Abstract
Biodegradable resins can enhance the environmental sustainability of wood-plastic composites (WPCs) by enabling methane (CH\(_4\)) recovery via anaerobic digestion (AD). An under appreciated step in biocomposite AD is the role of cracking and fragmentation due to moisture uptake by the wood fiber (WF) fraction. Here, we use batch microcosms to simulate AD at end-of-life and to assess the effects of fiber-matrix treatments used to retard in-service moisture uptake. The composites evaluated were injection molded poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) with WF (0, 20%) using two fiber-matrix compatibilization treatments: (1) hydrophobic silane treatment of the wood fiber and (2) grafting of hydrophilic maleic anhydride groups to the PHBV matrix. Both treatments accelerated rates of mass loss and CH\(_4\) production by a factor of 1.2–2.3 compared to neat PHBV. The fragmentation rate, as measured by mass loss, increased significantly for treated samples compared to untreated samples. A ranking of test samples from lowest to highest rates of mass loss gave the following sequence: neat PHBV \(\approx\) maleated PHBV < PHBV plus untreated WF < maleated PHBV plus untreated WF < PHBV plus silane-treated WF. Compared to the untreated samples, maleic anhydride treatment increased the mass loss rate by 30%, and silane treatment increased the mass loss rate by 92%. Onset of cracking in silane-treated composites was observed at 2 weeks (using X-ray micro-computed tomography). At the same time, solid mass loss and CH\(_4\) production peaked, implicating cracking and physical disintegration as the rate-limiting step for accelerated anaerobic degradation. When modified to account for bioplastic matrix degradation, a previously derived moisture-induced damage model could predict the onset of composite fragmentation at end-of-life. These results are significant for design of bio-WPCs and demonstrate that treatments designed to improve in-service performance can also improve end-of-life options.
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Acknowledgements
The authors thank BioProcess Control, SeaHold LLC, and Team Biogas for their generous support and collaboration with the AMPTS unit. We also thank the City of San Jose and the employees of the San Jose Waste Water Treatment Plant for their assistance in obtaining inoculum for these experiments. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF) and Soft and Hybrid Materials Facility (SMF) at Stanford University. Micro-CT imaging and analysis were performed at the Stanford Small Animal Imaging Facility, and in particular we thank Dr. Timothy Doyle for his expertise in establishing scan conditions and analysis and Dr. Frezghi Habte for his assistance in data analysis. This work was funded by NSF CMMI [Grant 0900325], California EPA Department of Toxic Substances Control [Project Ref. No. 07T3451], CalRecycle [Contract No. DRRR10020], and individual graduate funding from the EPA Star Graduate Fellowship and the Stanford Civil Engineering Charles H. Leavell Graduate Fellowship.
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Ryan, C.A., Billington, S.L. & Criddle, C.S. Biocomposite Fiber-Matrix Treatments that Enhance In-Service Performance Can Also Accelerate End-of-Life Fragmentation and Anaerobic Biodegradation to Methane. J Polym Environ 26, 1715–1726 (2018). https://doi.org/10.1007/s10924-017-1068-4
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DOI: https://doi.org/10.1007/s10924-017-1068-4