Predicting the Mechanical Properties of Carbon-Based Materials Using Molecular Dynamics

The development of innovative carbon-based materials can be greatly facilitated by molecular modeling techniques. Although molecular modeling has been used extensively to predict elastic properties of materials, modeling of more complex phenomenon such as fracture has only recently been possible with the development of new force fields such as ReaxFF, which is used in this work. It is not fully understood what molecular modeling parameters such as thermostat type, thermostat coupling, time step, system size, and strain rate are required for accurate modeling of fracture. Selection of modeling parameters to model fracture can be difficult and non-intuitive compared to modeling elastic properties using traditional force fields, and the errors generated by incorrect parameters may be non-obvious. These molecular modeling parameters are systematically investigated and their effects on the fracture of well-known carbon materials are analyzed. It is determined that for coupling coefficients of 250 fs and greater do not result in substantial differences in the stress-strain response of the materials using any thermostat type. A time step of 0.5 fs of smaller is required for accurate results. Strain rates greater than 2.2 ns-1 are sufficient to obtain repeatable results with slower strain rates for the materials studied. The results of this study indicate that further refinement of the Chenoweth parameter set is required to accurately predict the mechanical response of carbon-based systems. The ReaxFF has been used extensively to model systems in which bond breaking and formation occur. In particular ReaxFF has been used to model reactions of small molecules. Some elastic and fracture properties have been successfully modeled using ReaxFF in materials such as silicon and some metals. However, it is not clear if current parameterizations for ReaxFF are able to accurately reproduce the elastic and fracture properties of carbon materials. The stress-strain response of a new ReaxFF parameterization is compared to the previous parameterization and density functional theory results for well-known carbon materials. The new ReaxFF parameterization makes xv substantial improvements to the predicted mechanical response of carbon materials, and is found to be suitable for modeling the mechanical response of carbon materials. Finally, a new material composed of carbon nanotubes within an amorphous carbon (AC) matrix is modeled using the ReaxFF. Various parameters that may be experimentally controlled are investigated such as nanotube bundling, comparing multi-walled nanotube with single-walled nanotubes, and degree of functionalization of the nanotubes. Elastic and fracture properties are investigated for the composite systems and compared to results of pure-nanotube and pure-AC models. It is found that the arrangement of the nanotubes and degree of crosslinking may substantially affect the properties of the systems, particularly in the transverse directions.

PARAMETRIC STUDY OF REAXFF SIMULATION PARAMETERS FOR MOLECULAR DYNAMICS MODELING OF REACTIVE CARBON GASES

Abstract The development of innovative carbon-based materials can be greatly facilitated by molecular modeling techniques. Although the Reax Force Field (ReaxFF) can be used to simulate the chemical behavior of carbon-based systems, the simulation settings required for accurate predictions have not been fully explored. Using the ReaxFF, molecular dynamics (MD) simulations are used to simulate the chemical behavior of pure carbon and hydrocarbon reactive gases that are involved in the formation of carbon structures such as graphite, buckyballs, amorphous carbon, and carbon nanotubes. It is determined that the maximum simulation time step that can be used in MD simulations with the ReaxFF is dependent on the simulated temperature and selected parameter set, as are the predicted reaction rates. It is also determined that different carbon-based reactive gases react at different rates, and that the predicted equilibrium structures are generally the same for the different ReaxFF parameter sets, except in the case of the predicted formation of large graphitic structures with the Chenoweth parameter set under specific conditions.

Molecular modeling of EPON 862-DETDA polymer

EPON 862 is an epoxy resin which is cured with the hardening agent DETDA to form a crosslinked epoxy polymer and is used as a component in modern aircraft structures. These crosslinked polymers are often exposed to prolonged periods of temperatures below glass transition range which cause physical aging to occur. Because physical aging can compromise the performance of epoxies and their composites and because experimental techniques cannot provide all of the necessary physical insight that is needed to fully understand physical aging, efficient computational approaches to predict the effects of physical aging on thermo-mechanical properties are needed. In this study, Molecular Dynamics and Molecular Minimization simulations are being used to establish well-equilibrated, validated molecular models of the EPON 862-DETDA epoxy system with a range of crosslink densities using a united-atom force field. These simulations are subsequently used to predict the glass transition temperature, thermal expansion coefficients, and elastic properties of each of the crosslinked systems for validation of the modeling techniques. The results indicate that glass transition temperature and elastic properties increase with increasing levels of crosslink density and the thermal expansion coefficient decreases with crosslink density, both above and below the glass transition temperature. The results also indicate that there may be an upper limit to crosslink density that can be realistically achieved in epoxy systems. After evaluation of the thermo-mechanical properties, a method is developed to efficiently establish molecular models of epoxy resins that represent the corresponding real molecular structure at specific aging times. Although this approach does not model the physical aging process, it is useful in establishing a molecular model that resembles the physically-aged state for further use in predicting thermo-mechanical properties as a function of aging time. An equation has been predicted based on the results which directly correlate aging time to aged volume of the molecular model. This equation can be helpful for modelers who want to study properties of epoxy resins at different levels of aging but have little information about volume shrinkage occurring during physical aging.

Multiscale constitutive modeling of polymer materials

Materials are inherently multi-scale in nature consisting of distinct characteristics at various length scales from atoms to bulk material. There are no widely accepted predictive multi-scale modeling techniques that span from atomic level to bulk relating the effects of the structure at the nanometer (10-9 meter) on macro-scale properties. Traditional engineering deals with treating matter as continuous with no internal structure. In contrast to engineers, physicists have dealt with matter in its discrete structure at small length scales to understand fundamental behavior of materials. Multiscale modeling is of great scientific and technical importance as it can aid in designing novel materials that will enable us to tailor properties specific to an application like multi-functional materials. Polymer nanocomposite materials have the potential to provide significant increases in mechanical properties relative to current polymers used for structural applications. The nanoscale reinforcements have the potential to increase the effective interface between the reinforcement and the matrix by orders of magnitude for a given reinforcement volume fraction as relative to traditional micro- or macro-scale reinforcements. To facilitate the development of polymer nanocomposite materials, constitutive relationships must be established that predict the bulk mechanical properties of the materials as a function of the molecular structure. A computational hierarchical multiscale modeling technique is developed to study the bulk-level constitutive behavior of polymeric materials as a function of its molecular chemistry. Various parameters and modeling techniques from computational chemistry to continuum mechanics are utilized for the current modeling method. The cause and effect relationship of the parameters are studied to establish an efficient modeling framework. The proposed methodology is applied to three different polymers and validated using experimental data available in literature.

Electron transport in molecular systems

The remarkable advances in nanoscience and nanotechnology over the last two decades allow one to manipulate individuals atoms, molecules and nanostructures, make it possible to build devices with only a few nanometers, and enhance the nano-bio fusion in tackling biological and medical problems. It complies with the ever-increasing need for device miniaturization, from magnetic storage devices, electronic building blocks for computers, to chemical and biological sensors. Despite the continuing efforts based on conventional methods, they are likely to reach the fundamental limit of miniaturization in the next decade, when feature lengths shrink below 100 nm. On the one hand, quantum mechanical efforts of the underlying material structure dominate device characteristics. On the other hand, one faces the technical difficulty in fabricating uniform devices. This has posed a great challenge for both the scientific and the technical communities. The proposal of using a single or a few organic molecules in electronic devices has not only opened an alternative way of miniaturization in electronics, but also brought up brand-new concepts and physical working mechanisms in electronic devices. This thesis work stands as one of the efforts in understanding and building of electronic functional units at the molecular and atomic levels. We have explored the possibility of having molecules working in a wide spectrum of electronic devices, ranging from molecular wires, spin valves/switches, diodes, transistors, and sensors. More specifically, we have observed significant magnetoresistive effect in a spin-valve structure where the non-magnetic spacer sandwiched between two magnetic conducting materials is replaced by a self-assembled monolayer of organic molecules or a single molecule (like a carbon fullerene). The diode behavior in donor(D)-bridge(B)-acceptor(A) type of single molecules is then discussed and a unimolecular transistor is designed. Lastly, we have proposed and primarily tested the idea of using functionalized electrodes for rapid nanopore DNA sequencing. In these studies, the fundamental roles of molecules and molecule-electrode interfaces on quantum electron transport have been investigated based on first-principles calculations of the electronic structure. Both the intrinsic properties of molecules themselves and the detailed interfacial features are found to play critical roles in electron transport at the molecular scale. The flexibility and tailorability of the properties of molecules have opened great opportunity in a purpose-driven design of electronic devices from the bottom up. The results that we gained from this work have helped in understanding the underlying physics, developing the fundamental mechanism and providing guidance for future experimental efforts.

Synthesis of novel solid materials from carbon dioxide and carbon monoxide

The increase of atmospheric CO2 has been identified as the primary cause for the observed global warming over the past century. The geological and oceanic sequestration of CO2 has issues, such as cost and leakage as well as effects on sea biota. The ideal solution should be the conversion of CO2 into useful materials. However, most processes require high energy input. Therefore, it is necessary to explore novel processes with low energy demands to convert CO2 to useful solid materials. Amorphous carbon nitride and graphone received much attention due to their unusual structures and properties as well as their potential applications. However, to date there has been no attempt to synthesize those solid materials from CO2. Lithium nitride (Li3N) and lithium imide (Li2NH) are important hydrogen storage materials. However, their optical properties and reactivity has not yet studied. This dissertation research is aimed at the synthesis of carbon nitrides and graphone from CO2 and CO via their reaction with Li3N and Li2NH. The research was focused on (1) the evaluation of Li3N and Li2NH properties, (2) thermodynamic analysis of conversion of carbon dioxide and carbon monoxide into carbon nitride and other solid materials, (3) synthesis of carbon nitride from carbon dioxide, and (4) synthesis of graphone from carbon monoxide. First, the properties of Li3N, Li2NH, and LiNH2 were investigated. The X-ray diffraction measurements revealed that heat-treatment at 500°C introduce a phase transformation of β-Li3N to α-Li3N. Furthermore, the UV-visible absorption evaluation showed that the energy gaps of α-Li3N and β-Li3N are 1.81 and 2.14 eV, respectively. The UV-visible absorption measurements also revealed that energy gaps are 3.92 eV for Li2NH and 3.93 eV for LiNH2. This thermodynamic analysis was performed to predict the reactions. It was demonstrated that the reaction between carbon dioxide and lithium nitride is thermodynamically favorable and exothermic, which can generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

CHARACTERIZATION OF ASPHALT MATERIALS CONTAINING BIO OIL FROM MICHIGAN WOOD

The objective of this research is to develop sustainable wood-blend bioasphalt and characterize the atomic, molecular and bulk-scale behavior necessary to produce advanced asphalt paving mixtures. Bioasphalt was manufactured from Aspen, Basswood, Red Maple, Balsam, Maple, Pine, Beech and Magnolia wood via a 25 KWt fast-pyrolysis plant at 500 °C and refined into two distinct end forms - non-treated (5.54% moisture) and treated bioasphalt (1% moisture). Michigan petroleum-based asphalt, Performance Grade (PG) 58-28 was modified with 2, 5 and 10% of the bioasphalt by weight of base asphalt and characterized with the gas chromatography-mass spectroscopy (GC-MS), Fourier Transform Infra-red (FTIR) spectroscopy and the automated flocculation titrimetry techniques. The GC-MS method was used to characterize the Carbon-Hydrogen-Nitrogen (CHN) elemental ratio whiles the FTIR and the AFT were used to characterize the oxidative aging performance and the solubility parameters, respectively. For rheological characterization, the rotational viscosity, dynamic shear modulus and flexural bending methods are used in evaluating the low, intermediate and high temperature performance of the bio-modified asphalt materials. 54 5E3 (maximum of 3 million expected equivalent standard axle traffic loads) asphalt paving mixes were then prepared and characterized to investigate their laboratory permanent deformation, dynamic mix stiffness, moisture susceptibility, workability and constructability performance. From the research investigations, it was concluded that: 1) levo, 2, 6 dimethoxyphenol, 2 methoxy 4 vinylphenol, 2 methyl 1-2 cyclopentandione and 4-allyl-2, 6 dimetoxyphenol are the dominant chemical functional groups; 2) bioasphalt increases the viscosity and dynamic shear modulus of traditional asphalt binders; 3) Bio-modified petroleum asphalt can provide low-temperature cracking resistance benefits at -18 °C but is susceptible to cracking at -24 °C; 3) Carbonyl and sulphoxide oxidation in petroleum-based asphalt increases with increasing bioasphalt modifiers; 4) bioasphalt causes the asphaltene fractions in petroleum-based asphalt to precipitate out of the solvent maltene fractions; 5) there is no definite improvement or decline in the dynamic mix behavior of bio-modified mixes at low temperatures; 6) bio-modified asphalt mixes exhibit better rutting performance than traditional asphalt mixes; 7) bio-modified asphalt mixes have lower susceptibility to moisture damage; 8) more field compaction energy is needed to compact bio-modified mixes.

Molecular Modeling of PMR-15 Polyimide

PMR-15 polyimide is a polymer that is used as a matrix in composites. These composites with PMR-15 matrices are called advanced polymer matrix composite that is abundantly used in the aerospace and electronics industries because of its high temperature resistivity. Apart from having high temperature sustainability, PMR-15 composites also display good thermal-oxidative stability, mechanical properties, processability and low costs, which makes it a suitable material for manufacturing aircraft structures. PMR-15 uses the reverse Diels-Alder (RDA) method for crosslinking which provides it with the groundwork for its distinctive thermal stability and a range of 280-300 degree Centigrade use temperature. Regardless of such desirable properties, this material has a number of limitations that compromises its application on a large scale basis. PMR-15 composites has been known to be very vulnerable to micro-cracking at inter and intra-laminar cracking. But the major factor that hinders its demand is PMR-15's carcinogenic constituent, methylene dianilineme (MDA), also a liver toxin. The necessity of providing a safe working environment during its production adds up to the cost of this material. In this study, Molecular Dynamics and Energy Minimization techniques are utilized to simulate a structure of PMR-15 at a given density of 1.324 g/cc and an attempt to recreate the polyimide to reduce the number of experimental testing and hence subdue the health hazards as well as the cost involved in its production. Even though this study does not involve in validating any mechanical properties of the model, it could be used in future for the validation of its properties and further testing for different properties like aging, microcracking, creep etc.

THE USE OF LIFE-CYCLE ANALYSIS TO REDUCE THE ENVIRONMENTAL IMPACT OF MATERIALS IN MANUFACTURING

This thesis is composed of three life-cycle analysis (LCA) studies of manufacturing to determine cumulative energy demand (CED) and greenhouse gas emissions (GHG). The methods proposed could reduce the environmental impact by reducing the CED in three manufacturing processes. First, industrial symbiosis is proposed and a LCA is performed on both conventional 1 GW-scaled hydrogenated amorphous silicon (a-Si:H)-based single junction and a-Si:H/microcrystalline-Si:H tandem cell solar PV manufacturing plants and such plants coupled to silane recycling plants. Using a recycling process that results in a silane loss of only 17 versus 85 percent, this results in a CED savings of 81,700 GJ and 290,000 GJ per year for single and tandem junction plants, respectively. This recycling process reduces the cost of raw silane by 68 percent, or approximately $22.6 and $79 million per year for a single and tandem 1 GW PV production facility, respectively. The results show environmental benefits of silane recycling centered around a-Si:H-based PV manufacturing plants. Second, an open-source self-replicating rapid prototype or 3-D printer, the RepRap, has the potential to reduce the environmental impact of manufacturing of polymer-based products, using distributed manufacturing paradigm, which is further minimized by the use of PV and improvements in PV manufacturing. Using 3-D printers for manufacturing provides the ability to ultra-customize products and to change fill composition, which increases material efficiency. An LCA was performed on three polymer-based products to determine the CED and GHG from conventional large-scale production and are compared to experimental measurements on a RepRap producing identical products with ABS and PLA. The results of this LCA study indicate that the CED of manufacturing polymer products can possibly be reduced using distributed manufacturing with existing 3-D printers under 89% fill and reduced even further with a solar photovoltaic system. The results indicate that the ability of RepRaps to vary fill has the potential to diminish environmental impact on many products. Third, one additional way to improve the environmental performance of this distributed manufacturing system is to create the polymer filament feedstock for 3-D printers using post-consumer plastic bottles. An LCA was performed on the recycling of high density polyethylene (HDPE) using the RecycleBot. The results of the LCA showed that distributed recycling has a lower CED than the best-case scenario used for centralized recycling. If this process is applied to the HDPE currently recycled in the U.S., more than 100 million MJ of energy could be conserved per annum along with significant reductions in GHG. This presents a novel path to a future of distributed manufacturing suited for both the developed and developing world with reduced environmental impact. From improving manufacturing in the photovoltaic industry with the use of recycling to recycling and manufacturing plastic products within our own homes, each step reduces the impact on the environment. The three coupled projects presented here show a clear potential to reduce the environmental impact of manufacturing and other processes by implementing complimenting systems, which have environmental benefits of their own in order to achieve a compounding effect of reduced CED and GHG.

DENSITY OF AMORPHOUS CARBON BY USING DENSITY FUNCTIONAL THEORY

Amorphous carbon has been investigated for a long time. Since it has the random orientation of carbon atoms, its density depends on the position of each carbon atom. It is important to know the density of amorphous carbon to use it for modeling advance carbon materials in the future. Two methods were used to create the initial structures of amorphous carbon. One is the random placement method by randomly locating 100 carbon atoms in a cubic lattice. Another method is the liquid-quench method by using reactive force field (ReaxFF) to rapidly decrease the system of 100 carbon atoms from the melting temperature. Density functional theory (DFT) was used to refine the position of each carbon atom and the dimensions of the boundaries to minimize the ground energy of the structure. The average densities of amorphous carbon structures created by the random placement method and the liquid-quench method are 2.59 and 2.44 g/cm3, respectively. Both densities have a good agreement with previous works. In addition, the final structure of amorphous carbon generated by the liquid-quench method has lower energy.

THE PERFORMANCE AND MODIFICATION OF RECYCLED ELECTRONIC WASTE PLASTICS FOR THE IMPROVEMENT OF ASPHALT PAVEMENT MATERIALS

Bulk electric waste plastics were recycled and reduced in size into plastic chips before pulverization or cryogenic grinding into powders. Two major types of electronic waste plastics were used in this investigation: acrylonitrile butadiene styrene (ABS) and high impact polystyrene (HIPS). This research investigation utilized two approaches for incorporating electronic waste plastics into asphalt pavement materials. The first approach was blending and integrating recycled and processed electronic waste powders directly into asphalt mixtures and binders; and the second approach was to chemically treat recycled and processed electronic waste powders with hydro-peroxide before blending into asphalt mixtures and binders. The chemical treatment of electronic waste (e-waste) powders was intended to strengthen molecular bonding between e-waste plastics and asphalt binders for improved low and high temperature performance. Superpave asphalt binder and mixture testing techniques were conducted to determine the rheological and mechanical performance of the e-waste modified asphalt binders and mixtures. This investigation included a limited emissions-performance assessment to compare electronic waste modified asphalt pavement mixture emissions using SimaPro and performance using MEPDG software. Carbon dioxide emissions for e-waste modified pavement mixtures were compared with conventional asphalt pavement mixtures using SimaPro. MEPDG analysis was used to determine rutting potential between the various e-waste modified pavement mixtures and the control asphalt mixture. The results from this investigation showed the following: treating the electronic waste plastics delayed the onset of tertiary flow for electronic waste mixtures, electronic waste mixtures showed some improvement in dynamic modulus results at low temperatures versus the control mixture, and tensile strength ratio values for treated e-waste asphalt mixtures were improved versus the control mixture.