Lead-free organic-inorganic azetidinium alternating metal cation bromide: [(CH2)3NH2]2AgBiBr6, a perovskite-related absorber.

In the last decade, organic-inorganic hybrid halide perovskite materials have developed into a very large research area in photovoltaics and optoelectronics as promising light harvesters. Lead-free double perovskites have recently been investigated as an environmentally friendly alternative to the lead-containing compositions. However, lead-free organic-inorganic hybrid halide double perovskites have so far rarely been produced due to a certain complexity in their synthesis. A number of small molecular cations have been investigated, but compositions containing azetidinium, which is a 4-membered heterocyclic molecular ring, on the A-site have hardly been considered. This study investigates the potential of [(CH2)3NH2]2AgBiBr6 as an optical absorber in photovoltaics or optoelectronics. The use of this alternative cation changes the crystal symmetry significantly. Columns of alternating metal cation form which are separated by the organic ions. While crystal symmetry is rather different from the perovskites, the overall properties as an absorber are similar. It is thus worthwhile to further investigate alternate hybrid compositions which form into other symmetries than the perovskite base structure.

Brushite mineralised Scots pine (Pinus sylvestris L.) sapwood - revealing mineral crystallization within a wood matrix by in situ XRD.

Dicalcium phosphate dihydrate (CaHPO4·2H2O, DCPD, brushite) crystals were synthesised within Scots pine sapwood via a wet-chemistry route from aqueous solutions of Ca(CH3COO)2 and NH4H2PO4 salts. SEM/EDS analysis was used to assess the saturation of the wood cell lumina and cell wall as well as morphological features and elemental composition of the co-precipitated mineral. Brushite mineral crystallization and crystallite growth within the wood matrix was studied by in situ XRD. The chemical composition of the mineral before and after the dissolution was evaluated using FTIR spectroscopy. The overall impact of brushite on the thermal behaviour of wood was studied by TGA/DSC and TGA/DTA/MS analysis under oxidative and pyrolytic conditions. Bending and compression strength perpendicular and parallel to the fibre directions as well as bending strengths in longitudinal and transverse directions of the mineralised wood were also evaluated. Results indicate the viability of the wet-chemistry processing route for wood reinforcement with crystalline calcium phosphate (CaP)-based minerals, and imply a potential in producing hybrid bio-based materials that could be attractive in the construction sector as an environmentally friendly building material.

Annealing-Dependent Morphotropic Phase Boundary in the BiMg0.5Ti0.5O3-BiZn0.5Ti0.5O3 Perovskite System.

The annealing behavior of (1-x)BiMg0.5Ti0.5O3−xBiZn0.5Ti0.5O3 [(1-x)BMT−xBZT] perovskite solid solutions synthesized under high pressure was studied in situ via X-ray diffraction and piezoresponse force microscopy. The as prepared ceramics show a morphotropic phase boundary (MPB) between the non-polar orthorhombic and ferroelectric tetragonal states at 75 mol. % BZT. It is shown that annealing above 573 K results in irreversible changes in the phase diagram. Namely, for compositions with 0.2 < x < 0.6, the initial orthorhombic phase transforms into a ferroelectric rhombohedral phase. The new MPB between the rhombohedral and tetragonal phases lies at a lower BZT content of 60 mol. %. The phase diagram of the BMT−BZT annealed ceramics is formally analogous to that of the commercial piezoelectric material lead zirconate titanate. This makes the BMT−BZT system promising for the development of environmentally friendly piezoelectric ceramics.

Magnetic-field-assisted deposition of self-assembling crystallite layers of Co2+-containing layered double hydroxides.

Precipitation of nanocrystallites of cobalt-aluminium layered double hydroxides in a magnetic field has been studied. In a magnetic field perpendicular to the substrate, dense and homogeneous films have been obtained. Magnetic anisotropy of the crystallites is explained by deviation from the statistical cation distribution in favour of honeycomb-like coordination of cobalt.

Interplay of Magnetic Properties and Doping in Epitaxial Films of h-REFeO3 Multiferroic Oxides.

Multiferroic materials demonstrating coexistence of magnetic and ferroelectric orders are promising candidates for magnetoelectric devices. While understanding the underlying mechanism of interplaying of ferroic properties is important, tailoring their properties to make them potential candidates for magnetoelectric devices is challenging. Here, the antiferromagnetic Neel ordering temperature above 200 K is realized in successfully stabilized epitaxial films of (Lu,Sc)FeO3 multiferroic oxide. The first-principles calculations show the shrinkage of in-plane lattice constants of the unit cells of the films on different substrates which corroborates well the enhancement of the Neel ordering temperature (TN ). The profound effect of lattice strain/stress at the interface due to differences of in-plane lattice constants on out of plane magnetic properties and on spin reorientation temperature in the antiferromagnetic region is further elucidated in the epitaxial films with and without buffer layer of Mn-doped LuFeO3 . Writing and reading ferroelectric domains reveal the ferroelectric response of the films at room temperature. Detailed electron microscopy shows the presence of lattice defects in atomic scale. First-principles calculations show that orbital rehybridization of rare-earth ions and oxygen is one of the main driving force of ferroelectricity along c-axis in thin films of hexagonal ferrites.

Phase Transitions in the Metastable Perovskite Multiferroics BiCrO3 and BiCr0.9Sc0.1O3: A Comparative Study.

The temperature behavior of the crystal structure as well as dielectric and magnetic properties of the perovskite bismuth chromate ceramics with the 10 mol % Cr3+-to-Sc3+ substitution were studied and compared with those of the unmodified compound. Using a high-pressure synthesis, BiCrO3 and BiCr0.9Sc0.1O3 were obtained as metastable perovskite phases which are monoclinic C2/c with the √6ap × âˆš2ap × âˆš6ap superstructure (where ap is the primitive perovskite unit-cell parameter) under ambient conditions. At room temperature, the unit cell volume of BiCr0.9Sc0.1O3 is ∼1.3% larger than that of BiCrO3. Both perovskites undergo a reversible structural transition into a nonpolar GdFeO3-type phase (orthorhombic Pnma, √2ap × 2ap × âˆš2ap) in the temperature ranges of 410-420 K (BiCrO3) and 470-520 K (BiCr0.9Sc0.1O3) with a relative jump of the primitive perovskite unit cell volume of about -1.6 and -2.0%, respectively. Temperature dependences of the complex dielectric permittivity demonstrate anomalies in the phase transition ranges. The Pnma-to-C2/c crossover in BiCrO3 is accompanied by a decrease in the direct current (dc) conductivity, while in BiCr0.9Sc0.1O3 the conductivity increases. The onset of an antiferromagnetic order in BiCr0.9Sc0.1O3 is observed at the Néel temperature (TN) of about 85 K as compared with TN = 110 K in BiCrO3. In contrast to BiCrO3, which exhibits a spin reorientation at Tsr ∼ 72 K, no such a transition occurs in BiCr0.9Sc0.1O3.

Temperature-Induced Structural Transformations in Undoped and Eu3+-Doped Ruddlesden-Popper Phases Sr2SnO4 and Sr3Sn2O7: Relation to the Impedance and Luminescence Behaviors.

We report that luminescence of Eu3+ ion incorporated into Ruddlesden-Popper phases allows monitoring phase transition in powders (instead of single crystals), in a time-efficient manner (compared to neutron diffraction), and importantly, with greater sensitivity than previous methods. Crystal structure and dielectric response of undoped and 0.5%Eu3+-doped Sr3Sn2O7 ceramics were studied as a function of temperature over the temperature range of 300-800 K. The luminescence studies of 0.5%Eu3+-doped Sr2SnO4 and Sr3Sn2O7 samples were performed in the temperature range of 80-500 K. These results were compared with the respective dependences for the undoped compounds. The structural transformations in 0.5%Eu3+-doped Sr3Sn2O7 were found at 390 and 740 K. The former is associated with the isostructural atomic rearrangement that resulted in a negative thermal expansion along two of three orthorhombic crystallographic axes, while the latter corresponds to the structural transition from the orthorhombic Amam phase to the tetragonal I4/mmm one. A similar temperature behavior with the structural transformations in the same temperature ranges was observed in undoped Sr3Sn2O7, although the values of lattice parameters of the Eu3+-doped and undoped compounds were found to be slightly different indicating an incorporation of europium in the crystal lattice. A dielectric anomaly associated with a structural phase transition was observed in Sr3Sn2O7 at 390 K. Optical measurements performed over a wide temperature range demonstrated a clear correlation between structural transformations in Eu3+-doped Sr2SnO4 and Sr3Sn2O7 and the temperature anomalies of their luminescence spectra, suggesting the efficacy of this method for the determination of subtle phase transformations.

Sonication accelerated formation of Mg-Al-phosphate layered double hydroxide via sol-gel prepared mixed metal oxides.

Single-phase magnesium-aluminium layered double hydroxide (LDH) intercalated with dihydrogen phosphate was successfully produced by hydration of nanopowder of the respective mixed metal oxide (MMO) obtained using sol-gel based method followed by a two-step anion exchange hydroxide-to-chloride and chloride-to-phosphate. The MMO with the metal cation ratio of Mg/Al = 2:1 was prepared using the aqueous sol-gel method. Processes of the parent Mg2Al-OH LDH formation and the successive anion-exchanges, ОН- → Cl- and Cl- → H2PO4-, were considerably accelerated via the application of high-power (1.5 kW) ultrasound. The crystalline phases formed at all stages of the Mg2Al-H2PO4 LDH production were characterized using X-ray diffraction, scanning electron microscopy, scanning transmission electron microscopy, inductive coupled plasma optical emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Based on the data of chemical analysis and the XRD data, the type of the intercalated phosphate anion was determined and the arrangement of this anion in the interlayer was modelled.

One-step synthesis and growth mechanism of nitrate intercalated ZnAl LDH conversion coatings on zinc.

An approach for the synthesis of ZnAl-NO3 LDH conversion coatings on zinc in an aqueous acidic Al(NO3)3/NaNO3 solution is demonstrated for the first time. The growth mechanism has been investigated using time resolved structural, microstructural and analytical methods. A LDH growth model involving both electrochemical and chemical processes is suggested.

The phenomenon of conversion polymorphism in Bi-containing metastable perovskites.

A post-synthesis thermal treatment of metastable phases in the high-pressure stabilised perovskite BiFe1-yScyO3 system results in the irreversible formation of polymorphs which represent novel polar and antipolar structures with interesting magnetic properties. Such annealing-stimulated polymorphism is believed to be a general phenomenon which can be found in other systems.

Control of crystallite and particle size in the synthesis of layered double hydroxides: Macromolecular insights and a complementary modeling tool.

Zinc-aluminum layered double hydroxides with nitrate intercalated (Zn(n)Al-NO3, n=Zn/Al) is an intermediate material for the intercalation of different functional molecules used in a wide range of industrial applications. The synthesis of Zn(2)Al-NO3 was investigated considering the time and temperature of hydrothermal treatment. By examining the crystallite size in two different directions, hydrodynamic particle size, morphology, crystal structure and chemical species in solution, it was possible to understand the crystallization and dissolution processes involved in the mechanisms of crystallite and particle growth. In addition, hydrogeochemical modeling rendered insights on the speciation of different metal cations in solution. Therefore, this tool can be a promising solution to model and optimize the synthesis of layered double hydroxide-based materials for industrial applications.

Silica nanocontainers for active corrosion protection.

Novel self-healing protective coatings with nanocontainers of corrosion inhibitors open new opportunities for long-term anticorrosion protection of different metallic materials. In this paper a new type of functional nanoreservoir based on silica nanocapsules (SiNC) synthesized and loaded with corrosion inhibitor 2-mercaptobenzothiazole (MBT) in a one-stage process is reported for the first time. Unlike conventional mesoporous silica nanoparticles, SiNC possess an empty core and shell with gradual mesoporosity, arising from the particular conditions of the synthetic route adopted, which confers significant loading capacity and allows prolonged and stimuli-triggered release of the inhibiting species. The kinetics of inhibitor release was studied at different pH values and concentrations of NaCl. The results show a clear dependence of the release profiles on corrosion relevant triggers such as pH and Cl(-) concentration. When SiNC loaded with MBT are dispersed in NaCl solution, there is a significant decrease of the corrosion activity on aluminium alloy 2024. More importantly, when SiNC-MBT is added to a conventional water-based coating formulation, the modified coating hampers corrosion activity at the metal interface, better than in the case of direct addition of corrosion inhibitor. Furthermore, self-healing is observed before and after artificially inflicting defects in the modified coatings. As a result, the developed nanocontainers show high potential to be used in new generation of active protective coatings.