Computational modeling of biodegradable starch based polymer composites

Purpose. The goal of this study is to improve the favorable molecular interactions between starch and PPC by addition of grafting monomers MA and ROM as compatibilizers, which would advance the mechanical properties of starch/PPC composites. ^ Methodology. DFT and semi-empirical methods based calculations were performed on three systems: (a) starch/PPC, (b) starch/PPC-MA, and (c) starch-ROM/PPC. Theoretical computations involved the determination of optimal geometries, binding-energies and vibrational frequencies of the blended polymers. ^ Findings. Calculations performed on five starch/PPC composites revealed hydrogen bond formation as the driving force behind stable composite formation, also confirmed by the negative relative energies of the composites indicating the existence of binding forces between the constituent co-polymers. The interaction between starch and PPC is also confirmed by the computed decrease in stretching CO and OH group frequencies participating in hydrogen bond formation, which agree qualitatively with the experimental values. ^ A three-step mechanism of grafting MA on PPC was proposed to improve the compatibility of PPC with starch. Nine types of 'blends' produced by covalent bond formation between starch and MA-grafted PPC were found to be energetically stable, with blends involving MA grafted at the 'B' and 'C' positions of PPC indicating a binding-energy increase of 6.8 and 6.2 kcal/mol, respectively, as compared to the non-grafted starch/PPC composites. A similar increase in binding-energies was also observed for three types of 'composites' formed by hydrogen bond formation between starch and MA-grafted PPC. ^ Next, grafting of ROM on starch and subsequent blend formation with PPC was studied. All four types of blends formed by the reaction of ROM-grafted starch with PPC were found to be more energetically stable as compared to the starch/PPC composite and starch/PPC-MA composites and blends. A blend of PPC and ROM grafted at the ' a&d12; ' position on amylose exhibited a maximal increase of 17.1 kcal/mol as compared with the starch/PPC-MA blend. ^ Conclusions. ROM was found to be a more effective compatibilizer in improving the favorable interactions between starch and PPC as compared to MA. The ' a&d12; ' position was found to be the most favorable attachment point of ROM to amylose for stable blend formation with PPC.^

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.

Seismic performance of hybrid fiber reinforced polymer-concrete pier columns

As part of a multi-university research program funded by NSF, a comprehensive experimental and analytical study of seismic behavior of hybrid fiber reinforced polymer (FRP)-concrete column is presented in this dissertation. Experimental investigation includes cyclic tests of six large-scale concrete-filled FRP tube (CFFT) and RC columns followed by monotonic flexural tests, a nondestructive evaluation of damage using ultrasonic pulse velocity in between the two test sets and tension tests of sixty-five FRP coupons. Two analytical models using ANSYS and OpenSees were developed and favorably verified against both cyclic and monotonic flexural tests. The results of the two methods were compared. A parametric study was also carried out to investigate the effect of three main parameters on primary seismic response measures. The responses of typical CFFT columns to three representative earthquake records were also investigated. The study shows that only specimens with carbon FRP cracked, whereas specimens with glass or hybrid FRP did not show any visible cracks throughout cyclic tests. Further monotonic flexural tests showed that carbon specimens both experienced flexural cracks in tension and crumpling in compression. Glass or hybrid specimens, on the other hand, all showed local buckling of FRP tubes. Compared with conventional RC columns, CFFT column possesses higher flexural strength and energy dissipation with an extended plastic hinge region. Among all CFFT columns, the hybrid lay-up demonstrated the highest flexural strength and initial stiffness, mainly because of its high reinforcement index and FRP/concrete stiffness ratio, respectively. Moreover, at the same drift ratio, the hybrid lay-up was also considered as the best in term of energy dissipation. Specimens with glassfiber tubes, on the other hand, exhibited the highest ductility due to better flexibility of glass FRP composites. Furthermore, ductility of CFFTs showed a strong correlation with the rupture strain of FRP. Parametric study further showed that different FRP architecture and rebar types may lead to different failure modes for CFFT columns. Transient analysis of strong ground motions showed that the column with off-axis nonlinear filament-wound glass FRP tube exhibited a superior seismic performance to all other CFFTs. Moreover, higher FRP reinforcement ratios may lead to a brittle system failure, while a well-engineered FRP reinforcement configuration may significantly enhance the seismic performance of CFFT columns.

Periodic polymer photonic bandgap structures for on-chip optical cavities

Integrated on-chip optical platforms enable high performance in applications of high-speed all-optical or electro-optical switching, wide-range multi-wavelength on-chip lasing for communication, and lab-on-chip optical sensing. Integrated optical resonators with high quality factor are a fundamental component in these applications. Periodic photonic structures (photonic crystals) exhibit a photonic band gap, which can be used to manipulate photons in a way similar to the control of electrons in semiconductor circuits. This makes it possible to create structures with radically improved optical properties. Compared to silicon, polymers offer a potentially inexpensive material platform with ease of fabrication at low temperatures and a wide range of material properties when doped with nanocrystals and other molecules. In this research work, several polymer periodic photonic structures are proposed and investigated to improve optical confinement and optical sensing. We developed a fast numerical method for calculating the quality factor of a photonic crystal slab (PhCS) cavity. The calculation is implemented via a 2D-FDTD method followed by a post-process for cavity surface energy radiation loss. Computational time is saved and good accuracy is demonstrated compared to other published methods. Also, we proposed a novel concept of slot-PhCS which enhanced the energy density 20 times compared to traditional PhCS. It combines both advantages of the slot waveguide and photonic crystal to localize the high energy density in the low index material. This property could increase the interaction between light and material embedded with nanoparticles like quantum dots for active device development. We also demonstrated a wide range bandgap based on a one dimensional waveguide distributed Bragg reflector with high coupling to optical waveguides enabling it to be easily integrated with other optical components on the chip. A flexible polymer (SU8) grating waveguide is proposed as a force sensor. The proposed sensor can monitor nN range forces through its spectral shift. Finally, quantum dot - doped SU8 polymer structures are demonstrated by optimizing spin coating and UV exposure. Clear patterns with high emission spectra proved the compatibility of the fabrication process for applications in optical amplification and lasing.

Seismic Performance of Hybrid Fiber Reinforced Polymer-Concrete Pier Columns

As part of a multi-university research program funded by NSF, a comprehensive experimental and analytical study of seismic behavior of hybrid fiber reinforced polymer (FRP)-concrete column is presented in this dissertation. Experimental investigation includes cyclic tests of six large-scale concrete-filled FRP tube (CFFT) and RC columns followed by monotonic flexural tests, a nondestructive evaluation of damage using ultrasonic pulse velocity in between the two test sets and tension tests of sixty-five FRP coupons. Two analytical models using ANSYS and OpenSees were developed and favorably verified against both cyclic and monotonic flexural tests. The results of the two methods were compared. A parametric study was also carried out to investigate the effect of three main parameters on primary seismic response measures. The responses of typical CFFT columns to three representative earthquake records were also investigated. The study shows that only specimens with carbon FRP cracked, whereas specimens with glass or hybrid FRP did not show any visible cracks throughout cyclic tests. Further monotonic flexural tests showed that carbon specimens both experienced flexural cracks in tension and crumpling in compression. Glass or hybrid specimens, on the other hand, all showed local buckling of FRP tubes. Compared with conventional RC columns, CFFT column possesses higher flexural strength and energy dissipation with an extended plastic hinge region. Among all CFFT columns, the hybrid lay-up demonstrated the highest flexural strength and initial stiffness, mainly because of its high reinforcement index and FRP/concrete stiffness ratio, respectively. Moreover, at the same drift ratio, the hybrid lay-up was also considered as the best in term of energy dissipation. Specimens with glassfiber tubes, on the other hand, exhibited the highest ductility due to better flexibility of glass FRP composites. Furthermore, ductility of CFFTs showed a strong correlation with the rupture strain of FRP. Parametric study further showed that different FRP architecture and rebar types may lead to different failure modes for CFFT columns. Transient analysis of strong ground motions showed that the column with off-axis nonlinear filament-wound glass FRP tube exhibited a superior seismic performance to all other CFFTs. Moreover, higher FRP reinforcement ratios may lead to a brittle system failure, while a well-engineered FRP reinforcement configuration may significantly enhance the seismic performance of CFFT columns.