<p> The synthesis and X-ray crystallographic determination of solid derivatives of homo- and heteropolyatomic anions derived from Zintl phases has generally yielded the least soluble of the ions present in solution. Many other species present in these solutions have remained unidentified until recently when considerable effort directed towards the investigation of the solution chemistries of Zintl anions has been put forth.</p> <p> The present work is mainly concerned with the characterization of new Zintl anions in solution using multinuclear magnetic resonance spectroscopy as the primary investigative tool. These studies include (1) the tetrahedral SnCh4^4- (Ch = selenium and/or tellurium), (2) the dimer of SnSe3^2-, Sn2Se6^4-, (3) several interesting but, as-of-yet, unidentified species present in solutions derived from ternary Na/Sn/Te alloys and present in the reaction of Sn(II) Cl2 with Te2^2-, and (4) a set of possible multi-thallium-tellurium species. Relevant chemical shifts and nuclear spin-spin coupling constants are reported and trends discussed.</p> <p>119Sn Mössbauer investigations of all tin-containing species is also presented as is a brief discussion of the X-ray crystallographically determined polytelluride, Te4^2-.</p> / Thesis / Master of Science (MSc)

<p>Recent experiments have highlighted the efficacy of post-installed reinforcement in enhancing the capacity of groups of  bonded anchors undergoing concrete breakout failure mode. This technique is particularly useful to enhance the performance of anchorages installed in members of limited dimensions such as beams and columns. This thesis presents the results of corresponding numerical investigations on bonded anchor groups in concrete strengthened with post-installed supplementary reinforcement subjected to tension loads. The study is conducted using the 3D Finite Element (FE) approach. The constitutive law of concrete is the microplane model with relaxed kinematic constraint. The interface between anchor or reinforcement and concrete is modeled with two-node bar elements, which are assigned with corresponding bond-stress slip characteristics. The proposed FE approach is validated against experimental results available in the literature by comparing load-displacement behavior and failure mode. </p> <p>The validation incorporates anchor groups with different configurations of post-installed supplementary reinforcing steel bars. The numerical investigations provide a deeper insight into the detailed behavior of anchor groups with post-installed reinforcement through the visualization of crack patterns, stress flows, and strain development. The results show that the post-installed rebars can lead to a significant increase in the performance of post-installed anchorages, and the load increase depends on the number and arrangement of rebars and the failure mode of the system. </p> <p>Lastly, the thesis presents a parametric study on strengthened anchor groups with post-installed rebars in narrow reinforced concrete (RC) members under various configurations. These simulations mimic anchorages used for seismic retrofitting beam-column joints in RC structures using a fully fastened haunch retrofit solution. Due to the limited width and depth of beams and columns, the capacity of the anchorages is often the weakest link in such retrofitting methods. The results from the FE study indicate that the post-installed supplementary reinforcement can be an efficient solution for upgrading the performance of post-installed anchorages in such retrofitting techniques.</p>

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With the reliability requirements of automobile microelectronics pushing towards near 0 ppb levels of failure control, halide induced corrosion issues in wire bonded devices have to be tightly controlled to achieve such a high reliability goal. With real-time corrosion monitoring, for the first time we demonstrated that the explosive H2 evolution coupled with the oxygen reduction reaction, occurring at the critical Al/Cu interfaces, is the key driving force for the observed aggressive corrosion. Several types of passivation coating on Cu wire surfaces to effectively block the cathodic H2 evolution were explored with an aim to disrupt this explosive corrosion cycle. The properties of the protective coating were evaluated using various analytical techniques. The surface coating exhibited high thermal stability up to 260 °C (evaluated using TGA analysis). A uniform, highly hydrophobic coating (surface contact angle of >130° with water), was achieved by carefully controlling CVD parameters such as time of deposition, surface control of Cu metal, amount of inhibitor compound loading, temperature of coating process etc. FTIR spectroscopy combined with corrosion screening was used to optimize the CVD passivated coating with strong chemisorption. SEM and EDX, XPS were carried out on various coated surfaces to understand the composition and selectivity of the film formed through this surface treatment. The surface selective nature of this coating (towards Cu) proved helpful in preventing potential delamination issues during epoxy molding process. The corrosion testing was carried out via HAST testing at 130°C, 2 atm pressure and 100% RH for 48 hours. Delamination analysis and continuity test showed that the inhibitor compound was able to effectively prevent the corrosion even after exposure to harsh HAST conditions.

Using experimental data obtained from standard fracture test configurations, theoretical and numerical tools are developed to mathematically describe non-self-similar progression of cracks without specifying an initial crack. A cohesive-decohesive zone model, similar to the cohesive zone model known in the fracture mechanics literature as the Dugdale-Barenblatt model, is adopted to represent the degradation of the material ahead of the crack tip. This model unifies strength-based crack initiation and fracture-mechanics-based crack progression. The cohesive-decohesive zone model is implemented with an interfacial surface material that consists of an upper and a lower surface that are connected by a continuous distribution of normal and tangential nonlinear elastic springs that act to resist either Mode I opening, Mode II sliding, Mode III sliding, or a mixed mode. The initiation of fracture is determined by the interfacial strength and the progression of the crack is determined by the critical energy release rate. The adhesive is idealized with an interfacial surface material to predict interfacial fracture. The interfacial surface material is positioned within the bulk material to predict discrete cohesive cracks. The interfacial surface material is implemented through an interface element, which is incorporated in ABAQUS using the user defined element (UEL) option. A procedure is established to formulate a rate dependent model based on experiments carried out on compact tension test specimens. The rate dependent model is incorporated into the interface element approach to capture the unstable crack growth observed in experiments under quasi-static loading conditions. The compact tension test gives the variation of the fracture toughness with the rate of loading, this information is processed and a relationship between the fracture toughness and the rate of the opening displacement is established. The cohesive-decohesive zone model is implemented through a material model to be used in an explicit code (LS-DYNA). Dynamic simulations of the standard test configurations for Mode I (Double Cantilever Beam) and Mode II (End Load Split) are carried out using the explicit code. Verification of these coupon tests leads to the crash analysis of realistic structures like the square composite tube. Analyses of bonded and unbonded square tubes are presented. These tubes shows a very uncharacteristic failure mode: the composite material disintegrates on impact, and this has been captured in the analysis. Disadvantages of the interface element approach are well documented in the literature. An alternative method, known as the Extended Finite Element Method (XFEM), is implemented here through an eight-noded quadrilateral plane strain element. The method, based on the partition-of-unity, is used to study simple test configuration like the three-point bend problem and a double cantilever beam. Functionally graded materials are also simulated and the results are compared to the experimental results available in the literature. / Ph. D.

PR-2930 was developed by PPG Industries, Inc. to meet the challenging performance requirements of MIL-PRF-32662 Group-I-classified adhesives. PR-2930 is a high-strength, high-toughness, epoxy-based adhesive intended for automotive and aerospace applications. As PR-2930 functions as a structural adhesive, quantification of its mechanical properties and limit-states is a necessary task for designing joints bonded with the adhesive. The combination of both strength and ductility results in material non-linearities, making experimental characterization and numerical analyses more challenging. This work explores the quantification of fracture energy for PR-2930 bonded joints. Fracture can occur in one of three different modes, or in some combination. Many practical adhesive joints fail in the mixed-mode region involving both opening (mode I) and shearing (mode II) displacements. Mode I fracture was evaluated with double cantilever beam (DCB) tests, mode II fracture was characterized by end-notched flexure (ENF) tests, and varying degrees of mixed mode I/II fracture were assessed through single leg bend (SLB), single-lap joint (SLJ), and asymmetric DCB and SLB tests. Test specimens were fabricated by bonding Al 2024-T3 adherends, ranging from 1.6 mm to 25.4 mm thick, with a 0.25 mm thick PR-2930 adhesive layer. Digital image correlation (DIC) was used to experimentally measure local displacements and surface strains on the adherends. Standard data-reduction methods often used to determine fracture energies of bonded joint specimens were used to numerically analyze test results. These methods included the Corrected Beam Theory (CBT), the Compliance-Based Beam Method (CBBM), and the Paris and Paris J-Integral approach. Linear elastic fracture mechanics (LEFM) conditions must be valid to correctly apply these methods, however plastic deformations were observed in some adherends. Drawbacks of these approaches and their validity for analyzing PR-2930 joints were discussed. To account for non-linearities, more advanced numerical analysis was performed using finite element analysis (FEA) with cohesive zone models (CZMs) to model the adhesive layer. CZM parameters such as fracture energies and traction separation law (TSL) shapes were determined from experimental data and published literature. Results from CZMs were compared to experimental load, displacement, and strain data. Recommended TSLs for mode I and mode II fracture were formed in this work as well as a mixed-mode relationship using a Benzeggagh-Kenane damage evolution law. More ideal analytical methods were suggested to simplify analysis of joints using the same or similar material compositions. / M.S. / Structural adhesives are used to safely transmit loads in our furniture, automobiles, aircraft, and buildings. PR-2930 is a newly developed epoxy that exhibits top-of-the-line strength and ductility. To safely design joints utilizing PR-2930, the bonding material and its limit states must be defined. The most pertinent mechanical limit state for adhesively bonded joints is its resistance to fracture, also known as fracture toughness. Fracture often occurs due to a combination of opening (mode I) or shearing (mode II) displacements. In this work, standard and novel advanced fracture characterization techniques are employed and subsequently compared. Adhesive joints using a 0.25 mm layer thickness are bonded to Al 2024-T3 adherends varying from 1.6 mm to 25.4 mm of thickness and tested in quasistatic conditions. Mathematical models of mode I, mode II, and combined mode I/II stress displacement responses (AKA a traction-separation laws) of PR-2930 are developed and compared with experimental data. Future experimental and numerical methods for fracture analysis of structural adhesives are discussed.

The goal of this work is to develop and characterize a manufacturing process that is able to create metal matrix composites with complex cellular geometries. The novel manufacturing method uses two distinct additive manufacturing processes: i) fabrication of patternless molds for cellular metal castings and ii) printing an advanced cellular ceramic for embedding in a metal matrix. However, while the use of AM greatly improves the freedom in the design of MMCs, it is important to identify the constraints imposed by the process and its process relationships. First, the author investigates potential differences in material properties (microstructure, porosity, mechanical strength) of A356 — T6 castings resulting from two different commercially available Binder Jetting media and traditional 'no-bake' silica sand. It was determined that they yielded statistically equivalent results in four of the seven tests performed: dendrite arm spacing, porosity, surface roughness, and tensile strength. They differed in sand tensile strength, hardness, and density. Additionally, two critical sources of process constraints on part geometry are examined: (i) depowdering unbound material from intricate casting channels and (ii) metal flow and solidification distances through complex mold geometries. A Taguchi Design of Experiments is used to determine the relationships of important independent variables of each constraint. For depowdering, a minimum cleaning diameter of 3 mm was determined along with an equation relating cleaning distance as a function of channel diameter. Furthermore, for metal flow, choke diameter was found to be significantly significant variable. Finally, the author presents methods to process complex ceramic structure from precursor powders via Binder Jetting AM technology to incorporate into a bonded sand mold and the subsequently casted metal matrix. Through sintering experiments, a sintering temperature of 1375 °C was established for the ceramic insert (78% cordierite). Upon printing and sintering the ceramic, three point bend tests showed the MMCs had less strength than the matrix material likely due to the relatively high porosity developed in the body. Additionally, it was found that the ceramic metal interface had minimal mechanical interlocking and chemical bonding limiting the strength of the final MMCs. / Ph. D.