The electrochemical oxygen reduction reaction (ORR) steps on a noble metal catalyst in an acidic aqueous electrolyte depend on the nature of the catalytic surface with which the O₂ molecule interacts. It has been assumed that the O₂ molecules interact directly with a bare noble-metal surface. By studying the nature of chemisorbed species on the surface of a metal catalyst as a function of the voltage on the anodic and cathodic sweeps, it is shown here that the O₂ reacts with a surface covered with oxide species extracted from the aqueous electrolyte and not from the O₂ molecules; the ORR is more active when the surface species are OH rather than O. Moreover, the strength of the chemical bond of the adsorbed species was shown to depend on the relative strengths of the metal-metal versus metal-oxide bonds. The Pt-Pt bonds are stronger than the Pd-Pd bonds, and the relative Pd-O bonds are stronger than the relative Pt-O bonds. As a result, the chemisorbed O species is stable to lower anodic potentials on Pd. CO oxidation to CO₂ occurs at a higher potential on Pd than on Pt, which is why Pd (not Pt) is tolerant to methanol. Experiments with alloys show the following: (1) methanol tolerance decreases with the increase of Pt in the Pd-Pt alloys with Pd₃Pt/C showing an initial tolerance that decreases with cycling; (2) OH is formed on Pt₃Co/C and core-shell Pt-Cu/C, which results in a higher activity and durability for the ORR on these catalysts; (3) a 300°C anneal is needed to stabilize the Pd₃Au/C catalyst that forms an O adsorbate; and (4) OH is formed on Pd₃Co/C and Pd₃CoNi/C. These studies provide a perspective on possible pathways of the ORR on oxide-coated noble-metal alloy catalysts. / text

<p>The powder metallurgy (PM) process route is very competitive for mass production of structural steel components with complex shape, due to efficient material utilisation, low energy consumption, and short overall production time. The most commonly used alloying elements are the processing friendly metals Cu, Ni and Mo. However, the prices for these metals are today high and volatile, which threatens to make the PM process less competitive compared to conventional metal forming processes. Consequently, there is a strong desire in the PM industry to increase the use of less costly alloying elements. Cr is an attractive alternative since it, besides low cost, provides high hardenability and also recyclable components. The drawback is that Cr has high affinity for oxygen, which makes oxidation and oxide reduction in PM processing of Cr-alloyed materials a challenging issue. Furthermore, the interaction between nitrogen and Cr-alloyed powder during processing is important to consider, since Cr also has high nitrogen affinity and is prone to form nitrides.</p><p>The aim of the research work presented in this thesis was to study oxide reduction and nitrogen uptake in sintering of Cr-alloyed steel powder. Water-atomized powder grades pre-alloyed with 1.5-3% Cr were used as test materials. Sintering experiments were performed in N₂/H₂ (90/10) atmospheres with test bars pressed to density 7.0-7.2 g/cm3. The oxygen content of the sintering atmosphere was varied and different sintering temperatures and cooling rates were applied. The experimental study has been complemented with thermodynamic calculations using the software Thermo-Calc.</p><p>The oxygen partial pressure should be below 4 x 10^-18 atm in order to have reducing conditions during sintering at 1120°C of steel powder pre-alloyed with 3% Cr. With graphite added to the powder, conditions are reducing at higher oxygen partial pressures (up to 10^-16 atm) due to favourable conditions locally in the material. Sintering at 1120°C for 30 minutes leads to incomplete reduction of Cr-oxides in the Cr-alloyed PM grades, but remaining oxides are not detrimental for mechanical properties of the PM components. Increased sintering temperature is beneficial for the oxide reduction kinetics and practically all oxides are reduced after sintering for 30 minutes above 1200°C. Nitrogen uptake by Cr-alloyed steel powder from N₂-based sintering atmospheres is strongly dependent on the cooling rate applied after sintering. No nitrides appear in the sintered material and mechanical properties are not affected when normal cooling rates (0.5-1°C/s) are applied. Very low cooling rates (such as 0.05°C/s) may lead to grain boundary precipitation of Cr-nitrides in the sintered material.</p><p> </p>

The powder metallurgy (PM) process route is very competitive for mass production of structural steel components with complex shape, due to efficient material utilisation, low energy consumption, and short overall production time. The most commonly used alloying elements are the processing friendly metals Cu, Ni and Mo. However, the prices for these metals are today high and volatile, which threatens to make the PM process less competitive compared to conventional metal forming processes. Consequently, there is a strong desire in the PM industry to increase the use of less costly alloying elements. Cr is an attractive alternative since it, besides low cost, provides high hardenability and also recyclable components. The drawback is that Cr has high affinity for oxygen, which makes oxidation and oxide reduction in PM processing of Cr-alloyed materials a challenging issue. Furthermore, the interaction between nitrogen and Cr-alloyed powder during processing is important to consider, since Cr also has high nitrogen affinity and is prone to form nitrides. The aim of the research work presented in this thesis was to study oxide reduction and nitrogen uptake in sintering of Cr-alloyed steel powder. Water-atomized powder grades pre-alloyed with 1.5-3% Cr were used as test materials. Sintering experiments were performed in N2/H2 (90/10) atmospheres with test bars pressed to density 7.0-7.2 g/cm3. The oxygen content of the sintering atmosphere was varied and different sintering temperatures and cooling rates were applied. The experimental study has been complemented with thermodynamic calculations using the software Thermo-Calc. The oxygen partial pressure should be below 4 x 10-18 atm in order to have reducing conditions during sintering at 1120°C of steel powder pre-alloyed with 3% Cr. With graphite added to the powder, conditions are reducing at higher oxygen partial pressures (up to 10-16 atm) due to favourable conditions locally in the material. Sintering at 1120°C for 30 minutes leads to incomplete reduction of Cr-oxides in the Cr-alloyed PM grades, but remaining oxides are not detrimental for mechanical properties of the PM components. Increased sintering temperature is beneficial for the oxide reduction kinetics and practically all oxides are reduced after sintering for 30 minutes above 1200°C. Nitrogen uptake by Cr-alloyed steel powder from N2-based sintering atmospheres is strongly dependent on the cooling rate applied after sintering. No nitrides appear in the sintered material and mechanical properties are not affected when normal cooling rates (0.5-1°C/s) are applied. Very low cooling rates (such as 0.05°C/s) may lead to grain boundary precipitation of Cr-nitrides in the sintered material. / QC 20101105

This study is mainly aimed at interstital-free and dual-phase steels, analyzing the compositions and distribution of selective surface oxides after annealing and then to know the influence of these oxidation for the formation of FeAl inhibition layer in hot-dip galvanizing. Interstital-free and dual-phase steels were first annealed at 800 oC for 1-200 s in a 10% H2-N2 protected atmosphere of -70 oC and 0 oC dew point respectively and then dipped in zinc bath with Al content 0.12-0.18 wt% for 0-20 s. Using this combined SEM, Auger electron spectroscopy(AES), X-ray photoelectron spectroscopy(XPS) and ICP-AES etc. instruments, it is shown that the MnAl2O4 spinels were the major oxidation on the surface of IF steel after annealing. The average oxidation thickness was about 5-15 nm. Annealing times has little effect on the thickness. On the other hand, MnO were observed on DP steel surface after anneaing. The MnO paticles mainly distributed at the grain boundaries ,and the average oxdaiton thickness increase rapidly from 20 nm(10 s) to 110 nm(200 s) with annealing times. The growth of the FeAl inhibition layer can separate to nucleation in initial stage and diffusion growth later. The Fe2Al5 nucleation times were all about 0.1 s in both steels , and average thicknesses were approximately 20 nm. For IF steels , Al uptake in the zinc bath and steel interface was depleted in nucleation stage with 0.12 wt% Al content, so that delayed the growth of Fe2Al5, and the rate determining step was the diffusion of Al in zinc bath. When Al content raise up to 0.14 wt%, the phenomenon of growth delay was not happened, and the rate determining step of Fe2Al5 growth changed to the solid-state diffusion of Fe in Fe2Al5. For DP steels, when Al content up to 0.14 wt%, the growth mechanism was similar to IF steels, but the rate determining step of Fe2Al5 growth was mainly in the grain boundary diffusion of Fe in Fe2Al5. Moreover, where the MnO paticles was rich could obviously observe the delay of Fe2Al5 growth. It was probably because of consuming a great deal of Al to reduce the MnO oxides.

For many metal components the presence of hard, non-metallic inclusions such as oxides lowers the impact toughness by acting as fracture initiation points and easing crack propagation. In components produced by powder metallurgy hot isostatic pressing (PM HIP), oxides often form a continuous network of small, spherical inclusions after consolidation at the prior particle boundaries (PPB). It is therefore of great importance to reduce surface oxides before consolidation in order to improve mechanical properties. In this work, oxides were attempted to be reduced directly prior to the consolidation of one tool steel and one low-alloy steel by introducing H2 into sealed PM HIP capsules. The two H2-carriers were hollow glass microspheres and the compound ammonia borane (H3NBH3). The H2-carriers were placed separately from the metal powder. Microspheres were filled at 300 °C with a gas mixture at 675 bar resulting in a storage capacity of 0.16 wt%. Gaseous species released from the H2-carriers during heating were analysed by mass spectrometry. Results showed that the microspheres only release H2 while ammonia borane in addition releases other nitrogen and boron containing species. Impact testing as well as chemical and microstructural analysis were performed on the two consolidated materials with samples retrieved from different vertical and radial positions. Both H2-carriers had leaked into the material resulting in decreased impact toughness compared to the reference. Further from the source of the contaminants, oxygen content was reduced and impact toughness was improved. Microspheres showed overall better reduction ability even though they release less hydrogen compared to ammonia borane. Impact toughness was not improved as much with ammonia borane even though similar oxygen levels were achieved. Ammonia borane’s decomposition products likely obstruct the oxide reduction or introduce new inclusions lowering the impact toughness. / Det är för många metallkomponenter viktigt att så mycket som möjligt undvika hårda, icke metalliska inneslutningar. Detta eftersom de sänker slagsegheten genom sprickinitiering men även genom att underlätta spricktillväxt. Ytoxider i komponenter tillverkade genom pulvermetallurgisk het-isostatisk pressning (PM HIP) bildar ofta ett kontinuerligt nätverk av små, sfäriska inneslutningar efter konsolidering vid de tidigare partikelgränserna. Det är därför viktigt att reducera ytoxider före konsolidering för att förbättra de mekaniska egenskaperna av komponenter tillverkade genom PM HIP. I detta examensarbete har ytoxider reduceras direkt före konsolidering av ett låglegerat stål och ett verktygsstål genom att tillsätta H2 i de förseglade PM HIP kapslarna. Två vätgasbärare testades, ihåliga mikrosfärer av glas och ammoniak boran (H3NBH3). Vätgasbärarna var placerade i ett område avskilt från metallpulvret. Mikrosfärerna fylldes med en gasblandning vid 675 bar och 300 °C vilket resulterade i en lagringskapacitet på 0.16 vikt%. Gaser som frigjordes från vätgasbärarna vid uppvärmning analyserades med en masspektrometer. Resultatet visade att mikrosfärerna bara frigör H2 medan ammoniak boran också frigör andra ämnen innehållande kväve och bor. Slagprovning och analys av mikrostruktur samt syre- och kvävehalter utfördes på de två konsoliderade materialen med prover från olika vertikala och radiella positioner. Båda vätgasbärarna hade läckt in i materialet vilket resulterade i minskad slagseghet jämfört med referensmaterialet. Längre från vätgasbärarnas ursprungsposition var slagsegheten bättre och syrehalten lägre. De vätgasfyllda mikrosfärerna uppvisade överlag bättre förmåga att minska syrehalten trots att de innehöll mindre H2 jämfört med ammoniak boran. Slagsegheten förbättrades inte lika mycket med ammoniak boran trots att liknade syrenivåer uppmättes. Ammoniak boranets pyrolysprodukter förhindrar möjligtvis oxidreduktionen eller introducerar nya inneslutningar som resulterar i en försämrad slagseghet.

Thermoelectric generators (TEG) are re-emerging technology that can be used to recover heat waste from commercial and industrial processes to generate electricity, enhancing fuel utilization and lowering greenhouse gas emissions. TEG modules are solid-state heat engines that produce no noise or vibration during operation. Notably, TEG modules are also able to operate at low-temperature differences, which makes them ideal for a wide range of heat waste recovery applications. Annular thermoelectric generator (ATEG) modules are optimal in applications where either the heat source or sink are round in shape. Bi2Te3 solution-based compounds are of significant interest in the application of thermoelectric materials (TE) used in low-temperature cooling and power generation applications. The main objective of the current work is to design a mechanically reliable ring-shaped ATEG module with a predictable performance using spark plasma sintered Bi2Te3 TE material for low temperature waste heat recovery applications. In terms of structure, this work is divided into two parts. The first part investigates how the use of a powder pre-treatment technique affects the mechanical and thermoelectric properties of P- and N-type Bi2Te3. In addition, part one also presents the measurements of these materials’ mechanical and thermoelectric properties, which serve as inputs for the finite element models used to design thermoelectric modules with parallel and perpendicular configurations vis-a-vis the sintering pressing direction. The second part evaluates the thermoelectric performance and thermal stresses of a ring-shaped ATEG couple that has been integrated between hot-side and cold-side heat exchangers. To this end, two configurations are compared with respect to their heat/electrical current flow paths: one that allows for radial flow (radial configuration), and one that allows for axial flow (axial configuration). The P- and N-type Bi2Te3 powder was treated using a mechanically agitated fluidized powder reduction facility that was built in-house. The characteristic uniaxial tensile strength of the P-type Bi0.4Sb1.6Te3 increased from 13.9 MPa to 26.3 MPa parallel to the sintering pressure, and from 16.3 MPa to 30.6 MPa perpendicular to the sintering pressure following oxide reduction using 5% H2 ˗ 95% Ar at 380 ℃ for 24 h. The figure of merit, ZT, increased from 0.35 to 0.80 and from 0.42 to 1.13 at room temperature (25 ℃) in the parallel and the perpendicular directions, respectively, after the surface oxide reduction treatment. On the other hand, the annealing effects of the oxide reduction pr-treatment of the N-type (Bi0.95 Sb0.05)2(Se0.05 Te0.95)3 using 5% H2 ˗ 95% Ar at 380 ℃ for 24 h were found to be responsible for the majority of the mechanical properties and ZT enhancement. Additionally, the characteristic uniaxial tensile strengths for this material increased from 30.4 to 34.1 MPa and from 30.8 to 38 MPa in the parallel and the perpendicular directions, respectively. The ZTmax (150 ℃) increased from 0.54 to 0.63 in both the parallel and perpendicular directions due to oxide reduction, while annealing led to an increase to 0.58 and 0.62 in the parallel and the perpendicular directions, respectively. An analytical model was constructed to compare the thermoelectric performance of the two configurations under three different hot-side thermal resistances, and a 3D coupled finite element ANSYS model was constructed to study and compare the thermal stresses of the two configurations at different dimensions. The two models were then used to create 2D maps in order to investigate the effects of ATEG couple configuration and dimensions, as well as the hot-side thermal resistance, with the goal of identifying the optimum design. The optimization of module geometry requires a trade-off between performance and mechanical reliability. The results of these investigations showed that increases in the temperature difference across the ATEG couple (ΔT) led to increases in both power and thermal stresses in both configurations. When both configurations were generating the same power at ΔT = 105 ℃, the thermal stresses in the radial configuration were as much as 67 MPa higher than those in the axial configuration due to the formation of additional tensile hoop stresses. The lowest thermal stress obtained for the axial couple configuration was 67.8 MPa, which was achieved when the couple had an outer diameter of 16 mm, an axial thickness of 1 mm, a ΔT of 14.8 ℃, and power generation of 10.4 mW per couple. The maximum thermal stress values were located at the corners of the interface between the solder and the TE rings due to the mismatched coefficient of thermal expansion. This thesis makes a novel contribution to the state-of-the-art literature in ring-shaped ATEG modules, as it details a well-characterised spark plasma sintered Bi2Te3 TE material and a methodology for designing a ring-shaped ATEG module with reliable, robust, and predictable thermoelectric and mechanical performance. The details of the contribution made by this work have been disseminated in the form of three journal publications, which have been integrated into this sandwich Ph.D. thesis. / Thesis / Doctor of Science (PhD)