abstract: The exceptional mechanical properties of polymers with heterogeneous structure, such as the high toughness of polyethylene and the excellent blast-protection capability of polyurea, are strongly related to their morphology and nanoscale structure. Different polymer microstructures, such as semicrystalline morphology and segregated nanophases, lead to coordinated molecular motions during deformation in order to preserve compatibility between the different material phases. To study molecular relaxation in polyethylene, a coarse-grained model of polyethylene was calibrated to match the local structural variable distributions sampled from supercooled atomistic melts. The coarse-grained model accurately reproduces structural properties, e.g., the local structure of both the amorphous and crystalline phases, and thermal properties, e.g., glass transition and melt temperatures, and dynamic properties: including the vastly different relaxation time scales of the amorphous and crystalline phases. A hybrid Monte Carlo routine was developed to generate realistic semicrystalline configurations of polyethylene. The generated systems accurately predict the activation energy of the alpha relaxation process within the crystalline phase. Furthermore, the models show that connectivity to long chain segments in the amorphous phase increases the energy barrier for chain slip within crystalline phase. This prediction can guide the development of tougher semicrystalline polymers by providing a fundamental understanding of how nanoscale morphology contributes to chain mobility. In a different study, the macroscopic shock response of polyurea, a phase segregated copolymer, was analyzed using density functional theory (DFT) molecular dynamics (MD) simulations and classical MD simulations. The two models predict the shock response consistently up to shock pressures of 15 GPa, beyond which the DFT-based simulations predict a softer response. From the DFT simulations, an analysis of bond scission was performed as a first step in developing a more fundamental understanding of how shock induced material transformations effect the shock response and pressure dependent strength of polyurea subjected to extreme shocks. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2017

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The facile synthesis of engineering thermoplastics enabled the development of structure-morphology-property relationships for a wide range of applications. Utilizing step-growth polymerization techniques, a myriad of reaction conditions probed various polymer families including polysulfones, polyesters, polyimides and polyureas. Copolymers ranging from random to segmented sequences provided insight into the influence of segment length on physical properties. Melting temperatures, glass transition temperatures, and mechanical properties responded systematically to segment length and morphology. Leveraging several complementary analytical techniques identified critical segment lengths required for phase separation and crystallization within these copolymers. Introduction of hydrogen bonding further complicated the interrelationships between thermal and mechanical properties, and possible co-crystallization between dissimilar segments occurred. Finally, branching out from linear copolymers to other topologies determined the influence of branch length on rheological and mechanical properties. The commercially-viable synthesis of these various thermoplastics further highlights the immediate impact on state-of-the-art materials, and the fundamental development described herein provides a road map for future development in this field. / Ph. D.

Facile monomer synthesis provided routes towards novel step-growth polymers for emerging applications. Adjustment of reaction conditions enabled green synthetic strategies, and promising scalability studies offered impetus for industrial funding. Engineering thermoplastics, such as linear polyetherimides (PEIs), had carefully targeted molecular weights for analysis of the effect of molecular weight and regiochemistry on the thermomechanical and rheological properties of PEIs. The design of linear, high performance PEIs comprising 3,3'- and 4,4'-bisphenol-A dianhydride (bis-DA) and m-phenylene diamine (mPD) provided an opportunity to elucidate the influence of dianhydride regiochemistry on thermomechanical and rheological properties. This unique pair of regioisomers allowed the tuning of the thermal and rheological properties for high glass transition temperature polyimides for engineering applications. The selection of the dianhydride regioisomer influenced the weight loss profile, entanglement molecular weight, glass transition temperature (Tg), tensile strain-at-break, zero-shear melt viscosity, average hole-size free volume, and the plateau modulus prior to viscous flow during dynamic mechanical analysis (DMA). The 3,3'-PEI composition interestingly exhibited a ~20 °C higher Tg than the corresponding 4,4'-PEI analog. Moreover, melt rheological analysis revealed a two-fold increase in Me for 3,3'-PEI, which pointed to the origin of the differences in mechanical and rheological properties as a function of PEI backbone geometry. The frequently studied 4,4'-PEI exhibited exceptional thermal, mechanical, and rheological properties, yet the 3,3'-PEI regioisomer lacked significant study in the industrial and academic sectors due to its 'inferior' properties, namely poor mechanical properties. Introduction of long-chain branching (LCB) into PEIs provided a unique comparison between a commercially relevant PEI (Ultem® 1000) and a regioisomer infrequently found in the literature. Thermal stability remained consistent for each regioisomer, and Tgs for the 3,3'- and 4,4'-LCB-PEIs agreed well with prior literature. Rheological analysis demonstrated typical shear thinning and low-shear viscosity trends for LCB systems. The targeted molecular weights for the 3,3'-LCB-PEIs were well below the Me cutoff for "high molecular weight," and for this reason the rheological properties demonstrated inconsistent trends. Further study of PEIs led to the incorporation of ionic endgroups. These provided physical crosslinks, which enhanced mechanical and rheological properties of branched PEIs compared to their non-ionic analogs. The Tgs decreased with an increase in branching concentration for the phenyl-terminated PEI, while it remained unchanged for the ionically-endcapped PEIs. The divalent salts demonstrated higher mechanical strength and melt viscosities compared to the monovalent salt and the non-ionic PEIs. Interestingly, the zinc-endcapped PEI series exhibited decreased high-shear viscosities compared to the other PEIs, lending to promising industrial applications for the zinc-endcapped branched and linear PEIs for high temperature applications. Additional engineering thermoplastics in the form of bio-based polyureas exhibited mechanical properties similar to those of non-bio-based polyureas. The isocyanate-free synthetic route incorporated an essential urea degradation mechanism at elevated temperatures to produce isocyanic acid, which then reacted with amines to produce linear polyurea thermoplastics. Urea provided a sustainable and bio-friendly reagent for high molecular weight, isocyanate-free polyureas. Poly(propylene glycol) triamine enabled the long-chain branching of thermoplastic polyureas. Differential scanning calorimetry (DSC) showed no change in Tg for the series; however, melting peaks decreased in intensity as the branching concentration increased, indicating a reduction in crystallinity. Tensile testing eluded to a decrease in ultimate stress values for higher branching concentrations, while melt rheology showed significant differences in melt viscosities. Viscosities increased markedly with an increase in branching concentration, signifying greater entanglement and stronger physical crosslinks for the branched polyureas. Further analysis of possible isocyanate-free routes led to the use of 1,1'-carbonyldiimidazole (CDI) to generate polyureas and polyurethanes. CDI, known in the literature for its use in amidation and functionalization reactions, enabled the production of well-defined and stable polyurethane monomers. The functionalization of butanediol with CDI yielded an electrophilic biscarbamate monomer, bis-carbonylimidazolide (BCI), suitable for further step-growth polymerization in the presence of amines. The reaction of this novel monomer with aliphatic diamines produced thermoplastic polyurethanes with high thermal stability, tunable glass transition temperatures based on incorporation of flexible polyether segments, and creasable thin films. It is envisioned that CDI functionalized diols will afford access to various polymeric backbones without the use of toxic isocyanate-containing strategies. Additionally, non-isocyanate polyurethane (NIPU) foams were produced from BCI monomers without the need of blowing agents, catalysts, or solvents. These materials offered an alternative to existing foaming technology, which typically employed isocyanates. Polyurethanes were foamed through a CO2 thermal decomposition mechanism involving the BCI monomers. We investigated two series of polyurethane foams with a tunable Tg range from ~0 °C to ~110 °C. We found that the incorporation of aromatic amines vastly altered the foam thermomechanical properties, and the resulting foams were closed-cell in nature. / Doctor of Philosophy / Step-growth polymers play a significant role in commercial and industrial applications. On-going work in this field focuses on sustainability, biodegradability, and improved processability. This dissertation encompasses the improvement and innovation of current and novel engineering thermoplastics and foams. The careful purification and step-growth synthetic strategies herein, afforded targeted molecular weights for analysis of linear and long-chain branched (LCB) polyetherimides (PEIs). Further analysis of LCB-PEIs, with monovalent and divalent ionic endgroups, provided an opportunity to study the effect of ionic interactions and physical crosslinks at high temperatures (>300 °C). The long branches improved the melt processability compared to linear analogues at equivalent molecular weights. The challenge to investigate polyurethanes using non-isocyanate methodologies offered an opportunity to apply fundamental small-molecule, organic synthesis to macromolecular science. 1,1'-Carbonyldiimidazole (CDI) provided a platform to generate polymeric chains from industrially relevant monomers. Additional testing serendipitously discovered the generation of CO2 upon thermal degradation of the novel monomers. Harnessing the release of CO2, during the gelation of polyurethanes, provided an isocyanate-, catalyst-, and solvent-free synthetic route towards polyurethane foams that boasts scalability and industrial relevance.

The foundational studies of this dissertation concern the characterization of segmented polyurethanes and polyureas synthesized without the use of chain extenders'molecules that are typically used to promote a microphase separated morphology that gives these materials their useful characteristics. Polyurethanes in which a single asymmetric diisocyanate comprising the whole of the hard segment were found to display poor microphase separation. Conversely, polyurethanes in which a single symmetric diisocyanate composed the hard segment were found to display good microphase separation. The more efficient packing of the symmetric hard segments also led to an increase in hard segment connectivity and hence higher values of storage moduli in these systems. When hydroxyl-terminated diisocyanates were replaced with amine-terminated diisocyanates, polyureas were formed. Here too, diisocyanate symmetry was found to play a key role with symmetric diisocyanates leading to better microphase separation. In addition, the polyurea materials displayed broader service temperature windows than their polyurethane counterparts as the relatively stronger bidentate hydrogen bonding replaced monodentate hydrogen bonding in these materials. A thread-like, microphase separated morphology was visually confirmed using atomic force microscopy. Other techniques such as ambient temperature tensile testing, and wide and small angle x-ray scattering were employed to confirm the presence of the microphase separated structure. The investigation into the effects of diisocyanate chemistry and its symmetry was broadened to incorporate non-chain extended polyurethane materials with different soft segment molecular weights, as well as polyurethanes that did contain chain extenders. Once again the effect of using symmetric versus asymmetric diisocyanates was evident in the structure–property behavior of these systems, with symmetric diisocyanates forming materials that displayed better microphase separation and more connectivity of their hard domains. Lastly, in a departure from the segmented copolymer area, a study was conducted into the influence of casting variables on the solid-state structure of synthetic polypeptide films based on glutamate chemistry. The effect of solvent evaporation was determined to play a key role in the morphology of these polypeptide films. Measured small angle light scattering patterns were compared to computer calculated patterns to reveal information about the structure, shape, and length scale of the polypeptide structure. / Ph. D.

Lubrificantes são produtos gasosos, líquidos, semi sólidos ou sólidos (pó) que formam um filme entre duas partes evitando o atrito. Lubrificantes de alto desempenho são designados para trabalharem em condições severas de temperatura, pressão e contaminação. Os mais utilizados são os líquidos (óleos) e semi sólidos (graxas). As graxas são aplicadas aonde o óleo pode escorrer e em pontos de difícil acesso e são divididas basicamente em duas classes, sabão e não sabão. A graxa não sabão mais utilizada é a poliuréia, obtida pela reação entre aminas e isocianato, possui elevada tixotropia, alta rigidez dielétrica e excelente poder anticorrosivo, por isso é amplamente utilizada para lubrificação de motores elétricos e maquinário naval. Para obter uma graxa com altíssimo desempenho, nesse estudo foi utilizado o fluido lubrificante sintético polialfaolefina e também foi empregado o aditivo lubrificante sólido politetrafluoroetileno (PTFE) por apresentar o menor coeficiente de atrito conhecido, é comercialmente encontrado irradiado em ar para obter partículas menores e produzir grupos terminais oxigenados que são mais compatíveis com a superfície metálica. Os ensaios foram realizados de forma comparativa usando a graxa de poliuréia pura e aditivada com PTFE. As caracterizações foram feitas por espectroscopia de infravermelho, análise elementar de C, N, e H e índice de NCO livre, comprovando a formação de poliuréia de quatro carbonos (tetrauréia). As propriedades funcionais de ponto de gota e separação de óleo mostraram alta compatibilidade e estabilidade entre os polímeros, que aumentaram quando foi adicionado PTFE. A excelente resistência da graxa de tetrauréia pura ao desgaste e extrema pressão foram demonstradas pelo teste de quatro esferas e teste prático em rolamentos, caracterizando esta graxa como de alto desempenho quando comparada com as graxas mais utilizadas no mercado. / Lubricants are gaseous, liquid, semi solid or solid (powder) materials those form a film between two parties preventing friction. High performance lubricants are designed to work under severe conditions of temperature, pressure, and contamination. The most used are liquids (oils) and semi solids (greases). Greases are applied where oils can drain or in inaccessible places and are divided generally into two classes, soap and no soap. The most used non soap grease is polyurea, obtained by the reaction between amine and isocyanate, has highly thixotropic, high dielectric strength and excellent anticorrosive property, so it is widely used for lubrication of electric motors and shipbuilding machinery. For a grease with high performance, in this study was used a synthetic lubricant fluid, polyalphaolefin, and was also employed solid lubricant additive polytetrafluoroethylene (PTFE) due its lowest coefficient of friction, is found commercially irradiated in air to obtain smaller particles and to produce oxygenated terminal groups those are more compatible with the metal surface. The tests conducted were comparatively between pure polyurea grease and with PTFE additive. The characterizations were made by infrared spectroscopy and elemental analysis of C, N and H and Free NCO index, proving the formation of four carbons polyurea (tetraurea). The functional analysis of drop point and oil separation showed high stability and compatibility between the polymers increased when PTFE was added. The excellent resistance of pure tetraurea grease to wear and extreme pressure were demonstrated by four-ball and practical bearings tests, characterizing this grease as a high performance lubricant, when compared to most used greases in the market.

Lubrificantes são produtos gasosos, líquidos, semi sólidos ou sólidos (pó) que formam um filme entre duas partes evitando o atrito. Lubrificantes de alto desempenho são designados para trabalharem em condições severas de temperatura, pressão e contaminação. Os mais utilizados são os líquidos (óleos) e semi sólidos (graxas). As graxas são aplicadas aonde o óleo pode escorrer e em pontos de difícil acesso e são divididas basicamente em duas classes, sabão e não sabão. A graxa não sabão mais utilizada é a poliuréia, obtida pela reação entre aminas e isocianato, possui elevada tixotropia, alta rigidez dielétrica e excelente poder anticorrosivo, por isso é amplamente utilizada para lubrificação de motores elétricos e maquinário naval. Para obter uma graxa com altíssimo desempenho, nesse estudo foi utilizado o fluido lubrificante sintético polialfaolefina e também foi empregado o aditivo lubrificante sólido politetrafluoroetileno (PTFE) por apresentar o menor coeficiente de atrito conhecido, é comercialmente encontrado irradiado em ar para obter partículas menores e produzir grupos terminais oxigenados que são mais compatíveis com a superfície metálica. Os ensaios foram realizados de forma comparativa usando a graxa de poliuréia pura e aditivada com PTFE. As caracterizações foram feitas por espectroscopia de infravermelho, análise elementar de C, N, e H e índice de NCO livre, comprovando a formação de poliuréia de quatro carbonos (tetrauréia). As propriedades funcionais de ponto de gota e separação de óleo mostraram alta compatibilidade e estabilidade entre os polímeros, que aumentaram quando foi adicionado PTFE. A excelente resistência da graxa de tetrauréia pura ao desgaste e extrema pressão foram demonstradas pelo teste de quatro esferas e teste prático em rolamentos, caracterizando esta graxa como de alto desempenho quando comparada com as graxas mais utilizadas no mercado. / Lubricants are gaseous, liquid, semi solid or solid (powder) materials those form a film between two parties preventing friction. High performance lubricants are designed to work under severe conditions of temperature, pressure, and contamination. The most used are liquids (oils) and semi solids (greases). Greases are applied where oils can drain or in inaccessible places and are divided generally into two classes, soap and no soap. The most used non soap grease is polyurea, obtained by the reaction between amine and isocyanate, has highly thixotropic, high dielectric strength and excellent anticorrosive property, so it is widely used for lubrication of electric motors and shipbuilding machinery. For a grease with high performance, in this study was used a synthetic lubricant fluid, polyalphaolefin, and was also employed solid lubricant additive polytetrafluoroethylene (PTFE) due its lowest coefficient of friction, is found commercially irradiated in air to obtain smaller particles and to produce oxygenated terminal groups those are more compatible with the metal surface. The tests conducted were comparatively between pure polyurea grease and with PTFE additive. The characterizations were made by infrared spectroscopy and elemental analysis of C, N and H and Free NCO index, proving the formation of four carbons polyurea (tetraurea). The functional analysis of drop point and oil separation showed high stability and compatibility between the polymers increased when PTFE was added. The excellent resistance of pure tetraurea grease to wear and extreme pressure were demonstrated by four-ball and practical bearings tests, characterizing this grease as a high performance lubricant, when compared to most used greases in the market.

abstract: Polyurea is a highly versatile material used in coatings and armor systems to protect against extreme conditions such as ballistic impact, cavitation erosion, and blast loading. However, the relationships between microstructurally-dependent deformation mechanisms and the mechanical properties of polyurea are not yet fully understood, especially under extreme conditions. In this work, multi-scale coarse-grained models are developed to probe molecular dynamics across the wide range of time and length scales that these fundamental deformation mechanisms operate. In the first of these models, a high-resolution coarse-grained model of polyurea is developed, where similar to united-atom models, hydrogen atoms are modeled implicitly. This model was trained using a modified iterative Boltzmann inversion method that dramatically reduces the number of iterations required. Coarse-grained simulations using this model demonstrate that multiblock systems evolve to form a more interconnected hard phase, compared to the more interrupted hard phase composed of distinct ribbon-shaped domains found in diblock systems. Next, a reactive coarse-grained model is developed to simulate the influence of the difference in time scales for step-growth polymerization and phase segregation in polyurea. Analysis of the simulated cured polyurea systems reveals that more rapid reaction rates produce a smaller diameter ligaments in the gyroidal hard phase as well as increased covalent bonding connecting the hard domain ligaments as evidenced by a larger fraction of bridging segments and larger mean radius of gyration of the copolymer chains. The effect that these processing-induced structural variations have on the mechanical properties of the polymer was tested by simulating uniaxial compression, which revealed that the higher degree of hard domain connectivity leads to a 20% increase in the flow stress. A hierarchical multiresolution framework is proposed to fully link coarse-grained molecular simulations across a broader range of time scales, in which a family of coarse-grained models are developed. The models are connected using an incremental reverse–mapping scheme allowing for long time scale dynamics simulated at a highly coarsened resolution to be passed all the way to an atomistic representation. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2020