The synthesis, structural characterization, and magnetic properties of crystalline manganese oxide nanoparticles are presented. The procedure is based on the reaction of benzyl alcohol with the two ...precursors: potassium permanganate KMnO4 and manganese(II) acetylacetonate Mn(acac)2. Depending on the precursor used, the composition of the final product can be varied in such a way that in the case of KMnO4 mainly Mn3O4 is formed, whereas Mn(acac)2 leads predominantly to MnO. Rietveld refinement of the XRD powder patterns, high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and energy-dispersive X-ray (EDX) analysis, as well as electron energy loss spectroscopy (EELS) were employed for the structural characterization of the as-synthesized compounds. Especially the MnO manganosite nanocrystals exhibit some interesting features. HRTEM investigations point to the formation of a superstructure, which can be described as an ordered Mn vacancy cubic superstructure with the general formula of Mn0.875O x and a lattice parameter of 8.888 Å. The SQUID measurement proves a superparamagnetic behavior of the MnO nanoparticles.
Properties of mixed-metal MOFs depend on the distribution of different metals within their frameworks. Determination of this distribution is often very challenging. Using an example of aluminum- and ...iron-containing MIL-100, we demonstrate that 27Al NMR spectroscopy, when combined with first-principles calculations and magnetic, X-band electron paramagnetic resonance, Fe K-edge extended X-ray absorption fine structure, and Mössbauer measurements, enables one to accurately determine the arrangement of Al and Fe within the metal trimers, which are the basic building units of MIL-100. In this particular material, the incorporation of Fe and Al on the framework metal sites is random. Crucial for deciphering the arrangement is detecting NMR signals, shifted because of the strong hyperfine interaction between the 27Al nuclei and the unpaired electronic spins of Fe3+ ions, assigning the shifted signals aided by first-principles calculations of hyperfine couplings, and quantitatively evaluating the NMR intensities and the measured effective magnetic moment.
The retrofitting of cultural heritage buildings for energy efficiency often requires the internal thermal insulation of external walls. Most of the in situ studies of capillary active interior ...insulation were performed in mild oceanic climate regions, and they showed an excellent performance. However, as a large part of Central–Eastern Europe belongs to a continental climate with cold winters and long periods of temperatures below the freezing temperature, the applicability of the capillary active interior insulation in cold climate was studied. The hydrothermal behaviour of the three walls was determined—each consists of one of three different interior insulations—and the original wall is made of historic regular solid bricks. Two interior thermal insulations were capillary active (aerated cellular concrete, calcium silicate) and one vapour-tight (glass foam). A hot box–cold box experiment and a steady-state model were used to demonstrate an increase in the original wall mass due to the water condensation only when the capillary active interior insulation is used. The combination of the water condensation and the low sub-zero temperature may lead to a risk of freeze–thaw damage to the original wall. The numerical simulation of the water vapour condensation for the considered walls for the Slovenian town Bled with sub-zero average winter temperatures was performed to obtain the whole temperature and moisture profile. It showed good agreement between an experimentally and numerically obtained amount of water condensation. The capillary active interior insulation proved to be unsuitable for improving the thermal insulation of buildings in cold continental climate, and only a vapour-tight system can be recommended.
Various transition metal (TM) doped zinc oxide nanoparticles with the composition TM x Zn1−x O (TM = V, Mn, Fe, Co, and Ni; x = 0.01−0.3) were prepared by a microwave-assisted nonaqueous sol−gel ...route in benzyl alcohol within a few minutes. The high doping levels in the range 20−30 atom % achieved for Co and Fe provide a promising opportunity to study the magnetic properties of such potential diluted magnetic semiconductors. However, only Fe0.2Zn0.8O was ferromagnetic at room temperature. The Co-doped sample showed Curie−Weiss behavior up to a doping level of 30 atom %. According to X-ray absorption fine structure (XAFS) measurements, at high doping levels the Fe-doped ZnO samples contain an increasing fraction of Fe3+ ions (in addition to Fe2+), whereas Co is predominantly in the oxidation state of +2. Clustering of Fe ions into amorphous ferromagnetic Fe3O4 within the ZnO host and the magnetic interactions between the Fe3O4 regions is a possible explanation for the ferromagnetic properties.
Double perovskites have been extensively studied in materials chemistry due to their excellent properties and novel features attributed to the coexistence of ferro/ferri/antiferro-magnetic ground ...state and semiconductor band gap within the same material. Double perovskites with Sr2NiMO6 (M = Te, W) structure type have been synthesized using simple, non-toxic and costless aqueous citrate sol-gel route. The reaction yielded phase-pure nanocrystalline powders of two compounds: Sr2NiWO6 (SNWO) and Sr2NiTeO6 (SNTO). According to the Rietveld refinement of powder X-ray diffraction data at room temperature, Sr2NiWO6 is tetragonal (I4/m) and Sr2NiTeO6 is monoclinic (C12/m1), with average crystallite sizes of 49 and 77 nm, respectively. Structural studies have been additionally performed by Raman spectroscopy revealing optical phonons typical for vibrations of Te6+/W6+O6 octahedra. Both SNTO and SNWO possess high values of dielectric constants (341 and 308, respectively) with low dielectric loss (0.06 for SNWO) at a frequency of 1 kHz. These values decrease exponentially with the increase of frequency to 1000 kHz, with the dielectric constant being around 260 for both compounds and dielectric loss being 0.01 for SNWO and 0.04 for SNTO. The Nyquist plot for both samples confirms the non-Debye type of relaxation behavior and the dominance of shorter-range movement of charge carriers. Magnetic studies of both compounds revealed antiferromagnetic behavior, with Néel temperature (TN) being 57 K for SNWO and 35 K for SNTO.
Herein, we report the synthesis, microstructure, and magnetic properties of cadmium ferrite (CdFe2O4) thin films with both an ordered cubic network of 18 nm diameter pores and single-phase spinel ...grains averaging 13 nm in diameter. These mesoporous materials were produced through facile polymer templating of hydrated nitrate salt precursors. Both the morphology and the microstructure, including cation site occupancy and electronic bonding configuration, were analyzed in detail by electron microscopy, grazing incidence small-angle X-ray scattering, Raman and X-ray photoelectron spectroscopy, and N2-physisorption. The obtained data demonstrate that the network of pores is retained up to annealing temperatures as high as 650 °Cthe onset of crystallization is at ϑ = (590 ± 10) °C. Furthermore, they show that the polymer-templated samples exhibit a “partially” inverted spinel structure with inversion parameter λ = 0.40 ± 0.02. This differs from microcrystalline CdFe2O4 which shows virtually no inversion. Magnetic susceptibility studies reveal ferrimagnetic spin coupling below 147 K and further point to the likelihood of glassy behavior at low temperature (T f ≈ 60 K). In addition, analysis of room temperature magnetization data indicates the presence of sub-10 nm diameter superparamagnetic clusters in an otherwise paramagnetic environment.
The ab initio calculations of a heterostructure based on the ferroelectric phase of barium titanate and dielectrics lanthanum manganese (LaMnO3) or silicon (Si) are presented. We analyze structures ...of BaTiO3/LaMnO3 and BaTiO3/Si interfaces, investigate magnetic properties and the impact of ferroelectric polarization. The use of ferroelectrics in the heterostructure plays a crucial role; in particular, ferroelectric polarization leads to the appearance of the conducting state at the interface and in the layers close to it. We show that defects (here, oxygen vacancies) incorporated into the system may change the electronic and magnetic properties of a system. Experimental results of magnetic susceptibility measurements for the Ba0.8Sr0.2TiO3/LaMnO3 heterostructure are also presented. It is shown that a correlation between the behavior of the ferromagnetic ordering and the resistance takes place. In addition, the ferromagnetic ordering at the interface of the heterostructure can be associated with the exchange interaction through current carriers that appear in high carrier concentration regions.
We report on the electrodynamic properties of the single crystalline lead-substituted M-type barium hexaferrite, Ba0.3Pb0.7Fe12O19, performed in the broad frequency range including radio-frequency, ...terahertz and sub-terahertz bands, which are particularly important for the development of microelectronic devices. We demonstrate how changing on a molecular level the chemical characteristics (composition, intermolecular interaction, spin-orbital interaction) of lead-substituted M-type hexaferrite influences its radio-frequency and terahertz electrodynamic response. Our results indicate a critical temperature range, 50 K < T < 70 K, where significant changes of the electrodynamic response occur that are interpreted as freezing of dynamical oscillations of bi-pyramidal Fe(2b) ions. In the range 5-300 K, the heat capacity shows no sign of any phase transition and is solely determined by electron and phonon contributions. An anomalous electrodynamic response is detected at 1-2 THz that features a rich set of absorption resonances which are associated with electronic transitions within the fine-structured Fe2+ ground state and are visualized in the spectra due to magnetostriction and electron-phonon interaction. We show that lead substitution of barium in barium hexaferrite, BaFe12O19, leads to the emergence of a pronounced dielectric and magnetic relaxational dynamics at radio-frequencies and that both dynamics have the same characteristic relaxation times, thus evidencing the bi-relaxor-like nature of Ba0.3Pb0.7Fe12O19. We associate the origin of the relaxations as connected with the motion of magnetic domain walls. In order to unveil crucial influence of chemical substitution on electrodynamic characteristics of the compound, we analyze our results on substituted compound in comparison with the data available for pristine barium (BaFe12O19) and pristine lead (PbFe12O19) hexaferrites. The obtained spectroscopic data on the dielectric properties of Ba0.3Pb0.7Fe12O19 provide insight into fundamental phenomena responsible for the absorption mechanisms of the compound and demonstrates that chemical ionic substitution is an effective tool to tune the dielectric properties of the whole family of hexaferrites.
A novel one-dimensional (1D) oxalate-bridged coordination polymer of iron(III), {NH(CH3)(C2H5)2FeCl2(C2O4)}n (1), exhibits remarkable humidity-sensing properties and very high proton conductivity at ...room temperature (2.70 × 10−4 (Ω·cm)−1 at 298 K under 93% relative humidity), in addition to the independent antiferromagnetic spin chains of iron(III) ions bridged by oxalate groups (J = −7.58(9) cm−1). Moreover, the time-dependent measurements show that 1 could maintain a stable proton conductivity for at least 12 h. Charge transport and magnetic properties were investigated by impedance spectroscopy and magnetization measurements, respectively. Compound 1 consists of infinite anionic zig-zag chains FeCl2(C2O4)nn− and interposed diethylmethylammonium cations (C2H5)2(CH3)NH+, which act as hydrogen bond donors toward carbonyl oxygen atoms. Extraordinarily, the studied coordination polymer exhibits two reversible phase transitions: from the high-temperature phase HT to the mid-temperature phase MT at T ~213 K and from the mid-temperature phase MT to the low-temperature phase LT at T ~120 K, as revealed by in situ powder and single-crystal X-ray diffraction. All three polymorphs show large linear thermal expansion coefficients.
High-purity samples of potassium trifluoroargentate(II), KAgF3, have been obtained via a novel synthetic pathway. This compound is found to exhibit an order-disorder phase transition around 230 K. ...Susceptibility measurements indicate that KAgF3 exhibits strong antiferromagnetic (AFM) coupling reminiscent of that found in copper(II) oxides.
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