Fully Bio-Based Thermoplastic Lignin Composites 22.5.2013 Biomaterials - Towards Industrial Applications Kalle Nättinen, Antti Ojala, Lisa Wikström, VTT Technical Research Centre of Finland
2 Content VTT and plastics processing Materials Processing Results Conclusions
3 VTT Group in brief Turnover 316 M (2012) Personnel 3,206 (31.12.2012) Customer sectors Biotechnology, pharmaceutical and food industries Chemical industry and environment Electronics Energy Forest industry ICT Machine, vehicle and metal industries Real estate and construction Services and logistics Focus areas of research Applied materials Bio- and chemical processes Energy Information and communication technologies Industrial systems management Microtechnologies and electronics Services and the built environment VTT s operations Research and Development Strategic Research Business Solutions Business Development Group Services VTT s companies - VTT Expert Services Ltd (incl. Labtium Ltd and Enas Ltd) - VTT Ventures Ltd - VTT International Ltd (incl. VTT Brasil LTDA) - VTT Memsfab Ltd
4 Plastics processing Micro-scale melt processing Small Scale Processing Pilot Scale Processing Injection Molding Extrusion Pre- and Post-processing Thermo-Haake MiniLab Micro Compounder Injection moulding Collin(30 x 25D) blown film extruder
5 Thermoplastic lignin composites Materials Lignin: Softwood kraft lignin from Metso (LignoBoost) Plasticizers: Starch acetate (Ac-starch) and triethyl citrate (TEC) Fiber: Softwood TMP
6 Melt processable starch acetate Tensile performance 1 Effect of acetylation reduces hygroscopicity improves thermal processability by lowering Tg Plasticisation with triethyl citrate (TEC) Iower Tg improves ductility 1 K. Nättinen et al., Polym Comp., 2010.
7 Processing steps Wood fiber reinforced thermoplastic lignin composites Extraction of lignin Plasticization Lignin Plasticized lignin Compounding with fibers Pellets Cellulose fibers Injection molding
8 Thermoplastic lignin composites Processing steps in laboratory scale Plasticization and melt compounding (Brabender Plasti-Corder 50 cm 3 batch) Injection molding (Thermo-Haake Mini- Jet) Tensile testing (Instron 4505)
9 Thermoplastic lignin composites Processing steps in pilot scale Compounding Twin-screw extruder Berstorff ZE 25 x 48 D Injection molding Tensile testing Engel ES 200/50 HL High-speed twin-screw extruder KrausMaffei Berstorff Ze25A x 49D UTX Instron 4505 Advanced materials
12 Contents of the thermoplastic lignin composites 30-60% 15-30% 10-20% 0-40% SW lignin Acstarch TEC 0 50 100 Content / wt%
Tensile strength / MPa Young's modulus / GPa 23/05/2013 15 Ac-starch/TEC plasticised lignin composites Effect of TMP fiber content 35 5,5 SW lignin Ac-starch 30 TEC 25 4,5 0 50 100 Content / wt% TMP 20 15 10 3,5 5 0 0 5 10 15 20 25 30 35 TMP fibre / wt-% Fixed lignin/ac-starch/tec ratios 2,5
Mean fiber length / µm 23/05/2013 16 Effect of processing on TMP fiber lengths 2000 1 980 1 1500 1000 500 0 Native TMP fiber 156 2 Lignin composite (20% TMP) 1 FiberLab, R. Korpela, Åbo Akademie University, 2013. Finnish Bioeconomy Cluster FIBIC Oy 23.5.2013 2 X-ray computed microtomography, A. Miettinen, M. Kataja, University of Jyväskylä, 2012.
17 Fiber-matrix compatibility Tensile fracture surfaces of Ac-starch/TEC plasticised composites (SEM) Good compatibility Uniform dispersion of fibers Finnish Bioeconomy Cluster FIBIC Oy 23.5.2013
18 Thermoplastic lignin composites Ac-starch/TEC vs PEG plasticisation 30 29 Tensile Strength (MPa) Young's modulus (GPa) Strain at break (%) Impact Strenght (kj/m2) 4,8 5,9 1,7 0,6 0,5 4,2 Ac-starch/TEC PEG 30 wt% TMP fiber content Optimised lignin / plasticiser ratios
Weight change / % 23/05/2013 19 Water absorption of thermoplastic lignin composites Ac-starch/TEC vs PEG 50 40 30 Acstarch/TEC PEG 20 10 0 0,0 0,5 1,0 1,5 2,0 2,5 Time / weeks 20 wt% TMP reinforcement PEG dissolves from the composites
20 Comparison: 40% Wood fibers + PP vs 30% TMP + lignin + starch acetate + TEC vs 30% TMP + lignin + PEG Property PP + Lignin + PEG + Wood 1 TMP Tensile strength (MPa) Lignin + starch acetate + TMP 37 29 30 Stiffness (GPa) 3.0 6.5 5.4 Impact strength (kj/m 2 ) 1 Ichazo et al., Compos. Struct., 2001 15 4.4 2.0
21 Evaluation of TECNARO s thermoplastic lignin composites Tensile strength (MPa) Modulus (GPA) 61 60 Arboforms consist of thermoplastic lignin, natural additives and fibres (flax, hemp etc.) 29 18 8,5 6,3 6,7 4,9 5,0 2,0 0,3 0,7 1,3 3,64,8 15,0 33 5,3 2,6 0,7 Odour of the composites: F45: typical ZE50: low V3: very low Application areas: Automotive interiors Electronics Consumer articles Furniture industry etc Arboform F45 Arboform ZE50 Arboform L, V3 PLA 3051D FUMO74 The pic and the tensile properties are extracted from the web page: http://www.tecnaro.de/english/willkommen.htm?section=we Composition of FUMO 74: Ac-lignin 41% Ac-starch 23% TEC 16% TMP 20% FuBio JR2 23.5.2013
22 Conclusions Thermoplastic lignin composites based on fully renewable materials have been fabricated Kraft lignin can be efficiently plasticised with Ac-starch-TEC mixtures TMP fiber loading improves processability and mechanical performance of the composites Composites are very rigid yet brittle PEG improves ductility of the lignin composites Heavy breakage of TMP fibers during processing of the composites Northern lights in Tampere, Finland (17.3.2013)
23 Acknowledgements Funding from TEKES and Finnish bioeconomy cluster (FIBIC) within FuBio Joint Research 2 (FuBio JR2) project
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