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Laser sintering (LS) is an additive manufacturing process which uses laser surface heating to induce consolidation of powdered materials. This work investigates some of the process-structure-property relationships for LS of viscoelastic polymers. A one-dimensional closed-form analytical solution for heating of a semi-infinite body, with a convective boundary condition, by a moving surface heat flux was developed. This solution approximates the shape of the Gaussian energy distribution of the laser beam more accurately than previous solutions in the literature. A sintering model that combines the effects of viscoelastic deformation driven by attractive surface forces and viscous flow driven by curvature-based forces was developed. The powder-bed temperature was approximated using the thermal model developed herein. The effect of the enthalpy of melting for semi-crystalline polymers was accounted for using a temperature recovery approach. Time-temperature superposition was used to account for the temperature dependence of the tensile creep compliance. The results of the combined-mechanism sintering model will be compared to the classic Mackenzie-Shuttleworth sintering model. A lab-scale LS unit was constructed to fabricate test specimens for model validation and to test the applicability of materials to LS. In this work, sintering four materials, polycarbonate (PC) and three molecular weights of polyethylene-oxide (PEO) was predicted using the aforementioned thermal and sintering models. Samples were fabricated using the lab-scale LS unit and the sintered microstructures were investigated using scanning electron microscopy. The rheologic, thermal and physical properties of the materials were characterized using standard methods and the relevant properties were used in the models. The choice of an amorphous polymer, PC, and a semi-crystalline polymer, PEO, affords comparison of the effects of the two material forms on contact growth during LS. The three molecular weights of PEO exhibit significantly different tensile creep compliances, however, the thermal and physical properties are essentially the same, and therefore the effect of molecular weight and subsequently the rheologic characteristics on contact growth during LS will be investigated. The effects of particle size, laser power, and bed temperature were also investigated. Ph. D.

Aromatic polyimides have found widespread applicability which can be partially attributed to their thermal stability, chemical resistance, and high glass transition temperature. However, deficiencies in their processability, solubility, transparency, and relatively high dielectric constants do not always provide the optimum properties for many specialty microelectronics applications. The incorporation of aliphatic segments to form partially aliphatic polyimides, has been used to counteract these shortcomings. Many of the potential uses of partially aliphatic polyimides require them to adhere to ceramic substrates, a main topic of this research. Polyimides and copolyimides that varied in chemical composition by their aliphatic content were characterized by their molecular weight, glass transition temperature, thermal stability, coefficient of thermal expansion, refractive index, dielectric behavior, and mechanical properties. Structure-property relationships were established. The gamma and beta sub-Tg viscoelastic relaxations were investigated to understand their molecular origins. The adhesion performance of a selected series of partially aliphatic polyimides to SiO2/Si was examined using a shaft loaded blister test, which was designed and instrumented for use in a dynamic mechanical analysis instrument. The adhesion was studied at high and low percent relative humidities and for several temperatures to examine if adhesion strength is influenced by polymer chemical composition. The adhesion energy could not be quantified for the entire series of polyimides. It was possible to interpret the quantitative adhesive fracture energies along with the qualitative adhesion strength behaviors, the failure surface analyses, and to offer an understanding of the adhesive chemical structure-physical property relationships. These understandings provide a conclusion that the incorporation of aliphatic segments into the polyimide chemical structure improves the durability of the adhesive bond to SiO2/Si under high percent relative humidities. Ph. D.

The purpose of this work was to investigate the effects of structure, humidity and aging on the mechanical behavior of Nafion® and Dais® ionomers. It was determined that the majority of the properties of these membranes were controlled by the formation and growth of the ionic clusters that were the direct result of the ionic nature of these materials. In the process of this study, the properties of Nafion® and sulfonated Dais® polymers were investigated by dynamic mechanical analysis and thermal gravimetric analysis and their water uptake and sorption and desorption isotherms were measured. A mastercurve and a shift factor plot were constructed for 60% sulfonated Dais® membrane. It was determined that an increase in the degree of sulfonation raised the glass transition temperature of these materials by facilitating the formation of the ionic clusters which acted as physical crosslinks, thereby reducing the mobility of polymeric chains. Water was found to effectively plasticize the membranes, especially in the case of Dais® materials, by reducing the storage modulus and decreasing the structural integrity of the ionomers. The effect of pre-treatment of Nafion® was investigated and the glass transition temperature was found to increase as a function of the severity of the treatment procedure. The maximum water uptakes were determined for virgin and aged Nafion® and Dais® membranes and their vapor phase water sorption diffusion coefficients were calculated. The sorption process was found to follow pseudo-Fickian behavior, while the movement of water out of the membranes during the desorption process was determined to be controlled by mechanisms other than diffusion. Lastly, the effect of exposure of Nafion® and 30% sulfonated Dais® membranes to the saturated environment at elevated temperatures was investigated and found to result in the increase in the glass transition temperature of the materials. Results of the exposure effects on the diffusion properties of Nafion® and Dais® were inconclusive. Preliminary findings attributed the changes in the properties of the materials to the counteractive actions of physical aging and the growth of the ionic clusters. Master of Science

This work investigates processing-microstructure-property relationships of a model cryogenically mechanically alloyed polymer-polymer system: polycarbonate (PC) and poly (ether ether ketone) (PEEK). Mechanically milled and alloyed powders were characterized using a variety of techniques including microscopy and thermal analysis. Cryogenically mechanically alloyed powders processed for 10 hours were shown to have a sub-micron level two-phase microstructure. These powders were processed into testable coupons using a mini ram-injection molder; microstructure and bulk mechanical properties of the coupons were investigated as a function of mechanical alloying and injection molding parameters. Atomic force microscopy, transmission electron microscopy, and scanning transmission X-ray microscopy revealed that the intimate blending achieved during the mechanical alloying process is not retained upon post-processing using a conventional polymer processing technique. Injection molded coupons were tested in 3-point bend mode via dynamic mechanical and quasi-static mechanical testing. Results demonstrated that no improvement in energy to break, strain at failure, or failure strength was achieved in coupons made from cryogenically mechanically alloyed powders compared to those of coupons made from non-mechanically alloyed samples. Ph. D.

In this work, the thermo-mechanical response and failure of loaded, fire-exposed composite structures was studied. Unique experimental equipment and procedures were developed and experiments were performed to assess the effects of mechanical loading and fire exposure on the service life of composite beams. A series of analytical models was assembled to describe the fire growth and structural response processes for the system used in the experiments. This series of models consists of a fire model (to predict the heat flux to the fire-exposed beam), a thermal response model (to calculate the temperature distribution within the beam due to this heat flux), a stiffness-temperature model (to calculate the loss in stiffness at elevated temperatures), a mechanical response model (to compute the strain distribution within the loaded beam), and a material failure model (to calculate the strain at which the beam is expected to fail). Each of these models is independently validated by comparing predictions with experimental results. The models are then used to predict the times-to-failure for beams over a range of fire and loading conditions. The predicted failure times agree fairly well with experimental results, but it is expected that the agreement could be improved with improvements to the first model in the series - the fire model. Master of Science

The largest cost in manufacturing PEM fuel cells for automotive applications is due to the bipolar plate. The current graphite material used for the bipolar plate is very brittle and difficult to machine to the rigorous specifications needed for fuel cell stacks. This paper introduces the development of a fuel cell test stand for simultaneous testing of six individual fuel cells. To establish a long-term performance evaluation, the fuel cells incorporate a baseline graphite material that undergoes testing in the fuel cell environment. The graphite is an industry standard material that should not corrode when subjected to continual testing. The baseline model will be used in development of novel composite materials that will be tested under the same conditions for comparison to the graphite. Furthermore, the new materials and applied manufacturing methods could reduce the overall cost of fuel cell stacks in the future. Funding for this project was generously donated by the Virginia Center for Innovative Technology and the National Science Foundation. Master of Science

An ionic polymer actuator consists of a thin Nafion-117 sheet plated with gold or platinum on both sides. An ionic polymer actuator undergoes large deformation in the presence of low applied voltage across its thickness and exhibits low impedance. They can also be used as large displacement sensors by bending them to induce stresses and generate a voltage response. They operate best in a humid environment. Ionic polymer actuators have been used for various practical applications such as bio-mimetic robotic propulsion, flexible low mass robotic arms, propellors for swimming robotic structures, linear and platform type robotic actuators and active catheter systems. One of the disadvantages of ionic polymer actuators is that their settling time to a unit step voltage is on the order of 5-20 seconds in a cantilever configuration. The slow time constant of an ionic polymer limits the actuation bandwidth. The characteristics of ionic polymer actuators, low force and large displacement (as compared to other actuator technologies such as PZT or PVDF), cannot be used in applications requiring a faster response time for a given actuation signal. Due to this limitation, many applications will not be able to make use of the large displacement effectively because of the limited bandwidth of the actuator. Another disadvantage of using an ionic polymer actuator is that the stiffness of the actuator is a function of the hydration of the polymer. Difficulties in controlling the hydration, which changes with respect to time, results in inconsistencies in the mechanical response exhibited by the polymers during continual usage. Several physical models of ionic polymer actuators have been proposed. The physical phenomenon responsible for the bending is not completely understood and no clear set of principles have been able to explain the motion of the polymers completely. Physical phenomena like ionic motion, back diffusion of water and electrostatic force have been used to explain these models. This research demonstrates the use of feedback control to overcome the limitation of slow settling time. First, an empirical model of the ionic polymers developed by Kanno was modified by studying the step response of these actuators. The empirical model is used to design a feedback compensator by state space modeling techniques. Since the ionic polymer actuator has a slow settling time in the open-loop, the design objectives are to minimize the settling time and constrain the control voltage to be less than a prescribed value. The controller is designed using Linear Quadratic Regulator (LQR) techniques which reduced the number of design parameters to one variable. Simulations are performed which show settling times of 0.03 seconds for closed-loop feedback control are possible as compared to the open-loop settling time of 16-18 seconds. The maximum control voltage varied from 1.2 Volts to 3.5 Volts depending on the LQR design parameter. The controller is implemented and results obtained are consistent with the simulations. Closed-loop settling time is observed to be 4-8 seconds and the ratio of the peak response to the steady-state response is reduced by an order of magnitude. Discrepancies between the experiment and the simulations are attributed to the inconsistencies in the resonant frequency of the actuator. Experiments demonstrate that changes in the surface hydration of the polymer result in 20\% variations in the actuator resonance. Variations in the actuator resonance require a more conservative compensator design, thus limiting the performance of the feedback control system. Master of Science

Nanometer thick layers of clay and polymer were formed on mica, silicon, and aluminum 2024-T3 alloy using alternating solutions of positively and negatively charged polymer and clay, respectively. Atomic force microscopy was used to observe the morphology of the composite films on mica and silicon. It was found that solution concentrations of clay above 0.02 weight percent lead to the uncontrolled deposition of clay platelets on the substrate's surface. By using solution concentrations of clay above 0.02 weight percent and ultrasonic agitation together it is possible to deposit a uniform monolayer of clay platelets on a mica substrate in £ 20 seconds. Ultrasonic agitation also produced crude patterns of montmorillonite platelets. Thin films of poly(diallydimethylammonium chloride) (PDDA) were made using concentrations ³ 2 weight percent of PDDA. It was found that the PDDA formed several unusual morphologies. Spherulites of PDDA were observed with AFM and the glass transition temperature of high molecular weight PDDA was measured using differential scanning calorimetry (DSC). Circular regions of positive charge were discovered on silicon wafers provided by three different sources. These areas of charge have never been reported in literature, but can easily be detected by placing wafers into solutions containing negatively or positively charged solutions of clay or polymer, respectively. The exact nature of these charged regions is unknown, but it is hypothesized that impurities on silicon wafers create the circular regions of positive charge. ISAM films made of a polyamide salt and a synthetic clay, Laponite RD®, demonstrated significant corrosion resistance on 2024-T3 Al alloys after 168 hours of salt spray testing. The ISAM films offered corrosion protection only if there was a significant layer of underlying surface oxide present, however. It was found that ISAM deposited films of polyarylic acid (PAA) and polyallylamine hydrochloride (PAH) may offer some corrosion resistance on 2024-T3 Al alloys, but these films' corrosion resistance is severely hampered by the presence of Cl- in the PAH solution. Funding from this project was gratefully received from the Materials Science and Engineering Department at Virginia Tech; Luna Innovations Inc; the American Chemical Society / Petroleum Research Fund #34412-G5 and the Environmental Protection Agency Contract #68-D-00-244. Master of Science

In this thesis, the morphology, crystallization and melting behavior of polypropylene copolymers (propylene/ethylene, propylene/1-butene, propylene/1-hexene and propylene/1-octene) has been examined. The multiple melting behavior has been correlated with the presence of alpha and gamma phases and with the occurrence of cross-hatching morphology. The Crystallization and melting behavior of propylene/ethylene and propylne/1-butene are qualitatively similar and compatible with the expectations that the ethylene and butene comonomers are partly included in the propylene lattice. Propylene/1-hexene and propylene/1-octene copolymers exhibit remarkably similar behavior and morphologies consistent with the expectations that the hexene and the octene comonomers are rigorously excluded from the crystal lattice. The origin and the crystallization time dependence of the multiple melting behavior is very different for these two pairs of copolymers. For PE and PB it is consistent with the melting of parent a-phase lamellae and alpha or gamma-phase daughter lamellae. For PH and PO copolymers it is very similar to that observed for ethylene-octene(EO) and ethylene-styrene(ES) copolymers and compatible with the melting of primary lamellae and secondary mosaic or fringed micellar structures. Master of Science

This work describes the development of an improved mode I fracture testing procedure for adhesively-bonded wood, and demonstrates the sensitivity of this approach. The two significant improvements were: 1) the use of the flat double cantilever beam (DCB) geometry, which has been uncommon for wood and 2) the application of an established and powerful data analysis using a corrected compliance method from beam theory. Three studies were conducted using various wood adhesives and DCB specimens were fabricated from yellow﷓poplar (Liriodendron tulipifera) sapwood. The sensitivity of this methodology showed significant differences in fracture performance as the degree of cure increased for a phenol formaldehyde adhesive, and yielded maximum strain energy release rate (SERR) values of 370 - 560 J/m2. A second study showed performance differences between two polymeric diphenylmethane diisocyanate (pMDI) adhesives and one polyurethane adhesive. Typical maximum SERR values were 160 and 130 J/m2 for the pMDI adhesives and 160 J/m2 for the polyurethane adhesive. A third study investigated the effect of loading rates on a cross-linked polyvinyl acetate adhesive and maximum SERR values of 370 - 560 J/m2 were achieved. Adhesive penetration and cure were determined by image analysis with fluorescence microscopy, and by micro-dielectric analysis, respectively. Since the geometry of the fracture procedure dictates the absence of wood failure, the resulting fractured surfaces were readily analyzable. The surface analysis techniques of laser ionization mass analysis, solid-state nuclear magnetic resonance and field emission scanning electron microscopy were used to investigate the locus of failure for the smooth fractured surfaces. Master of Science

The initial objective of this research project was to determine the feasibility of manufacturing carbon fiber-reinforced (CFR) composites with a matrix consisting of a phenylethynyl-terminated version of a thermoplastic poly(etherimide) termed PETU. Successful composite manufacture with 3,000 g/mol (3k) PETU led to a survey of CFR 3kPETU mechanical properties for comparison with other high-performance composites. Encouraging results led to a study of moisture sorption effects on CFR 3kPETU properties. The success of these initial studies spawned the large scale production of 2,500 g/mol (2.5k) PETU. Thermal characterization of neat and CFR 2.5kPETU via differential scanning calorimetry, dynamic mechanical thermal analysis, and parallel plate rheometry resulted in an understanding of the influence of cure time and temperature on reaction progress via both reaction kinetics and monitoring of the glass transition temperature. From the rheological characterization, a two-stage, dual-Arrhenius model was developed to successfully model isothermal complex viscosity over the range of processing temperatures. Neat 2.5kPETU and CFR 2.5kPETU specimens were exposed separately to elevated temperature environments of different moisture and different oxygen concentrations to evaluate the effects of moisture absorption, moisture desorption, and thermal oxidation on material properties. Moisture absorption took place in a 90 °C / 85% relative humidity environment followed by moisture desorption in a 90 °C / 10% relative humidity environment. Thermal-oxidative aging for up to 5000 hours took place at 204 204 °C in environments of four different oxygen partial pressures: 0.0 kPa, 2.84 kPa, 20.2 kPa, and 40.4 kPa. Following exposure to the different aging environments, the specimens were tested for retention of mechanical properties. In addition, moisture sorption properties were measured. Results from the moisture sorption studies on CFR 3kPETU and CFR 2.5kPETU suggest that fully cured composites will withstand moisture absorption and desorption with negligible effects on mechanical properties, whereas, lack of full cure allows moisture sorption to permanently damage the composites. Despite a lack of mass loss or visual evidence of degradation following thermal-oxidative aging, a decline in mechanical properties was observed with the reduction becoming greater with longer aging times and higher oxygen partial pressures. Ph. D.

The purpose of this study was to characterize the craze growth behavior of polycarbonate (PC) as a function of stress level, model the residual mechanical properties of PC at various craze levels and strain rates, and determine if the total surface area of crazing is the sole factor in residual properties or if the crazing stress plays a role. To obtain these goals, a new in-situ reflective imaging technique was developed to quantify the craze severity in transparent polymers. To accomplish the goal of craze growth rate characterization, polycarbonate samples were placed under a creep load in a constant temperature, constant humidity environment. Using the new technique, the relative craze density was measured as a function of time under load at stresses of 40, 45, and 50 MPa. The craze growth rates were found to increase exponentially with stress level, and the times to 1% relative craze density were found to decrease exponentially with stress level. One exception to this behavior was found at a crazing stress of 50 MPa at which over half of the samples tested experienced delayed necking, indicating competitive mechanisms of crazing and shear yielding. The draw stress was found to be a lower bound below which delayed necking will not occur in a reasonable time frame. The yield stress, elastic modulus, failure stress, and ductility were correlated to crazing stress, relative craze density, and strain rate using a Design of Experiments (DOE) approach. The yield stress was found to correlate only to the strain rate, appearing to be unaffected by the presence of crazes. No correlation was found between the elastic modulus and the experimental factors. The failure stress was found to decrease with an increase in relative craze density from 0 to 1%, increase with an increase in crazing stress from 40 to 45 MPa, and correlate to the interaction between the crazing stress and the strain rate. The ductility of polycarbonate was found to decrease significantly with an increase in relative craze density, a decrease in crazing stress, and an increase in strain rate. The craze microstructure was correlated to the magnitude of stress during craze formation. The area of a typical craze formed at 40 MPa was measured to be more than 2.5 times larger than the area of a typical craze formed at 45 MPa. The fewer, but larger, crazes formed at the lower stress level were found to decrease the failure strength and ductility of polycarbonate more severely than the large number of smaller crazes formed at the higher stress level. Ph. D.

The primary differences between the solventborne and waterborne epoxy printed circuit board (PCB) impregnating resins arise from the distinct physical compositions and drying characteristics of the polymer solution and the latex emulsion. The presence of residual surfactant from the waterborne epoxy emulsion poses a concern for dielectric performance and adhesive durability. Another problem involves the crystallization of insoluble solid dicyandiamide (DICY), which is significantly different in morphology than that found in solution cast resins. A two-stage drying model was employed to gain a better understanding the drying and coalescence processes. The process of surface DICY crystal formation during the drying of glass prepreg sheet was related to a threshold concentration of the curing agent in the impregnating latex resin formulation. Conditions favoring faster drying lead to the rapid formation of a coalesced skin layer of latex resin, thereby trapping the curing agent in the bulk and reducing the surface deposition of DICY by percolating water. Surfactant is believed to remain concentrated in a receding wet zone until it is driven to the surfaces of the glass fibers upon the completion of drying. The copper foil/laminate interface was evaluated by a 90° peel test as part of two different studies: an analysis of the viscoelastic response of the interface during peel and a study of the thermal durability of the copper/laminate interfacial peel strength. The surfactant acted as a plasticizer to toughen the fiber/matrix interphase, resulting in larger observed peel strengths in the latex resin impregnated materials relative to the solventborne system. Surfactant segregated to the fiber surface during coalescence to form a plasticized fiber/matrix interphase; surfactant migrated into the bulk during postcure to yield a more homogeneously plasticized epoxy matrix. Dielectric measurements of neat resin and laminate materials revealed that the dielectric constants of the model resin-impregnated laminates met the performance criteria for PCB substrates of their class, regardless of surfactant content. Overall, the adhesive performance, adhesive durability, and dielectric properties of PCB systems fabricated with model latex epoxy resin, containing native surfactant (5 wt %), met or exceeded the performance of an equivalent solventborne resin impregnated system. Ph. D.

When bonded joints are subjected to harsh environmental conditions, the interphase, the three-dimensional region surrounding the adhesive/substrate interface, becomes critically important. Frequently, failure occurs in this region after adhesively bonded systems are subjected to elevated temperature oxidative aging. In a previous study, this was found to be the case with a polyimide adhesive bonded to chromic acid anodized (CAA) Ti-6Al-4V. The objective of the current research has been twofold: 1) to investigate the effect of thermal aging on the interphase region of polyimide/titanium adhesive joints, and 2) to evaluate the method used in the current study for durability characterization of other adhesive/substrate systems. The method used in this research has been to characterize the effect of elevated temperature aging on the following systems: 1) Notched coating adhesion (NCA) specimens and 2) bulk samples of dispersed substrate particles in an adhesive matrix. The NCA test has the advantages of an accelerated aging geometry and a mode mix that leads to failure through the interphase, the region of interest. The bulk samples have the advantage of an increased interphase volume and allow for the application of bulk analysis techniques to the interphase, a region that is traditionally limited to surface analysis techniques. The adhesive systems studied consisted of one of two polyimide adhesives, LaRC© PETI-5 or Cytec Fiberite© FM-5, bonded to CAA Ti-6Al-4V. The model filled system consisted of a PETI-5 matrix with amorphous titanium dioxide filler. Through the use of the NCA test, it was determined that bonded specimens made with FM-5 lose approximately 50% of their original fracture energy when aged in air at 177°C for 30 days. This aging temperature is well below the glass transition temperature of the adhesive, 250°C. At the same time, the failure location moves from the anodized oxide layer to the adhesive that is directly adjacent to the substrate surface, the interphase region. Through surface analysis of this region, it is determined that the adhesive penetrates the pores of the CAA surface to a depth of 70 to 100 nm, promoting adhesion at the interface. With aging, the adhesive in the interphase region appears to be weakening, although analysis of the bulk adhesive after aging shows little change. This indicates that adhesive degradation is enhanced in the interphase compared to the bulk. Analysis of the model filled system gave similar information. Specimens containing titanium dioxide filler had glass transition temperatures that were approximately 20°C lower than the neat polyimide samples. In addition, the filled samples contained a significant portion of low molecular weight extractable material that was not present in the neat specimens. The tan delta spectra from dynamic mechanical thermal analysis of the filled specimens exhibited a shoulder on the high-temperature side of the glass transition peak. This shoulder is attributed to the glass transition of the interphase, a distinct phase of the polyimide which is constrained by adsorption onto the filler particle surfaces. As a function of aging time at 177° or 204°C, the shoulder decreases substantially in magnitude, which may relate to loss of adhesive strength between the polyimide and the filler particles. From this research, it has been illustrated that information relating to the durability of adhesively bonded systems is gained using an interfacially debonding adhesive test and a model system of substrate particles dispersed in an adhesive matrix Ph. D.

One of the most common environmental exposures that nylon undergoes, when used for automotive applications, is that of salt splash, which commonly occurs during winter driving. This study looks at the effect of various salts (NaCl, KCl, CaCl2) on the thermal and mechanical properties of nylon when exposed to one and four molar aqueous salt solutions. It was found that the diffusion of salt solutions into nylon 6,6 occurred in a pseudo-Fickian manner. Also, it was found that the presence of salt had an effect on the rate of decrease of yield stress with increasing exposure time. The presence of residual salt was found to accelerated deterioration of nylon 6,6, possibly via hydrolysis. In addition, it was found that residual salt was left after water was removed from the system and that this salt was removable. Master of Science

In this study, a micromechanics-based method is developed to predict the off-axis strength of unidirectional linear elastic laminae. These composites fail by matrix cracking along a plane parallel to the fiber direction. The stresses in the matrix are calculated using a local stress analysis based on a concentric cylinder model. This model consists of a unique fiber embedded in matrix; both constituents are represented by cylinders. A finite element model is also constructed and the results of the two models compared. The stresses and strains from the concentric cylinder model are averaged over the volume of the matrix and used in a local failure function. This failure function has the form of a reduced and normalized strain energy density function where only transverse and shear terms are considered. The off-axis strength prediction method is validated using data from the literature. This failure function will be used in the near future for composites with a matrix having nonlinear properties. Experimental tensile tests on steel-cord/rubber laminae and laminates as well as on the nonlinear rubber matrix were performed. Stress-strain behavior and off-axis strength data were obtained. An approach for off-axis strength prediction for these laminae is defined based on a finite element stress analysis. The finite element analysis approach is motivated by the one used for linear composites. Master of Science

The purpose of this study was learn how the diffusion, swelling, and crystallization processes are coupled during solvent-induced crystallization of poly(ether ether ketone) (PEEK). Unoriented amorphous PEEK films were immersed in aprotic organic liquids at ambient temperature and bulk properties or characteristics were monitored as a function of immersion time. The sorption behavior, Tg and Tm° suppression, crystallinity, and dynamic mechanical response were correlated as a function of solvent chemistry and immersion time. The saturation time of methylene chloride, 1,3-dichloropropane, tetrahydrofuran, cyclopentanone, chlorobenzene, toluene, diethyl ketone, and ethylbenzene in amorphous PEEK films were found to range from hours to days depending on the level of polymer-solvent interactions. In-situ isochronal DMA spectra show that the Tg of PEEK was suppressed from 150 ° C to below ambient temperature such that crystallization was kinetically feasible during ambient immersion. In addition, an increase in viscoelastic dispersion was attributed to the presence of crystallinity. From dynamic mass uptake and wide-angle x-ray diffraction (WAXD) results, it was found that the bulk sorption rate was equal to the bulk crystallization rate for all solvent systems that promoted SINC and PEEK exhibited diffusion-limited crystallization, irrespective of the nature of the transport mechanism. In addition, the solvent-induced crystals exhibit preferred orientation as supported by photographic WAXD. A distinct sorption front, observed with scanning electron microscopy, further supports the scenario of diffusion-controlled crystallization and one-dimensional diffusion. Isothermal DMA spectra for THF, cyclopentanone, and chlorobenzene, indicate that, as the solvent diffuses into the films, the stiffness of the polymer decreases at short times, begins to increase, and then reaches a relatively time-independent value. It was determined that the initial decrease in the storage modulus was due to the incredible plasticization of the amorphous phase. When the films contained greater than 60 % of the ultimate crystallinity, the storage modulus was observed to increase as a result of the reinforcing effect of the solvent-induced crystals. WAXD and mass uptake results confirm that the plateau in the storage modulus coincides with the completion of bulk crystallization and saturation of the amorphous phase. Ph. D.

There are instances where efficiency and safety may be compromised as a result of wear and tear of fluid transporting pipe systems. Consequently, it is sometimes necessary to shut down the entire operation to fix the problem. Thus, it is worth evaluating other methods that can repair the damage for a temporary period without shutting down the operation while a new pipe is being constructed. The objective was to evaluate the durability of the epoxy bonded steel in aqueous environments that might be the conditions of such a repair. EPON(registered mark)828 was chosen as the epoxy resin, and dicyandiamide and polyamidoamine were two types of curing agent evaluated in this study. The epoxy bonded steels were exposed in either distilled water or 3.4% NaCl solution for various time periods. The mechanical strengths of the bonded joints were evaluated using a three-point flexure test. The neat epoxy samples were also aged under the same conditions, and three-point flexure test and dynamic mechanical analysis (DMA) were performed to evaluate their mechanical properties. The moisture uptake of the neat epoxy increased with exposure time, and the bending modulus of the neat epoxy decreased with aging time and moisture uptake. It was found that the interfacial shear strength decreased with aging time for both epoxy bonded systems. Scanning Electron Microscopy (SEM), optical microscopy, and X-ray Photoelectron Spectroscopy (XPS) were used to determine the locus of failure of the bonded joints. It was concluded that failure occurred cohesively within the oxide layer if oxides were present on the substrate surface prior to the bonding procedure. Master of Science

In this work the relationships between penetrant structure, its transport properties, and its effects on the mechanical properties of a polymer matrix were investigated. Although there is a vast amount of data on the diffusion of low molecular weight molecules into polymeric materials and on the mechanical properties of various polymer-penetrant systems, no attempts have been made to inter-relate the two properties with respect to the chemical structure of the diffusant. Therefore, two series of penetrants - n-alkanes and esters - were examined in this context, with the goal of correlating molecular size, shape, and chemical nature of the penetrant to its final transport and matrix mechanical properties. These correlations have been demonstrated to allow quantitative prediction of one property, given a reasonable set of data on the other parameters. A series of n-alkanes (C6-C17) and esters (C5-C17) have been used to separate the effects of penetrant size and shape, from those due to polymer-penetrant interactions, in the diffusion through a polyamide polymeric adhesive. These effects have been taken into account in order to yield a qualitative relationship that allows for prediction of diffusivity based upon penetrant structural information. Transport properties have been analyzed using mass uptake experiments as well as an in-situ FTIR-ATR technique to provide detailed kinetic as well as thermodynamic information on this process. The phenomenon of diffusion and its effects on the resulting dynamic mechanical response of a matrix polymeric adhesive have been studied in great detail using the method of reduced variables. The concept of a diffusion-time shift factor (log aDt) has been introduced to create doubly-reduced master curves, taking into account the effects of temperature and the variations in the polymer mechanical response due to the existence of a low molecular weight penetrant. Ph. D.

The most promising strategy for reducing the cost of manufacturing polymer matrix composites while improving their reliability is the use of sensors during processing to permit control of the cure cycle based on measurements of the material's internal state. While sensors have been demonstrated that infer the material state indirectly through measurements of acoustic impedance, electrical impedance, or refractive index, sensors that directly measure parameters critical to composite manufacturing, such as resin rheology and resin hydrostatic pressure, would improve characterization of thermoset resins during cure. Here we describe the development of a multifunctional fiber optic sensor that may be embedded in a composite part during lay-up to monitor the state of the polymer matrix during processing. This sensor will output quantitative data which will indicate the viscoelasticity of the thermoset matrix resin. The same sensor will additionally function as a strain sensor following fabrication, capable of monitoring residual strains due to manufacturing or in-service internal strains. Ph. D.

Existing layered manufacturing systems fabricate parts using a constant build layer thickness. Hence, operators must compromise between rapid production with large surface inaccuracies, and slow production with high precision, by choosing between thick and thin build layers, respectively. Adaptive layered manufacturing methods alleviate this decision by automatically adjusting the build layer thickness to accommodate surface geometry, thereby potentially enabling part fabrication in significantly less time. Unfortunately, conventional adaptive layered manufacturing techniques are often unable to realize this potential when transitioning from the laboratory to an industrial setting. The problem is that they apply the variable build layer thickness uniformly across each horizontal build plane, applying the same build layer thickness to all parts and part features across that plane even though they have different build layer thickness needs. When this happens, the advantage of using adaptive build layer thicknesses is lost. This thesis demonstrates how to minimize fabrication times when implementing adaptive layered manufacturing. Specifically, it presents a new method in which each part or individual part feature is assigned a distinct, independent build layer thickness according to its particular surface geometry. Additionally, this thesis presents a calibration procedure for the Fused Deposition Modeler (FDM) rapid prototyping system that enables accurate, adaptively sliced parts to be physically realizable. Experimental software has been developed and sample parts have been fabricated to demonstrate both aspects of this work. Master of Science

Steam exploded fibers from Yellow Poplar (Liriodendron tulipifera) wood were assessed in terms of (a) their impact on torque during melt processing of a thermoplastic cellulose ester (plasticized CAB); (b) their fiber incorporation and dispersion characteristics in a CAB-based composite by SEM and image analysis, respectively; and (c) their impact on the mechanical properties (under tension) of CAB-based composites having fiber contents of between 10 and 40% by weight. The fibers included water-washed steam exploded fibers (WEF), alkali-extracted fibers (AEF), acetylated fibers (AAEF), all from Yellow poplar (log Ro = 4.23), and oat fillers (COF) as control. The stepwise increase in cellulose content by extraction, and especially the (surface) modification by acetylation, contributed to increased torque during melt processing, and to improved interfacial adhesion as well as fiber dispersion. As compared to pure CAB, AAEF generated the highest increase in torque (+ 421%) followed by AEF (+ 260%) and WEF (+ 190%) at 40% fiber content by weight. AAEF was also found to enhance the tensile properties of the resulting composites. SEM studies of the tensile fracture surfaces indicated significant interfacial delamination and also pull - out of fibers when WEF, AEF, and COF were used to reinforce the CAB matrix. Composites with AAEF, by contrast, revealed fracture surfaces with reduced interfacial delamination and with significant fiber fracturing during failure. Image analysis was used to determine fiber dispersion within the resulting composites quantitatively. Significant improvement in fiber dispersion was achieved when the matrix was reinforced with acetylated fibers (AAEF). Fiber addition to the matrix resulted in loss of strain at break (- 80 to - 93%) and slight or significant increases in modulus (+ 47 to + 103%) depending on fiber type at 40% fiber content. Maximum stress declined for all fibers except AAEF at all fiber contents. AAEF-based composites revealed a decline in maximum stress when fiber content rose to 10%, and this reversed when fiber content increased beyond 10%. This increase in strength is consistent with the rule of mixtures that stipulates reinforcement of the matrix by fibers that are capable of transferring stresses across the fiber-matrix interface. All fibers suffered length decreases during melt processing. Master of Science

The objective of this study was to evaluate and develop an understanding of durability of an adhesive bonded system, for application in a future high speed civil transport (HSCT) aircraft structure. The system under study was comprised of Ti-6Al-4V metal adherends and a thermosetting polyimide adhesive, designated as FM-5, supplied by Cytec Engineered Materials, Inc. An approach based on fracture mechanics was employed to assess Ti-6Al-4V/FM-5 bond durability. Initially, wedge tests were utilized to find a durable surface pretreatment for the titanium adherends. Based on an extensive screening study, chromic acid anodization (CAA) was chosen as the standard pretreament for this research project. Double cantilever beam specimens (DCB) were then made and aged at 150° C, 177° C, and 204° C in three different environments; ambient atmospheric air (14.7 psia), and reduced air pressures of 2 psi air (13.8 KPa) and 0.2 psi air (1.38 KPa). Joints were aged for up to 18 months (including several intermediate aging times) in the above environments. The strain energy release rate (G) of the adhesive joints was monitored as a function of exposure time in the different environments. A 40% drop in fracture toughness was noted over the 18 month period, with the greatest degradation observed in samples aged at 204° C in ambient atmospheric air pressure. The loss in adhesive bond performance with time was attibutable to a combination of physical and chemical aging phenomena in the FM-5 resin, and possible degradation of the metal-adhesive interface(s). Several mechanical and material tests, performed on the bonded joints and neat FM-5 resin specimens, confirmed the above statement. It was also noted that physical aging could be "erased" by thermal rejuvenation, partially restoring the toughness of the FM-5 adhesive material. The FM-5 adhesive material displayed good chemical resistance towards organic solvents and other aircraft fluids such as jet fuel and hydraulic fluid. The results from the FM-5 adhesive and its bonded joints were compared and contrasted with VT Ultem and REGULUS polyimide adhesives. The FM-5 adhesive showed the best performance among the three adhesive systems. The effect of mode-mixity on the fracture toughness of the Ti-6Al-4V/FM-5 adhesive bonded system was also evaluated. DCB tests in conjunction with end-notched flexure (ENF) and mixed-mode flexure (MMF) tests, were used to fracture the bonded joints under pure mode I, pure mode II, and a combination of mode I and II loadings. The results showed that the mode I fracture toughness was twice as large as the mode II toughness. This was a rather surprising find, in sharp contrast to what several researchers have observed in the past. Our current understanding is that the crack path selection during the failure process plays a significant role in explaining this anomalous behavior. Finally, failure envelopes were generated for the titanium/FM-5 bonded system, both prior to and following thermal aging. These envelopes could serve as useful tools for engineers designing with Ti-6Al-4V/FM-5 bonds. Ph. D.

The performance of fiber-reinforced composites is often controlled by the properties of the fiber-matrix interface. Good interfacial bonding (or adhesion), to ensure load transfer from matrix to reinforcement, is a primary requirement for effective use of reinforcement properties. Thus, a fundamental understanding of interfacial properties and a quantitative characterization of interfacial adhesion strength can help in evaluating the mechanical behavior and capabilities of composite materials. A large number of analytical techniques have been developed for understanding interfacial adhesion of glass fiber reinforced polymers. Common adhesion tests include contact angle measurements, tension or compression of specially shaped blocks of polymer containing a single fiber, the single fiber pull-out test, single-fiber fragmentation test, short beam shear and transverse tensile tests, and the vibration damping test. Among these techniques, the vibration damping technique has the advantage of being nondestructive as well as highly sensitive for evaluating the interfacial region, and it can allow the materials industry to rapidly determine the mechanical properties of composites. In this work, we contributed a simple optical system for measuring the damping factor of uniaxial fiber-reinforced-polymer composites in the shape of cantilever beams. A single glass fiber- and three single metallic wire-reinforced epoxy resin composites were tested with the optical system. The fiber- (wire-) matrix interfacial adhesion strength measurements were made by microbond test. A reasonable agreement was found between the measured interfacial adhesion strength and micromechanics calculations using results from vibration damping experiments. The study was also extended to multi-fiber composites. The interfacial damping factors in glass-fiber reinforced epoxy-resin composites were correlated with transverse tensile strength, which is a qualitative measurement of adhesion at the fiber-matrix interface. Four different composite systems were tested. For each system, glass fibers with three different surface treatments were used at three different volume fractions. The experimental results also showed an inverse relationship between damping contributed by the interface and composite transverse tensile strength for all of the multi-fiber composites. Ph. D.

High density polyethylene (HDPE) films having simple and well-defined stacked lamellar morphology, either with or without a distinct presence of row-nucleated fibril structures, have been utilized as model materials to carry out investigations on solid state structure-property relationships. Four different subjects that were addressed are: 1) mechanical properties and deformation morphologies, 2) orientation anisotropy of the dynamic mechanical α relaxation, 3) orientation dependence of creep behavior, and 4) crystalline lamellar thickness and its distribution. For the first three topics, appropriate mechanical tests, including tensile (INSTRON), creep (TMA), and dynamic mechanical (DMTA) tests, were performed at different angles with respect to the original machine direction (MD) of the melt extruded films; morphological changes as a result of these mechanical tests were detected by WAXS, SAXS, and TEM. For the forth topic, crystalline lamellar thickness and its distribution were determined by DSC, SAXS, TEM and AFM experiments. In the large strain deformation study (chapter 4.0), samples were stretched at 00°, 45° and 90° angles with respect to the original MD. A distinct orientation dependence of the tensile behavior was observed and correlated to the corresponding deformation modes and morphological changes, namely 1) lamellar separation and fragmentation by chain slip for the 00° stretch, 2) lamellar break-up via chain pull-out for the 90° stretch, and 3) lamellar shear, rotation and break-up through chain slip and/or tilt for the 45° stretch. A strong strengthening effect was observed for samples with row-nucleated fibril structures at the 00° stretch; whereas for the 90° stretch, the presence of such structures significantly limited deformability of the samples. In the dynamic strain mechanical α relaxation study (chapter 5.0), samples were tested at nine different angles with respect to the original MD, and the morphologies of samples before and after the dynamic tests were also investigated. The mechanical dispersions for the 00° and 90° tests were believed to arise essentially from the crystalline phase, and they contain contributions from two earlier recognized sub-relaxations of αI and αII. While for the 45° test, in addition to a high temperature αII relaxation, a interlamellar shear induced low temperature mechanical relaxation was also observed. It is concluded that the low temperature relaxation is related to the characteristics of the interface between the crystalline lamellae and amorphous layers. In the small strain creep study (chapter 6.0), samples were tested at the 00°, 45° and 90° angles at the original MD. Both creep strain and creep rate for samples at the three angles were very different. An Eyring-rate model was utilized to analysis the observed creep behavior, and structural parameters associated with this model, including population of creep sites, activation energy and volume, were obtained by fitting the experimental data to the Eyring-rate equation. It was concluded that the plateau creep rate in these model materials is primarily controlled by the density and physical state of tie-chains in the amorphous phase. For the lamellar thickness and distribution study, DSC, SAXS, TEM and AFM experiments were conducted for samples having a well-defined stacked lamellar morphology. It was found that the most probable lamellar thickness from SAXS and TEM agreed very well; however, these values did not match with those obtained by DSC and AFM. It was pointed out that the use of DSC to determine lamellar thickness and distribution is so sensitive to heating rate and numerical values for the parameters in the Gibbs-Thomson equation that it is not believed to be suitable for quantitative analysis. Ph. D.

A new method for stress-rupture experiments in bending has been developed and used to characterize unidirectional polymer matrix composites. The method. which makes use of very simple fixtures, led to coherent results. These results have been modeled using the large deflection of buckled bars theory (elastica) and it is possible to predict with good accuracy the strain at each point of the specimen if the end-to-end distance is known. The failure process has been experimentally characterized. The formation and propagation of microbuckles leads to a compressive failure. Based on the elastica and the classical lamination theory, a model for the distribution of the Young's modulus along the length of the specimen has been established. Three different micromechanical models have been applied to analyze the time-to-failure versus strain behavior at two temperatures - one below and one above the glass transition. The first micromechanical model considers the nucleation of the microbuckles as the main cause of failure. In addition, the stiffness and stress distributions at any time before failure are calculated based upon the rotation of the fibers in the damaged region. The second and last models, respectively based upon a Paris Law and energy considerations relate the time-to-failure to the propagation of the main microbuckle. For this last model, a good correlation between experimental and theoretical data has been obtained. Finally the influence of the temperature on these models has been studied. Master of Science

Long time annealing of semicrystalline PEEK above the glass transition results in the observation of several time dependent phenomena - "physical aging", "secondary crystallization", "multiple melting" of lamellae with different thermal stability etc. Their interrelation - common origin and kinetics of development, is characterized extensively for the first time in this study. The evolution of the crystallinity during the secondary crystallization process was monitored by DSC and density measurements. Crystallinity was characterized according to the standard two-phase model of semicrystalline polymers and analyzed with respect to the failure of the model to adequately describe the physical state of the polymer. A discrepancy was observed between DSC and density crystallinity values and their respective rates of development during the secondary crystallization stage. WAXS reveals that the crystal density is not a physical constant, but depends on the crystallization and/or annealing temperature. Furthermore, the crystalline lamellae densify with time during crystallization and/or annealing. This observation leads to the conclusion that there is no one-to-one correspondence between density and crystallinity and necessitates the application of a revised equation for density crystallinity which accounts for the dynamics of crystal densification. The characteristics of the low temperature endothermic peak in the DSC scan of PEEK (peak maximum, transition enthalpy etc.) were found to evolve with annealing time and temperature during the secondary crystallization process in a way similar to the kinetics of development of the enthalpy relaxation process in amorphous polymeric glasses. This study reports for the first time in the literature the observation of "physical aging" above the glass transition in the case of PEEK (according to the definition of this term given by Struik). An extensive investigation of the "double melting"/"multiple melting" phenomenon, which is observed as a result of isothermal treatment of the polymer above Tg, was performed and several new observations reported. After the end of the primary crystallization process, the semicrystalline polymer is a nonequilibrium system due to the fact that crystallinity is less than unity. The system's continuing approach to equilibrium and its response to mechanical perturbations follow kinetics similar to that of segmental relaxation below the glass transition. Ph. D.

This dissertation discusses the polymorphism, crystallization and melting behavior of propylene-ethylene random copolymers. It also discusses the results of studies of the miscibility and the competitive liquid-liquid demixing and crystallization processes in blends of poly(propylene) and poly(1-butene). In the first part of this study, polymorphism of propylene-ethylene copolymers is studied by wide angle X-ray diffraction. By comparing the a and y crystal phase contents in samples with different ethylene content as well as samples isothermally crystallized at different temperatures, it was shown that increasing ethylene content as well as increasing crystallization temperature promotes the formation of the y-phase. Comparison of the results from fractionated samples and unfractionated samples with similar ethylene contents reveals that in propylene-ethylene copolymers with similar micro-structure, the polymorphism, crystallization and melting behavior are mainly determined by their ethylene content. The issue of co-unit inclusion and its effect on crystallization and melting behavior are also discussed. In the second part of this dissertation, the miscibility behavior of atactic - poly(propylene) (at-PP) and atactic poly(1-butene) (ai-P1B) with different molecular weights is investigated by differential scanning calorimetry. The phase diagram of at-PP and at-P1B blend of molecular weight (87K/48.5K) shows a upper critical solution temperature (UCST) behavior. The UCST behavior is consistent with predictions by the group contribution method. Miscibility behavior of high molecular weight isotactic poly(propylene) (it-PP) and isotactic poly(1-butene) (it-P1B) blend is investigated by a combination of optical microscopy and scanning electron microscopy, differential scanning calorimetry and dynamic mechanical analysis. These studies reveal that for the molecular weights investigated, it-PP and it-P1B form blends that are partially miscible in the liquid state. Liquid-liquid demixing is observed by optical microscopy at temperatures above the melting temperature of the it-PP component and is also inferred from scanning electron micrographs of the freeze fracture surface of quenched blends after extraction of the it- P1B component with cyclohexane. It-PP spherulites grow through both liquid phases at relative rates that depend markedly on the crystallization temperature. The complex multiple-melting behavior of the it-PP component in the blend is explained in terms of a bimodal distribution of it-PP lamellar crystals which result from crystal growth in the phase-separated liquid. Finally, the dynamic mechanical analysis data are explained in terms of a liquid-liquid demixing process that results in a significant degree of phase mixing. Ph. D.