Solids

By a molecular dynamics (MD) simulation method which ensures the system will be under hydrostatic pressure, dynamic and elastic properties of glassy metatstable states are investigated. In the MD method, the simulation cell fluctuates not only in volume but also in shape under constant hydrostatic pressure and temperature. As observed in experiments for many glass forming materials, metastable states in our simulation show a sharp increase in mean-square-displacement at certain temperatures $T_D$. Dynamic heterogeneity is also observed at $T_D$. Elastic properties are calculated from stress and strain relations obtained from the spontaneous fluctuation of internal stress tensor and simulation cell parameters. Each investigated state shows distinctive dynamics while maintaining solid-like elastic properties. The elastic properties stay intact even above $T_D$. It has been shown that the rigidity and mobility of glassy metastable states are compatible under dynamic heterogeneity. Full article

Global increasing demand in the need of energy leads to the development of non-conventional, high power energy sources. Supercapacitors (SCs) are one of the typical non-conventional energy storage devices which are based on the principle of electrochemical energy conversion. SCs are promising energy storage devices for better future energy technology. Increasing progress has been made in the development of applied and fundamental aspects of SCs. Manganese oxide electrode materials have been well studied; however, their capacitive performance is still inadequate for practical applications. Recent research is mainly focused on enhancing manganese oxide capacitive performance through the incorporation of electrically conductive materials and by controlling its morphology to reveal a more active surface area for redox reactions. In this review, progress in the applications of manganese oxide carbon-based materials towards the development of highly effective SCs is briefly discussed. In this regard, manganese oxide carbon-based nanocomposites synthesis methods and techniques used to approximate the capacitance of electrode materials are discussed. Full article

Metalloporphyrins (MP) and metallophtalocyanines (MPc) are innovative materials with catalytic properties that have attracted attention for their application for diverse electrochemical purposes. The presence of metallic centers in their structure offers a redox-active behavior that is being applied in the design of solid electrodes for the quantification of biomolecules, water contaminants, and pharmaceuticals, among others. Herein, we collect the recent information about porphyrin and phthalocyanine complexes as modifiers of electrodes, and the important aspects of the design, characterization, and application of these electrodes. Full article

Calcium carbonate (CaCO₃) from the seaweed Lithothamnium calcareum is a suitable dietary supplement for the prevention of osteoporosis, due to its chemical composition. This study compared CaCO₃ from L. calcareum to CaCO₃ from oyster shell and inorganic minerals that are already used in the pharmaceutical industry. The Rietveld refinement of the XRD showed that the mineral fraction of L. calcareum is composed of aragonite (50.3 wt%), magnesian calcite (45.3 wt%), calcite (4.4 wt%), comin contrast to oyster shell and inorganic minerals, which contain only calcite. The morphology of L. calcareum carbonate particles is granular xenomorphic, which is distinct from the scalenohedral form of inorganic calcite and the fibrous and scale-like fragments of oyster shell. The crystal structures of aragonite and magnesian calcite, present in L. calcareum, have higher contents of oligoelements than the pure calcite in other materials. The isotopic composition (stable isotopes of carbon and oxygen) is heavy in the CaCO₃ from L. calcareum (δ¹³C = 1.1‰; δ¹⁸O = −0.1‰) and oyster shell (δ¹³C = −4‰; δ¹⁸O = −2.8‰) in marked contrast to the much lighter isotopic composition of inorganic mineral CaCO₃ (δ¹³C = −19.2‰; δ¹⁸O = −26.3‰). The differences indicated above were determined through principal component analysis, where the first and second principal components are sufficient for the clear distinction and traceability of CaCO₃ sources. Full article

Ammonia produced using renewable hydrogen is being viewed as a promising media for the export of energy from locations rich in renewable energy sources. Solid oxide fuel cells (SOFCs) are efficient devices for converting such exported ammonia back into electricity at the point of use; however, investigations on materials and operating regimes for direct ammonia fuelled SOFCs are limited. In this work, we evaluated the direct ammonia SOFC performance with a Silver-Lanthanum Strontium Cobalt Ferrite (Ag-LSCF) composite anode and a novel Palladium (Pd) nanoparticle decorated Silver-Lanthanum Strontium Cobalt Ferrite (Pd-Ag-LSCF) composite anode in the temperature range of 500 °C to 800 °C. It is hypothesised that palladium nanoparticles in the anode provide hydrogen dissolution and shift the ammonia decomposition reaction towards the right. The cell performance was evaluated with both hydrogen and ammonia as fuels and a clear-cut improvement in the performance was observed with the addition of Pd for both the fuels. The results showed performance enhancements of 20% and 43% with hydrogen and ammonia fuels, respectively, from the addition of Pd to the Ag-LSCF anode. Open-circuit voltage (OCV) values of the cells with hydrogen and ammonia fuels recorded over the temperature range of 500 °C to 800 °C indicated the possibility of direct electro-oxidation of ammonia in SOFCs. Full article

A systematic study of the thermal decomposition of hybrid perovskites of formula [AH][M(HCOO)₃] under inert atmosphere was performed by means of thermogravimetry and simultaneous infrared spectroscopy of the evolved gases. The influence of: (i) the metal ion of the [M(HCOO)₃]^- framework and (ii) the guest [AH]⁺ cation, in the composition of the final residue was evaluated. In this work, it has been demonstrated that these materials can be used as precursors of metal or metal-oxide compounds—obtained free of carbon—, and that the composition of the final residue is determined by the standard reduction potential of the metal cation of the framework. Full article

The use of optical absorbance kinetics to identify micro-porous regions in doped polymer films is evaluated. Data are presented for a series of hydrazone doped polymer films which are found to optically bleach upon exposure to an ultra violet (UV) radiation source. The UV absorbance kinetics are found to exhibit distinctive characteristics for the various polymers studied, with changes in film absorbance occurring either in a fast (<10³ s) or slow (>10⁴ s) timescale. An interpretation of these distinctive timescales based upon a cellular-automata model of the absorbance kinetics suggests that the underlying photo-oxidation of the hydrazone is highly sensitive to underlying micro-porosity in the films which controls the necessary supply of absorbed oxygen for photo-cyclic reaction. Full article

There are varieties of methods available for the exploration of solids using nuclear magnetic resonance (NMR) spectroscopy. Some of these methods are quite sophisticated, others require specialized equipment. This review is addressed to those for whom NMR is not the main research method. It discusses simple methods that can be applied to solids with little or no adaptation to a specific system. Despite their technical simplicity and ease of use, these methods are powerful analytical tools that provide unique insights into the structure, dynamics, and noncovalent interactions in homo- and heterogeneous systems. Particular attention is paid to the characterization of porous materials and solids containing phosphorus. ³¹P NMR of organometallic compounds has been used as an example of how theoretical calculations can help in deeper analysis of experimental data. Full article

We applied photoreflectance (PR) spectroscopy for contactless determination of the electric field strength at buried interfaces in metal–insulator–semiconductor (MIS) structures. The PR is an all-optical version of an electromodulated reflectance spectroscopy. The tradeoff of this adoption is that this requires an additional feedback system to eliminate background problems induced by scattered pump light and/or photoluminescence. A microcomputer-based feedback system has been developed for this elimination. Despite the very tiny signal intensity, we successfully attained a sufficiently good signal–noise ratio to determine the electric field strength in oxide-based MIS interfaces that exhibits a large, unwanted photoluminescence signal. The field strength was evaluated to be ca. 0.25 kV/cm. Full article

Low-temperature heat capacities (C_p) of nanostructured rock salt (rs-ZnO) and wurtzite (w-ZnO) polymorphs of zinc oxide were measured in the 2–315 K temperature range. No significant influence of nanostructuring on C_p of w-ZnO has been observed. The measured C_p of rock salt ZnO is lower than that of wurtzite ZnO below 100 K and is higher above this temperature. Using available thermodynamic data, we established that the equilibrium pressure between nanocrystalline w-ZnO and rs-ZnO is close to 4.6 GPa at 300 K (half as much as the onset pressure of direct phase transformation) and slightly changes with temperature up to 1000 K. Full article

Dynamic mechanical analysis (DMA) provides reliable information about the viscoelastic behavior of neat and filled polymers. The properties of filled polymers are relevant to different industries as protective organic coatings, composites etc. Interfacial interactions in filled polymers play an important role in determining their bulk properties and performance during service life. In this brief review article, studies that used DMA to characterize the interfacial interactions in filled polymers have been reviewed. The available open literature provides a mixed opinion about the influence of interfacial interactions on the glass transition temperature of filled polymers. Nevertheless, it appears that in the case of strong interfacial interactions between the filler particles and the polymeric matrix, the peak value of tan δ is reduced in comparison to that of a filled polymer where these interactions are weak. Full article

Over the past several decades, research on anomalous thermal expansion materials has been rapidly growing, and increasing numbers of compounds exhibiting negative thermal expansion (NTE) have been reported. In particular, compounds with formula A₂M₃O₁₂ have attracted considerable attention. A₂M₃O₁₂ family materials offer a wide range of possible compositions due to the chemical flexibility of the A and M sites. According to published research, more than half of them possess NTE properties. This paper reviews the range of physical properties displayed by materials in the A₂M₃O₁₂ family. Research on improving material imperfections and controlling the coefficient of thermal expansion in the A₂M₃O₁₂ family are systematically summarized. Finally, challenges and questions about the developments of these A₂M₃O₁₂ NTE compounds in future studies are also discussed. Full article

Double doped layered double hydroxide thin films were developed directly on the aluminum substrate in two steps: Initially cerium-based MgAl-layered double hydroxide (LDH) were synthesized directly on the anodic aluminum surface via the in situ growth method, and were then modified with the stearate anions through an ion-exchange mechanism to achieve compact multifunctional protective thin films. The structural and morphological characteristics of the developed LDH films were investigated, and the surface contact angle measurements (CA) and self-cleaning properties were analyzed. The obtained double doped LDH film displayed the superhydrophobic characteristic with a water contact angle of ~155°. Furthermore, the superhydrophobic behavior of LDH on exposure to UV radiation (λ = 310 nm) was examined to evaluate outdoor applications. Long-term Electrochemical Impedance Spectroscopy (EIS) analysis was performed to understand the corrosion resistance properties. The introduction of double doped LDHs demonstrates significantly higher corrosion resistance properties than only cerium-modified LDHs and has shown superior stability against 0.1 M NaCl solution. Full article

Because of the rapid development of nanotechnologies, materials, in particular, solid dispersions (SDs), which are actively introduced into the life of modern man, have been obtained. Special progress in this area is observed in industry and medicine. The use of SDs in agriculture is lagging far behind, despite the growing number of scientific papers on this topic. At the same time, the prospects for the introduction of SDs in the agro-industrial complex are obvious. The review presents the results of research on the development of innovative preparations based on SD to protect plants from diseases and pests of cultivated plants, as well as parasiticides to protect animal health based on modern achievements of nanotechnology. One of these technologies is the methods of mechanochemistry, which improve the properties of poorly soluble biologically active substances by their joint mechanical treatment with water-soluble polymers and auxiliary substances. Full article

This paper is dedicated to the extended solid (continuum) model of tensegrity structures or lattices. Tensegrity is defined as a pin-joined truss structure with an infinitesimal mechanism stabilized by a set of self-equilibrated normal forces. The proposed model is inspired by the continuum model that matches the first gradient theory of elasticity. The extension leads to the second- or higher-order gradient formulation. General description is supplemented with examples in 2D and 3D spaces. A detailed form of material coefficients related to the first and second deformation gradients is presented. Substitute mechanical properties of the lattice are dependent on the cable-to-strut stiffness ratio and self-stress. Scale effect as well as coupling of the first and second gradient terms are identified. The extended solid model can be used for the evaluation of unusual mechanical properties of tensegrity lattices. Full article

Framework silicates form about 70% of the Earth’s crust, mainly feldspars ~50–60% and quartz ~10–15%. Less-abundant feldspathoids include nepheline-, leucite-, and sodalite-group minerals, rich in structurally challenging properties. This review paper deals with anhydrous feldspar-, nepheline-, and leucite/pollucite groups, emphasising the importance of parallel studies on natural and synthetic samples. Four topics are covered. For decades, petrologists have analysed nephelines and recalculated their compositions as endmember molecules but, by not following rules of stuffed-tridymite crystal chemistry, have not estimated reliably the excess SiO₂ present in solid solution. Some materials scientists make similar mistakes, and a new approach is described here. Synthesis studies of analogue feldspars, nephelines, and leucite/pollucites led to collaborative studies, mainly using laboratory and synchrotron X-ray powder diffraction methods at room and elevated temperatures, to study thermal expansion and displacive phase transitions. Such work was recently expanded to address the spontaneous strain relations. Topics covered here include work on nepheline/kalsilite analogues in the system SrAl₂O₄—BaAl₂O₄; thermal expansion of (K,Na)Al-, RbAl-, RbGa-, and SrAl-feldspars; and thermal expansion and phase transitions in analogue leucites KGaSi₂O₆ (tetragonal to cubic) and K₂MgSi₅O₁₂ (monoclinic to orthorhombic). Results are reviewed in the context of research published in mineralogical and more-widely in physical sciences journals. Full article

The synthesis of YBa₂Cu₃O_7−x (YBCO or 123) was carried out via the use of a variety of deep eutectic solvents (DESs), all formed by the interaction of choline hydroxide (as the cation source) and alkyl carboxylic acids with C_nH_2n+1 ranging from n = 2 to n = 10, namely acetic acid, propionic acid, butyric acid, pentanoic acid, nonanoic acid, and decanoic acid, as providers of the anion, all prepared in equimolar solutions. The behaviour of the synthetic media and the resulting morphology displayed by the crystallite product, using different molar ratios of DESs (X):1 YBaCu metal nitrates mixes, with x values of 20 ≤ x ≤ 60, is also reported. Synthetic performance results show a tendency to generate higher total phase percentage of the desired crystal with the increase of the alkyl chain length of the carboxylic acid up to butyric acid (92% belonging to the metal oxide), after which no enhancement was observed. Furthermore, the synthetic performance of the remaining, i.e., DES formed with pentanoic acid to decanoic acid, displayed a constant decay in total desired phase percentage belonging to the metal oxide. Morphological results were also analysed for all DESs (X):1 YBaCu metal nitrates mixes, with x values of 20 ≤ x ≤ 60. Well defined plate-like particles were generally observed however, in some cases fused plate-like particles of significantly bigger size were observed. Full article

When oxide glasses are modified by dissimilar alkali ions, a maximum in the electric resistivity or the expansion coefficient appears, called the mixed-alkali effect (MAE). This paper reviews the MAE on the thermal, elastic, and vibrational properties of the mixed-cesium lithium borate glasses, x{(1−y)Cs₂O-yLi₂O}-(1−x)B₂O₃. For the single-alkali borate glasses, xM₂O(1−x)-B₂O₃ (M = Li, Na, K, Rb, and Cs), the glass transition temperature, T_g = 270 °C, of a borate glass monotonically increases as the alkali content x increases. However, for the mixed-cesium lithium borate glasses the T_g shows the minimum against the lithium fraction y. The dependences of the elastic properties on the lithium fraction y were discussed regarding the longitudinal modulus, Poisson’s ratio, and Cauchy-type relation. The internal vibrational bands related to the boron-oxide structural groups and the splitting of a boson peak were discussed based on Raman scattering spectroscopy. The MAE on various physical properties are discussed on the basis of the changes in the coordination number of the borons and the nonbridging oxygens caused by the dissimilar alkali ions. Full article