Hf3Al2 and Zr3Al2 Isostructural Aluminides Studied by PAC with 181Ta and 111Cd Probes

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline Zr₃Al₂ and Hf₃Al₂ compounds were measured in the temperature range 24–1100 K. The hyperfine quadrupole interaction parameters were determined after different doping techniques and heat treatments of the samples.¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr sites and the ¹¹¹In/¹¹¹Cd impurities appear to substitute both the 8(j) Al sites and the three nonequivalent Hf/Zr sites.     

Oxidation of cerium and titanium studied by photoelectron spectroscopy

Cerium and titanium are examples of reactive metals that form protective oxide films on their surfaces upon exposure to oxygen. In order to study the building up of these oxide films we have undertaken photoemission measurements with X-ray and ultraviolet radiation (ESCA and UPS). Cerium and titanium levels were studied using ESCA on freshly in situ evaporated metal films. These levels, as well as the O 1s level, were studied after different oxygen exposures. In order to vary the probing depth, spectra have been recorded at two different electron emission angles. All measurements were performed at room temperature. Effects of oxygen exposures upon core levels were quite different in the two metals. In the Ce 3d spectrum a strong peak related to the oxide was observed at an exposure of only 2 L. Such a strong peak was not observed in the Ti 2p spectrum even after an exposure of 3000 L. The valence band spectrum of Ti as observed both by UPS and ESCA measurements, however, changed significantly at much smaller exposures.     

Oxidation of nickel studied by UV and X-ray photoelectron spectroscopy

The nature of argon-ion bombarded nickel surfaces (polycrystalline, and (111), (110) and (100) single crystals) and their subsequent interaction with oxygen at ordinary temperatures have been studied using X-ray and UV photoelectron spectroscopy, including angular variation measurements and the determination of work function changes, in combination in the same apparatus. Variations between the HeI spectra of the four clean substrates were taken to confirm the presence of substantial order within the depth sampled by UPS. The four surfaces exhibited similar but not identical behaviour during oxidation, resembling that reported by other workers from studies of both annealed single crystals and evaporated polycrystalline films. The initial process was deduced to be essentially dissociative chemisorption: no evidence supporting a previous suggestion of associative adsorption at low coverages was found. Oxygen commenced to penetrate below the surface of all samples before oxygen equivalent to a monolayer had been taken up (~10 L exposure) and further substantial uptake followed resulting in the formation of a stable film (~18 Å) of nickel oxide by ~100 L exposure. This oxide layer was not stoichiometric nickel(II) oxide: it was characterized by the presence of two distinct O 1s signals, the relative intensities of which depended on the crystallographic nature of the surface. It is tentatively suggested that the oxygen signal with the higher BE be associated with Ni^III. Comparison of the X-ray and UV spectra suggests that the oxide film is very non-uniform in thickness, some Ni metal remaining very close to the surface.     

The Electric Field Gradients in (Zr/Hf)Al3 and (Zr/Hf)2Al3 Intermetallic Compounds Studied by 181Ta- and 111Cd-PAC Spectroscopy

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline ZrAl₃ and Zr₂Al₃ compounds were measured in the temperature range 30–1100 K and compared with the results for isostructural hafnium aluminides. On the basis of the similarities of the numbers, sizes and asymmetries of electric field gradients, lattice site allocations were made. In all matrices, ¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr site. The ¹¹¹In/¹¹¹Cd impurities were also assigned to the Hf/Zr site in the compounds (Zr/Hf)Al₃, but appear to substitute the two non-equivalent Al sites in the Zr₂Al₃ and Hf₂Al₃ phases. This revised version was published online in September 2006 with corrections to the Cover Date.     

Adsorption of Na onto γ-alumina studied by solid-state Na and Al nuclear magnetic resonance spectroscopy

The adsorption of Na⁺ on γ-alumina surfaces at four coverages of Na₂CO₃ [5, 10, 15 and 20% (w/w)] was characterized by solid-state ²³Na and ²⁷Al nuclear magnetic resonance (NMR) spectroscopy. The experimental results suggest that two distinct adsorbed species are present on the alumina surface: surface species and surface salts. At the lower coverages of Na₂CO₃ (5 and 10%), the surface species is predominant, in which the Na⁺ cations are associated with the oxygen atoms of γ-alumina. Increasing the loading level to 15% results in the appearance of a second adsorbed species that is attributed to the surface salt, Na₂CO₃, deposited on the solid surface. Further adsorption of Na₂CO₃ leads to an increase in the amount of surface salt while the amount of surface species remains unchanged. ¹H---²⁷Al Cross-polarization magic angle spinning (CP-MAS) experiments give the evidence that some Na⁺ cations in the form of surface species are coordinated with the Brönsted acid sites of γ-alumina. This may be the main driving force that improves appreciably the catalytic efficiency of an Na₂CO₃---Al₂O₃ catalyst.     

Ion bombardment of ordered Zr3Al

The behaviour of the ordered alloy Zr₃Al was investigated by transmission electron microscopy following ion bombardments at temperatures ranging from 30 to 850 K. Utilizing high energy(0.5–2.0 MeV) C⁺, N⁺ and Ar⁺ ion bombardments, observations were made of the irradiation-induced transformation from the ordered → disordered → amorphous states. Information about individual damage cascades was also obtained using both high energy (C⁺. N⁺ and Ar⁺) and low energy (15–120 keV Cu⁺) ion bombardments.     

Levels in179W studied in the181Ta(p, 3n) reaction by on-line electron and gamma ray spectroscopy

Levels in¹⁷⁹W have been deduced from in-beam gamma and conversion electron studies of the¹⁸¹Ta(p, 3n)¹⁷⁹W reaction. The gamma-ray spectrum was studied with Ge(Li) detectors and a crystal diffraction spectrometer; the conversion electrons were measured with a broad range transport solenoid Si(Li) spectrometer. The multipolarities of some 50 transitions could be determined. Coriolis mixing of the Nilsson orbits withN=6 was calculated.     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.     

Ar 3s, 3p satellite lines studied by fluorescence spectroscopy

The fluorescent radiation emitted by the Ar 3s, 3p satellite states (observed by photoelectron spectroscopy) has been recorded in the wavelength range between 400 and 780 Å with an energy resolution ranging from 50 to 100 mV. The fluorescence was stimulated by use of undispersed synchrotron radiation.     

Chemical shifts in Al—Si compounds by Zr Lα photo-electron spectrometry

The excitation of XPS spectra by Zr Lα radiation has the advantage that both the 1s peaks and their KLL Auger series are excited. This paper compares the peak positions, of metals, oxide and certain aluminosilicates, obtained using Zr Lα radiation and thus demonstrates a dependence of the Auger parameter on structures. This method of characterisation is particularly suitable for minerals such as silicates which are prone to charging, but is not possible for silicon with the conventional Mg and Al sources.     

Oxidation of iron studied by PAC and CEMS

A metallic Fe specimen, implanted with ¹¹¹In, was oxidized and subsequently annealed in a high vacuum for PAC spectroscopy. This treatment gave rise to a huge PAC signal. The magnitude of the hyperfine field was found to be one third of that in metallic Fe. CEMS on an enriched Fe foil given exactly the same treatment has revealed that a maghemite phase (γ-Fe₂O₃) is formed right after the oxidation treatment and a magnetite phase (Fe₃O₄) after the vacuum annealing. ¹¹¹In in the magnetite phase was found to give rise to a PAC signal with large amplitude. PAC spectroscopy in an external magnetic field has revealed that the site of ¹¹¹In is the tetrahedral site of the magnetite with the hyperfine field of +12 T, which is in excellent agreement with those in the ferrites. The present method of oxidation of metallic Fe with nuclear probes in it is quite useful for the study of oxidation processes. Also, it provides us with a simple means to prepare ferrite specimens incorporated with nuclear probes. This revised version was published online in August 2006 with corrections to the Cover Date.     

4f ground state properties of cerium in AuCu3 intermetallic compounds studied by x-ray absorption spectroscopy

L_III absorption edges of cerium in ternary AuCu₃ compounds Ce(Pd_1?xM_x)₃ (M = Ag and Rh) and (Ce_1?xY_x)Pd₃ are presented. We find that Ce in these compounds is mixed valent with n_f ? 0.7. The valence V of Ce(Pd_1?xRh_x)₃ becomes concentration independent of V = 3.29 ± 0.02 for x ? 0.18. In Ce_1?xY_xPd₃ we observe the valence to increase up to V = 3.32 ± 0.02 at the highest concentration of Y. We show, that a critical volume, available for the Ce atom, is associated with the concentration independent valence around 3.3. For both systems, linewidths W₁, W₀ and Δ = E(4f¹) ? E(4f⁰), as derived from L_III double-bump structure, are given. Possible falsifications due to “final states effects” on the valence are discussed.     

Na and K on Al(100) studied by low-energy electron diffraction and high-resolution core-level spectroscopy

The temperature effects on sub-monolayers of V deposited at the TiO₂(001) surface have been studied by ultraviolet and X-ray photoelectron spectroscopies, UPS and XPS, from 300 up to 623 K.

V coverages, Θ_v, between 0.2 and 0.7 monolayers (ML) were deposited by an e-beam evaporator at 300 K. The V 2p_3/2 core line region exhibits two well-defined components whose relative intensity depends on Θ_v. These two components, assigned to different oxidation states of V, are correlated with two features, with a dominant V 3d character, detected within the TiO₂(001) band gap of the UPS valence band spectra.

UPS and XPS measurements performed after in-situ thermal treatments show unambiguous and reproducible changes of these spectral components. After annealing at 623 K only the higher binding energy component is present in the V 2p_3/2 spectra; the Ti 2_p core lines recover the typical symmetry of the clean and stoichiometric TiO₂(001) surface and the higher binding energy feature only is detected in the TiO₂ band gap. These data suggest that, within the volume probed by XPS and UPS, Ti ions have a mainly d⁰ configuration, while V has a single and stable open-shell configuration, as revealed by the significant intensity detected within the TiO₂ band gap. These annealing-induced changes are due, as suggested by the O 1s/Ti 2p core line intensity trend, to an oxygen diffusion from the TiO₂ bulk to the surface. Finally, a detailed analysis of the data indicates that different V/TiO₂(001) interfaces exhibit different behaviours after annealing treatments, depending on Θ_v. For Θ_v = 0.7 ML, V interdiffuses into the TiO₂ sub-surface layers, whereas for Θ_v = 0.2 ML it remains at the surface. This finding is consistent with a rearrangement of V atoms. which under annealing occupy first the energetically most favorable surface sites (Θ_v = 0.2 ML) before interdiffusing into the TiO₂ lattice (Θ_v = 0.7 ML).     

Electronic structure of amorphous Zr based alloys with V,Cr and Mn studied by photoelectron spectroscopy and bandstructure calculations

The electronic structure of the amorphous alloys V₃₆Zr₆₄, Cr₃₀Zr₇₀ and Mn₃₀Zr₇₀ has been studied by photoelectron spectroscopy (UPS, XPS) and bandstructure calculations for the ordered analogs. The valence band photoelectron spectra and the calculated density of states reveal a large contribution to the state density at the Fermi level from the 3d metal. This behavior is characteristic of Zr based alloys with early 3d transition metals and differs from alloys with higher 3d electron numbers in which the 3d band is located at higher energies. The implications of the high density of states at E_F of the amorphous Zr-(V, Cr, Mn) alloys for magnetism and the occurrence of superconductivity is discussed.     

Nanostructured Zr/Hf/Zr multilayer studied by perturbed angular correlations technique

In this work the perturbed angular correlation technique is used to locally monitor the epitaxy and thermal stability of the hafnium layer in a Zr/Hf/Zr multilayer. The studies reveal that the system is highly homogeneous and presents high epitaxy. Measurements at high temperatures show that no HfO_x formation occurs up to 562 K but at this temperature the Hf layer is no longer oxygen-defect free.