV
Mean
Stdev
CV
Number
21.35
2.59
12.13
0.50
0.04
8.00
7.58
0.86
11.35
31
18.62
2.97
15.95
0.47
0.062
13.19
8.72
1.56
17.89
27
15.96
2.41
15.10
0.47
0.07
14.89
8.87
1.25
14.09
23
16.83
2.53
15.03
0.45
0.05
11.11
8.63
1.29
14.95
28
15.32
2.51
16.38
0.43
0.067
15.58
8.24
1.09
13.23
30
14.05
2.87
20.43
0.43
0.079
18.37
9.68
1.79
18.49
28
13.09
3.42
26.13
0.39
0.078
20.00
12.30
3.89
29.25
14
12.22
3.29
26.92
0.37
0.095
25.68
13.08
3.91
29.89
13
Results Finite element analysis
Siqun Wang
Poplar cell wall
Manchurian Ash
cell wall
Adhesive transition
zone from the fiber
to matrix
Matrix
Fiber
Indents
Results Finite element analysis
Siqun Wang
Results Finite element analysis
Siqun Wang
Fiber
E=18.65Gpa,
H= 0.69 Gpa
Epoxy
E =4.67 Gpa ,
H =0.16 Gpa
Perform one simulation
when the location of the
flat punch moves to the
left or the right with every
1um
Rigid Flat punch
radius =1um
1um
8 simulations 8 simulations
Total 16 simulations
Results Finite element analysis
Siqun Wang
Boundary Conditions:
Penetration depth: 50nm applied to the indenter
Axisymmetry BCs: applied to the center face.
Roller BC: applied to the bottom face.

Results Finite element analysis
Siqun Wang
Mesh
Rigid flat cylindrical punch
Symmetry
plane
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
Fiber
Matrix
1
0
0
u
m
Rigid flat cylindrical punch
Symmetry
plane
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
Fiber
Matrix
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
Fiber
Matrix
1
0
0
u
m
Rigid flat cylindrical punch
Symmetry
plane
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
Fiber
Matrix
1
0
0
u
m
Rigid flat cylindrical punch
Symmetry
plane
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
Fiber
Matrix
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
1
0
0
u
m
Fiber
Matrix
1
0
0
u
m
Results Finite element analysis
Siqun Wang
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
-8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8
Centerline location of flat cylinderical punch (um)
S
t
i
f
f
n
e
s
s
(
m
N
/
n
m
)
FEA
Sneddon's solution-Epoxy
Sneddon's solution-Fiber
Fiber
Epoxy
Variation of the stiffness measured from the FEA with position from the interface. The punch
radius is 1 m.
Summary
Siqun Wang
Nanoindentation with continuous stiffness measurement is well
suited to the evaluation nano-mechanical and time-dependent
mechanical properties of cellulose fibers in longitudinal and
transverse direction. There is no significant difference between
modulus values obtained by nanoindentation and single fiber
tensile test.

There are some advantages using nanoindentation than tensile
test.

Using existing nanoindentation technique it would be difficult to
calculate the exact mechanical properties without the effect of
neighboring material property in at least 8 times smaller region
than indent size.
Acknowledgements
Siqun Wang
Haitao Xu, Yan Wu, Matthew Kant, Dayakar
Penumadu

USDA NRI grant number # 2005-02645

USDA Wood Utilization Research Grant

Tennessee Agricultural Experiment Station MS#96

Oak Ridge National Laboratory