SurFunCell - Surface functionalization of cellulose matrices using - - PowerPoint PPT Presentation
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,
THEME NMP-2007-2.1-1
Institute of Chemistry, University Graz, Heinrichstrassse 28, A-8010 Graz, Austria
PLASTiCE International Launch Conference: Europe for sustainable plastics
Overall budget: 8,000,000 € Duration: Dec 2008 – Dec 2012 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).
layers with embedded nanoparticles.
Advantages
(films, membranes, fibres)
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.
Coating of solid cellulose surfaces with soluble 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
Soluble Polysaccharide Functionalization in solution Stabilization of nanoparticles Irreversible Adsorption Embedding of nanoparticles Solid Cellulose Surface Solid Cellulose Surface
A B
Irreversible Adsorption
Separation technologies
Packaging foils based on renewable resources
Technical fibres
(formation of depots for humidity, drugs controlled release, antimicrobial compounds) High yield pulp
Hot topics Sensors, displays, electronic devices, Structural changes under the influence of external stimulation, Conducting cellulose composite materials
Governing Board
Work Package Leader
Management Board
Scientific Advisory Group (SAG) Project Coordinator
European Comission
Financial Manager Scientific Manager
Exploitation Advisory Group (EAG) 2 external R&D executives 2 external scientists 2 internal industry Partners 2 internal Scientists
Executive Board WP1 WP2 WP3 WP4 WP6 WP7
P3, P4, P6, P10, P12 P1-P3, P5, P8, P12 P1-P6, P8, P12 P1, P3, P5, P6, P8-P10, P12 P2, P5, P6, P8, P9, P11, P12 P7, P8-P12 P1-P12
WP5
Chemical modification Nanoparticle systems
BASIC RESEARCH
Formulation of possible approaches based on combination of chemical modification and nanoparticle systems
Final strategy selection Upscaling TITK NanoMePS Supply chain CHT NanoMePS
Scientific hot topics
Demonstrators
Litija Pentair Mondi Innovia
Mondi
Demonstrator 1 UV protected high-yield pulp enabling reduced paper weight
Litija
Demonstrator 2 UV stable/protective and antimicrobial yarns
Innovia
Demonstrator 3 Nanocellulose films (cellophane) with reduced permeability
Pentair
Demonstrator 4 Cellulose acetate membranes for hormone removal from drinking water Technology platform: Cellulose – nanoparticle compounds Providing new sustainable materials with tailored properties
Code Beneficiary Country Business segment Involvement in project Responsibilities P1 Uni Graz AUT University Month 1-48 Coordination, Interface processes, Simulation and modelling P2 Uni Maribor SLO University Month 1-48 Coating of cellulose matrices, Embedding of 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
* Small and Medium sized Enterprise
O O OH HO O O ONa O O OH HO O OH N H3C CH3 CH3 Cl
Carboxymethyl starch
Hydroxypropyltrimethyl- ammonium starch chloride
Trimethylsilyl cellulose
O O O O O Si H3C CH3 CH3 Si H3C CH3 H3C Si H3C CH3 H3C
Chemical derivatization of cellulose and polysaccharides Partners: Uni Jena
Cellulose sulphate
Carboxymethyl-6-deoxy- 6-aminopropargyl cellulose
Carboxymethyl-6-deoxy- 6-azido cellulose
O O O HO NH O ONa O O O HO N3 O ONa O O OH HO O S O O ONa
Up-scaling of chemical derivatization Partners: TITK
Carboxymethyl cellulose
Carboxymethyl starch
Hydroxyethyl cellulose
6-Deoxy-6-ethylenediamino cellulose
Results summary
(Regio-selectively) derivatized polysaccharides Up-scaling to 1 kg scale Up-scaling of chemical derivatization Partners: TITK
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
Innovia Demonstrator: Cellulose films with reduced water vapor permeability Partners: Uni Graz, Uni Maribor
Current strategies
transmission rate
Aims SurFunCell approach
1) Sol-gel coatings 2) Layer-by-layer coatings*
* G. Findenig et al. ‘Adsorption of Laponite on a Cellulose Model Surface’, Macromolecular Symposia, accepted for publication.
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
Pentair Demonstrator: CA membranes for hormone removal from drinking water Partners: Uni Graz, Uni Hull
Aims SurFunCell approach
Binding of receptors on nanoparticle surface Immobilization of nanoparticles Surface activation
* Kulterer et al. Adv. Funct. Mater, 2011, submitted for publication.
Hydrophilic modifier Hydrophobic matrix
SurFunCell approach*
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
Pentair Demonstrator: CA membranes for hormone removal from drinking water Partners: Uni Graz, Uni Hull
Litija Demonstrator: Antimicrobial yarns, UV protecting fabrics Partners: Uni Maribor, CHT
Current state SurFunCell approach
Utilization: Textiles for medical applications Hygienic textiles Underwear Military Sportsware
Mondi Demonstrator: High yield pulp paper (Life cycle assessment) Partners: Uni Utrecht, Mondi
Conventional paper High yield pulp paper with CaCO3/TiO2 nanoparticles
Aims
Paper making with NP Distribution Packaging Use Collection Disposal Incineration Recycling land filling Wood NP Synthesis Chemicals Unbleached pulp
Pulp & paper making
Raw material Steam Electricity Recycled fiber Saved wood Power generation Avoided grid electricity
I II
Patel, M. K., Environmental Life Cycle Assessment – Principles, challenges and application’, 2nd End Year Meeting of STEP and EPNOE, Ecole des Mines de Paris / Cemef, Sophia Antipolis, France, 28 September 2010.
REU Renewable energy use (wind, solar, hydro, biomass, etc.) NREU Non-renewable energy use (from fossil and nuclear fuels) GHG Glasshouse gases 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 5 10 15 20 25 30 35 40 45 50 Conventional paper NP virgin paper NP:GCC (30:70) NP virgin paper NP:micro:GCC (12:18:70) Micro TiO2 virgin paper Micro:GCC (30:70) NP virgin Paper NP:GCC (10:90) NP paper NP:GCC (30:70) with 50% recovered pulp NP Paper NP:GCC (10:90)with 50% recovered pulp
GHG, tonne CO2 eq./tonne paper Energy GJ/tonne paper
REU NREU GHG
Energy and GHG emissions
A C B D E F G
Mondi Demonstrator: High yield pulp paper (Life cycle assessment)* Partners: Uni Utrecht
* B. M. K. Manda et al. ‘Innovations in papermaking : A case of nano-particle coated printing and writing paper’, 2nd international Polysaccharide Conference, Wageningen, The Netherlands, 29 Aug – 02 Sep 2011.
Substance NREU, MJ/kg TiO2 86 TiOSO4 45 Silver 1 358 Gold 202 000 Palladium 172 000 Platinum 272 000 Rhodium 532 000 AgNO3
(64% silver)
881 Dicyclohexylzinc 209 Zinc 49 Zinc dichloride 42 ZnO 51 Diethyl ether 48 Cellulose acetate 232 CMC 78 SiCl4 30 Substance NREU, MJ/kg Trimethoxysilane 53 Organic chemicals (substitute of Cyclohexyl Mg Cl) 65 THF 122 Triethanolamine 98 Tetramethoxysilane 26 3-glycidyloxy-propyl- triethoxysilane 80 H2SO4 2 HCl 17 Deionized water 0.02 KOH 35 KCl 9 CaCl2 11 Aluminium 113 Steel (SS) 63 PE 74 PP 75
Sources:
Life cycle assessment: Non-renewable energy use of reagents and solvents Partners: Uni Utrecht
Scientific hot topics: Bacterial growth tests directly on surfaces* Partners: Uni Graz, Uni Maribor
Current approach: Plating-out techniques SurFunCell approach
→ Morphology (for method evaluation only)
→ Visualization of death/living cells
→ Bacteria quantification
* V. E. Reichel et al. ‘Testing antimicrobial properties of polysaccharide surfaces’, 2nd international Polysaccharide Conference, Wageningen, The Netherlands, 29 Aug – 02 Sep 2011.
SEM measurements Fluorescence microscopy RT-PCR Fixing sterile model surfaces onto culture well plates Incubation of model films with E.coli cell suspension Incubation with LIVE/DEAD kit
Scientific hot topics: Bacterial growth tests directly on surfaces* Partners: Uni Graz, Uni Maribor
* V. E. Reichel et al. ‘Testing antimicrobial properties of polysaccharide surfaces’, 2nd international Polysaccharide Conference, Wageningen, The Netherlands, 29 Aug – 02 Sep 2011.
Biofilm Cytoplasm Dead cells
Untreated cellulose acetate Chitosan coated cellulose acetate
30000 3000
1 2 Chitosan coated cellulose acetate Untreated cellulose acetate
Scanning electron microscopy Real-time PCR
Death and living cells Death cells
Fluorescence staining
(Chitosan coated cellulose acetate) Amount of cells on the surface
Scientific hot topics: Bacterial growth tests directly on surfaces* Partners: Uni Graz, Uni Maribor
* V. E. Reichel et al. ‘Testing antimicrobial properties of polysaccharide surfaces’, 2nd international Polysaccharide Conference, Wageningen, The Netherlands, 29 Aug – 02 Sep 2011.
Methods and programs used
GLYCAM06 Force Field method
DL_POLY (static properties and molecular dynamics of polymers)
ChemShell (molecular dynamics and quantum mechanic/ molecular modelling)
TURBOMOLE (quantum mechanics)
SAPT2008 (QM intermolecular interaction energies)
Molecular Modelling: Structure of the cellulose–water interface and adsorption kinetics* Partners: Uni Graz
Cellulose 1β-water interface Cellulose 1α-water interface Cellulose 1α: Rough surface resulting from tilted cellulose molecules Cellulose 1β: Smooth surface
* L. Grossar, R. J. Maurer, A. F. Sax, ’Adsorption of water layers of variable thickness on crystalline cellulose surfaces’, 10th Central European Symposium on Theoretical Chemistry, Torun, Poland, 25-28 Sep 2011.
Results summary
Molecular models of different cellulose allomorph structures Interaction, position of water molecules Interaction with small saccharide mono- and oligomers Driving forces: Coulomb and Van der Waals forces
Molecular Modelling: Structure of the cellulose–water interface and adsorption kinetics Partners: Uni Graz
Scientific hot topics: Microarray sensor surfaces Partners: Uni Maribor, Uni Graz
Demands Achievements
Avoid non-selective adsorption of protein and DNA Reduced to a high degree Immobilization of high amount of receptors Fluorescence via hair pin effect / cease quenching Sensoric effect – fluorescence resp. Fluorescence quenching in the presende of an analyt Discrimination between 20 and 19 complimentary nucletides in a DNA chain High selectivity
+
Fluorophor Quencher ss DNA Fluorescence