Nanocellulose in Packaging March 14, 2013

Size: px

Start display at page:

Download "Nanocellulose in Packaging March 14, 2013"

Marcus Harper
5 years ago
Views:

1 Nanocellulose in Packaging March 14, 2013 Pia Qvintus, Tekla Tammelin, Soledad Peresin, Ali Harlin, Erkki Hellen, Ulla Forsström VTT Technical Research Centre of Finland

2 14/03/ Nanocellulose research at VTT Wood Bacteria Straw Sugar Beet Banana Potato Safety and sustainability 0

3 14/03/ Worlwide production of natural fibers and chemical composition Raw material Production (MT) Fibers yield (MT) Chemical Composition (%) (2011) Cellulose Hemicelluloses Lignin Ash Corn stover Sugarcane bagasse ,5-5 (0.7-3 SiO 2 ) Banana fiber Sugar beet (25-30% pectins) Soybeans (hulls) Palm oil (EFB) Cotton (inters) (<1 SiO 2 ) Jute (<1 SiO 2 ) Flax Coir Sisal (<1 SiO 2 ) Hemp (Bast fibers) Hemp (woody core)

4 14/03/ The main steps involved in the preparation of cellulose nanoparticles/fibers Millled Fibers Alkali Treatment (80 oc) NaOH 4% (wt/wt) Bleaching Treatment (80 C) NaCIO / Acetate buffer (ph=4.8) 2 o Hydrolysis Dialysis Nanocrystals Mechanical Homogenization Defibrilation MFC Source: Future Markets,Inc.

14/03/2013 5 Nanocellulose family of materials Properties of

Specific surface area: 10s - 100s of m 2 /g Surface modification:

(analogue to cellulose macrofibers) Main characterization methods:

BET Lengths: Electron Microscopy / Rheology Surface properties: IR /

5 14/03/ Nanocellulose family of materials Properties of nanocelluloses: Diameter: 5 nm nm Length: 10s nm - 100s m Specific surface area: 10s - 100s of m 2 /g Surface modification: anionic, cationic, grafted, carboxymethylated, etc. (analogue to cellulose macrofibers) Main characterization methods: Diameter: AFM / TEM / FE-SEM Crystallinity: NMR / WAXS Surface area: BET Lengths: Electron Microscopy / Rheology Surface properties: IR / NMR / Titration Hans-Peter Hentze, VTT - From Nanocellulose Science towards Applications - 2nd of June 2010

14/03/2013 6 Different kinds of nano- and

fibrils) width: 10-20 nm (fibril aggregates)

6 14/03/ Different kinds of nano- and microcelluloses Micro/nanofibrillated cellulose (M/NFC) Nanocrystalline cellulose (NCC) Bacterial nanocellulose (BC) width: 5-6 nm (cellulose fibrils) width: nm (fibril aggregates) length > 1µm width: 2-20 nm length: nm width: , length > 1µm

7 14/03/ 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: esa.laurinsilta@upm.com, antti.laukkanen@upm.com

8 14/03/ 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

14/03/2013 9 Potential application areas are based on specific advantages of

Biocompatibility High strength & modulus High surface area High aspect ratio Chemical

for modification) Dimensional stability Moisture absorption Thermal stability (~200 C)

Web Structures (e.g. Paper & Board) Coatings Functional Surfaces Functional Additives (e.

9 14/03/ Potential application areas are based on specific advantages of nanocellulose Properties of nanocellulose 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 Potential applications Composites Construction Materials Porous Materials Fiber Web Structures (e.g. Paper & Board) Coatings Functional Surfaces Functional Additives (e.g. rheological modifiers) Others Function of nanocellulose fibres in applications Reinforcement Viscosity modifier Stabilizer Binder Barrier Film forming Structural material in foams Others

10 14/03/ Patent applications for nanocellulose, by market segments, 2011 (Source:KETEK)

14/03/2013 11 Nanocellulose production volumes ton

11 14/03/ Nanocellulose production volumes ton per year, all types, forecast 3548 Tons per year Year

12 14/03/ From research and development to applications

13 14/03/ Fiber based packages Strength additive Binder Barrier Role of nanocellulose in packaging? Plastic packaging Reinforcement Barrier Part of multilayer structures Packaging films and foams

14 14/03/ Nanocellulose (NFC) in (bio)plastics

14/03/2013 15 Compatibilisation of hydrophilic NFC fibres Hydrophobisations through 1) silylations, 2) etherifications with epoxy compounds, 3) esterifications Laccase catalysed hydrophobisation of

15 14/03/ Compatibilisation of hydrophilic NFC fibres Hydrophobisations through 1) silylations, 2) etherifications with epoxy compounds, 3) esterifications Laccase catalysed hydrophobisation of lignin rich NFC in composites Reactive, allylic and epoxified NFC Cationised and anionised NFC R = Diphenyl Acetyl R = Benzyl R = Butyryl => Surface modification according to the need of applications NASEVA

16 14/03/ 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) WO Source: Naseva 1 project, a cross disciplinary project aiming at novel applications of nanocellulose

14/03/2013 17 Thermoplastic NFC composites In-situ polymerisation of NFC-g-PCL materials (<1% NFC) => Increases in melt

17 14/03/ 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 Patent pending

18 14/03/ 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

19 Example of polyolefine-nfc composites PP/NFC films prepare by prof. Hiroyuki Yano. Kyoto University 14/03/

20 Nanocellulose (NFC) in paper and board 14/03/

21 Strength with nanocellulose 14/03/

14/03/2013 22 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

22 14/03/ 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/m 2 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 TAPPI International Conference on Nanotechnology for Renewable Materials

23 14/03/

24 Oxygen barrier with nanocellulose in paper coating

14/03/2013 25 Binding of active components with nanocellulose to paper/board surface S. aureus K.

**) Bacteriostatic activity (log reduction) untreated paper (control) Foam coated paper *) **) Bactericidal activity (log reduction) 8,00 7,00 6,00

coated paper *) **) Bactericidal activity (log reduction) NFC/ZnO has significant antibacterial activity against S. aureus and K. pneumoniae.

25 14/03/ 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 6,00 5,00 4,00 3,00 2,00 1,00 0,00 *) **) after contact (log CFU T18h) *) **) Bacteriostatic activity (log reduction) untreated paper (control) Foam coated paper *) **) Bactericidal activity (log reduction) 8,00 7,00 6,00 5,00 4,00 3,00 2,00 1,00 0,00 *) **) after contact (log CFU T18h) *) **) Bacteriostatic activity (log reduction) untreated paper (control) Foam coated paper *) **) Bactericidal activity (log reduction) NFC/ZnO has significant antibacterial activity against S. aureus and K. pneumoniae. Patrizia Sadocco, INNOVHUB - Stazioni Sperimentali Industria The research leading to these results has received funding from the European Community's 7th Frame work Programme under grant agreement no

26 Rigid foams of nanocellulose 14/03/

14/03/2013 27 Plastic-like translucent films of nanocellulose Solvent casting method Pilot scale, roll-to-roll production of films SutCo surface treatment concept (VTT)

27 14/03/ 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)

28 14/03/ Water tolerance of modified NFC film Untreated Ref_UVNFC film Modified Silyl_UV NFC film Contact angle (degrees) Time (seconds)

29 NFC film as a barrier Comparision to commercial products 14/03/

30 What about safety? 14/03/

31 14/03/ Evaluation of safety aspects focused on NFC/MFC and occupational exposure, environmental toxicity in vitro and in vivo Focus Source: Pöyry NASEVA

14/03/2013 32 Nano/microfibrillated cellulose Safety issues and assessment of nanotechnology based products Exposure assessment Determination

Behaviour of ENPs during recycling, reuse and final treatment Human safety assessment Monolayer and organotypic human cell culture systems

microarraysmultiplex protein analysis for generation of broad activity or toxicity profiles of NPs Environmental safety assessment

32 14/03/ 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

33 14/03/ Because of specific advantages Why nanocellulose? 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

34 14/03/ Thank you for your attention! Additonal information:

35 14/03/ VTT - 70 years of technology for business and society