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Characterization of small precipitates is important for development of new alloys. One inherent  difficulty  in  characterisation  of  small  precipitates  with  electron microscopy techniques  while  the  particles  are  embedded  in  the  matrix,  is  that the surrounding bulk material will contribute to the analysed signal- limiting, for example, the quantification of the composition of particles.  In order to avoid the matrix contribution, the extraction replica technique was developed in the 1950's. Extraction replicas are made by extracting only the particles from a material onto a thin film for further analysis by scanning or transmission electron microscopy. Different types of particles can be examined by this technique, including various carbides, nitrides, oxides and borides, as well as many intermetallic phases.  In this work, direct replication techniques were compared to two-stage replication for low-alloyed steel, concluding that both are suitable for qualitative analysis, but direct replication is preferred for quantitative analysis.  Successful replication of the zirconium-based Zirlo and the stainless steel 254 SMO was performed, where the precipitated phases were isolated and the composition quantified.   Particle extraction was successful also for the zirconium-based Zircaloy-2 and two types of  aluminium  alloys,  but  no  quantification of  composition  could  be  made  due to different problems associated with etching of each alloy, showing that properchoice of etchant is crucial for the quality of the replicas. / Karaktärisering av små utskiljningar är viktigt för utveckling av nya legeringar. En svårighet  vid  karaktärisering  av  små  utskiljningar  med elektronmikroskopi när partiklarna  sitter  kvar  i  matrisen  är  att  matrisen kommer  ge  ett  bidrag till den analyserade signalen,  därför är t.ex.   möjligheterna för kvantifiering av sammansättning begränsade. För att undvika bidraget från matrisen utvecklades extraktionsrepliker  på  1950-talet.  Extraktionsrepliker  tillverkas  genom  att extrahera partiklar från ett material till en tunn film som sedan kan analyseras med hjälp av svep- eller transmissionselektronmikroskopi. Olika sorters partiklar kan  undersökas  med hjälp  av  denna  metod.     Dessa  inkluderar  olika  typer av  karbider, nitrider, borider, oxider  och  många  olika  sorters  intermetalliska partiklar. I  detta arbete  jämfördes direkta  metoder  med  tvåstegsrepliker  på låglegerat  stål. Slutsatsen  blev  att  båda metoderna  lämpar  sig  för  kvalitativ analys av små partiklar, men direkta metoder är att föredra för kvantitativ analys. Lyckade repliker tillverkades även av zirkoniumlegeringen Zirlo och det rostfria stålet  254  SMO,  där  utskiljningarna  kunde isoleras  och sammansättningen kvantifieras.   Extraktion  av  partiklar  var  lyckad  även  för zirkoniumlegeringen Zircaloy-2  samt  två  typer  av  aluminiumlegeringar, men ingen  kvantifiering  av sammansättningen  kunde  göras  på  grund  av  olika problem  relaterade  till  den valda etsmetoden för varje legering, vilket visar att valet av etsmedel ar avgörande för kvaliteten av replikerna.

Nanocrystalline metals exhibit a high strength/hardness but generally poor ductility during deformation regardless of their crystal structure which is often called the strength-ductility trade-off relationship and generally appears in most ultrafine-grained metals. The ultrafine-grained (UFG) high manganese austenitic twinning-induced plasticity (TWIP) steels have been found to overcome the strength-ductility trade-off but their underlying mechanism of discontinuous yielding behavior has not been well understood. In this study, our systematic TEM characterization suggests that the plastic deformation mechanisms in the early stage of deformation, around the macroscopic yield point, show an obvious association with grain size and nucleation of deformation twin was promoted rather than suppressed in UFG. More specifically, the main mechanism shifts from the conventional slip in grain interior to twinning nucleated from grain boundaries with decreasing the grain size down to less than 1 m. We also provide insights into the atomistic process of deformation twin nucleation at 3{111} twin boundaries, the dominant type of grain boundary in the UFG-TWIP steel of interest. In response to the external tensile stresses, the structure of coherent 3{111} twin boundary changes from atomistically smooth to partly defective by the grain boundary migration mechanism thus the "kink-like" defective step can act as a nucleation site for deformation twin, which deformation process is different from the one induced by dislocation pile-ups in coarse-grained counterparts and explain why UFG TWIP steel can retain the moderate ductility. In addition to the effect of grain size on deformation twin nucleation, grain boundary character was also taken into account. In coarse-grained TWIP steel, we experimentally reveal that deformation twin nucleation occurs at an annealing twin () boundary in a high-Mn austenitic steel when dislocation pile-up at boundary produced a local stress exceeding the twining stress, while no obvious local stress concentration was required at relatively high-energy grain boundaries such as or  A periodic contrast reversal associated with a sequential stacking faults emission from boundary was observed by in-situ transmission electron microscopy (TEM) deformation experiments, proving the successive layer-by-layer stacking fault emission was the deformation twin nucleation mechanism. The correlation between grain boundary character and deformation behavior was discussed both in low- and high-sigma value grain boundaries. On the other hand, localized strain concentration causes the nucleation of deformation twins at grain boundaries regardless of the grain boundary misorientation character in UFG TWIP steel. The invisibility of stacking fault (zero contrast) was also observed to be emitted at 3{111} boundaries in the coarse-grained TWIP steel, which deformation twin nucleation mechanism is found to be identical to UFG Fe-31Mn-3Si-3Al TWIP steel. / Doctor of Philosophy / High manganese (Mn) twin-induced plasticity (TWIP) steel is a new type of steels which exhibit pronounced strain hardening rate so that offering an extraordinary potential to adjust the strength-ductility relationship. This key advantage will help implement the current development of lightweighting components in automobile industry due to a considerable reduction of material use and an improved press formability. Such outstanding ductility can be contributed by the pronounced strain hardening rate during every such deformation processes, which is highly associated with several different controlling parameters, i.e., SFE, grain orientation, grain size, and grain boundary characters. In this study, we take particular attention to the effect of grain size and grain boundary characters on deformation twinning behavior besides well-known parameters such as SFE and grain orientation. The effect of grain size on deformation twinning behavior was found to be deeply associated with the yielding behavior in TWIP steel, i.e., a discontinuous yielding behavior with a unique yield drop was observed in ultrafine-grained TWIP while a continuous yielding behavior was observed in coarse-grained counterpart. Our TEM characterization indicates that the microstructural features of grains >10 m are different from the microstructural features in grains < 1 m. In over-10 m grains, normal dislocation slips and the formation of in-grain stacking faults are the main deformed microstructure. However, in the under-1 m grains, the in-grain dislocation slip is inhibited, but the deformation twinning is promoted at grain boundaries. This deformation transition from in-grain slip to twinning at grain boundary appears to be responsible for the discontinuous yielding behavior observed in stress-strain curve. The effect of grain boundary character on deformation twinning was examined in both coarse- and ultrafine-grained TWIP steels. In coarse-grained TWIP steel, we found that deformation twinning behavior varies as the function of boundary structure, i.e., different atomic configuration. Coherent twin boundary can act as a nucleation site for deformation twin as a localized strain concentration was introduced by dislocation pile-ups. On the other hand, incoherent boundaries can act as a deformation twin nucleation site by a boundary relaxation mechanism, i.e., grain-boundary dislocations can dissociate into partial dislocations to both side of boundary to accommodate the misfit between grains. In UFG TWIP steel, we found that the coherent twin boundary can act as a deformation twin nucleation site without presence of dislocation pile-ups. Alternatively, twin boundary becomes defective with a "kink-like" step by boundary migration. As a result, this defective step would progressively accumulate localized strain field thus stimulate the nucleation of deformation twin. Such study provides a novel insight into the UFG TWIP steel and a roadmap toward controlling TWIP effect.

The breast cancer susceptibility protein, BRCA1, is a tumor suppressor that helps maintain genomic integrity. Changes in BRCA1 that effect DNA repair processes can fuel cancer induction. The Kelly lab, at the Virginia Tech Carilion Research Institute, has recently developed a new methodology that employs silicon nitride (SiN) microchips to isolate BRCA1 assemblies from the nuclear material of breast cancer cells. These microchips are coated with adaptor proteins that include antibodies against target proteins of interest. The adaptor proteins are added in sequential steps to the coated microchips, followed by an aliquot of sample containing the protein of interest, such as BRCA1. The Kelly lab, partnered with Protochips Inc., developed these devices as a robust, tunable platform to monitor molecular processes, and refer to them as 'Cryo-SiN' in cryo-Electron Microscopy (EM) imaging. We are currently using Cryo-SiN to recruit BRCA1 protein assemblies to the microchip surface under mild conditions, while simultaneously preparing them for cryogenic preservation and EM imaging. This strategy presents a viable alternative to antibody affinity columns that require stringent elution steps to obtain protein complexes from the column. Another advantage of the microchip strategy is that it requires only a 30-minute nuclear extraction, a 60-minute enrichment procedure, and a 5-minute microchip capture step--a total of 95 minutes from initially lysing the cells to plunge-freezing the EM specimens. Therefore, these novel approaches represent a major departure from classical separation procedures that often require days to complete, during which time active protein assemblies can readily dissociate or become inactive. Overall, our use of BRCA1-specific microchips may reveal changes in the BRCA1 architecture during various stages of cancer progression--a major gap in knowledge that persists in cancer research. / M. S. / Modern advances in the imaging technology used for cryogenic electron microscopy (cryo-EM) have offered researchers an extraordinary view into the world of biology at the nanoscale. Supplemental to these technical innovations is the development of tunable substrates based on functional new materials that revolutionize the sequestering of biological components from human cells, such as protein complexes formed in breast cancer cells. New developments of novel viewing substrates, given traditional electron microscopy viewing grids have remained unchanged for decades, is the logical next step into the future of enhanced cryo-EM imaging. Tunable microchip substrates, made using recently enhanced micro-engineering techniques, are currently under development for use in cryo-EM imaging. In this work I have examined these microchip substrates for their capacity to streamline the isolation of biomolecules such as the protein most prominently cited in breast cancer, known as the breast cancer susceptibility protein (BRCA1). Utilizing these novel microchip substrates in the Kelly Lab, I have collected and analyzed data containing BRCA1 proteins, formed in human breast cancer cells, toward the development of 3-dimensional protein structures that allow us to peer into the structure-function relationships of these proteins. New and exciting Cryo-EM data, collected using these newly developed microchips, has the potential to reveal obscure disease mechanisms being propagated at the molecular level in modern clinical practice, such as breast cancer.

Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo-/electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as NBT-derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric crystals. For instance, in addition to enhancing our understanding the nature of the piezoelectric third-rank tensor coefficients such as d₃₃ and d₁₅, a thorough knowledge of the Curie temperature, leakage current, and electromechanical properties is also essential for increasing the applications potential of these crystals. As detailed herein, multiple dopants may have to be incorporated into NBT to modify its microstructure and properties to meet these specific requirements, which may further complicate its chemical structure-property relationships. This study, therefore, was designed to investigate the heterogeneous structure of NBT-based single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling of morphotropic phase boundary (MPB) and the maximum property responses in A-site disordered perovskite Pb-free piezoelectric systems. Using the framework of polar nanoregions and adaptive phase theory, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. Diffuse scattering, domain morphology, and phonon dispersions were used to investigate both the static and dynamic properties of these heterogeneous structures. / Ph. D. / Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo- /electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as (Na_1/2Bi_1/2)TiO₃ (NBT) -derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric single crystals. In addition to enhancing our understanding the nature of the piezoelectric properties, increasing the applications potential of these crystals is also essential. And these specific requirements from different applications further push the researchers to find a more effective model to lead the piezoelectric single crystals growth as well as developments. This study, therefore, was designed to investigate the unique microstructure of NBTbased single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling between the chemical compositions and the maximum property responses in these specific Pb-free piezoelectric systems. Using the framework of an advanced microstructure description model, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. The results from different experiment methods also successfully supported each other and brought new perspectives to the Pb-free material researches.

Two-dimensional conjugated metal−organic frameworks (2D c-MOFs) have emerged as a new class of crystalline layered conducting materials that hold significant promise for applications in electronics and spintronics. However, current 2D c- MOFs are mainly made from organic planar ligands, whereas layered 2D c-MOFs constructed by curved or twisted ligands featuring novel orbital structures and electronic states remain less developed. Herein, we report a Cu-catecholate wavy 2D c-MOF (Cu3(HFcHBC)2) based on a fluorinated core-twisted contorted hexahydroxy-hexa-cata-hexabenzocoronene (HFcHBC) ligand. We show that the resulting film is composed of rod-like single crystals with lengths up to ∼4 μm. The crystal structure is resolved by high-resolution transmission electron microscopy (HRTEM) and continuous rotation electron diffraction (cRED), indicating a wavy honeycomb lattice with AA-eclipsed stacking. Cu3(HFcHBC)2 is predicted to be metallic based on theoretical calculation, while the crystalline film sample with numerous grain boundaries apparently exhibits semiconducting behavior at the macroscopic scale, characterized by obvious thermally activated conductivity. Temperature-dependent electrical conductivity measurements on the isolated single-crystal devices indeed demonstrate the metallic nature of Cu3(HFcHBC)2, with a very weak thermally activated transport behavior and a room-temperature conductivity of 5.2 S cm−1. Furthermore, the 2D c-MOFs can be utilized as potential electrode materials for energy storage, which display decent capacity (163.3 F g−1) and excellent cyclability in an aqueous 5 M LiCl electrolyte. Our work demonstrates that wavy 2D c-MOF using contorted ligands are capable of intrinsic metallic transport, marking the emergence of new conductive MOFs for electronic and energy applications.

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