Re-engineering materials management: a case study on an Indian refinery

Materials management function is always a major concern to the management of any industrial organisation as high inventory and an inefficient procurement process affect the profitability to a great extent. Problems multiply due to a very current business environment in India. Hence, existing materials planning and procurement processes and inventory management systems require a re-look with respect to a changing business environment. This study shows a radical improvement in materials management function of an Indian petroleum refinery through business process re-engineering (BPR) by analysing current processes, identifying key issues, deriving paradigm shifts and developing re-engineered processes through customer value analysis. BPR has been carried out on existing processes of “materials planning and procurement” and “warehousing and surplus disposal”. The re-engineered processes for materials management function trigger a few improvement projects that were identified by the group of executives who took part in the re-engineering exercise. Those projects were implemented in an integrated framework with the application of the state of art information technology tools.

Lattice Engineering of III-Nitride Heterostructures and Their Applications

III-Nitride materials have recently become a promising candidate for superior applications over the current technologies. However, certain issues such as lack of native substrates, and high defect density have to be overcome for further development of III-Nitride technology. This work presents research on lattice engineering of III-Nitride materials, and the structural, optical, and electrical properties of its alloys, in order to approach the ideal material for various applications. We demonstrated the non-destructive and quantitative characterization of composition modulated nanostructure in InAlN thin films with X-ray diffraction. We found the development of the nanostructure depends on growth temperature, and the composition modulation has impacts on carrier recombination dynamics. We also showed that the controlled relaxation of a very thin AlN buffer (20 ~ 30 nm) or a graded composition InGaN buffer can significantly reduce the defect density of a subsequent epitaxial layer. Finally, we synthesized an InAlGaN thin films and a multi-quantum-well structure. Significant emission enhancement in the UVB range (280 – 320 nm) was observed compared to AlGaN thin films. The nature of the enhancement was investigated experimentally and numerically, suggesting carrier confinement in the In localization centers.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Developing Low Fouling Peptides and Zwitterionic Materials for Biomedical Applications

Thesis (Ph.D.)--University of Washington, 2015

Crevassing and Calving of Glacial Ice

Calving of ice is a relatively new area of research in the still young field of glaciology. In the short time that calving has been studied, it has been mainly treated as an afterthought, with the predominant mode of thinking being that it will happen so to concern oneself with why is not important. Many studies dealt with observations of calving front positions over time vs. ice velocity in an attempt to quantify the calving rate as the difference between the two, while others have attempted to deduce some empirical relationship between calving rate and variables such as water depth or temperature. This study instead addresses the question of why, where, and when ice will first become crevassed, which is an obviously necessary condition for a later calving event to occur. Previous work examining the causes of calving used ideas put forth from a variety of fields, including civil engineering, materials science, and results from basic physics and mechanics. These theories are re-examined here and presented as part of a larger whole. Important results from the field of fracture mechanics are utilized frequently, and these results can be used as a predictor of ice behavior and intrinsic properties of ice, as well as properties like back stresses induced by local pinning points and resistive shears along glacial ice boundaries. A theory of fracture for a material experiencing creep is also presented with applications to ice shelves and crevasse penetration. Finally, a speculative theory regarding large scale iceberg formation is presented. It is meant mainly as an impetus to further discussion on the topic, with the hope that a model relating crevasse geometries to flow parameters can result in crevasse spacings that could produce the tabular icebergs which are so newsworthy. The primary focus of this thesis is to move away from the "after the fact" studies that are so common in calving research, and instead devote energy to determining what creates the conditions that drive the calving of ice in the first place.

Novel hybrid columns made of ultra-high performance concrete and fiber reinforced polymers

The application of advanced materials in infrastructure has grown rapidly in recent years mainly because of their potential to ease the construction, extend the service life, and improve the performance of structures. Ultra-high performance concrete (UHPC) is one such material considered as a novel alternative to conventional concrete. The material microstructure in UHPC is optimized to significantly improve its material properties including compressive and tensile strength, modulus of elasticity, durability, and damage tolerance. Fiber-reinforced polymer (FRP) composite is another novel construction material with excellent properties such as high strength-to-weight and stiffness-to-weight ratios and good corrosion resistance. Considering the exceptional properties of UHPC and FRP, many advantages can result from the combined application of these two advanced materials, which is the subject of this research. The confinement behavior of UHPC was studied for the first time in this research. The stress-strain behavior of a series of UHPC-filled fiber-reinforced polymer (FRP) tubes with different fiber types and thicknesses were tested under uniaxial compression. The FRP confinement was shown to significantly enhance both the ultimate strength and strain of UHPC. It was also shown that existing confinement models are incapable of predicting the behavior of FRP-confined UHPC. Therefore, new stress-strain models for FRP-confined UHPC were developed through an analytical study. In the other part of this research, a novel steel-free UHPC-filled FRP tube (UHPCFFT) column system was developed and its cyclic behavior was studied. The proposed steel-free UHPCFFT column showed much higher strength and stiffness, with a reasonable ductility, as compared to its conventional reinforced concrete (RC) counterpart. Using the results of the first phase of column tests, a second series of UHPCFFT columns were made and studied under pseudo-static loading to study the effect of column parameters on the cyclic behavior of UHPCFFT columns. Strong correlations were noted between the initial stiffness and the stiffness index, and between the moment capacity and the reinforcement index. Finally, a thorough analytical study was carried out to investigate the seismic response of the proposed steel-free UHPCFFT columns, which showed their superior earthquake resistance, as compared to their RC counterparts.

A Generalized Methodology to Characterize Composite Materials for Pyrolysis Models

The predictive capabilities of computational fire models have improved in recent years such that models have become an integral part of many research efforts. Models improve the understanding of the fire risk of materials and may decrease the number of expensive experiments required to assess the fire hazard of a specific material or designed space. A critical component of a predictive fire model is the pyrolysis sub-model that provides a mathematical representation of the rate of gaseous fuel production from condensed phase fuels given a heat flux incident to the material surface. The modern, comprehensive pyrolysis sub-models that are common today require the definition of many model parameters to accurately represent the physical description of materials that are ubiquitous in the built environment. Coupled with the increase in the number of parameters required to accurately represent the pyrolysis of materials is the increasing prevalence in the built environment of engineered composite materials that have never been measured or modeled. The motivation behind this project is to develop a systematic, generalized methodology to determine the requisite parameters to generate pyrolysis models with predictive capabilities for layered composite materials that are common in industrial and commercial applications. This methodology has been applied to four common composites in this work that exhibit a range of material structures and component materials. The methodology utilizes a multi-scale experimental approach in which each test is designed to isolate and determine a specific subset of the parameters required to define a material in the model. Data collected in simultaneous thermogravimetry and differential scanning calorimetry experiments were analyzed to determine the reaction kinetics, thermodynamic properties, and energetics of decomposition for each component of the composite. Data collected in microscale combustion calorimetry experiments were analyzed to determine the heats of complete combustion of the volatiles produced in each reaction. Inverse analyses were conducted on sample temperature data collected in bench-scale tests to determine the thermal transport parameters of each component through degradation. Simulations of quasi-one-dimensional bench-scale gasification tests generated from the resultant models using the ThermaKin modeling environment were compared to experimental data to independently validate the models.

An Investigation of Waste Glass-Based Geopolymers Supplemented with Alumina

An increased consideration of sustainability throughout society has resulted in a surge of research investigating sustainable alternatives to existing construction materials. A new binder system, called a geopolymer, is being investigated to supplement ordinary portland cement (OPC) concrete, which has come under scrutiny because of the CO2 emissions inherent in its production. Geopolymers are produced from the alkali activation of a powdered aluminosilicate source by an alkaline solution, which results in a dense three-dimensional matrix of tetrahedrally linked aluminosilicates. Geopolymers have shown great potential as a building construction material, offering similar mechanical and durability properties to OPC. Additionally, geopolymers have the added value of a considerably smaller carbon footprint than OPC. This research considered the compressive strength, microstructure and composition of geopolymers made from two types of waste glass with varying aluminum contents. Waste glass shows great potential for mainstream use in geopolymers due to its chemical and physical homogeneity as well as its high content of amorphous silica, which could eliminate the need for sodium silicate. However, the lack of aluminum is thought to negatively affect the mechanical performance and alkali stability of the geopolymer system. Mortars were designed using various combinations of glass and metakaolin or fly ash to supplement the aluminum in the system. Mortar made from the high-Al glass (12% Al2O3) reached over 10,000 psi at six months. Mortar made from the low-Al glass (<1% Al2O3) did not perform as well and remained sticky even after several weeks of curing, most likely due to the lack of Al which is believed to cause hardening in geopolymers. A moderate metakaolin replacement (25-38% by mass) was found to positively affect the compressive strength of mortars made with either type of glass. Though the microstructure of the mortar was quite indicative of mechanical performance, composition was also found to be important. The initial stoichiometry of the bulk mixture was maintained fairly closely, especially in mixtures made with fine glass. This research has shown that glass has great potential for use in geopolymers, when care is given to consider the compositional and physical properties of the glass in mixture design.

Measurement of 1/f noise and its application in materials science

This is a review of the measurement of I If noise in certain classes of materials which have a wide range of potential applications. This includes metal films, semi-conductors, metallic oxides and inhomogeneous systems such as composites. The review contains a basic introduction to this field, the theories and models and follows it up with a discussion on measurement methods. There are discussions on specific examples of the application of noise spectroscopy in the field of materials science. (C) 2002 Elsevier Science Ltd. All rights reserved.

Numerical study on rainfall infiltration in rock-soil slop

A mathematical model for the rain infiltration in the rock-soil slop has been established and solved by using the finite element method. The unsteady water infiltrating process has been simulated to get water content both in the homogeneous and heterogeneous media. The simulated results show that the rock blocks in the rock-soil slop can cause the wetting front moving fast. If the rain intensity is increased, the saturated region will be formed quickly while other conditions are the same. If the rain intensity keeps a constant, it is possible to accelerate the generation of the saturated region by properly increasing the vertical filtration rate of the rock-soil slop. However, if the vertical filtration rate is so far greater than the rain intensity, it will be difficult to form the saturated region in the rock-soil slop. The numerical method was verified by comparing the calculation results with the field test data.

Advanced density functional theory methods for materials science

In this work we chiefly deal with two broad classes of problems in computational materials science, determining the doping mechanism in a semiconductor and developing an extreme condition equation of state. While solving certain aspects of these questions is well-trodden ground, both require extending the reach of existing methods to fully answer them. Here we choose to build upon the framework of density functional theory (DFT) which provides an efficient means to investigate a system from a quantum mechanics description.

Zinc Phosphide (Zn₃P₂) could be the basis for cheap and highly efficient solar cells. Its use in this regard is limited by the difficulty in n-type doping the material. In an effort to understand the mechanism behind this, the energetics and electronic structure of intrinsic point defects in zinc phosphide are studied using generalized Kohn-Sham theory and utilizing the Heyd, Scuseria, and Ernzerhof (HSE) hybrid functional for exchange and correlation. Novel 'perturbation extrapolation' is utilized to extend the use of the computationally expensive HSE functional to this large-scale defect system. According to calculations, the formation energy of charged phosphorus interstitial defects are very low in n-type Zn₃P₂ and act as 'electron sinks', nullifying the desired doping and lowering the fermi-level back towards the p-type regime. Going forward, this insight provides clues to fabricating useful zinc phosphide based devices. In addition, the methodology developed for this work can be applied to further doping studies in other systems.

Accurate determination of high pressure and temperature equations of state is fundamental in a variety of fields. However, it is often very difficult to cover a wide range of temperatures and pressures in an laboratory setting. Here we develop methods to determine a multi-phase equation of state for Ta through computation. The typical means of investigating thermodynamic properties is via ’classical’ molecular dynamics where the atomic motion is calculated from Newtonian mechanics with the electronic effects abstracted away into an interatomic potential function. For our purposes, a ’first principles’ approach such as DFT is useful as a classical potential is typically valid for only a portion of the phase diagram (i.e. whatever part it has been fit to). Furthermore, for extremes of temperature and pressure quantum effects become critical to accurately capture an equation of state and are very hard to capture in even complex model potentials. This requires extending the inherently zero temperature DFT to predict the finite temperature response of the system. Statistical modelling and thermodynamic integration is used to extend our results over all phases, as well as phase-coexistence regions which are at the limits of typical DFT validity. We deliver the most comprehensive and accurate equation of state that has been done for Ta. This work also lends insights that can be applied to further equation of state work in many other materials.

Materials science: The ultrasmoothness of diamond-like carbon surfaces

The ultrasmoothness of diamond-like carbon coatings is explained by an atomistic/continuum multiscale model. At the atomic scale, carbon ion impacts induce downhill currents in the top layer of a growing film. At the continuum scale, these currents cause a rapid smoothing of initially rough substrates by erosion of hills into neighboring hollows. The predicted surface evolution is in excellent agreement with atomic force microscopy measurements. This mechanism is general, as shown by similar simulations for amorphous silicon. It explains the recently reported smoothing of multilayers and amorphous transition metal oxide films and underlines the general importance of impact-induced downhill currents for ion deposition, polishing, and nanopattering.

Deep level defects in high temperature annealed InP

Deep level defects in high temperature annealed semi-conducting InP have been studied by deep level transient spectroscopy (DLTS). There is obvious difference in the deep defects between as-grown InP, InP annealed in phosphorus ambient and iron phosphide ambient, as far as their quantity and concentration are concerned. Only two defects at 0.24 and 0.64 eV can be detected in InP annealed in iron phosphide ambient, while defects at 0.24, 0.42, 0.54 and 0.64 eV have been detected in InP annealed in phosphorus ambient, in contrast to two defects at 0.49 and 0.64 eV or one defect at 0.13 eV in as-grown InP. A defect suppression phenomenon related to iron diffusion process has been observed. The formation mechanism and the nature of the defects have been discussed.