From Nanocellulose Science towards Applications - · PDF fileFrom Nanocellulose Science towards Applications ... Transparent NFC paper Yano ... Nordic Pulp & Paper Research Journal,

From Nanocellulose Science

towards Applications

Hans-Peter Hentze

VTT – Technical Research Center of Finland

PulPaper 2010 - June 2nd ’10 - Helsinki

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Agenda

I. A Brief History of Nanocellulose Science

II. Structure-Properties Relationships

III. Towards Applications

IV. Summary & Outlook

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I. A Brief History of Nanocellulose Science

Nanocellulose Science:

Synthesis, modification, characterization &

study of structure-properties relationships

Some Highlights:

1980 1990 2000 2010

Esau (1977)

NFC fibrils First NFC

production &

thickener in

food applications

Turbak / Rayonier /

Daicel (since 1980s)

Cast-iron paperBerglund (2008)

Transparent

NFC compositesNogi (2005)

Transparent

NFC paperYano (2009)

(e.g. Eichhorn et. al, „Review: current international research into cellulose nanofibres and nanocomposites‟

J Mater Sci (2010) 45:1–33)

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Nanocelluloses – A Class of Nanomaterials

Examples of Raw Materials:

Examples of Production Methods:

Top-Down / Bottom-Up

Grinding, Homogenizer, Intensification, Hydrolysis / Electrospinning, Ionic liquids

Wood Bacteria Straw Sugar Beet Banana Potato

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Nanocelluloses – A Class of Nanomaterials

Properties of Nanocelluloses:

Diameter: 5 nm - 500 nm

Length: 10s nm - 100s mm

Specific surface area: 10s - 100s of m2/g

Surface modification: anionic, cationic, grafted, carboxymethylated, etc.

(analogue to cellulose macrofibers)

Main Characterization Methods:

Diameter: AFM / TEM / FE-SEM Lengths: Electron Microscopy / Rheology

Crystallinity: NMR / WAXS Surface properties: IR / NMR / Titration

Surface area: BET

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Deriving Potential Applications

Technology push AND Market Pull as Complementary Drivers:

Technology Push Market Pull

Product Development & Production

- Efficiency:Savings of raw materials & energy

- Productivity:e.g. Runability &new processes

- Added value products & new functionalities

Potentialapplications& production

processes

Science & Fundamental

Research- Synthesis &

modification

- Characterization

- Structure-Properties Relationships

- Demonstrationof new properties

Applied Science &

Technology

Development

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II. Structure-Properties Relationships

Nanocelluloses – Comparison with Related Applied Materials

MACROFIBERS

NANOPARTICLES

POLYMERS /

POLYELECTROLYTES

CNC

MFC

oxidized

NFC

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Structure-Properties Relationships

NFCs as Functional Materials – Identifying potential applications

MACROFIBERS

NANOPARTICLES

POLMERS / POLYELECTROLYTES

Pigments, Fillers, Strength-enhancing additives,

Nanocomposites, Coatings (Packaging),

Functional Surfaces, etc.

Fiber Web Structures

(Paper, Board),

Wood Fiber Composites,

Construction Materials,

Membranes, Filters,

Absorbents, etc.

Rheological Modifiers,

Flocculants (Retention aids),

Binders, Adhesives,

Coatings, etc.

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Identification of Potential Application Areas based on

Specific Properties of Nanocelluloses

III. Towards Applications

Potential Applications Composites

Construction Materials

Porous Materials

Fiber Web Structures

(e.g. Paper & Board)

Coatings

Functional Surfaces

Functional Additives

(e.g. rheological modifiers)

Others …

NFC Properties Natural & renewable

Biodegradability

Biocompatibility

High strength & modulus

High surface area

High aspect ratio

Chemical functionality

(e.g. for modification)

Dimensional stability

Moisture absorption

Thermal stability (~200°C)

Others …

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Composite & Construction Materials

Renewable and Biodegradable Composites

NFC as a strength enhancing additive for renewable

and biodegradable matrix polymers: (e.g. Okubo et. al, JSME Series A 48, 199–204 (2005))

Applications: Packaging, construction materials, appliances,

renewable fibers (Zoppe et al., Appl.Mat.Int., 1996-2004 (2009))

(Juntaro J, et. al (2008)

Adv Mater 20:3122)

Poly(lactid acid)-Sisal composite

with (right) and without (left) NFC

NFC as a binder between

the two organic phases

(improved fracture toughness &

prevention of crack formation)

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Composite & Construction Materials

Transparent Polymer-NFC Nanocomposites

NFC as a transparent and dimensional stable strength-enhancing

additive and substrates (Nakagaito, et. al, MRS Bulletin, 214-218 (2010),

Okahisa et. al, Composites Science and Technology, 1958–1961 (2009))

Application: - Large flexible screens, solar panels, flexible computers

- Paper-like, flexible displays (e.g. textiles by R2R)

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Composite & Construction Materials

Concrete and Cementicious Materials

Strength enhancement of cellular concrete (e.g. ‘Nanocrete Technologies‟)

Application: - Light-weight, foamed, cellular concrete structures

- Crack reduction, combining toughness & strength

(Walther et. al, Nano Letters (2010))

Foamed, cellular NFC-concrete

hybrid materials

Dense, silica-polymer

hybrid materials

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Porous Materials & Fiber Web Structures

Paper & Board Strength Enhancement

Wood fiber web structures – Paper as a porous nanocomposite(e.g. Gardner et. al, J. Adhesion Sci. and Tech. (2008) 545–567,

Eriksen et. al, Nordic Pulp & Paper Research Journal, 299-304 (2008))

NFC increased both:

binding area and binding strength (Stot ~ AB · SB)

Applications:

High strength / high bulk / high filler content paper & board

NFC

Wood fiber Filler

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Porous Materials & Fiber Web Structures

Porous Nanocellulosic Materials for Insulation & Packaging

Highly porous & strong nanocellulose web structures(e.g. Svagan et. al, Advanced Materials, 1263-1269 (2008))

Applications: Cellular Bioplastics, Insulation and Packaging,

(bio)active membranes & filters

X-ray microtomography:

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Porous Materials & Fiber Web Structures

Nanocellulose Scaffolds for Tissue Engineering

Bacterial nanocellulose as biocompatible, highly porous scaffolds(e.g. Bodin et. al, Biomacromolecules, 3697-3704 (2007))

Applications: Bone implants, artificial blood vessels,

stem cell therapy

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Coatings & Functional Surfaces

Nanocelluloses for Coating Applications

Nanocelluloses as barrier materials

Specific advantages: high oxygen barrier, affinity to wood fibers

Disadvantage: Moisture sensitive (hydrophobic compound required)(e.g. Hult et. al, Cellulose (2010))

Application: Food packaging, printing papers

(smooth surfaces, NFC as an organic pigment)

Multilayered coating

with oxygen and water

vapor barrier properties

NFC

Shellac

Paper

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Functional Additives

Nanocelluloses as Flocculants and Retention Aids

Functionalized nanocelluloses as retention aids, combing

a large hydrodynamic radius and high collision efficiency(e.g. Link Magazine 2008/2)

Applications: Retention aids, wet web strength additives,

dry strength additives, water-treatment

Cationic nanocelluloses

as flocculants e.g. retention aids

NFC

Fiber/fines/filler

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Functional Additives

Nanocelluloses as Rheological Modifiers

NFC as a thixotropic, biodegradable, dimensionally stable

thickener (stable against temperature and salt addition)

Low-calories food applications

Thickener in cosmetics

Pharma (tablet binder, diagnostics: bioactive paper)

Pickering stabilizer for emulsions & particle stabilized foams

Paint formulations

Enhanced oil recovery

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Other Applications

Manifold Opportunities for Other Applications

Flexible Energy Storage Devices (Batteries, supercapacitors)

Adaptive, biomimetic nanocomposites

(e.g. mimicking sea cucumber dermis)

(Capadona JR et. al, (2008) Science 319:1370)

(e.g. Nyström, Nano Letters (2009))

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Additional Aspects of Nanocellulose Applications

Multiscale Modelling of Nanocellulosic Materials

Optimized product properties & target-directed development

Life Cycle Analysis (LCA)

Quantification of eco-efficiency and sustainability factors

Nanosafety

Risk assesment of nanomaterials ongoing

Highest potential risk: Inhalation of airborne nanoparticles

Experience in food applications and medical applications

of nanocelluloses: no implications

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IV. Summary & Outlook

Nanocelluloses resemble a class of novel nanomaterials

Wide properties range of different modified and

non-modified nanocelluloses

Nanocellulose applications are based on the same principles:

Design of nanostructure, interfacial interactions,

& assembly into systems

Specific advantages of nanocelluloses:

Abundant, natural nanomaterials

Renewable, biodegradable & biocompatible

High strength & modulus

High aspect ratios & high surface areas

Chemical functionality & modification

Dimensional Stability

… and combinations of those !

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Summary & Outlook

Additional Long-term Perspectives for Papermaking, e.g.:

Wood-free papermaking:

- Use of NFC e.g. from bio-residues and other raw materials

instead of wood fibers

- NFCs show similar properties, independent from raw

materials sources (Abe et. al, Cellulose (2009) 16:1017–1023)

Water-free papermaking:

- Paper-like NFC web structures might be produced

from volatile solvents (e.g. alcohol) or dry processes

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Nanochemistry: What Is Next?Geoffrey A. Ozin et. al

“We believe that the major conceptual contribution of

nanochemistry … lies in the interdisciplinarity that it

has imprinted. … This transformation can probably be

considered as the greatest success story of

nanochemistry, as it has brought the science, engineering,

biology … together in a unique way to dream up and

create new materials that solve problems.”

small 2009, 5, No. 11, 1240–1244

“ There is an increasingly common feeling that nanoscience

has not yet delivered on its initial promises, especially from

a technological perspective. ”

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Thanks for your attention !