Conventional liquid lubricants are faced with limitations under extreme cyclic operating conditions, such as in applications that require lubrication when changing from atmospheric pressure to ultrahigh vacuum and ambient air to dry nitrogen (e.g., satellite components), and room to elevated (>500°C) temperatures (e.g., aerospace bearings). Alternatively, solid lubricant coatings can be used in conditions where synthetic liquid lubricants and greases are not applicable; however, individual solid lubricant phases usually perform best only for a limited range of operating conditions. Therefore, solid lubricants that can adequately perform over a wider range of environmental conditions are needed, especially during thermal cycling with temperatures exceeding 500°C. One potential material class investigated in this dissertation is lubricious oxides, because unlike other solid lubricant coatings they are typically thermodynamically stable in air and at elevated temperatures. While past studies have been focused on binary metal oxide coatings, such as ZnO, there have been very few ternary oxide and no reported quaternary oxide investigations. The premise behind the addition of the third and fourth refractory metals Ti and Zr is to increase the number of hard and wear resistant phases while maintaining solid lubrication with ZnO. Therefore, the major focus of this dissertation is to investigate …

The thermophysical properties and deformation behavior of a systematic series of model metallic glasses was investigated. For Zr-based metallic glasses with all metallic constituents, the activation energy of glass transition was determined to be in the range of 74-173 kJ/mol while the activation energy of crystallization was in the range of 155-170 kJ/mol. The reduced glass transition temperature was roughly the same for all the alloys (~ 0.6) while the supercooled liquid region was in the range of 100-150 K, indicating varying degree of thermal stability. In contrast, the metal-metalloid systems (such as Ni-Pd-P-B) showed relatively higher activation energy of crystallization from short range ordering in the form of triagonal prism clusters with strongly bonded metal-metalloid atomic pairs. Deformation mechanisms of all the alloys were investigated by uniaxial compression tests, strain rate sensitivity (SRS) measurements, and detailed characterization of the fracture surface morphology. For the metal-metal systems, plasticity was found to be directly correlated with shear transformation zone (STZ) size, with systems of larger STZ size showing better plasticity. In metal-metalloid amorphous alloys, plasticity was limited by the distribution of STZ units, with lower activation energy leading to more STZ units and better plasticity. The alloys with relatively higher plasticity …

In this study, the surface degradation behavior was studied for typical examples from bulk metallic glasses (BMGs), metallic glass composites (MGCs) and high entropy alloys (HEAs) alloy systems that are of scientific and commercial interest. The corrosion and wear behavior of two Zr-based bulk metallic glasses, Zr41.2Cu12.5Ni10Ti13.8Be22.5 and Zr57Cu15.4Ni12.6Al10Nb5, were evaluated in as-cast and thermally relaxed states. Significant improvement in corrosion rate, wear behavior, and friction coefficient was seen for both the alloys after thermal relaxation. Fully amorphous structure was retained with thermal relaxation below the glass transition temperature. This improvement in surface properties was explained by annihilation of free volume, the atomic scale defects in amorphous metals resulting from kinetic freezing. Recently developed MGCs, with in situ crystalline ductile phase, demonstrate a combination of mechanical properties and fracture behavior unseen in known structural metals. The composites showed higher wear rates but lower coefficient of friction compared to monolithic amorphous glasses. No tribolayer formation was seen for the composites in sharp contrast to that of the monolithic metallic glasses. Corrosion was evaluated by open circuit potential (OCP) analysis and potentiodynamic polarization. Site-specific corrosion behavior was studied by scanning vibration electrode technique (SVET) to identify formation of galvanic couples. Scanning kelvin …

The design and fabrication of porous ceramic materials with anisotropic properties has, in recent years, gained popularity due to their potential application in various areas that include medical, energy, defense, space, and aerospace. Freeze-casting is an effective, low-cost, and safe method as a wet shaping technique to create these structures. To control the morphology of these materials, many critical factors were found to play an important role. In this dissertation, the processing parameters of the magnetic field-assisted freeze-casting method were optimized with a focus on comparing the structure obtained using vertical and horizontal magnetic fields and understanding the mechanisms that occur under different freezing modes. More specifically, this processing method was used to produce Al2O3 and B4C porous ceramics materials with unidirectionally-aligned pore channels. The effect of the vertical and horizontal magnetic field strength and direction, concentration of magnetic material (Fe3O4), cooling rate, and freezing time were examined. The resulting ceramics with highly aligned pore channels were infiltrated with molten metal to create metal matrix composites. The mechanical properties of these structures were measured and were subsequently correlated to their morphology and composition.

A systematic development of 2D alloy catalyst with synergistic performance of high lithium polysulfide (LiPS) binding energy and efficient Li+ ion/electron conduction is presented. The first section of work found that Li+ ions can flow through the percolated ion transport pathway in polycrystalline MoS2, while Na+ and K+ ions can easily flow through the percolated 1D ion channel near the grain boundaries. An unusually high ionic conductivity of extrinsic Li+, Na+, and K+ ions in 2D MoS2 film exceeding 1 S/cm was measured that is more than two orders of magnitude higher than those of conventional solid ionic materials, including 2D ionic materials. The second section of this dissertation focus on catalyzing the transformation of LiPSs to prevent the shuttle effect during the battery cycling by synthesizing 2H (semiconducting) – 1T (metallic) mixed phase 2D Mo0.5W0.5S2 alloy on CNF paper, using two step sputtering and sulfurization method. The lithium sulfur (Li-S) battery cell assembled with the 2D Mo0.5W0.5S2/CNF/S cathode shows a high specific capacity of 1228 mAh g-1 at 0.1C and much higher cyclic stability over 4 times as compared to the pristine cathodes. The high LiPSs binding energy of catalyst efficiently prevents the shuttling effect and corrosion of Li …

Carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) are attractive reinforcements for lightweight and high strength metal matrix composites due to their excellent mechanical and physical properties. The present work is an attempt towards investigating the effect of CNT and GNP reinforcements on the mechanical properties of nickel matrix composites. The CNT/Ni (dry milled) nanocomposites exhibiting a tensile yield strength of 350 MPa (about two times that of SPS processed monolithic nickel ~ 160 MPa) and an elongation to failure ~ 30%. In contrast, CNT/Ni (molecular level mixed) exhibited substantially higher tensile yield strength (~ 690 MPa) but limited ductility with an elongation to failure ~ 8%. The Ni-1vol%GNP (dry milled) nanocomposite exhibited the best balance of properties in terms of strength and ductility. The enhancement in the tensile strength (i.e. 370 MPa) and substantial ductility (~40%) of Ni-1vol%GNP nanocomposites was achieved due to the combined effects of grain refinement, homogeneous dispersion of GNPs in the nickel matrix, and well-bonded Ni-GNP interface, which effectively transfers stress across metal-GNP interface during tensile deformation. A second emphasis of this work was on the detailed 3D microstructural characterization of a new class of Ni-Ti-C based metal matrix composites, developed using the laser engineered net …

Two series monodispersed nanoparticles of hydroxylpropyl cellulose (HPC) and functionalized poly-N-isopropylamide (PNIPAM) particles have been synthesized and used as building blocks for creating three-dimensional networks, with two levels of structural hierarchy. The first level is HPC nanoparticles were made from methacrylated or degradable cross-linker attached HPC. These nanoparticles could be stabilized at room temperature by residual methacrylate or degradable groups are present both within and on the exterior of HPC nanoparticles. Controlled release studies have been performed on the particle and networks .The nearly monodispersed nanoparticles have been synthesized on the basis of a natural polymer of hydropropylcellulose (HPC) with a high molecular weight using the precipitation polymerization method and self-assembly of these particles in water results in bright colors. The HPC nanoparticles can be potential using as crosslinkers to increase the hydrogels mechanical properties, such as high transparency and rapid swelling/de-swelling kinetics. The central idea is to prepare colloidal particles containing C=C bonds and to use them as monomers - vinylparticles, to form stable particle assemblies with various architectures. This is accomplished by mixing an aqueous suspension of hydrogel nanoparticles (PNIPAM-co-allylamine) with the organic solvent (dichloromethane) to grow columnar crystals. The hydrogels with such a unique crystal structure behavior …

NiTi-based shape memory alloys (SMAs) offer a good combination of high-strength, ductility, corrosion resistance, and biocompatibility that has served them well and attracted the attention of many researchers and industries. The alloys unique thermo-mechanical ability to recover their initial shape after relatively large deformations by heating or upon unloading due to a characteristic reversible phase transformation makes them useful as damping devices, solid state actuators, couplings, etc. However, there is a need to increase the temperature of the characteristic phase transformation above 150 °C, especially in the aerospace industry where high temperatures are often seen. Prior researchers have shown that adding ternary elements (Pt, Pd, Au, Hf and Zr) to NiTi can increase transformation temperatures but most of these additions are extremely expensive, creating a need to produce cost-effective high temperature shape memory alloys (HTSMAs). Thus, the main objective of this research is to examine the relatively unstudied NiTiZr system for the ability to produce a cost effective and formable HTSMA. Transformation temperatures, precipitation paths, processability, and high-temperature oxidation are examined, specifically using high energy X-ray Diffraction (XRD) measurements, in NiTi-20 at.% Zr. This is followed by an in situ XRD study of the phase growth kinetics of the favorable …

Lithium-sulfur (Li-S) batteries are faced with practical drawbacks of poor cycle life and low charge efficiency which hinder their advancements. Those drawbacks are primarily caused by the intrinsic issues of the cathodes (sulfur) and the anodes (Li metal). In attempt to resolve the issues found on the cathodes, this work discusses the method to prepare a binder-free three-dimensional carbon nanotubes-sulfur (3D CNTs-S) composite cathode by a facile and a scalable approach. Here, the 3D structure of CNTs serves as a conducting network to accommodate high loading amounts of active sulfur material. The efficient electron pathway and the short Li ions (Li+) diffusion length provided by the 3D CNTs offset the insulating properties of sulfur. As a result, high areal and specific capacities of 8.8 mAh cm−2 and 1068 mAh g−1, respectively, with the sulfur loading of 8.33 mg cm−2 are demonstrated; furthermore, the cells operated at a current density of 1.4 mA cm−2 (0.1 C) for up to 150 cycles. To address the issues existing on the anode part of Li-S batteries, this work also covers the novel approach to protect a Li metal anode with a thin layer of two-dimensional molybdenum disulfide (MoS2). With the protective layer of MoS2 …

Nickel based superalloys have superior high temperature mechanical strength, corrosion and creep resistance in harsh environments and found applications in the hot sections as turbine blades and turbine discs in jet engines and gas generator turbines in the aerospace and energy industries. The efficiency of these turbine engines depends on the turbine inlet temperature, which is determined by the high temperature strength and behavior of these superalloys. The microstructure of nickel based superalloys usually contains coherently precipitated gamma prime (?) Ni3Al phase within the random solid solution of the gamma () matrix, with the ? phase being the strengthening phase of the superalloys. How the alloying elements partition into the and ? phases and especially in the site occupancy behaviors in the strengthening ? phases play a critical role in their high temperature mechanical behaviors. The goal of this dissertation is to study the site substitution behavior of the major alloying elements including Cr, Co and Ti through first principles based calculations. Site substitution energies have been calculated using the anti-site formation, the standard defect formation formalism, and the vacancy formation based formalism. Elements such as Cr and Ti were found to show strong preference for Al sublattice, whereas Co …

In this study, we used UV-ozone Ar sputtering, X-ray photoelectron and ultra-violet photoelectron spectroscopies and sputtering based depositions of RuO2 and Se nano-layers on indium tin oxides (ITOs). We elucidated the effect of Ar sputtering on the composition and chemistry of Sn rich ITO surface. We demonstrated that while a combination of UV-ozone radiation and Ar sputtering removes most of the hydrocarbons responsible for degrading the work function of ITO, it also removes significant amount of the segregated SN at the ITO surface that's responsible for its reasonable work function of 4.7eV. We also demonstrated for the first time that sputtering cleaning ITO surface leads to the reduction of the charge state of Sn from Sn4+ to Sn2+ that adds to the degradation of the work function. For the nano-layers coverage of ITO studies, we evaluated both RuO2 and Se. For RuO2 coated ITO, XPS showed the formation of a Ru-Sn-O ternary oxide. The RuO2 nano-layer reduced the oxidation state of Sn in the Sn-rich surface of ITO from +4 to +2. The best work function obtained for this system is 4.98eV, raising the effective work function of ITO by more than 0.5 eV. For the Se coated ITO studies, …

Thermoelectric (TE) devices can undergo degradation from reactions in corrosive environments and at higher operating temperatures by sublimation and oxidation. To prevent the degradation, we have applied two high temperature polymers (HTPs) as coatings for TE materials. Sintering temperatures were from 250°C to 400°C. We explain why dip coating is better technique in our study and had two potential HTPs for tests. By applying TGA (thermogravimetric analysis), we were able to figure out which HTPs have better thermal resistivity. Besides, TGA also help us to find proper curing cycles for HTPs. EDS and SEM results show that the coatings prevent oxidation and sublimation of TE materials. We also shorten HTP curing cycle time and lower the energy costs.

Zinc oxide (ZnO) is a versatile environmentally benign II-VI direct wide band gap semiconductor with several technologically plausible applications such as transparent conducting oxide in flat panel and flexible displays. Hence, ZnO thin films have to be processed below the glass transition temperatures of polymeric substrates used in flexible displays. ZnO thin films were synthesized via aqueous polymeric precursor process by different metallic salt routes using ethylene glycol, glycerol, citric acid, and ethylene diamine tetraacetic acid (EDTA) as chelating agents. ZnO thin films, derived from ethylene glycol based polymeric precursor, exhibit flower-like morphology whereas thin films derived of other precursors illustrate crack free nanocrystalline films. ZnO thin films on sapphire substrates show an increase in preferential orientation along the (002) plane with increase in annealing temperature. The polymeric precursors have also been used in fabricating maskless patterned ZnO thin films in a single step using the commercial Maskless Mesoscale Materials Deposition system.

In this dissertation, small and large NaCl particle-derived surfaces (Ra > 40 microns) were generated on 2D Zn materials, and the surfaces were carefully studied concerning topography, corrosion behavior, and bone cell compatibility. Increases in surface roughness accelerated the corrosion rate, and cell viability was maintained. This method was then extended to 3D porous scaffolds prepared by a hybrid AM/casting technique. The scaffolds displayed a near-net shape, an interconnected pore structure, increasing porosity paralleled to an increased corrosion rate, an ability to support cell growth, and powerful antibacterial properties. Lastly, nano/micro (Rz 0.02–1 microns) topographies were generated on 2D Zn materials, and the materials were comprehensively studied with special attention devoted to corrosion behavior, biocompatibility, osteogenic differentiation, immune cell response, hemocompatibility, and antibacterial performance. For the first time, the textured nonhemolytic surfaces on Zn were shown to direct cell fate, and the micro-textures promoted bone cell differentiation and directed immune cells away from an inflammatory phenotype.

The development of a "cradle-to-cradle" mindset with both material performance during utilization and end of life disposal is a critical need for both ecological and economic considerations. The main limitation to the use of the biopolymers is their mechanical properties. Reinforcements are therefore a good alternative but disposal concerns then arise. Thus the objective of this dissertation is to investigate a biopolymer nanocomposite where the filler is a synthetically prepared layer double hydroxide (inorganic interface); and a biopolymer paper (organic interface) based coating or laminate. The underlying issues driving performance are the packing density of the biopolymer and the interaction with the reinforcement. Since the polyhydroxyalkanoates or PHAs (the biopolymers used for the manufacture of the nanocomposites and coatings) are semicrystalline materials, the glass transition was investigated using dynamic mechanical analysis (DMA) and dielectric spectroscopy (DES), whereas the melt crystallization, cold crystallization and melting points were investigated using differential scanning calorimetry (DSC). Fourier transform infrared (FTIR) spectroscopy was used to estimate crystallinity in the coated material given the low thermal mass of the PHA in the PHA coating. The significant enhancement of the crystallization rate in the PHA nanocomposite was probed using DSC and polarized optical microscopy (POM) and analyzed …

Magnesium is the lightest metal with a very high specific strength. However, its practical applicability is limited by its toughness and reliability. Mg, being HCP has low ductility. This makes the improvement of toughness a grand challenge in Mg alloys. Friction stir processing (FSP) is a thermomechanical technique used to effect microstructural modification. Here, FSP was utilized to affect the toughness of WE43 sheets through microstructural modification. Room temperature Kahn-type tests were conducted to measure the toughness of WE43 sheets. Microscopic techniques (SEM, TEM) was utilized to study the effect of various microstructural factors like grain size, texture, constituent particles, precipitates on crack initiation and propagation. Tensile properties were evaluated by mini-tensile tests. Crack growth in WE43 sheets was also affected by mechanics and digital image correlation (DIC) was utilized to study the plastic zone size. The underlying mechanisms affecting toughness of these sheets were understood which will help in formulating ways in improving it. WE43 nanocomposites were fabricated via FSP. Uniform distribution of reinforcements was obtained in the composites. Improved mechanical properties like that of enhanced strength, increased hardness and stiffness were obtained. But contrary to other metal matrix composites which show reduction in ductility with incorporation of ceramic …

The current work investigates how the interactions among constituent elements in high entropy alloys or complex concentrated alloys (HEA/CCAs) can lead to lattice instability and local chemical ordering which in turn affects the microstructure and properties of these alloys. Using binary enthalpies of mixing, the degree of ordering in concentrated multi-component solid solutions was successfully tailored by introducing Cr, Al and Ti in a CoFeNi HEA/CCA. CoFeNi was selected as the base alloy to achieve a close to random solid solution as indicated by the near-zero binary enthalpies in CoFeNi alloy system. The room temperature tensile properties of these alloys with varied degree of ordering follow a consistent trend where yield stress increased with degree of ordering. This novel approach provides a new alloy design strategy to obtain controlled ordering tendencies and consequently targeted mechanical properties. Further studies on specific alloys have been conducted to utilize this ordering tendency in attaining precipitation strengthening. For this purpose, Al, Ti and Ni were selected to promote ordering and Co, Fe, and Cr were chosen to strengthen the solid solution matrix. In Al0.25CoFeNi HEA/CCA, the ordering tendency between Al and Ni results in a competition between two long-range ordered phases, L12 and B2. …

Potential parameters that can handle multi-component oxide glass systems especially boron oxide are very limited in literature. One of the main goals of my dissertation is to develop empirical potentials to simulate multi-component oxide glass systems with boron oxide. Two approaches, both by introducing the composition dependent parameter feature, were taken and both led to successful potentials for boron containing glass systems after extensive testing and fitting. Both potential sets can produce reasonable glass structures of the multi-component oxide glass systems, with structure and properties in good agreement with experimental data. Furthermore, we have tested the simulation settings such as system size and cooling rate effects on the results of structures and properties of MD simulated borosilicate glasses. It was found that increase four-coordinated boron with decreasing cooling rate and system size above 1000 atoms is necessary to produce converged structure. Another application of the potentials is to simulate a six-component nuclear waste glass, international simple glass (ISG), which was for first time simulated using the newly developed parameters. Structural features obtained from simulations agree well with the experimental results. In addition, two series of sodium borosilicate and boroaluminosilicate glasses were simulated with the two sets of potentials to compare …

The current understanding of the atomic scale phenomenon associated with the influence of beta phase instabilities on the evolution of microstructure in titanium alloys is limited due to their complex nature. Such beta phase instabilities include phase separation and precipitation of nano-scale omega and alpha phases in the beta matrix. The initial part of the present study focuses on omega precipitation within the beta matrix of model binary titanium molybdenum (Ti-Mo) alloys. Direct atomic scale observation of pre-transition omega-like embryos in quenched alloys, using aberration-corrected high resolution scanning transmission electron microscopy and atom probe tomography (APT) was compared and contrasted with the results of first principles computations performed using the Vienna ab initio simulation package (VASP) to present a novel mechanism of these special class of phase transformation. Thereafter the beta phase separation and subsequent alpha phase nucleation in a Ti-Mo-Al ternary alloy was investigated by coupling in-situ high energy synchrotron x-ray diffraction with ex-situ characterization studies performed using aberration corrected transmission electron microscopy and APT to develop a deeper understanding of the mechanism of transformation. Subsequently the formation of the omega phase in the presence of simultaneous development of compositional phase separation within the beta matrix phase of a …

The semiconductor industry has decreased silicon-based device feature sizes dramatically over the last two decades for improved performance. However, current technology has approached the limit of achievable enhancement via this method. Therefore, other techniques, including introducing stress into the silicon structure, are being used to further advance device performance. While these methods produce successful results, there is not a proven reliable method for stress and strain measurements on the nanometer scale characteristic of these devices. The ability to correlate local strain values with processing parameters and device performance would allow for more rapid improvements and better process control. In this research, x-ray diffraction and convergent beam electron diffraction have been utilized to quantify the strain behavior of simple and complex strained silicon-based systems. While the stress relaxation caused by thinning of the strained structures to electron transparency complicates these measurements, it has been quantified and shows reasonable agreement with expected values. The relaxation values have been incorporated into the strain determination from relative shifts in the higher order Laue zone lines visible in convergent beam electron diffraction patterns. The local strain values determined using three incident electron beam directions with different degrees of tilt relative to the device structure have …

Mechanical properties of structural materials are highly correlated to their microstructure. The relationship between microstructure and mechanical properties can be established experimentally. The growing need for structural materials in industry promotes the study of microstructural evolution of materials by design using computational approaches. This thesis presents the microstructural evolution of two different structural materials. The first uses a genetic algorithm approach to study the microstructural evolution of a high-temperature nickel-based oxide-dispersion-strengthened (ODS) alloy. The chosen Ni-20Cr ODS system has nano Y2O3 particles for dispersion strengthening and submicron Al2O3 for composite strengthening. Synergistic effects through the interaction of small dispersoids and large reinforcements improved high-temperature strength. Optimization considered different weight factors on low temperature strength, ductility, and high temperature strength. Simulation revealed optimal size and volume fraction of dispersoids and reinforced particles. Ni-20Cr-based alloys were developed via mechanical alloying for computational optimization and validation. The Ni-20Cr-1.2Y2O3-5Al2O3 alloy exhibited significant reduction in the minimum creep rate (on the order of 10-9 s-1) at 800oC and 100 MPa. The second considers the microstructural evolution of AA 7050 alloy during friction stir welding (FSW). Modeling the FSW process includes thermal, material flow, microstructural and strength modeling. Three-dimensional material flow and heat transfer model was …

This dissertation presents an assortment of research aimed at understanding the composition-dependence of deformation behavior and the response to thermomechanical processing, to enable efficient design and processing of low stacking fault energy (SFE) high entropy alloy (HEAs). The deformation behavior and SFE of four low SFE HEAs were predicted and experimentally verified using electron microscopy and in-situ neutron diffraction. A new approach of employing a minimization function to refine and improve the accuracy of a semi-empirically derived expression relating composition with SFE is demonstrated. Ultimately, by employing the minimization function, the average difference between experimental and predicted SFE was found to be 2.64 mJ m-2. Benchmarking with currently available approaches suggests that integrating minimization functions can substantially improve prediction accuracy and promote efficient HEA design with expansion of databases. Additionally, in-situ neutron diffraction was used to present the first in-situ measurement of the interspacing between stacking faults (SFs) which were correlated with work hardening behavior. Electron transparent specimens (< ~100 nm thick) were used in order to resolve nanoscale planar faults instead of the thicker sub-sized specimens (on the order of millimeters in thickness) which exhibit the classical stages III work hardening behavior characteristic of low SFE metals and alloys. …

The historical success of friction stir welding (FSW) on materials such as aluminum and magnesium alloys is associated with the absence of melting and solidification during the solid-state process. However, commercial adoption of FSW on steels and other non-ferrous high-strength, high-temperature materials such as nickel-base and titanium-base alloys is limited due to the high costs associated with the process. In this dissertation, the feasibility of using an FSW approach to fabricate certain structural components made of nitrogen containing austenitic stainless steels that go into the vacuum vessel and magnetic systems of tokamak devices was demonstrated. The FSW weldments possessed superior application-specific mechanical and functional properties when compared to fusion weldments reported in the technical literature. However, as stated earlier, the industrial adoption of FSW on high temperature materials such as the ferrous alloys used in the present study is greatly limited due to the high costs associated with the process. The cost is mainly dictated by the high temperature FSW tools used to accomplish the weldments. Commercially available high temperature FSW tools are exorbitantly priced and often have short lifetimes. To overcome the high-cost barrier, we have explored the use of integrated computational materials engineering (ICME) combined with experimental prototyping …

In this study, the time-dependent deformation behavior of several model bulk metallic glasses (BMGs) was studied. The BMGs were obtained in different structural states by thermal relaxation below their glass transition temperature, cryogenic thermal cycling, and chemical rejuvenation by micro-alloying. The creep behavior of Zr52.5Ti5Cu17.9Ni14.6Al10 BMG in different structural states was investigated as a function of peak load and temperature. The creep strain rate sensitivity (SRS) indicated a transition from shear transformation zone (STZ) mediated deformation at room temperature to diffusion dominated mechanisms at high temperatures. The relaxation enthalpy of Zr47Cu46Al7 BMG was found to increase significantly with the addition of 1 at% Ti, namely for Zr47Cu45Al7Ti1. Comparison of their respective free volumes indicated that chemical rejuvenation had a more pronounced effect compared to cryogenic thermal rejuvenation. Micro-pillar compression tests supported the improved plasticity with increase in free volume from the rejuvenation effect. Effect of chemistry change on mechanical response and time-dependent deformation was investigated for topologically equivalent Pt-Pd BMGs, where the Pt atoms were systematically replaced with Pd atoms (Pt42.5-xPdx)Cu27Ni9.5P21: x=0, 7.5, 20, 22.5, 35, 42.5). The hardness and reduced modulus increased while the degree of plasticity decreased with increase in Pd-content, which was attributed to the increase in …