Country Presentation: France · 2011-08-10 · Country Presentation: France Nanocellulose 2. The state of development of nanocellulose and its target application in France HISTORY

Country Presentation:FranceFrance

Alain DUFRESNEAlain DUFRESNEThe French School of Paper, Print Media and Biomaterials (Pagora)

Grenoble Institute of Technology, France

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2011 TAPPI International Conference on Nanotechnology for Renewable MaterialsWorkshop on International Standards for Nanocellulose

June 9, 2011, Arlington

Country Presentation: France

NanocelluloseNanocellulose

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The state of development of nanocellulose and its target application in France

HISTORY OF NCC

1951 Rånby (acid hydrolysis of cellulose)1951 Rånby (acid hydrolysis of cellulose)

1959 Marchessault et al. (birefringent, ordered, liquid crystal behavior)

1961 Battista (commercialization of MCC)

1992 Revol et al. (chiral nematic behavior)

1997 Revol et al. (Solidified liquid crystals of cellulose with optically variable properties)variable properties)

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2011 Commercialization of NCC (FPInnovation)

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HISTORY OF NCC

1951 Rånby (acid hydrolysis of cellulose)1951 Rånby (acid hydrolysis of cellulose)

1959 Marchessault et al. (birefringent, ordered, liquid crystal behavior)

1961 Battista (commercialization of MCC)

1992 Revol et al. (chiral nematic behavior)

1995 Favier et al. (polymer nanocomposites reinforced with NCC)

1997 R l l (S lidifi d li id l f ll l i h i ll 1997 Revol et al. (Solidified liquid crystals of cellulose with optically variable properties)

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2011 Commercialization of NCC (FPInnovation)

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EARLY WORKS


EARLY WORKS

Pioneering works on nanocellulose reinforced polymer nanocomposites in Grenoble (1995)

PhD Vé i F i T i i hi k i f d l ( B )PhD Véronique Favier : Tunicin whiskers reinforced poly(S-co-BuA)

Objective: reinforcement of a model latex-form polymeric matrix with nano-sized renewable particles extracted from tunicate

Main outcome : outstanding mechanical properties ascribed to a mechanical percolation effect of the cellulosic nanoparticles

-2

-1

0

G' T/

G' 20

0

6 wt%

12 wt%

1 Hz

R

-5

-4

-3

log

G

0 wt%

1 wt%

3 wt%

R

S

5

200 300 400 500

Temperature (K)


CURRENT STATE OF DEVELOPMENT

Development of a pilot set-up for production of MFC at The Pulp and Paper p f p p f p f p pResearch & Technical Center (CTP), Grenoble

Homogenizer GEA Niro Soavi ARIETE NS3075H

Production 1 m3 h-1 55 kW 30 100 kg day-1Production 1 m3.h-1, 55 kW → 30-100 kg.day-1

Available for MFC production in September 2011

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Target applications (liquid medium)Target applications (liquid medium)

- Paper : in bulk (mechanical strength) or on the surface (barrier properties or functionality) → problem of low concentration

-Treatment of timber or wood panels

- Paints

- …

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Commercialization and marketing outlook

N hiNothing

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The need for international standards - Terminology

Pääkkö, et al. 2007

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Pääkkö, et al. 2007


Sugar Beet Pulp Potato Pulp Opuntia ficus-indica

D f t l 1997 D f t l 2000 M l i i t l 2005Dufresne et al., 1997 Dufresne et al., 2000 Malainine et al., 2005

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Acronym Terminology Reference


MFC Microfibrillated Cellulose (Herrick et al., 1983; Turbak et al., 1983)

─ Cellulose Microfibrils (Dufresne et al., 1997; Dinand et al., 1999)

Fibrillated Cellulose (Azizi Samir et al 2004)─ Fibrillated Cellulose (Azizi Samir et al., 2004)

─ Nanofibrillar Cellulose (Jin et al, 2004)

─ Fibril Aggregates (Cheng et al., 2007)

─ Nanoscale Cellulose Fibrils (Pääkkö et al., 2007)

─ Microfibrillated Cellulose Nanofibers (Henriksson et al., 2007)

─ Cellulose Fibril Aggregates (Cheng et al., 2007)

CNF Cellulose Nanofibers (Abe et al., 2007; Alemdar and Sain, 2008)

─ Cellulose Nanofibrils (Henriksson et al., 2008 ; Ahola et al., 2008a ; 2008b)

─ Cellulose Microfibers (Bhattacharya et al., 2008)

Microfibril Aggregates (Abe et al 2009)─ Microfibril Aggregates (Abe et al., 2009)

─ Cellulose Microfibril Aggregates (Abe and Yano, 2009)

─ Cellulose Fibrils (Cheng et al., 2009a; 2009b)

NFC Nanofibrillated Cellulose (Mörseburg and Chinga-Carrasco, 2009 ; Chinga-C d S d 2010)

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Carrasco and Syverud, 2010)

─ Microfibrillar Cellulose (Spence et al., 2010)


ysis

Crystalline Region Amorphous Region

Aci

d H

ydro

ly

Nanocrystals

Tunicin RamieTunicin400 nm

Habibi et al., 2008Favier et al., 1995 Helbert et al., 1996

Wheat Straw

Fleming et al., 2000

Cotton

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Acronym Terminology Reference

─ Cellulose micelles (Rånby, 1949)

─ Level-off D.P. cellulose product (Battista and Smith, 1961)

Wh Cellulose Whiskers (Helbert et al., 1996; Dufresne, 2008)

─ Cellulose Crystallites (Dong et al., 1996)

─ Cellulose Microcrystals (Araki et al., 2001)

CNC Cellulose Nanocrystals (Grunert and Winter, 2002 ; Paralikar et al., 2008; Mangalam et al., 2009)

CNW Cellulose Nanowhiskers (Oksman et al., 2006 ; Petersson et al., 2007; Habibi et al., 2008; Braun et al., 2008 ; Rojas et al.,

2009)

─ Nanocellulose (Morán et al., 2008)

NCC Nanocrystalline Cellulose (Bai et al., 2009)

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l We can try to find an universal terminology for each group of

ll lnanocellulose…

but it’s not so simplebut it s not so simple…

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MFC H2SO4 20%MFC H2SO4 20%

H2SO4 60%

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Azizi Samir et al., 2004


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Siqueira et al., 2010


MFC H2SO4 45°CMFC H2SO4 45 C

H2SO4 50°C H2SO4 60°C

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E: Ecopulp Energy (exoglucanase activity)E: Ecopulp Energy (exoglucanase activity)

C: Celluclast (endoglucanase activity)

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19



T

20Siqueira et al., 2011


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Different terminologies to describe mechanically-sheared and acid-hydrolyzed cellulose

Depending on the preparation conditions of the nanoparticles and sequence of the treatment, the belonging to a given group of nanocellulose is not obviousnanocellulose is not obvious

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The need for international standards – Metrology and Characterization

Nanoparticles are defined as particles with at least one dimension in the 1 100 range 1-100 nm

Size distribution: from which concentration of nanoparticles a material can pbe classified as nano ?

Concentration of nanoparticles : should this concentration be regarded by weight or by number ?g y

Shape and size : difficulties to characterize shape and size of non-spherical nanoparticles (except TEM)

Organic nanoparticles : observation more difficult by microscopic Organic nanoparticles : observation more difficult by microscopic techniques than inorganic nanoparticles

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Current challenge: processing of nanocomposites by dispersion of cellulose nanoparticles in the melt

The concept of dispersion and distribution of nanoparticles in nanocomposites:

(a) poor dispersion and distribution,(a) poor d spers on and d str but on,

(b) poor dispersion and good distribution,

(c) good dispersion and poor distribution,

(d) good dispersion and distribution.

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Current challenge: processing of nanocomposites by dispersion of cellulose ti l i th ltnanoparticles in the melt

Development of methods for dispersing in the meltp p g

Development of methods to assess the quality of the homogeneity of dispersions (microscopy, other ...)

Understanding the various parameters affecting the dispersion in Understanding the various parameters affecting the dispersion in heterogeneous phase (solid in liquid)

Application of existing equipments / tools that allow the dispersion of nanoscale colloidal fillersnanoscale colloidal fillers

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Documents

Country Presentation: France · 2011-08-10 · Country Presentation: France Nanocellulose 2. The state of development of nanocellulose and its target application in France HISTORY