The phenomenon of hydrogen embrittlement in steel has been known for over 150 years. Hydrogen-resistant alloys have been developed to mitigate this effect and three types of alloys with optimised structures have been enhanced over the years: nickel alloys, stainless steels, and quenched and tempered martensitic low alloy steels. Nevertheless, those alloys are limited in terms of strength and ductility. The aim of the work presented in this thesis was to design bainitic alloys with hydrogen embrittlement resistance, and with a better combination of strength and ductility than conventional alloys. In the novel alloys, two microstructural features were produced to mitigate the damaging effects of hydrogen: 1. A percolating austenite structure, in which hydrogen diffusion is orders of magnitude lower than in bainitic ferrite. This feature was introduced to impede the ingress of hydrogen through the structure. 2. Iron carbide traps, which can form at the bainite transformation temperature. This feature was introduced to trap diffusible hydrogen and prevent it from causing damage. The alloys, designed with the aid of computer models and phase transformation theory, contained a volume fraction of retained austenite above its percolation threshold, theorised as 0.1, which was proven to form an effcient barrier to hydrogen ingress. The effective diffusivity of hydrogen, measured using an electrochemical permeation technique, was shown to decrease with increasing austenite fraction up to the percolation threshold. It was seen to plateau for austenite fractions comprised between 0.1 and 0.18, and to decrease further for fractions above 0.18. The compositions of the alloys were precisely selected to allow for iron carbides to precipitate during the bainitic transformation reaction. Until the present work, only alloy carbides V4C3, TiC and NbC had been reported to strongly trap hydrogen. The literature was very inconsistent regarding the trapping ability of cementite, with reported trap binding energies ranging from 11 to 66 kJ mol−1. The carbides produced in the alloys were identified as cementite. The cementite fraction was measured to be 0.001 ± 0.0001 for one of the designed alloys, which is the lowest ever reported carbide fraction in steel measured using a simple X-ray diffraction technique. Experimental thermal desorption spectroscopy data were used to determine the binding energy of hydrogen to cementite to be 37.5 kJ mol−1, suggesting that cementite is not a strong hydrogen trap. Further tests performed after room temperature hydrogen degassing displayed insignifcant amount of trapped hydrogen, thus confrming the reversible nature of cementite traps. The comparison of two successive transients using the electrochemical permeation technique confirmed that result. The influence of the heat treatments on the microstructures and on the mechanical properties of the designed alloys was extensively studied. The novel alloys met all the set requirements, and successfully outperformed conventional alloys in terms of strength and ductility. They did not meet the NACE TM0316-2016 standard requirement for operation in hydrogen-rich environments, likely owing to the inadequate trapping ability of cementite. Future work should focus on exploring the possible use of alternative carbides for hydrogen trapping in bainitic structures.

The adsorption of oxygen on Rh(110) was investigated by thermal desorption spectroscopy (TDS), X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM). The desorption of chemisorbed oxygen was observed at 700 K to 1200 K. Above 1400 K exists another desorption peak which is attributed to subsurface oxygen. The content of subsurface oxygen in Rh(110) influences the chemisorption states on the surface, so that the desorbing character of the surface oxygen species is changed. The subsurface-state needs high preparation temperature and has not any reaction with residual gas or added hydrogen in the chamber, which clarifies its spatial isolation. The XPS result showed that the binding energy of subsurface species is higher than the one of surface oxygen. This confirms the TDS observation. The subsurface-oxygen containing surface showed in STM oxygen induced hillock-like structures.

Demands for zero greenhouse-gas emission vehicles have sharpened with today’s increased focus on global warming. Hydrogen storage is a key technology for the implementation of hydrogen powered vehicles. Metal hydrides can claim higher energy densities than alternative hydrogen storage materials, but a remaining challenge is to find a metal hydride which satisfies all current demands on practical usability. Several metals store large amounts of hydrogen by forming a metal hydride, e.g., Mg, Ti and Al. The main problems are the weight of the material and the reaction energy between the metal and hydrogen. Magnesium has a high storage capacity (7.6 wt.% hydrogen) in forming MgH2; this is a slow reaction, but can be accelerated either by minimizing the diffusion length within the hydride or by changing the diffusion properties. Light-metal hydrides have been studied in this thesis with the goal of finding new hydrogen storage compounds and of gaining a better understanding of the parameters which determine their storage properties. Various magnesium-containing compounds have been investigated. These systems represent different ways to address the problems which arise in exploiting magnesium based materials. The compounds were synthesized in sealed tantalum tubes, and investigated by in situ synchrotron radiation X-ray powder diffraction, neutron powder diffraction, isothermal measurements, thermal desorption spectroscopy and electron microscopy. It is demonstrated that hydrogen storage properties can be improved by alloying magnesium with yttrium or scandium. Mg-Y-compounds decompose in hydrogen to form MgH2 nano-structures. Hydrogen desorption kinetics are improved compared to pure MgH2. The influence of adding a third element, gallium or zinc has also been studied; it is shown that gallium improves hydrogen desorption from YH2. ScAl1-xMgx is presented here for the first time as a hydrogen storage material. It absorbs hydrogen by forming ScH2 and Al(Mg) in a fully reversible reaction. It is shown that the hydrogen desorption temperature of ScH2 is reduced by more than 400 °C by alloying with aluminium and magnesium.

ermal desorption spectroscopy (TDS) is a common method for surface analysis of adsorbed molecules. In chapter 1 the work deals with the theoretical background of this method and shows the principles of a desorption process influenced by subsurface diffusion. Chapter 2 first shows application of TDS for detection of surface molecules and determination of binding energy.Experiments were mainly focused on ditermination of surface adsorbents and impurities on Si wafers. The second part of chapter 2 describes desorption of atoms of a Ga layer on Si surface and their subsurface diffusion. A Ga diffusion process was also observed by with secondary ion mass spectrometry (SIMS) and numerically simulated.

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