Use of nanocellulose in fibre-based packaging: from ......Future Markets, The global market for nanocellulose to 2020, 2nd ed. Future Markets Inc, 2012 USDA Global production estimate:

Use of nanocellulose in fibre-based packaging: from barrier to activeand intelligent packaging

Julien BRAS

November 23th, 2016

University Grenoble Alpes, Grenoble INP - LGP2

Institut Universitaire de France (IUF 2016-2021) [email protected]

1

AT THE CROSSROAD OF LEADING DISCIPLINES

CHEMISTRY, MATERIALS, PROCESSES

Biorefinery: woodchemistry and eco-

process

Multi-scale bio-basedmaterials

Surface functionalization by

printing

www. pagora.grenoble-inp.fr

Laboratory of Paper science & Graphic arts

LGP2 - UMR 5518

10 Permanent researchers, 5 technical staff, 25 PhD & Post-doc

3 research departments

http://pagora.grenoble-inp.fr/

1. Nanocellulose & production

2. From barrier packaging…

3. To active & intelligent packaging

OUTLINE

NanoCellulose

Evolution of annual non-cumulative

number of publications and patents

on nanocellulose(Source: SciFinder, July 2016 –

descriptors : cellulose nanofibrils, cellulose microfibrils, cellulose

nanocrystals, cellulose nanowhiskers, microfibrillated cellulose)

AmorphousCrystalline

fiber

microfibril

Hierarchical Structure

Adapted from Pääkkö, et al. 2007

Multi-level Organization

(Nano)Cellulose

1. Hydrolysis

2. Dialysis /UF

2. Mechanical

Homogenization

1. Defibrillation

D 2-10 nmL 150-1000 nm

D 2-20 nmL ˃ 1000 nm

Cellulose fiber

Mic

ro

fib

ril

Cellulose Nanocrystals (CNC)

Microfibrillated cellulose (MFC)

6

NanoCellulose

World Production by Type

Bacterial Cellulose

1%

Cellulose Nanocrystals

34%

Cellulose Nanofibrils

65%

Future Markets, The global market for nanocellulose to 2020, 2nd ed. Future Markets Inc, 2012

USDA

Global production

estimate: 34 million

tons/year by 2050

FPI market estimate:

$250 million in North

America by 2020

Production cost:

Pulp: $0.75-1.00/kg

Nanocellulose: $4-40/kg

Cranston 2015

Nanocellulose

Slide provided by Robert Moon, USDA FPL

Nanocellulose

=> Nanocellulose = 2nd priority of european Bioeconomy

=> Not only fashionable but also sustainable

NanoCellulose

10

(figure in ktons)

NanoCellulose




OUTLINE

Paper & Nanocellulose: In Bulk

Bardet R.., Bras J., MFC in Paper, 2014, Handbook of Green Materials, K.Oksman,

Several strategies

BUT not with NCC

Adapted from Voith, 2013

Coating Formula &

rheology process Drying PropertiesCoating process

Paper & Nanocellulose : On Surface

Why not coating nanocellulose ?

Bardet R.., Bras J., MFC in Paper, 2014, Handbook of Green Materials, K.Oksman

Paper & Nanocellulose : On Surface

MFC

15

Water Vapor Permeability

(x10-11g/(m.s.Pa)

Oxyge

n p

erm

eab

ility

(cm

3.µ

m)/

(m².

da

y.kP

a)

10000

1000

100

10

1

0.1

0.01

1000010010.010.0001

Lavoine et al. (2012)

=> CNF = The best bio-based barrier

…at low HR

Paper & Nanocellulose : Barrier

Structure properties (SEM, coat weights, thickness)

Mechanical properties (Young modulus, strength, elongation at break, burst index, bending

stiffness)

Barrier properties (Air permeability, grease resistance, water absorption)

MFC

suspension

Base paper

Bar coating process Size press process

ANALYSIS

MFC MFC

&

MFC

COATING

MATERIALS

Lavoine N.,et al (2014), Impact of

different coating processes of

microfibrillated cellulose on the

mechanical and barrier properties of

paper, J. Mater. Sci., 49, 2879-2893.


0

1

2

3

4

5

6

7

8

9

10

Base paper x5 x10

Bendin

g s

tiff

ness (

x1

00

mN

.m)

Water treatment_Cross direction

MFC coating_Cross direction

0

1000

2000

3000

4000

5000

6000

7000

8000

5 10

Air

perm

ean

ce (n

m/P

a.s

)

Number of treatments/coatings

Bar coating - H2O Bar coating - MFC

Size press - H2O Size Press - MFC

Base paper

=> Positive impact on air barrier &

stiffness only for bar coating


Paper Paper+MFC

GR

EA

SE

BA

RR

IER

0

20

40

60

80

100

0 5 10 15

Pa

per s

urfa

ce c

ov

ered

by

th

e o

il (

%)

Number of layers

Water treatment

MFC coating

Lavoine N.,et al (2014), J. Mater. Sci., 49, 2879-2893.

=> Interesting grease barrier of MFC coating


19Bardet, Reverdy, Belgacem, Leirset, Syverud, Bras, J

(2015) Cellulose, 22(2), 1227-1241


Adapted from Voith, 2013

0,0

2,0

4,0

6,0

8,0

10,0

12,0

14,0

16,0

50 60 70 80 90 100

Oxy

gen

Pe

rme

abili

ty(c

m3

.µm

/m².

d.k

Pa)

Relative Humidity (%)

CNF

CNF overdried

CNF/CNC-T

CNF/CNC-T overdried30%


Guezennec et al, SunPap conference, 2013


=> CNF = network controlling-

dispersing drying energy

=> No more BlisteringAdapted from Guezennec et al,

SunPap conference, 2013


Adapted from Guezennec et al,

SunPap conference, 2013





OUTLINE

25

Release mechanism Antimicrobial agents incorporated in

the packaging. Migrate into food through

diffusioning and partitioning. Very positive impact of MFC for

release monitoring=> prolonged antimicrobial activity

whatever molecules

(i) Incorporation into CNF network

Lavoine, N.; Desloges, I.; Sillard, C.; Bras, J. (2014)

Controlled release and long-term antibacterial activity of chlorhexidine

digluconate through the nanoporous network of microfibrillated cellulose,

Cellulose, 21(6), 4429-4442.

BUT Decreasing effect over time.

Antimicrobial packaging

26

Release mechanism Antimicrobial agents incorporated in

the packaging. Migrate into food through

diffusioning and partitioning. Decreasing effect over time.

Contact mechanism Antimicrobial agents immobilized on the

packaging. Microbial suppression at the contact

surface without diffusion. Prolong effect.

(i) Incorporation into CNF network (ii) Immobilisation onto CNF

- Saini, ; Belgacem, N; Mendes, J; Elegir, G; Bras, J

Contact Antimicrobial Surface Obtained by Chemical Grafting of Microfibrillated Cellulose in Aqueous Solution Limiting Antibiotic Release,

ACS Applied Materials & Interfaces (2015), 7(32), 18076-18085

-Saini, M. N. Belgacem, K. Missoum, J. Bras,

Natural active molecule chemical grafting on the surface of microfibrillated cellulose for fabrication of contact active antimicrobial

surfaces, Industrial Crops and Products (2015), Accepted-in press.

BUT solvent system or bacteria selectivity


27

Chitosan - (1, 4)-linked 2-amino-deoxy-b-D glucan units

Sources in the form of chitin : Sea crustaceans

Limited applications due to:

ˣ insolubility in water

ˣ high viscosity

ˣ tendency to coagulate with

proteins

ˣ difficulties to obtain high

specific area nanofibre (cost)

Responsible for antibacterial activity


CNF functionnalization

Nechyporchuk, Belgacem, Bras

Production of cellulose nanofibrils: a review of recent advances,

Ind crops (2016), in press

Mechanical Treatment(Homogeniser, Microfluidiser, Grinding) Pretreatment

29

*Pääkkö et al. (2007) Biomacromolecules

Enzymatic Hydrolysis

( Cellulase or endoglucanase)

Tempo oxidation

(Tempo/NaBr/NaClO)

Cationization

(2,3-epoxypropyl

trimethylammonium chloride or

chlorocholine chloride)

*Pei et al. (2013) Soft matter

L>2 µm / D>30 nm

L>2 µm / D>30

nm

L ~2,2 µm / D = 2-5 nm

*Siqueira et al. (2009) Biomacromolecules

*Saito et al. (2006) Biomacromolecules

CNF Pre-treatment

30

2,3-epoxypropyl trimethylammonium chloride (EPTMAC)

NaOH, EPTMAC (65°C)

Step 1: Optimisation of pretreatment for different DS

Degree of substitution

Energy consumption

Cationized nanofibrils

+

++

++

+ +

+

++

++

+ +

Morphology

Qualitative and quantitative

antimicrobial activityActivity against

Gram +ve and Gram

–ve bacteria

Step 2: Antibacterial activity

evaluation of cationic CNF

CNF Pre-treatment

Surface cationized cellulose nanofibrils for the production of contact active antimicrobial surfaces ,

S. Saini, C. Yucel-Falco, M. N. Belgacem, J. Bras Carbohydrate polymers (2015), 135, pp 239-247.

31

• No Zone of inhibtion: No free EPTMAC leaching• Antimicrobial by contact

Bacteria: Bacillus subtilis (Level 1) Gram +ve

CAT-MFC DS= 0.18PENICILLIN: Positive Control ENZY MFC: Negative Control


CATMFC DS=0,04: Antimicrobial agents lower than Minimum inhibitory concentration.

CATMFC DS=0,18: 3 log reduction with high SD => samples are heterogenous.

E.coli – need to increase degree of substitution.

32

1,00E+00

1,00E+01

1,00E+02

1,00E+03

1,00E+04

1,00E+05

1,00E+06

1,00E+07

1,00E+08

1,00E+09

0 0,05 0,1 0,15 0,2

CF

U/

ml

Degree of substitution

B. subtilis (Gram +ve) S. aureus (Gram +ve) E.Coli (Gram -ve)

Initial CFU 1,65E+05

S. Saini, C. Yucel-Falco, M. N. Belgacem, J. Bras, « Surface cationized

cellulose nanofibrils for the production of contact active antimicrobial

surfaces », Carbohydrate polymers (2015), 135, pp 239-247.


Industrial Pilot trial at Multipackaging Solutions

33

Towards demonstrator


0

200

400

600

800

1000

1200

2000 2005 2010 2015

Pa

ten

t +

pu

bli

cati

on

nu

mb

er

Year

Nanocellulose

Nanocellulose+Electronics

- High value added expectations

- Less than 10 years

- Very new field: only few research groups and companies

Hoeng , Denneulin, Bras, Use of Nanocellulose in printed electronics,

Nanoscale, 2016

Nanocellulose & printed electronics

Nanocellulose as dispersing agent for mineral/conductive particles

Carbon nanotubes –CNC (Oliver et al. 2012, Moreau et al. 2016)

TiO2 - CNF(Bardet et al. 2013)

Polypyrrole- CNF(Sasso et al. 2010Wu et al. 2014 )

MoS2 and BN - CNF (Li et al. 2015)

OH OHOH

Carbon nanotubes –CNF(Koga et al. 2013, Tang et al. 2014)

No work with silver nanowires

Nanocellulose for printed electronics

Materials and methods

Conductive ink based on nanocelluloses: process

Cellulose microfibrilsL= 1 µm

d= 20 nm

Silver NW in solvent

PolyBioWire® Ink(Patent protected –

FR1553131)

Easy process

No addition of others chemicals

AdaptedMixing

Stable silvernanowires ink

Stable aqueous silver nanowires ink based on renewable materials

Silver nanowiresL= 50 µm

d= 150-200 nm

Cellulose microfibrils gel

Conductive ink based on nanocelluloses: process

0,4

0,5

0,6

0,7

0,8

0,9

1

1,1

1,2

1,3

0 5 10 15 20 25

Sed

imen

t h

eig

ht

(cm

)

Time (days)

CNF

CNC

HPMC

Neat CNF

Neat CNF Functionnalized

CNF

Funct. CNF

Stable aqueous silver nanowires ink only with Functionnalized CNF

PolyBioWire®: opto-electrical properties

PolyBioWire® film properties on PET PolyBioWire® film

Substrate PET

Rsh (Ω/)* 22 ± 3

T% (%)* 88 ± 0,4

L* 3,1 ± 1,8

a* 0,56 ± 0,08

b* 0,78 ± 0,31

*Best compromise in opto-electrical properties

No color deviation

High transmittance

Low resistance

PolyBioWire® coated film

PolyBioWire® film patent protected FR1553131)

PolyBioWire®: PolyBioWire® film properties

PolyBioWire® flexibility

PolyBioWire® adhesion on substrate

Rsh (Ω/)

Before scotch test After scotch test

Silver nanowires 61 ± 22 /

MFC-Silver nanowires 22 ± 2 23 ± 4

Conductive properties evenunder flexion

PolyBioWire® is flexible

Increase adhesion thanksto MFC

No change in conductiveproperties

PolyBioWire® film flexibility (patent protected FR1553131)

Flexible conductive film with no need of protection layer

Hoeng et al , PE-US, 2015




OUTLINE

Conclusions

Nanocellulose in MatBio

Lab scale trials from CTP

(Dynamic handsheets)

CTP’s curtain coater located above Grenoble INP Pagora’s paper machine

THANK YOU FOR YOUR ATTENTION

Join us in the LinkedIn group « Nanocellulose Materials »

[email protected]

Acknowledgement to my collaborators in this work:

Seema, Charlene, Oleksander, Nathalie, Isabelle, Naceur

2 Post-doc positions

open: Contact me

Use of nanocellulose in fibre-based packaging: from ......Future Markets, The global market for nanocellulose to 2020, 2nd ed. Future Markets Inc, 2012 USDA Global production estimate:

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