Novel biopolymer or biobased materials & Nanotechnology

Transcription

1 Novel biopolymer or biobased materials & Nanotechnology Dr. Jeroen J.G. van Soest Ir. G. Schennink Ir. M. van den ever Biopolymer Science & Technology - BU Biobased Products (BbP) A&F BV - formerly AT BV Wageningen University & Research Centre

2 Content - Bullet points Nanocomposite or nanostructured bioplastics Nanoclay, Cellulose & Carbon Nanofibre Processing & nanotechnology material / performance enhancement Properties mechanical, electrical, optical, barrier Structural features micro- & nano-metric

3 courtesy, Biopolymer Technologies AG BIPAR: A successful material development a micro-structured material film out of dispersive blend film out of co-continuous blend

4 Products & NAN - technology Important issues to improve on for biobased materials Properties Water resistance, barrier properties Clarity, optical properties Flow, thermal stability Price/performance (economical feasible) Processing (technical feasible) Additives What can nanotechnology offer? nanocomposite nanoclay nanofibre

5 Biopolymer nanocomposites Possible nanoscale reinforcement materials Equi-axed Carbon black, silica Tubular Cellulose nanofibre Carbon nanofibre Platelet Nanoclay

6 Biopolymer nanocomposites & added value Heat stability Barrier gas, water Mechanical strength, stiffness Nanocla y Cellulos e nanofibr e Carbon nanofibr e Water-solvent sensitivity Biocompatibility Electrical anti-static ESD, EMI conductivity Transparancy & ptics Fire retardancy

7 Starch - nanocomposites Processing How? Film casting Kneading Moulding Extrusion Effect nanofiller source

8 Starch - nanocomposites Analysis How? XRD PM SEM Tensile (stress-strain) WVP Conductivity

9 Starch - clay nanocomposites Nanoclay Natural material Layered structure P.e. montmorillonite thickness 1 nm lateral dimensions nm ~1 nm 200~1000 nm 200~1000 nm

10 Starch - clay nanocomposites intercalated polymer How? layered inorganic partly exfoliated fully exfoliated Thermoplastic polymer composite based on starch containing integrated nanoscopic particle EP (2002) by Berger; Jeromin; pitz; De Vlieger; Fischer -- Applicants: BIP + TN

11 Starch - clay nanocomposites What? Barrier properties TPSmatrix watermolecule TPSmatrix watermolecule conventional composite clay particle clay platelet torturous path in nanocomposite

12 Starch - clay nanocomposites - film casting (XRD) intercalated Na-Clay 6%Clay 15%Clay Starch exfoliated angle (2theta)

13 Clay nanocomposites - film casting (tensile) E-modulus E modulus (GPa) Tensile stress (MPa) Elongation (%) % Clay Elongation & Tensile stress

14 Clay nanocomposites - film casting (WVP) Permeability (g/m.pa.s) Na+ Clay CaC3 0% 5% 10% 15% Na+ Clay / CaC3 (%)

15 Clay nanocomposites: extruded sheets (XRD) exfoliated Montmorillonite Hectorite SE7 Starch angle (2theta)

16 Clay nanocomposites: sheets (tensile) 2.6 E-modulus (GPa) Starch Hectorite Montmorrilonite Tensile stress (0.1xMPa)

17 Clay nanocomposites: sheets (WVP) Permeability Starch Hectorite Montmorrilonite 1 Montmorrilonite 2

18 Nanofiber Bundle courtesy Part 2: Carbon nanofibre composites Advantages CNF: Improvements at low weight percent nanofiller Mechanical & tribological Anti-static Electrical conductivity EMI shielding UV stability Applications: plastics (packaging, panels, medical implants) elastomers for rubbers, tyres, hoses, belts,.. anti-static & base coatings filler for adsorption cement, concrete

19 CNF : vapor grown / CVD Geometry nm µm length 100 x smaller than conventional carbon fibers larger than nanotubes (1-10 nm diameter) Elastic Properties rthotropic Longitudinal modulus up to 600 GPa Transverse properties not well known Single nanofiber, Pyrograph courtesy apsci.com

20 CNF - structure ENF-100 l 100 µm, 100 nm ENF-200 l 100 µm, 200 nm 2 µm 5 µm Courtesy, Electrovac & Gabriel-Chemie Nanocomposites 2004 Brussels

21 CNF - TPS vs. PP composites CNF - PP 1 µm 10 µm 2 µm Courtesy, Carbon Based Matrix Materials by E. Hammel, T. Schmitt, (Electrovac) Werkstoffseminar Frankreich-Österreich

22 Starch CNF composites - conductivity Vol. resistivity (hm.cm) 1E+14 1E+12 1E+10 1E+08 1E PP 200-PP 150-Starch Antistatic 1E+04 1E %CNF Courtesy, PP data from Electrovac & Gabriel-Chemie, Nanocomposites 2004 Brussels

23 Starch CNF composites - Mechanical Modulus (MPa) 300 Stress (MPa) %CNF % CNF Elongation (%) % RH 15 50% RH %CNF

24 Part 3: Cellulose Nano/Micro-Fibre composites Sources (waste) paper, pulp, potato juice, wood, hemp, flax, sisal, kenaf, ramie, straw, cocos, bran Not right morphology, color thermo-mechanical, milling, bleaching, chemistry Processing pulping, extrusion, moulding, compounding Markets automotive packaging, plastics consumer - hygiene products Extrusion Compounding Technology building, construction EP Process and apparatus for continuously manufacturing composites of polymer and cellulosic fibres & US Extruder for continuously manufacturing composites of polymer and cellulosic fibres, Snijder et al

25 Cellulose fibre composites hackling breaking scutching bast fibre bundle technical fibre µm FLAX structure elementary fibre µm meso fibre 0.5 µm micro-nano fibre flax stem 2-3 mm 4-10 nm

26 Cellulose nanofibre composites Why starch? Good adhesion starch to cellulose (micro-) fibre SEM

27 Cellulose nanofibre composites SEM

28 1st results: Cellulose nanofibre composites GPa % 8 E-MD STRAIN STRENGTH MPa STARCH PP Microflax- PP GMT(30%) Nanoflax- STARCH 0 GMT= Glass Fibre Mat Thermoplastic

29 Conclusions Possible to make nanoclay composite starch plastics structure: full exfoliation depends on clay & process mechanical properties: increased stiffness WVP: Up to 50% reduction, <6% clay needed 1st CNF starch composites made structure: homogenous blend mechanical & electrical properties?? Cellulose starch composites prepared structure: homogenous blend exceptional properties --> high E-modulus, strength, elongation

30 Colloidal Particle Technology Looking for new functionalities: no retrogradation low viscosity at high solids colloidal stability in water Shear stress (N/ m 2 ) emulsion X-linking versatile multiple emulsion encapsulation starch non-solvent cheap, easy extrusion latex, cheap, large scale Shear (1/ sec) Reference Starch additive No additive Environmentally friendly biopolymer adhesives, W , Bloembergen (Ecosynthetix), Kappen & Beelen (AT) Biopolymer nanoparticles, EP , Giezen et al (AT)

31 Carbohydrate IPN s Advantages: strength less brittle - flexibility low shrinking, sensitivity to solvents / heat less wearing improved compatibility Comparison of Networks without Starch C.L. (0.5% in water) 25 C XS 10 PAA spindle 27 IPN XS 10 PAA next spindle 21 Viscosity [mpa.s] XS 13 Semi-IPN, no Starch- C.L. spindle 21 Blend XS 10+Paselli (0.25% each) spindle Shear Rate [s-1] Transparent - lucent & strong network Resistant to carbohydrate non-solvent low shrinkage p.e. in EtH

32 Polymer nanofoam & polysaccharides Highly transparent Very light weight Good insulating Solar cell Green house Membraneseparation example of part of a cross linked structure H H H H H H H H H H H - H H H H - H H H - H H - H H - H H H H - H H - sc-c 2 drying 100 nm

33 Conclusions - verall Range of improved novel biopolymer materials sub-micron particles or colloids Interpenetrating networks (IPN) nanofoam BIPLASTICS nanoclay-biopolymer or Inorganic-organic hybrid bioplastics cellulose nanofibre composite CNF composite structural features into nanometric range improved properties still properties can be improved!!!

34 Acknowledgements BIP technologies (starch blends) Electrovac (CNF) EC Sustainpack - IP FP A&F (formerly AT) Sustainable Chemistry & Technology R. Stevens, G. Zietek (nanoclay) Y. Dziechciarek, H. Mulder (microgels) V. Blanchard, K. Ralla, R. Koelewijn, X. Samain, X. Rioche (IPN) J. Timmermans, A. Kunze, R. Koelewijn, R. Blaauw (nanofoam) J. Ritterbex (CNF) Fibre & Paper Technology M. Snijder, M. Junco (cellulose nanofiber)