Dissertations / Theses on the topic 'Powder Characterization'

The aim of this master thesis project was to statistically correlate various powder characteristics to the quality of additively manufactured parts. An additional goal of this project was to find a potential second source supplier of powder for GKN Aerospace Sweden in Trollhättan. Five Inconel® alloy 718 powders from four individual powder suppliers have been analyzed in this project regarding powder characteristics such as: morphology, porosity, size distribution, flowability and bulk properties. One powder out of the five, Powder C, is currently used in production at GKN and functions as a reference. The five powders were additively manufactured by the process of laser metal deposition according to a pre-programmed model utilized at GKN Aerospace Sweden in Trollhättan. Five plates were produced per powder and each cut to obtain three area sections to analyze, giving a total of fifteen area sections per powder. The quality of deposited parts was assessed by means of their porosity content, powder efficiency, geometry and microstructure. The final step was to statistically evaluate the results through the analysis methods of Analysis of Variance (ANOVA) and simple linear regression with the software Minitab. The method of ANOVA found a statistical significant difference between the five powders regarding their experimental results. This made it possible to compare the five powders against each other. Statistical correlations by simple linear regression analysis were found between various powder characteristics and quality of deposited part. This led to the conclusion that GKN should consider additions to current powder material specification by powder characteristics such as: particle morphology, powder porosity and flowability measurements by a rheometer. One powder was found to have the potential of becoming a second source supplier to GKN, namely Powder A. Powder A had overall good powder properties such as smooth and spherical particles, high particle density at 99,94% and good flowability. The deposited parts with Powder A also showed the lowest amount of pores compared to Powder C, a total of 78 in all five plates, and sufficient powder efficiency at 81,6%.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1991.
Includes bibliographical references (leaves 271-275).
by David Edward Dombrowski.
Ph.D.

In the present study, the effect of S and Se substitution on structural, electrical and optical properties of AgGa(Se2-xSx) thin films has been investigated. AgGa(Se0.5S0.5 )2 thin films were prepared by using the thermal evaporation method. X-ray diffraction (XRD) analysis has revealed that the transformation from amorphous to polycrystalline structure took place at about 450 oC. The detailed information about the stoichometry and the segregation mechanisms of the constituent elements in the structure has been obtained by performing both energy dispersive X-ray analysis (EDXA) and X-ray photoelectron spectroscopy (XPS) measurements. AgGaSe2 thin films were deposited by using both electron-beam (e-beam) and sputtering techniques. In e-beam evaporated thin films, the effect of annealing on the structural and morphological properties of the deposited films has been studied by means of XRD, XPS, scanning electron microscopy (SEM) and EDXA measurements. Structural analysis has shown that samples annealed between 300 and 600 oC were in polycrystalline structure with co-existance of Ag, Ga2Se3, GaSe, and AgGaSe2. The variation of surface morphology, chemical composition and bonding nature of constituent elements on post-annealing has been determined by EDXA and XPS analyses. AgGaSe2 thin films were also prepared by using sputtering technique. XRD measurements have shown that the mono-phase AgGaSe2 structure is formed at annealing temperature of 600 oC. The crystal-field and spin-orbit splitting levels were resolved. These levels around 2.03 and 2.30 eV were also detected from the photospectral response measurements. Thin films of Ag-Ga-S (AGS) compound were prepared by using AgGaS2 single crystalline powder and deposition of the excess silver (Ag) intralayer with double source thermal evaporation method. As a consequence of systematic optimization of thickness of Ag layer, Ag(Ga,S) with the stoichiometry of AgGa5S8 and AgGaS2 were obtained and systematic study to obtain structural, electrical and optical properties was carried out.

In recent years, dry granulation using roll compaction (DGRC) attracts considerable interest of engineers and researchers, especially in the pharmaceutical industry, due to its distinct feature that no liquid binder is needed. It is generally anticipated that as a size enlarge process, DGRC would improve properties of feed powders (such as flowability and bulk density), but it was also reported that DGRC could cause a reduction in powder compactibility. A wide range of powder properties, such as size, shape, flowability, compactibility and compressibility, were analysed for several pharmaceutical excipients using the state of art techniques. Elastic-plastic properties of single component powders and mixtures were also determined using the Drucker Prager Cap (DPC) model and an example of FEM application was presented. All the properties determined were used to investigate: 1) the prediction of ribbon milling from friability tests and 2) the effect of granule size on die filling and die compaction behaviour of pharmaceutical powders. A new and easy method was developed for predicting fines produced during ribbon milling. An exponential relation between the filling ratio and the shoe speed was found. Furthermore, it is shown that flowability is strongly influenced by the granule size, and there is a decrease in the tensile strength with the increase of the granule size. Additionally, for all the materials analysed a strong correlation between the flow indexes and the critical filling speed was observed and an empirical equation is obtained.

Mechanical alloying, compaction by cold isostatic pressing, and pressureless sintering were used to study the potential for W â 3 wt% Ni â 1 wt% Fe to be processed into the bulk nanocrystalline form as a replacement material for depleted uranium in kinetic energy penetrators. Milling time and sintering temperature were varied from 15 to 100 hours and 1000 to 1300°C respectively. Particle size analysis and SEM showed a bimodal particle size distribution with most of the particles below 10 µm in size. XRD peak broadening analysis showed crystallite size to be reduced to below 50 nm, while peak shifting indicated a reduction in W lattice parameter due to dissolution of Ni and Fe atoms into the W BCC lattice. Post-sintering bulk characterization showed density increasing strongly with increasing sintering temperature to above 90% of theoretical density at 1200°C. Apparent activation energy for sintering decreased strongly with increasing milling time. SEM micrographs showed a bimodal grain size distribution with some areas of smaller submicron grains and others with larger grains on the order of 1 â 4 µm, likely connected to the bimodal particle size distribution from milling. XRD and SEM also showed the precipitation of two secondary phases during sintering: (Fe, Ni)6W6C incorporating carbon from the grinding media and an FCC solid solution of Ni, Fe, and W. The intermetallic carbide phase will increase strength but reduce ductility of the bulk material, which is not desirable. Micro and macrohardness testing show similar trends as density with a strong correlation with sintering temperature.
Master of Science

In this study, prealloyed austenitic stainless steel and premixed soft magnetic Ni-Fe permalloy compacts were consolidated through microwave and conventional sintering routes at combinations of various sintering temperatures and compaction pressures. Sintered alloys were characterized in terms of their densification, microstructural evolution as well as mechanical and magnetic properties. The effect of sintering method in terms of the applied sintering parameters on the final properties of the compacts were investigated in a comparative manner. It was determined that microwave sintered permalloys are superior compared to their conventionally sintered counterparts in densification response, microstructural characteristics such as pore shape and distribution as well as mechanical properties for both austenitic stainless steel and permalloy compacts. However, permeability of the microwave sintered permalloys was inferior to their conventionally sintered counterparts in some cases due to microstructural refinement associated with microwave sintering route.

High purity silicon material in solar cell fabrication constitutes 40% of the total cost for conventional solar cell production. One approach to reduce costs would be to use less of this expensive silicon by making thin film solar cells and use a cheaper substrate as mechanical carrier.In this work the main objective has been to manufacture silicon substrates from powder by hot-pressing. The effect of the sintering parameters has been characterized. A secondary objective was to look at the possibility to achieve larger grains by recrystallization.Samples processed by hot-pressing silicon powder of metallurgical grade with varying temperatures (1200-1375 °C), pressures (30-50 MPa) and sintering time (30-60 min) has been carried out. Halogen lamps were used for heat treatment for specific samples after hot-pressing. Microstructure and porosity were characterized using optical and electronic microscopy. EBSD was used to determine the grain size and grain orientation. The density was determined by Archimedes’ method. Resistivity was measured by a conductive probe.Densities higher than 90 % were obtained at high temperatures and pressures. The time conducted at maximum temperature during hot-pressing was not of vital importance with respect to density.The mean particle size of the powder was determined to ~20 μm, while hot-pressed samples had an average grain size of ~30 μm. The samples showed low resistivity due to high impurities of the silicon powder. High surface porosity was found for the less dense samples. Recrystallization was successfully achieved for the sample hot-pressed at 1350 °C, 30 MPa and 30 min, resulting in elimination of pores and significant grain growth from 31,83 to 56,96 μm.Characterizations of the hot-pressed samples are limited to the methods and techniques described above.

Micro-Powder Injection Moulding (Micro-PIM) technology is one of the key technologies that permit to fit with the increasing demands for smaller parts associated to miniaturization and functionalization in different application fields. The thesis focuses first on the elaboration and characterization of polymer-powder mixtures based on 316L stainless steel powders, and then on the identification of physical and material parameters related to the sintering stage and to the numerical simulations of the sintering process. Mixtures formulation with new binder systems based on different polymeric components have been developed for 316L stainless steel powders (5 µm and 16 µm). The characterization of the resulting mixtures for each group is carried out using mixing torque tests and viscosity tests. The mixture associated to the formulation comprising polypropylene + paraffin wax + stearic acid is well adapted for both powders and has been retained in the subsequent tests, due to the low value of the mixing torque and shear viscosity. The critical powder volume loading with 316L stainless steel powder (5 µm) according to the retained formulation has been established to 68% using four different methods. Micro mono-material injection (with 316L stainless steel mélange) and bi-material injection (with 316L stainless steel mélange and Cu mélange) are properly investigated. Homogeneity tests are observed for mixtures before and after injection. A physical model well suited for sintering stage is proposed for the simulation of sintering stage. The identification of physical parameters associated to proposed model are defined from the sintering stages in considering 316L stainless steel (5 µm)mixtures with various powder volume loadings (62%, 64% and 66%). Beam-bending tests and free sintering tests and thermo-Mechanical-Analyses (TMA) have also investigated. Three sintering stages corresponding to heating rates at 5 °C/min, 10 °C/min and 15 °C/min are used during both beam-bending tests and free sintering tests. On basis of the results obtained from dilatometry measurements, the shear viscosity module G, the bulk viscosity module K and the sintering stress σs are identified using Matlab® software. Afterwards, the sintering model is implemented in the Abaqus® finite element code, and appropriate finite elements have been used for the support and micro-specimens, respectively. The physical material parameters resulting from the identification experiments are used to establish the proper 316L stainless steel mixture, in combination with G, K and σs parameters. Finally, the sintering stages up to 1200 °C with three heating rates (5 °C/min, 10 °C/min and 15 °C/min) are also simulated corresponding to the four micro-specimen types (powder volume loading of 62%, 64% and 66%). The simulated shrinkages and relative densities of the sintered micro-specimens are compared to the experimental results indicating a proper agreement

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 1990.
Title as it appears in the Sept. 1990 M.I.T. Graduate List: Characterization of powder/binder interaction in the three dimensional printing process.
Includes bibliographical references (leaves 131-132).
by Marcos Esterman, Jr.
M.S.

The proteins found in milk are largely important in the functionality of many dairy products and dairy processes. The casein micelle system in milk is a complex and highly studied system. The micelle is thought to be a sponge like structure containing four caseins, αs1, αs2, β, and κ casein, and bound together with colloidal calcium phosphate. When a chelating agent such as a citrate, phosphate, or polyphosphate are added to milk systems, the CCP is bound to the chelator and removed from the micelle. It has been shown through past research that the use of calcium chelating agents disrupts the calcium phosphate equilibrium and allows for the dissociation of the casein micelle and release of the individual caseins. Once the caseins are disrupted from micellar form and in solution, it may be possible to separate out different casein streams for functional usage in dairy products using common separation techniques. This thesis project seeks to evaluate the feasibility of separating milk treated with calcium chelators using various separation techniques to evaluate the individual casein fractions of this disrupted system. Four separation methods (ultracentrifugation, membrane filtration, heat coagulation, and coagulation based on pH) were employed to separate out the caseins based on selected properties, specifically density, molecular weight, and solubility. In ultracentrifugation, three speeds were tested, the heat coagulation study tested two temperatures, and pH based coagulation tested four different pHs to determine their impact on overall protein levels and individual casein yields. Skim milk powder was reconstituted and chelator was added at 1, 50, or 100 mEq/L treatment level. These samples were then separated using aforementioned techniques, and the supernatant or permeate was analyzed for total protein content, individual casein composition, turbidity, and mean particle size. Analysis of centrifugal separation studies shows the interaction between chelator type, chelator level, and centrifugation speed had a significant impact on the amount of protein released from the casein micelle (p Coagulation trials based on pH were also shown to have a significant interaction between chelator type, chelator level, and sample pH effecting the protein levels and casein composition (p Membrane filtration showed low protein yields in permeate, however trisodium citrate 100 mEq was still shown to have significantly higher permeate % protein levels (p The use of heat based coagulation as an individual casein separation technique for chelated samples is not recommended, as the casein micelle system itself is extremely heat stable, and the use of calcium chelators only increases the heat stability further. Because of the increased heat stability, no coagulum was formed in samples upon heating, and therefore, no separation and analysis could be done. Improving our knowledge of pretreatment of milk prior to separation and the effectiveness of different separation methods on chelated milk products may result in information leading to the ability to separate out milk fractions that provide unique or improved properties for product applications.

This work details an investigation into the production of porous shape memory alloys (SMAs) via hot isostatic press (HIP) from prealloyed powders. HIPing is one of three main methods for producing porous SMAs, the other two are conventional sintering and selfpropagating hightemperature synthesis (SHS). Conventional sintering is characterized by its long processing time at near atmospheric pressure and samples made this way are limited in porosity range. The SHS method consists of preloading a chamber with elemental powders and then initiating an explosion at one end, which then propagates through the material in a very short time. HIPing provides a compromise between the two methods, requiring approximately 5 hours per cycle while operating in a very controlled environment. The HIPing method gives fine control of both temperature and pressure during the run which allows for the production of samples with varying porosity as well as for finetuning of the process for other characteristics. By starting with prealloyed powder, this study seeks to avoid the drawbacks while retaining the benefits of HIPing with elemental powders. In an extension of previous work with elemental powders, this study will apply the HIP method to a compact of prealloyed powders. It is hoped that the use of these powders will limit the formation of alternate phases as well as reducing oxidation formed during preparation. In addition, the nearspherical shape of the powders will encourage an even pore distribution. Processing techniques will be presented as well as a detailed investigation of the thermal and mechanical properties of the resulting material.

The KTH Department of Materials Science and Engineering has lacked powder metallurgy research for many years, and as this field is constantly gaining in importance, such research needs to be reestablished. This requires the department to be able to accurately and efficiently characterize the properties of a powder, such as size distribution and composition, and in the short term, this needs to be done using non-specialized equipment. This project aimed to assess the availability and usefulness of both traditional and novel characterization methods by way of trial characterization experiments as well as a literature review.   The experiments resulted in some data about three sample powders, as well as the conclusions that size distribution could be effectively characterized by automatized image analysis, composition could be characterized using Energy Dispersive X-ray Spectroscopy and that sample preparation was key to good results. It was concluded that the department could conceivably evaluate the most important properties, but that sampling and sample preparation routines need to be established to ensure efficient characterization and representative data.
Materialinstitutionen på Kungliga Tekniska högskolan har i många år helt saknat pulvermetallurgiforskning och eftersom detta fält ständigt blir mer relevant behöver denna forskning återetableras. Detta kräver att institutionen med tillräcklig noggrannhet och effektivitet kan bestämma egenskaper hos ett pulver, såsom storleksfördelning och sammansättning, och på kort sikt behöver detta ske med ickespecialiserad utrustning. I detta projekt har tillgänglighet och användbarhet hos både traditionella och innovativa analysmetoder utvärderats med hjälp av experimentell karaktärisering av pulver samt en litteraturstudie. Experimenten gav data om de tre undersökta pulvren och resulterade även i slutsatsen att storleksfördelning kunde bestämmas med automatiserad bildanalys, att samansättning kunde bestämmas med Energi Dispersiv Röntgen Spektroskopi och att provpreparering äravgörande för bra resultat. Av detta följer att institutionen rimligtvis kan bestämma de viktigaste egenskaperna hos ett pulver, men att rutiner för provtagning och provpreparering behöver etableras för att säkerställa effektiv analys och representativ data.

Knowledge on metal release processes from stainless steel powder, which can be potentially inhaled at occupational settings, is essential within the framework of human health and environmental risk assessments. An in-depth knowledge concerning powder history, physical properties of particles (e.g. size, morphology, and active surface area) combined with their chemical properties (such as the chemical composition of the particles and their metal release behavior) is needed for better understanding of the interaction mechanisms between metal powders and humans. So far, limited in vitro and in vivo studies exist that assess the correlation between stainless steel surface properties, protein adsorption effects, and metal release processes. The aim of this study is to add information to fill this knowledge gap through in vitro investigations of protein-induced metal release (iron, nickel, chromium, and manganese) and induced surface changes of five differently sized and/or produced (water-atomized (WA) and gas-atomized (GA)) stainless steel powder particles (three austenitic: AISI 316L, 310B, and 304B; one martensitic: AISI 410L; and one ferritic: AISI 430L) after exposure up to one week into a phosphate buffer saline (PBS) solution of pH 7.2-7.4 containing either lysozyme (LYS) or bovine serum albumin (BSA). The results show that the outmost surface oxide composition of the powders strongly depends on the production method and particle size. Gas-atomized 316L powder particles (with spherical shapes) indicated a high relative manganese content in their surface oxide (more significant in the case of 316L particles sized <4µm), while no manganese compounds were detectable in the surface oxide of water-atomized powders (of irregular particle shapes). Although austenitic stainless steels should present non-magnetic properties, the investigation of magnetic properties indicated that differently sized gas-atomized 316L particles and water-atomized 304B were to some extent ferromagnetic suggesting the presence of ferrite. BSA induced a significant enrichment of chromium in the surface oxide of all investigated powders (especially for ferritic WA430L and austenitic WA316L), except in the case of 316L powders (<4µm) showing no significant change. Metal release studies illustrated that both proteins enhanced the amount of released metal, with a preferential iron release from water-atomized particles and manganese release from gas-atomized powders. BSA-containing medium induced the highest extent of metal release in comparison with other tested biological media (up to 35-fold increase in the case of ferritic 430L particles produced by water atomization). Comparison between the metal release behavior of particulate and massive stainless steel indicated a significantly higher extent of metal released from abraded stainless steel sheets compared with particles, which is most probably an effect of freshly abraded surfaces of the massive metal sheets, not true for the particles with aged surface oxides, along with the presence of higher relative chromium content in the surface oxide.

A study was carried out on the selection of processing condition that would yield Mg-Ti with most favourable hydrogenation properties. Processing routes under consideration were
mechanical milling under inert atmosphere, reactive milling i.e. milling under hydrogen atmosphere, ECAP (equal channel angular pressing) and thermal plasma synthesis. Structure resulting from each of these processing routes was characterized with respect to size reduction, coherently diffracting volume and the distribution of Ti catalyst. Mechanical milling yielded a particulate structure made up of large Mg agglomerates with embedded Ti fragments with a uniform distribution. Mg agglomerates have sizes larger than 100 µ
m which arises as a result of a balance between cold welding process and ductile fracture. Repeated folding of Mg particles entraps Ti fragments inside the Mg agglomerates resulting in a very uniform distribution. Coherently diffracting volumes measured by X-ray Rietveld analysis have small sizes ca. 26 nm which implies that the agglomerates typically comprise 1011 crystallites. Mechanical milling under hydrogen, i.e. reactive milling, led to drastic reduction in particle size. Mg and Ti convert to MgH2 and TiH2 which are milled efficiently due to their brittleness resulting in particle sizes of sub-micron range. Hydrogenation experiments carried out on Mg-10 vol % Ti milled under argon yields enthalpy and entropy values of -76.74 kJ/mol-H2 and -138.64 J/K.mol-H2 for absorption and 66.54 kJ/mol H2 and 120.12 J/K.mol H2 for desorption, respectively. For 1 bar of hydrogen pressure, this corresponds to a hydrogen release temperature of 280 °
C. This value is not far off the lowest desorption temperature reported for powder processed Mg based alloys. ECAP processing is a bulk process where the powders, consolidated in the first pass, have limited contact with atmosphere. This process which can be repeated many times lead to structural evolution similar to that of milling, but for efficient mixing of phases it was necessary to employ multi-pass deformation. An advantage of ECAP deformation is strain hardening of the consolidated powders which has improved milling ability. Based on this, a new route was proposed for the processing of ductile hydrogen storage alloys. This involves several passes of ECAP deformation carried out in open atmosphere and a final milling operation of short duration under inert atmosphere. The plasma processing yields Mg particles of extremely small size. Evaporation of Mg-Ti powder mixture and the subsequent condensation process yield Mg particles which are less than 100 nm. Ti particles, under the current experimental condition used, have irregular size distribution but some could be quite small, i.e. in the order of a few tens of nanometers. Of the four processing routes, it was concluded that both reactive milling and thermal plasma processing are well suited for the production of hydrogen storage alloys. Reactive milling yield particles in submicron range and plasma processing seems to be capable of yielding nanosize Mg particles which, potentially, could be decorated with even smaller Ti particles.

Metallic glasses exhibit many attractive attributes such as outstanding mechanical, magnetic, and chemical properties. Due to the absence of crystal defects, metallic glasses display remarkable mechanical properties including higher specific strength than crystalline alloys, high hardness and larger fracture resistance than ceramics. The technological breakthrough of metallic glasses, however, has been greatly hindered by the limited plastic strain to failure. Thus, several strategies have been employed to improve the intrinsic and extrinsic effects on the flow behavior of metallic glasses with respect to their fracture toughness and overall plastic strain. One of the suggested strategies is the production of a composite consisting of the brittle metallic glass along with a ductile second phase that either acts as an active carrier of plastic strain or passively enhances the multiplication of shear bands via shear-band splitting . Another approach for increasing plastic deformation consists of introducing pores as a gaseous second phase into the material. The pores are similarly effective in delaying catastrophic failure resulting from shear band localization. In metallic glasses with high porosity, propagation of shear bands can even become stable, enabling macroscopic compressive strains of more than 80 % without fracture. In this thesis, Ni59Zr20Ti16Si2Sn3 glass and its composites have been fabricated using mechanical milling and consolidation by hot pressing followed by extrusion of Ni59Zr20Ti16Si2Sn3 metallic glass powder or Ni59Zr20Ti16Si2Sn3 metallic glass powder reinforced with 40 vol.% of brass particles to obtained bulk composite materials with high strength and enhanced compressive plasticity and to generate porous structure in Ni59Zr20Ti16Si2Sn3 metallic glass using selective dissolution. The brass–glass powder mixtures to be consolidated were prepared using two different approaches: manual blending and ball milling to properly vary size and morphology of the second phase in the composites. Powder consolidation was carried out at temperatures within the supercooled Liquid (SCL) region, where the glassy phase displays a strong decrease of viscosity, with using the sintering parameters which were chosen after analysis of the crystallization behavior of the glassy phase to avoid its crystallization during consolidation. Ball milling has a significant effect on the microstructure of the powder mixtures: a refined layered structure consisting of alternating layer of glass and brass is formed as a result of the mechanical deformation. However, ball milling reduces the amorphous content of the composite powders due to mechanically induced crystallization and reaction of the glass and brass phases during heating. In addition, the milling of the composite powders and the following consolidation step reduces the amorphous content by about 50 %. The bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy synthesized by hot pressing exhibits higher strength (2.28 GPa) than that of the as-cast bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy (2.2 GPa). The mechanical behavior of the glass-brass composites is significantly affected by the control of the microstructure between the reinforcement and the nano-grained matrix phase through the different methods used for the preparation of the powder mixtures. The strength of the composites increases from 500 MPa for pure brass to 740 and 925 MPa for the composites with 40 and 60 vol.% glass reinforcement prepared by manual blending. The strength further increases to 1240 and 1640 MPa for the corresponding composites produced by ball milling caused by the remarkable effect of the matrix ligament size on the strengthening of the composites. The porous metallic glass was obtained by the selective dissolution in a HNO3 solution of the fugitive brass phase in the Ni59Zr20Ti16Si2Sn3 composite. The microstructure of the porous samples consists of highly elongated layered pore structures and/or irregularly shaped pores. The average size of the pores depends on the processing parameters and can be varied in the range of 0.4–15 µm. Additional porous samples were prepared from different extruded composite precursors of blended and milled powder mixtures. This leads to customized hybrid porous structures consisting of a combination of large and small pores. The specific surface area of the porous Ni-based metallic glass powder measured by the BET method is 16 m2/g, while the as-atomized Ni59Zr20Ti16Si2Sn3 powder has a specific surface area of 0.29 m2/g. This indicates a mechanical milling induced enhancement in surface area by refinement of the fugitive brass phase. However the specific surface area of the porous Ni-based metallic glass obtained from as-extruded precursors is 10 m2/g caused by a breakdown of the porous structure during selective dissolution of the nano-scale fugitive phase. Although milling of the present composite powders and the following consolidation step reduces the amorphous content by about 50 %, through the use of glassy phases with improved stability against mechanically induced crystallization along with reduced affinity with the fugitive phase to avoid unwanted reactions during processing, this approach using powder metallurgical offers the possibility to produce highly active porous bulk materials for functional applications, such as catalysis, which require the fast transport of reactants and products provided by the large pores along with high catalytic activity ensured by the large surface area characterizing the small pores. Accordingly, gas absorption ability tests of porous Ni-based metallic glass powders have been performed in order to evaluate the possibility of replacement of conventional support materials. From these first tests it can be conclude that additional opportunities should exist for nano-porous MGs with designed architecture of porous structures that are tailored to specific functional applications
Metallische Gläser weisen viele attraktive mechanische, magnetische und chemische Eigenschaften auf. Aufgrund der fehlenden Kristallstruktur zeigen metallische Gläser bemerkenswerte mechanische Eigenschaften, einschließlich höherer spezifischer Festigkeit, höherer Härte und größerer Bruchfestigkeit als Keramik. Der technologischen Durchbruch metallischer Gläser wird jedoch bis heute stark von ihremspröden Bruchverhalten behindert. Deshalb wurden verschiedene Herstellungsverfahren entwirkt, um sowohl die plastische Verformung der metallischer Massivgläser zu erhöhen, als auch um die mechanischen Eigenschaften generell zu verbessern. Eine mögliche Methode, zur Erhöhung der Plastizität und zur Beeinflussung der mechanischen Eigenschaften der metallischen Gläser ist der Einbau zweiter Phasen, wie z.B. durch Fremdpartikel Verstärkung oder Poren in Kompositen. Die Scherband bewegung wird durch die Wechselwirkung mit zweiten Phasen behindert, und gleichzeitig werden durch die in den Grenzflächen entstehenden Spannungsspitzen zwischen der zweiten Phase und der Matrix neue Scherbänder initiert. Dies führt zur Bildung einer Vielzahl von Scherbändern, was eine höhere plastische Dehnung zur Folge hat, da die Deformationsenergie auf ein größeres Volumen verteilt wird. In der vorliegenden Arbeit wurden Ni59Zr20Ti16Si2Sn3 Massivglas und mit Messing- verstärkte Komposite durch Kugelmahlen und Heißpressen mit anschließender Extrusion von Ni59Zr20Ti16Si2Sn3 Pulver oder Ni59Zr20Ti16Si2Sn3 Pulver mit 40 vol.% Messing Partikeln hergestellt. Neben der Herstellung der Ni59Zr20Ti16Si2Sn3 Komposite mit Messing Partikeln, wurden auch Ni59Zr20Ti16Si2Sn3 Komposite mit definierter Porösität durch die selektive Auflösung der zweiten Phase erzeugt. Die verwendete Mischung von Messing und metallischem Glaspulver wurde über zwei verschiedene Ansätzen hergestellt: die Pulver wurden manuell gemischt oder gemahlen, um die optimale Größe und Morphologie der zweiten Phase in den Komositen zu erzeugen. Das Sintern der Pulver erfolgte bei Temperaturen im Bereich der unterkühlten Schmelze, wobei die Legierung eine starke Abnahme der Viskosität zeigte, mit Hilfe optimierter Sinterparameter, die nach der Analyse des Kristallisationsverhaltens der gläsernen Phase ausgewählt wurden, um deren Kristallisation während der Konsolidierung zu vermeiden. Kugelmahlen hat einen signifikanten Einfluss auf die Mikrostruktur der gemahlenen Pulver: Eine verfeinerte Lamellare Struktur, teils bestehend aus Glas und teils aus Messing, wird durch mechanische Verformung gebildet. Kugelmahlen reduziert jedoch den amorphen Anteil der Komposite durch mechanische induzierte Kristallisation und die Reaktion der Glas- und Messing- Phasen durch Erwärmung. Das Kugelmahlen der Komposite (Pulver) und das darauf folgende Sintern führte zur eine Absenkung der freien Enthalpie der amorphen Phase um ca. 50%. Ni59Zr20Ti16Si2Sn3 metallische Massivgläser, welche durch Heißpressen hergestellt werden, weisen eine höhere Streckgrenze von 2.28 GPa als das gegossene Ni59Zr20Ti16Si2Sn3 Massivglas (2.2 GPa) auf. Die mechanischen Eigenschaften der mit Messing Ni59Zr20 Ti16Si2Sn3 verstärkten Komposite sind abhängig von der Kontrolle der Mikrostruktur zwischen den zweiten Phasen und der Matrixphase durch die verschiedenen Verfahren zur Herstellung von Pulvermischungen. Die Festigkeiten der Komposite, welche durch Handmischen und Heißpressen mit nachfolgender Extrusion hergestellt wurden, erhöhten sich von 500 MPa für reines Messing bis auf 740 und 925 MPa für die Komposite mit 40 und 60 Vol. % Glaspartikel- Verstärkung durch Handmischen. Die Festigkeiten erhöhten sich nochmals auf 1240 und 1640 MPa für die Komposite mit 40 und 60 Vol. % an Glaspartikel-Verstärkung mit lamellare Stuktur, die durch Kugelmahlen hergestellt würden. Die Ursache hier für liegt in der Wirkung der Ligamentabmessungen zwischen den Matrixbestandteilen hinsichtlich der Verfestigung der Komposite. Die Porösität im metallischen Glas wurde durch die selektive Auflösung der flüchtigen Messingphasen in den Kompositen mit Salpetersäure-Lösung erhalten. Die Mikrostuktur der porösen metallischen Gläser besteht aus stark elongiert geschichteten Porenstrukturen und/oder unregelmäßig geformten Poren. Die durchschnittliche Größe einer Pore hängt von den behandelnden Parametern ab und kann von 0.4–15 µm variieren. Weitere poröse Proben wurden ausgehend von verschiedenen extrudierten Komposit-Precursoren aus handgemischten und kugelgemahlenen Pulvermixturen erzeugt. Dies führte zu angepassten hybrid-porösen Strukturen bestehend aus einer Kombination von großen und kleinen Poren. Die spezifische Oberfläche des porösen Glaspulvers gemessen mit Hilfe der BET- Methode, beträgt 16m2/g, wohingegen das atomisierte Ni59Zr20Ti16Si2Sn3 MG Ausgangspulver eine spezifische Oberfläche von 0.29 m2/g besitzt. Dies weist darauf hin, dass das Mahlen eine Vergrößerung der Oberfläche durch die Verfeinerung der flüchtigen Messingphase induziert. Die spezifische Oberfläche der porösen-metallischen Gläser beträgt 10 m2/g und entsteht durch die Zerstörung der porösen Struktur während der selektiven Auflösung der nanoskaligen flüchtigen Phase. Obwohl das Kugelmahlen der Komposite (Pulver) und die darauf folgende Konsolidierung zwar den amorphen Anteil um etwa 50% reduziert, bietet die Pulvermetallurgische Herstellung durch die Verwendung von gläsernen Phasen mit verbesserter Stabilität gegenüber mechanisch induzierter Kristallisation, sowie einer reduzierten Affinität mit der flüchtigen Messingphase zur Vermeidung von unerwünschten Reaktionen während des Prozesses eine Möglichkeit, hochaktive poröse metallische Gläser für funktionelle Anwendungen, wie z.B. Katalyse, zu entwickeln. Hier ist eine schnelle Transport von Reaktanten und Produkten, welcher von den großen Poren, sowie eine hohe katalytische Aktivität, die von kleinen Poren und einer großen Oberfläche sichergestellt wird wesentlich. Daher wurden Untersuchungen zur Gasabsorptionsfähigkeit von porösem metallischen Glaspulver durchgeführt, um die Möglichkeit der Ersetzung von konventionellen Trägermaterialen bewerten zu können. Diese ersten Versuche zeigen die grundsäLzliche Eignung nano poröse metallischer Gläser zur Herstellung von porösen Strukturen mit einstellbarer Porenarchitektur auf die Langfristig für spezifische funktionelle Anwendungen von Interesse sein könnten

Metallic glasses exhibit many attractive attributes such as outstanding mechanical, magnetic, and chemical properties. Due to the absence of crystal defects, metallic glasses display remarkable mechanical properties including higher specific strength than crystalline alloys, high hardness and larger fracture resistance than ceramics. The technological breakthrough of metallic glasses, however, has been greatly hindered by the limited plastic strain to failure. Thus, several strategies have been employed to improve the intrinsic and extrinsic effects on the flow behavior of metallic glasses with respect to their fracture toughness and overall plastic strain. One of the suggested strategies is the production of a composite consisting of the brittle metallic glass along with a ductile second phase that either acts as an active carrier of plastic strain or passively enhances the multiplication of shear bands via shear-band splitting . Another approach for increasing plastic deformation consists of introducing pores as a gaseous second phase into the material. The pores are similarly effective in delaying catastrophic failure resulting from shear band localization. In metallic glasses with high porosity, propagation of shear bands can even become stable, enabling macroscopic compressive strains of more than 80 % without fracture. In this thesis, Ni59Zr20Ti16Si2Sn3 glass and its composites have been fabricated using mechanical milling and consolidation by hot pressing followed by extrusion of Ni59Zr20Ti16Si2Sn3 metallic glass powder or Ni59Zr20Ti16Si2Sn3 metallic glass powder reinforced with 40 vol.% of brass particles to obtained bulk composite materials with high strength and enhanced compressive plasticity and to generate porous structure in Ni59Zr20Ti16Si2Sn3 metallic glass using selective dissolution. The brass–glass powder mixtures to be consolidated were prepared using two different approaches: manual blending and ball milling to properly vary size and morphology of the second phase in the composites. Powder consolidation was carried out at temperatures within the supercooled Liquid (SCL) region, where the glassy phase displays a strong decrease of viscosity, with using the sintering parameters which were chosen after analysis of the crystallization behavior of the glassy phase to avoid its crystallization during consolidation. Ball milling has a significant effect on the microstructure of the powder mixtures: a refined layered structure consisting of alternating layer of glass and brass is formed as a result of the mechanical deformation. However, ball milling reduces the amorphous content of the composite powders due to mechanically induced crystallization and reaction of the glass and brass phases during heating. In addition, the milling of the composite powders and the following consolidation step reduces the amorphous content by about 50 %. The bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy synthesized by hot pressing exhibits higher strength (2.28 GPa) than that of the as-cast bulk amorphous Ni59Zr20Ti16Si2Sn3 alloy (2.2 GPa). The mechanical behavior of the glass-brass composites is significantly affected by the control of the microstructure between the reinforcement and the nano-grained matrix phase through the different methods used for the preparation of the powder mixtures. The strength of the composites increases from 500 MPa for pure brass to 740 and 925 MPa for the composites with 40 and 60 vol.% glass reinforcement prepared by manual blending. The strength further increases to 1240 and 1640 MPa for the corresponding composites produced by ball milling caused by the remarkable effect of the matrix ligament size on the strengthening of the composites. The porous metallic glass was obtained by the selective dissolution in a HNO3 solution of the fugitive brass phase in the Ni59Zr20Ti16Si2Sn3 composite. The microstructure of the porous samples consists of highly elongated layered pore structures and/or irregularly shaped pores. The average size of the pores depends on the processing parameters and can be varied in the range of 0.4–15 µm. Additional porous samples were prepared from different extruded composite precursors of blended and milled powder mixtures. This leads to customized hybrid porous structures consisting of a combination of large and small pores. The specific surface area of the porous Ni-based metallic glass powder measured by the BET method is 16 m2/g, while the as-atomized Ni59Zr20Ti16Si2Sn3 powder has a specific surface area of 0.29 m2/g. This indicates a mechanical milling induced enhancement in surface area by refinement of the fugitive brass phase. However the specific surface area of the porous Ni-based metallic glass obtained from as-extruded precursors is 10 m2/g caused by a breakdown of the porous structure during selective dissolution of the nano-scale fugitive phase. Although milling of the present composite powders and the following consolidation step reduces the amorphous content by about 50 %, through the use of glassy phases with improved stability against mechanically induced crystallization along with reduced affinity with the fugitive phase to avoid unwanted reactions during processing, this approach using powder metallurgical offers the possibility to produce highly active porous bulk materials for functional applications, such as catalysis, which require the fast transport of reactants and products provided by the large pores along with high catalytic activity ensured by the large surface area characterizing the small pores. Accordingly, gas absorption ability tests of porous Ni-based metallic glass powders have been performed in order to evaluate the possibility of replacement of conventional support materials. From these first tests it can be conclude that additional opportunities should exist for nano-porous MGs with designed architecture of porous structures that are tailored to specific functional applications.
Metallische Gläser weisen viele attraktive mechanische, magnetische und chemische Eigenschaften auf. Aufgrund der fehlenden Kristallstruktur zeigen metallische Gläser bemerkenswerte mechanische Eigenschaften, einschließlich höherer spezifischer Festigkeit, höherer Härte und größerer Bruchfestigkeit als Keramik. Der technologischen Durchbruch metallischer Gläser wird jedoch bis heute stark von ihremspröden Bruchverhalten behindert. Deshalb wurden verschiedene Herstellungsverfahren entwirkt, um sowohl die plastische Verformung der metallischer Massivgläser zu erhöhen, als auch um die mechanischen Eigenschaften generell zu verbessern. Eine mögliche Methode, zur Erhöhung der Plastizität und zur Beeinflussung der mechanischen Eigenschaften der metallischen Gläser ist der Einbau zweiter Phasen, wie z.B. durch Fremdpartikel Verstärkung oder Poren in Kompositen. Die Scherband bewegung wird durch die Wechselwirkung mit zweiten Phasen behindert, und gleichzeitig werden durch die in den Grenzflächen entstehenden Spannungsspitzen zwischen der zweiten Phase und der Matrix neue Scherbänder initiert. Dies führt zur Bildung einer Vielzahl von Scherbändern, was eine höhere plastische Dehnung zur Folge hat, da die Deformationsenergie auf ein größeres Volumen verteilt wird. In der vorliegenden Arbeit wurden Ni59Zr20Ti16Si2Sn3 Massivglas und mit Messing- verstärkte Komposite durch Kugelmahlen und Heißpressen mit anschließender Extrusion von Ni59Zr20Ti16Si2Sn3 Pulver oder Ni59Zr20Ti16Si2Sn3 Pulver mit 40 vol.% Messing Partikeln hergestellt. Neben der Herstellung der Ni59Zr20Ti16Si2Sn3 Komposite mit Messing Partikeln, wurden auch Ni59Zr20Ti16Si2Sn3 Komposite mit definierter Porösität durch die selektive Auflösung der zweiten Phase erzeugt. Die verwendete Mischung von Messing und metallischem Glaspulver wurde über zwei verschiedene Ansätzen hergestellt: die Pulver wurden manuell gemischt oder gemahlen, um die optimale Größe und Morphologie der zweiten Phase in den Komositen zu erzeugen. Das Sintern der Pulver erfolgte bei Temperaturen im Bereich der unterkühlten Schmelze, wobei die Legierung eine starke Abnahme der Viskosität zeigte, mit Hilfe optimierter Sinterparameter, die nach der Analyse des Kristallisationsverhaltens der gläsernen Phase ausgewählt wurden, um deren Kristallisation während der Konsolidierung zu vermeiden. Kugelmahlen hat einen signifikanten Einfluss auf die Mikrostruktur der gemahlenen Pulver: Eine verfeinerte Lamellare Struktur, teils bestehend aus Glas und teils aus Messing, wird durch mechanische Verformung gebildet. Kugelmahlen reduziert jedoch den amorphen Anteil der Komposite durch mechanische induzierte Kristallisation und die Reaktion der Glas- und Messing- Phasen durch Erwärmung. Das Kugelmahlen der Komposite (Pulver) und das darauf folgende Sintern führte zur eine Absenkung der freien Enthalpie der amorphen Phase um ca. 50%. Ni59Zr20Ti16Si2Sn3 metallische Massivgläser, welche durch Heißpressen hergestellt werden, weisen eine höhere Streckgrenze von 2.28 GPa als das gegossene Ni59Zr20Ti16Si2Sn3 Massivglas (2.2 GPa) auf. Die mechanischen Eigenschaften der mit Messing Ni59Zr20 Ti16Si2Sn3 verstärkten Komposite sind abhängig von der Kontrolle der Mikrostruktur zwischen den zweiten Phasen und der Matrixphase durch die verschiedenen Verfahren zur Herstellung von Pulvermischungen. Die Festigkeiten der Komposite, welche durch Handmischen und Heißpressen mit nachfolgender Extrusion hergestellt wurden, erhöhten sich von 500 MPa für reines Messing bis auf 740 und 925 MPa für die Komposite mit 40 und 60 Vol. % Glaspartikel- Verstärkung durch Handmischen. Die Festigkeiten erhöhten sich nochmals auf 1240 und 1640 MPa für die Komposite mit 40 und 60 Vol. % an Glaspartikel-Verstärkung mit lamellare Stuktur, die durch Kugelmahlen hergestellt würden. Die Ursache hier für liegt in der Wirkung der Ligamentabmessungen zwischen den Matrixbestandteilen hinsichtlich der Verfestigung der Komposite. Die Porösität im metallischen Glas wurde durch die selektive Auflösung der flüchtigen Messingphasen in den Kompositen mit Salpetersäure-Lösung erhalten. Die Mikrostuktur der porösen metallischen Gläser besteht aus stark elongiert geschichteten Porenstrukturen und/oder unregelmäßig geformten Poren. Die durchschnittliche Größe einer Pore hängt von den behandelnden Parametern ab und kann von 0.4–15 µm variieren. Weitere poröse Proben wurden ausgehend von verschiedenen extrudierten Komposit-Precursoren aus handgemischten und kugelgemahlenen Pulvermixturen erzeugt. Dies führte zu angepassten hybrid-porösen Strukturen bestehend aus einer Kombination von großen und kleinen Poren. Die spezifische Oberfläche des porösen Glaspulvers gemessen mit Hilfe der BET- Methode, beträgt 16m2/g, wohingegen das atomisierte Ni59Zr20Ti16Si2Sn3 MG Ausgangspulver eine spezifische Oberfläche von 0.29 m2/g besitzt. Dies weist darauf hin, dass das Mahlen eine Vergrößerung der Oberfläche durch die Verfeinerung der flüchtigen Messingphase induziert. Die spezifische Oberfläche der porösen-metallischen Gläser beträgt 10 m2/g und entsteht durch die Zerstörung der porösen Struktur während der selektiven Auflösung der nanoskaligen flüchtigen Phase. Obwohl das Kugelmahlen der Komposite (Pulver) und die darauf folgende Konsolidierung zwar den amorphen Anteil um etwa 50% reduziert, bietet die Pulvermetallurgische Herstellung durch die Verwendung von gläsernen Phasen mit verbesserter Stabilität gegenüber mechanisch induzierter Kristallisation, sowie einer reduzierten Affinität mit der flüchtigen Messingphase zur Vermeidung von unerwünschten Reaktionen während des Prozesses eine Möglichkeit, hochaktive poröse metallische Gläser für funktionelle Anwendungen, wie z.B. Katalyse, zu entwickeln. Hier ist eine schnelle Transport von Reaktanten und Produkten, welcher von den großen Poren, sowie eine hohe katalytische Aktivität, die von kleinen Poren und einer großen Oberfläche sichergestellt wird wesentlich. Daher wurden Untersuchungen zur Gasabsorptionsfähigkeit von porösem metallischen Glaspulver durchgeführt, um die Möglichkeit der Ersetzung von konventionellen Trägermaterialen bewerten zu können. Diese ersten Versuche zeigen die grundsäLzliche Eignung nano poröse metallischer Gläser zur Herstellung von porösen Strukturen mit einstellbarer Porenarchitektur auf die Langfristig für spezifische funktionelle Anwendungen von Interesse sein könnten.

Thesis (M.S.)--Michigan State University. Materials Science and Engineering, 2008.
Title from PDF t.p. (viewed on Aug. 7, 2009) Includes bibliographical references (p. 151-159). Also issued in print.

Metal alloy honeycomb structures were fabricated using a paste extrusion technique and characterized for potential application as interconnects in solid oxide fuel cells. Thermal expansion characteristics of Fe-Cr, Fe-Ni, Ni-Cr, Fe-Ni-Cr, and similar alloys containing an oxide dispersion were determined and compared with the thermal expansion behavior of yttria-stabilized zirconia (YSZ). A method was developed to calculate thermal expansion mismatch between two materials under a variety of heating and cooling conditions. It was shown that Fe 20 wt% Cr and Fe 47.5 wt% Ni alloys have low expansion mismatch with YSZ under a wide range of heating and cooling conditions. Oxidation experiments showed that Fe-Cr alloys have superior oxidation resistance in air at 700℃compared with Fe-Ni-Cr alloys with similar chromium contents. The inclusion of oxide dispersions (Y₂O₃ and CaO) into an alloy honeycomb was shown to improve oxidation resistance without affecting thermal expansion behavior. The honeycomb extrusion process provides a method by which experimental alloys can be produced and characterized rapidly to develop an alloy suitable for use as an interconnect in a solid oxide fuel cell.

For biomedical applications, the implants always require specific shapes to fulfill the requirements of the different bone tissues. Recently, laser powder bed fusion (L-PBF) in additive manufacturing techniques (e.g., selective laser melting) has attracted extensive attention in manufacturing complex and near net-shaped parts with almost no geometric constraints on the final product. It also has the advantage of less production cycle with high material utilization rate when compared with the conventional manufacturing methods (materials removal from ingot). The L-PBF-produced alloys are proved to have enhanced or comparable mechanical properties that benefit from the rapid cooling rate in the manufacturing process. However, the corrosion resistance of some produced alloys has been proved to have inferior corrosion resistance in some harsh environments. Although the corrosion mechanism of the L-PBFproduced alloys has been studied gradually in recent, and the results are still not enough to support the L-PBF-produced alloys for commercial use. Therefore, some of the corrosionrelated aspects are investigated in this thesis, which include feedstock types for the L-PBF process, electrolyte types and conditions, plastic deformation, and long-term immersions. In the aspect of feedstock types, the corrosion behavior and mechanism of L-PBFproduced Ti35Nb are separately produced by using mixed powder (Ti35Nb-M) and pre-alloyed powder (Ti35Nb-P) were investigated (in Hank’s solution). Both produced alloys demonstrate similar corrosion behavior, but the oxide film formed on Ti35Nb-M shows inferior stability with more defects. Dual-layered films are found on the TiNb regions both in Ti35Nb-M and Ti35Nb-P, while the outer porous layer on Ti35Nb-M exhibits more defects due to the microgalvanic effect. In the aspect of electrolyte condition, the corrosion behavior and passivation behavior of L-PBF-produced Ti-6Al-4V were investigated in different concentrations of NaCl solutions under static and dynamic conditions. The results indicate the higher concentration of Cl- could promote the reactions between metal matrix and electrolyte, and therefore, increase the thickness of the produced oxide film. The effect of Cl- on corrosion is mainly attributed to the dissolution of the TiO2 where located in the outermost oxide film. In addition, the corrosion behavior and passivation behavior of L-PBF-produced Ti-6Al- 4V were also investigated under various compressive strains (from initial until failure). A decreased corrosion resistance of the alloy was found with an increase in the compressive strain. The reason could be attributed to the deformation and breakages of the acicular α'-Ti phase, resulting in the enhancement of the oxide film growth with an inferior corrosion resistance (oxide film containing more point defects). In the aspect of long-term immersion, the L-PBF-produced CoCrW alloys also used the electrochemical methods and surface characterization method to investigate their corrosion behavior and mechanisms in 0.9 wt% NaCl solution with a pH of 2. The corrosion resistance of the produced alloys decreased during the 28 days of immersion due to the diffusion of element W in the oxide film, which results in the decreased stability of the formed oxide film (Cr2O3). In addition, the corrosion of the L-PBF-produced CoCrW alloy on a macro-scale is related to the dissolution of the melt pool that results from the scan strategy in the PBF process. The results suggest that the L-PBF-produced Ti-35Nb, Ti-6Al-4V, and CoCrW are highly corrosion-resistant, although there is a small difference in the electrochemical behavior and the formed oxide film. Therefore, this research demonstrates that the alloy produced through LPBF- produced alloy has more desirable properties in corrosion performance, and it also laid a foundation for the application of L-PBF-produced metallic biomaterials in biomedical applications.

In the scope of this study, TiNi foams with porosities in the range of 39-64 vol% were processed from prealloyed powders by Mg space holder technique. Porous TiNi alloys displayed homogeneously distributed spherical pores with interconnections, which is suitable for bone ingrowth. Porous Ti-50.8 at%Ni alloys were processed by sintering at 1200 °
C for 2 h to analyze the microstructure as well as mechanical behavior. SEM, TEM and XRD studies were conducted for the characterization of microstructure and phase analyses in addition to the mechanical characterization performed by monotonic and superelasticity compression tests as well as compressive fatigue tests. It was observed that stress required to trigger martensitic transformation was decreased via increasing porosity. The monotonic compression test results also indicated that altering the porosity content of TiNi foams leads to different monotonic compression behaviors. It was observed that the foams display more bulk deformation like behavior as a composite structure composed of TiNi and macropores when the porosity content was low. As the porosity content has increased, the struts became more effective and deformation proceeds by the collapse of favorable struts. On the other hand, cyclic superelasticity tests results indicated that maximum achieved and recovered strain values at the end of fifth cycle increase while the fraction of strain recovered at the end of fifth cycle decreases with decreasing porosity content. Furthermore, the fatigue lives of the processed foams were observed to vary within a band which has a width decreasing with decreasing &sigma
max / &sigma
y yielding an endurance limit ranging in between 26-89 MPa or 0.5-0.6 &sigma
y. Fractography studies on the failed foams after fatigue testing revealed that the failure occurs by the coalescence of micro-cracks initiated from pore walls leading to macro-cracks aligned at 45o with respect to the loading axis. In addition to the mentioned characterization studies, the effects of sintering temperature and time on TiNi foams with 58 vol% porosity as well as heat treatment on the microstructure and the mechanical behavior of TiNi foams with 49 vol% porosity were analyzed with SEM and compression tests. Aging of TiNi foams with 49 vol% porosity at 450 °
C for 1.5 h has shown that the presence of Ti3Ni4 precipitates improve the superelastic response.

A newly developed martensitic stainless steel powder, called “powder A”, designed for surface coating with laser cladding and PTA cladding was characterized. The purpose with powder A is to achieve both good corrosion resistance and wear resistance in a stainless steel grade. The investigation of powder A was divided into cladding characterization, microstructural investigation and a property comparison to existing grades 316 HSi and 431 L. Powder A was successfully deposited with laser cladding, exhibiting a wide process window, and PTA cladding. In both cases no preheating was required and no cracks were formed. The microstructure examination indicates that powder A has a martensitic structure possibly containing small amounts of ferrite in the grain boundaries. Thermodynamic calculations in computer software Thermo-Calc 4.1 supported this theory. The microstructure of powder A proved to be very stable over a wide range of cladding parameters. Powder A was significantly harder than 316 HSi and 431 L and had better corrosion resistance than 431 L in a chloride environment. Powder A had similar corrosion properties as 316 HSi in the experiments made .The wear performance of the powder A coatings was similar to 431 L. This was surprising since the hardness of the powder A coatings is significantly higher compared to 431 L.

Cemented carbide powder production is the first step in the manufacturing of cemented carbide inserts.The quality of the powder affects the successive process steps in the production of the cemented carbide inserts. The powder is produced by spray drying of a slurry. The slurry consists of polymer, water, ethanol, and dry components. The operating conditions of the spray dryer have been studied greatly to optimize the powder properties but less is known about the influence of the slurry on the powder. This work examines the effect of slurry composition on the cemented carbide powder properties. The work is necessary to predict optimum slurry composition to produce good quality cemented carbide powders. To characterise the powders, flowability, density, particle morphology and hollowness of the powder granules were measured for different slurry compositions. No direct correlation was observed between slurry viscosity and the powder properties but a change in the amount of raw material and organic additives in the slurry affected various powder properties. An optimum slurry composition was obtained which can produce better quality of cemented carbide powder. Additionally, it was found that an increase in slurry viscosity can hinder the spray drying process.
Tillverkning av hårdmetallpulver är det första steget i tillverkningen av hårdmetallinsatser. Pulverkvaliteten påverkar de successiva processstegen vid tillverkningen av hårdmetallinsatserna. Pulvret framställs genom spraytorkning av en uppslamning. Uppslamning består av polymer, vatten, etanol och torra komponenter. Driftförhållandena för spraytork har studerats mycket för att optimera pulveregenskaperna, men mindre är känt om påverkan av uppslamningen på pulvret. Detta arbete undersöker effekten av uppslamningskomposition på egenskaperna för hårdmetallpulver. Arbetet är nödvändigt för att förutsäga optimal uppslamningskomposition för att producera hårdmetallpulver av god kvalitet. För att karakterisera pulvren mättes flytbarhet, densitet, partikelmorfologi och hålighet hos pulvergranulerna för olika uppslamningskompositioner. Ingen direkt korrelation observerades mellan uppslamningsviskositet och pulveregenskaperna men en förändring i mängden råmaterial och organiska tillsatser i uppslamningen påverkade olika pulveregenskaper. En optimal uppslamningskomposition erhölls som kan ge bättre kvalitet på hårdmetallpulver. Dessutom fann man att en ökning av uppslamningsviskositeten kan hindra spraytorkningsprocessen.

Cold Spray is a solid-state additive manufacturing process that uses metallic feedstock powders to create layers on a substrate through plastic deformation. This process can be used for the repair of mechanical parts in the aerospace industry as well as for structural applications. Aluminum alloy powders, including Al 6061, 7075, 2024, and 5056, are typically used in this process as feedstock material. Since this process takes place all in the solid state, the properties and microstructure of the initial feedstock powder directly influence the properties of the final consolidated Cold Spray part. Given this, it is important to fully understand the internal powder microstructure, specifically the secondary phases as a function of thermal treatment. This work focuses on the understanding of the internal microstructure of Al 6061, 7075, 2024, and 5056 through the use of light microscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive x-ray spectroscopy, electron backscatter diffraction, and differential scanning calorimetry. Thermodynamic models were used to predict the phase stability in these powders and were calibrated using the experimental results to give a more complete understanding of the phase transformations during thermal processing.

With a view to design processes based on gas-solid reactiontowards the production of fine-grained novel alloys andintermetallics, studies of the reduction of the mixed oxides ofFe and Mo by hydrogen towards the production of Fe-Mo alloyshave been carried out in the present work. The route offersexcellent potentials toward the bulk production of nano-grainedmaterial of tailored-composition in bulk in a green processpath. As a case study, the reduction of the mixed oxides ofiron and molybdenum were carried out from the viewpoint ofmaterials processing, chemical reaction kinetics, as well asmechanical and structural properties. The reduction kinetics ofthin layer of fine oxide particles of Fe2MoO4 was studied usingthermogravimetric technique. This technique allowed determiningreduction parameters such as temperature of reduction as wellas the activation energies for the chemical reaction as therate-controlling step. The end products were analyzed by X-raydiffraction. The reduction product was found to be reduced topure, homogeneous Fe2Mo. In order to examine the upscaling ofthe process, production of the alloy in larger amounts wascarried out in a laboratory-scale fluidized reactor and theprocess parameters were optimized. It was found that, under theconditions of the experiments, the chemical reaction was therate-controlling step. TEM, SEM and X-ray analyses of thereaction product showed the presence of a monolithicintermetallic with micro- and nanocrystalline structure. Themechanical properties of this alloy were determined.Compositions of microcrystalline Fe-Mo alloys were varied byreducing mixtures of Fe2MoO4 with MoO2 or FeO with differentFe/Mo ratios. The products after the reduction consisted of twophases, viz. intermetallic FexMoy compound and metallic Fe orMo. XRD analyses revealed that the former had microcrystallinestructure while the latter were in crystalline form. This workshows that gas-solid reaction method, together with powdermetallurgy technique is a promising process route towards theproduction of novel metallic alloys such as Fe2Mo intermetallicwith micro- and nanocrystalline grains.

Key words: nanoalloys, intermetallics, iron-molybdenumalloy, hydrogen reduction, thermogravimetry, fluidized bed,mechanical properties, structure

La spectroscopie de plasma induit par laser (En anglais LIBS: laser-induced breakdown spectroscopy) est une méthode analytique de spectroscopie d'émission optique qui utilise un plasma induit par laser comme source de vaporisation, d'atomisation et d'excitation. Bien que la LIBS ait démontré sa polyvalence et ses caractéristiques attrayantes dans de nombreux domaines, les aspects quantitatifs de la LIBS sont considérés comme son talon d'Achille. D'un point de vue fondamental, cela peut être dû à la nature complexe du plasma induit par laser comme source d'émission spectroscopique. La caractérisation temporelle et spatiale du plasma induit par laser est considérée comme l'un des points clés pour comprendre les fondements de la technique LIBS. D'autre part, la LIBS est habituellement caractérisée par l'utilisation d'une ablation laser directe, sans traitement préalable de l'échantillon. Cela pourrait être assez limitant en particulier pour certains types de matériaux tels que des poudres ou des liquides. Une préparation adéquate ou un traitement approprié de l'échantillon permettant le dépôt d'un film mince et homogène de l'échantillon sur une surface métallique pourrait grandement augmenter le potentiel de la LIBS en vue d'obtenir de meilleures performances analytiques, et notamment une meilleure sensibilité et un effet de matrice réduit. On parle alors de LIBS assistée par surface car la matrice métallique contribue à une augmentation de la température du plasma. Le présent travail de thèse est donc motivé par deux aspects importants de la technique LIBS: la connaissance du plasma induit par laser comme source d'émission spectroscopique, et de nouvelles méthodes de préparation des échantillons pour améliorer la performance analytique de la LIBS, notamment pour des échantillons comme poudres et liquides visqueux. La première partie de cette thèse (chapitre 2) est consacrée à la caractérisation du plasma induit sur des échantillons de verre, en fonction de la longueur d'onde du laser, infrarouge (IR) ou ultraviolet (UV), et du gaz ambiant, de l'air ou de l'argon. L'imagerie spectroscopique et la spectroscopie d'émission résolue en temps et en espace sont utilisées pour le diagnostic du plasma. La deuxième partie de cette thèse est de développer des méthodes de préparation d'échantillons, déposés sur des surfaces métalliques pour l'analyse LIBS de poudres ainsi que de vins comme exemples de liquide. Au chapitre 3, nous avons appliqué la LIBS pour l'analyse quantitative dans des poudres (exemples de poudres : cellulose, alumine ainsi que de la terre). Au chapitre 4, nous avons appliqué la LIBS pour la classification des vins français selon leurs régions de production. Deux modèles de classification basées sur l'analyse des composants principaux (PCA) et la forêt aléatoire (RF) sont utilisés pour la classification. A l'aide de ces applications, ce travail de thèse démontre l'efficacité de la méthode LIBS assistée par surface pour l'analyse de poudres (cellulose, alumine et sols) et de liquides (vins), avec une limite de détection dans l'ordre de ou sous la ppm et une réduction significative de l'effet de matrice
Laser-induced breakdown spectroscopy (LIBS) is an analytical method with optical emission spectroscopy that uses a laser pulse to vaporize, atomize, and excite a hot plasma as the spectroscopic emission source. Although LIBS has demonstrated its versatility and attractive features in many fields, the quantitative analysis ability of LIBS is considered as its Achilles’ heel. From a fundamental point of view, this can be due to the complex nature of laserinduced plasma as the spectroscopic emission source for LIBS application. The temporal and spatial characterization of laser-induced plasma is considered as one of the key points for the LIBS technique. On the other hand, from the analytical point of view, LIBS is usually characterized by direct laser ablation. This can be however quite limiting, especially for some types of materials such as powders or liquids. Proper sample preparation or treatment allowing the deposition of a thin homogeneous film on a metallic surface could greatly improve the analytical performance of LIBS for these types of materials. Since the metallic surface is expected to contribute to increase the temperature and the density of the plasma and, consequently, to a better overall sensitivity, we call this technique surface-assisted LIBS. The present thesis work is therefore motivated by two basic aspects of LIBS analysis: the need of an improved knowledge of laser-induced plasma as a spectroscopic emission source, and new methods to improve the analytical performance of LIBS, including a higher sensibility and a reduced matrix effect. The first part of this thesis (Chapter 2) is dedicated to an extensive characterization of the plasma induced on glass samples, as a function of the laser wavelength, infrared (IR) or ultraviolet (UV), and the ambient gas, air or argon. Both the spectroscopic imaging and time- and space-resolved emission spectroscopy are used for plasma diagnostics in this work. The second part of this thesis is to develop a surface-assisted LIBS method for the elemental analysis in powders, and in wines as examples of liquids. We applied the surface-assisted LIBS for the quantitative elemental analysis in cellulose powders, alumina powders, and soils (Chapter 3). Special attentions are paid on the figures-of-merit, matrix effects, and normalization approaches in LIBS analysis. We also used the surfaceassisted LIBS for the classification of French wines according to their production regions (Chapter 4). Two classification models based on the principal component analysis (PCA) and random forest (RF) are used for the classification. Through these applications, this thesis work demonstrates the efficiency of the surface-assisted LIBS method for the analysis of powders (cellulose, alumina and soils) and of liquids (wines), with ppm or sub-ppm sensitivities and a reduced matrix effect

The lattice parameters, structure factors, and Debye-Waller temperature factor of a homogenized, binary Ti-51at.%Al intermetallic alloy were determined using powder X-ray diffraction (XRD). Previous studies have been hampered by extinction at low Bragg angles, therefore improved powdering methods were implemented. The powder was produced by pulverizing lathe turnings taken from the sample ingot using a ceramic mortar and pestle. then the powder was passed through a U.S. Standard 400 sieve mesh (38 microns). After further grinding a new acoustical sieving procedure was performed where powder particles were passed through a 2000 line per inch sieve mesh (5-7 microns). Next the powder was annealed to relieve induced stress produced during grinding. An X-ray diffraction study was conducted for Bragg angles 10-140 deg. The L1 structured TiAl lattice parameters of a =4.002 and c=4.081 were determined using XRD peak positions. the resulting c/a ratio equalled 1.02. The measured integrated intensities of the fundamental reflections were used to determine a Debye-Waller temperature factor of B=0.65 using the Wilson method. these values were determined to be accurate based on comparison to previous research and theoretical approximations. The effects of extinction at low angles were not completely avoided with the refined powder particle size however, they were significantly reduced

The major part of my dissertation consists of thin films deposited using atomic layer deposition on flat and powder substrates. It details the various optimization experiments for process parameters like dose time, purge time, temperature, and pressure on silicon shards and powder substrates. Spectroscopic ellipsometry (SE) was used to characterize these films over a wide wavelength range (191-1688 nm). An optical model with a BEMA (Bruggeman effective medium approximation) layer was used to fit the ellipsometric data to investigate the optical properties of the alumina surface. The optimized process parameters on the flat surfaces were used for coating powder substrates. I propose a set of experiments to optimize the conditions for coating of powders and high aspect ratio structures by atomic layer deposition (ALD). The coated powders were analyzed by surface analytical techniques like X-ray photoelectron spectroscopy, spectroscopic ellipsometry, transmission electron microscopy, energy X-ray dispersive spectroscopy (EDAX), and BET. The first chapter introduces the technique of atomic layer deposition, and details its advantages and limitations over conventional thin film deposition techniques like chemical vapor deposition and physical vapor deposition. The second chapter details the initial deposition experiments performed on flat surfaces and characterization of thin films using surface analytical tools. I conducted multi-sample analysis on eleven different thin films for calculation of optical constants of alumina. The third chapter introduces thin film deposition experiments performed on powder substrates, several challenges associated with achieving conformal thin films and characterization. The fourth chapter details the experiments to achieve unilateral ALD achieved on one side of the substrates. The fifth chapter details various unconventional materials including liquid water, Coca-Cola, a coffee bean, nitrogen gas, human tooth, and printed office paper, which were analyzed by near ambient pressure XPS (NAP-XPS). This dissertation contains appendices of other tutorial articles I wrote on obtaining optical constants liquid samples using spectroscopic ellipsometry, and good experimental techniques for maintenance of vacuum equipment.

In the present study, production of titanium and Ti6Al4V alloy foams has been investigated using powder metallurgical space holder technique in which magnesium powder were utilized to generate porosities in the range 30 to 90 vol. %. Also, sintering of titanium and Ti-6Al-4V alloy powders in loose and compacted condition at various temperatures (850-1250oC) and compaction pressures (120-1125 MPa), respectively, were investigated to elucidate the structure and mechanical properties of the porous cell walls present due to partial sintering of powders in the specimens prepared by space holder technique. In addition, microstructure and mechanical response of the porous alloys were compared with the furnace cooled bulk samples of Ti-6Al-4V-ELI alloy subsequent to betatizing. It has been observed that the magnesium also acts as a deoxidizer during foaming experiments, and its content and removal temperature is critical in determining the sample collapse. Stress-strain curves of the foams exhibited a linear elastic region
a long plateau stage
and a densification stage. Whereas, curves of loose powder sintered samples were similar to that of bulk alloy. Shearing failure in foam samples occurred as series of deformation bands formed in the direction normal to the applied load and cell collapsing occured in discrete bands. Average neck size of samples sintered in loose or compacted condition were found to be different even when they had the same porosity, and the strength was observed to change linearly with the square of neck size ratio. The relation between mechanical properties of the foam and its relative density, which is calculated considering the micro porous cell wall, was observed to obey power law. The proportionality constant and the exponent reflect the structure and properties of cell walls and edges and macro pore character.

The development of a process chain for Inconel 718 production utilizing Binder Jetting has been investigated. Different powder sources were compared by the effect they had on machine compatibility, powder bed packing, recyclability, green density, sintering parameters, final density, porosity, and mechanical properties. The three powder lots investigated originated from two different production sites. One of the three powder lots has a finer powder size distribution, due it being produced simultaneously with another powder lot with a coarser powder size distribution fraction. This synergy production results in a higher yield of the atomization process and thus is economically and environmentally beneficial. The compatibility between powder lots and Binder Jetting machine was investigated using new powder and recycled powder. By using recycled powder in the process an increase in green density by 5% could be achieved. Several temperature and hold time relations were tested to develop a sintering program with an acceptable final density above 94% of theoretical density. 1270◦C with a hold time of 4h generated the best results. Sintered samples did not reach acceptable strength properties. The elongation value was twice as high as required for one of the powder lots using recycled powder. Post heat treatment generated samples with an acceptable yield strength but highly reduced elongation properties.

Selective Laser Melting is a rapidly developing additive manufacturing technique that can be used to create unique metal parts with tailormade properties not possible using traditional manufacturing. To understand the process from a most basic level, this study investigates system capabilities when melting single tracks of material. Individual tracks allow for a wide range of scan speeds and laser powers to be utilized and the melt pools analyzed. I discuss how existing studies and simulations can be used to narrow down the selection of potentially successful parameter combinations as well as the limitations of interpretation for single track information. Once we attain a solid understanding of what parameters perform well at a bead level, we can move onto looking at complete 3D parts. A challenge we have faced is creating near fully dense parts and determining a reliable density measurement technique that is accessible for operators at our university. Our results show that the previously determined optimized scan speed and laser power can consistently create parts with >99.5% density over a range of sizes using an analysis method utilizing readily available equipment and software.

Additive manufacturing (AM) is a general name used for manufacturing methods which have the capabilities of producing components directly from 3D computeraided design (CAD) data by adding material layer-by-layer until a final componentis achieved. Included here are powder bed technologies, laminated object manufacturing and deposition technologies. The latter technology is used in this study. Laser Metal Powder Deposition (LMPD) is an AM method which builds components by fusing metallic powder together with a metallic substrate, using a laser as energy source. The powder is supplied to the melt-pool, which is created by the laser, through a powder nozzle which can be lateral or coaxial. Both the powder nozzle and laser are mounted on a guiding system, normally a computer numerical control (CNC) machine or a robot. LMPD has lately gained attentionas a manufacturing method which can add features to semi-finished components or as a repair method. LMPD introduce a low heat input compared to conventional arc welding methods and is therefore well suited in, for instance, repair of sensitive parts where too much heating compromises the integrity of the part. The main part of this study has been focused on correlating the main process parameters to effects found in the material which in this project is the superalloy Alloy 718. It has been found that the most influential process parameters are the laser power, scanning speed, powder feeding rate and powder standoff distance.These process parameters have a significant effect on the temperature history ofthe material which, among others, affects the grain structure, phase transformation, and cracking susceptibility of the material. To further understand the effects found in the material, temperature measurements has been conducted using a temperature measurement method developed and evaluated in this project. This method utilizes a thin stainless steel sheet to shield the thermocouple from the laser light. This has proved to reduce the influence of the laser energy absorbed by the thermocouples.

The effects of mechanical alloying milling time and carbon concentration on microstructural evolution and hardness of high-carbon Fe-C alloys were investigated. Mechanical alloying and powder metallurgy methods were used to prepare the samples. Mixtures of elemental powders of iron and 1.4, 3, and 6.67 wt.% pre-milled graphite were milled in a SPEX mill with tungsten milling media for up to 100h. The milled powders were then cold-compacted and pressure-less sintered between 900°C and 1200°C for 1h and 5h followed by furnace cooling. Milled powders and sintered samples were characterized using X-ray diffraction, differential scanning calorimetry, Mossbauer spectroscopy, scanning and transmission electron microscopes. Density and micro-hardness were measured. The milled powders and sintered samples were studied as follows: In the milled powders, the formation of Fe_3 C was observed through Mossbauer spectroscopy after 5h of milling and its presence increased with milling time and carbon concentration. The particle size of the milled powders decreased and tended to become more equi-axed after 100h of milling. Micro-hardness of the milled powders drastically increased with milling time as well as carbon concentration. A DSC endothermic peak around 600°C was detected in all milled powders, and its transformation temperature decreased with milling time. In the literature, no explanation was found. In this work, this peak was found to be due to the formation of Fe_3 C phase. A DSC exothermic peak around 300°C was observed in powders milled for 5h and longer; its transformation temperature decreased with milling time. This peak was due to the recrystallization and/or recovery α-Fe and growth of Fe_3 C . In the sintered samples, almost 100% of pearlitic structure was observed in sintered samples prepared from powders milled for 0.5h. The amount of the pearlite decreased with milling time, contrary to what was found in the literature. The decrease in pearlite occurred at the same time as an increase in graphite-rich areas. With milling, carbon tended to form graphite instead of Fe_3 C. Longer milling time facilitated the nucleation of graphite during sintering. High mount of graphite-rich areas were observed in sintered samples prepared from powders milled for 40h and 100h. Nanoparticles of Fe_3 C were observed in a ferrite matrix and the graphite-rich areas in samples prepared from powders milled for 40h and 100h. Micro-hardness of the sintered samples decreased with milling time as Fe_3 C decreased. The green density of compacted milled powders decreased with milling time and the carbon concentration that affected the density of sintered samples.
Ph. D.

Porous Ti-6Al-4V alloys are widely used in the biomedical applications for hard tissue implantation due to its biocompatibility and elastic modulus being close to that of bone. In this study, porous Ti-6Al-4V alloys were produced with a powder metallurgical process, space holder technique, where magnesium powders were utilized in order to generate porosities in the range of 50 to 70 vol. %. In the productions of Ti-6Al-4V foams, first, the spherical Ti-6Al-4V powders with an average size of 55 &mu
m were mixed with spherical magnesium powders sieved to an average size of 375 &mu
m, and then the mixtures were compacted with a hydraulic press under 500 MPa pressure by using a double-ended steel die and finaly, the green compacts were sintered at 1200