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NANOCERIA PREPARED BY ELECTRON BEAM EVAPORATION
Pizúrová, Naděžda ; Hlaváček, Antonín ; Kavčiaková, Zuzana ; Roupcová, Pavla ; Kuběna, Ivo ; Buršík, Jiří ; Sokovnin, S. Y.
Cerium oxide nanoparticles (nanoceria) are currently one of the most investigated nanomaterials because of their attractive properties used in biomedical applications, catalysis, fuel cells, and many others. These attractive properties are connected with the Ce3+ and Ce4+ valency state ratio. In the nanoparticle form, cerium oxides contain a mixture of Ce3+ and Ce4+ on the nanoparticle surfaces. Switching between these two states requires oxygen vacancies. Therefore, nanoceria's inherent ability to act as an antioxidant in an environmentally-dependent manner and a “redox switch” to confer auto-regenerating capabilities by automatically shifting between Ce4+ and Ce3+ oxidation states is significantly affected by surface morphology. Regarding this demanded behavior, we aimed to characterize synthesized nanoparticle surface quality and its influence on the cerium oxidation states. The received results were used to evaluate the synthesis method's suitability for suggested utilization. We used nanoparticles prepared by electron beam evaporation. This unique physical method includes nanoparticle creation through the fast cooling process followed by breaking radiation damaging nanoparticle surfaces to create surface off-stoichiometry. We prepared a sample containing clusters of a mixture of ultra-small nanoparticles and approximately 100 nm particles. X-ray diffraction confirmed the CeO2 phase in both components. To extract the finest component, we used centrifugal size fractionation. We received 200 nm clusters of 2-10 nm nanoparticles. Nanoparticle shapes and facet types were analyzed using transmission electron microscopy methods. We found out most nanoparticles were formed with truncated octahedrons containing {1,1,1} and {1,0,0} facet types and truncated cuboctahedrons containing {1,1,1}, {1,0,0}, and additional {1,1,0} facets. No octahedron (without truncation) containing only {1,1,1} facets was observed. Nanoparticle shapes containing {1,1,0} and {1,0,0} are suitable for redox activity. Some amount of irregular shapes, beneficial for redox activity, was also observed. Spectroscopy methods confirmed Ce3+ content.
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PHASE COMPOSITION OF CHOSEN Mg-BASED MATERIALS DURING HYDROGEN SORPTION
Čermák, Jiří ; Král, Lubomír ; Roupcová, Pavla
Phase transformation during hydrogen sorption was investigated in ten chosen magnesium-based hydrogen storage (HS) materials. Chemical composition of the materials consisted of Mg, as a principal hydrogen-binding element, additive X and amorphous carbon (CB), as an anti-sticking component. In order to assess the effect of X itself upon the structure, values of concentration of both X and CB were fixed to about 12 wt. %. The influence of X = Mg2Si, Mg2Ge, Mg17Al12, Mg5Ga2, NaCl, LiCl, NaF, LiF and two combinations Ni+Mg17Al12 and Ni+Mg2Si upon the changes in phase composition was tested. Phase content in HS materials was observed (i) after the intensive ball milling (BM), (ii) after the BM followed by hydrogen charging at 623 K and (iii) after the BM and one hydrogen charging/discharging cycle (C/D) at temperature 623 K. The study was carried out by SEM and XRD. It was found that, the C/D is approximately structurally reversible for X = Mg2Ge, Mg17Al12, NaF and LiF. However, additives X = Mg17Al12 and NaF decompose already during the BM. In alloys with combination of Ni with Mg17Al12, new phases NimAln are formed. Phase composition changed during C/D for X = Mg2Si Mg5Ga2 and Ni+Mg2Si due to equilibration of phases composition. Observed structure changes of HS materials with chloride ionic additives NaCl and LiCl are, most likely caused by the relatively strong affinity between Mg and Cl. Hydrogen storage capacity of all studied alloys was 6.0 +/- 0.3 wt. % H-2.
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HYDROGEN SORPTION IN ORDERED Mg-In ALLOYS
Čermák, Jiří ; Král, Lubomír ; Roupcová, Pavla
Hydrogen storage (HS) performance of three Mg- x In- y CB alloys (CB - amorphous carbon, x = 55, 64, 73 y =\n10 wt%) was studied. Indium concentration covered an area of ordered β structures. Alloys were prepared by\nball-milling in hydrogen atmosphere. Kinetic curves and PCT isotherms were measured in the temperature\ninterval from 200 °C to 325 °C. X-ray diffraction spectroscopy (XRD) was used for structure investigation. Alloy\nwith x = 73 wt% In ( β ’’ structure) showed reversible amorphization during temperature cycling between about\n100 °C and 350 °C. Hydrogen sorption experiments were done by the Sieverts method under the hydrogen\ngas pressure ranging from 0.1 MPa to 2.5 MPa. It was found that hydrogen sorption capacity varied between\n0.47 and 1.1 wt% H 2 . Hydride formation enthalpy ∆H calculated from desorption PCT experiments was\nsignificantly lower than ∆H , known for pure Mg. This invoked an idea that atomic order of Mg-based HS\nmaterials might decrease the high thermodynamic stability of hydride phase.
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MICROSTRUCTURE AND COMPOSITION OF FINE PARTICLES RELEASED BY CAR BRAKING
Švábenská, Eva ; Roupcová, Pavla ; Pizúrová, Naděžda ; Schneeweiss, Oldřich
Vehicular traffic is connected with large volume of fine particles released during brake processes of cars. Our research is focused on the phase, structure and chemical analysis of the fine particles taken from some car brake parts by their services. The information on structure and phase composition was obtained by X-Ray Powder Diffraction, Mossbauer Spectroscopy, scanning electron microscopy with EDX and transmission electron microscopy. The results of the wear debris analysis are compared with original brake materials components. Most of recognized particles are based mainly on iron oxides. Wear brake particles are discussed in the relation to the potential risk to the environment and human health.
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MICROSTRUCTURE AND COMPOSITION OF FINE PARTICLES RELEASED BY CAR BRAKING
Švábenská, Eva ; Roupcová, Pavla ; Pizúrová, Naděžda ; Schneeweiss, Oldřich
Vehicular traffic is connected with large volume of fine particles released during brake processes of cars. Our research is focused on the phase, structure and chemical analysis of the fine particles taken from some car brake parts by their services. The information on structure and phase composition was obtained by X-Ray Powder Diffraction, Mossbauer Spectroscopy, scanning electron microscopy with EDX and transmission electron microscopy. The results of the wear debris analysis are compared with original brake materials components. Most of recognized particles are based mainly on iron oxides. Wear brake particles are discussed in the relation to the potential risk to the environment and human health.
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INFLUENCE OF GRAPHITE UPON THE KINETICS OF HYDROGEN SORPTION IN Mg@Mg17Al12
Čermák, Jiří ; Král, Lubomír ; Roupcová, Pavla
Influence of graphite addition to the ball-milling charge composed of Mg splinters and Mg17Al12 particles upon the hydrogen sorption was investigated at sorption temperature 623 K. Measurements were carried out by Sieverts method. Graphite facilitates the ball-milling: It prevents re-agglomeration of crushed particles into large secondary particles. It also suppresses sticking the milled material to the balls and walls of the milling jar. It was found that an increase of carbon concentration up to a certain limit c(L) lying between 14 and 23 wt. % C, carbon increases both the absorption and the desorption rates and hydrogen storage capacity. Above c(L), carbon causes a considerable decrease in HS capacity, which spoils the application potential of Mg@Mg17Al12/C. Crystallite size of the material under study, obtained by XRD, is in the order of tens of nm.
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Wavelength modulation spectroscopy for multicomponent ana-lytics of biomass burning tracers
Dostál, Michal ; Válek, V. ; Suchánek, Jan ; Kristlová, E. ; Roupcová, P. ; Zelinger, Zdeněk ; Nevrlý, Václav ; Bitala, P. ; Vašinek, M. ; Kubát, Pavel ; Ferus, Martin ; Civiš, Svatopluk
The potential of Tunable Diode Laser Absorption Spectroscopy (TDLAS) for monitoring of several species produced by biomass burning is in focus of this work. The infrared spectra of selected molecules (HCOOH, C2H2, CH3CN, N2O, CH3OH, CH3COCH3) are measured in laboratory conditions and the selectivity and of this method is demonstrated.
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Nanoscale phases on surface Fe-6Si magnetic sheets
Švábenská, Eva ; Roupcová, Pavla ; Král, Lubomír ; Bulín, Tomáš ; Vondráček, Martin ; Foldyna, Josef ; Čechal, J. ; Schneeweiss, Oldřich
Analysis of the nanoscale phases which appear on the surface Fe-6Si samples were carried out after the various treatments – grinding and etching, annealing, and water jet abrasion. The basic information on structure, chemical and phase composition was obtained by X-Ray Powder Diffraction (XRD), Scanning Electron Microscopy with EDX, Glow Discharge Optical Emission Spectrometry (GDOES), Mössbauer Spectroscopy and X-ray Photoelectron Spectrometry (XPS). The results show high stability of the surface phase composition after the mechanical and heat treatments. Results obtained from the surface analysis in micrometer depth (XRD, EDX, GDOES) do not show any changes after the different treatments. Iron oxides were detected in XPS and conversion electron Mössbauer spectra (CEMS) which analyze the surface composition in a nanometer scale. In addition to, fine changes in atomic ordering on the surface can be observed after mechanical and heat treatments in the CEMS spectra.
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HYDROGENATION OF CHOSEN MgMXN INTERMETALLICS (X=Al, Ga, In, Si, Sn)
Čermák, Jiří ; Král, Lubomír ; Roupcová, Pavla
Hydrogen sorption in chosen intermetallics MgmXn (Mg17Al12 , Mg2Ga, mixture of beta-Mg-In phases, Mg2Si and Mg2Sn) formed by magnesium and elements from the 13 th (X: Al, Ga, In) and 14 th (X: Si, Sn) groups was studied between the room temperature and T = 350 °C. Hydrogen pressure p varied from 10-3 MPa to 6 MPa.\nHydrogen solubility in alpha phase (solid solution of hydrogen in MgmXn before the hydride phase was nucleated) was close to hydrogen solubility in pure Mg. Concentration cH of hydrogen solved in Mg m X n depended linearly on pressure p , dependence of cH on temperature T was relatively weak. MgH2 was the main hydrogen storage phase in all the compounds MgmXn . Nucleation of MgH2 at 350 °C was observed at pressure above approximately 1 MPa in Mg17Al12 and above 2 Ma in other compounds. Maximum values of c H in hydride-containing compounds MgmXn detected at T = 350 °C depended on the stability of MgmXn .
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