Nanocellulose in Packaging
March 14, 2013
Pia Qvintus, Tekla Tammelin, Soledad Peresin, Ali
Harlin, Erkki Hellen, Ulla Forsström
VTT Technical Research Centre of Finland
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Nanocellulose research at VTT
Wood Bacteria Straw Sugar Beet Banana Potato
20
15
10
5
Safety and sustainability
0
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Worlwide production of natural fibers and chemical composition
Raw Production Fibers yield Chemical
material (MT) (MT) Composition (%)
2009 2011 (2011) Cellulose Hemicelluloses Lignin Ash
Corn stover 786 832 666 37.4 27.6 18 5.2
1,5-5
Sugarcane bagasse 1680 1794 431 32-44 27-32 19-24
(0.7-3 SiO2)
Banana fiber 96 105 47 31 15 15 9
Sugar beet 228 272 15 20 25 (25-30% pectins)
Soybeans (hulls) 224 261 19 56 12.5 18
Palm oil (EFB) 45 48 19 48 19 25 3.2
Cotton (inters) 27 25 2.5 80-85 3.0-3.3 1-2 (<1 SiO2)
Jute 2.9 2.6 2.6 61 18-21 12-26 0.5-1.0 (<1 SiO2)
Flax 0.8 0.5 0.5 45-68 6-17 10-15 2-5
Coir 0.40 0.5 0.5 20-30 8.5 65-70 3.6
Sisal 0.3 0.2 0.2 43-56 21-24 8-9 0.6-1.0 (<1 SiO2)
Hemp (Bast fibers) 55-72 7-19 2-5 4
0.07 0.09 0.1
Hemp (woody core) 34-44 31-37 19-28 1-2
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The main steps involved in the preparation
of cellulose nanoparticles/fibers
Millled Fibers
Alkali Treatment (80 oC)
NaOH 4% (wt/wt)
Bleaching Treatment (80 oC)
NaCIO 2/ Acetate buffer (pH=4.8)
Hydrolysis Mechanical
Homogenization
Dialysis Defibrilation
Nanocrystals MFC
Source:
Future Markets,Inc.
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Nanocellulose – family of materials
Properties of nanocelluloses:
Diameter: 5 nm - 500 nm
Length: 10s nm - 100s m
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
Hans-Peter Hentze, VTT - ’From Nanocellulose Science towards Applications’ - 2nd of June 2010
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Different kinds of nano- and microcelluloses
Micro/nanofibrillated cellulose Nanocrystalline cellulose Bacterial nanocellulose
(M/NFC) (NCC) (BC)
width: 5-6 nm (cellulose width: 2-20 nm width: 20-100, length >
fibrils) 1µm
length: 100-600 nm
width: 10-20 nm (fibril
aggregates)
length > 1µm
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Lab scale production of nano/microfibrillated
cellulose at VTT
Masuko Super Masscolloider Microfluidics Fluidizer Processor M-700
UPM started precommercial production of fibrillated cellulose grades in November 2011
Contact information for samples:
[email protected],
[email protected] 14/03/2013 8
Appearance of fibrillated nanocellulose gels
Masscolloider Fluidizer
Carboxymethylation TEMPO oxidation Cationization
Tiina Pöhler et al, 2010 TAPPI International Conference on Nanotechnology for the Forest Product Industry
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Potential application areas are based on specific
advantages of nanocellulose
Properties of nanocellulose Function of nanocellulose
Potential applications
fibres in applications
Natural & renewable
Composites
Biodegradability Reinforcement
Construction Materials
Biocompatibility Viscosity modifier
Porous Materials
High strength & modulus Stabilizer
Fiber Web Structures
High surface area (e.g. Paper & Board) Binder
High aspect ratio Coatings Barrier
Chemical functionality Functional Surfaces Film forming
(e.g. for modification)
Functional Additives Structural material in foams
Dimensional stability (e.g. rheological modifiers)
Others …
Moisture absorption Others …
Thermal stability (~200°C)
Others …
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Patent applications for nanocellulose,
by market segments, 2011
(Source:KETEK)
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Nanocellulose production volumes ton per year,
all types, forecast 3548
Tons per year
Year
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From research and development to
applications
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Role of nanocellulose in packaging?
Fiber based packages
Strength additive
Binder
Barrier
Plastic packaging
Reinforcement
Barrier
Part of multilayer
structures
Packaging films and foams
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Nanocellulose (NFC) in (bio)plastics
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Compatibilisation of hydrophilic NFC fibres
R = Benzyl
Hydrophobisations through 1)
silylations, 2) etherifications with epoxy
compounds, 3) esterifications
R = Diphenyl Acetyl
Laccase catalysed hydrophobisation of
R
=B
uty
ryl
lignin rich NFC in composites
Reactive, allylic and epoxified NFC
Cationised and anionised NFC
=> Surface modification according to the
need of applications
NASEVA 2008 - 2011
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NFC reinforced biodegradable polymer composites
with controlled melt rheology
Good distribution of NFC in polymer has been achieved by so called in-situ polymerisation of
NFC with -caprolactone (CL). The NFC network formed in the polymer increases the melt
strength and mechanical properties of the polymer e.g. stiffness, tensile strength and impact
strength. A strong indication of good dispersion can be seen in the rheology of the polymer with <
1% NFC content. Rheology measurements show the shear thinning effect of the NFC-g-PCL
polymer.
The increased melt
strength is expected to be
advantageous for
Films
Extrusion coatings
Pipes & profiles
Blow moulding products
Patent application Härkönen, M., Wikström, L., Nättinen, K., Nurmi, L., Mikkonen, H. (VTT) WO2012093205
Source: Naseva 1 project, a cross disciplinary project aiming at novel applications of nanocellulose
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Thermoplastic NFC composites
In-situ polymerisation of NFC-g-PCL
materials (<1% NFC) => Increases in
melt strength and mechanical
properties. Orientation further improves
mechanical properties.
NASEVA 2008 - 2011
Patent pending
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NFC reinforced biodegradable polymer composites
Production of biodegradable polymer (PVA) and NFC composites with improved
mechanical performance and good optical properties
Composite has 474 % and 224 % greater modulus and strength, respectively,
compared to pure PVA polymer
Solution: improvement in PVA’s mechanical properties is achieved by addition of
functionalized cellulose nanofibres in biopolymer matrix
Patent pending
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Example of polyolefine-NFC composites
• PP/NFC films prepare by prof. Hiroyuki Yano. Kyoto University
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Nanocellulose (NFC) in paper and board
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Strength with nanocellulose
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Addition of 1-2% of nanocellulose to paper –
10% decrease in grammage
Trial at VTT’s SUORA environment (hybrid former, shoe press)
When adding nanocellulose
Reduction of wire section dewatering
Dry solids 1-3%-unit higher after press section
No changes in formation or retention
Tensile strength increases (~8g/m2 basis weight reduction)
Elastic modulus increases strongly
Bending stiffness remains the same
20-30% lower porosity
Opacity ~4%-units lower
Nanocellulose increases strength even at low dosages
Good overall runnability
Applicability: Packaging papers, board, graphic papers, layered products…
I. Kajanto and M. Kosonen, UPM - 2012 TAPPI International Conference on Nanotechnology for Renewable Materials
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Oxygen barrier with nanocellulose in paper
coating
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Binding of active components with nanocellulose
to paper/board surface
S. aureus K. pneumoniae
*) Standard solar light lamp (6 h) **) 15 h room light
7,00 8,00 *) **)
*) **) untreated
6,00 7,00
paper (control) untreated paper
5,00 6,00
Foam coated 5,00
(control)
4,00
paper 4,00 Foam coated
3,00 paper
*) **) 3,00
2,00 *) **)
2,00
1,00 1,00
*) **) *) **)
0,00 0,00
after contact Bacteriostatic activity Bactericidal activity after contact Bacteriostatic activity Bactericidal activity
(log CFU T18h) (log reduction) (log reduction) (log CFU T18h) (log reduction) (log reduction)
NFC/ZnO has significant antibacterial activity against S. aureus and
K. pneumoniae.
The research leading to these results has received funding from the
European Community's 7th Frame work Programme under grant
Patrizia Sadocco, INNOVHUB - Stazioni Sperimentali Industria agreement no 228802
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Rigid foams of nanocellulose
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Plastic-like translucent films of nanocellulose
Solvent casting method
Pilot scale, roll-to-roll
production of films
SutCo surface treatment
concept (VTT)
Several meters of
extremely smooth,
translucent ”plastic-like”
film
Based on filed patent application (Tammelin et al., Method for the Preparation of NFC films on Supports)
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Water tolerance of modified NFC film
100
Ref_UVNFC film
Untreated
Silyl_UV
Modified NFC film
80
Contact angle (degrees)
60
40
20
0
0 10 20 30 40 50 60
Time (seconds)
.
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NFC film as a barrier
Comparision to
commercial products
.
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What about safety?
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Evaluation of safety aspects
focused on NFC/MFC and occupational exposure, environmental
toxicity in vitro and in vivo
Focus
Source: Pöyry NASEVA 2008 - 2011
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Nano/microfibrillated cellulose
Safety issues and assessment of nanotechnology
based products
Exposure assessment
Determination of exposure levels of engineered nanoparticles
(ENPs) in industrial facilities
Sampling, identification and characterisation of ENPs
Behaviour of ENPs during recycling, reuse and final treatment
Human safety assessment
Monolayer and organotypic human cell culture systems for
determination of uptake and toxicity effects of NPs
Cell-based high throughput functional screening of NPs
Tissue or cell lysate microarraysmultiplex protein analysis for
generation of broad activity or toxicity profiles of NPs
Environmental safety assessment
Degradability/Biodegradability
Aquatic biodegradability, Composting tests, Soil applications
Effect on waste water treatment and effluent quality
Ecotoxicological assessment
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Why nanocellulose?
Because of specific advantages
Abundant, natural nanomaterials
Renewable, biodegradable & biocompatible
High strength & modulus
High aspect ratios & high surface areas
Chemical functionality & modification
Dimensional Stability
Wide property range of different modified and non-modified nanocelluloses
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Thank you for your attention!
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