Lignin: A Biopolymer from Forestry Biomass for Biocomposites and 3D Printing
Abstract
:1. Introduction
2. Materials and Methods
2.1. Raw Materials
2.2. Lignin Extraction
2.3. Lignin Precipitation
2.4. Filaments and 3D Printing
2.5. Characterisation
2.5.1. Thermo-Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC)
2.5.2. Scanning Electron Microscopy (SEM)
2.5.3. Mechanical Testing
2.5.4. Fourier Transform Infrared (FTIR) Spectroscopy
2.5.5. X-ray Diffraction Analysis (XRD)
2.5.6. Antioxidant Activity
3. Results and Discussion
3.1. Lignin Composition
3.2. TGA
3.3. DSC
3.4. Mechanical Properties
3.5. Scanning Electron Microscopy (SEM)
3.6. FT-IR Spectra and XRD Analysis
3.7. Antioxidant Properties
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Calvo-Flores, F.G.; Dobado, J.; Isac-García, J.; Martin-Martinez, F. Applications of Modified and Unmodified Lignins. In Lignin and Lignans as Renewable Raw Material; John Wiley & Sons Ltd.: New York, NY, USA, 2015; pp. 247–288. [Google Scholar]
- Oksman, K.; Skrifvars, M.; Selin, J.F. Natural fibres as reinforcement in polylactic acid (PLA) composites. Compos. Sci. Technol. 2003, 63, 1317–1324. [Google Scholar] [CrossRef]
- Lim, L.T.; Auras, R.; Rubino, M. Processing technologies for poly(lactic acid). Prog. Polym. Sci. 2008, 33, 820–852. [Google Scholar] [CrossRef]
- Ray, S.S.; Yamada, K.; Okamoto, M.; Ueda, K. Polylactide-Layered Silicate Nanocomposite: A Novel Biodegradable Material. Nano Lett. 2002, 2, 1093–1096. [Google Scholar] [CrossRef]
- Pang, X.; Zhuang, X.; Tang, Z.; Chen, X. Polylactic acid (PLA): Research, development and industrialization. Biotechnol. J. 2010, 5, 1125–1136. [Google Scholar] [CrossRef] [PubMed]
- Cohn, D.; Salomon, A.H. Designing biodegradable multiblock PCL/PLA thermoplastic elastomers. Biomaterials 2005, 26, 2297–2305. [Google Scholar] [CrossRef] [PubMed]
- Nofar, M.; Sacligil, D.; Carreau, P.J.; Kamal, M.R.; Heuzey, M.-C. Poly (lactic acid) blends: Processing, properties and applications. Int. J. Biol. Macromol. 2019, 125, 307–360. [Google Scholar] [CrossRef]
- Ochi, S. Mechanical properties of kenaf fibers and kenaf/PLA composites. Mech. Mater. 2008, 40, 446–452. [Google Scholar] [CrossRef]
- Vatansever, E.; Arslan, D.; Nofar, M. Polylactide cellulose-based nanocomposites. Int. J. Biol. Macromol. 2019, 137, 912–938. [Google Scholar] [CrossRef]
- Rinaldi, R.; Jastrzebski, R.; Clough, M.T.; Ralph, J.; Kennema, M.; Bruijnincx, P.C.A.; Weckhuysen, B.M. Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis. Angew. Chem. Int. Ed. 2016, 55, 8164–8215. [Google Scholar] [CrossRef] [Green Version]
- Figueiredo, P.; Lintinen, K.; Hirvonen, J.T.; Kostiainen, M.A.; Santos, H.A. Properties and chemical modifications of lignin: Towards lignin-based nanomaterials for biomedical applications. Prog. Mater. Sci. 2018, 93, 233–269. [Google Scholar] [CrossRef]
- Schutyser, W.; Renders, T.; Van den Bosch, S.; Koelewijn, S.F.; Beckham, G.T.; Sels, B.F. Chemicals from lignin: An interplay of lignocellulose fractionation, depolymerisation, and upgrading. Chem. Soc. Rev. 2018, 47, 852–908. [Google Scholar] [CrossRef] [PubMed]
- Liu, L.; Qian, M.; Song, P.A.; Huang, G.; Yu, Y.; Fu, S. Fabrication of Green Lignin-based Flame Retardants for Enhancing the Thermal and Fire Retardancy Properties of Polypropylene/Wood Composites. ACS Sustain. Chem. Eng. 2016, 4, 2422–2431. [Google Scholar] [CrossRef]
- Zhao, W.; Simmons, B.; Singh, S.; Ragauskas, A.; Cheng, G. From lignin association to nano-/micro-particle preparation: Extracting higher value of lignin. Green Chem. 2016, 18, 5693–5700. [Google Scholar] [CrossRef]
- Grossman, A.; Vermerris, W. Lignin-based polymers and nanomaterials. Curr. Opin. Biotechnol. 2019, 56, 112–120. [Google Scholar] [CrossRef] [PubMed]
- Gellerstedt, G.; Tomani, P.; Axegard, P.; Backlund, B. Lignin recovery and lignin-based products. In Integrated Forest Biorefineries: Challenges and Opportunities; RSC Green Chemistry: Cambridge, UK, 2013; Chapter 8; pp. 180–210. [Google Scholar]
- Ragauskas, A.J.; Beckham, G.T.; Biddy, M.J.; Chandra, R.; Chen, F.; Davis, M.F.; Davison, B.H.; Dixon, R.A.; Gilna, P.; Keller, M.; et al. Lignin Valorization: Improving Lignin Processing in the Biorefinery. Science 2014, 344, 1246843. [Google Scholar] [CrossRef]
- Christopher, L.P. Integrated Forest Biorefineries: Current State and Development Potential. In Integrated Forest Biorefineries: Challenges and Opportunities; RCS Green Chemistry: Cambridge, UK, 2013; Chapter 1; pp. 1–66. [Google Scholar]
- Wang, H.; Pu, Y.; Ragauskas, A.; Yang, B. From lignin to valuable products–strategies, challenges, and prospects. Bioresour. Technol. 2019, 271, 449–461. [Google Scholar] [CrossRef] [PubMed]
- Thakur, V.K.; Thakur, M.K.; Raghavan, P.; Kessler, M.R. Progress in Green Polymer Composites from Lignin for Multifunctional Applications: A Review. ACS Sustain. Chem. Eng. 2014, 2, 1072–1092. [Google Scholar] [CrossRef]
- Kun, D.; Pukánszky, B. Polymer/lignin blends: Interactions, properties, applications. Eur. Polym. J. 2017, 93, 618–641. [Google Scholar] [CrossRef] [Green Version]
- Gordobil, O.; Delucis, R.; Egüés, I.; Labidi, J. Kraft lignin as filler in PLA to improve ductility and thermal properties. Ind. Crop. Prod. 2015, 72, 46–53. [Google Scholar] [CrossRef]
- Pouteau, C.; Dole, P.; Cathala, B.; Averous, L.; Boquillon, N. Antioxidant properties of lignin in polypropylene. Polym. Degrad. Stab. 2003, 81, 9–18. [Google Scholar] [CrossRef]
- Domenek, S. Potential of Lignins as Antioxidant Additive in Active Biodegradable Packaging Materials. J. Polym. Environ. 2013, 21, 692–701. [Google Scholar] [CrossRef] [Green Version]
- Mishra, S.B.; Mishra, A.K.; Kaushik, N.K.; Khan, M.A. Study of performance properties of lignin-based polyblends with polyvinyl chloride. J. Mater. Process. Technol. 2007, 183, 273–276. [Google Scholar] [CrossRef]
- De Chirico, A.; Armanini, M.; Chini, P.; Cioccolo, G.; Provasoli, F.; Audisio, G. Flame retardants for polypropylene based on lignin. Polym. Degrad. Stab. 2003, 79, 139–145. [Google Scholar] [CrossRef]
- Thielemans, W.; Can, E.; Morye, S.S.; Wool, R.P. Novel applications of lignin in composite materials. J. Appl. Polym. Sci. 2002, 83, 323–331. [Google Scholar] [CrossRef]
- Thielemans, W.; Wool, R.P. Kraft lignin as fiber treatment for natural fiber-reinforced composites. Polym. Compos. 2005, 26, 695–705. [Google Scholar] [CrossRef]
- Graupner, N. Application of lignin as natural adhesion promoter in cotton fibre-reinforced poly(lactic acid) (PLA) composites. J. Mater. Sci. 2008, 43, 5222–5229. [Google Scholar] [CrossRef]
- Kim, J.S.; Lee, Y.Y.; Kim, T.H. A review on alkaline pretreatment technology for bioconversion of lignocellulosic biomass. Bioresour. Technol. 2016, 199, 42–48. [Google Scholar] [CrossRef] [PubMed]
- Saratale, G.D.; Oh, M.-K. Improving alkaline pretreatment method for preparation of whole rice waste biomass feedstock and bioethanol production. RSC Adv. 2015, 5, 97171–97179. [Google Scholar] [CrossRef]
- González-García, S.; Moreira, M.T.; Artal, G.; Maldonado, L.; Feijoo, G. Environmental impact assessment of non-wood based pulp production by soda-anthraquinone pulping process. J. Clean. Prod. 2010, 18, 137–145. [Google Scholar] [CrossRef]
- Rodríguez, A.; Sánchez, R.; Requejo, A.; Ferrer, A. Feasibility of rice straw as a raw material for the production of soda cellulose pulp. J. Clean. Prod. 2010, 18, 1084–1091. [Google Scholar] [CrossRef]
- Vishtal, A.G.; Kraslawski, A. Challenges in industrial applications of technical lignins. BioResources 2011, 6, 3547–3568. [Google Scholar]
- Gosselink, R.J.A.; Abächerli, A.; Semke, H.; Malherbe, R.; Käuper, P.; Nadif, A.; van Dam, J.E.G. Analytical protocols for characterisation of sulphur-free lignin. Ind. Crop. Prod. 2004, 19, 271–281. [Google Scholar] [CrossRef]
- Tejado, A.; Peña, C.; Labidi, J.; Echeverria, J.M.; Mondragon, I. Physico-chemical characterization of lignins from different sources for use in phenol–formaldehyde resin synthesis. Bioresour. Technol. 2007, 98, 1655–1663. [Google Scholar] [CrossRef] [PubMed]
- Baurhoo, B.; Ruiz-Feria, C.A.; Zhao, X. Purified lignin: Nutritional and health impacts on farm animals—A review. Anim. Feed Sci. Technol. 2008, 144, 175–184. [Google Scholar] [CrossRef]
- Nadif, A.; Hunkeler, D.; Käuper, P. Sulfur-free lignins from alkaline pulping tested in mortar for use as mortar additives. Bioresour. Technol. 2002, 84, 49–55. [Google Scholar] [CrossRef]
- Wörmeyer, K.; Ingram, T.; Saake, B.; Brunner, G.; Smirnova, I. Comparison of different pretreatment methods for lignocellulosic materials. Part II: Influence of pretreatment on the properties of rye straw lignin. Bioresour. Technol. 2011, 102, 4157–4164. [Google Scholar] [CrossRef]
- Nguyen, N.A.; Bowland, C.C.; Naskar, A.K. A general method to improve 3D-printability and inter-layer adhesion in lignin-based composites. Appl. Mater. Today 2018, 12, 138–152. [Google Scholar] [CrossRef]
- Zhao, D.X.; Cai, X.; Shou, G.Z.; Gu, Y.Q.; Wang, P.X. Study on the Preparation of Bamboo Plastic Composite Intend for Additive Manufacturing. Key Eng. Mater. 2016, 667, 250–258. [Google Scholar] [CrossRef]
- Henke, K.; Treml, S. Wood based bulk material in 3D printing processes for applications in construction. Eur. J. Wood Wood Prod. 2013, 71, 139–141. [Google Scholar] [CrossRef]
- Le Duigou, A.; Castro, M.; Bevan, R.; Martin, N. 3D printing of wood fibre biocomposites: From mechanical to actuation functionality. Mater. Des. 2016, 96, 106–114. [Google Scholar] [CrossRef]
- Domínguez-Robles, J.; Martin, N.K.; Fong, M.L.; Stewart, S.A.; Irwin, N.J.; Rial-Hermida, M.I.; Donnelly, R.F.; Larrañeta, E. Antioxidant PLA Composites Containing Lignin for 3D Printing Applications: A Potential Material for Healthcare Applications. Pharmaceutics 2019, 11, 165. [Google Scholar] [CrossRef] [PubMed]
- García, A.; González Alriols, M.; Spigno, G.; Labidi, J. Lignin as natural radical scavenger. Effect of the obtaining and purification processes on the antioxidant behaviour of lignin. Biochem. Eng. J. 2012, 67, 173–185. [Google Scholar] [CrossRef]
- Huijgen, W.J.J.; Telysheva, G.; Arshanitsa, A.; Gosselink, R.J.A.; de Wild, P.J. Characteristics of wheat straw lignins from ethanol-based organosolv treatment. Ind. Crop. Prod. 2014, 59, 85–95. [Google Scholar] [CrossRef]
- Constant, S.; Wienk, H.L.J.; Frissen, A.E.; de Peinder, P.; Boelens, R.; van Es, D.S.; Grisel, R.J.H.; Weckhuysen, B.M.; Huijgen, W.J.J.; Gosselink, R.J.A.; et al. New insights into the structure and composition of technical lignins: A comparative characterisation study. Green Chem. 2016, 18, 2651–2665. [Google Scholar] [CrossRef]
- Sameni, J.; Krigstin, S.; de Santos Rosa, D.; Leao, A.; Sain, M. Thermal Characteristics of Lignin Residue from Industrial Processes. BioResources 2013, 9, 725–737. [Google Scholar] [CrossRef]
- Yang, H.; Yan, R.; Chen, H.; Lee, D.H.; Zheng, C. Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel 2007, 86, 1781–1788. [Google Scholar] [CrossRef]
- Watkins, D.; Nuruddin, M.; Hosur, M.; Tcherbi-Narteh, A.; Jeelani, S. Extraction and characterization of lignin from different biomass resources. J. Mater. Res. Technol. 2015, 4, 26–32. [Google Scholar] [CrossRef] [Green Version]
- Schmidl, G. Molecular Weight Characterization and Rheology of Lignins for Carbon Fibers. Ph.D. Thesis, University of Florida, Gainesville, FL, USA, 1992. [Google Scholar]
- Heitner, C.; Dimmel, D.; Schmidt, J.A. Lignin and Lignans: Advances in Chemistry; CRC Press, Tylor & Francis Group: Boca Raton, FL, USA, 2010. [Google Scholar]
- Gordobil, O.; Egüés, I.; Llano-Ponte, R.; Labidi, J. Physicochemical properties of PLA lignin blends. Polym. Degrad. Stab. 2014, 108, 330–338. [Google Scholar] [CrossRef]
- Al-Itry, R.; Lamnawar, K.; Maazouz, A. Reactive extrusion of PLA, PBAT with a multi-functional epoxide: Physico-chemical and rheological properties. Eur. Polym. J. 2014, 58, 90–102. [Google Scholar] [CrossRef]
- Weng, Y.-X.; Jin, Y.-J.; Meng, Q.-Y.; Wang, L.; Zhang, M.; Wang, Y.-Z. Biodegradation behavior of poly(butylene adipate-co-terephthalate) (PBAT), poly(lactic acid) (PLA), and their blend under soil conditions. Polym. Test. 2013, 32, 918–926. [Google Scholar] [CrossRef]
- Rahman, M.; Afrin, S.; Haque, P.; Islam, M.; Islam, M.S.; Gafur, M. Preparation and Characterization of Jute Cellulose Crystals-Reinforced Poly (L-lactic acid) Biocomposite for Biomedical Applications. Int. J. Chem. Eng. 2014, 2014, 842147. [Google Scholar] [CrossRef]
- Lu, Q.; Liu, W.; Yang, L.; Zu, Y.; Zu, B.; Zhu, M.; Zhang, Y.; Zhang, X.; Zhang, R.; Sun, Z.; et al. Investigation of the effects of different organosolv pulping methods on antioxidant capacity and extraction efficiency of lignin. Food Chem. 2012, 131, 313–317. [Google Scholar] [CrossRef]
- Mahmood, Z.; Yameen, M.; Jahangeer, M.; Riaz, M.; Ghaffar, A.; Javid, I. Lignin as Natural Antioxidant Capacity. In Lignin-Trends and Applications; IntechOpen: London, UK, 2018; pp. 181–205. [Google Scholar]
- Gkartzou, E.; Koumoulos, E.P.; Charitidis, C.A. Production and 3D printing processing of bio-based thermoplastic filament. Manuf. Rev. 2017, 4. [Google Scholar] [CrossRef]
3D Printed Sample | Et (MPA) | σM (MPa) | ꜪM % |
---|---|---|---|
PLA | 2890 ± 14.14 | 58.45 ± 0.55 | 2.45 ± 0.10 |
PLA + 20%Lignin | 2460 ± 155.56 | 39.35 ± 1.05 | 1.8 ± 0.10 |
PLA + 40%Lignin (205 °C) | 1955 ± 19.92 | 32 ± 2.10 | 1.8 ± 0.20 |
PLA + 40%Lignin (215 °C) | 2695 ± 148.49 | 45.65 ± 0.05 | 1.9 ± 0.08 |
PLA + 40%Lignin (230 °C) | 1930 ± 183.85 | 29.25 ± 1.35 | 1.65 ± 0.10 |
© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Tanase-Opedal, M.; Espinosa, E.; Rodríguez, A.; Chinga-Carrasco, G. Lignin: A Biopolymer from Forestry Biomass for Biocomposites and 3D Printing. Materials 2019, 12, 3006. https://doi.org/10.3390/ma12183006
Tanase-Opedal M, Espinosa E, Rodríguez A, Chinga-Carrasco G. Lignin: A Biopolymer from Forestry Biomass for Biocomposites and 3D Printing. Materials. 2019; 12(18):3006. https://doi.org/10.3390/ma12183006
Chicago/Turabian StyleTanase-Opedal, Mihaela, Eduardo Espinosa, Alejandro Rodríguez, and Gary Chinga-Carrasco. 2019. "Lignin: A Biopolymer from Forestry Biomass for Biocomposites and 3D Printing" Materials 12, no. 18: 3006. https://doi.org/10.3390/ma12183006