[en] The morphology and the structure of TiO₂ films, grown on Si (1 0 0) substrates by metal organic chemical vapour deposition (MOCVD) was investigated in 5-500 nm thick films. It was shown that the TiO₂ layer is mainly amorphous at the first stages of deposition. The growth of nanocrystallites begins inside the amorphous TiO₂ layer, and it continues at the expense of the amorphous phase until the crystallized grains occupy the whole layer. Then, the film growth continues with a columnar structure. The coexistence of anatase and rutile phases was evidenced from the beginning of the growth by high resolution transmission electron microscopy and grazing incidence x-ray diffraction. However, the anatase growth overcomes that of rutile, leading to an inhomogeneous phase distribution as a function of the film thickness.

[en] For the first time, functionalized magnetite nanoparticles (Fe_3O_4 NPs) that form aggregates with a nanoflower morphology were synthesized using a rapid (11 s) one-step continuous hydrothermal process, which was recently modified, and their application as a T _2 magnetic resonance imaging (MRI) contrast agent was evaluated. The nanoparticles functionalized with 3,4-dihydroxy-L-phenylalanine (LDOPA) or 3,4-dihydroxyhydrocinnamic acid (DHCA) consisted of small crystallites of approximately 15 nm of diameter that assembled to form flower-shaped aggregate structures. The Fe_3O_4–LDOPA nanoflowers exhibited a high transverse relaxivity, r _2 of 418 ± 10 l mmol_F_e "−"1 s"−"1 at 3 T owing to magnetic dipolar interactions, which is twice as that of the commercial Feridex®/Endorem®. The prepared nanostructures were compared with bare Fe_3O_4 NPs and citrated Fe_3O_4 NPs. DHCA, LDOPA, and citric acid (CA) were found to have an anti-oxidizing effect and to influence the crystallite size and the lattice parameter of the NPs. DHCA and LDOPA increased the crystallite size, whereas CA decreased it. Surface modification increased the colloidal stability of NPs as compared to bare NPs. Nanoflower suspensions of Fe_3O_4–LDOPA NPs were found to be stable in the phosphate-buffered saline, saline medium, and minimal essential medium and formed aggregates of sizes smaller than 120 nm. All samples were found to be superparamagnetic in nature and the highest saturation magnetization was obtained for the Fe_3O_4–LDOPA samples. These NPs can bind to polymers such as PEG, and to fluorescent and chelating agents owing to the presence of free –NH_2 or –COOH groups on the surface of NPs, allowing their use in dual imaging applications. (paper)

[en] Highlights: • The TiO_2 structures have been obtained by the MOCVD technique using ferrocene, cobalt layer (annealed at 350 °C) and Ti(OC_3H_7)_4. • The TiO_2 growth at 550 °C, during 20 min on the cobalt layer (obtained by electron beam evaporation method) on soda-lime glass has as result TiO_2 nanomembranes. • The TiO_2 nanomembranes grow on the cobalt nuclei. • The TiO_2 nanomembranes are polycrystalline, built from TiO_2 anatase and rutile crystals. - Abstract: Nanostructures of TiO_2 were grown using the metal oxide chemical vapor deposition (MOCVD) technique. The procedure used induction heating on a graphite susceptor. This specific feature and the use of cobalt and ferrocene catalysts resulted in nanomembranes never obtained by common MOCVD reactors. The present study discusses the preparation of TiO_2 nanomembranes and the dependence of nanomembrane structure and morphology on growth parameters.

[en] Laser irradiation of a mixture of single-element micro/nanomaterials may lead to their alloying and fabrication of multi-element structures. In addition to the laser induced alloying of particulates in the form of micro/nanopowders in ambient atmosphere (which forms the basis of the field of additive manufacturing technology), another interesting problem is the laser-induced alloying of a mixture of single-element nanoparticles in liquids since this process may lead to the direct fabrication of alloyed-nanoparticle colloidal solutions. In this work, bare-surface ligand-free Ag and Pd nanoparticles in solution were prepared by laser ablation of the corresponding bulk target materials, separately in water. The two solutions were mixed and the mixed solution was laser irradiated for different time durations in order to investigate the laser-induced nanoparticles alloying in liquid. Nanoparticles alloying and the formation of AgPd alloyed nanoparticles takes place with a decrease of the intensity of the surface-plasmon resonance peak of the Ag nanoparticles (at ∼405 nm) with the irradiation time while the low wavelength interband absorption peaks of either Ag or Pd nanoparticles remain unaffected by the irradiation for a time duration even as long as 30 min. The nanoalloys have lattice constants with values between those of the pure metals, which indicates that they consist of Ag and Pd in an approximately 1:1 ratio similar to the atomic composition of the starting mixed-nanoparticle solution. Formation of nanoparticle networks consisting of bimetallic alloyed nanoparticles and nanoparticles that remain as single elements (even after the end of the irradiation), joining together, are also formed. The binding energies of the 3d core electrons of both Ag and Pd nanoparticles shift to lower energies with the irradiation time, which is also a typical characteristic of AgPd alloyed nanoparticles. The mechanisms of nanoparticles alloying and network formation are also discussed. (paper)

[en] Laser ablation of a bulk Hf target in deionized (DI) water, ethanol, or toluene was carried out for the production of nanoparticles' colloidal solutions. Due to the interaction of the ablation plasma plume species with the species which are produced by the liquid decomposition at the plume-liquid interface, hafnia (HfO_2) nanoparticles are synthesized in DI water, hafnium carbide (HfC) nanoparticles in toluene, and a mixture of these in ethanol. The hafnia nanoparticles are in the monoclinic low temperature phase and in the tetragonal and fcc high temperature phases. Their size distribution follows log-normal function with a median diameter in the range of 4.3–5.3 nm. Nanoparticles synthesized in DI water have band gaps of 5.6 and 5.4 eV, in ethanol 5.72 and 5.65 eV (using low and high pulse energy), and in toluene 3 eV. The values for the relative permittivity in the range of 7.74–8.90 were measured for hafnia nanoparticles' thin films deposited on substrates by drop-casting (self-assembled layers) in parallel plate capacitor structures.

[en] Highlights: • Study of surface finishing effect on the corrosion behaviour of a stainless steel. • Mirror polished samples were compared to as-rolled material. • Two oxidation mechanisms were identified depending on the surface finishing. • Before oxidation, native chemical phases are identical for both samples. • Subsurface dislocations generated by the polishing process promote Cr_2O_3 formation. - Abstract: The corrosion behaviour and the oxidation mechanism of a ferritic stainless steel, K41X (AISI 441), were evaluated at 800 °C in water vapour hydrogen enriched atmosphere. Mirror polished samples were compared to as-rolled K41X material. Two different oxidation behaviours were observed depending on the surface finishing: a protective double (Cr,Mn)_3O_4/Cr_2O_3 scale formed on the polished samples whereas external Fe_3O_4 and (Cr,Fe)_2O_3 oxides grew on the raw steel. Moreover, isotopic marker experiments combined with SIMS analyses revealed different growth mechanisms. The influence of surface finishing on the corrosion products and growth mechanisms was apprehended by means of X-ray photoelectron spectroscopy (XPS) and residual stress analyses using XRD at the sample surfaces before ageing.

[en] Highlights: • Microstructure of grade X4CrNiMo16.5.1 stainless steel down to the nanoscale. • Influence of microstructure on the properties of the native passive film. • Influence of microstructure on pitting of grade X4CrNiMo16.5.1 stainless steel. - Abstract: The microstructure of grade X4CrNiMo16.5.1 stainless steel was studied at different scales. The chemical composition of the native passive film formed on the different phases was then determined at the microscale. The degree of homogeneity of the native passive film is discussed. Subsequently, the susceptibility to pitting corrosion of X4CrNiMo16.5.1 was quantified using the electrochemical microcell technique. The nature of precursor sites and the morphology of pits were investigated by combining scanning electron microscopy with Electron BackScatter Diffraction and potentiostatic pulse tests. The role of the microstructure and the cold-worked layer generated by polishing in pitting is discussed

[en] The crystallization kinetics of amorphous silicon carbide films was studied by means of X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films were deposited by radio frequency (r.f.) magnetron sputtering on glassy carbon and single crystalline silicon substrates, respectively. TEM micrographs and XRD patterns show the formation of nano-crystalline β-SiC with crystallite sizes in the order of 50 nm during annealing at temperatures between 1200 and 1600 deg. C. A modified Johnson-Mehl-Avrami-Kolmogorov (JMAK) formalism was used to describe the isothermal transformation of amorphous SiC into β-SiC as an interface controlled, three-dimensional growth processes from pre-existing small crystallites in the order of 10 nm. These pre-existing crystallites are formed in a transient process in the early stages of crystallization. For films deposited on the silicon substrate, the obtained rate constants of crystallite growth obey an Arrhenius behavior with an activation enthalpy of 4.1 ± 0.5 eV in accordance with literature data. Films deposited on glassy carbon show an increased stability of amorphous SiC films, which is reflected in smaller rate constants of crystallite growth of several orders of magnitude at low temperatures and a higher activation enthalpy of 8.9 ± 0.9 eV. A model is proposed, where the faster crystallization of films on silicon substrates can be explained with the presence of superabundant point defects, which diffuse from the substrate into the film and accelerate the incorporation of atoms from the amorphous into the crystalline phase