Skip to main content
Log in

Thermally Stable Pyrolytic Biocarbon as an Effective and Sustainable Reinforcing Filler for Polyamide Bio-composites Fabrication

  • Original Paper
  • Published:
Journal of Polymers and the Environment Aims and scope Submit manuscript

Abstract

Natural fibers are limited in their use as reinforcement to commodity polymers. They cannot be used to reinforce engineering polymers due to their low thermal stability at high processing temperatures. This study presents an approach to successfully reinforce polyamides using a derivative of natural fibers as reinforcement without the effects of thermal degradation during melt processing. Biocarbon from miscanthus fibers was used to reinforce polyamide 6 up to 40 wt%. At 40 wt% filler content, the tensile and flexural strengths increased by 19.6 and 47% respectively in comparison to the neat polyamide. The moduli were also increased by 31.5 and 63.7% respectively. A maximum increase in impact strength of 43.7% was achieved at 20 wt% biocarbon loading. The morphology of the tensile fractured samples showed stretched polyamide ligaments attached to the biocarbon particles, indicating the presence of interaction between filler and matrix. Interestingly, more bonded interfaces were observed between the polyamide and biocarbon particles with increasing biocarbon content possibly stemming from increased biocarbon surfaces with functional groups. These composites show great potential to substitute in part or whole, some particulate filled polyamides currently used in the automotive industry.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Stewart R (2010) Automotive composites offer lighter solutions. Reinf Plast 54:22–28. https://doi.org/10.1016/S0034-3617(10)70061-8

    Article  Google Scholar 

  2. Mohanty AK, Misra M, Drzal LT (2001) Surface modifications of natural fibers and performance of the resulting biocomposites: an overview. Compos Interfaces 8:313–343. https://doi.org/10.1163/156855401753255422

    Article  CAS  Google Scholar 

  3. Li X, Tabil LG, Panigrahi S (2007) Chemical treatments of natural fiber for use in natural fiber-reinforced composites: a review. J Polym Environ 15:25–33. https://doi.org/10.1007/s10924-006-0042-3

    Article  CAS  Google Scholar 

  4. Bledzki A (1999) Composites reinforced with cellulose based fibres. Prog Polym Sci 24:221–274. https://doi.org/10.1016/S0079-6700(98)00018-5

    Article  CAS  Google Scholar 

  5. Ichazo M, Albano C, González J, Perera R, Candal M (2001) Polypropylene/wood flour composites: treatments and properties. Compos Struct 54:207–214. https://doi.org/10.1016/S0263-8223(01)00089-7

    Article  Google Scholar 

  6. Štrumberger N, Gospočić A, Hvu M, Bartulić Č (2005) Polymeric materials in automobiles. Promet Traffic Traffico 17:149–160. https://doi.org/10.7307/ptt.v17i3.630

    Article  Google Scholar 

  7. Mohanty A, Tummala P, Misra M, Drzal L (2009) Filler reinforced thermoplastic compositions and process for manufacture. US Pat 7:582,241 2

  8. Elsabbagh A, Steuernagel L, Ring J (2017) Natural Fibre/PA6 composites with flame retardance properties: extrusion and characterisation. Compos B Eng 108:325–333. https://doi.org/10.1016/j.compositesb.2016.10.012

    Article  CAS  Google Scholar 

  9. Garcia-Ramirez M, Cavaillé JY, Dupeyre D, Péguy A (1994) Cellulose-polyamide 66 blends. I. Processing and characterization. J Polym Sci B Polym Phys 32:1437–1448. https://doi.org/10.1002/polb.1994.090320815

    Article  CAS  Google Scholar 

  10. Vold JL, Ulven CA, Chisholm BJ (2014) Torrefied biomass filled polyamide biocomposites: mechanical and physical property analysis. J Mater Sci 50:725–732. https://doi.org/10.1007/s10853-014-8632-2

    Article  CAS  Google Scholar 

  11. Collard FX, Blin, J (2014) A review on pyrolysis of biomass constituents: mechanisms and composition of the products obtained from the conversion of cellulose, hemicelluloses and lignin. Renew Sustain Energy Rev 38:594–608. https://doi.org/10.1016/j.rser.2014.06.013

    Article  CAS  Google Scholar 

  12. Kan T, Strezov V, Evans TJ (2016) Lignocellulosic biomass pyrolysis: a review of product properties and effects of pyrolysis parameters. Renew Sustain Energy Rev 57:126–1140

    Article  CAS  Google Scholar 

  13. Lehmann J, Joseph S; Biochar for Environmental Management: Science, Technology and Implementation, Chapt. 4, Biochar production technology, Boateng AA, Garcia-Perez M, Masek O, Brown R, del Campo B pp 63–88, 2nd edn., Earthscan from Routledge

  14. Behazin E, Ogunsona E, Rodriguez-Uribe A, Mohanty AK, Misra M, Anyia AO (2016) Mechanical, chemical, and physical properties of wood and perennial grass biochars for possible composite application. BioResources 11:1334–1348. https://doi.org/10.15376/biores.11.1.1334-1348

    Article  CAS  Google Scholar 

  15. Behazin E, Misra M, Mohanty AK (2017) Sustainable biocarbon from pyrolyzed perennial grasses and their effects on impact modified polypropylene biocomposites. Compos B Eng 118:116–124. https://doi.org/10.1016/j.compositesb.2017.03.003

    Article  CAS  Google Scholar 

  16. Salak F, Uemura S, Sugimoto K (2015) Thermal pretreatment of kudzu biomass (pueraria lobata) as filler in cost-effective pla biocomposite fabrication process. Polym Eng Sci 55:340–348. https://doi.org/10.1002/pen.23909

    Article  CAS  Google Scholar 

  17. Qian S, Sheng K, Yao W, Yu H (2016) Poly(lactic acid) biocomposites reinforced with ultrafine bamboo-char: Morphology, mechanical, thermal, and water absorption properties. J Appl Polym Sci. https://doi.org/10.1002/app.43425

    Article  Google Scholar 

  18. Peterson SC, Chandrasekaran SR, Sharma BK (2016) Birchwood biochar as partial carbon black replacement in styrene-butadiene rubber composites. J Elastomers Plast 48:305–316. https://doi.org/10.1177/0095244315576241

    Article  CAS  Google Scholar 

  19. Jong L, Peterson SC, Jackson MA (2014) Utilization of porous carbons derived from coconut shell and wood in natural rubber. J Polym Environ 22:289–297. https://doi.org/10.1007/s10924-013-0637-4

    Article  CAS  Google Scholar 

  20. Peterson SC (2011) Evaluating corn starch and corn stover biochar as renewable filler in carboxylated styrene-butadiene rubber composites. J Elastomers Plast 44:43–54. https://doi.org/10.1177/0095244311414011

    Article  CAS  Google Scholar 

  21. Peterson S (2013) Utilization of low-ash biochar to partially replace carbon black in styrene–butadiene rubber composites. J Elastomers Plast 45:487–497. https://doi.org/10.1177/0095244312459181

    Article  CAS  Google Scholar 

  22. Das O, Sarmah AK, Bhattacharyya D (2016) Biocomposites from waste derived biochars: mechanical, thermal, chemical, and morphological properties. Waste Manag 49:560–570. https://doi.org/10.1016/j.wasman.2015.12.007

    Article  CAS  PubMed  Google Scholar 

  23. Ahmetli G, Kocaman S, Ozaytekin I, Bozkurt P (2013) Epoxy composites based on inexpensive char filler obtained from plastic waste and natural resources. Polym Compos 34:500–509. https://doi.org/10.1002/pc.22452

    Article  CAS  Google Scholar 

  24. Richard S, Rajadurai JS, Manikandan V (2016) Influence of particle size and particle loading on mechanical and dielectric properties of biochar particulate-reinforced polymer nanocomposites. Int J Polym Anal Charact 21:462–477. https://doi.org/10.1080/1023666X.2016.1168602

    Article  CAS  Google Scholar 

  25. Sri Aprilia N, Khalil H, Bhat A, Dungani R, Hossain M (2014) Exploring material properties of vinyl ester biocomposites filled carbonized jatropha seed shell. BioResources 9:4888–4898

    Article  Google Scholar 

  26. Ojha S, Acharya SK, Raghavendra G (2015) Mechanical properties of natural carbon black reinforced polymer composites. J Appl Polym Sci. https://doi.org/10.1002/app.41211

    Article  Google Scholar 

  27. Ogunsona EO, Misra M, Mohanty AK (2017) Impact of interfacial adhesion on the microstructure and property variations of biocarbons reinforced nylon 6 biocomposites. Compos A Appl Sci Manuf 98:32–44

    Article  CAS  Google Scholar 

  28. Ogunsona EO, Misra M, Mohanty AK (2017) Sustainable biocomposites from biobased polyamide 6,10 and biocarbon from pyrolyzed miscanthus fibers. J Appl Polym Sci 134:44221. https://doi.org/10.1002/app.44221

    Article  CAS  Google Scholar 

  29. Ogunsona EO, Misra M, Mohanty AK (2017) Accelerated hydrothermal aging of biocarbon reinforced nylon biocomposites. Polym Degrad Stab 139:76–88. https://doi.org/10.1016/j.polymdegradstab.2017.03.013

    Article  CAS  Google Scholar 

  30. Ogunsona EO, Misra M, Mohanty AK (2017) Influence of epoxidized natural rubber on the phase structure and toughening behavior of biocarbon reinforced nylon 6 biocomposites. RSC Adv 7:8727–8739. https://doi.org/10.1039/C6RA27177D

    Article  CAS  Google Scholar 

  31. Chrissafis K, Bikiaris D (2011) Can nanoparticles really enhance thermal stability of polymers? Part I: an overview on thermal decomposition of addition polymers. Thermochim Acta 523:1–24. https://doi.org/10.1016/j.tca.2011.06.010

    Article  CAS  Google Scholar 

  32. Xenopoulos A, Wunderlich B (1990) Heat capacities of solid polyamides. Polymer 31:1260–1268. https://doi.org/10.1016/0032-3861(90)90217-M

    Article  CAS  Google Scholar 

  33. Achhammer BG, Reinhart FW, Kline GM (1951) Mechanism of the degradation of polyamides. J Res Natl Bur Stand 46:391. https://doi.org/10.6028/jres.046.044

    Article  CAS  Google Scholar 

  34. Dabrowski F, Bourbigot S, Delobel R, Le Bras M (2000) Kinetic modelling of the thermal degradation of polyamide-6 nanocomposite. Eur Polym J 36:273–284. https://doi.org/10.1016/S0014-3057(99)00079-8

    Article  CAS  Google Scholar 

  35. Amintowlieh Y, Sardashti A, Simon LC (2012) Polyamide 6-wheat straw composites: degradation kinetics. Polym Compos 33:985–989. https://doi.org/10.1002/pc.22229

    Article  CAS  Google Scholar 

  36. Lahijani P, Zainal ZA, Mohamed AR, Mohammadi M (2013) CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts. Bioresour Technol 144:288–295. https://doi.org/10.1016/j.biortech.2013.06.059

    Article  CAS  PubMed  Google Scholar 

  37. Mani S, Kastner JR, Juneja A (2013) Catalytic decomposition of toluene using a biomass derived catalyst. Fuel Process Technol 114:118–125. https://doi.org/10.1016/j.fuproc.2013.03.015

    Article  CAS  Google Scholar 

  38. Zhang ZZ, Zhu MM, Liu PF, Wan WC, Zhou WX, Chan YL, Zhang DK (2015) Effect of biochar on the cracking of tar from the pyrolysis of a pine sawdust in a fixed bed reactor. Energy Procedia 75:196–201. https://doi.org/10.1016/j.egypro.2015.07.299

    Article  CAS  Google Scholar 

  39. Dabrowski F, Bourbigot S, Delobel R, Le Bras M (2000) Kinetic modelling of the thermal degradation. Eur Polym J 36:273–284. https://doi.org/10.1016/S0014-3057(99)00079-8

    Article  CAS  Google Scholar 

  40. Ogunsona EO, Anstey J, Torres SE, Codou AMFM-S., Jubinville DF (2018) Biocarbon and nylon based hybrid carbonaceous biocomposites and methods of making those and using thereof. US Application Patent: US20180022921A1

  41. Nuñez A, Sturm P, Kenny J, Aranguren M, Marcovich N, Reboredo M (2003) Mechanical characterization of polypropylene–wood flour composites. J Appl Polym Sci 88:1420–1428

    Article  CAS  Google Scholar 

  42. Ahmed S, Jones F (1990) A review of particulate reinforcement theories for polymer composites. J Mater Sci 25:4933–4942

    Article  CAS  Google Scholar 

  43. Liu Z (2002) Effects of coupling agent and morphology on the impact strength of high density polyethylene/CaCO3 composites. Polymer 43:2501–2506. https://doi.org/10.1016/S0032-3861(02)00048-4

    Article  CAS  Google Scholar 

  44. Huber T, Misra M, Mohanty AK (2014) The effect of particle size on the rheological properties of polyamide 6/biochar composites. In AIP Conference Proceedings; Cleveland, Ohio, USA p. 150004

Download references

Acknowledgements

The authors acknowledge the financial support by the Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA) – University of Guelph Product Development and Enhancement through Value Chains Research Theme (Project # 200399, 200388, 200245), The Natural Sciences and Engineering Research Council (NSERC), Canada Discovery grant (Project # 400322) and Ontario Research Fund, Research Excellence Program; Round-7 (ORF-RE07) from the Ontario Ministry of Research and Innovation, currently known as the Ontario Ministry of Research, Innovation and Science (MRIS) (Project # 052644 and # 052665).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Manjusri Misra.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ogunsona, E.O., Codou, A., Misra, M. et al. Thermally Stable Pyrolytic Biocarbon as an Effective and Sustainable Reinforcing Filler for Polyamide Bio-composites Fabrication. J Polym Environ 26, 3574–3589 (2018). https://doi.org/10.1007/s10924-018-1232-5

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10924-018-1232-5

Keywords

Navigation