Additive manufacturing processes of many alloys are known to develop texture during the deposition process due to the rapid reheating and the directionality of the dissipation of heat. Titanium alloys and with respect to this study beta titanium alloys are especially susceptible to these effects. This work examines Ti-20wt%V and Ti-12wt%Mo deposited under normal additive manufacturing process parameters to examine the texture of these beta-stabilized alloys. Both microstructures contained columnar prior beta grains 1-2 mm in length beginning at the substrate with no visible equiaxed grains. This microstructure remained constant in the vanadium system throughout the build. The microstructure of the alloy containing molybdenum changed from a columnar to an equiaxed structure as the build height increased. Eighteen additional samples of the Ti-Mo system were created under different processing parameters to identify what role laser power and travel speed have on the microstructure. There appears to be a correlation in alpha lath size and power density. The two binary alloys were again deposited under the same conditions with the addition of 0.5wt% boron to investigate the effects an insoluble interstitial alloying element would have on the microstructure. The size of the prior beta grains in these two alloys were reduced with the addition of boron by approximately 50 (V) and 100 (Mo) times.
While amorphous phases have been reported in immiscible alloy systems, there is still some controversy regarding the reason for the stabilization of these unusual amorphous phases. Direct evidence of nanoscale phase separation within the amorphous phase forming in immiscible Cu-Nb alloy thin films using 3D atom probe tomography has been presented. This evidence clearly indicates that the nanoscale phase separation is responsible for the stabilization of the amorphous phase in such immiscible systems since it substantially reduces the free energy of the undercooled liquid (or amorphous) phase, below that of the competing supersaturated crystalline phases. The devitrification of the immiscible Cu-Nb thin film of composition Cu-45% Nb has been studied in detail with the discussion on the mechanism of phase transformation. The initial phase separation in the amorphous condition seems to play a vital role in the crystallization of the thin film. Detailed analysis has been done using X-ray diffraction, transmission electron microscopy and 3D atom probe tomography.
The recent advancements in electronics and the advents of small scaled instruments has increased the attachment of life and functionality of devices to electrical power sources but at the same time granted the engineers and companies the ability to use smaller sources of power and batteries. Therefore, many scientists have tried to come up with new solutions for a power alternatives. Piezoelectric is a promising material which can readily produce continuous electric power from mechanical inputs. However, their power output is dependent upon several factors such as, system natural frequency, their position in the system, the direction of vibration and many other internal and external factors. In this research the working bandwidth of the system is increased through utilizing of two different piezoelectric beam in different directions. The dependency of output power with respect to rotation angle and also the frequency shift due to the rotation angle is studied.
The current study focuses on phase stability and evolution in the titanium-zinc titanium-copper and titanium-antimony systems. The study utilized the Laser Engineering Net Shaping (LENS™) processing technique to deposit compositionally graded samples of three binary system in order to allow the assessment of phase stability and evolution as a function of composition and temperature the material is subjected to. Through LENS™ processing it was possible to create graded samples from Ti-xSb (up to 13wt%) and Ti-xCu (up to 16wt%). The LENS™ deposited gradient were solutionized, and step quenched to specific aging temperature, and the resulting microstructures and phase were characterized utilizing XRD, EDS, SEM, FIB and TEM. The Ti-Zn system proved incapable of being LENS™ deposited due to the low vaporization temperature of Zn; however, a novel processing approach was developed to drip liquid Zn onto Ti powder at temperatures above β transus temperature of Ti (882 ◦C) and below the vaporization temperature of Zn (907 ◦C). The product of this processing technique was characterized in a similar way as the graded LENS™ depositions. From measurements performed on Ti-Sb it seems that Sb could be a potential α stabilizer in Ti due to the presence of a mostly homogeneous α grains throughout the gradient; however, from XRD it can be understood that a titanium antimonide phase is present. From results obtained from the Ti-Zn samples, it can be surmised that the eutectoid reaction seems to be active, i.e. The eutectoid reaction is kinetically fast, as concluded by the presence of pearlitic structures. Finally, for the Ti-Cu system this work has been attempted to prove or disprove the existence of the Ti3Cu through the use of XRD and TEM SAD patterns. From XRD spectra collected there are peaks belonging to the Ti3Cu orthorhombic phase along with Ti2Cu and α-Ti phase. In ...
Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Perovskite-structured LLT is a promising solid electrolyte with high lithium ion conductivity. LLT also serves as a good model system to understand lithium ion diffusion behaviors in solids. In this thesis, molecular dynamics and related atomistic computer simulations were used to study the diffusion behavior and diffusion mechanism in bulk crystal and grain boundary in lithium lanthanum titanate (LLT) solid state electrolytes. The effects of defect concentration on the structure and lithium ion diffusion behaviors in LLT were systematically studied and the lithium ion self-diffusion and diffusion energy barrier were investigated by both dynamic simulations and static calculations using the nudged elastic band (NEB) method. The simulation results show that there exist an optimal vacancy concentration at around x=0.067 at which lithium ions have the highest diffusion coefficient and the lowest diffusion energy barrier. The lowest energy barrier from dynamics simulations was found to be around 0.22 eV, which compared favorably with 0.19 eV from static NEB calculations. It was also found that lithium ions diffuse through bottleneck structures made of oxygen ions, which expand in dimension by 8-10% when lithium ions pass through. By designing perovskite structures with large bottleneck sizes can lead to materials with higher lithium ion conductivities. The structure and diffusion behavior of lithium silicate glasses and their interfaces, due to their importance as a grain boundary phase, with LLT crystals were also investigated by using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces were investigated. It was found that there existed a minor segregation ...
Generation and migration of helium and other point defects under irradiation causes ferritic steels based on the Fe-Cr system to age and fail. This is motivation to study point defect migration and the He equation of state using atomistic simulations due to the steels' use in future reactors. A new potential for the Fe-Cr-He system developed by collaborators at the Lawrence Livermore National Laboratory was validated using published experimental data. The results for the He equation of state agree well with experimental data. The activation energies for the migration of He- and Fe-interstitials in varying compositions of Fe-Cr lattices agree well with prior work. This research did not find a strong correlation between lattice ordering and interstitial migration energy
Tissue engineering merges the disciplines of study like cell biology, materials science, engineering and surgery to enable growth of new living tissues on scaffolding constructed from implanted polymeric materials. One of the most important aspects of tissue engineering related to material science is design of the polymer scaffolds. The polymer scaffolds needs to have some specific mechanical strength over certain period of time. In this work bioresorbable aliphatic polymers (PCL and PLLA) were blended using extrusion and solution methods. These blends were then extruded and electrospun into fibers. The fibers were then subjected to FDA standard in vitro immersion degradation tests where its mechanical strength, water absorption, weight loss were observed during the eight weeks. The results indicate that the mechanical strength and rate of degradation can be tailored by changing the ratio of PCL and PLLA in the blend. Processing influences these parameters, with the loss of mechanical strength and rate of degradation being higher in electrospun fibers compared to those extruded. A second effort in this thesis addressed the potential separation of the scaffold from the tissue (loss of apposition) due to the differences in their low strain responses. This hypothesis that using knit with low tension will have better compliance was tested and confirmed.
Lack of crystalline order and microstructural features such as grain/grain-boundary in metallic glasses results in a suite of remarkable attributes including very high strength, close to theoretical elasticity, high corrosion and wear resistance, and soft magnetic properties. By altering the morphology and tuning of composition, MGs may be transformed into high-performance catalytic materials. In this study, the catalytic properties of metallic glass powders were demonstrated in dissociating toxic organic chemicals such as AZO dye. BMG powders showed superior performance compared to state of the art crystalline iron because of their high catalytic activity, durability, and reusability. To enhance the catalytic properties, high energy mechanical milling was performed to increase the surface area and defect density. Iron-based bulk metallic glass (BMG) of composition Fe48Cr15Mo14Y2C15B6 was used because of its low cost and ability to make large surface area by high energy ball milling. AZO dye was degraded in less than 20 minutes for the 9 hours milled Fe-BMG. However, subsequent increase in ball milling time resulted in devitrification and loss of catalytic activity as measured using UV-Visible spectroscopy. Aluminum-based bulk metallic glass (Al-BMG) powder of composition Al82Fe3Ni8Y7 was synthesized by arc-melting the constituent elements followed by gas-atomization. The particle size and morphology were similar to Fe-BMG with a fully amorphous structure. A small percentage of transition metal constituents (Fe and Ni) in a mostly aluminum alloy showed high catalytic activity, with no toxic by-products and no change in surface characteristics. Al-alloy particles, being light-weight, were easily dispersed in aqueous medium and accelerated the redox reactions. The mechanism of dye dissociation was studied using Raman and Infrared (IR) spectroscopy. Breaking of -C-H- and - C-N- bonds of AZO dye was found to be the primary mechanism. Mechanical behavior of individual BMG particles was evaluated by in situ pico-indentation in a scanning electron ...
In recent years, additive manufacturing (AM) has become an increasingly promising method used for the production of structural metallic components. There are a number of reasons why AM methods are attractive, including the ability to produce complex geometries into a near-net shape and the rapid transition from design to production. Ti-6Al-4V is a titanium alloy frequently used in the aerospace industry which is receiving considerable attention as a good candidate for processing via electron beam additive manufacturing (EBAM). The Sciaky EBAM method combines a high-powered electron beam, weld-wire feedstock, and a large build chamber, enabling the production of large structural components. In order to gain wide acceptance of EBAM of Ti-6Al-4V as a viable manufacturing method, it is important to understand broadly the microstructural features that are present in large-scale depositions, including specifically: the morphology, distribution and texture of the phases present. To achieve such an understanding, stereological methods were used to populate a database quantifying key microstructural features in Ti-6Al-4V including volume fraction of phases, a lath width, colony scale factor, and volume fraction of basket weave type microstructure. Microstructural features unique to AM, such as elongated grains and banded structures, were also characterized. Hardness and tensile testing were conducted and the results were related to the microstructural morphology and sample orientation. Lastly, fractured surfaces and defects were investigated. The results of these activities provide insight into the process-structure-properties relationships found in EBAM processed Ti-6Al-4V.
Building waste and disposable packaging are a major component in today's landfills. Most of these are structural or thermally insulative polymer foams that do not degrade over a long period of time. Currently, there is a push to replace these foams with thermoplastic or biodegradable foams that can either be recycled or composted. We propose the use of compostable soy-based polyurethane foams (PU) with kenaf core modifiers that will offer the desired properties with the ability to choose responsible end-of-life decisions. The effect of fillers is a critical parameter in investigating the thermal and mechanical properties along with its effect on biodegradability. In this work, foams with 5%, 10%, and 15% kenaf core content were created. Two manufacturing approaches were used: the free foaming used by spray techniques and the constrained expansion complementary to a mold cavity. Structure-property relations were examined using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermal conductivity, compression values, scanning electron microscopy (SEM), x-ray micro-computed tomography (micro-CT), and automated multiunit composting system (AMCS). The results show that mechanical properties are reduced with the introduction of kenaf core reinforcement while thermal conductivity and biodegradability display a noticeable improvement. This shows that in application properties can be improved while establishing a responsible end-of-life choice.
Magnesium alloys exhibit desirable properties for use in transportation technology. In particular, the low density and high specific strength of these alloys is of interest to the aerospace community. However, the concerns of flammability and susceptibility to corrosion have limited the use of magnesium alloys within the aircraft cabin. This work studies a magnesium alloy containing rare earth elements designed to increase resistance to ignition while lowering rate of corrosion. The microstructure of the alloy was documented using scanning electron microscopy. Specimens underwent salt spray testing and the corrosion products were examined using energy dispersive spectroscopy.
Wear is an important phenomenon that occurs in all the polymer applications in one form or the other. However, important links between materials properties and wear remain illusive. Thus optimization of material properties requires proper understanding of polymer properties. Studies to date have typically lacked systematic approach to all polymers and wear test developed are specific to some polymer classes. In this thesis, different classes of polymers are selected and an attempt is made to use multiple scratch test to define wear and to create a universal test procedure that can be employed to most of the polymers. In each of the materials studied, the scratch penetration depth s reaches a constant value after certain number of scratches depending upon the polymer and its properties. Variations in test parameters like load and speed are also studied in detail to understand the behavior of polymers and under different conditions. Apart from polystyrene, all the other polymers studied under multiple scratch test reached asymptotes at different scratch numbers.
The goal is to perform heat measurements examine of selected roofing material samples. Those roofing materials are asphalt shingles, ceramics, and cedar. It’s important to understand the concept of heat transfer, which consists of conduction, convection, and radiation. Research work was reviewed on different infrared devices to see which one would be suitable for conducting my experiment. In this experiment, the main focus was on a specific property of radiation. That property is the emissivity, which is the amount of heat a material is able to radiate compared to a blackbody. An infrared measuring device, such as the infrared camera was used to determine the emissivity of each sample by using a measurement formula consisting of certain equations. These equations account for the emissivity, transmittance of heat through the atmosphere and temperatures of the samples, atmosphere and background. The experiment verifies how reasonable the data is compared to values in the emissivity table. A blackbody method such as electrical black tape was applied to help generate the correct data. With this data obtained, the emissivity was examined to understand what factors and parameters affect this property of the materials. This experiment was conducted using a suitable heat source to heat up the material samples to high temperature. The measurements were taken during the experiment and displayed by the IR camera. The IR images show the behavior of surface temperatures being distributed throughout the different materials. The main challenge was to determine the most accurate emissivity values for all material samples. The results obtained by the IR camera were displayed in figures and tables at different distances, which was between the heap lamp and materials. The materials exhibited different behaviors in temperature and emissivity at certain distances. The emissivity of each material varied with different temperatures. The results led to suggestions ...
Recent commercial developments have created a need for alternative materials and methods for imparting oil/grease resistance to paper and/or paperboard used in packaging. The performance of a novel grease resistant functional coating comprised of polyvinyl alcohol (PVA), sodium tetraborate pentahydrate (borate) and acetonedicarboxylic acid (ACDA) and the application of said coating by means of flexographic press is presented herein. Application criteria is developed, testing procedures described, and performance assessment of the developed coating materials are made. SEM images along with contact angle data suggest that coating performance is probably attributable to decreased mean pore size in conjunction with a slightly increased surface contact angle facilitated by crosslinking of PVA molecules by both borate ions and ACDA.
Strong size effects in plastic deformation of thin films have been experimentally observed, indicating non-traditional deformation mechanisms. These observations require improved understanding of the behavior of dislocation in small size materials, as they are the primary plastic deformation carrier. Dislocation dynamics (DD) is a computational method that is capable of directly simulating the motion and interaction of dislocations in crystalline materials. This provides a convenient approach to study micro plasticity in thin films. While two-dimensional dislocation dynamics simulation in thin film proved that the size effect fits Hall-Petch equation very well, there are issues related to three-dimensional size effects. In this work, three-dimensional dislocation dynamics simulations are used to study model cooper thin film deformation. Grain boundary is modeled as impenetrable obstacle to dislocation motion in this work. Both tension and cyclic loadings are applied and a wide range of size and geometry of thin films are studied. The results not only compare well with experimentally observed size effects on thin film strength, but also provide many details on dislocation processes in thin films, which could greatly help formulate new mechanisms of dislocation-based plasticity.
Magnesium alloys are the lightweight structural materials with high strength to weigh ratio that permits their application in fuel economy sensitive automobile industries. Among the several flavors of of Mg-alloys, precipitation hardenable Mg-rare earth (RE) based alloys have shown good potential due to their favorable creep resistance within a wide window of operating temperatures ranging from 150°C to 300°C. A key aspect of Mg-RE alloys is the presence of precipitate phases that leads to strengthening of such alloys. Several notable works, in literature, have been done to examine the formation of such precipitate phases. However, there are very few studies that evaluated the effect stress induced deformation on the precipitation in Mg-RE alloys. Therefore, the objective of this work is to examine influence of deformation on the precipitation of Mg-Nd based alloys. To address this problem, precipitation in two Mg-Nd based alloys, subjected to two different deformation conditions, and was examined via transmission electron microscopy (TEM) and atom probe tomography (APT). In first deformation condition, Md-2.6wt%Nd alloy was subjected to creep deformation (90MPa / 177ºC) to failure. Effect of stress-induced deformation was examined by comparing and contrasting with precipitation in non-creep tested specimens subjected to isothermal annealing (at 177ºC). In second condition, Mg-4.0Y-3.0Nd-0.5Zr (wt %) or WE43 alloy (with comparable Nd content as model Mg-Nd system) was subjected to hot rolling deformation at a sub-solvus temperature.
Bulk metallic glasses (BMGs) have received significant research interest due to their completely amorphous structure which results in unique structural and functional properties. Absence of grain boundaries and secondary phases in BMGs results in high corrosion resistance in many different environments. Understanding and tailoring the corrosion behavior can be significant for various structural applications in bulk form as well as coatings. In this study, the corrosion behavior of several Zr-based and Fe-Co based BMGs was evaluated to understand the effect of chemistry as well as quenched in free volume on corrosion behavior and mechanisms. Presence of Nb in Zr-based alloys was found to significantly improve corrosion resistance due to the formation of a stable passive oxide. Relaxed glasses showed lower rates compared to the as-cast alloys. This was attributed to lowering of chemical potential from the reduced fraction of free volume. Potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) techniques helped in quantifying the corrosion rate and polarization resistance. The effect of alloy composition was quantified by extensive surface analysis using Raman spectroscopy, energy dispersive x-ray spectroscopy and auger spectroscopy. Pitting intensity was higher in the as-cast glasses than the relaxed glasses. The electrochemical behavior of a Zr-Ti-Cu-Ni-Be bulk metallic glass subjected to high strain processing was studied. High strain processing caused shear band formation and an increase in the free volume. Potentiodynamic polarization and EIS showed a strong correlation between the enthalpy of structural relaxation and corrosion rate and polarization resistance. Pitting was observed to preferentially occur on shear bands in the processed samples, while it was stochastic in unprocessed glass. The corrosion analysis of Co-Fe glasses showed an increase in corrosion current density when Fe content was increased from 0 to 7 at%. The corrosion resistance improved when Fe content was further increased to 15 at%. Similar trend was ...
Sustainability through replacement of non-renewable fibers with renewable fibers is an ecological need. Impact of transportation costs from South-east Asia on the life cycle analysis of the composite is detrimental. Kenaf is an easily grown crop in America. Farm based processing involves placing the harvested crop in rivers and ponds, where retting of the fibers from the plant (separation into fibers) can take 2 weeks or more. The objective of this thesis is to analyze industrially viable processes for generating fibers and examine their synergistic impact on mechanical performance, surface topography and chemistry for functional composites. Comparison has been made with commercial and conventional retting process, including alkali retting, enzymatic retting, retting in river and pond water (retting occurs by natural microbial population) with controlled microbial retting. The resulting kenaf fibers were characterized by dynamic mechanical analysis (DMA), Raman spectroscopy (FT-Raman), Fourier transform infrared spectroscopy (FT-IR), polarized optical microscopy (POM), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM) optical fluorescence microscopy, atomic force microscopy (AFM) and carbohydrate analysis. DMA results showed that pectinase and microbe treated fibers have superior viscoelastic properties compared to alkali retting. XPS, Raman, FT-IR and biochemical analysis indicated that the controlled microbial and pectinase retting was effective in removing pectin, hemicellulose and lignin. SEM, optical microscopy and AFM analysis showed the surface morphology and cross sectional architecture were preserved in pectinase retting. Experimental results showed that enzymatic retting at 48 hours and controlled microbial retting at 72 hours yield uniform and superior quality fibers compared to alkali and natural retting process. Controlled microbial retting is an inexpensive way to produce quality fibers for polymer composite reinforcement.
Hafnium based high-κ dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in complementary metal oxide semiconductor (CMOS) devices. Hydrogen is one of the most significant elements in semiconductor technology because of its pervasiveness in various deposition and optimization processes of electronic structures. Therefore, it is important to understand the properties and behavior of hydrogen in semiconductors with the final aim of controlling and using hydrogen to improve electronic performance of electronic structures. Trap transformations under annealing treatments in hydrogen ambient normally involve passivation of traps at thermal SiO2/Si interfaces by hydrogen. High-κ dielectric films are believed to exhibit significantly higher charge trapping affinity than SiO2. In this thesis, study of hydrogen trapping in alternate gate dielectric candidates such as HfO2 during annealing in hydrogen ambient is presented. Rutherford backscattering spectroscopy (RBS), elastic recoil detection analysis (ERDA) and nuclear reaction analysis (NRA) were used to characterize these thin dielectric materials. It was demonstrated that hydrogen trapping in bulk HfO2 is significantly reduced for pre-oxidized HfO2 prior to forming gas anneals. This strong dependence on oxygen pre-processing is believed to be due to oxygen vacancies/deficiencies and hydrogen-carbon impurity complexes that originate from organic precursors used in chemical vapor depositions (CVD) of these dielectrics.
In this thesis, I utilize first principles density functional theory (DFT) based calculations to investigate the structure and electronic properties including charge transfer behaviors and work function of two types of materials: pentacene based organic semiconductors and ZnO transparent conducting oxides, with an aim to search for high mobility n-type organic semiconductors and fine tuning work functions of ZnO through surface modifications. Based on DFT calculations of numerous structure combinations, I proposed a pentacene and perfluoro-pentacene alternating hybrid structures as a new type of n-type semiconductor. Based on the DFT calculations and Marcus charge transfer theory analysis, the new structure has high charge mobility and can be a promising new n-type organic semiconductor material. DFT calculations have been used to systematically investigate the effect of surface organic absorbate and surface defects on the work function of ZnO. It was found that increasing surface coverage of organic groups and decreasing surface defects lead to decrease of work functions, in excellent agreement with experimental results. First principles based calculations thus can greatly contribute to the investigating and designing of new electronic materials.
PVC are extensively applied in many fields, such as cables, pipes, vehicles, shoes, toys and infusion bags. Generally, plasticizers are blended with PVC to improve the ability of process in industrial production; however, the toxic plasticizers will gradually migrate to the surface of products and such a leakage results in brittleness of plasticized PVC and environmental pollution. In other words, humans are frequently exposed to the potential risks. According to previous researches, cross-linked PVC was proved that it was able to hinder the migration of plasticizer. Thus, in this research, we selected some commercially used cross-linking agents and employed six different tests based on mechanical, tribological and microscopy analysis in order to seek the best solution against plasticizer migration. Thus, we expected to develop a cross-linked flexible PVC which performed improved long-term performance and extended lifetime.
Nanoindentation has brought in many features of research over the past decade. This novel technique is capable of producing insights into the small ranges of deformation. This special point has brought a lot of focus in understanding the deformation behavior under the indenter. Nickel, iron, tungsten and copper-niobium alloy system were considered for a surface deformation study. All the samples exhibited a spectrum of residual deformation. The change in behavior with indentation and the materials responses to deformation at low and high loads is addressed in this study. A study on indenter geometry, which has a huge influence on the contact area and subsequently the hardness and modulus value, has been attempted. Deformation mechanisms that govern the plastic flow in materials at low loads of indentation and their sensitivity to the rate of strain imparted has been studied. A transition to elastic, plastic kind of a tendency to an elasto-plastic tendency was seen with an increase in the strain rate. All samples exhibited the same kind of behavior and a special focus is drawn in comparing the FCC nickel with BCC tungsten and iron where the persistence of the elastic, plastic response was addressed. However there is no absolute reason for the inconsistencies in the mechanical properties observed in preliminary testing, more insights can be provided with advanced microscopy techniques where the study can be focused more to understand the deformation behavior under the indenter. These experiments demonstrate that there is a wealth of information in the initial stages of indentation and has led to much more insights into the incipient stages of plasticity.
In this study an initial assessment of the composition – microstructure – property relationships in binary and ternary Ti – based systems are made possible using LENSTM technology. Laser Engineering Net Shaping (LENSTM), a rapid prototyping, directed laser deposition methodology of additive manufacturing (AM) was used to create bulk homogenous specimens that are compositionally graded. Compositionally graded specimens were made possible by incorporating elemental blends of powder during the LENSTM process. While there have been numerous studies assessing the influence of common elements (e.g., V, Mo, Al, and Cr) on the resulting microstructure in titanium alloys, other elements have been neglected. A systematic study of the Ti – Fe – Al ternary system based upon varying compositions of the eutectoid former, Fe with Al to stabilize the a and b phases respectively has also been neglected. This research effort focuses on exploiting the LENSTM process by rapidly assessing the composition – microstructure – property relationships in a combinatorial approach for the Ti – W, Ti – Fe, and Ti – Fe – Al systems. Compositionally graded specimens of Ti – xW (0<x<40wt.%(14.79at.%)), Ti – xFe (0<x<35wt.%(36.37at.%)), and Ti – xFe – yAl (0<x<40wt.%(36.37at.%)), y=5,10, 15wt.%) have been heat treated to also assess the influence of thermal history on microstructural features such as phase composition and volume fraction. Lastly, a Ti – xMo (0<x<40wt.%(24.96at.%)) compositionally graded specimen was deposited to re-assess the Mo-equivalency nature of W, as well as assess the role of phase separation in microstructural evolution at temperatures above and below the invariant point (~695°C) of the Ti – W binary system.
It is highly desirable to be able to make predictions of properties in metallic materials based upon the composition of the material and the microstructure. Unfortunately, the complexity of real, multi-component, multi-phase engineering alloys makes the provision of constituent-based (i.e., composition or microstructure) phenomenological equations extremely difficult. Due to these difficulties, qualitative predictions are frequently used to study the influence of microstructure or composition on the properties. Neural networks were used as a tool to get a quantitative model from a database. However, the developed model is not a phenomenological model. In this study, a new method based upon the integration of three separate modeling approaches, specifically artificial neural networks, genetic algorithms, and monte carlo was proposed. These three methods, when coupled in the manner described in this study, allows for the extraction of phenomenological equations with a concurrent analysis of uncertainty. This approach has been applied to a multi-component, multi-phase microstructure exhibiting phases with varying spatial and morphological distributions. Specifically, this approach has been applied to derive a phenomenological equation for the prediction of yield strength in a+b processed Ti-6-4. The equation is consistent with not only the current dataset but also, where available, the limited information regarding certain parameters such as intrinsic yield strength of pure hexagonal close-packed alpha titanium.
Mechanics of bone is widely studied and researched, mainly for the study of fracture. This has been done mostly on a macro scale. In this work hierarchical nature of bone has been explored to investigate bone mechanics in more detail. Flexural test were done to classify the bones according to their strength and deflection. Raman spectroscopy analysis was done to map the mineralization, collagen crosslinking changes across the thickness of the bone. Nanoindentation was done to map indentation hardness and indentation modulus across femoral cortex of the bone. The results indicate that the composition of the bone changes across the thickness of the femoral cortex. The hypothesis is confirmed as increase in mineralization, carbonate to phosphate ratio and collagen crosslinking shows the effect as increased indentation hardness and modulus and decreased deflection.
Absorption of octadecanethiol and p-nitrobenzenethiol onto gold surfaces from ethanol solutions has been studied by means of contact angle, optical ellipsometry, angle-resolved XPS (ARXPS), and with grazing angle total reflection FTIR. Growth of the monolayers from dilute solutions has been monitored and Langmuir isotherm adsorption curves were fitted to experimental data. A saturated film is formed within approximately 5h after immersion in solutions of concentrations ranging from 0.0005mM to 0.01mM. We found, that the final density of monolayer depends on the concentration of the solution.
A matrix of variably processed Fe-30at%Ni was deposited with variations in laser travel speeds as well and laser powers. A complete shift in phase stability occurred as a function of varying laser travel speed. At slow travel speeds, the microstructure was dominated by a columnar fcc phase. Intermediate travel speeds yielded a mixed microstructure comprised of both the columnar fcc and a martensite-like bcc phase. At the fastest travel speed, the microstructure was dominated by the bcc phase. This shift in phase stability subsequently affected the magnetic properties, specifically saturation magnetization. Ni-Fe-Mo and Ni-Fe-V permalloys were deposited from an elemental blend of powders as well. Both systems exhibited featureless microstructures dominated by an fcc phase. Magnetic measurements yielded saturation magnetizations on par with conventionally processed permalloys, however coercivities were significantly larger; this difference is attributed to microstructural defects that occur during the additive manufacturing process.
The present research seeks to characterization of an additively manufactured and heat-treated Ti-xMn gradient alloy, a binary system that has largely been unexplored. In order to rapidly assess this binary system, compositionally graded Ti-xMn (0<x<15 wt%) specimens were fabricated using the LENS (Laser Engineered Net Shaping) and were subsequently heat-treated and characterized using a wide range of techniques. Microstructural changes with respect to the change in thermal treatments, hardness and chemical composition were observed and will be presented. These include assessments of both continuous cooling, leading to observations of both equilibrium and metastable phases, including the titanium martensites, and to direct aging studies looking for composition regimes that produce highly refined alpha precipitates – a subject of great interest given recent understandings of non-classical nucleation and growth mechanisms. The samples were characterized using SEM, EDS, TEM, and XRD and the properties probed using a Vickers Microhardness tester.
Laser surface modification involves rapid melting and solidification is an elegant technique used for locally tailoring the surface morphology of alumina in order to enhance its abrasive characteristics. COMSOL Multiphysics® based heat transfer modeling and experimental approaches were designed and used in this study for single and multiple laser tracks to achieve densely-packed multi-facet grains via temperature history, cooling rate, solidification, scanning electron micrographs, and wear rate. Multi-facet grains were produced at the center of laser track with primary dendrites extending toward the edge of single laser track. The multiple laser tracks study indicates the grain/dendrite size increases as the laser energy density increases resulting in multiplying the abrasive edges which in turn enhance the abrasive qualities.
Laser surface modification of AZ31B Magnesium alloy changes surface composition and roughness to provide improved surface bio-wettability. Laser processing resulted in phase transformation and grain refinement due to rapid quenching effect. Furthermore, instantaneous heating and vaporization resulted in removal of material, leading the textured surface generation. A study was conducted on a continuum-wave diode-pumped ytterbium laser to create multiple tracks for determining the resulting bio-wettability. Five different laser input powers were processed on Mg alloy, and then examined by XRD, SEM, optical profilometer, and contact angle measurement. A finite element based heat transfer model was developed using COMSOL multi-physics package to predict the temperature evolution during laser processing. The thermal histories predicted by the model are used to evaluate the cooling rates and solidification rate and the associated changes in the microstructure. The surface energy of laser surface modification samples can be calculated by measuring the contact angle with 3 different standard liquid (D.I water, Formamide, and 1-Bromonaphthalen). The bio-wettability of the laser surface modification samples can be conducted by simulated body fluid contact angle measurement. The results of SEM, 3D morphology, XRD, and contact angle measurement show that the grain size and roughness play role for wetting behavior of laser processing Mg samples. Surface with low roughness and large grain size performs as hydrophilicity. On the contrast, surface with high roughness and small grain size performs as hydrophobicity.
Single wall carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were dispersed in mineral oil and epoxy resin. The magnetorheological properties of these dispersions were studied using a parallel plate rheometer. Strain sweeps, frequency sweeps, magneto sweeps and steady shear tests were conducted in various magnetic fields. G', G", h* and ty increased with increasing magnetic field, which was partially attributed to the increasing degree of the alignment of nanotubes in a stronger magnetic field. The SWNT/mo dispersions exhibited more pronounced magnetic field dependence than SWNT/ep and MWNT/mo counterparts due to their much lower viscosity. The alignment of SWNTs in mineral oil increased with rising nanotube concentration up to 2.5vol% but were significantly restricted at 6.41vol% due to nanotube flocculation.
Polymeric coatings are being used in a growing number of applications, contributing to protection against weather conditions and localized corrosion, reducing the friction and erosion wear on the substrate. In this study, various polypropylene (PP) coatings were applied onto steel substrates by compression molding. Chemical modification of PP has been performed to increase its adhesion to metallic surfaces by grafting of maleic anhydride (MAH) onto PP in the presence of dicumyl peroxide (DCP). Influence of different concentrations of MAH and DCP on the properties of resulting materials have been examined. The coated steel samples are characterized by scanning electron microscopy (SEM), shear adhesion testing, FTIR and tribometry. The coatings with 3 wt. % MAH have shown the maximum adhesion strength due to maximum amount of grafting. The wear rates increased with increasing the amount of MAH due to simultaneous increase in un-reacted MAH.
Low density polyethylene (LDPE) and Hytrel (a thermoplastic elastomer) were used as polymeric matrices in polymer + metal composites. The concentration of micrometric (Al, Ag and Ni) as well as nanometric particles (Al and Ag) was varied from 0 to 10 %. Composites were prepared by blending followed by injection molding. The resulting samples were analyzed by scanning electron microscopy (SEM) and focused ion beam (FIB) in order to determine their microstructure. Certain mechanical properties of the composites were also determined. Static and dynamic friction was measured. The scratch resistance of the specimens was determined. A study of the wear mechanisms in the samples was performed. The Al micro- and nanoparticles as well as Ni microparticles are well dispersed throughout the material while Ag micro and nanoparticles tend to form agglomerates. Generally the presence of microcomposites affects negatively the mechanical properties. For the nanoparticles, composites with a higher elastic modulus than that of the neat materials are achievable. For both micro- and nanocomposites it is feasible to lower the friction values with respective to the neat polymers. The addition of metal particles to polymers also improves the scratch resistance of the composites, particularly so for microcomposites. The inclusion of Ag and Ni particles causes an increase in the wear loss volume while Al can reduce the wear for both polymeric matrices.
A compositionally graded Ti-xCr (10≤x≤30 wt%) alloy has been fabricated using Laser Engineered Net Shaping (LENSTM) to study the microstructural phase evolution along a compositional gradient in both as-deposited and heat treated conditions (1000°C followed by furnace cooling or air cooling). The alloys were characterized by SEM BSE imaging, XRD, EBSD, TEM and micro-hardness measurements to determine processing-structure-property relations. For the as-deposited alloy, α-Ti, β-Ti, and TiCr2 (C15 Laves) phases exist in varying phase fractions, which were influential in determining hardness values. With the furnace cooled alloy, there was more homogeneous nucleation of α phase throughout the sample with a larger phase fraction of TiCr2 resulting in increased hardness values. When compared to the air cooled alloy, there was absence of wide scale nucleation of α phase and formation of ω phase within the β phase due to the quicker cooling from elevated temperature. At lower concentrations of Cr, the kinetics resulted in a diffusionless phase transformation of ω phase with increased hardness and a lower phase fraction of TiCr2. In contrast at higher Cr concentrations, α phase separation reaction occurs where the β phase is spinodally decomposed to Cr solute-lean β1 and solute-rich β2 resulting in reduced hardness.
Ni/TiC metal matrix composites have been processed using the laser engineered net shaping (LENS) process. As nickel does not form an equilibrium carbide phase, addition of a strong carbide former in the form of titanium reinforces the nickel matrix resulting in a promising hybrid material for both surface engineering as well as high temperature structural applications. Changing the relative amounts of titanium and carbon in the nickel matrix, relatively low volume fraction of refined homogeneously distributed carbide precipitates, formation of in-situ carbide precipitates and the microstructural changes are investigated. The composites have been characterized in detail using x-ray diffraction, scanning electron microscopy (including energy dispersive spectroscopy (XEDS) mapping and electron backscatter diffraction (EBSD)), Auger electron spectroscopy, and transmission (including high resolution) electron microscopy. Both primary and eutectic titanium carbides, observed in this composite, exhibited the fcc-TiC structure (NaCl-type). Details of the orientation relationship between Ni and TiC have been studied using SEM-EBSD and high resolution TEM. The results of micro-hardness and tribology tests indicate that these composites have a relatively high hardness and a steady-state friction coefficient of ~0.5, both of which are improvements in comparison to LENS deposited pure Ni.
A commercial epoxy was modified by adding fluorinated poly (aryl ether ketone) and in turn metal micro powders (Ni, Al, Zn, and Ag) and coated on mild steel. Two curing agents were used; triethylenetetramine (curing temperatures: 30 oC and 70 oC) and hexamethylenediamine (curing temperature: 80 oC). Variation in tribological properties (dynamic friction and wear) and surface energies with varying metal powders and curing agents was evaluated. When cured at 30 oC, friction and wear decreased significantly due to phase separation reaction being favored but increased when cured at 70 oC and 80 oC due to cross linking reaction being favored. There was a significant decrease in surface energies with the addition of modifiers.
Rare earth ion doped glasses find applications in optical and photonic devices such as optical windows, laser, and optical amplifiers, and as model systems for immobilization of nuclear waste. Macroscopic properties of these materials, such as luminescence efficiency and phase stability, depend strongly on the atomic structure of these glasses. In this thesis, I have studied the atomic level structure of rare earth doped silicate and aluminophosphate glasses by using molecular dynamics simulations. Extensive comparisons with experimental diffraction and NMR data were made to validate the structure models. Insights on the local environments of rare earth ions and their clustering behaviors and their dependence on glass compositions have been obtained. In this thesis, MD simulations have been used to investigate the structure of Eu2O3-doped silica and sodium silicate glasses to understand the glass composition effect on the rare earth ions local environment and their clustering behaviors in the glass matrix, for compositions with low rare earth oxide concentration (~1mol%). It was found that Eu–O distances and coordination numbers were different in silica (2.19-2.22 Å and 4.6-4.8) from those in sodium silicate (2.32 Å and 5.8). High tendencies of Eu clustering and short Eu-Eu distances in the range 3.40-3.90 Å were observed in pure silica glasses as compared to those of silicate glasses with much better dispersed Eu3+ ions and lower probability to form clusters. The results show Eu3+ clustering behavior dependence on the system size and suggest for low doping levels, over 12,000 atoms to obtain statistical meaningful results on the local environment and clustering for rigid silica-based glasses. The structures of four cerium aluminophosphate glasses have also been studied using MD simulations for systems of about 13,000 atoms to investigate aluminum and cerium ion environment and their distribution. P5+ and Al3+ local structures were found stable while those of ...
The effect of incorporation of montmorillonite layered silicate (MLS) on poly (ethylene terephthalate) (PET) matrix was investigated. MLS was added in varying concentration of 1 to 5 weight percent in the PET matrix. DSC and polarized optical microscopy were used to determine the crystallization effects of MLS addition. Non isothermal crystallization kinetics showed that the melting temperature and crystallization temperature decrease as the MLS percent increases. This delayed crystallization along with the irregular spherulitic shape indicates hindered crystallization in the presence of MLS platelets. The influence of this morphology was related with the fracture toughness of PET nanocomposites using essential work of fracture coupled with the infra red (IR) thermography. Both the essential as well as non essential work of fracture decreased on addition of MLS with nanocomposite showing reduced toughness.
Polymer nanocomposites are a going part of Materials Science and Engineering. These new composite materials exhibit dimensional and thermal stability of inorganic materials and toughness and dielectric properties of polymers. Development of nanocomposites become an important approach to create high-performance composite materials. In this study silica, fly ash, silica nanotubes and carbon black particles have been added to modify polyurethane foam and thermoplastic polyurethanes. It has been found that the addition of silica can diminish the size of foam bubbles, resulting in an increased stiffness of the material, increase of the compressive strength, and greater resistance to deformation. However, the uniformity of bubbles is reduced, resulting in increased friction of the material. Fly ash added to the foam can make bubbles smaller and improve uniformity of cells. Therefore, the material stiffness and compressive strength, resistance to deformation, and has little impact on the dynamic friction of the material. Adding nanotubes make bubble size unequal, and the arrangement of the bubble uneven, resulting in decreased strength of the material, while the friction increases. After the addition of carbon black to the polyurethane foam, due to the special surface structure of the carbon black, the foam generates more bubbles during the foaming process changing the foam structure. Therefore, the material becomes soft, we obtain a flexible polyurethane foam. The results of mechanical properties determination of the thermoplastic polyurethane that adding particles may increase the stiffness and wear resistance of the thermoplastic polyurethane, while the tensile properties of the material are reduced. This phenomenon may be due to agglomeration of particles during the mixing process. Possibly the particles cannot be uniformly dispersed in the thermoplastic polyurethane.
This study deals with crystal orientation effect along with the effects of microstructure on the pile-ups which affect the nanoindentation measurements. Two metal classes, face centered cubic (FCC) and body centered cubic (BCC, are dealt with in the present study. The objective of this study was to find out the degree of inaccuracy induced in nanoindentation measurements by the inherent pile-ups and sink-ins. Also, it was the intention to find out how the formation of pile-ups is dependant upon the crystal structure and orientation of the plane of indentation. Nanoindentation, Nanovision, scanning electron microscopy, electron dispersive spectroscopy and electron backscattered diffraction techniques were used to determine the sample composition and crystal orientation. Surface topographical features like indentation pile-ups and sink-ins were measured and the effect of crystal orientation on them was studied. The results show that pile-up formation is not a random phenomenon, but is quite characteristic of the material. It depends on the type of stress imposed by a specific indenter, the depth of penetration, the microstructure and orientation of the plane of indentation. Pile-ups are formed along specific directions on a plane and this formation as well as the pile-up height and the contact radii with the indenter is dependant on the aforesaid parameters. These pile-ups affect the mechanical properties like elastic modulus and hardness measurements which are pivotal variables for specific applications in micro and nano scale devices.
This thesis examines the value of using dispersed conductive fillers as a stress/strain sensing material. The effect of the intrinsic conductivity of the filler on the ability to be effective and the influence of filler concentration on the conductivity are also examined. To meet these objectives, nanocomposites of polyvinylidene fluoride (PVDF) with carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were prepared by melt-blending using a twin screw extruder. Since PVDF has a potential to be piezoresistive based on the type of crystalline phase, the effect of CNFs on PVDF crystallinity, crystalline phase, quasi static and dynamic mechanical property was studied concurrently with piezoresponse. Three time dependencies were examined for PVDF/CNTs nanocomposites: quasi-static, transient and cyclic fatigue. The transient response of the strain with time showed viscoelastic behavior and was modeled by the 4-element Burger model. Under quasi-static loading the resistance showed negative pressure coefficient below yield but changed to a positive pressure coefficient after yield. Under cyclic load, the stress-time and resistance-time were synchronous but the resistance peak value decreased with increasing cycles, which was attributed to charge storage in the nanocomposite. The outcomes of this thesis indicate that a new piezoresponsive system based on filled polymers is a viable technology for structural health monitoring.
The effect of incorporation two clays; layered double hydroxides (LDH) and montmorillonite layered silicates (MLS) in linear low density polyethylene (PE) matrix was investigated. MLS and LDH were added of 5, 15, 30 and 60 weight percent in the PE and compounded using a Brabender. Ground pellets were subsequently compression molded. Dispersion of the clays was analyzed using optical microscopy, SEM and XRD. Both the layered clays were immiscible with the PE matrix and agglomerates formed with increased clay concentration. The thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Both clays served as nucleation enhancers increasing recrystallization temperatures in the composites. Flame retarding properties were determined by using the flammability HVUL-94 system. LDH indicated better flame retarding properties than MLS for PE. The char structure was analyzed by environmental scanning electron microscopy. Mechanical properties were studied by tensile testing and Vickers microhardness testing apparatus.
Since their discovery in the 1930s, polymeric foams have been widely used in the industry for a variety of applications such as acoustical and thermal insulation, filters, absorbents etc. The reason for this ascending trend can be attributed to factors such as cost, ease of processing and a high strength to weight ratio compared to non-foamed polymers. The purpose of this project was to develop an “indestructible” material made of polycarbonate (PC) for industrial applications. Due to the high price of polycarbonate, two foaming methods were investigated to reduce the amount of material used. Samples were foamed physically in supercritical CO2 or chemically with 5-phenyl-1H-tetrazole. After thermal characterization of the foams in differential scanning calorimetry (DSC), we saw that none of the foaming methods had an influence on the glass transition of polycarbonate. Micrographs taken in scanning electron microscopy (SEM) showed that foams obtained in physical and chemical foaming had different structures. Indeed, samples foamed in supercritical CO2 exhibited a microcellular opened-cell structure with a high cell density and a homogeneous cell distribution. On the other hand, samples foamed with 5-phenyl-1H-tetrazole had a macrocellular closed-cell structure with a much smaller cell density and a random cell distribution. Compression testing showed that polycarbonate foamed physically had a compression modulus a lot greater. Then, XLPE mesh 35 or 50 and wollastonite were added to the polymeric matrices to enhance the foaming process and the mechanical properties. DSC experiments showed that the addition of fillers changed the thermal properties of polycarbonate for both foaming methods by inducing a shift in glass transition. SEM revealed that fillers lowered the average cell diameter and increased the cell density. This phenomenon increased the compression modulus for polycarbonate foamed in supercritical CO2. However, mechanical properties decreased for samples foamed with 5-phenyl-1H-tetrazole due to their relative brittleness and ...
Solid lubricant coatings with controlled microstructures are good candidates in providing lubricity in moving mechanical assembly applications, such as orthopedics and bearing steels. Nanocrystalline ZnO coatings with a layered wurtzite crystal structure have the potential to function as a lubricious material by its defective structure which is controlled by sputter deposition. The interrelationships between sputtered ZnO, its nanocrystalline structure and its lubricity will be discussed in this thesis. The nanocrystalline ZnO coatings were deposited on silicon substrates and Ti alloys by RF magnetron sputtering with different substrate adhesion layers, direct current biases, and temperatures. X-ray diffraction identified that the ZnO (0002) preferred orientation was necessary to achieve low sliding friction and wear along with substrate biasing. In addition, other analyses such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) were utilized to study the solid lubrication mechanisms responsible for low friction and wear.
Polystyrene (PS) nanocomposite foams were prepared using supercritical fluid (SCF) CO2 as a solvent and blowing agent. PS was first in-situ polymerized with a range of concentrations of montmorillonite layered silicate (MLS). The polymerized samples were then compression molded into 1 to 2mm thick laminates. The laminates were foamed in a batch supercritical CO2 process at various temperatures and pressures from 60°-85°C and 7.6-12MPa. The resulting foams were analyzed by scanning electron microscopy to determine effect of MLS on cellular morphology. Differential scanning calorimetry was used to determine the impact of nanocomposite microstructure on glass transition of the foamed polymer. X-ray diffraction spectra suggested that the PS/MLS composite had an intercalated structure at both the 1% and 3% mixtures, and that the intercalation may be enhanced by the foaming process.
It is impossible to determine the amount of money that is spent every replacing products damaged from wear, but it is safe to assume that it is in the millions of dollars. With metallic materials, liquid lubricants are often used to prevent wear from materials rubbing against one another. However, with polymeric materials, liquid lubricants cause swelling, creating an increase in friction and therefore increasing the wear. Therefore, a different method or methods to mitigate wear in polymers should be developed. For better understanding of the phenomenon of wear, scratch resistance testing can be used. For this project, classic molecular dynamics is used to study the mechanics of nanometer scale scratching on amorphous polymeric materials. As a first approach, a model was created for polyethylene, considering intramolecular and intermolecular interactions as well as mass and volume of the CH2 monomers in a polymer chain. The obtained results include analysis of penetration depth and recovery percentage related to indenter force and size.
Structure-tribological property relations have been studied for five high entropy alloys (HEAs). Microhardness, room and elevated (100°C and 300°C) temperature sliding friction coefficients and wear rates were determined for five HEAs: Co0.5 Cr Cu0.5 Fe Ni1.5 Al Ti0.4; Co Cr Fe Ni Al0.25 Ti0.75; Ti V Nb Cr Al; Al0.3CoCrFeNi; and Al0.3CuCrFeNi2. Wear surfaces were characterized with scanning electron microscopy and micro-Raman spectroscopy to determine the wear mechanisms and tribochemical phases, respectively. It was determined that the two HEAs Co0.5 Cr Cu0.5 Fe Ni1.5 Al Ti0.4 and Ti V Nb Cr Al exhibit an excellent balance of high hardness, low friction coefficients and wear rates compared to 440C stainless steel, a currently used bearing steel. This was attributed to their more ductile body centered cubic (BCC) solid solution phase along with the formation of tribochemical Cr oxide and Nb oxide phases, respectively, in the wear surfaces. This study provides guidelines for fabricating novel, low-friction, and wear-resistant HEAs for potential use at room and elevated temperatures, which will help reduce energy and material losses in friction and wear applications.
The thesis studied quantized conductance in nanocontacts formed between two thin gold wires with one of the wires coated by alkainthiol self assembly monolayers (SAM), by using the cross-wire junction. Using the Lorenz force as the driving force, we can bring the two wires in contact in a controlled manner. We observed conductance with steps of 2e2 / h. The conductance plateaus last several seconds. The stability of the junction is attributed to the fact that the coating of SAM improves the stability and capability of the formed contact.
Lead's uptake on magnetite has been quantitatively evaluated in the present study at a temperature of 200°C and pH of 8.5 with lead concentrations ranging from 5 ppm to175 ppm by equilibrium adsorption isotherms. The pH independent sorption behavior suggested lead sorption due to pH independent permanent charge through weak electrostatic, non-specific attraction where cations are sorbed on the cation exchange sites. The permanent negative charge could be a consequence of lead substitution which is supported by increase in the lattice parameter values from the X-ray diffraction (XRD) results. Differential scanning calorimetry (DSC/TGA) results showed an increase of exothermic (magnetite to maghemite transformation) peak indicating substitution of lead ions due to which there is retardation in the phase transformation. Presence of outer sphere complexes and physical sorption is further supported by Fourier transformed infrared spectroscopy (FTIR). None of the results suggested chemisorption of lead on magnetite.
Metastable b-Ti alloys are titanium alloys with sufficient b stabilizer alloying additions such that it's possible to retain single b phase at room temperature. These alloys are of great advantage compared to a/b alloys since they are easily cold rolled, strip produced and can attain excellent mechanical properties upon age hardening. Beta 21S, a relatively new b titanium alloy in addition to these general advantages is known to possess excellent oxidation and corrosion resistance at elevated temperatures. A homogeneous distribution of fine sized a precipitates in the parent b matrix is known to provide good combination of strength, ductility and fracture toughness. The current work focuses on a study of different mechanisms to engineer homogeneously distributed fine sized a precipitates in the b matrix. The precipitation of metastable phases upon low temperature aging and their influence on a precipitation is studied in detail. The precipitation sequence on direct aging above the w solvus temperature is also assessed. The structural and compositional evolution of precipitate phase is determined using multiple characterization tools. The possibility of occurrence of other non-classical precipitation mechanisms that do not require heterogeneous nucleation sites are also analyzed. Lastly, the influence of interstitial element, oxygen on a precipitation during the oxidation of Beta 21S has been determined. The ingress of oxygen and its influence on microstructure have also been correlated to measured mechanical properties.
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