nanocellulose in packaging march 14, 2013 in packaging march 14, 2013 pia qvintus, tekla tammelin,...
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Nanocellulose in PackagingMarch 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 VTTWood Bacteria Straw Sugar Beet Banana Potato
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Safety and sustainabilitySafety and sustainability
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Rawmaterial
Production(MT)
Fibers yield(MT)
ChemicalComposition (%)
2009 2011 (2011) Cellulose Hemicelluloses Lignin Ash
Corn stover 786 832 666 37.4 27.6 18 5.2
Sugarcane bagasse 1680 1794 431 32-44 27-32 19-24 1,5-5(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)0.07 0.09 0.1
55-72 7-19 2-5 4
Hemp (woody core) 34-44 31-37 19-28 1-2
Worlwide production of natural fibers and chemical composition
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The main steps involved in the preparation of cellulose nanoparticles/fibers
Source: Future Markets,Inc.
Millled Fibers
Alkali Treatment (80 C)NaOH 4% (wt/wt)
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Bleaching Treatment (80 C)NaCIO / Acetate buffer (pH=4.8)
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Hydrolysis
Dialysis
Nanocrystals
MechanicalHomogenization
Defibrilation
MFC
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Nanocellulose – family of materials
Properties of nanocelluloses:Diameter: 5 nm - 500 nmLength: 10s nm - 100s mSpecific surface area: 10s - 100s of m2/gSurface modification: anionic, cationic, grafted, carboxymethylated, etc.
(analogue to cellulose macrofibers)
Main characterization methods:Diameter: AFM / TEM / FE-SEM Lengths: Electron Microscopy / RheologyCrystallinity: NMR / WAXS Surface properties: IR / NMR / TitrationSurface 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 (M/NFC)
width: 5-6 nm (cellulose fibrils)width: 10-20 nm (fibril aggregates)length > 1µm
Nanocrystalline cellulose (NCC)
width: 2-20 nmlength: 100-600 nm
Bacterial nanocellulose (BC)
width: 20-100, length > 1µm
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Lab scale production of nano/microfibrillatedcellulose at VTT
Masuko Super Masscolloider Microfluidics Fluidizer Processor M-700
UPM started precommercial production of fibrillated cellulose grades in November 2011Contact information for samples: [email protected], [email protected]
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Appearance of fibrillated nanocellulose gelsMasscolloider Fluidizer
Carboxymethylation TEMPO oxidation Cationization
Tiina Pöhler et al, 2010 TAPPI International Conference on Nanotechnology for the Forest Product Industry
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Properties of nanocellulose
Natural & renewableBiodegradabilityBiocompatibilityHigh strength & modulusHigh surface areaHigh aspect ratioChemical functionality(e.g. for modification)Dimensional stabilityMoisture absorptionThermal stability (~200°C)Others …
Potential applications
CompositesConstruction MaterialsPorous MaterialsFiber Web Structures(e.g. Paper & Board)CoatingsFunctional SurfacesFunctional Additives(e.g. rheological modifiers)Others …
Potential application areas are based on specific advantages of nanocellulose
Function of nanocellulosefibres in applications
ReinforcementViscosity modifierStabilizerBinderBarrierFilm formingStructural material in foamsOthers …
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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 y
ear
Year
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From research and development to applications
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Role of nanocellulose in packaging?Fiber based packages
Strength additiveBinderBarrier
Plastic packagingReinforcementBarrierPart of multilayerstructures
Packaging films and foams
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Nanocellulose (NFC) in (bio)plastics
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Compatibilisation of hydrophilic NFC fibres
Hydrophobisations through 1) silylations, 2) etherifications with epoxy compounds, 3) esterificationsLaccase catalysed hydrophobisation of lignin rich NFC in compositesReactive, allylic and epoxified NFCCationised and anionised NFC
=> Surface modification according to the need of applications
R=
Ben
zyl
R=
Butyryl
R=
Dip hen yl A
ce tyl
NASEVA 2008 - 2011
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NFC reinforced biodegradable polymer composites with controlled melt rheology
The increased melt strength is expected to be advantageous for
Films Extrusion coatings Pipes & profilesBlow moulding products
Source: Naseva 1 project, a cross disciplinary project aiming at novel applications of nanocellulose
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.
Patent application Härkönen, M., Wikström, L., Nättinen, K., Nurmi, L., Mikkonen, H. (VTT) WO2012093205
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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 - 2011Patent 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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Trial at VTT’s SUORA environment (hybrid former, shoe press)
When adding nanocelluloseReduction of wire section dewateringDry solids 1-3%-unit higher after press sectionNo changes in formation or retention Tensile strength increases (~8g/m2 basis weight reduction)Elastic modulus increases stronglyBending stiffness remains the same20-30% lower porosityOpacity ~4%-units lower
Nanocellulose increases strength even at low dosagesGood overall runnabilityApplicability: Packaging papers, board, graphic papers, layered products…
Addition of 1-2% of nanocellulose to paper –10% decrease in grammage
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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after contact(log CFU T18h)
Bacteriostatic activity(log reduction)
Bactericidal activity(log reduction)
untreated paper(control)Foam coatedpaper
Binding of active components with nanocelluloseto paper/board surface
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after contact(log CFU T18h)
Bacteriostatic activity(log reduction)
Bactericidal activity(log reduction)
untreatedpaper (control)
Foam coatedpaper
S. aureus K. pneumoniae*) Standard solar light lamp (6 h) **) 15 h room light
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 agreement no 228802Patrizia Sadocco, INNOVHUB - Stazioni Sperimentali Industria
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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-rollproduction of films
SutCo surface treatmentconcept (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
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tact
ang
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egre
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Time (seconds)
Ref_UV Silyl_UV
Untreated NFC filmModified NFC film
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NFC film as a barrierComparision 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 celluloseSafety issues and assessment of nanotechnology
based productsExposure assessment
Determination of exposure levels of engineered nanoparticles (ENPs) in industrial facilitiesSampling, identification and characterisation of ENPsBehaviour of ENPs during recycling, reuse and final treatment
Human safety assessmentMonolayer and organotypic human cell culture systems for determination of uptake and toxicity effects of NPsCell-based high throughput functional screening of NPsTissue or cell lysate microarraysmultiplex protein analysis for generation of broad activity or toxicity profiles of NPs
Environmental safety assessmentDegradability/BiodegradabilityAquatic biodegradability, Composting tests, Soil applicationsEffect on waste water treatment and effluent qualityEcotoxicological assessment
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Why nanocellulose?
Because of specific advantagesAbundant, natural nanomaterialsRenewable, biodegradable & biocompatibleHigh strength & modulusHigh aspect ratios & high surface areasChemical functionality & modificationDimensional Stability
Wide property range of different modified and non-modified nanocelluloses
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