Progress in nanotechnology has promoted an increasing interest in the rational design of the emerging hierarchical aerogels, which represents a second stage of the NC-based aerogel research. By fine-tuning the surface properties of the backbones, metallic hierarchical aerogels are able to address the growing demands of advanced electrocatalysts. In this dissertation, three types of metallic hierarchical aerogels were designed by introducing different nanostructures (i.e. hollow, porous/dendritic and core-shell) and alloy effects (with noble or transition metals) into the aerogels. Thus, as a proof-of-concept for fuel cells, advanced electrocatalytic performances have been achieved on the resulting metallic hierarchical aerogels towards both anode (oxidation of ethanol) and cathode (reduction of oxygen) reactions. First, alloyed PdxNi hollow nanospheres with controlled composition and shell thickness were utilized as building blocks for the design of hierarchical aerogels. The combination of transition-metal doping, hollow interior, as well as the 3D aerogel structure make the resulting aerogels promising electrocatalysts for ethanol oxidation with a mass activity up to 5.6-fold higher than that of the Pd/C. Second, continuously shape-engineering of the building blocks (ranging from hollow shells to dendritic shapes) was achieved by the synthesis of a series of multimetallic Ni-PdxPty hierarchical aerogels. By optimization of the nanoscale morphology and the chemical composition, the Ni-Pd60Pt40 aerogel exhibits remarkable electrocatalytic activity for oxidation of ethanol. Moreover, the particle growth mechanism underlying the galvanic replacement was revealed in terms of nanowelding of the nanoparticulate reaction intermediates based on experimental and theoretical results. Third, a universal approach was demonstrated for core-shell structuring of metallic aerogels by coating of an ultrathin Pt shell on a composition-tunable Pd-based alloyed core. Their activities for oxygen reduction exhibit a volcano-type relationship as a function of the lattice parameter of the core substrate. Largely improved Pt utilization efficiency was accomplished based on the core-shell motifs, as the mass activity reaches 5.25 A mg-1Pt which are 18.7 times higher than those of Pt/C. Different from the conventional aerogels with nanowire-like backbones, those hierarchical aerogels are generally comprised of at least two levels of architectures, i.e. an interconnected porous structure on the macroscale and a specially designed configuration at local backbones at the nanoscale. This combination “locks in” the inherent properties of the NCs, so that the beneficial genes obtained by nano-engineering are retained in the resulting monolithic hierarchical aerogels. These results expand the exploitation approach of the electrocatalytic properties of aerogels into morphology control of their NBBs and are of great importance for the future development of aerogels for many other electrochemical reactions.

This study aims on characterization of non-metallic inclusions (oxides and sulfides) in steel with and without Calcium treatment. In this paper, the three-dimensional (3-D) investigation method of inclusions on film filter after Electrolytic Extraction (EE) of steel samples is applied on two different steel grades (280, 316L). Image analysis of non-metallic inclusions is carried out on Scanning Electron Microscope (SEM) images following with inclusion characteristic analysis. Steel samples with calcium treatment in the production process and reference samples was investigated and compared in density, size and composition. It shows that higher magnification and larger inclusion size correspond to more accurate result. With restriction of equipment and measurement, 2μm is the smallest size could be measured in ×500 magnification within 5% error. The comparison of distribution of inclusions varies with different zones: center has the largest size with least number of NMI; surface has the smallest size with largest number of NM; middle part has the median properties. In 316L steel, Ca treatment increases the number of oxides inclusions significantly; the content of Ca and Si in oxides inclusions is also increased. Two shapes of oxides inclusions, oval and elongated ones, are found with Ca treatment. In 280 steel, the total amount of NMI decreases slightly with Ca treatment; CaS is found in spherical inclusions; Because of earlier formation of larger size spherical inclusions, higher Ca content is found than that in smaller size spherical inclusions.

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This thesis covers some aspects of hard part turning of carburised steels using a poly‑crystalline cubic boron nitride (PCBN) cutting tool during fine machining. The emphasis is on the influence of the steel cleanliness and the characteristics of non‑metallic inclusions in the workpiece on the active wear mechanisms of the cutting tool. Four carburising steel grades suitable for automotive applications were included, including one that was Ca‑treated. A superior tool life was obtained when turning the Ca-treated steel. The superior machinability is associated with the deposition of lubricating (Mn,Ca)S and (CaO)x-Al2O3-S slag layers, which are formed on the rake face of the cutting tool during machining. Moreover, the transfer of work material to the rake face crater is characteristic in hard part turning of clean steels. It can be because of the lack of sulfides that protect the cutting edge when turning machinability treated steels. This corresponds to the more pronounced crater wear caused by the low‑sulfur steels than that of the steels with higher sulfur contents. It was also concluded that the composition of the non‑metallic inclusions in the Ca‑treated steel is a more important factor than the inclusion number and size, in hard part turning using a PCBN cutting tool. Also, a 3D analysis after electrolytic extraction was found to give a more precise characterisation of non‑metallic inclusions than the conventional 2D analysis by SEM‑EDS. In turn, better correlations to machinability and mechanical properties can be obtained. Hence, the use of this technique is beneficial for future material development. Finally, the challenge for future metallurgy is to manufacture high‑performance steels with improved combined properties of mechanical strength and machinability. / <p>QC 20150422</p>

The inclusions have a different chemical composition and give the steel different mechanical properties. These inclusions affect several properties of steel. In order to understand how the inclusions will affect the steel properties, the electrolytic extraction of 3D investigate method is applied on the steel grade of 42CrMo4. Then follow with Scanning Electron Microscope (SEM) observation. Steel samples from both ingot and rolling with and without heat treatment are observed and compared with different ratios. The result shown that, heat treatment can be applied for removing carbides successfully. And most inclusions are belonging to Type RS which is rod like MnS. The percentage of broken particles can be up to 80%, which means that the reason for the inclusions broken should be find. And heat treatment can affect the characteristics of elongated MnS.

The focus of this thesis work is to optimize rare earth metal (REM) addition in Therma 253MA, an austenitic stainless-steel grade in order to get a good trade-off between oxidation resistance property and the amount of big REM inclusions formed. Big REM inclusions are detrimental to material properties and REM is required to be dissolved in the matrix for improving the oxidation resistance. REM optimization can also lead to economical savings for Outokumpu. The distribution of REM between matrix and inclusion is affected by factors such as REM addition, initial oxygen and sulphur contents and time to casting of the melt. The re-oxidation of melt in the tundish also affects the REM distribution. Hence, the effect of these factors on the inclusion characteristics is investigated by analysing samples with different REM additions, using light optical microscope (LOM) and scanning electron microscope (SEM). LOM analysis focussed on stringer inclusion characteristics. SEM+EDS analysis is done using automated "INCA Feature" software with focus on overall inclusion characteristics. Oxidation and creep tests are also performed to study the effect of different REM additions on oxidation and creep behaviour. The results from inclusion analysis show that increasing REM addition and time to casting has a bad effect on stringer and overall inclusion characteristics. The re-oxidation in the tundish influences the inclusion formation, but does not affect the stringer characteristics. The resistance to oxidation of the samples is also compared and is observed to increase within increasing REM addition. Finally, this works suggests an optimal REM addition for Therma 253MA to get a good balance between oxidation resistance and amount of big inclusions. / Fokus för detta avhandlingsarbete är att optimera tillsats av sällsynt jordartsmetall (REM) i Therma 253MA, en austenitisk rostfritt stålkvalitet för att få en bra avvägning mellan oxidationsbeständighetsegenskap och mängden stora REM-inneslutningar som bildas. Stora REM-inneslutningar är skadliga för materialegenskaperna och REM måste lösas i matrisen för att förbättra oxidationsbeständigheten. REM-optimering kan också leda till ekonomiska besparingar för Outokumpu. Fördelningen av REM mellan matris och inkludering påverkas av faktorer såsom REM-tillsats, initialt syre- och svavelinnehåll och tid till gjutning av smältan. Re-oxidation av smälta i tunden påverkar också REM-fördelningen. Följaktligen undersöks effekten av dessa faktorer på inkluderingsegenskaperna genom att analysera prover med olika REM-tillsatser, med användning av ljusoptiskt mikroskop (LOM) och avsökning av elektronmikroskop (SEM). LOM-analys fokuserade på stringer-inkluderingsegenskaper. SEM + EDS-analys görs med hjälp av automatiserad "INCA Feature" -programvara med fokus på övergripande inkluderingsegenskaper. Oxidations- och krypningstest utförs också för att studera effekten av olika REM-tillsatser på oxidation och krypbeteende. Resultaten från inkluderingsanalys visar att ökande REM-tillsats och tid till gjutning har en dålig effekt på stringer och totala inkluderingsegenskaper. Återoxidationen i tunden påverkar inkluderingsbildningen, men påverkar inte stringeregenskaperna. Motståndet mot oxidation av proverna jämförs också och observeras öka inom ökande REM-tillsats. Slutligen föreslår detta ett optimalt REM-tillägg för Therma 253MA för att få en bra balans mellan oxidationsmotstånd och mängd stora inneslutningar.

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 microscope (SEM) to understand the fracture mechanisms. Catastrophic shear banding was found to be the primary fracture mode, which supported the observation of flake formation during high energy ball milling.

Plastic flow in bulk metallic glasses (BMGs) localizes into narrow bands, which, in the absence of a microstructure that could obstruct them, propagate unhindered under tensile loading. In constrained deformation conditions such as indentation and at notch roots, extensive shear band formation can occur. A key issue in the context of fracture of BMGs that is yet to be understood comprehensively is how their toughness is controlled by various state parameters. Towards this end, the change in fracture toughness and plasticity with short term annealing above and below the glass transition temperature, Tg, is studied in a Zr-based BMG. Elastic properties like shear modulus, Poisson's ratio as well as parameters defining the internal state like the fictive temperature, Tf, density, and free volume are measured and correlation with the toughness was attempted at. While the elastic properties may help in distinguishing between tough and brittle glasses, they fail to reveal the reasons behind the toughness variations. Spherical-tip nanoindentation and microindentation tests were employed to probe the size, distributions and activation energies of the microscopic plastic carriers with the former and shear band densities with the latter. Results indicate that specimens annealed at a higher temperature, Ta, exhibit profuse shear banding with negligible changes in the local yield strengths. Statistical analysis of the nanoindentation data by incorporating the nucleation rate theory and the results of the cooperative shear model (CSM), reveals that short term annealing doesn't alter the shear transformation zone (STZ) size much. However, density estimates indicate changes in the free volume content across specimens. A model combining STZ activation and free volume accumulation predicts a higher rate in the reduction of the cumulative STZ activation barrier in specimens with a higher initial free volume content. Of the macroscopic physical properties, the specimen density is revealed to be a useful qualitative measure of enhancement in fracture toughness and plasticity in BMGs. We turn our attention next to the brittle fracture in BMGs, with the specific objective of understanding the mechanisms of failure. For this purpose, mode I fracture experiments were conducted on embrittled BMG samples and the fracture surface features were analyzed in detail. Wallner lines, which result from the interaction between the propagating crack front and shear waves emanating from a secondary source, were observed on the fracture surface and geometric analysis of them indicates that the maximum crack velocity to be ~800 m/s, which corresponds to ~0.32 times the shear wave speed. Fractography reveals that the sharp crack nucleation at the notch tip occurs at the mid-section of the specimens with the observation of flat and half-penny shaped cracks. On this basis, we conclude that the crack initiation in brittle BMGs occurs through hydrostatic stress assisted cavity nucleation ahead of the notch tip. High magnification scanning electron and atomic force microscopies of the dynamic crack growth regions reveal highly organized, nanoscale periodic patterns with a spacing of ~79 nm. Juxtaposition of the crack velocity with this spacing suggests that that the crack takes ~10-10 s for peak-to-peak propagation. This, and the estimated adiabatic temperature rise ahead of the propagating crack tip that suggests local softening, are utilized to critically discuss possible causes for the nanocorrugation formation. The Taylor’s fluid meniscus instability is unequivocally ruled out. Then, two other possible mechanisms, viz. (a) crack tip blunting and resharpening through nanovoid nucleation and growth ahead of the crack tip and eventual coalescence, and (b) dynamic oscillation of the crack in a thin slab of softened zone ahead of the crack-tip, are critically discussed. One way of alleviating the fracture-related issues in BMGs is to impart a microstructure to it, which would either impede the growth of shear bands or promote the multiplication of them. One such approach is through the BMG composites (BMGCs) route, wherein a crystalline second phase incorporated in the BMG matrix. There is a need to study the effects of reinforcement content, size and distribution on the mechanical behavior of the BMGC so as to achieve an optimum combination of strength and ductility. For this purpose, an investigation into the microstructure and tensile properties of Zr/Ti-based BMG composites of the same composition, but produced by different routes, was conducted so as to identify “structure–property” connections in these materials. This was accomplished by employing four different processing methods—arc melting, suction casting, semi-solid forging and induction melting on a water-cooled copper boat—on composites with two different dendrite volume fractions, Vd. The change in processing parameters only affects microstructural length scales such as the interdendritic spacing, λ, and dendrite size, δ, whereas compositions of the matrix and dendrite are unaffected. Broadly, the composite’s properties are insensitive to the microstructural length scales when Vd is high (∼75%), whereas they become process dependent for relatively lower Vd (∼55%). Larger δ in arc-melted and forged specimens result in higher ductility (7–9%) and lower hardening rates, whereas smaller dendrites increase the hardening rate. A bimodal distribution of dendrites offers excellent ductility at a marginal cost of yield strength. Finer λ result in marked improvements in both ductility and yield strength, due to the confinement of shear band nucleation sites in smaller volumes of the glassy phase. Forging in the semi-solid state imparts such a microstructure.

Metal matrix composites can produce mechanical and physical properties better than those of the monolithic metal. Titanium alloys are widely used matrix materials as they can offer outstanding specific strength, corrosion resistance and other advantages over its competitors, such as aluminium, magnesium and stainless steel. In past decades, titanium matrix composites served in broad areas, including aerospace, military, automobile and biomedical industries. In this project, a revised powder metallurgy method, which contains cold isostatic pressing and hot isostatic pressing, was adopted to refine the microstructure of monolithic titanium. It was also used to manufacture titanium matrix composites. TiH2 powder was selected as the starting material to form Ti matrix and the reinforcements were sub-micron and nano-metric TiB particles. Mechanical properties and microstructure of commercial titanium composites exhaust valves from Toyota Motor Corporation have been studied as the reference of properties of titanium composites manufactured in this project. It has been shown that tensile strength and hardness of exhaust valves increase about 30% than those of similar matrix titanium alloys. Examination on powder starting materials of this project was also carried out, especially the dehydrogenation process shown in the DSC result. Mechanical properties and microstructures of titanium matrix composites samples in this project, as related to the process parameter, have also been investigated. The density of these samples reached 96% of theoretical one but cracks were found through out the samples after sintering. Fast heating rates during the processing was suspected to have caused the crack formation, since the hydrogen release was too fast during dehydrogenation. Hardness testing of sintered samples was carried out and the value was comparable and even better than that of commercial exhaust valves and titanium composites in literature. Microstructure study shows that the size of reinforcements increased and the size of grains decreased as the increasing amount of TiB reinforcements. And this condition also resulted in the increasing amount of the acicular alpha structure.

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. In particular, low coercivity and high permeability of iron and cobalt based metallic glass compositions could potentially lead to extensive commercial use as magnetic heads, transformer cores, circuits and magnetic shields. In the current study, few metallic glass compositions were synthesized by systematically varying the iron and cobalt content. Thermal analysis was done and included the measurement of glass transition temperature, crystallization temperature, and the enthalpies of relaxation and crystallization. Magnetic properties of the alloys were determined including saturation magnetization, coercivity, and Curie temperature. The coercivity was found to decrease and the saturation magnetization was found to increase with the increase in iron content. The trend in thermal stability, thermodynamic properties, and magnetic properties was explained by atomic interactions between the ferromagnetic metals and the metalloids atoms in the amorphous alloys. Mechanical behavior of iron based metallic glasses was evaluated in bulk form as well as in the form of coatings. Iron based amorphous powder was subjected to high power mechanical milling and the structural changes were evaluated as a function of time. Using iron-based amorphous powder precursor, a uniform composite coating was achieved through microwave processing. The hardness, modulus, and wear behavior of the alloys were evaluated using nano-indentation.