A. Delimitis

Pilot-scale validation of Co-ZSM-5 catalyst performance in the catalytic upgrading of biomass pyrolysis vapours

The main objective of the present work was the evaluation of commercial ZSM-5 catalysts (diluted with a silica–alumina matrix) in the in situ upgrading of lignocellulosic biomass pyrolysis vapours and the validation of their bench-scale reactor performance in a pilot scale circulating fluidized bed (CFB) pyrolysis reactor. The ZSM-5 based catalysts were tested both fresh and at the equilibrium state, and were further promoted with cobalt (Co, 5% wt%) using conventional wet impregnation techniques. All the tested catalysts had a significant effect on product yields and bio-oil composition, both at bench-scale and pilot scale experiments, producing less bio-oil but of better quality. Incorporation of Co exhibited no additional effect on water or coke production induced by ZSM-5, compared to non-catalytic fast pyrolysis. On the other hand, Co addition significantly increased the formation of CO2 compared to the CO increase which was favored by the use of ZSM-5 alone. These changes in CO2/CO yields are indicative of the different decarbonylation/decarboxylation mechanism that applies for Co3O4 compared to ZSM-5 zeolite, due to the differences in their acidic properties (mainly type of acid sites). Co-promoted ZSM-5 catalysts simultaneously enhanced the production of aromatics and phenols with a more pronounced performance in the pilot-scale experiments resulting in the formation of a three phase bio-oil, rather than the usual two phase catalytic pyrolysis oil (aqueous and organic phases). The third phase produced is even lighter than the aqueous phase and consists mainly of aromatic hydrocarbons and phenolic compounds. Addition of Co in ZSM-5 is thus suggested to strongly enhance aromatization reactions that result in selectivity increase towards aromatics in the bio-oil produced. Possible routes of catalyst deactivation in the pilot plants continuous operation process have been suggested and are related to pore blocking and masking of acid sites by formed coke (reversible deactivation), partial framework dealumination of the fresh zeolitic catalyst, and accumulative ash deposition on the catalyst that depends on the nature of biomass (content of ash).

Misfit accommodation of compact and columnar InN epilayers grown on Ga-face GaN (0001) by molecular-beam epitaxy

The interfacial structural properties of compact InN films and of noncoalesced three-dimensional InN islands, grown by molecular-beam epitaxy on Ga-face GaN/Al2O3 (0001) substrates, were investigated by transmission electron microscopy. Compact film growth was accomplished employing an InN nucleation layer, grown at low substrate temperatures. A 60° misfit dislocation network effectively accommodated the lattice mismatch in the InN/GaN interface in both cases of epilayers. The lattice constants of InN were determined by electron diffraction analysis, revealing a 0.28% larger in-plane parameter of the compact InN film relative to the corresponding lattice parameter of the InN islands. This is attributed to thermal tensile strain developed during post-growth cooling down of the epilayers, which also compensated the remaining compressive strain originating from the in-plane lattice mismatch of InN and GaN.

Morphology influence on nanoscale magnetism of Co nanoparticles: Experimental and theoretical aspects of exchange bias

Co-based nanostructures ranging from core-shell to hollow nanoparticles were produced by varying the reaction time and the chemical environment during the thermal decomposition of Co2(CO)8. Both structural characterization and kinetic model simulation illustrate that the diffusivities of Co and oxygen determine the growth ratio and the final morphology of the nanoparticles. Exchange coupling between Co and Co-oxide in core/shell nanoparticles induced a shift of field-cooled hysteresis loops that is proportional to the shell thickness, as verified by numerical studies. The increased nanocomplexity when going from core/shell to hollow particles, also leads to the appearance of hysteresis above 300 K due to an enhancement of the surface anisotropy resulting from the additional spin-disordered surfaces.

Strain distribution of thin InN epilayers grown on (0001) GaN templates by molecular beam epitaxy

A structural characterization of thin InN films is performed to determine the post-growth strain distribution, using electron microscopy techniques. A 60° misfit dislocation network at the InN∕GaN interface effectively accommodates the lattice mismatch. The InN in-plane lattice parameter, which remained practically constant throughout the epilayer thickness, was precisely determined by electron diffraction analysis, and cross-section and plan-view lattice images. Image analysis using the geometric phase and projection methods revealed a uniform distribution of the residual tensile strain along the growth and lateral directions. The in-plane strain is primarily attributed to InN island coalescence during the initial stages of growth.

Induced spin-polarization of EuS at room temperature in Ni/EuS multilayers

Ni/EuS multilayers with excellent multilayer sequencing are deposited via e-beam evaporation on the native oxide of Si(100) wafers at 4 × 10−9 millibars. The samples have very small surface and interface roughness and show sharp interfaces. Ni layers are nanocrystalline 4–8 nm thick and EuS layers are 2–4 nm thick and are either amorphous or nanocrystalline. Unlike for Co/EuS multilayers, all Eu ions are in divalent (ferromagnetic) state. We show a direct antiferromagnetic coupling between EuS and Ni layers. At room temperature, the EuS layers are spin-polarized due to the proximity of Ni. Therefore, Ni/EuS is a candidate for room-temperature spintronics applications.

Gallium-doped VPO catalysts for the oxidation of n-butane to maleic anhydride

Vanadium phosphate (VPO) catalyst materials have been doped with gallium and subsequently tested for the mild oxidation of n-butane to maleic anhydride. At low Ga concentrations, this impurity is shown to be beneficial for n-butane conversion. For low dopant levels (Ga/V ⩽ 1 at%), the crystallinity of the hemihydrate (VOHPO4·0.5H2O) precursor phase is improved and its specific area is increased relative to the undoped material as a result of decreased platelet thickness. Electron diffraction and energy dispersive X-ray analysis (XEDS) revealed that the Ga is uniformly distributed in a substitutional manner throughout the hemihydrate structure. The presence of Ga also significantly shortens the activation time required to convert the hemihydrate precursor into a well crystallized vanadyl pyrophosphate (VO)2P2O7 phase under an n-butane/air gas flow at 400 °C. The intimate presence of Ga distributed within the VOHPO4·0.5H2O unit cell has also been confirmed by XANES and EXAFS. Such studies also show that the Ga is partially redistributed within the (VO)2P2O7 structure after catalyst activation. A complementary electrical conductivity study on these materials revealed that Ga3+ substitutes for (VO)2+ species in (VO)2P2O7 giving rise to an n-type semiconductivity which partially compensates the natural p-type conductivity character of the (VO)2P2O7 phase. For higher Ga doping levels (Ga/V ≈ 5 at%), the excess of Ga concentrates as a GaPO4 impurity phase, which is shown to have a detrimental effect on the catalytic performance of the Ga-doped VPO catalyst.

Depth profile of the biaxial strain in a 10μm thick InN (0001) film

Raman spectroscopy is employed to study the evolution of the residual stresses along the growth direction of an ∼10μm thick wurtzite InN film. The analysis of the spectra, recorded with the excitation laser beam being parallel as well as perpendicular to the c axis of the film, clearly reveals the compressive character of the biaxial strain in the InN layer. The residual compressive strain increases with increasing distance from the InN∕GaN interface in agreement with the transmission electron microscopy observations, which additionally reveal that this is accompanied by a reduction of the threading dislocation density. The interplay between the epilayer/template lattice mismatch and the thermal expansion coefficients may account for these observations.

OXIDATION PROCESS OF Fe NANOPARTICLES

The natural oxidation process is studied in the case of 15 nm iron nanoparticles produced by the thermal decomposition of Fe(CO)5. X-ray diffraction spectra of the nanoparticles at different timescales after exposure to air revealed the instant oxidation of iron and the formation of wustite and magnetite. Wustite mainly occupies the interior of nanoparticles, as evidenced by microscopy, but is slowly transformed to a spinel structure. The shape, the dispersion and the role of surfactant were investigated by conventional microscopy and Fourier Transformed-Infrared (FT-IR) spectroscopy. Magnetic hysteresis loops confirmed the expected variation of magnetic properties till the steady state.

Layering and temperature-dependent magnetization and anisotropy of naturally produced Ni/NiO multilayers

Ni/NiO multilayers were grown by magnetron sputtering at room temperature, with the aid of the natural oxidation procedure. That is, at the end of the deposition of each single Ni layer, air is let to flow into the vacuum chamber through a leak valve. Then, a very thin NiO layer (∼1.2 nm) is formed. Simulated x-ray reflectivity patterns reveal that layering is excellent for individual Ni-layer thickness larger than 2.5 nm, which is attributed to the intercalation of amorphous NiO between the polycrystalline Ni layers. The magnetization of the films, measured at temperatures 5–300 K, has almost bulk-like value, whereas the films exhibit a trend to perpendicular magnetic anisotropy (PMA) with an unusual significant positive interface anisotropy contribution, which presents a weak temperature dependence. The power-law behavior of the multilayers indicates a non-negligible contribution of higher order anisotropies in the uniaxial anisotropy. Bloch-law fittings for the temperature dependence of the magnetization in the spin-wave regime show that the magnetization in the multilayers decreases faster as a function of temperature than the one of bulk Ni. Finally, when the individual Ni-layer thickness decreases below 2 nm, the multilayer stacking vanishes, resulting in a dramatic decrease of the interface magnetic anisotropy and consequently in a decrease of the perpendicular magnetic anisotropy.Ni/NiO multilayers were grown by magnetron sputtering at room temperature, with the aid of the natural oxidation procedure. That is, at the end of the deposition of each single Ni layer, air is let to flow into the vacuum chamber through a leak valve. Then, a very thin NiO layer (∼1.2 nm) is formed. Simulated x-ray reflectivity patterns reveal that layering is excellent for individual Ni-layer thickness larger than 2.5 nm, which is attributed to the intercalation of amorphous NiO between the polycrystalline Ni layers. The magnetization of the films, measured at temperatures 5–300 K, has almost bulk-like value, whereas the films exhibit a trend to perpendicular magnetic anisotropy (PMA) with an unusual significant positive interface anisotropy contribution, which presents a weak temperature dependence. The power-law behavior of the multilayers indicates a non-negligible contribution of higher order anisotropies in the uniaxial anisotropy. Bloch-law fittings for the temperature dependence of the magnetizati...

Positive surface and perpendicular magnetic anisotropy in natural nanomorphous Ni/NiO multilayers

Ni/NiO multilayers with excellent sequencing are grown via radiofrequency magnetron sputtering with the use of one Ni target and natural oxidation. Ni layers consist of very small Ni nanocrystals interrupted by amorphous NiO layers. When Ni is deposited at 0.3 Pa Ar-pressure, the hard-magnetization axis is the film normal and saturation field decreases by decreasing Ni layer thickness. Considerable positive surface anisotropy is found, which is remarkable for Ni-based multilayers. If Ni is deposited at 3 Pa Ar-pressure, perpendicular magnetic anisotropy is observed at low temperatures even for 5.4 nm thick Ni layers. This anisotropy results in the formation of stripe magnetic domains.