SurFunCell - Surface functionalization of cellulose matrices using cellulose embedded nanoparticles Grant Agreement No.: 214653 THEME NMP-2007-2.1-1 Coordinator: Volker Ribitsch Institute of Chemistry, University Graz, Heinrichstrassse 28, A-8010 Graz, Austria PLASTiCE International Launch Conference: Europe for sustainable plastics
PROJECT 8,000,000 € Overall budget: Dec 2008 – Dec 2012 Duration: Research partners: 7 Industrial partners: 6 Objectives To create new, smart, bio-based surface nanostructured polymer composites showing exceptional surface functionality (mechanical, chemical, selective interaction properties). • Materials composed of cellulose matrices and nanoscaled polysaccharides layers with embedded nanoparticles. • Compounding being restricted to the biopolymers surface and outer layers.
PROJECT Advantages • No incorporation of filler into the bulk material • Unchanged technical process of cellulose matrix production (films, membranes, fibres) • No deterioration of the matrix materials mechanical properties • Small quantities of nanoparticles needed to gain the desired effects New effects such as cellulose derivatives adsorption, cellulose dissolution, structuring with nanoparticles and irreversible coating will be investigated. Development of completely new class of high value bio-based materials with tailored functions and properties applicable in many different fields.
OVERALL STRATEGY Coating of solid cellulose surfaces with soluble polysaccharides: - Irreversible adsorption (chemically similar molecules) - True even for oppositely charged and derivatized polysaccharides as long as they do not have a significant amount of side chains Incorporation of nanoparticles into these polysaccharide layers High potential to provide a wide variety of surface and material properties Transfer of this strategic route into new materials Up-scaling into an industrial production
OVERALL STRATEGY Functionalization in solution A Irreversible B Adsorption Soluble Stabilization of Polysaccharide nanoparticles Solid Cellulose Surface Irreversible Adsorption Embedding of nanoparticles Solid Cellulose Surface
FIELDS OF APPLICATION Separation technologies - selective interactions tunable by environmental properties Packaging foils based on renewable resources - improved water vapor and oxygen barrier properties Technical fibres - specific surface modifications (strength, abrasion, thermal/chemical stability, hydrophilicity) - flame resistance, conductivity, antimicrobial activity, barrier properties - applicatory potential in medical and hygienic devices (formation of depots for humidity, drugs controlled release, antimicrobial compounds) High yield pulp - UV-protected paper based on less-processed pulp - reduced paper weight Hot topics Sensors, displays, electronic devices, Structural changes under the influence of external stimulation, Conducting cellulose composite materials
MANAGEMENT STRUCTURE Governing Board European Comission 2 external R&D executives 2 external scientists Management Board Executive Board Project Coordinator Scientific Advisory Group Exploitation Advisory Financial Manager Scientific Manager (SAG) Group (EAG) Work Package Leader 2 internal industry Partners 2 internal Scientists WP1 WP2 WP3 WP4 WP5 WP6 WP7 P1-P3, P2, P5, P3, P4, P1-P6, P1, P3, P7, P1-P12 P5, P8, P6, P8, P6, P10, P8, P12 P5, P6, P8-P12 P12 P8-P10, P9, P11, P12 P12 P12
OVERALL STRATEGY Demonstrators Litija Mondi Pentair Innovia Scientific hot topics Supply chain NanoMePS CHT Upscaling NanoMePS TITK Final strategy selection Formulation of possible approaches based on combination of chemical modification and nanoparticle systems Chemical modification Nanoparticle systems BASIC RESEARCH
DEMONSTRATORS Mondi Demonstrator 1 UV protected high-yield pulp enabling reduced paper weight Pentair Litija Technology platform: Demonstrator 4 Cellulose acetate membranes Demonstrator 2 Cellulose – nanoparticle compounds UV stable/protective and Providing new sustainable materials with for hormone removal from antimicrobial yarns tailored properties drinking water Innovia Demonstrator 3 Nanocellulose films (cellophane) with reduced permeability
LIST OF BENEFICIARIES Business Involvement Code Beneficiary Country Responsibilities segment in project Coordination, Interface processes, Simulation and P1 Uni Graz AUT University Month 1-48 modelling Coating of cellulose matrices, Embedding of P2 Uni Maribor SLO University Month 1-48 nanoparticles P3 ARMINES FRA University Month 1-48 Polysaccharides structure and dissolution P4 Uni Jena GER University Month 1-48 Chemical derivatization of polysaccharides P5 Uni Hull GB University Month 1-48 Nanoparticle preparation and characterization P6 TITK GER Public research Month 1-48 Fibre derivatization and coating, Scale-up P7 Uni Utrecht NED University Month 1-48 Life cycle assessment P8 NanoMePS FRA SME* Month 1-48 Pilot production of nanoparticles P9 Pentair X-Flow NED Industry Month 1-48 Filtration membranes functionalization , Scale-up P10 Innovia Films GB Industry Month 1-48 Functionalized nanocoated films and foils, Scale-up P11 Litija SLO Industry Month 1-48 Pilot production of functionalized yarns P12 CHT GER Industry Month 1-48 Production of special finishing compounds P13 Mondi AUT Industry Month 12-48 Pilot production of high yield pulp/paper * S mall and M edium sized E nterprise
ACHIEVEMENTS Chemical derivatization of cellulose and polysaccharides Partners: Uni Jena O O Carboxymethyl starch ONa Cellulose sulphate O S ONa O O • DS 0.30, 0.45, and 1.30 • From spruce sulphite pulp O O O HO • DS 0.37, 0.99, and 1.74 HO O OH OH H 3 C OH Carboxymethyl-6-deoxy- CH 3 Cl Hydroxypropyltrimethyl- N NH 6-aminopropargyl cellulose CH 3 O O ammonium starch chloride HO O • From spruce sulphite pulp O O O • DS 1 HO • DS amin 0.49, DS CM 1.51 OH ONa O CH 3 N 3 Trimethylsilyl cellulose H 3 C Si CH 3 Carboxymethyl-6-deoxy- O O 6-azido cellulose • From microcrystalline cellulose HO O O • From spruce sulphite pulp O H 3 C O O • DS 2.55 • DS azid 0.79, DS CM 1.59 Si O H 3 C ONa H 3 C CH 3 Si CH 3 O H 3 C
ACHIEVEMENTS Up-scaling of chemical derivatization Partners: TITK Carboxymethyl cellulose Hydroxyethyl cellulose • regio-selective derivatization • kg-scale • kg-scale Carboxymethyl starch 6-Deoxy-6-ethylenediamino cellulose • regio-selective derivatization • kg-scale • 1% aq. solution • kg-scale
ACHIEVEMENTS Up-scaling of chemical derivatization Partners: TITK Results summary (Regio-selectively) derivatized polysaccharides Up-scaling to 1 kg scale
ACHIEVEMENTS Nanoparticle synthesis Partners: Uni Hull, NanoMePS, Uni Graz Results summary Synthesis of different noble metal nanoparticles Synthesis of cellulose acetate (CA) and CA-functionalized nanoparticles Nanoparticle characterization and stabilization Nanoparticle compounding on cellulose surfaces
ACHIEVEMENTS Innovia Demonstrator: Cellulose films with reduced water vapor permeability Partners: Uni Graz, Uni Maribor Current strategies SurFunCell approach 1) Sol-gel coatings Aims 2) Layer-by-layer coatings* • Substantial decrease of water vapor transmission rate • Increase of dimensional stability of foils * G. Findenig et al. ‘Adsorption of Laponite on a Cellulose Model Surface’, Macromolecular Symposia , accepted for publication.
ACHIEVEMENTS Innovia Demonstrator: Cellulose films with reduced water vapor permeability Partners: Uni Graz, Uni Maribor Results summary Improvement of dimensional stability up to 40 % was achieved Water vapor transmission rate was reduced by 75 % Pilot trials under preparation
ACHIEVEMENTS Pentair Demonstrator: CA membranes for hormone removal from drinking water Partners: Uni Graz, Uni Hull Aims • Removal of steroid hormones • Improvement of fouling properties • (Introduction of antimicrobial properties) SurFunCell approach Surface Immobilization of Binding of receptors on nanoparticle surface activation nanoparticles
ACHIEVEMENTS Pentair Demonstrator: CA membranes for hormone removal from drinking water Partners: Uni Graz, Uni Hull SurFunCell approach* • Surface functionalized CA nanoparticles • Immobilization of receptors Hydrophobic matrix Hydrophilic modifier * Kulterer et al. Adv. Funct. Mater , 2011, submitted for publication.
ACHIEVEMENTS Pentair Demonstrator: CA membranes for hormone removal from drinking water Partners: Uni Graz, Uni Hull Results summary Stable dispersions of mixed cellulose acetate - polysaccharide nanoparticles which are resistant against mechanical stress Successful immobilization of receptors for hormone removal • Highly active coatings resistant against standard cleaning procedures • Removable coatings enabling cleaning of the surface
ACHIEVEMENTS Litija Demonstrator: Antimicrobial yarns, UV protecting fabrics Partners: Uni Maribor, CHT Current state • No antimicrobial Modal available on the market SurFunCell approach • Immobilization of Ag nanoparticles in sol-gel matrix • In-situ synthesis of Ag nanoparticles on fiber surfaces Utilization: Textiles for medical applications Hygienic textiles Underwear Military Sportsware
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