Page 1
Nanoparticles and Nanostructures from Direct-and Self- Assembly of Components Cleaved From Fiber Cell WallsProf. Orlando J. [email protected] /cig
Photo Courtesy of Prof. Pablo Zavattieri (Purdue)
Link to publications in this talk: click here
Page 2
Dr. Hannes
OrelmaBioactive
surfaces
Dr. Abdel
AbdelgawadNanofibers
chitosan
Dr. Tiina
NypeloOr/Inor-
ganic hybrids
Dr. Ana
FerrerComposites
residual fibers
Dr. Ingrid
HoegerSuper-
absorbents
Prof. Carlos
SalasNanocellulose
thermo, soy
Prof. Hironori
Izawa. Tottori U
Prof. Huiyu Bai
Jiangnan U
Prof. J. YanGuangdong Ind. Col
Anurodh
TripathiCA aerogels
Ben
JeuckBio-
processing
Carlos
CarrilloComplex fluids
Rheo
Consuelo
FritzBio-
processing
Egbe
EneSoy
composites
Joseph
LavoieElectret
phenomena
Parham
TayebSoy Lipoxy-
genases
Prajesh
AdhikariProtein
separation
Shuai
LiValue added
lignin
Wenyi
XieOr/Inor-ganic
(ALD) hybrids
Xiaomin
LuNanocell
composites
Biobased Colloids and Materials (BiCMat)
Group 2014-2015
De-zhan Ye
Sichuan Univ
A. Araujo
U Sao Paulo
L. Morales
Helsinki U
J. Silva
UFV
A. Pereira
CSIC
Prof. O. Rojas
Dr. Ilari
FilpponenClick chem,
nanocellulose
Dr. Julio
ArboledaSoy chem
Fibers&Textiles
Dr. Lokanathan
ArcotSupraColloids,
nanotechnol
Dr. Ester
RojoFiber
composites
Rese
arc
h
Fello
ws
Jiaqi
GuoFunctional
Nanocell.
Alexey
KhakaloProteins &
Thermoforming
Maija
VuoriluotoBioactive
Cellulose
Ahsan
UddinEnzyme
Sensing
Miika
NikinmaaFoam
formation
Meri
LundahlSuper-strong
Fibers
Xi
ChenSensing
Wenchao
XiangSensing
Gra
du
ate
Stu
den
ts
Prof. Mariko Ago
Tokushima Bunri
Prof. Junlong Song
Nanjing Forest U
Vis
itin
g
Sch
ola
rs: go.ncsu.edu/cig
: [email protected] @ncsu.edu
Associates: Dr. Leena-Sisko Johansson, Dr. Joe Campbell (XPS), Ritva Kivelä, Marja Kärkkäinen, Anna-Leena Anttila.
Haishu
LinNanocellulose
Page 3
Nanocellulose
• Nanotechnology/nanomaterials:
enablers for new generation
products and processes.
• The graphene market continued to
grow (government investments and
public listings by producers). Numerous
graphene-enabled products coming to
the market
• Nanocellulose moved to the forefront
and regulatory initiatives are multiplying. Production will likely increase by 500% at
least by 2017 (Future Markets, Inc. 2012)
Future Markets, Inc.
Page 4
Cryo-fracture deep-etch EM
C. Haigler, NCSU
Cellulose
Nanofiber
bundles
6 Assembly
proteins
(rosette) which
produces
cellulose
nanofibers
~28nm
Bottom-up:
Nature working
across 1010
scale
(construction)
Top-down
deconstruction
Page 5
Illustrations adapted from Zimmerman et al., Adv. Eng. Mat. 6,
754, 2004, Ikkala et al., Faraday Discuss. 143, 95, 2009
Fiber
deconstruction
5x5 mm
1x1 mm
Nanofibrillar
Cellulose (NFC)
Cellulose nanocrystals
(CNC)
Pretreatment and shear
Hydrolysis with strong acids
Cellulose, 14 , 539 (2007)BioResources, 3, 929 (2008)“The Nanoscience & Technological Aspects of Renewable Biomaterials” (Lucia and Rojas, Eds.), Wiley-Blackwell, 2009.Cellulose, 17, 835 (2010)Bioresource Technol, 101, 596 (2010)Eichhorn et al., J. Materials Sci. , 1 (2010)Habibi et al. Chem Rev, 3479 (2010)Moon at al., Chem. Soc. Rev., 3941 (2011)Cellulose, 18:1097 (2011)Bioresources, 6, 4370 (2011)
Pulp &
paper
Page 6
Textiles &
clothingLow volumeWallboard Facing
Insulation
Aerospace Structure
Aerospace Interiors
Aerogels for Oil & Gas
Paint-Architectural
Paint-Special Purpose
Paint Applications
NOVEL +
Emerging ApplicationsSensors (medical, env., ind.)Reinforcement fiberWater & air filtration
Viscosity modifiersPurificationCosmeticsExcipientsOrganic LED
PhotovoltaicsRecyclable Electronics
Market Projections For Nanocellulose-enabled
Products, J. A. Shatkin (October, 2013)
High Volume
3D printingPhotonicFilms
Page 7
Preston, R. D., Nicolai, E., Reed, R., Millard,
A. (Botany Dept., Univ. Leeds)
Nature, 162, 666 (1948)
Supramolecular unit of structures ranging from “fibrils”
…to…spherical or ellipsoidal particles
Page 8
Illustrations adapted from Zimmerman et al., Adv. Eng. Mat. 6,
754, 2004, Ikkala et al., Faraday Discuss. 143, 95, 2009
Fiber
deconstruction
5x5 mm
1x1 mm
Nanofibrillar
Cellulose (NFC)
Cellulose nanocrystals
(CNC)
Pretreatment and shear
Hydrolysis with strong acids
Cellulose, 14 , 539 (2007)BioResources, 3, 929 (2008)“The Nanoscience & Technological Aspects of Renewable Biomaterials” (Lucia and Rojas, Eds.), Wiley-Blackwell, 2009.Cellulose, 17, 835 (2010)Bioresource Technol, 101, 596 (2010)Eichhorn et al., J. Materials Sci. , 1 (2010)Habibi et al. Chem Rev, 3479 (2010)Moon at al., Chem. Soc. Rev., 3941 (2011)Cellulose, 18:1097 (2011)Bioresources, 6, 4370 (2011)
Pulp &
paper
Page 9
21 mm
Surfactant-Oil-Water Systems
Winsor phase diagrams
R < 1 R > 1R = 1
Microemulsion treatment: Flooding and deconstruction
Fluid penetration
M43M44M42M41
Page 10
(a) (b) (c)
Hydrophobic domain
Hydrophilic domain
Sodium dodecylsulfate
Sodium lignosulfonate
Limonene
0 1 2 3 4 50
25
50
75
100
125
WaterM33
MGL
MSSL
iqu
id U
pta
ke (
g/1
00g
)
Time (min)
MSL
0 50 100 150 200 2500
25
50
75
100
125
Water
M33
MGL
MSS
Liq
uid
Up
take (
g/1
00g
)
Time (min)
MSL
Page 11
0.0 0.5 1.0 1.5 2.00
250
500
750
1000
1250
1500
1750
2000
WR
V (
%)
Energy Consumption (x106 J)
Urea Microemulsion
Aqueous Urea
NFC from bleached fibers
• Microfluidization not possible directly form fibers
• Microemulsions facilitates deconstruction
• Energy savings of ~50% if microemulsions are compared to single
component solution
42%
0.0 0.5 1.0 1.5 2.00
250
500
750
1000
1250
1500
1750
2000
WR
V (
%)
Energy Consumption (x106 J)
Urea Microemulsion
Aqueous Urea
NFC from unbleached fibers
55%
Microemulsions in CNF production
Page 12
NFC and BC
Composites
(reinforced materials)
Super-strong Hydrogels &
Aerogels
Rheology
modification
Bioactive materials
Nanopaper
Conductive nanopaper (+ Pyrrole, click chemistry): 37.4 10-3 S/cm
Appl. Mater. Interfaces
2012, 4, 536
0 1 2 3 4 5 6-80
-60
-40
-20
0
20
40
f 3(H
z)
Time (min)
Bioconversion
Cellulose 20, 2417 (2013)
Appl. Mat. Interfaces, 2013
Anal. Chem, 2013
Biointerphases, 7, 61 (2012)
Biomacromolecules, 12, 4311 (2011)
Biomacromolecules, 13, 2802 (2012)
Carbohydrate Polymers,
doi:10.1016/j.carbpol.2012.11.063
BITE, 2013
Cellulose, 2013
ACS Macro Letters, 1, 1321 (2012)
Biomacromolecules, 13, 3228 (2012)
Biomacromolecules, 14, 1637-1644(2013)
BITE125, 249 (2012)
Cellulose, 19, 2179 (2012)
Bioresources, 6, 4370 (2011)
Cellulose, 18,1097 (2011)
Cellulose, 17, 835 (2010)
BITE 101, 5961 (2010)
0.01 0.1 1 10 100 10001E-3
0.01
0.1
1
10
100
0mM
10mM Ca+
25mM Ca+
50mM Ca+
vis
co
sit
y (
Pa.s
)
shear rate (1/s)
J. Renewable Resources, 2013, 1, 195
Carbohydrate Polymers, 89,1033-1037 (2012)
Cellulose Nanofibrils (NFC and BC)
Reference 14L
2x2 µm22x2 µm2
AFM
SEM
Page 13
Appl. Mater. Interfaces 2012, 4, 536
Aerogels:
low density solid foam
materials that contain ~98%
air (very light, extremely
strong, and excellent
insulators)
0%
CNF
17 %
CNF
33-100% CNF
(up to 67 %
SPs!)
NFC-based Composite Aerogels
Page 14
High specific surface area + low density:
Thermal/sound insulation
Nonwovens
Filters
Packaging
Absorption Surface chemistry and catalysis
Packaging
Applications
Page 15
10 100 1000
1E-3
0.01
0.1
1
10
0.5%
3.0%
5.0%
8.0%
10.0%
Vis
co
sit
y (
Pa*s
)
Shear rate (1/s)
0.01 0.1 1 10 100 1000
0.01
0.1
1
10
100 No electrolyte
10 mM Na
25mM Na
50 mM Na
Vis
co
sit
y (
Pa*s
)
Shear rate (1/s)
CNC CNF
NFC: Rheology
Page 16
v
Biactive Cellulose: detection,
biofiltration, etc.
cellulose
1 cm
20 c
m
a) b)
c) Pure TEMPO-ox. CMC-modified
NFC: Bioseparation
Page 17
Water contact angle
HYSTERESIS (H)
76.2°61.8°35.7° 48.1°
4 L 14 L0 L 2 L
+ % Lignin
0L 2L 4L 14L
θa 35.4 ± 0.5 48.6 ± 1.1 60.9 ± 4.1 77.7 ± 3
θr 25.8 ± 1 25.7 ± 0.7 25.9 ± 1.7 25.8 ± 1.8
H 9.6 22.9 35.1 51.9
• Roughness
• Heterogeneity
~
Nanopaper with Control of Surface Energy (lignin)
Page 18
Relative water absorption capacity
RWAC: 25.9 %
WAC: 15.5 g/m2
RWAC: 11.5 %
WAC: 6.5 g/m2
0 20 40 60 80 100 120
10
15
20
25
30
35
40
RW
AC
(%
)
t (min)
Reference
2L
4L
14L
0 L
2 L
4 L
14 L
RWAC: 36.4 %
WAC: 19.5 g/m2
RWAC: 34.7 %
WAC: 17.4 g/m2
+ %L
Page 19
Mechanical and Barrier properties
H2
O
O2
Page 20
Illustrations adapted from Zimmerman et al., Adv. Eng. Mat. 6,
754, 2004, Ikkala et al., Faraday Discuss. 143, 95, 2009
Fiber
deconstruction
5x5 mm
1x1 mm
Cellulose Nano/Micro
fibrils (CNF)
Cellulose nanocrystals
(CNC)
Pretreatment and shear
Hydrolysis with strong acids
Cellulose, 14 , 539 (2007)BioResources, 3, 929 (2008)“The Nanoscience & Technological Aspects of Renewable Biomaterials” (Lucia and Rojas, Eds.), Wiley-Blackwell, 2009.Cellulose, 17, 835 (2010)Bioresource Technol, 101, 596 (2010)Eichhorn et al., J. Materials Sci. , 1 (2010)Habibi et al. Chem Rev, 3479 (2010)Moon at al., Chem. Soc. Rev., 3941 (2011)Cellulose, 18:1097 (2011)Bioresources, 6, 4370 (2011)
paper
Page 21
Cellulose
Nanocrystals
CNC
Spin coating Langmuir-SchaefferFilm castingMoving (withdrawal)
plate
Solid support
CNC dispersion
Shear/Convection
20
40
60
80
100
30°
60°
90°
0°
Coatings
and anti-
scratch
surfaces
Piezoelectric
materials
10 Hz signal at low & high
voltage: oscillation
perpendicular to the z-
direction of the image
Piezoelectric constant:
(2 kHz and 800 V/cm): 2.1 Å/V.
Piezoelectric charge constant
d33 of reference 400 nm ZnO
film = 1.3 Å/V,
15 V
0 V (field off)
10 V
+ =
CNCs
200 nm
Composite nanofibers
Reductive amination at the reducing ends of a CNC
and Ag silver NP labeling of thiol functionalized CNCs
Asymmetric
CNC
0 10 20 30 400
10
20
30
40
50
60
70
Ela
stic T
ran
sve
rsa
l M
od
ulu
s (
GP
a)
Load (m)
Organic-inorganic hybrids
Magnetic separation
0 500 1000 1500 2000 250024
25
26
27
28
29
30
31
32
T ( °C
)
Time (s)
Hyperthermia
Biomacromoleules, 2013
ACS Macro Letters, 1, 867 (2012)
JCIS, 363, 206 (2011)
Soft Matter, 7, 1957 (2011)
Soft Matter 7 , 1957 (2011)
Biomacromolecules, 11, 2683 (2010)
Biomacromolecules , 11, 674 (2010)
Biomacromolecules,13: 918 (2012)
J. Polym. Env, 20, 1075 (2012).
Biomacromolecules, 11, 2471 (2010)
Biomacromolecules, 11, 674 (2010)
Appl. Mater. Interfaces, 1, 1996 (2009)
J. Appl. Polym. Sci. 113, 927 (2009)
Appl. Mater. Interfaces , 1, 1996 (2009)
Langmuir, 26, 990 (2010)
Thin Solid Films, 517(15), 4348 (2009)
0.3T
Bioresource Technol, 101, 596 (2010)
Chem Rev, 3479 (2010)
Stimuli responsive CNCs
1
10
100
1000
0 10 20 30
F/R
(m
N/m
)
Separation (nm)
10 mM100 mM250 mM
poly(NiPAAm)-g-CNCs
Biomacromolecules, 12, 2788 (2011)
J Colloid & Interface Sci, 369, 202 (2012)
Page 22
CNC: assemblies on solids - coatings
Spin coating Langmuir-SchaefferFilm castingMoving
(withdrawal) plate
Solid support
CNC dispersion
Shear/Convection
20
40
60
80
100
30°
60°90°
0°
Song, et al., Thin Solid Films, 517, 4348 (2009)
Hoeger, et al., Langmuir, 26, 990 (2010)
Hoeger, et al., Soft Matter, 7, 1957 (2011)
Csoka, et al., J. Colloid & Interface Sci. 363:206(2011)
Page 24
CNC: Energy Harvesting
• Radiation
• Thermal
• Gravitational
• Nuclear
• Magnetic
• Chemical (battery, fuel
cell, fossil fuels)
• Mechanical (kinetic
or vibration, elastic,
fluid)Electromagnetic, electrostatic and
piezoelectric transductions
• First observations in wood: Bazhenov
(1950) and Fukada (1955) [shear
piezoelectric modulus d14 and d25]
• Depends on the type of wood,
orientation, moisture and temperature
• Piezoelectric effect due to the
chemical and asymmetric crystalline
structure of cellulose fibrils.
Converse Piezoelectric Effect in Cellulose I Revealed by Wide-Angle X-ray Diffraction , Gindl et al. (2010)
278 pm/V
Page 25
Dielectrophoresis of CNCs and alignment in films by electric field-
assisted shearin
du
ced p
ola
rizatio
n o
f th
e
CN
Cs le
ad
s to a
sse
mbly
via
dip
ola
r in
tera
ctions
substrate
CNCs
withdrawal direction
deposition
plate
V
Al
electrodes
Films of aligned CNCs
200 400 600 800 1000
500
1000
1500
2000
2500
3000
Electric field strength [V/cm]
Fre
qu
en
cy o
f e
lec
tric
fie
ld [
Hz]
Calculated values of the oriented order parameter
1.3158E-2
1.3
158E
-27.8
947E
-2
7.8
947E
-2
7.8
947E
-2
1.4
474E
-1
1.4474E-1
1.4
474E
-1
2.1053E-1
2.1053E-1
2.7632E-1
2.7
632E
-1
3.4211E-1
3.4
211E
-1
3.4211E-1
4.0789E-1
4.0
789E
-14.7368E-1
4.7368E-1
4.7368E-1
5.3
947E
-1
5.3
947E
-1
6.0526E-1
6.7105E-1
6.7
105E
-1
7.3
684E
-18.0
263E
-1
8.0
263E
-1
1E+09.3421E-18.6842E-18.0263E-17.3684E-16.7105E-16.0526E-15.3947E-14.7368E-14.0789E-13.4211E-12.7632E-12.1053E-11.4474E-17.8947E-21.3158E-2-5.2632E-2-1.1842E-1-1.8421E-1-2.5E-1
Bivariate map for the orientation parameter map of CNCs as a function
of field strength and frequency
Hoeger, et al., 7, 1957 (2011)
Csoka, et al., JCIS 363, 206 (2011)
Csoka, et al., ACS Macro Letters, 1, 867 (2012)
Page 26
indu
ced p
ola
rizatio
n o
f th
e
CN
Cs le
ad
s to a
sse
mbly
via
dip
ola
r in
tera
ctions
substrate
CNCs
withdrawal direction
deposition
plate
V
Al
electrodes
Films of aligned CNCs
10 Hz signal at low & high
voltage: oscillation
perpendicular to the z-
direction of the image
Piezoelectric constant:
(2 kHz and 800 V/cm): 2.1 Å/V.
Piezoelectric charge constant
d33 of reference 400 nm ZnO
film = 1.3 Å/V,
20
40
60
80
100
30°
60°90°
0°
Hoeger, et al., 7, 1957 (2011)
Csoka, et al., JCIS 363, 206 (2011)
Csoka, et al., ACS Macro Letters, 1, 867 (2012)
Top electrode
CNC film
Mica substrateGold-coated glass slide
connected to a function
generator
AFM tip
AFM stage
15 V
0 V (field off)
10 V
Electrode
Electrode
+
-
~
P
Polarized
cellulose
nanocrystal
AFM tipOn-OffDirect Piezoelectric Effect
Page 27
Converse Piezoelectric Effect
Page 28
Synthesis mediated by
TOCNCs:Metal nanoparticle
manufacture and hybrid materials
Silver NPs
(non site-
specific)
Silver NPs
(site-specific)
Magnetic NPs
(non site-specific)
Beads &
capsules
via Pickering
emulsions
Anisotropic hybrids (Ag, Au , etc.): Supra-colloidal self-assembly,
biosensing, electro-mechanical actuation , light emitting,
semiconducting/ conducting
0.3T
Proof of
magnetic
fluid
hyperthermia
Shape-anisotropic, magnetic responsive:Optical sensing, protein separation, celltreatment, etc.
30 40 50 60 70 80 90 100
magnetic particles
Magneto CNC - CNC
Inte
nsity (
cp
s)
Scattering angle 2 (deg)
Fe3O4
CoFe2O4
“oil”
water
CNC-
CoFe2O4
shell
Saturation magnetization= 62 emu g-1 at 300 K.
Coercive field =0.3 kOe
Remanence of 15 emu/g.
Super-strong hollow and solid m
particles:Light-weight component in
composites, carriers + drugrelease, smart separation
Uddin, Green Mat., Accepted.
Nypelö, Cellulose 21, 2557 (2014).
Lokanathan, Biomacromol.15, 373 (2014).
Lokanathan Biomacromol. 14, 2807 (2013).
Nypelo, Am. Ceramic Society Bulletin, 91, 28 (2012).
Lokanathan, Submitted.
Nypelö, Submitted.With the support of Dr. Leena-Sisko Johansson + Dr. Joe Campbell (XPS) and Ritva Kivelä, Marja Kärkkäinen, Anna-Leena Anttila.
CNC: Site-specific and non-specific functionalization
of cellulose nanocrystals
Page 29
Surface in aqueous medium
Surface after directional dryingG/S
S/L
Page 30
CNC in Pickering Emulsions
Hydrophilic
particles
water
oil
Emulsion type depends on particle wettability
Solid particles to stabilize emulsions (Ramsden (1903), Pickering (1907))
water
oil
< 90o
22cos1 owdes RE
R = 10 nm – 5 µm
ow = 30 - 50 mN/m
= 30o – 150o
kTEdes
Energy of
particle
desorptionsurfacebulk EE
Hydrophilic to hydrophobic
O/W emulsion W/O emulsion
Hydrophobic
particles
water
oil
> 90o
oil
water
Page 31
CNC-Cobalt ferrite-shell
PS
core
Microcapsules of Magnetic CNC-iron oxide hybrid
coprecipitation FeSO4/CoCl2 precursors
Kalashnikova et al.:
Langmuir 2011, 7471
Biomacromolecules 2011, 267.
Soft Matter 2013, 9,952
Zoppe, et al. JCIS. 2012, 202
Alargova et al. Langmuir, 2004, 10371
Styrene +
2,2´ Azobis(2,4-dimethyl) valeronitrile
Page 32
Magneto-responsive systems
Magnetic fluid hyperthermia
Fortin et al. 2008, Eur. Biophys. J., 223
Lee et al. Nat. Nanotech. 2011, 418
0 500 1000 1500 2000 250024
25
26
27
28
29
30
31
32
T (C
)Time (s)
H = 200 Gauss
f = 869 KHz
Shape-anisotropic: Alignement by external stimuli
Optical sensing, protein separation, cell treatment, etc.
Purification
Separation
Emulsion stabilization
Phase separation
1 mm
1 mm
Annealing in 80°C for 48 h in magnetic
field
(polarized lenses)
Optical sensing Detection
200 nm
Reinforcement in fibersInorganic loading for magnetic
response
Page 33
PVA
d = 235 nm
+CNCsd = 182 nm
PCL
d = 210 nm
10 µmd = 120 nm
+CNCs
+CNCs
CA
PS
PP
Nylon
… composite fibers
reinforced with
CNCs
Bi-component fibers
(electrospinning, etc.)
+
Lignin-CNC
CNC: Reinforcing fibers
Page 34
beads
Beads-free fibers
Lignin-
based
composite
fibers
(90% L)
Ago, et al., Biomacromolecules,13: 918 (2012)
+ =
CNCs
200 nm
Lig/PVA
5%
10%
15%