Origin and stability of the dipolar response in a family of tetragonal tungsten bronze relaxors

A new family of relaxor dielectrics with the tetragonal tungsten bronze structure (nominal composition Ba6M3+Nb9O30, M3+ = Ga, Sc or In) were studied using dielectric spectroscopy to probe the dynamic dipole response and correlate this with the crystal structure as determined from powder neutron diffraction. Independent analyses of real and imaginary parts of the complex dielectric function were used to determine characteristic temperature parameters, TVF, and TUDR, respectively. In each composition both these temperatures correlated with the temperature of maximum crystallographic strain, Tc/a determined from diffraction data. The overall behaviour is consistent with dipole freezing and the data indicate that the dipole stability increases with increasing M3+ cation size as a result of increased tetragonality of the unit cell. Crystallographic data suggests that these materials are uniaxial relaxors with the dipole moment predominantly restricted to the B1 cation site in the structure. Possible origins of the relaxor behaviour are discussed.Comment: Main article 32 pages, 8 figures; Supplementary data 24 pages, 4 figure

Analyses of Sulfur and Iron in Waterlogged Archaeological Wood: The Case of Polyethylene-Glycol-Treated Yenikapı 12 Shipwreck

The Yenikapı (YK) 12 shipwreck is 1 of 37 shipwrecks found at Yenikapı, Istanbul. This merchantman has been dated to AD 672–876 by radiocarbon analyses. The conservation of YK 12, which was assembled with iron nails, was completed with the pre-impregnation of polyethylene glycol (PEG) and using vacuum freeze-drying processes. However, after conservation, dust formation was observed on some wooden parts of the shipwreck during storage. In this study, iron–sulfur-related problems detected in the woods of YK 12 were evaluated. We analysed samples taken from YK 12 to study the sulfur and iron content in woods from oak (Quercus), walnut (Juglans), and hornbeam (Carpinus), representing taxa with different wood properties. Fourier-transform infrared spectroscopy (FTIR) analyses, X-ray diffraction (XRD), and pH measurements were conducted on five samples. The results of these studies showed that the dust consisted of wood particles, PEG, and hydrated iron sulfates, such as FeSO4·4H2O and FeSO4·7H2O. Additionally, one sample included SiO2, whilst another exhibited a low pH value. These findings highlight the importance of optimum ambient conditions for the storage and display of these shipwrecks in order to prevent the irreversible degradation of YK 12 and other recovered shipwrecks

Treatment of waste from a confined hog feeding unit by using artificial marshes

A 1-year study has been completed to evaluate use nf artificial marshes as a teatment system for waste from confined hog feeding operatiuns, A 3 x 2 factor ial experimental design was employed to evaluate the performance of marshes planted with one of three emergent species (Sparganium eurycarpum Phragniites austi:alis, glauca)and receiving three different loadings of hog waste. Each treatment was replicated twice, For each marsh, a complete hydrological and nutrient (N, P) budget was deter­ mined. Data on COD and solids were also collected. The growth of the plants, particularly rates of vegetative reproduction, were also monitored regularly throughout the growing season to examine the effect of sludge accumulation on plant vigor. Because the odor associated with present animal waste handling systems has been a major problem, the most important feature of artificial marshes treating hog waste is that they seem not to have developed any odors during their first year of operation . Emergent plants have a system of inter­nal air spaces that allows oxygen from the leaves to diffuse into the rhizomes and roots, Enough oxygen seems to be diffusing out of the roots and into the accumulating sludge to prevent it from becoming completely anaerobic. During the summer of 1977, the marshes produced a superior effluent to that of an anaerobic lagoon. Up to 70% of the TVS and 50% nf the COD waa re­ moved by the marshes, largely through meuhanical filtration. Approximately 17% of the N and P was removed, mostly by uptake into the plants. Design criteria for these marshes and suggested modifications are pre­sented

Nanostructured Cu2_2O Synthesized via Bipolar Electrochemistry

Cuprous oxide (Cu$_2$O) was synthesized for the first time via an open bipolar electrochemistry (BPE) approach and characterized in parallel with the commercially available material. As compared to the reference, Cu$_2$O formed through a BPE reaction demonstrated a decrease in particle size; an increase in photocurrent; more efficient light scavenging; and structure-correlated changes in the flat band potential and charge carrier concentration. More importantly, as-synthesized oxides were all phase-pure, defect-free, and had an average crystallite size of 20 nm. Ultimately, this study demonstrates the impact of reaction conditions (e.g., applied potential, reaction time) on structure, morphology, surface chemistry, and photo-electrochemical activity of semiconducting oxides, and at the same time, the ability to maintain a green synthetic protocol and potentially create a scalable product. In the proposed BPE synthesis, we introduced a common food supplement (potassium gluconate) as a reducing and complexing agent, and as an electrolyte, allowing us to replace the more harmful reactants that are conventionally used in Cu$_2$O production. In addition, in the BPE process very corrosive reactants, such as hydroxides and metal precursors (required for synthesis of oxides), are generated in situ in stoichiometric quantity, providing an alternative methodology to generate various nanostructured materials in high yields under mild conditions

Comprehensive Solid-State Characterization of Rare Earth Flouride Nanoparticles

The combination of multinuclear solid-state NMR spectroscopy and powder X-ray diffraction has been applied to characterize the octahedron-shaped crystalline nanoparticle products resulting from an inverse micelle synthesis. Rietveld refinements of the powder X-ray diffraction data from the nanoparticles revealed their general formula to be (H3O)Y3F10·xH2O. 1H magic-angle spinning (MAS) NMR experiments provided information on sample purity and served as an excellent probe of the zeolithic incorporation of atmospheric water. 19F MAS NMR experiments on a series of monodisperse nanoparticle samples of various sizes yielded spectra featuring three unique 19F resonances arising from three different fluorine sites within the (H3O)Y3F10·xH2O crystal structure. Partial removal of zeolithic water from the internal cavities and tunnels of the nanoparticles led to changes in the integrated peak intensities in the 19F MAS NMR spectra; the origin of this behavior is discussed in terms of 19F longitudinal relaxation. 19F–89Y variable-amplitude cross-polarization (VACP) NMR experiments on both stationary samples and samples under MAS conditions indicated that two distinct yttrium environments are present, and on the basis of the relative peak intensities, the population of one of the two sites is closely linked to the nanoparticle size. Both 19F MAS and 19F–89Y VACP/MAS experiments indicated small amounts of an impurity present in certain nanoparticles; these are postulated to be spherical amorphous YF3 nanoparticles. We discuss the importance of probing molecular-level structure in addition to microscopic structure and how the combination of these characterization methods is crucial for understanding nanoparticle design, synthesis, and application

Complementary analysis to de-convolute co-located contaminants in marine archaeological bricks

Marine archaeological artefacts contain unexpected compounds due to prolonged exposure to the sea. These can remain dormant and embedded within materials until a change in their surrounding environment, such as exposure to oxygen, prompts a transformation. These changes can pose a problem, as acidic compounds are formed which disintegrate the material, or crystals form which physically break the artefact apart. The extent of these transformations is highly heterogeneous due to its dependence on the ability for oxygen to reach and catalyse these reactions. Additionally, these transformations are heavily dependent on the environment the artefact is exposed to, and the pathways available for ingress, either naturally or through previous degradation. This results in materials with a range of different compounds which are often co-located on the macro, micro and nano-scale. Trying to de-convolute these compounds is challenging, and usually requires a suite of complementary techniques to achieve. Here we report on damaging salts found within marine archaeological bricks and show how it is only possible to qualitatively and quantitatively understand what is present by employing a range of analytical techniques, such as XRD, SEM-EDS and SR-XPD. The marine archaeological bricks studied were found to contain a range of different sulfate-based salts, which had grown crystals in preferred orientations. This provides information which will guide further conservation strategies such as how these bricks are stored, conserved and protected in the future

Interlayer strain effects on the structural behavior of BiFeO3/LaFeO3 superlattices

Artificial (BiFeO3)0.5Λ/(LaFeO3)0.5Λ superlattices have been grown by pulsed laser deposition. The periodicity Λ was varied from 150 Å to 25 Å and the relative ratio between BiFeO3 (BFO) and LaFeO3 (LFO) is kept constant in each period. X-ray diffraction, transmission electron microscopy, and Raman spectroscopy investigations indicate antiferroelectric-like structures for large periodicity (Λ ≥ 76 Å), while Pnma LaFeO3-like structures are observed for small periodicity Λ ≤ 50 Å. Room temperature magnetic measurements were obtained by vibrating sample magnetometry and suggest antiferromagnetic ordering with weak ferromagnetism. Temperature dependent x-ray diffraction studies show an important shift of paraelectric-antiferroelectric phase transition scaling with BFO thickness. Strain and size effects explain this behavior and discussion is also made on the possible role of the oxygen octahedral rotation/tilt degree of freedom

Anti-polar state in BiFeO3_3/NdFeO3_3 superlattices

Antiferroelectrics are promising materials for high energy density capacitors and the search for environmentally-friendly and efficient systems is actively pursued. An elegant strategy to create and design new (anti)ferroic system relies on the use of nanoscale superlattices. We report here the use of such strategy and the fabrication of nanoscale BiFeO$_3$/NdFeO$_3$ superlattices and in depth characterization using high resolution X-ray diffraction and Transmission Electron Microscopy. The structural analysis at atomic scale demonstrates that such superlattices host anti-polar ordering most likely described by an antiferroelectric-like Pbnm symmetry. Temperature dependence of anti-polar state and structural transition further hint that the stability of the anti-polar state is controlled by the BiFeO$_3$ layer thickness within the stacking and, in a more moderate way, by interlayer strain. Discovery of such polar arrangement in superlattices and the possible generalization to the whole rare-earth family pave the way to new platforms for energy storage application as well as nano-electronic devices

Structural study of bismuth ferrite BiFeO3BiFeO_3 by neutron total scattering and the reverse Monte Carlo method

We report a study of the atomic structure of the multiferroic material bismuth ferrite $BiFeO_3$ using neutron total scattering measurements coupled with analysis using the Reverse Monte Carlo method. We have examined average neighboring interatomic distances and local coordination environments, together with their fluctuations, for temperatures between 16 and 800 K (the sample decomposed at higher temperatures). There is little change in the average structure as a function of temperature, but the results show unusually large thermal motion at higher temperatures. No anomalous behavior is seen within this range, suggesting that the anomalies reported to occur below room temperature most likely arise due to effects associated with surfaces and interfaces