Ionic and electronic transport in calcium-substituted LaAlO3 perovskites prepared via mechanochemical route

The present work explores mechanosynthesis of lanthanum aluminate-based perovskite ceramics and corresponding effects on ionic-electronic transport properties. La1-xCaxAlO3-δ (x = 0.05-0.20) nanopowders were prepared via one-step high-energy mechanochemical processing. Sintering at 1450°C yielded dense ceramics with submicron grains. As-prepared powders and sintered ceramics were characterized by XRPD, XPS and SEM. Electrochemical studies showed that partial oxygen-ionic conductivity in prepared La1-xCaxAlO3-δ increases with calcium content up to 10 at.% in the lanthanum sublattice and then levels off at ~6×10-3 S/cm at 900°C. La1-xCaxAlO3-δ ceramics are mixed conductors under oxidizing conditions and ionic conductors with negligible contribution of electronic transport in reducing atmospheres. Oxygen-ionic contribution to the total conductivity is 20-68% at 900°C in air and increases with Ca content, with temperature and with reducing p(O2). Impedance spectroscopy results showed however that electrical properties of mechanosynthesized La1-xCaxAlO3-δ ceramics below ~800°C are determined by prevailing grain boundary contribution to the total resistivity.This work was supported by the Slovak Research and Development Agency APVV (contracts SK-PT-18-0039 and 15-0438) and the Slovak Grand Agency (contract No. 2/0055/19). BIAS and AAY would like to acknowledge financial support by the FCT, Portugal (bilateral project Portugal-Slovakia 2019-2020, project CARBOSTEAM (POCI01-0145-FEDER-032295) and project CICECO-Aveiro Institute of Materials (FCT ref. UID/CTM/50011/2019), financed by national funds through the FCT/MCTES and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement). HK thanks to SAIA, n.o. for financial support within National Scholarship Programme of the Slovak republic (NSP).in publicatio

Biochar from Wood Chips and Corn Cobs for Adsorption of Thioflavin T and Erythrosine B

Biochars from wood chips (WC) and corn cobs (CC) were prepared by slow pyrolysis and used for sorption separation of erythrosine B (EB) and thioflavin T (TT) in batch experiments. Biochar-based adsorbents were extensively characterized using FTIR, XRD, SEM-EDX, and XPS techniques. The kinetics studies revealed that adsorption on external surfaces was the rate-limiting step for the removal of TT on both WC and CC biochar, while intraparticle diffusion was the rate-limiting step for the adsorption of EB. Maximal experimental adsorption capacities Q(maxexp) of TT reached 182 +/- 5 (WC) and 45 +/- 2 mg g(-1) (CC), and EB 12.7 +/- 0.9 (WC) and 1.5 +/- 0.4 mg g(-1) (CC), respectively, thereby indicating a higher affinity of biochars for TT. The adsorption mechanism was found to be associated with pi-pi interaction, hydrogen bonding, and pore filling. Application of the innovative dynamic approach based on fast-field-cycling NMR relaxometry indicates that variations in the retention of water-soluble dyes could be explained by distinct water dynamics in the porous structures of WC and CC. The obtained results suggest that studied biochars will be more effective in adsorbing of cationic than anionic dyes from contaminated effluents

Evolution of the fishtail-effect in pure and Ag-doped MG-YBCO

We report on magnetic measurements carried out in a textured YBa$_2$Cu$_3$O$_{7-\delta}$ and YBa$_2$(Cu$_{1-x}$Ag$_x$)$_3$O$_{7-\delta}$ (at $x \approx$ 0.02) crystals. The so-called fishtail-effect (FE) or second magnetization peak has been observed in a wide temperature range 0.4~$<T/T_c<$~0.8 for $\textbf{H}\parallel c$. The origin of the FE arises for the competition between surface barrier and bulk pinning. This is confirmed in a non-monotonically behavior of the relaxation rate $R$. The value $H_{max}$ for Ag-doped crystals is larger than for the pure one due to the presence of additional pinning centers, above all on silver atoms.Comment: 6 pages, 6 figure

A sustainable reaction process for phase pure LiFeSi2O6 with goethite as an iron source

Lithium-iron methasilicate (LiFeSi$_{2}$O$_{6}$, LFS), a member of clinopyroxene family, is an attractive compound for its multiferroic properties and applicability in energy-related devices. Conventional preparative method requires heating at elevated temperatures for long periods of time, with inevitable severe grain growth. We demonstrate that α-FeO(OH) (goethite) is superior as an iron source toward phase pure LFS over conventional hematite, α-Fe$_{2}$O$_{3}$. The exact phase purity, i.e., no trace of iron containing reactant, is confirmed in the goethite-derived LFS by 57Fe Mössbauer spectroscopy. The grain growth of LFS during heating is suppressed to keep its crystallite size of 120 nm. Higher reactivity of goethite in comparison with hematite is mainly attributed to the dehydration of goethite, which in our case was accelerated by Li$_{2}$O. Related reaction mechanisms with the possible product pre-nucleation during mechanical activation are also mentioned. The magnetic properties of goethite-derived LFS are equivalent to those prepared via a laborious solid-state route. Thus, the presented preparative method offers a more sustainable route than conventional processing, and thus enables practical application of LFS

Nanostructure and magnetic anomaly of mechanosynthesized Ce1−x_{1-x}Yx_{x}O2−δ_{2-δ} (x ≤ 0.3) solid solutions

Electromagnetic properties of complex oxide solid solutions containing Ce and Y attract increasing interests due to their high application potential. Their properties are known to be dependent on many factors including grain size and crystal defects. Here we focus on unique features of nanocrystalline Ce$_{1-x}$Y$_{x}$O$_{2-δ}$ (x ≤ 0.3) solid solutions prepared via a mechanosynthesis. Mechanically activated CeO$_{2-δ}$ and mechanosynthesized Ce$_{1-x}$Y$_{x}$O$_{2-δ}$ exhibit room-temperature ferromagnetism. The saturation magnetization reaches maximum for the Ce$_{0.9}$Y$_{0.1}$O$_{2-δ}$ solid solution. XPS and Raman spectra show that Ce$^{Zahl}$4+s are partially reduced to Ce$^{3+}$, with simultaneous introduction of oxygen vacancies accumulated on surface of the solid solutions. An analysis of the experimental magnetization data and the determination of both the spin state and the concentration of magnetic carriers revealed that a small part of the Ce$^{3+}$ spins (<1%) is responsible for the magnetic state of the Ce$_{1-x}$Y$_{x}$O$_{2-δ}$ system. Existence of clusters with a short-range antiferromagnetic order is also suspected

A Unique Mechanochemical Redox Reaction Yielding Nanostructured Double Perovskite Sr2_{2}FeMoO6_{6} With an Extraordinarily High Degree of Anti-Site Disorder

Strontium ferromolybdate, Sr(2)FeMoO(6), is an important member of the family of double perovskites with the possible technological applications in the field of spintronics and solid oxide fuel cells. Its preparation via a multi-step ceramic route or various wet chemistry-based routes is notoriously difficult. The present work demonstrates that Sr(2)FeMoO(6) can be mechanosynthesized at ambient temperature in air directly from its precursors (SrO, α-Fe, MoO(3)) in the form of nanostructured powders, without the need for solvents and/or calcination under controlled oxygen fugacity. The mechanically induced evolution of the Sr(2)FeMoO(6) phase and the far-from-equilibrium structural state of the reaction product are systematically monitored with XRD and a variety of spectroscopic techniques including Raman spectroscopy, (57)Fe Mössbauer spectroscopy, and X-ray photoelectron spectroscopy. The unique extensive oxidation of iron species (Fe(0) → Fe(3+)) with simultaneous reduction of Mo cations (Mo(6+) → Mo(5+)), occuring during the mechanosynthesis of Sr(2)FeMoO(6), is attributed to the mechanically triggered formation of tiny metallic iron nanoparticles in superparamagnetic state with a large reaction surface and a high oxidation affinity, whose steady presence in the reaction mixture of the milled educts initiates/promotes the swift redox reaction. High-resolution transmission electron microscopy observations reveal that the mechanosynthesized Sr(2)FeMoO(6), even after its moderate thermal treatment at 923 K for 30 min in air, exhibits the nanostructured nature with the average particle size of 21(4) nm. At the short-range scale, the nanostructure of the as-prepared Sr(2)FeMoO(6) is characterized by both, the strongly distorted geometry of the constituent FeO(6) octahedra and the extraordinarily high degree of anti-site disorder. The degree of anti-site disorder ASD = 0.5, derived independently from the present experimental XRD, Mössbauer, and SQUID magnetization data, corresponds to the completely random distribution of Fe(3+) and Mo(5+) cations over the sites of octahedral coordination provided by the double perovskite structure. Moreover, the fully anti-site disordered Sr(2)FeMoO(6) nanoparticles exhibit superparamagnetism with the blocking temperature T (B) = 240 K and the deteriorated effective magnetic moment μ = 0.055 μ (B) per formula unit

Proton and electron irradiations of CH4:H2O mixed ices

The organic chemistry occurring in interstellar environments may lead to the production of complex molecules that are relevant to the emergence of life. Therefore, in order to understand the origins of life itself, it is necessary to probe the chemistry of carbon-bearing molecules under conditions that simulate interstellar space. Several of these regions, such as dense molecular cores, are exposed to ionizing radiation in the form of galactic cosmic rays, which may act as an important driver of molecular destruction and synthesis. In this paper, we report the results of a comparative and systematic study of the irradiation of CH4:H2O ice mixtures by 1 MeV protons and 2 keV electrons at 20 K.We demonstrate that our irradiations result in the formation of a number of new products, including both simple and complex daughter molecules such as C2H6, C3H8, C2H2, CH3OH, CO, CO2, and probably also H2CO. A comparison of the different irradiation regimes has also revealed that proton irradiation resulted in a greater abundance of radiolytic daughter molecules compared to electron irradiation, despite a lower radiation dose having been administered. These results are important in the context of the radiation astrochemistry occurring within the molecular cores of dense interstellar clouds, as well as on outer Solar System objects.Comment: Published as an open access article in the MDPI journal Atom

Infrared study on the thermal evolution of solid state formamide

Laboratory experiments have shown that the energetic processing, i.e. ion bombardment and UV photolysis, of interstellar grain mantles and cometary surfaces is efficient in the production of formamide. To explain its presence in the gas-phase in these astrophysical environments, a desorption mechanism has to be taken into account. In this work we show experimental results on the thermal evolution of formamide when deposited at 17 K as pure and in mixture with water or carbon monoxide. In these samples, we observed formamide desorption at 220 K. Moreover, we discuss its synthesis in a mixture containing molecular nitrogen, methane and water (N2:CH4:H2O) deposited at 17 K and bombarded with 200 keV H+. Heating the sample, we observed that the newly formed formamide remains trapped in the refractory residue produced after the ion bombardment up to 296 K. To analyse the samples we used Fourier transform-infrared spectroscopy (FT-IR) that allowed us to study the infrared spectra between the deposition and the complete desorption of formamide. Here we discuss the experimental results in view of their astrophysical relevance

Vacuum ultraviolet photoabsorption spectroscopy of space-related ices: formation and destruction of solid carbonic acid upon 1 keV electron irradiation

Context. Carbonic acid (H2CO3) is a weak acid relevant to astrobiology which, to date, remains undetected in space. Experimental work has shown that the β-polymorph of H2CO3 forms under space relevant conditions through energetic (UV photon, electron, and cosmic ray) processing of CO2- and H2O-rich ices. Although its α-polymorph ice has been recently reassigned to the monomethyl ester of carbonic acid, a different form of H2CO3 ice may exist and is synthesized without irradiation through surface reactions involving CO molecules and OH radicals, that is to say γ-H2CO3. Aims. We aim to provide a systematic set of vacuum ultraviolet (VUV) photoabsorption spectroscopic data of pure carbonic acid that formed and was destroyed under conditions relevant to space in support of its future identification on the surface of icy objects in the Solar System by the upcoming Jupiter ICy moons Explorer mission and on interstellar dust by the James Webb Space Telescope spacecraft. Methods. We present VUV photoabsorption spectra of pure and mixed CO2 and H2O ices exposed to 1 keV electrons at 20 and 80 K to simulate different interstellar and Solar System environments. Ices were then annealed to obtain a layer of pure H2CO3 which was further exposed to 1 keV electrons at 20 and 80 K to monitor its destruction pathway. Fourier-transform infrared (FT-IR) spectroscopy was used as a secondary probe providing complementary information on the physicochemical changes within an ice. Results. Our laboratory work shows that the formation of solid H2CO3, CO, and O3 upon the energetic processing of CO2:H2O ice mixtures is temperature-dependent in the range between 20 and 80 K. The amorphous to crystalline phase transition of H2CO3 ice is investigated for the first time in the VUV spectral range by annealing the ice at 200 and 225 K. We have detected two photoabsorption bands at 139 and 200 nm, and we assigned them to β-H2CO3 and γ-H2CO3, respectively. We present VUV spectra of the electron irradiation of annealed H2CO3 ice at different temperatures leading to its decomposition into CO2, H2O, and CO ice. Laboratory results are compared to Cassini UltraViolet Imaging Spectrograph observations of the 70−90 K ice surface of Saturn’s satellites Enceladus, Dione, and Rhea