Wear of high aluminium zinc-based alloys in plain bearing applications

Two zinc-based alloys of high aluminium content, Super Cosmal alloy containing 60% Al, 6% Si, 1% Cu, 0.3% Mn and HAZCA alloy containing 60% Al, 8% Si, 2% Cu, 0.06% Mg were produced by sand casting. Foundry characteristics in particular, fluidity, mode of solidification and feeding ability were examined. Metallographic analysis of structures was carried out using optical and scanning electron microscopy and their mechanical properties were determined using standard techniques. Dry wear characteristics were determined using a pin-on-disc test, and boundary-lubricated wear was studied using full bearing tests. Results from casting experiments were evaluated and compared with the behaviour of a standard ZA-27 alloy and those from tribological tests with both ZA-27 alloy and a leaded tin-bronze (SAE660) under the same testing conditions. The presence of silicon was beneficial, reducing the temperature range of solidification, improving feeding efficiency and reducing gravity segregation of phases. Use of chills and melt degassing was found necessary to achieve soundness and enhanced mechanical properties. Dry wear tests were performed against a steel counterface for sliding speeds of 0.25, 0.5, 1.0 and 2 m/s and for a range of loads up to 15 kgf. The high aluminium alloys showed wear rates as low as those of ZA-27 at speeds of 0.25 and 0.5 m/s for the whole range of applied loads. ZA-27 performed better at higher speeds. The build up of a surface film on the wearing surface of the test pins was found to be responsible for the mild type of wear of the zinc based alloys. The constitution of the surface film was determined as a complex mixture of aluminium, zinc and iron oxides and metallic elements derived from both sliding materials. For full bearing tests, bushes were machined from sand cast bars and were tested against a steel shaft in the presence of a light spindle oil as the lubricant. Results showed that all zinc based alloys run-in more rapidly than bronze, and that wear in Super Cosmal and HAZCA alloys after prolonged running were similar to those in ZA-27 bearings and significantly smaller than those of the bronze.

Comparison of crack growth behaviour between spray-formed and commercial plate Al-Zn-Mg-Cu alloy 7150

This paper compares the crack growth resistance of an experimental spray-formed extrusion with that of a commercial aluminium alloy, the two alloys having similar compositions but markedly different grain structures. Tensile and fracture behaviour is similar in both materials and is influenced by inclusion content. The two materials differ in their crack growth resistance, which is shown to be dependent upon grain size and shape. Environmentally-induced crack growth is favoured by aligned grain boundaries and small grain size.

Serrated yielding and the localized shear failure mode in aluminium alloys

A study has been made of serrated yielding in two commercial Al-Zn-Mg alloys in the as-quenched condition. The different serration types produced in the two alloys and the shear failure mechanism observed in both notched-bend and tensile testing are related to the mechanisms of dynamic strain ageing occurring during the test. An estimate of 19.7 kJ/mole for the activation energy for exchange of a solute atom and a vacancy in Al-6.2 wt% Zn, 2.5 wt% Mg has been made. © 1981.

Study of carbon nanotube film and shape memory alloys treatment for sensing and structural vibration control

Structural vibration control is of great importance. Current active and passive vibration control strategies usually employ individual elements to fulfill this task, such as viscoelastic patches for providing damping, transducers for picking up signals and actuators for inputting actuating forces. The goal of this dissertation work is to design, manufacture, investigate and apply a new type of multifunctional composite material for structural vibration control. This new composite, which is based on multi-walled carbon nanotube (MWCNT) film, is potentially to function as free layer damping treatment and strain sensor simultaneously. That is, the new material integrates the transducer and the damping patch into one element. The multifunctional composite was prepared by sandwiching the MWCNT film between two adhesive layers. Static sensing test indicated that the MWCNT film sensor resistance changes almost linearly with the applied load. Sensor sensitivity factors were comparable to those of the foil strain gauges. Dynamic test indicated that the MWCNT film sensor can outperform the foil strain gage in high frequency ranges. Temperature test indicated the MWCNT sensor had good temperature stability over the range of 237 K-363 K. The Young’s modulus and shear modulus of the MWCNT film composite were acquired by nanoindentation test and direct shear test, respectively. A free vibration damping test indicated that the MWCNT composite sensor can also provide good damping without adding excessive weight to the base structure. A new model for sandwich structural vibration control was then proposed. In this new configuration, a cantilever beam covered with MWCNT composite on top and one layer of shape memory alloy (SMA) on the bottom was used to illustrate this concept. The MWCNT composite simultaneously serves as free layer damping and strain sensor, and the SMA acts as actuator. Simple on-off controller was designed for controlling the temperature of the SMA so as to control the SMA recovery stress as input and the system stiffness. Both free and forced vibrations were analyzed. Simulation work showed that this new configuration for sandwich structural vibration control was successful especially for low frequency system.

Assessment of biodegradable magnesium alloys for enhanced mechanical and biocompatible properties

Biomaterials have been used for more than a century in the human body to improve body functions and replace damaged tissues. Currently approved and commonly used metallic biomaterials such as, stainless steel, titanium, cobalt chromium and other alloys have been found to have adverse effects leading in some cases, to mechanical failure and rejection of the implant. The physical or chemical nature of the degradation products of some implants initiates an adverse foreign body reaction in the tissue. Some metallic implants remain as permanent fixtures, whereas others such as plates, screws and pins used to secure serious fractures are removed by a second surgical procedure after the tissue has healed sufficiently. However, repeat surgical procedures increase the cost of health care and the possibility of patient morbidity. This study focuses on the development of magnesium based biodegradable alloys/metal matrix composites (MMCs) for orthopedic and cardiovascular applications. The Mg alloys/MMCs possessed good mechanical properties and biocompatible properties. Nine different compositions of Mg alloys/MMCs were manufactured and surface treated. Their degradation behavior, ion leaching, wettability, morphology, cytotoxicity and mechanical properties were determined. Alloying with Zn, Ca, HA and Gd and surface treatment resulted in improved mechanical properties, corrosion resistance, reduced cytotoxicity, lower pH and hydrogen evolution. Anodization resulted in the formation of a distinct oxide layer (thickness 5-10 μm) as compared with that produced on mechanically polished samples (~20-50 nm) under ambient conditions. It is envisaged that the findings of this research will introduce a new class of Mg based biodegradable alloys/MMCs and the emergence of innovative cardiovascular and orthopedic implant devices.^

An assessment of novel biodegradable magnesium alloys for endovascular biomaterial applications

Magnesium alloys have been widely explored as potential biomaterials, but several limitations to using these materials have prevented their widespread use, such as uncontrollable degradation kinetics which alter their mechanical properties. In an attempt to further the applicability of magnesium and its alloys for biomedical purposes, two novel magnesium alloys Mg-Zn-Cu and Mg-Zn-Se were developed with the expectation of improving upon the unfavorable qualities shown by similar magnesium based materials that have previously been explored. The overall performance of these novel magnesium alloys has been assessesed in three distinct phases of research: 1) analysing the mechanical properties of the as-cast magnesium alloys, 2) evaluating the biocompatibility of the as-cast magnesium alloys through the use of in-vitro cellular studies, and 3) profiling the degradation kinetics of the as-cast magnesium alloys through the use of electrochemical potentiodynamic polarization techqnique as well as gravimetric weight-loss methods. As compared to currently available shape memory alloys and degradable as-cast alloys, these experimental alloys possess superior as-cast mechanical properties with elongation at failure values of 12% and 13% for the Mg-Zn-Se and Mg-Zn-Se alloys, respectively. This is substantially higher than other as-cast magnesium alloys that have elongation at failure values that range from 7-10%. Biocompatibility tests revealed that both the Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. Gravimetric and electrochemical testing was indicative of the weight loss and initial corrosion behavior of the alloys once immersed within a simulated body fluid. The development of these novel as-cast magnesium alloys provide an advancement to the field of degradable metallic materials, while experimental results indicate their potential as cost-effective medical devices.^

An Investigation on Biocompatibility of Bio-Absorbable Polymer Coated Magnesium Alloys

Advances in biomaterials have enabled medical practitioners to replace diseased body parts or to assist in the healing process. In situations where a permanent biomaterial implant is used for a temporary application, additional surgeries are required to remove these implants once the healing process is complete, which increases medical costs and patient morbidity. Bio-absorbable materials dissolve and are metabolized by the body after the healing process is complete thereby negating additional surgeries for removal of implants. Magnesium alloys as novel bio-absorbable biomaterials, have attracted great attention recently because of their good mechanical properties, biocompatibility and corrosion rate in physiological environments. However, usage of Mg as biodegradable implant has been limited by its poor corrosion resistance in the physiological solutions. An optimal biodegradable implant must initially have slow degradation to ensure total mechanical integrity then degrade over time as the tissue heals. The current research focuses on surface modification of Mg alloy (MZC) by surface treatment and polymer coating in an effort to enhance the corrosion rate and biocompatibility. It is envisaged that the results obtained from this investigation would provide the academic community with insights for the utilization of bio-absorbable implants particularly for patients suffering from atherosclerosis. The alloying elements used in this study are zinc and calcium both of which are essential minerals in the human metabolic and healing processes. A hydrophobic biodegradable co-polymer, polyglycolic-co-caprolactone (PGCL), was used to coat the surface treated MZC to retard the initial degradation rate. Two surface treatments were selected: (a) acid etching and (b) anodization to produce different surface morphologies, roughness, surface energy, chemistry and hydrophobicity that are pivotal for PGCL adhesion onto the MZC. Additionally, analyses of biodegradation, biocompatibility, and mechanical integrity were performed in order to investigate the optimum surface modification process, suitable for biomaterial implants. The study concluded that anodization created better adhesion between the MZC and PGCL coating. Furthermore, PGCL coated anodized MZC exhibited lower corrosion rate, good mechanical integrity, and better biocompatibility as compared with acid etched.

Water temperature reconstructions based on paired Uk'37 and Tex86 records, and paired surface and subsurface Mg/Ca records

This dataset contains the collection of available published paired Uk'37 and Tex86 records spanning multi-millennial to multi-million year time scales, as well as a collection of Mg/Ca-derived temperatures measured in parallel on surface and subsurface dwelling foraminifera, both used in the analyses of Ho and Laepple, Nature Geoscience 2016. As the signal-to-noise ratios of proxy-derived Holocene temperatures are relatively low, we selected records that contain at least the last deglaciation (oldest sample >18kyr BP).

Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.

(Appendix) Stable carbon and oxygen isotopes, and Mg/Ca ratios of foraminifera from ODP Hole 154-925A

To better understand the links between the carbon cycle and changes in past climate over tectonic timescales we need new geochemical proxy records of secular change in silicate weathering rates. A number of proxies are under development, but some of the most promising (e.g. palaeoseawater records of Li and Nd isotope change) can only be employed on such large samples of mono-specific foraminifera that application to the deep sea sediment core archive becomes highly problematic. "Dentoglobigerina" venezuelana presents a potentially attractive target for circumventing this problem because it is a typically large (> 355 ?m diameter), abundant and cosmopolitan planktic foraminifer that ranges from the early Oligocene to early Pliocene. Yet considerable taxonomic and ecological uncertainties associated with this taxon must first be addressed. Here, we assess the taxonomy, palaeoecology, and ontogeny of "D." venezuelana using stable isotope (oxygen and carbon) and Mg/Ca data measured in tests of late Oligocene to early Miocene age from Ocean Drilling Program (ODP) Site 925, on Ceara Rise, in the western equatorial Atlantic. To help constrain the depth habitat of "D." venezuelana relative to other species we report the stable isotope composition of selected planktic foraminifera species within Globigerina, Globigerinoides, Paragloborotalia and Catapsydrax. We define three morphotypes of "D." venezuelana based on the morphology of the final chamber and aperture architecture. We determine the trace element and stable isotope composition of each morphotype for different size fractions, to test the validity of pooling these morphotypes for the purposes of generating geochemical proxy datasets and to assess any ontogenetic variations in depth habitat. Our data indicate that "D." venezuelana maintains a lower thermocline depth habitat at Ceara Rise between 24 and 21 Ma. Comparing our results to published datasets we conclude that this lower thermocline depth ecology for the Oligo-Miocene is part of an Eocene-to-Pliocene evolution of depth habitat from surface to sub-thermocline for "D." venezuelana. Our size fraction data advocate the absence of photosymbionts in "D." venezuelana and suggest that juveniles calcify higher in the water column, descending into slightly deeper water during the later stages of its life cycle. Our morphotype data show that d18O and d13C variation between morphotypes is no greater than within-morphotype variability. This finding will permit future pooling of morphotypes in the generation of the "sample hungry" palaeoceanographic records.

On the microstructure, growth pattern and original porosity of belemnite rostra: insights from calcitic Jurassic belemnites

Calcitic belemnite rostra are usually employed to perform paleoenvironmental studies based on geochemical data. However, several questions, such as their original porosity and microstructure, remain open, despite they are essential to make accurate interpretations based on geochemical analyses.This paper revisits and enlightens some of these questions. Petrographic data demonstrate that calcite crystals of the rostrum solidum of belemnites grow from spherulites that successively develop along the apical line, resulting in a “regular spherulithic prismatic” microstructure. Radially arranged calcite crystals emerge and diverge from the spherulites: towards the apex, crystals grow until a new spherulite is formed; towards the external walls of the rostrum, the crystals become progressively bigger and prismatic. Adjacent crystals slightly vary in their c-axis orientation, resulting in undulose extinction. Concentric growth layering develops at different scales and is superimposed and traversed by a radial pattern, which results in the micro-fibrous texture that is observed in the calcite crystals in the rostra.Petrographic data demonstrate that single calcite crystals in the rostra have a composite nature, which strongly suggests that the belemnite rostra were originally porous. Single crystals consistently comprise two distinct zones or sectors in optical continuity: 1) the inner zone is fluorescent, has relatively low optical relief under transmitted light (TL) microscopy, a dark-grey color under backscatter electron microscopy (BSEM), a commonly triangular shape, a “patchy” appearance and relatively high Mg and Na contents; 2) the outer sector is non-fluorescent, has relatively high optical relief under TL, a light-grey color under BSEM and low Mg and Na contents. The inner and fluorescent sectors are interpreted to have formed first as a product of biologically controlled mineralization during belemnite skeletal growth and the non-fluorescent outer sectors as overgrowths of the former, filling the intra- and inter-crystalline porosity. This question has important implications for making paleoenvironmental and/or paleoclimatic interpretations based on geochemical analyses of belemnite rostra.Finally, the petrographic features of composite calcite crystals in the rostra also suggest the non-classical crystallization of belemnite rostra, as previously suggested by other authors.

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.

An Assessment of Novel Biodegradable Magnesium Alloys for Endovascular Biomaterial Applications

Magnesium alloys have been widely explored as potential biomaterials, but several limitations to using these materials have prevented their widespread use, such as uncontrollable degradation kinetics which alter their mechanical properties. In an attempt to further the applicability of magnesium and its alloys for biomedical purposes, two novel magnesium alloys Mg-Zn-Cu and Mg-Zn-Se were developed with the expectation of improving upon the unfavorable qualities shown by similar magnesium based materials that have previously been explored. The overall performance of these novel magnesium alloys has been assessesed in three distinct phases of research: 1) analysing the mechanical properties of the as-cast magnesium alloys, 2) evaluating the biocompatibility of the as-cast magnesium alloys through the use of in-vitro cellular studies, and 3) profiling the degradation kinetics of the as-cast magnesium alloys through the use of electrochemical potentiodynamic polarization techqnique as well as gravimetric weight-loss methods. As compared to currently available shape memory alloys and degradable as-cast alloys, these experimental alloys possess superior as-cast mechanical properties with elongation at failure values of 12% and 13% for the Mg-Zn-Se and Mg-Zn-Se alloys, respectively. This is substantially higher than other as-cast magnesium alloys that have elongation at failure values that range from 7-10%. Biocompatibility tests revealed that both the Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. Gravimetric and electrochemical testing was indicative of the weight loss and initial corrosion behavior of the alloys once immersed within a simulated body fluid. The development of these novel as-cast magnesium alloys provide an advancement to the field of degradable metallic materials, while experimental results indicate their potential as cost-effective medical devices.

Enhanced 3-Dimensional Carbon Nanotube Based Anodes for Li-ion Battery Applications

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg-1). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg-1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg-1 at 0.17C and cycling stability of 130 mAhg-1 up to 50 cycles at 1.7C.

Innovative Al Alloys for High Performance Automotive Pistons: Enhancement of Specific Strength at High Temperature and Resistance to Knock Damage

The increasingly strict regulations on greenhouse gas emissions make the fuel economy a pressing factor for automotive manufacturers. Lightweighting and engine downsizing are two strategies pursued to achieve the target. In this context, materials play a key role since these limit the engine efficiency and components weight, due to their acceptable thermo-mechanical loads. Piston is one of the most stressed engine components and it is traditionally made of Al alloys, whose weakness is to maintain adequate mechanical properties at high temperature due to overaging and softening. The enhancement in strength-to-weight ratio at high temperature of Al alloys had been investigated through two approaches: increase of strength at high temperature or reduction of the alloy density. Several conventional and high performance Al-Si and Al-Cu alloys have been characterized from a microstructural and mechanical point of view, investigating the effects of chemical composition, addition of transition elements and heat treatment optimization, in the specific temperature range for pistons operations. Among the Al-Cu alloys, the research outlines the potentialities of two innovative Al-Cu-Li(-Ag) alloys, typically adopted for structural aerospace components. Moreover, due to the increased probability of abnormal combustions in high performance spark-ignition engines, the second part of the dissertation deals with the study of knocking damages on Al pistons. Thanks to the cooperation with Ferrari S.p.A. and Fluid Machinery Research Group - Unibo, several bench tests have been carried out under controlled knocking conditions. Knocking damage mechanisms were investigated through failure analyses techniques, starting from visual analysis up to detailed SEM investigations. These activities allowed to relate piston knocking damage to engine parameters, with the final aim to develop an on-board knocking controller able to increase engine efficiency, without compromising engine functionality. Finally, attempts have been made to quantify the knock-induced damages, to provide a numerical relation with engine working conditions.