Nanotechnology refers to the use of the materials or particles ranging from a few nanometers (nm) to 100 nanometers (nm) in a wide range of applications. Use of nanomaterials in cement composite to enhance the mechanical properties, fracture toughness and other functionalities has been studied for decades. In this regard, one of the carbon-based nanomaterials, Graphene Oxide (GO), has received attentions from researchers for its superior mechanical properties (e.g. tensile strength, yield strength, and Young's modulus). Although GO is not lucrative in increasing electrical conductivity (EC) of cement paste compared to that of graphene- another derivative of GO, reduced graphene oxide (rGO), might be a solution to increase EC. Another derivative of GO is the solution to the problem. In this research, the compressive strength and flexural strength of GO-cement composite (GOCC) and rGO-cement composite (rGOCC) have been investigated with 0.01% and 0.05% GO and rGO content. GOCC-0.05% showed 27% increase in compressive strength compared to the control cement paste after 28 days (d) of hydration. GOCC-0.01% showed only 3.4% increase in compressive strength compared to the control. rGOCC-0.05% showed 21% increase in compressive strength and 15.5% increase in Modulus of Rupture (MOR) compared to the control cement paste after 28 d of hydration. On the other hand, rGOCC-0.01% showed 7% increase in compressive strength and 0.35% increase in MOR after 28 d. GOCC-0.05% showed increasing trends in compressive strength after 28 d indicating continuation of hydration. Similarly, rGOCC-0.05% also showed increasing trends in compressive and flexural strength after 28 d, possibly due to the reason described earlier. Microstructural investigation on GOCC-0.05% and GOCC-0.01% by X-ray Diffraction (XRD) illustrated that the crystallite sizes of tobermorite-Å and jennite, which are mineralogical counterpart of disordered Calcium-Silicate-Hydrate (C-S-H), increases from 3 d to 28 d, representing the crystallite growth due to continued hydration. However, the crystallite size of GOCC-0.05% was smaller than that of GOCC-0.01% at both 3 d and 28 d, indicating finer nucleated grains. According to Hall-Petch equation, mechanical strength increases with decreasing particle size. Finer particles or grains can increase the strength in cement composites in several other ways: (1) GO acted as heterogeneous nucleation sites because of reactive functional groups. Activation energy was decreased by these "defects" in the cement paste, and consequently, numerous nuclei of C-S-H. with high surface area were formed, (2) because of finer grains, cracks are forced to move along a tortuous path, which makes the structure difficult to fail, and strength increased consequently (3) Finer grains of GOCC-0.05% created compacted hydration products decreasing porosity which can indirectly increase the strength. The above reasons, separately or in conjunction, might increase the strength of GOCC-0.05% and proved that GO is responsible for increasing heterogeneous nucleation sites during cement hydration. Early age hydration (EAH) characteristics were investigated for rGOCC specimens with 0.1% and 0.5% rGO content. Scanning Electron Microscope (SEM), Energy Dispersive X-ray analysis (EDX), and X-ray Diffraction (XRD) were employed to study the EAH characteristics. SEM/EDX, and XRD analysis were performed after 15 min, 1 h, 3 h and 24 h of hydration. (EAH) study on rGOCC-0.1% showed that at 15 min hydration, numerous precipitates of, possibly, C-S-H formed along the grain boundary (GB) of unhydrated cement grains. This served as visual confirmation of Thomas and Scherer's Boundary Nucleation and Growth (BNG) model that hydration of cement grains was initiated by the short burst of nucleation of C-S-H embryos along GB. EDX on rGOCC-0.1% and rGOCC-0.5% showed that Ca/Si ratio in C-S-H was ~2.0. This finding indicated that C-S-H structure in this study was concurrent with that of impure jennite. XRD analysis also evidently showed that jennite was present, possibly possessing a short range ordered (SRO) structure, referring to local crystalline structure in a very short area. After consulting Chen's work, it would be appropriate to say that C-S-H found in this study resembled more as C-S-H (II), which is disordered jennite. It was also observed that as expected with cement with nanomaterials, with continuing hydration, pore spaces were filled with hydration products such as C-S-H, ettringite, CH, sulfoaluminates etc,. Lastly, Electrical resistivity (ER) testing on 9 sets of rGOCC specimens was conducted. The specimen includes 0.5%, 1%, 5% rGO content, and the control conditioned in both oven dry (OD) and saturated surface dry (SSD). ER increased with the increase of rGO content from 0.5% and 1% compared to that of the control. However, the ER of rGOCC-5% was significantly decreased, showing 93% reduction compared to the control, which can be interpreted as a threshold value for sensing applications to be explored. As expected, large reduction of ER value occurred on the specimens with the SSD condition. This reduction can be attributed to the ionic conduction though the pore solution of the composites. As the rGO content increased, so did the potential nucleation sites for hydration (as can be seen in SEM images), which might block the number of contact points among the rGO, resulting in low conduction and high resistivity. However, as rGO content increased to 5%, the contact areas/points increased to a degree that could trump the nucleation seeding sites, resulting in decreased ER. The ER measured with the rGOCC specimens was comparable to that of cement composites incorporating carbon fibers (CF), and steel fibers, but higher content of rGO are required to have a similar ER range of those fiber cement composites. This might be due to smaller sizes of rGO sheets and lower aspect ratio compared to other nanofibers causing drastic reduction of electron tunneling mechanism compared to other fibers.

Advanced aerospace materials require extensive testing and characterization to anticipate and ensure their integrity under hostile environments. Characterization methods utilizing synchrotron X-Ray diffraction and spectroscopy can decrease the time required to determine an emerging material's readiness for application through intrinsic information on the material response and failure mechanisms. In this study, thermal barrier coating samples applicable to turbine blades of jet engines were studied using Raman and Photoluminescence spectroscopy as well as Synchrotron X-ray diffraction while Kevlar based fiber composites applicable to ballistic resistant armor were studied using Raman spectroscopy to investigate the mechanical state and corresponding damage and failure mechanisms. Piezospectroscopic studies on the stress state of the thermally grown oxide (TGO) within the thermal barrier coatings, on a hollow cylindrical specimen, provided results that indicate variations within the TGO. Comparison of measured photo-luminescence spectra of the specimen before and after long duration thermal aging showcases the development of the system and the initiation of micro-damage. Raman spectroscopy performed on Kevlar ballistic composites with nano-scale additives, presented insight into the additives' role in load transfer and damage propagation through a comparison of the shift in optical spectra to that of the pristine fibers. The results presented herein utilize changes in the measured emission from these non-destructive testing techniques to link the phenomena with material response. Techniques to optimize imaging and spectral collection are addressed as well. The findings will advance the use of the techniques in the development of aerospace materials, providing a more complete understanding of land and aircraft turbine blade coatings, and fiber composite response to complex loading.

Li-ion batteries have enabled the widespread adoption of portable electronics and are becoming the technology of choice for electric vehicles and grid storage. One of the most promising ways to accommodate this demand is to increase the energy density and cycle life of battery electrode materials. Key strategies promoted in the literature include the use of nickel-rich cathodes as well as high-capacity anodes like silicon and lithium metal. While these materials enable a high energy density, this advantage is often counterbalanced with deficits such as poor stability and high cost. Multicomponent electrodes refer to strategies that try to leverage the relative advantages of different materials to offer an attractive compromise of energy density, cost, and cycle life. This thesis has investigated various aspects of multicomponent electrodes with a special emphasis on silicon-based anodes and high-entropy materials. Silicon (Si) is the second-most abundant element on earth and has one of the highest gravimetric capacities. However, silicon anodes are notorious for their poor cycle stability. Herein, improvements in the stability of silicon-based electrodes are achieved with multicomponent composite strategies involving the use of nanostructured spherical silicon. The nanosilicon is studied in high-fraction (80 wt% Si) and low-fraction (≤20 wt% Si) formulations to investigate both failure mechanisms and practical capacity retention, respectively. Composite strategies in which nanosilicon is encapsulated within a Li₄Ti₅O₁₂ ceramic or MOF-derived carbon matrix are shown to deliver superior capacity retention compared to simple composites of silicon and graphite. Considerable attention is given to the selection of a water-soluble binder and its role in electrochemical stability and electrode cohesion in high-loading silicon electrodes. It is found that unmodified high-molecular-weight sodium carboxymethyl cellulose offers better capacity retention compared to xanthan gum or low-molecular-weight binders. The high-entropy design strategy has created a diverse and largely unexplored set of multicomponent oxides and alloys with great potential as electrode materials. This strategy is applied to the family of layered cathodes, where the synthesis and electrochemical properties of the best-performing Li(NiCoMnTiFe)₁O₂ are reported. Despite the low Ni content, the cathode delivers a high initial capacity with unique overlithiation stability despite being charged to 4.4 V. Throughout the thesis, Operando XRD is used to reveal important insight into the lithiation mechanisms of the multicomponent electrodes including intercalation-based graphite, alloying-based silicon, and a novel organic azaacene.

Multiple strain path changes during forming lead to complex geometrically necessary dislocation (GND) development in strain gradient fields, inducing internal stresses that contribute to the Bauschinger effect, residual stresses, and springback which alters the final geometrical shape of the part. In order to analyze and design improved processing routes, models must capture the evolution of these internal stresses. However, most models capture the effects of these stresses via phenomenological approaches that require calibration to each new material and strain path. The development of models that capture the underlying physics at the sub-grain level is underway but requires in-depth studies of dislocation behavior (at the relevant meso length scale) in order to guide and validate them. The novel experimental campaign central to this thesis aims to tackle this problem by capturing unprecedented data of dislocation activity for several sheet metals during multiple strain path deformation. The resultant insights provide a new window into multi-path forming of metals, while also aiding the development and validation of two crystal plasticity (CP) models by collaborators at the University of New Hampshire (UNH). The models incorporate internal stresses at the grain and sub-grain levels, respectively. The hardening response due to strain path change during forming of AA6016-T4 was studied at the macro- and micro-level via combined experiments and an elasto-plastic self-consistent (EPSC) model. The experiments demonstrated that possible recombination and/or redirection of dislocations onto different slip systems under strain path change allowed for a gradual elasto-plastic transition, in comparison to a much sharper response upon continued deformation under the same strain path due to buildup and immediate activation of backstresses. The phenomenological backstress law of the EPSC model underpredicted the yield stress response for the strain path change deformations, possibly due to missing sub-grain GND development and an accurate description of associated backstresses. A more detailed experimental study of multi-path deformation for the AA6016-T4 was required in order to guide development of a strain gradient elasto-visco plasticity self-consistent model (SG-EVPSC); the model includes sub-grain strain gradient fields, and related internal stress fields. Total dislocation and GND density were tracked at various points of the deformation, and a complete 3D statistical volume element was characterized, to enable accurate modeling of the microstructure. The tests revealed a relatively lower yield stress response following strain path change, presumably aided by lower latent hardening than self hardening; the tests then showed a rapid accumulation of dislocations on the newly activated slip systems resulting in much higher final dislocation density without affecting the ductility of the pre-strained material. Interestingly, GND development was dominated by the precipitates instead of grain boundaries. These observations are vital for an accurate forming prediction from CPFEA models. Finally, optimized forming conditions of continuous bending under tension produced a ratcheting strain path resulting in a gradual GND development and a more complete retained austenite transformation in quenched-&-partitioned- and TRIP-assisted bainitic ferritic-1180 steels increasing their ductility by at least 360%.

Silicates analogous to cosmic dust were synthesized, modified, and analyzed utilizing ion-beam techniques with Rutherford backscattering spectrometry (RBS) and x-ray diffraction (XRD). Silicate dust is a common constituent in interstellar space, with an estimated 50% of dust produced in the stellar winds of M class Asymptotic Giant Branch (AGB) stars. Silicate dust acts as a surface upon which other chemicals may form (water ice for example), increasing significance in the cosmochemistry field, as well as laboratory astrophysics. Silicate formation in the stellar winds of AGB stars was simulated in the laboratory environment. Three sequential ion implantations of Fe-, MgH2-, and O- with thermal annealing were used to synthesize a mixture appropriate to silicate dust in the surface layers of a p-type Si substrate. Post implantation He+ irradiation was shown to preferentially induce crystalline formation in the analogue prior to thermal annealing. This effect is believed to originate in the ion-electron interaction in the Si substrate. The effects of ionization and ion energy loss due to electronic stopping forces is believed to precipitate nucleation in the amorphous media. For annealing temperatures of 1273 K, predominant quartz formation was found in the substrate, whereas lower annealing temperatures of 1000 K formed enstatite without post-implantation He+ irradiation, and olivine with He+ irradiation. Post annealed crystalline phase modification was investigated via x-ray diffraction and elemental compositions were investigated utilizing RBS. Finally, the interdiffusion of Fe and Mg at temperatures of 900-1100 K was investigated with RBS, and activation energies for interdiffusion were extracted for the transition from amorphous to crystalline phase in the silicate analogues. Fe had an interdiffusion energy of 1.8 eV and Mg 1.5eV. The produced analogues have similar properties to those inferred from infrared spectroscopy of the stellar winds of M-class AGB stars with an oxygen-rich outflow. This work established a method of silicate production using ion beam modifications, explored He+ irradiation effects in the annealed structures, and derived interdiffusion activation energies for Fe and Mg in the amorphous structure. Grain sizes were <100 nm with the observed formation of quartz, enstatite, and olivine.

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SammanfattningSyfte:Syftet med studien är att få fram information om hur kristallstrukturen i högtranslucent Y-TZP påverkas av åldrande i vatten vid låga temperaturer jämfört med ett traditionellt Y-TZP material och hur det i sin tur påverkar böjhållfastheten. Material och metod: 16 provkroppar skapades i två högtranslucenta Y-TZP-material samt åtta provkroppar i ett traditionellt Y-TZP-material. Provkropparna utformades enligt ISO-standard:6872, med måtten 20x4x2 mm och en avfasning på 45o på långsidorna. Provkropparna genomgick en termocykling på 10 000 cykler vid 5°C ±2oC respektive 55°C ±2oC. Därefter utsattes provkropparna för ett 3-punktböjhållfasthetstest och en röntgendiffraktion (XRD) för att undersöka skillnaderna i övergången från tetragonal till monoklin fas.Resultat: Resultatet visade att det finns en signifikant skillnad (p = 0,000) i böjhållfastheten mellan grupperna. Resultaten från röntgendiffraktionen visade på att ingen signifikant skillnad (p = 0,260) fanns mellan grupperna. Inget statistiskt signifikant samband (p = 0,285) kunde ses mellan ökad monoklin fas och minskad böjhållfasthet.Slutsats:Böjhållfasthet hos högtranslucent Y-TZP-material påverkas mer av ett termocykliskt åldrande i vatten jämfört med ett traditionellt Y-TZP-material. Efter termocykliskt åldrande i vatten, kan monoklin kristallstruktur i högtranslucent T-TZP och traditionell Y-TZP påvisas. Det fanns inget statistiskt signifikant samband mellan minskad böjhållfasthet och ökad mängd monoklin fas.

Needle-based intervention insertion is one of the common surgical techniques used in many diagnostic and therapeutic percutaneous procedures. The success of such procedures highly depends on the accuracy of needle placement at target locations. An active needle has the potential to enhance the accuracy of needle placement as well as to improve clinical outcome. Bending forces provided by the attached actuators can assist the maneuverability in order to reach the targets following a desired trajectory. There are three major research parts in the development of active needle project in the Composites Laboratory of Temple University. They are thermomechanical characterization of shape memory alloy (SMA) or Nitinol as an actuator for smart needle, mechanical modeling and design of smart needles, and study of tissue needle interaction. The characterization of SMA is the focus of this dissertation. Unique thermomechanical properties of Nitinol known as shape memory effect and superelasticity make it applicable for different fields such as biomedical, structural and aerospace engineering. These unique behaviors are due to the comparatively large amount of recoverable strain which is being produced in a martensitic phase transformation. However, under certain ranges of stresses and temperatures, Nitinol wires exhibit unrecovered strain (also known as residual strain); which limits their applicability. Therefore, for applications that rely on the strain response in repetitive loading and unloading cycles, it is important to understand the generation of the unrecovered strain in the Nitinol wires. In this study, the unrecovered strain of Nitinol wires with various diameters was investigated, using two experimental approaches: constant stress and uniaxial tensile tests. Moreover, a critical range of stress was found beyond which the unrecovered strain was negligible at temperatures of 70 to 80&#61616;C depending on the wire diameter. Wire diameters varied from 0.10 to 0.29 mm were tested and different ranges of critical stress were found for different wire diameters. The transformation temperatures of different wire diameters at zero stress have been achieved by performing the Differential Scanning Calorimetry (DSC) test. The actuation force created by Nitinol wire is measured through constant strain experiment. X-Ray Diffraction (XRD) study was also performed to investigate the phase of Nitinol wires under various thermomechanical loading conditions. In summary, the effect of wire diameter on the required critical stresses to avoid the unrecovered strain between first and second cycle of heating and cooling are presented and the results of both mechanical tests are justified by the results obtained from the XRD study. / Mechanical Engineering