Cellulose Micro/Nano fibers (CMNF)
from Bioresources in Malaysia
Fauziah Abdul Aziz
Physics Department
Centre For Defence Foundation Studies
National Defence University of Malaysia (NDUM)
Sg. Besi, Kuala Lumpur
8-Apr-15
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Regional Conference on Solid State Science
and Technology
(RCSSST 2014)
Copthorne Hotel,
Cameron Highlands, Pahang
25 – 27 November 2014
8-Apr-15
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OUTLINE
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ii.
iii.
iv.
v.
vi.
vii.
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Introduction
Term CMNF
Why Used CMNF?
Bioresources of CMNF
Some Analysis
Potential Benefits of CMNF
Conclusions
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INTRODUCTION
• Cellulose is a renewable, biodegradable &
the most abundant natural biopolymer
in the world
• Natural cellulosic fibers are synthesized mainly
in plants
• cellulose constitutes 40 to 50% of wood
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TERM CMNF
(Chakraborty et al., 2006)
• Microfibres are defined as fibres of
cellulose of 0.1-1 µm in diameter
• corresponding minimum length of
5-50 µm nanofibrils are at least 1-D
at the nanometer scale (1-100 nm)
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TERM CMNF (con’t)
• While the small fibrils isolated from
natural fibers normally have a wide range
of diameters, most are below 100 nm &
some are above 0.1 µm
• A term of cellulose micro/nanofibrils
(CMNF) used
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Hardwoods-Tropical
•
•
•
•
•
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dicot angiosperm trees; flowers / seeds ;
broad leaves; evergreen
presence of pores / vessels (obvious)
Gardening plants – shrubs, non-woody
Due to physical structure, hardwood tend to be
more expensive than softwood
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SUPRASTRUCTURES FIBRE
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CMNF
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Hierarchical structure of the wood cell wall
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Some eg of cellulose (whiskers) from
different cellulosic sources
I
Source of
Cellulose
1 Cotton
2 Tunicin
3 Bacterial
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L (nm)
70 - 300
100 – several
microns
100 - several
microns
D (nm)
References
5 - 70
Dong et al. ,
1998
10 - 20 Favier et al.,
1995
5 - 50 Chisuzu et al.,
1998
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Scale of Cellulose
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(Wang, 2008)
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Structural Formula of Cellulose, (C5H10O5)n
(Cave & Walker, 1994)
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Lattice parameter for various cellulose allomorphs
Chain
Cell Contant
Arrangement
i
Type
References
a
b
c
α
β
γ
(Crystal
Z
System)
1
Parallel
Iα
2
Sugiyama et. al (1991)
6.74
5.93
10.36
117
81
113
7.85
8.27
10.38
90
90
96.3
(1998)
II
Klemm et. al (2003)
9.08
7.92
10.34
90
90
117.3
III1
Wada et. al (2001)
4.48
7.85
10.34
90
90
105.1
10.25
7.78
10.34
90
90
90
8.03
8.13
10.34
90
90
90
7.99
8.1
10.34
90
90
90
5
(2001)
IV1
7
Egal M.M (2006)
(2001)
2
(Orthormbic)
Antiparallel
Zugenmaier
IV2
2
(Orthormbic)
Parallel
6
1
(Monoclinic)
Antiparallel
Zugenmaier et. al
III2
2
(Monoclinic)
Parallel
4
2
(Monoclinic)
Antiparallel
3
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(Triclinic)
Parallel
Finkenstadt & Millane
Iβ
1
2
(Orthormbic)
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Unit Cell of Cellulose Iβ
Parallel mode of
repeating unit of
cellulose Iβ
(Nishiyama et al., 2002; Penttilä, 2013)
along the a-axis (left, centre chain only) and along the b-axis (right)
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Cellulose I
• Natural cellulose = native cellulose =
cellulose I - ordered
• best crystalline allomorph of cellulose
• two allomorphs ie
 cellulose Iα
 cellulose Iβ
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Cellulose I (con’t)
• The parallel packing of native cellulose
make it metastable arrangement
• this irregular chain arrangement
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Cellulose I (con’t)
• the microfibrils, consisting of about
• 36 parallel cellulose chains in a crystal are
arranged into bundles with outer lateral
dimensions in the order of 20 nm
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Cellulose Iβ & Cellulose Iα
• cellulose Iβ is more disordered of cellulose than
cellulose Iα
• cellulose Iα is more crystalline than cellulose Iβ
• Iβ allomorph is recognized to be dominant in
higher plants
• higher stability of cellulose Iβ compared to
cellulose Iα
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WHY USED CMNF?
• Renewable materials from nature
• Most environmentally friendly materials
combined with a biogradable polymer as
a matrix
• Low abrasion compared to glass-fibre
• Non-toxic
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WHY USED CMNF? (con’t)
• Light
• Porous
• High mechanical strength
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WHY USED CMNF? (con’t)
• nonlinear
• optical behavior has been the subject of
many - design of smart materials
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BIORESOURCES OF CMNF
• Once upon a time, a living cell of biological
origin
• Natural sources
• Organic
• In this work, used plants
 Non-Woody
 Hardwood
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Non-Woody Plants
• Banana (Musa acuminata) pseudo-stem
• Pineapple (Ananas comosus)
leaf
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Hardwood
• Resak (Vatica spp.)
waste
• Merbau (Intsia bijuga)
waste
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Methods & Techniques
• chemical treatment
• Amorphous region - removed
• Purification (lessen DP=no of repeating units
per molecule)
• Segal’s method
• Scherrer equation
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SOME ANALYSIS
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DIFFICULTY
• producing purely single solid crystal due
to its polymorphic behaviour
• The increase of defibrillation of cellulose
molecule & rearrangement of hydrogen
bonds during isolation
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STRUCTURAL CHARACTERIZATION
• x-ray diffraction (XRD)
• field emission scanning electron
microscopy (FESEM)
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Chemical composition of various plants samples
i
1
2
3
4
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Samples
Cellulose
Holocellulose
Lignin
Resak
(Vatica
spp.) waste
41.80
29.70
20.0
Merbau
(Intsia
bijuga)
waste
35.40
49.80
38.40
Banana
(Musa
acuminata)
pseudostem
21.45
39.30
7.12
Pineapple
(Ananas
comosus )
leaf
32.60
55.10
11.80
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Abbreviations of bioresources
i
Untreated
Treated
1.
Resak (Vatica spp.) waste
R1
R2
1.
Merbau (Intsia bijuga) waste
M1
M2
1.
Banana (Musa acuminata)
pseudo-stem
B1
B2
Pineapple (Ananas comosus )
leaf
P1
P2
1.
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Samples
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Hardwood Merbau (Intsia bijuga) sample
Wood powder
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The cellulose residue before dry of alkali
treatment process
Plate
Alkali-treated
cellulose (AT)
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Cellulose delignification cellulose (DL) of Merbau
(Intsia bijuga)
After deliglification
cellulose (DL) powder
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Micrographic of FESEM of
after delignification cellulose
(DL) of Merbau (Intsia bijuga)
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Structure and appearance of CMNF
by SEM - Regenerated cellulose
fiber - nano-scale,
Wang et al, 2006
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Commercial celluloses,
Moran et al, 2008
Product acid-bleached
cellulose (BA) of
Merbau (Intsia bijuga)
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Micrographic of FESEM of acidbleached cellulose (BA)
of Merbau (Intsia bijuga)
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SEM Microstructure of
PP/CMNF composites –
overview (Wang et al, 2006)
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R1
M1
P1
B1
FESEM images of untreated :
R1, M1, P1 & B1
Structure and appearance
of CMNF by SEM,
Wang at al, 2006
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FESEM images of treated samples
: R2, M2, P2 and B2
P2
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B2
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Simulation Diffractogram [XRPD] of
microcrystalline states of cellulose (Crowder &
Fawcett, ICDD)
Estimates crystallites size parameters
Compute comparable FWHMs for peaks, 3.5nm
Software simulates pattern using d-space &
intensity values
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Simulation Diffractogram of microcrystalline
states of cellulose (Crowder & Fawcett, ICDD)
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Diffractogram (XRPD) - Experimental & Standard of
Cellulose Iβ Crowder & Fawcett, ICDD
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Diffractograms of untreated
various CMNF of plants samples
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Diffractograms of cotton & tunicate
cellulose whiskers, Pullawan, 2012
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Diffractograms of treated various
CMNF plants sample
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Simulation Diffractogram of
microcrystalline states of cellulose
(Crowder & Fawcett, ICDD)
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CMNF Crystalline cellulose Iα & cellulose Iβ
• Presents of cellulose Iα & cellulose Iβ
• cellulose Iβ more dorminant than cellulose Iα
• Lack of long range order means have no
conventional Bragg diffractions
• Broad features due to interatomic distances
within the disordered structure
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XRD of CMNF Pattern
• Presents at least more than one phase
system
• Maxima are shifted from the underlying
positions of the major Bragg peaks due to
the significant overlap
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ICDD Data Base
• Best integral index fit is 50-2241,
cellulose Iβ
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Crystallite size, D (nm) & crystallinity, Xc ( % ) of
various CMNF plants samples
Parameters
Samples
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Untreated
Treated
R1
M1
B1
P1
R2
M2
B2
P2
2θ002
22.3
22.6
22.0
22.3
21.6
21.8
21.5
22.0
FWHM
0.83
0.79
1.84
2.45
1.36
2.00
3.23
3.34
I002
1979
1460
822
2491
1789
1997
1278
3155
Iam
929
624
289
1120
507
441
264
688
Xc (%)
53.1
57.3
64.8
55.0
71.6
77.9
79.3
78.2
D (nm)
5.56
9.61
4.34
3.03
3.77
3.78
2.47
2.22
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Some XRD Results
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Some XRD Results
• The percentages of crystallinity of CMNF
of all samples increased after passing
the chemical treatment
• CMNF banana (Musa acuminata) is
more crystalline (79.29%) than other
CMNF samples
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Some Results (con’t)
• Significance size reduction in diameter
were seen when the fiber was treated
during the chemical treatment process
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Potential Benefits of CMNF
Some products from CMNF: Cosmetics & phamaceuticals
 Paints, varnishes, coatings
 Films
 Adhesives
 Nanocomposites
 Catalysts
 Hydrogels
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Potential Benefits of CMNF
Products from CMNF: Paints, varnishes, coatings
 Films
 Adhesives
 Nanocomposites
 Cosmetics & phamaceuticals
 Reinforcing filler
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CONCLUSIONS
• CMNF from some bioresources were
prepared & compared with literature
work
• Presence of more than 1 solid state phase
in the CMNF
• cellulose Iβ more dorminant than
cellulose Iα
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CONCLUSIONS
• treated cellulose prepared via chemical
treatment (alkali and bleaching
treatment) was more crystalline the
untreated materials
• Significance size reduction in diameter
were seen when the fiber was treated
during the chemical treatment process
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ACKNOWLEDGEMENT
The authors would like to acknowledge the financial
support from The Ministry of Education Malaysia under
the :
• Fundamental Research Grant Scheme (FRGS)
FRGS/1/2013/SG06/UPNM/01/1
• Niche Research Grant Scheme (NRGS)
NRGS/2013/UPNM/PK/P1
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GRADUATE ASSISTANTS (GRA)
1.
2.
3.
4.
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NORIEAN BINTI AZRAAIE
NURUL AIMI BINTI MOHD ZAINUL ABIDIN
NUR AIN BINTI IBRAHIM
NUR AMIRA BINTI MAMAT RAZALI
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THANK YOU
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