Rare earth compounds are interesting from both a theoretical point of view and for their applications. That is the reason why determining their optical and electrical properties deserves special attention. In this article, we present the conditions we obtained homogenous CeNi5 thin films of nanometer thicknesses. To achieve this goal, our method of choice was laser-induced vaporization, using short and modulated impulses, with electro-optical tuning for the quality factor. The layers that were deposited at a single laser burst had thicknesses between 1.5 and 2.5 nm, depending on the geometry of the experimental setup.Structural and compositional studies of the nanoscale films were made using XRD. The temperature dependence of electrical conductivity was also determined. The following optical properties of the specimens were computed using the Kramers-Krönig framework and discussed: absolute reflection and transmission coefficients for a single wavelength and relative ones for the wide UV-VIS-IR spectra, spectral dependence of the refractive index, and extinction coefficient as real and imaginary parts of the complex refractive index. The valence band studies were made with X-ray photoelectron spectroscopy. All these determinations were well correlated and permitted the evaluation of the energy densities of states in the deeper bands, near the Fermi energy, and at the surface states.
The objective of this study is to describe the mineralogical composition and chemical properties of the Oraşu Nou bentonite, from northwestern Romania. For mineralogical determinations, the following were used: X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FR-IR), thermogravimetric analysis, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The chemical compositions and physical properties of the bentonites and bentonitized rocks were also determined. Calcium type montmorillonite is the predominant mineral in this deposit. Its average mass fraction is between 35% and 75%, reaching up to 95%. A small amount of halloysite and very fine cristobalite were also identified in the fine fraction. Quartz, feldspar, and kaolinite were identified as impurities. The average pH of natural bentonite is 6.2. Its cation exchange capacity (CEC) is in the lower-middle range for smectites at 45.89 cmol/kg, absorption capacity 43.58 mL/g, swelling degree 9.41%. Because of the high amounts and purity of montmorillonite, the valuable component mineral, the way is open to an easy refinement of this important resource. This way very high-quality colloidal suspensions can be obtained which can be used in the most modern applications of micro- and nanostructured materials.
Valentinite forms through the alteration of stibnite in sulphide deposits. Colloform sphalerite is a widespread mineral in low-temperature deposits, particularly those of the Mississippi-Valley type. We identified valentinite and colloform sphalerite in hydrothermal deposits occurring in the Baia Mare area. The Baia Mare metallogenic district of Neogene age occurs in the northwestern part of the Neogene volcanic chain within the Eastern Carpathians. The Neogene volcanism from Baia Mare area is related to the subduction processes of the East European plate under two microplates, Alcapa and Tisza-Dacia/Tisia, in the post-collisional compressive phase. We have identified valentinite in the Dealul Crucii and Baia Sprie deposits, associated with other epithermal minerals, in the absence of the stibnite. Valentinite is deposited in the final phase of the epithermal process after calcite and manganese-bearing calcite. Micro-Raman and microprobe determinations indicate the presence of valentinite. The formula of valentinite is close to stoichiometric Me2O3 and contains small amounts of tin as an antimony substituent. Colloform sphalerite was identified in the Baia Sprie ore deposit associated with minerals formed in the final epithermal phase. It was deposited on idiomorphic crystals of stibnite, which it corrodes. Its structure and an alternate banding, exhibited on the nano-/microscale, were identified by optical microscopy, SEM (scanning electron microscopy), and BSE (backscattered electron microscopy) imaging. These structures are typical for colloform sphalerite and suggest a genesis due to episodic precipitation. The spherical nano/micro-particles (nodules) are characteristic of the colloform sphalerite from Baia Sprie. Raman analysis indicates the presence of a colloform sphalerite with low iron content. The typical diffraction lines for sphalerite were identified in X-ray diffraction: 3.118 Å (111), 1.907 Å (220), 1.627 Å (311). Microprobe analysis certifies the presence of sphalerite with the stoichiometric formula close to ZnS. Iron content is low (0%–0.0613%), but Sb (0.7726%–2.6813%), Pb (0.56%–1.1718%), Bi (0%–0.1227%) are also present. The negative correlation between Zn and Sb suggests the simultaneous deposition from the same epithermal fluids. Valentinite and colloform sphalerite were formed at low temperatures (100–150 °C) at the end of the epithermal process.
This work presents pulsed laser deposition as a method to obtain unoxidized LaNi5 nanoscale films and describes their temperature and thickness dependent electrical conductivity and the spectral dispersions of some optical properties. AB5-type rare earth element (REE)-nickel compounds are currently studied from both theoretical and practical points of view. Special challenges are posed during the preparation of these nanomaterials, which can be overcome using finely tuned parameters in a preparation process that always involves the use of high energies. Film deposition was made by laser—induced vaporization, with short and modulated impulses and electro–optical tuning of the quality factor, mainly on glass and one SiO2 substrate. Deposition geometry dependent linear thickness increase, between 1.5–2.5 nm per laser burst, was achieved. Film structures and phase compositions were determined using XRD and discussed in comparison with films obtained by similar deposition procedures. Temperature and scale dependent properties were determined by studying electrical conductivity and optical properties. Electrical conductivity was measured using the four-probe method. The observed semiconductor-like conductivity for film thicknesses up to 110 nm can be explained by thermal activation of electrons followed by inter-insular hopping or quantum tunneling, which, on the other hand, modulates the material’s native metallic conductance. Films with thicknesses above this value can be considered essentially metallic and bulk-like. The spectral behaviors of the refractive index and absorption coefficient were deduced from differential reflectance spectroscopy data acquired on a broad ultraviolet, visible, near- and mid-infrared (UV-VIS-NIR-MIR) domain, processed using the Kramers-Krönig formalism. Their study led to the identification of the allowed interband transitions. Electronic behavior in the energy bands near the Fermi level and in the surface and interface-states was described, discussing the differences between experimental data and the classical free-electron theoretical model applied for the bulk intermetallic alloy, in correlation with theoretical optical properties or experimental X-ray photoelectron spectroscopy (XPS) results from references. However, the dielectric-like shape of the reflectance of the thinnest film was in accordance with the Lorentz–Drude model.
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