Nanoparticles and Nanostructures from Direct-and Self- Assembly of Components Cleaved From Fiber Cell WallsProf. Orlando J. Rojasorlando.rojas@aalto.figo.ncsu.edu/cig

Photo Courtesy of Prof. Pablo Zavattieri (Purdue)

Link to publications in this talk: click here

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

: orlando.rojas@aalto.fiojrojas@ncsu.edu

Associates: Dr. Leena-Sisko Johansson, Dr. Joe Campbell (XPS), Ritva Kivelä, Marja Kärkkäinen, Anna-Leena Anttila.

Haishu

LinNanocellulose

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.

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

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

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

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

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

21 mm

Surfactant-Oil-Water Systems

Winsor phase diagrams

R < 1 R > 1R = 1

Microemulsion treatment: Flooding and deconstruction

Fluid penetration

M43M44M42M41

(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

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

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

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

High specific surface area + low density:

Thermal/sound insulation

Nonwovens

Filters

Packaging

Absorption Surface chemistry and catalysis

Packaging

Applications

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

v

Biactive Cellulose: detection,

biofiltration, etc.

cellulose

1 cm

20 c

m

a) b)

c) Pure TEMPO-ox. CMC-modified

NFC: Bioseparation

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)

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

Mechanical and Barrier properties

H2

O

O2

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

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)

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)

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

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)

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

Converse Piezoelectric Effect

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

Surface in aqueous medium

Surface after directional dryingG/S

S/L

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

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

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

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

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%

Thank you