Date post: | 06-Jul-2018 |
Category: |
Documents |
Upload: | otavio-augusto-titton-dias |
View: | 222 times |
Download: | 0 times |
of 25
8/17/2019 A Paradigm in Nanocellulose Materials
1/25
A Paradigm in Nanocellulose Materials ‐ From nanofibers to nanostructured fibers ‐
Hiroyuki Yano
Research Institutes for Sustainable Humanosphere,
Kyoto University
NSCF
Nano-Structured Cellulose Fibers
8/17/2019 A Paradigm in Nanocellulose Materials
2/25
Close‐up viewNSCF
Nano‐Structured Cellulose Fibers
150μm
Dissolving pulp ( 100)
8/17/2019 A Paradigm in Nanocellulose Materials
3/25
Dissolving pulp 2,000
10μm
Dissolving pulp 30,000
500nm
8/17/2019 A Paradigm in Nanocellulose Materials
4/25
$0.6-0.8/kg
$20-100/kg
$0.1-0.2/kg
The advantage of pulp: NSCF
over CNC , CNF and BC is
“cost”
A Paradigm in Nanocellulose Materials ‐ From nanofibers to nanostructured fibers ‐
8/17/2019 A Paradigm in Nanocellulose Materials
5/25
Optically transparent nanocellulose
A component less than one‐tenth the size of the
optical wavelength can eliminate scattering
Mechanical Reinforcement of
Transparent Plastic
8/17/2019 A Paradigm in Nanocellulose Materials
6/25
Cell Wall
Structure
Cell Structure
Nano fibers and Matrix
Hierarchical Structure of Wood
10‐50μm
10‐20nmMicrofibril
bundles
Cellulose Nanofibers
Hemicellulose
Lignin
Nano‐Structured Cellulose Fibers
8/17/2019 A Paradigm in Nanocellulose Materials
7/25
Fibrillation by a Grinder
Never- dried pulp
Cellulose nanofibers
isolated from wood
K. Abe, et al.,
Biomacromolecules,
2007
8/17/2019 A Paradigm in Nanocellulose Materials
8/25
1% Never-dried Pulp SlurryGrinder treatment
Vacuuming filtration
Acrylic Resin impregnationNanocomposites
Fiber content::5-90 wt%
UV cure
Preparation of Cellulose Nanofiber Composites
Semi-crystalline extended chains
Tensile strength:3GPa→ aramid fibers
(Based on D.H. Page, F., El-Hosseiny J. Pulp Paper Sci. 1983)
Young’s modulus:138-141GPa -200~+200
(T. Nishino et al. J. Polym Sci., Part B, 1995, Proc.2nd Intn'l Cellulose Conf,2007 )
Thermal expansion coefficient 0.1 ppm/K→ quartz glass
(T. Nishino, Personal communication, 2004)
High specific surface area
Cellulose Nanofibers:CNF
8/17/2019 A Paradigm in Nanocellulose Materials
9/25
Wood Nanofiber Bacterial Cellulose
Density
(g/cm3)
Light
Transmittance1
(%)
CTE2
(10-6oC-1)
E
(GPa)
Tensile
Strength
(MPa)
Wood NanofiberComposites
1.4 82.3 9.8 16.3 283
Bacterial Cellulose
Composites1.4 83.7 6.0 21.0 325
1600nm 220 150S. Iwamoto, et al., Biomacromolecules (2007)
Optically Transparent Cellulose Nanofiber
Reinforced Composite
As strong as steel, as thermally stable as glass,
and as bendable as plastics
8/17/2019 A Paradigm in Nanocellulose Materials
10/25
Passivation Film
Organic Layers
SiON Barrier Film
Resin (Smoothing Layer)Wood Cellulose Nanocomposites
Anode
Cathode
Device structure
Luminescence of an OLED
deposited on the wood nanofiber‐composite
Y. Okahisa, et al., Comp. Sci. Technol . (2009)
A demonstration of
production of OLED by R2R process
(GE, USA, Press Release, 13 March, 2008)
A future FPD processing; Continuous “Roll to Roll”
R2R process simple and inexpensive.
R2R processing enables the
continuous deposition of
functional materials such as
semiconductor, transparentconductive films and gas barrier
films on a roll of substrate.
8/17/2019 A Paradigm in Nanocellulose Materials
11/25
BCWood
nanofibers
100%
Wood
nanofibers
Transparent
Crab
Transparent materials developed in Kyoto Uni.
Schematic presentation of the exoskeleton structure of
crustacean shell. (Ifuku, et al. Biomacro, 2009)
Micro to Nano Structure of Crab
Chitin molecule
8/17/2019 A Paradigm in Nanocellulose Materials
12/25
Crab shell powder, Red king
Deproteinization by NaOH
Demineralization (CaCO3) by HCl
Pigment removal by ethanol
I. Md. Shams and Yano, 2009
SEM image of chitin particle sheet surface
1 mm x 1mm particle of
matrix removed crab shell
8/17/2019 A Paradigm in Nanocellulose Materials
13/25
SEM image of chitin particle sheet surface
SEM image of chitin particle sheet surface
8/17/2019 A Paradigm in Nanocellulose Materials
14/25
SEM image of chitin particle sheet surface
50mm
1mm
8/17/2019 A Paradigm in Nanocellulose Materials
15/25
0
20
40
60
80
100
200 400 600 800
L i g h t T r a n s m i t t a
n c e ,
%
Wave length, nm
Cellulose nanofibers composites
Chitin powder composites
Acrylic resin
(a) Light transmittance of the chitin powder reinforced acrylic resin sheet
(thickness 190 µm, Powder content: 22wt%) and cellulose nanofibers reinforced
acrylic resin sheet (thickness 100 µm and Fiber content: 60wt%).
Comparison of Micro to Nano structures
Crab Wood
8/17/2019 A Paradigm in Nanocellulose Materials
16/25
The transition from nanofibers
to nanostructured fibers
• Encouraged by the transparent crab powder
sheet, we undertook the preparation of
optically transparent pulp-fiber composites.
Slow
Dewatering
Speed
Low
ProductivityNanofibrillation
of Pulp
Difficulty in the production of
nanocellulose reinforced composites
8/17/2019 A Paradigm in Nanocellulose Materials
17/25
Optically transparent pulp sheet
The pulp‐fiber sheet was acetylated, with care taken to
maintain a never‐dried condition, and it was then dried
and impregnated with acrylic resin.
Drying
CNF of Never
Dried Pulp
Resin
Impregnation
Acetylation Acetyl
Group
Acetylated Pulp Sheet
Acetylated
dry pulpNever dried
Pulp Resin
impregnated
acetylated
dry pulp
8/17/2019 A Paradigm in Nanocellulose Materials
18/25
Acetylated
Pulp Sheet
After resin impregnationBefore resin impregnation
200um
Effect of surface fibrillation using beads mill
200um
Surface
fibrillation
Pulp sheet
Pulp, NBKP Surface fibrillated pulp
Surface fibrillated pulp sheet
8/17/2019 A Paradigm in Nanocellulose Materials
19/25
0
10
20
30
40
50
6070
80
90
100
300 500 700
L i n e a r l i g h t t r a n s m i t t a n c e
%
Wave length nm
Acrylic resin
+Surface fibrillation
Untreated Pulp
Acetylation
CNF + resin
Changes in transparency of acrylic resin impregnated paper
After resin
impregnation
Before resin
impregnation
Thickness
um
Fiber
content
%
CTEppm/K
Linear
Light
Transmit.
%
Total
Light
Transmit.
(%)
Acetylated surface
fibrillated pulp60 18.0 11.9 70.0 88.1
Acetylated pulp 100 26.0 8.30 54.1 87.8
Untreated pulp 100 28.5 3.64 43.7 87.0
Nanofiber1) 100 35‐40 12.1 82.0 90.0
Resin1) ― 0 213.0 91.0 92.0
CTE:20‐150
1) Y. Okahisa, et al., Composite Science and Technology ,2009
8/17/2019 A Paradigm in Nanocellulose Materials
20/25
0.6-0.8US$/kg
20-100US$/kg
0.1-0.2US$/kg
The advantage of pulp: NSCF
over CNC , CNF and BC is
“cost & performance”
Another example using NSCF
Chemically modified surface fibrillated pulpor Chemically modified NSCF
8/17/2019 A Paradigm in Nanocellulose Materials
21/25
Development of high performance cellulose nanofibers reinforcedplastics for automotive parts
Organizations: Kyoto University, Kyoto Municipal Institute, Oji Paper,
Mitsubishi Chemical , DIC, Seiko PMCAdvisers: Toyota Autobody, Nissan, Suzuki, Denso, Nippon Paint , Panasonic,
Japan Steel Works
NEDO Green Sustainable Chemical Process Programsfrom 2009 to 2013
NEDO: New Energy and Industrial Technology
Development Organization of Japan
Project Title
Sustainable ForestAutomotive Parts
CO2 Fixation
Twin screw extruder
Chemically modified
dry pulp
Chemically modified
CNF reinforced plastic
Injection molding
Samples
PE, PP, PA pellets
+Additives
Nanofibrillation
& Compounding
Disintegration and well‐dispersion of chemically modified
pulp in HDPE,PP and PA12 during melt compounding
8/17/2019 A Paradigm in Nanocellulose Materials
22/25
X‐ray tomography of
injection molded samples
Modified Pulp Modified CNF
Unmodified Pulp HDPE
SEM Images
10μm
10μm
Pulp (Surface fibrillated)
Unmodified Pulp
after removal of HDPE
10μm
Modified Pulp
after removal of HDPE
8/17/2019 A Paradigm in Nanocellulose Materials
23/25
Stain (%)
S t r e s s ( M P a )
HDPE + Modified Pulp
E:3.3GPa, σ: 57MPa
(Pulp or CNF 10%)
Tensile properties
HDPE + Unmodified Pulp
E: 1.6GPa, σ: 38MPa
Neat HDPE
E: 0.8GPa, σ: 23MPa
HDPE + Modified CNF
E:3.5GPa, σ: 56MPa
S t r e s s ( M P a )
Strain (%)
Chemically modified CNF reinforced Bio‐HDPE
Modified CNF/HDPE
E: 2.4GPa, σ: 48MPa
Neat Bio-HDPE
E: 0.7GPa, σ: 21MPa
Pulp 10%
8/17/2019 A Paradigm in Nanocellulose Materials
24/25
S t r e s s ( M P a )
Strain (%)
Pulp 10%
Chemically modified CNF reinforced PP
Modified CNF/PPE: 1.7GPa, σ: 46MPa
Neat PP
E: 0.7GPa, σ: 26MPa
0
10
20
30
40
50
60
70
0 5 10 15 20
s t r e s s [ M P a ]
strain[%]
0
10
20
30
40
50
60
70
0 5 10 15 20
s t r e s s [ M P a ]
strain[%]
0
10
20
30
40
50
60
70
0 5 10 15 20
s t r e s s [ M P a ]
strain[%]
Unmodified CNF/PA12E: 1.8GPa, σ: 42MPa
Modified CNF/PA12
E: 3.0GPa, σ: 63MPa
Neat PA12
E: 1.3GPa, σ: 35MPa
Chemically modified CNF reinforced PA12
Pulp 10%
8/17/2019 A Paradigm in Nanocellulose Materials
25/25
49
CTE (0‐100 )
ppm/K
PA12 92
Modified CNF/PA12 24
Aluminum alloy 23
0
100
200
300
400
500
0 20 40 60 80 100
(
μ m )
( )
PA12
Modified CNF/PA12
Polymer
Composites
Chemically modified CNF reinforced PA12
Temperature ( )
D e f o r m a t i o
n ( μ m )
Thank you very much for your kind attention!