Scholarly Work - Mechanical & Industrial Engineering
Permanent URI for this collectionhttps://scholarworks.montana.edu/handle/1/8878
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Item Incorporation of Carbon Nanofillers Tunes Mechanical and Electrical Percolation in PHBV:PLA Blends(2018-12) Arroyo, Jesse; Ryan, Cecily A.Biobased fillers, such as bio-derived cellulose, lignin byproducts, and biochar, can be used to modify the thermal, mechanical, and electrical properties of polymer composites. Biochar (BioC), in particular, is of interest for enhancing thermal and electrical conductivities in composites, and can potentially serve as a bio-derived graphitic carbon alternative for certain composite applications. In this work, we investigate a blended biopolymer system: poly(lactic acid) (PLA)/poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), and addition of carbon black (CB), a commonly used functional filler as a comparison for Kraft lignin-derived BioC. We present calculations and experimental results for phase-separation and nanofiller phase affinity in this system, indicating that the CB localizes in the PHBV phase of the immiscible PHBV:PLA blends. The addition of BioC led to a deleterious reaction with the biopolymers, as indicated by blend morphology, differential scanning calorimetry showing significant melting peak reduction for the PLA phase, and a reduction in melt viscosity. For the CB nanofilled composites, electrical conductivity and dynamic mechanical analysis supported the ability to use phase separation in these blends to tune the percolation of mechanical and electrical properties, with a minimum percolation threshold found for the 80:20 blends of 1.6 wt.% CB. At 2% BioC (approximately the percolation threshold for CB), the 80:20 BioC nanocomposites had a resistance of 3.43 x 108 as compared to 2.99 x 108 for the CB, indicating that BioC could potentially perform comparably to CB as a conductive nanofiller if the processing challenges can be overcome for higher BioC loadings.Item Incorporation of carbon nanofillers tunes mechanical and electrical percolation in PHBV:PLA blends(2018-12) Arroyo, Jesse; Ryan, Cecily A.Biobased fillers, such as bio-derived cellulose, lignin byproducts, and biochar, can be used to modify the thermal, mechanical, and electrical properties of polymer composites. Biochar (BioC), in particular, is of interest for enhancing thermal and electrical conductivities in composites, and can potentially serve as a bio-derived graphitic carbon alternative for certain composite applications. In this work, we investigate a blended biopolymer system: poly(lactic acid) (PLA)/poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), and addition of carbon black (CB), a commonly used functional filler as a comparison for Kraft lignin-derived BioC. We present calculations and experimental results for phase-separation and nanofiller phase affinity in this system, indicating that the CB localizes in the PHBV phase of the immiscible PHBV:PLA blends. The addition of BioC led to a deleterious reaction with the biopolymers, as indicated by blend morphology, differential scanning calorimetry showing significant melting peak reduction for the PLA phase, and a reduction in melt viscosity. For the CB nanofilled composites, electrical conductivity and dynamic mechanical analysis supported the ability to use phase separation in these blends to tune the percolation of mechanical and electrical properties, with a minimum percolation threshold found for the 80:20 blends of 1.6 wt.% CB. At 2% BioC (approximately the percolation threshold for CB), the 80:20 BioC nanocomposites had a resistance of 3.43 × 108 Ω as compared to 2.99 × 108 Ω for the CB, indicating that BioC could potentially perform comparably to CB as a conductive nanofiller if the processing challenges can be overcome for higher BioC loadings.Item Code to calculate interfacial interactions for polymer blends and composites(Montana State University, 2018-12) Arroyo, Jesse; Ryan, Cecily A.This code uses the Owens-Wendt theory to calculate surface energies of polymers and fillers from contact angle measurements and predict phase separation and nanofiller localization based on interfacial tensions. This code predicts the morphology of a 2-phase polymer blend and the localization of a nano-particulate using the geometric mean equation, and contact angles of each polymer.Item Assessment of models for anaerobic biodegradation of a model bioplastic: Poly(hydroxybutyrate-co-hydroxyvalerate)(2017-03) Ryan, Cecily A.; Billington, Sarah L.; Criddle, Craig S.Kinetic models of anaerobic digestion (AD) are widely applied to soluble and particulate substrates, but have not been systematically evaluated for bioplastics. Here, five models are evaluated to determine their suitability for modeling of anaerobic biodegradation of the bioplastic poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV): (1) first-order kinetics with and without a lag phase, (2) two-step first-order, (3) Monod (4) Contois, and (5) Gompertz. Three models that couple biomass growth with substrate hydrolysis (Monod, Contois, and Gompertz) gave the best overall fits for the data , with reasonable estimates of ultimate CH4 production. The particle size limits of these models were then evaluated. Below a particle size of 0.8 mm, rates of hydrolysis and acetogenesis exceeded rates of methanogenesis with accumulation of intermediates leading to a temporary inhibition of CH4 production. Based on model fit and simplicity, the Gompertz model is recommended for applications in which particle size is greater than 0.8 mm.Item Methodology to assess end-of-life anaerobic biodegradation kinetics and methane production potential for composite materials(2017-04) Ryan, Cecily A.; Billington, Sarah L.; Criddle, Craig S.Composites made with bio-based resins are promising candidates for replacement of conventional plastic composites made with petroleum-based resins in many applications (e.g., decking, paneling, furniture, molded automotive parts). For any such applications, end-of-life management needs consideration. Here, we describe a methodology to assess end-of-life anaerobic degradation to methane (CH4) within landfills or anaerobic digestion (AD) facilities in batch anaerobic microcosms. The core methodology combines stoichiometric considerations, chemical oxygen demand (COD) analysis, a CH4 production assay, and modeling. Additional analyses, such as thermogravimetric analysis (TGA), can complement this core set of analyses. We apply the methodology to injection molded poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) composites with wood fiber (WF) (0%, 20%, 40%) and two fiber-matrix compatibilization treatments that enhance in-service performance: (1) hydrophobic silane treatment of the WF and (2) grafting of hydrophilic maleic anhydride groups to the PHBV matrix. The methodology successfully quantifies process kinetics, ultimate CH4 production capacity, and biodegradability, and allows comparison to reference materials (positive controls).Item Biocomposite Fiber-Matrix Treatments that Enhance In-Service Performance Can Also Accelerate End-of-Life Fragmentation and Anaerobic Biodegradation to Methane(2017-07) Ryan, Cecily A.; Billington, Sarah L.; Criddle, Craig S.Biodegradable resins can enhance the environmental sustainability of wood-plastic composites (WPCs) by enabling methane (CH4) 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 CH4 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 ~ 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 CH4 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.