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In the current work, a simple mechanochemical route has been employed to preparatively access three spinel‐type compositionally complex ceramics, i. e., (Co, Fe, Mn)3O4, (Co, Fe, Mn, Ni)3O4, and (Co, Cr, Fe, Mn, Ni)3O4. Hydrated nitrate salts of the respective transition metal elements were mechanically ground with ammonium hydrogen carbonate. The resulting paste‐like mixture of metal hydroxides, oxyhydroxides, and carbonates was rinsed with water to remove the byproduct (NH4NO3) and converted into the respective single‐phase spinel‐type oxides via calcination. In situ X‐ray diffraction (XRD) revealed the formation of the spinel‐type structure (Fd3‾ ${\bar{3}}$ m) already at temperatures as low as 150 °C. Typically, the calcination of the precursors at temperatures beyond 500 °C led to the formation of well‐crystallized, single‐phase spinel‐type oxides with nearly equimolar composition and highly homogeneous distribution of the transition metals within the structure. The mechanochemical synthesis route in the present study is considered to be an easy, straightforward, and scalable access to compositionally complex oxides. [ABSTRACT FROM AUTHOR]

In the present work, the solvent‐deficient synthesis of the high‐entropy rare‐earth carbonate hydroxide RE(CO3)(OH) (RE=La, Ce, Pr, Nd, Sm, and Gd) and its thermal conversion into bixbyite‐type sesquioxide RE2O3 are reported for the first time. The high‐entropy rare earth carbonate hydroxide was prepared via mechanochemical reaction of the corresponding metal nitrate hydrates with ammonium hydrogen carbonate followed by the removal of the NH4NO3 by‐product. Calcination of the carbonate hydroxide precursor in ambient atmosphere at temperatures in the range from 500 to 1000 °C led to the high‐entropy rare earth sesquioxide which exhibited a bixbyite‐type structure (Ia3‾ ${Ia\bar{3}}$) independent of the calcination temperature. Transmission electron microscopy (TEM) investigation revealed the homogeneous distribution of all six rare earth cations in the high‐entropy sesquioxide lattice, however, with some compositional variation between individual grains. The bixbyite‐type structure may be considered as the result of heavy doping of the fluorite‐type CeO2 lattice with the other rare earth cations, which leads to a high concentration of oxygen vacancies, as revealed by electron diffraction and Raman spectroscopy data. The solvent‐deficient synthesis method used in the present study is considered as a valuable, straightforward and easily up‐scalable method to synthesize compositionally complex oxide ceramics. [ABSTRACT FROM AUTHOR]

Lithium is in high demand: this is driven by current trends in e-mobility and results in increased global production and record prices for lithium ores and compounds. Pegmatite ores, in addition to brines, remain of particular interest because of their higher lithium content and lower geopolitical risks. In this work, we investigated lithium extraction via the mechanochemical treatment of the three most common lithium minerals: lepidolite, spodumene, and petalite. Indeed, we determine that the petalite crystal structure was much more suitable due to its less dense packing and the formation of cleavage planes along lithium sites, resulting in substantial lithium extraction of 84.9% and almost complete conversion to hydrosodalite after 120 min of ball milling in alkaline media. Further processing of the leach liquor includes desilication, the precipitation of lithium phosphate, and the conversion and crystallization of pure LiOH·H2O. Special attention was paid to a holistic approach entailing the generation of by-products, each of which has a specific intended application. The leaching residues were investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy, N2 adsorption/desorption, and scanning electron microscopy. Moreover, hydrosodalite was found to have a high potential as an adsorbent for heavy metal ions which were studied separately using aqueous solutions containing Cu2+, Ni2+, Pb2+, and Zn2+. [ABSTRACT FROM AUTHOR]

Manganese monoboride has a low- (α) and a high-temperature (β) modification, as well as a defect-rich low-temperature variant (α′). The crystal structure (FeB-type structure, s.g. Pnma) and properties of high-temperature MnB are well-known. In this work, single crystals were grown via chemical vapor transport reactions, both of β-MnB and the low-temperature modification, α-MnB. This allowed for determining the crystal structure of defect-free α-MnB [CrB-type structure, s.g. Cmcm, a = 3.0098(6) Å, b = 7.6390(2) Å, and c = 2.94620(6) Å]. Furthermore, α′-MnB, the stacking fault-dominated CrB-variant, was obtained as crystalline powder and characterized by X-ray powder diffraction and transmission electron microscopy. Direction-resolved measurements of the magnetic properties of α-MnB revealed spin-canted magnetic behavior along c and ferromagnetism along a and b with a Curie temperature of 456 K; ferromagnetic β-MnB has a Curie temperature of 568 K. [ABSTRACT FROM AUTHOR]

Reversible field-induced phase transitions define antiferroelectric perovskite oxides and lay the foundation for high-energy storage density materials, required for future green technologies. However, promising new antiferroelectrics are hampered by transition´s irreversibility and low electrical resistivity. Here, we demonstrate an approach to overcome these problems by adjusting the local structure and defect chemistry, delivering NaNbO3-based antiferroelectrics with well-defined double polarization loops. The attending reversible phase transition and structural changes at different length scales are probed by in situ high-energy X-ray diffraction, total scattering, transmission electron microcopy, and nuclear magnetic resonance spectroscopy. We show that the energy-storage density of the antiferroelectric compositions can be increased by an order of magnitude, while increasing the chemical disorder transforms the material to a relaxor state with a high energy efficiency of 90%. The results provide guidelines for efficient design of (anti-)ferroelectrics and open the way for the development of new material systems for a sustainable future. Antiferroelectrics are important in emerging energy-storage technologies. Here, the authors present an approach to adjust their local structure and defect chemistry, in order to overcome the current limitations and make them suitable for environmentally-friendly dielectric energy storage. [ABSTRACT FROM AUTHOR]

Dislocations are usually expected to degrade electrical, thermal and optical functionality and to tune mechanical properties of materials. Here, we demonstrate a general framework for the control of dislocation–domain wall interactions in ferroics, employing an imprinted dislocation network. Anisotropic dielectric and electromechanical properties are engineered in barium titanate crystals via well-controlled line-plane relationships, culminating in extraordinary and stable large-signal dielectric permittivity (≈23100) and piezoelectric coefficient (≈2470 pm V–1). In contrast, a related increase in properties utilizing point-plane relation prompts a dramatic cyclic degradation. Observed dielectric and piezoelectric properties are rationalized using transmission electron microscopy and time- and cycle-dependent nuclear magnetic resonance paired with X-ray diffraction. Succinct mechanistic understanding is provided by phase-field simulations and driving force calculations of the described dislocation–domain wall interactions. Our 1D-2D defect approach offers a fertile ground for tailoring functionality in a wide range of functional material systems. Dislocations are often perceived as a culprit for degradation in functionality. Here, the authors introduce a general framework for engineering dislocations and domain walls and demonstrate its full potential on a ferroelectric BaTiO3 single crystal. [ABSTRACT FROM AUTHOR]

The different structural features of labradorite and its incommensurate atomic structure have long been in the eye of science. In this transmission electron microscopy (TEM) study, all of the structural properties of labradorite could be investigated on a single crystal with an anorthite–albite–orthoclase composition of An 53.4 Ab 41.5 Or 5.1. The various properties of labradorite could thus be visualized and connected to form a hierarchical structure. Both albite and pericline twins occur in the labradorite. The size of alternating Ca-rich and Ca-poor lamellae could be measured and linked to the composition and the color of labradorescence. Furthermore, a modulation vector of 0.0580(15) a* + 0.0453(33) b* - 0.1888(28) c* with a period of 3.23 nm was determined. The results indicate an eα labradorite structure, which was achieved by forming Ca-rich and Ca-poor lamellae. The average structure and subsequently the incommensurate crystal structure were solved with a three-dimensional electron diffraction (3DED) data set acquired with automated diffraction tomography (ADT) from a single lamella. The results are in good agreement with the structure solved by X-ray diffraction and demonstrate that 3DED–ADT is suitable for solving even incommensurate structures. [ABSTRACT FROM AUTHOR]

A ZrB2‐based ceramic, containing short Hi‐Nicalon SiC fibers, was fabricated with a Mo‐impermeable buffer layer sandwiched between bulk and the outermost oxidation resistant ZrB2–MoSi2 layer, in order to prevent inward Mo diffusion and associated fiber degradation reactions. This additional layer consisted of ZrB2 doped with either Si3N4 or with the polymer‐derived ceramics (PDCs) SiCN and SiHfBCN. Scanning electron microscopy imaging and elemental mapping via energy‐dispersive X‐ray spectroscopy showed that this tailored sample geometry provides an effective diffusion barrier to prevent the SiC fibers from deterioration due to reactions with Mo or Mo‐compounds. In contrast, the structure of the SiC fibers in a reference sample without buffer layer is strongly degraded by MoSi2 diffusion into the fiber core. The comparison of the three buffer‐layer systems showed a moderate alteration of the fiber structure in the case of Si3N4 addition, whereas in the PDC‐doped samples hardly any structural change within the fibers was observed. A stepwise reaction mechanism is deduced, based on the continuous progression of a reaction zone that propagates toward the ZrB2–MoSi2 top layer. The progression of such a reaction zone as a consequence of the different eutectic melts forming in the different layers, that is, first in the SiC‐fiber‐containing bulk, then in the buffer layer itself, and finally in the top layer at high temperature, allows for an effective separation of the ZrB2–MoSi2 top layer from the SiC fibers. Subsequent oxidation at 1500°C and 1650°C for 15 min did not affect the efficiency of all three buffer layers, since no structural changes regarding buffer layer and fibers were observed, as compared to the non‐oxidized samples. [ABSTRACT FROM AUTHOR]

Quenching relaxor ferroelectric 0.94(Na1/2Bi1/2)TiO3–0.06BaTiO3 (NBT‐6BT) enhances the depolarization temperature (Td), linked to the stabilization of ferroelectric order. The thermal evolution of the domain structure and phase assemblage provides insights about the onset of ferroelectric order in quenched materials. Unpoled furnace cooled and quenched NBT‐6BT ceramics were studied using in situ temperature‐dependent transmission electron microscopy. The rhombohedral to tetragonal structural transition in furnace cooled and quenched samples occurs in a comparable temperature range of 120°C–220°C. While the tetragonal phase is characterized by polar nanoregions (PNRs) and no domain contrast in the furnace cooled state, the quenched composition exhibits an increased fraction of lamellar domains, which are partially stable up to 300°C, thus benefiting the delayed depolarization. This is further corroborated by the dielectric data indicating earlier freezing of PNR dynamics in the quenched state. The reversibility of the phase transition is demonstrated by successive cooling, where quenched NBT‐6BT features an increased grainy PNR contrast after the experiment, followed by a kinetically delayed coalescence of PNRs back into lamellar domains. This demonstrates that the stabilized ferroelectric state upon quenching is associated with the conversion of polar units on the nanometer scale into long‐range domain structures. [ABSTRACT FROM AUTHOR]

Cellulose‐based paper samples were surface‐modified by a polymeric single‐source precursor prepared from perhydropolysilazane (PHPS) and iron(III)acetylacetonate (Fe(acac)3) and ammonolyzed at 500°C, 700°C, 900°C, and 1000°C, leading to C/SiFe(N,C)O‐based ceramic papers with in situ‐generated hierarchical micro/nano‐morphology. As reference, cellulose‐free samples were prepared under the same conditions. Upon thermal treatment, the microstructure evolutions of the resulting ceramic paper and the reference sample were comparatively investigated. Scanning electron microscopy (SEM) showed that for all temperatures, the ceramic papers exhibit the same morphology as the template, however, with noticeable shrinkage and curling, particularly evident at higher temperatures. X‐ray diffraction (XRD) measurements of the reference samples and the ceramic papers showed a similar crystallization behavior and phase evolution in both materials. In the ceramic paper, the crystallization process seems to occur at a later time. The results provide a comprehensive understanding of the investigated C/SiFe(N,C)O‐based ceramic system. It was shown that use of the cellulose‐based paper template has the benefit of retaining the microstructure and furthermore, apart from transforming the cellulose fibers into turbostratic carbon, does not change the phase evolution during the polymer‐to‐ceramic transformation, allowing at the same time the manufacturing of novel morphologically complex parts by a convenient one‐pot synthesis approach. [ABSTRACT FROM AUTHOR]

SiFeO(N,C)‐based ceramic papers were prepared via a one‐pot synthesis approach by dip‐coating a cellulose‐based paper template with a polymeric perhydropolysilazane precursor modified with iron(III)acetylacetonate. The preceramic composites were subsequently pyrolyzed in ammonia atmosphere at 500, 700, and 1000°C, respectively, and the characteristics of the three resulting ceramic papers were comparatively investigated. Scanning electron microscopy revealed that in each sample, the morphology of the template is successfully transferred on the ceramic system, with the cellulose‐derived fibers being converted to elemental carbon encased by a SiFeO(N,C) coating. Electron transparent cross‐sectional samples for transmission electron microscopy (TEM) were prepared from the ceramic papers, employing a standard ultramicrotomy slice cutting procedure, allowing for a detailed characterization of their in situ generated micro‐/nanostructure as well as occurring crystalline phases. TEM imaging and diffraction revealed that depending on pyrolysis temperature a different microstructure with a distinct phase assemblage is generated in the polymer‐derived ceramic papers. Crystallization from the polymer precursor starts with the precipitation of wüstite (Fe(1‐x)O) nanoparticles at 700°C inside the ceramic coating and secondary ε‐FexN at the fiber‐coating interface. Upon pyrolysis at 1000°C however, the sample primarily accommodates metallic α‐iron nanocrystals that impart ferromagnetic characteristics to the ceramic paper. The results show that the template‐assisted polymer‐derived ceramic route is a feasible approach in the production of complex ceramic compounds with fibrous paper‐like morphology. By adjusting the pyrolysis temperature, microstructure and phase composition of the ceramic paper can be conveniently tailored to the needs of its respective application. [ABSTRACT FROM AUTHOR]

In the present work, dense ZrB2‐based monoliths were produced via hot‐pressing of ZrB2 powders coated with amorphous polymer‐derived SiCN, SiZrCN, or SiZrBCN at relatively moderate temperatures (i.e., 1800℃). Thus, ZrB2 particles were embedded in polymer‐derived ceramic shell were realized by coating their surface with the corresponding polymeric precursors (polysilazane, Zr‐modified polysilazane, Zr‐ and B‐modified polysilazane, as for SiCN, SiZrCN, and SiZrBCN; respectively), followed by cross‐linking at 200℃ and pyrolysis at 1100℃ in Ar atmosphere. The obtained monolithic samples were carefully characterized concerning their phase composition and microstructure. Typically, the densified samples exhibit a homogeneous microstructure consisting of ZrB2 grains and a multi‐phasic polymer‐derived ceramic grain boundary phase (β‐SiC, t‐BCN, ZrO2, and ZrC). The prepared monoliths exhibited fair hardness values, that is, 12.5, 14.2, and 13.3 GPa for ZrB2/SiCN, ZrB2/SiZrCN, and ZrB2/SiZrBCN. [ABSTRACT FROM AUTHOR]

Naturally occurring single crystals of bixbyite, (Fe,Mn)2O3, from the Thomas Mountain Range in Utah, U.S.A., were studied via (scanning) transmission electron microscopy (S)TEM. With up to 5 cm edge length, these mineral specimens are the largest bixbyite crystals found worldwide. Their hexahedral shapes are often modified by {211} facets at the corners and small {211} truncations along their cube edges. Characteristic lamellar defects, running parallel to the {100} planes, can be observed via TEM imaging. The defects are, according to EDS analyses, attributed to the tetragonal manganese silicate braunite, Mn7[SiO12]. In the present study, electron nano-diffraction and atomic resolution (S)TEM were employed to verify the presence of braunite lamellae and to investigate their orientation relationship with bixbyite. The analysis confirmed an epitaxial intergrowth of both phases, with their main-axes being parallel and the unique c-axis of braunite always aligned perpendicularly to the lamellar plane. Moreover, small rectangular-shaped precipitates, which had been, due to their almost identical chemical composition, previously interpreted as small bixbyite inclusions within the host crystal, were often observed in contact with the braunite lamellae. Electron nano-diffraction and atomic resolution (S)TEM imaging revealed these crystallites not to be bixbyite but jacobsite, a cubic iron-manganese spinel with the stoichiometric formula MnFe2O4, whose occurrence in this unique context had not been reported before. Moreover, due to the higher temperatures needed for spinel crystallization, the occurrence of jacobsite may serve as a geo-thermometer. (S)TEM in conjunction with automated crystal orientation mapping (ACOM)-TEM showed that no orientation relationship exists between the jacobsite inclusions and the bixbyite/braunite matrix. Nevertheless, their characteristic rectangular shape is typically aligned concordantly with the (001) plane of the braunite lamellae. The resulting crystal shape of jacobsite is determined by the presence of the braunite lamellae, while the respective crystallites maintain their freedom of rotation. To the authors' knowledge, this is a novel observation of exomorphosis of jacobsite, i.e., the change in the habit of the spinel crystallites due to external conditions. Note that the term "exomorphosis" is used here in the mineralogical sense in contrast to the often-used petrological aspect. Based on the TEM results, the formation of the jacobsite precipitates is discussed and a growth model suggested. [ABSTRACT FROM AUTHOR]

Reversible antiferroelectric‐ferroelectric phase transitions were recently observed in a series of SrSnO3‐modified NaNbO3 lead‐free antiferroelectric materials, exhibiting well‐defined double polarization hysteresis loops at ambient conditions. Here, transmission electron microscopy was employed to investigate the crystallography and domain configuration of this newly designed system via electron diffraction and centered dark‐field imaging. It was confirmed that antiferroelectricity is maintained in all compositions, manifested by the characteristic ¼ superlattice reflections in the electron‐diffraction patterns. By investigating the antiferroelectric domains and domain boundaries in NaNbO3, we demonstrate that antiphase boundaries are present and their irregular periodicity is responsible for the streaking features along the ¼ superlattice reflections in the electron‐diffraction patterns. The signature domain blocks observed in pure NaNbO3 are maintained in the SrSnO3‐modified ceramics, but disappear when the amount of SrSnO3 reaches 7 mol.%. In particular, a well‐defined and distinct domain configuration is observed in the NaNbO3 sample modified with 5 mol.% SrSnO3, which presents a parallelogram domain morphology. [ABSTRACT FROM AUTHOR]

In this paper, we report on electron microscopy studies of single crystals of the natural mineral lorándite, TlAsS2. The main focus of this investigation was to address the question as to whether those lorándite crystals are chemically and structurally homogeneous, in order to be utilized as an effective neutrino detector within the lorándite experiment (LOREX) project. Apart from few secondary minerals, being present only at the surface of the lorándite samples, scanning electron microscopy (SEM) indicated homogeneous crystals. Similarly, transmission electron microscopy (TEM) imaging revealed a homogenous and undisturbed crystal structure, with the only exception of local coffee-bean contrasts; however, rarely observed. These specific contrast variations are known to be a typical strain indicator caused by a local deformation of the crystal lattice. Energy-dispersive X-ray spectroscopy (EDS) in conjunction with electron energy-loss spectroscopy (EELS) did not show any significant chemical difference when analysing regions on or off those coffee-bean features, indicating a chemically homogenous mineral. Since the presence of lattice disturbing secondary phase precipitates could be excluded by imaging and complementary chemical analysis, crystal defects such as dislocations and stacking faults or minor fluid inclusions are discussed as the probable origin of this local elastic strain. The experimental results confirm that the studied lorándite single crystals fulfil all structural and chemical requirements to be employed as the natural mineral that allows to determine solar neutrino fluxes. In addition, critical issues regarding the rather challenging sample preparation of lorándite are reported and a quantification of the maximum tolerable electron dose in the TEM is presented, since lorándite was found to be sensitive with respect to electron beam irradiation. Furthermore, the limits of EDS measurements due to peak overlapping are shown and discussed utilizing the case of Pb in lorándite. In this regard, a comparison with the Tl- and Pb-containing natural mineral hutchinsonite, TlPbAs5S9, is also included. [ABSTRACT FROM AUTHOR]

Quenching has been established as a viable method to increase the depolarization temperature in (100-x) Na1/2Bi1/2TiO3–xBaTiO3 (NBT–xBT). The proposed hypothesis of a stabilized ferroelectric order would entail changes in the polarized volume. To this end, air-quenched and furnace cooled samples of four compositions of NBT–xBT with x = 3, 6, 9, and 12 mol. % BT were studied. Upon quenching, all the compositions demonstrate an increase in the ferroelectric to relaxor transition temperature, TF-R, by 23–44 °C and enhanced lattice distortion. Resonance frequency damping analysis was utilized to measure Young's modulus in the temperature range of 25 °C to 800 °C and to estimate the volume fraction of polar nanoregions using a composite model. Quenching leads to an 8% decrease in Young's modulus, but to an increase in the volume fraction of polar nanoregions by 12% at 300 °C for NBT-6BT. Transmission electron microscopy investigations of quenched NBT-6BT reveal a combination of lamellar domains and more homogenous areas with nanometer-sized domains. The existence of lamellar domains in quenched morphotropic phase boundary compositions together with enhanced lattice distortion and a decrease in dielectric frequency dispersion substantiate the premise of a stabilized ferroelectric order. [ABSTRACT FROM AUTHOR]

A zirconium and a zirconium/boron containing single‐source precursor were synthesized via chemical modification of a commercially available polysilazane (Durazane 1800) with tetrakis (dimethylamido) zirconium (IV) (TDMAZ) as well as with both TDMAZ and borane dimethyl sulfide complex, respectively. The polymer‐to‐ceramic transformation of the precursors into SiZrCN and SiZrBCN ceramics as well as the thermal evolution of their phase composition and microstructure was studied. The pyrolysis of the precursors led to the formation of amorphous SiZrCN and SiZrBCN ceramics. Interestingly, the as prepared SiZrBCN ceramic was single‐phasic and fully featureless; whereas SiZrCN exhibited the presence of nano‐sized ZrO2 particles; however, only very localized in close proximity to internal surfaces. Heat treatment at higher temperatures induced crystallization processes in both prepared ceramics. Thus, at temperatures beyond 1500°C, cubic ZrCxNy, β‐Si3N4 as well as β‐SiC were generated. It was shown that the incorporation of B into SiZrCN suppressed the crystallization of ZrCxNy and, in addition, impeded the reaction of SiNx with C, resulting in an improved thermal stability of SiZrBCN compared to SiZrCN ceramic. Moreover boron was shown to be mainly located in the sp2‐hybridized "free" carbon present in SiZrBCN, forming a turbostratic BCN phase which has been unequivocally detected by means of high‐resolution transmission electron microscopy (HRTEM) and energy‐dispersive X‐ray spectroscopy (EDS). [ABSTRACT FROM AUTHOR]

Cobalt‐doped zinc oxide single crystals with the shape of hexagonal platelets were synthesized by thermohydrolysis of zinc acetate, cobalt acetate, and hexamethylenetetramine (HMTA) in mixtures of ethanol and water. The mineralization proceeds by a low‐temperature dissolution–reprecipitation process from the liquid phase by the formation of basic cobalt zinc salts as intermediates. The crystal shape as well as twin formation of the resulting oxide phase can be influenced by careful choice of the solvent mixture and the amount of doping. An understanding of the course of the reaction was achieved by comprehensive employment of analytical techniques (i.e., SEM, XRD, IR) including an in‐depth HRTEM study of precipitates from various reaction stages. In addition, EPR as well as UV/Vis spectroscopic measurements provide information about the insertion of the cobalt dopant into the zincite lattice. The Langmuir–Blodgett (LB) technique is shown to be suitable for depositing coatings of the platelets on glass substrates functionalized with polyelectrolyte multilayers and hence is applied for the formation of monolayers containing domains with ordered tessellation. No major differences are found between deposits on substrates with anionic or cationic surface modification. The adherence to the substrates is sufficient to determine the absolute orientation of the deposited polar single crystals by piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) studies. [ABSTRACT FROM AUTHOR]

Herein we report the synthesis of novel 0D-nanocarbon-based silicon-containing ceramic composites by a facile salt-free synthesis method followed by polymer-to-ceramic transformation. 0D-nanocarbon–silica composites were synthesized via a one-pot sol–gel process using tetramethyl orthosilicate (TMOS) and functionalized nanodiamonds and converted subsequently via pyrolysis under an argon atmosphere into nanodiamond/silica nanocomposites. The thermal conversion of the nanodiamond phase to a multilayer fullerene phase was carefully investigated by integral and local characterization methods such as vibrational spectroscopy, X-ray diffraction, BET, SEM and HRTEM. The incorporation of nanodiamonds in a silica matrix enhances the crystallization temperature of the silica phase, as α-cristobalite, to 1500 °C, while their full graphitization is shifted to T > 1700 °C under an argon atmosphere. The thermal decomposition of the nanodiamond/silica composites leads to the formation of materials with a high specific surface area (up to 562 m2 g−1) and a mesoporous structure. No carbothermal reaction of composing phases was identified. The results obtained in the present study allow for designing advanced and highly-defined mesoporous 0D-nanocarbon-containing composites with tailored structural features and multifunctional property profiles. [ABSTRACT FROM AUTHOR]

Functionalized ordered mesoporous materials are relevant in technologies, such as drug release, sensing, and separation. To design functionality, the silica framework can be functionalized with responsive molecules or polymers. Often, the pH value in those hybrid materials determines performance. Even though pH/pKa differences between polymers in bulk solutions and nanoscale confinement have been observed, the influence of confinement on pH‐ and pore filling dependent polyelectrolyte oligomer chain charge has yet not been investigated systematically. Here, mesoporous silica films are functionalized with (2‐dimethylamino)ethyl methacrylate) (DMAEMA) and 2‐(methacryloyloxy)ethyl phosphate (MEP) oligomers using photoiniferter initiated polymerization. This approach allows a controlled and environmentally friendly mesopore functionalization in water. The obtained oligomer functionalized pores are tunable with respect to pore filling. For both, poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2‐(methacryloxy)ethyl phosphate) (PMEP), the charge generation inside mesopore confinement is significantly delayed toward harsher pH conditions resulting in pKa shifts of 1–2 pH units. Polymer amount and ionic strength show to further influence the pKa of PDMAEMA in mesopores. The technological importance of the pH value in confinement and its effect on enzyme stabilization is demonstrated. Lipase from Aspergillus oryzae loses its activity upon encapsulation in silica nanoparticles at pH values where the enzyme is stable in bulk solution. [ABSTRACT FROM AUTHOR]

TEM and SEM investigations of ZnO bicrystal interfaces were undertaken with an aim to study the correlation of local grain‐boundary structure, segregation, and electrical transport perpendicular to the interface. To this end, varistor‐like ZnO bicrystals with piezotronic characteristics were chosen with (0001¯)║(0001¯) tail‐to‐tail orientation with respect to the c‐axis. In order to contrast different local grain‐boundary structures with different coherency and segregation of bismuth, but identical macroscopic polarization state, two complementary processing techniques were applied. A diffusion‐bonded bicrystal with an intermediate thin film containing Zn–Bi–Co–O provided a straight interface as reference. In contrast, a ZnO bicrystal prepared by epitaxial solid‐state transformation was manufactured by bonding two ZnO single crystals with a 100 µm thick polycrystalline ZnO varistor material with a typical dopant composition including bismuth and cobalt. This structure was annealed to the point that a bicrystal was formed with the varistor concentration at the boundary, which was strongly curved due to the polycrystalline microstructure still providing a shadow image at the interface. The results highlight a distinct correlation between local interfacial morphology, degree of segregation of bismuth, and degree of nonlinearity of the electrical transport across the interface. [ABSTRACT FROM AUTHOR]

Dislocations in oxides can be described as charged line defects and means for one‐dimensional doping, which can tune electrical and thermal properties. Furthermore, theoretically it was shown that dislocations can pin ferroelectric domain walls. Broader application of this concept hinges on the development of a methodology to avail this approach to polycrystalline ceramics. To this end, we use different creep mechanisms as a method to introduce multidimensional defects and quantify structural changes. A deformation map for fine‐grained barium titanate is provided and the influences of the defects and creep regimes are correlated in this first study to modifications of electrical conductivity, dielectric, ferroelectric, and piezoelectric properties. A plastic deformation of 1.29% resulted in an increase in the Curie temperature by 5°C and a decrease in electromechanical strain by 30%, pointing toward electromechanical hardening by dislocations. [ABSTRACT FROM AUTHOR]

Temperature-dependent dielectric permittivity of 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3 (BNT-6BT) lead-free piezoceramics was studied to disentangle the existing unclear issues over the crystallographic aspects and phase stability of the system. Application of existing phenomenological relaxor models enabled the relaxor contribution to the entire dielectric permittivity spectra to be deconvoluted. The deconvoluted data in comparison with the temperature-dependent dielectric permittivity of a classical perovskite relaxor, La-modified lead zirconate titanate, clearly suggest that BNT-6BT belongs to the same relaxor category, which was also confirmed by a comparative study on the temperature- dependent polarization hysteresis loops of both materials. Based on these results, we propose that the low-temperature dielectric anomaly does not involve any phase transition such as ferroelectric- to-antiferroelectric. Supported by transmission electron microscopy and X-ray diffraction experiments at ambient temperature, we propose that the commonly observed two dielectric anomalies are attributed to thermal evolution of ferroelectric polar nanoregions of R3c and P4bm symmetry, which coexist nearly throughout the entire temperature range and reversibly transform into each other with temperature. [ABSTRACT FROM AUTHOR]

The crystal structure of the lead-free piezoelectric ceramic (Bi1/2Na1/2TiO3)0.94–(BaTiO3)0.06 was investigated by first-principles calculations and high-resolution transmission electron microscopy (HRTEM) imaging. Structures with different A-site occupation were relaxed by total energy calculations within density functional theory and then used for simulating the corresponding HRTEM images. Simulated and experimental HRTEM images were compared and the closest match selected for structure interpretation. By combining these techniques, we have identified the Bi(Ba)/Na distribution on the A-site to be homogeneous. We exclude the possibility that regions visible in HRTEM images within one grain can be attributed to different ordering but to a slight tilting of the structure with respect to the electron beam. [ABSTRACT FROM AUTHOR]

Lead-free piezoelectric ceramics, (1-x-y)Bi0.5Na0.5TiO3–xBaTiO3–yK0.5Na0.5NbO3 (0.05≤x≤0.07 and 0.01≤y≤0.03), have been synthesized by a conventional solid state sintering method. The room temperature ferroelectric and piezoelectric properties of these ceramics were studied. Based on the measured properties, the ceramics were categorized into two groups: group I compositions having dominant ferroelectric order and group II compositions displaying mixed ferroelectric and antiferroelectric properties at room temperature. A composition from group II near the boundary between these two groups exhibited a strain as large as ∼0.45% at an electric field of 8 kV/mm. Polarization in this composition was not stable in that the piezoelectric coefficient d33 at zero electric field was only about 30 pm/V. The converse piezoelectric response becomes weaker when the composition deviated from the boundary between the groups toward either the ferroelectric or antiferroelectric compositions. These results were rationalized based on a field induced antiferroelectric-ferroelectric phase transition. [ABSTRACT FROM AUTHOR]

Ca‐ and/or B‐modified silicon oxycarbides were synthesized via pyrolysis of suitable polysilsesquioxane‐based single‐source precursors. Their polymer‐to‐ceramic transformation was investigated with thermogravimetric analysis, coupled with in situ evolved gas analysis. The prepared silicon oxycarbides were investigated with respect to their crystallization behavior, network architecture, and chemical compositions. The network connectivity in silicon oxycarbides can be affected/tuned upon using two different "tools": (a) first, the use of network modifiers, such as Ca in our study, leads to a slight depolymerization of the network via generation of a small amount of Q3 sites; (b) second, the modification of silicon oxycarbide with B/Ca leads to a decrease of the carbon content in the network and thus to a significant decrease of its connectivity. Using these two different effects, the network connectivity in silicon oxycarbides can be finely tuned. [ABSTRACT FROM AUTHOR]

Point defects largely determine the properties of functional oxides. So far, limited knowledge exists on the impact of cation vacancies on electroceramics, especially in (Na1/2Bi1/2)TiO3 (NBT)-based materials. Here, we report on the drastic effect of A-site non-stoichiometry on the cation diffusion and functional properties in the representative ferroelectric (Na1/2Bi1/2)TiO3–SrTiO3 (NBT–ST). Experiments on NBT/ST bilayers and NBT–ST with Bi non-stoichiometry reveal that Sr2+-diffusion is enhanced by up to six orders of magnitude along the grain boundaries in Bi-deficient material as compared to Bi-excess material with values of grain boundary diffusion ∼10−8 cm2 s−1 and ∼10−13 cm2 s−1 in the bulk. This also means a nine orders of magnitude higher diffusion coefficient compared to reports from other Sr-diffusion coefficients in ceramics. Bi-excess leads to the formation of a material with a core–shell microstructure. This results in 38% higher strain and one order of magnitude lower remanent polarization. In contrast, Bi-deficiency leads to a ceramic with a grain size six times larger than in the Bi-excess material and homogeneous distribution of compounds. Thus, the work sheds light on the rich opportunities that A-site stoichiometry offers to tailor NBT-based materials microstructure, transport properties, and electromechanical properties. [ABSTRACT FROM AUTHOR]

In this work we investigate the electrochemical behaviour of two silicon oxycarbide (SiOC) glasses synthesized from the same starting precursor. In one case we perform pyrolysis in an Ar flow, while in the second case, the glass is synthesized under a CO2 flow. The microstructural characterization of the glasses unambiguously demonstrates that the Ar-pyrolyzed material (SiOC–Ar) is a SiOC/Cfree nanocomposite with mixed SiCxO4−x 0 ≤x≤ 4 units, whereas the CO2-pyrolyzed sample (SiOC–CO2) is a SiO2/Cfree nanocomposite with exclusively SiO4 units forming the amorphous network. Therefore, in this study we investigate two model systems, addressing the question as to whether the mixed SiCxO4−x units in the SiOC glass play an essential role regarding electrochemical performance. The UV-Raman analysis reveals that the sp2 carbon present in the mixed bond-containing sample is more disordered/has more defects than the one dispersed in the SiO2 matrix. Apart from the above dissimilarities, the materials present comparable microstructures and a similar amount of free carbon. Nevertheless, SiOC–Ar recovers almost twice higher reversible Li-ion storage capacity than SiOC–CO2 (325 vs. 165 mA h g−1, respectively). We rationalize this difference in terms of the enhanced Li-ion storage in the more disorder free carbon phase of SiOC–Ar, while this disorder is induced by the presence of the mixed-bond units. [ABSTRACT FROM AUTHOR]

Transmission electron microscopy was performed on a model system of a novel CuMn2O4 spinel catalyst in order to study the effects of reduction by carbon monoxide and subsequent reoxidation by oxygen both processed at 600°C. A phase transition from CuMn2O4 spinel into separated MnO and Cu-rich phases, which are CuO or Cu depending on the reduction period, was observed in the reduced samples. Furthermore, a surface coverage of the MnO grains by epitaxially grown, nanocrystalline Mn3O4 was found in all reduced samples. These Mn3O4 nanocrystals are assumed to act as seed crystals in the subsequent reoxidation step completely reversing the phase transitions and reconstituting single-phase CuMn2O4 spinel. In addition, superlattice reflections due to cation ordering occurred as a typical feature in the as-prepared spinel. In the reoxidized spinel, the superlattice reflections were absent, hence indicating a disordered cation distribution. [ABSTRACT FROM AUTHOR]

Hafnium oxide (HfO x)-based memristive devices have tremendous potential as nonvolatile resistive random access memory (RRAM) and in neuromorphic electronics. Despite its seemingly simple two-terminal structure, a myriad of RRAM devices reported in the rapidly growing literature exhibit rather complex resistive switching behaviors. Using Pt/HfO x/TiN-based metal-insulator-metal structures as model systems, it is shown that a well-controlled oxygen stoichiometry governs the filament formation and the occurrence of multiple switching modes. The oxygen vacancy concentration is found to be the key factor in manipulating the balance between electric field and Joule heating during formation, rupture (reset), and reformation (set) of the conductive filaments in the dielectric. In addition, the engineering of oxygen vacancies stabilizes atomic size filament constrictions exhibiting integer and half-integer conductance quantization at room temperature during set and reset. Identifying the materials conditions of different switching modes and conductance quantization contributes to a unified switching model correlating structural and functional properties of RRAM materials. The possibility to engineer the oxygen stoichiometry in HfO x will allow creating quantum point contacts with multiple conductance quanta as a first step toward multilevel memristive quantum devices. [ABSTRACT FROM AUTHOR]

Randall's plaques (RP) are preferred sites for the formation of calcium oxalate monohydrate (COM) kidney stones. However, although processes of interstitial calcium phosphate (CaP) plaque formation are not well understood, the potential of plaque microstructures as indicators of CaP precipitation conditions received only limited attention. We investigated RP-associated COM stones for structural details of the calcified tissues and microstructural features of plaque-stone interfaces as indicators of the initial processes of stone formation. Significantly increased CaP supersaturation can be expected for interstitial fluid, if reabsorbed ions from the tubular system continuously diffuse into the collagenous connective tissue. Densely packed, fine-grained CaP particles were found in dense textures of basement membranes while larger, laminated particles were scattered in coarse-meshed interstitial tissue, which we propose to be due to differential spatial confinements and restrictions of ion diffusion. Particle morphologies suggest an initial precipitation as metastable amorphous calcium phosphate (ACP). Morphologies and arrangements of first COM crystals at the RP-stone interface ranged from stacked euhedral platelets to skeletal morphologies and even porous, dendritic structures, indicating, in this order, increasing levels of COM supersaturation. Furthermore, these first COM crystals were often coated with CaP. On this basis, we propose that ions from CaP-supersaturated interstitial fluid may diffuse through porous RP into the urine, where a resulting local increase in COM supersaturation could trigger crystal nucleation and, hence, initiate stone formation. Ion-depleted fluid in persistent pores of initial COM layers may get replenished from interstitial fluid, leading to CaP precipitation in porous COM. [ABSTRACT FROM AUTHOR]

This basic research deals with the microstructure evolution of a W-doped ZrB2 ceramic, as-sintered and upon oxidation at 1650°C. Transmission electron microscopy enabled to disclose microstructural features occurred during oxidation never observed before. In the pristine material, (Zr,W)B2 solid solutions surround the original ZrB2 nuclei, whereas refractory W-compounds at triple junctions and clean grain boundaries are distinctive of this ceramic. After oxidation, the microstructure is typified by intragranular nanostructures, in which nanosized W inclusions remained trapped within ZrO2 grains, or decorate their surfaces. The understanding of the oxidation reactions occurring in the system as a function of the oxygen partial pressure was fundamental to conclude that W-based compounds do not notably suppress or retard the oxidation of ZrB2 ceramics. [ABSTRACT FROM AUTHOR]

Thermoelectric modules based on half-Heusler compounds offer a cheap and clean way to create eco-friendly electrical energy from waste heat. Here we study the impact of the period composition on the electrical and thermal properties in non-symmetric superlattices, where the ratio of components varies according to (TiNiSn)n:(HfNiSn)6-n, and 0 ≤ n ≤ 6 unit cells. The thermal conductivity (K) showed a strong dependence on the material content achieving a minimum value for n = 3, whereas the highest value of the figure of merit ZT was achieved for n = 4. The measured can be well modeled using non-symmetric strain relaxation applied to the model of the series of thermal resistances. [ABSTRACT FROM AUTHOR]

The influence of B-site disorder on the dielectric, microstructural, and structural characteristics of unpoled, lead-free (Bi1/2Na1/2)TiO3-0.06Ba(Zr xTi1- x)O3 piezoelectric ceramics with x = 0.02, 0.10, and 0.15 was investigated. The low and medium doping level introduced a stabilization of polar nanoregions reflected in the shift of the dispersive permittivity anomalies to higher temperatures and the development of lamellar rhombohedral domains embedded in the prevalent tetragonal nanodomain matrix. For higher Zr level, the regions of lamellar domains remain, but the dielectric characteristics indicate a reduction in the previous stabilization effect. This behavior is rationalized by a reduction in the correlation length due to the increasing amount of nonpolar sample volume with increasing Zr addition. [ABSTRACT FROM AUTHOR]

The present review gives an overview of the various reports on properties of line and planar defects in Cu(In,Ga)(S,Se)2 thin films for high-efficiency solar cells. We report results from various analysis techniques applied to characterize these defects at different length scales, which allow for drawing a consistent picture on structural and electronic defect properties. A key finding is atomic reconstruction detected at line and planar defects, which may be one mechanism to reduce excess charge densities and to relax deep-defect states from midgap to shallow energy levels. On the other hand, nonradiative Shockley-Read-Hall recombination is still enhanced with respect to defect-free grain interiors, which is correlated with substantial reduction of luminescence intensities. Comparison of the microscopic electrical properties of planar defects in Cu(In,Ga)(S,Se)2 thin films with two-dimensional device simulations suggest that these defects are one origin of the reduced open-circuit voltage of the photovoltaic devices. (© 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim) [ABSTRACT FROM AUTHOR]

The design of core-shell materials affords additional degrees of freedom to tailor functional properties as compared to solid solution counterparts. Although to date most of the work in core-shell materials has focused on dielectrics, piezoelectric core-shell ceramics may gain similar interest. Generalities of core-shell functional ceramics features are addressed in this work. A model system, Bi1/2Na1/2TiO3-SrTiO3, is introduced to discuss structure-property relationships. We demonstrate that this system features a core-shell microstructure for the composition corresponding to 25 at.% Sr. The material is studied by means of macroscopic functional properties and in situ structural characterization techniques at different length scales, such as X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The evolution of the core-shell with field and temperature determines its functional properties. The high strain of the system, ~0.3% at 4 kV/mm, is due to an electric-field-induced phase transition of the core and shell. Upon field removal the core remains in a poled state, whereas the shell is characterized by a reversible transformation. The reversibility of the phase transition of shells and associated switching are key features in the observed giant strain. Dielectric anomalies are found to be related to changes in oxygen octahedral tilting angles within the core and shell. [ABSTRACT FROM AUTHOR]

We present a versatile approach for the fabrication of well-defined networks of interconnected metal nanotubes, which applies electroless plating to ion-track-etched polymer templates that enclose designed pore networks. In order to obtain self-supporting structures, the deposition reactions must be optimized to yield conformal nanoscale metal films on microstructured substrates possessing extensive inner surfaces. Using this route, gold, copper, silver, nickel, and platinum nanotube networks are synthesized. The resulting structures can be handled macroscopically and combine a large surface area with continuous mass transport and conduction pathways, rendering them promising for application in, for example, electrocatalysis and sensing. This potential is demonstrated by employing a gold nanotube network for the amperometric detection of hydrogen peroxide, in which excellent sensitivity, catalyst utilization, and stability is achieved. [ABSTRACT FROM AUTHOR]

We report the formation of novel microstructured Si CNO films with 'smooth,' 'egg-shaped,' and 'strawberry-like' spheres by a block copolymer micellar-templating approach, in which polyvinylsilazne ( PVSZ) swelled F127 micelles are allowed to evaporate at different temperatures over the different periods of time, followed by the cross-linking at 140°C and the pyrolysis at 800°C. The evolution process of 'smooth,' 'egg-shaped,' and 'strawberry-like' spheres in the microstructured Si CNO films is observed by controlling the evaporation temperature and time of the multistep thermal treatment. The Si CNO films with varied internal microstructures have potential for harsh environment applications including high-temperature sensors and high oxidation/corrosion resistance. [ABSTRACT FROM AUTHOR]

LiCoCaPO-graphitic carbon foam composites are prepared using a sol-gel method. The structural analysis reveals LiCoPO as major crystalline phase and CoPO (for x = 0.0) and CoP, LiPO, and (Ca,Co)(PO) (for x ≥ 0.05) as secondary phases. The morphology consists of microcrystalline 'islands' with acicular crystallites (5-50 μm size). Transmission electron microscopy (TEM) of the powders showed that the Ca is incorporated into the crystal structure evoking exaggerated grain growth. The voltammetric profiles show a decrease of the voltammetric surface between anodic and cathodic sweeps and a shift of the reduction potentials toward higher values (∼4.6 V, x = 0.1). The electrochemical measurements, at a discharge rate of C/10 (room temperature), show an increase of the discharge-specific capacity from 100 mAhg for x = 0.0 to 104 mAhg for x = 0.1. The ac impedance spectroscopy data revealed an improvement of the Li-ion conductivity at high content of Ca ions ( x = 0.1). [ABSTRACT FROM AUTHOR]

Transparent polycrystalline magnesium aluminate spinel is one of few materials capable of fulfilling certain demanding optical applications. However, LiF additive typically required to enhance sintering and impart transparency also degrades mechanical properties and causes scatter, precluding wider application. To shed light on the cause of altered properties, electrochemical impedance spectroscopy was performed between 500°C and 900°C, in oxidizing and reducing atmosphere, on fully dense, polycrystalline spinel compacts hot-pressed with and without LiF. In combination with electron microscopy, chemical analysis, and secondary-ion mass spectroscopy, bulk and grain-boundary dielectric behavior were related to microstructure and chemistry. Decades higher conductivity than for comparable single crystals correlated with Al2O3-rich stoichiometry, impurities, and small grain size, and suggested increased conduction and current-line detouring along Mg-depleted, impurity-rich, field-parallel grain boundaries. LiF addition reduced conductivity by one decade and increased the activation energy for conductivity, attributed to impurity removal, larger grain size, and point defects caused by lithium incorporation. [ABSTRACT FROM AUTHOR]

Wet strengthening of paper products is typically performed by thermo-crosslinking reactive polymers or polymer precursors. In this article we introduce a novel concept for generating wet-strength paper grades by using photoreactive polymers and light as the energy source. Statistical, hydrophilic copolymers of dimethylacrylamide and benzophenone-methacrylate monomer, respectively, were synthesised and surface-applied to model paper handsheets. Benzophenone, as a photoreactive group, was selected because of its high crosslinking efficiency when illuminated with UV light (365 or 254 nm). After photo-crosslinking of the polymer-modified handsheets, first results of mechanical testing showed a significant increase of the wet tensile strength. The wet strength is a function of the molar content of the photoreactive group (benzophenone) within the polymer, the mass of the polymer relative to the dry fibre, the wavelength of irradiation and the intensity of UV exposure. Hence, there are a number of options to control and modulate the wet strength of paper sheets between less than 2 % (relative to the dry strength of the paper sheet) up to more than 15 %. In comparison to commercially available wet strength additives, crosslinking can be achieved even in the presence of humidity (up to 10 % water in the handsheet by weight) and at room temperature. [ABSTRACT FROM AUTHOR]

The influence of heat treatment in lead zirconate titanate Pb( Zr, Ti) O3 ( PZT) ferroelectrics on the domain structure and strain behavior has been investigated. Temperature-induced changes in the domain configuration, for example, appearance of nanodomains within microdomains, were observed by in situ hot-stage transmission electron microscopy. During the transient post annealing state the strain behavior under electric field differed from that of the nonheat-treated ferroelectrics. Directly after cooling the difference was most pronounced and decreased as a function of time. The enhanced response to an electric field of 4 kV/mm resulted in qualitatively different effects on strain for PZT from the tetragonal side and from the rhombohedral side of the morphotropic phase boundary. [ABSTRACT FROM AUTHOR]

Three silicon oxycarbide samples with different carbon contents are analyzed in the present study with respect to their high-temperature creep behavior. The tests were performed in compression at 1100°C, 1200°C, and 1300°C; in this temperature range the mechanism of creep relies on viscoelastic flow within the samples and has been modeled with the Jeffreys viscoelastic model. After the release of the applied mechanical stress, a viscoelastic recovery behavior was observed in all samples. The creep behavior of the investigated samples indicates two rheological contributions in SiOC: (i) a high viscous answer, coming from the silica-rich network, and (ii) an elastic response from the segregated carbon phase within the samples. Furthermore, two distinct effects of the carbon phase on the HT creep behavior of SiOC were identified and are discussed in the present paper: the effect of the carbon presence within the SiOC network (the 'carbidic' carbon), which induces a significant increase in the viscosity and a strong decrease in the activation energy for creep, as compared to vitreous silica; and the influence of the segregated carbon phase (the 'free' carbon), which has been shown to affect the viscosity and the activation energy of creep and dominates the creep behavior in phase-separated silicon oxycarbides. [ABSTRACT FROM AUTHOR]

We present a facile approach to design micro- and mesoporous ceramic nanocomposites, which avoids the sintering of nanoparticles even at high synthesis temperatures and in situ forms nanoparticles in high temperature stable porous silicon oxycarbonitride (SiOC(N)) matrices. Our case study includes the synthesis of micro-and mesoporous polymer nanocomposites (c-WO3 -- x/WO3xH2O/[-Si(O)CH2-]n) which contain cubic tungsten oxide and tungsten oxide monohydrate (c-WO3 -- x/WO3×H2O) nanowhiskers in highly micro- and mesoporous polycarbosilane-siloxane matrices. The thermolysis of c-WO3-x/WO3×H2O/ [-Si(O)CH2-]n nanocomposites under a suitable atmosphere and temperature leads to the in situ formation of well-dispersed nanoparticles of cubic tungsten oxide (c-WO3 -- x), tungsten oxycarbide (W2CO), tungsten carbide (WC) and tungsten nitride (WN) in micro- and mesoporous matrices. [ABSTRACT FROM AUTHOR]

Silicon oxycarbide/tin nanocomposites (SiOC/Sn) are prepared by chemical modification of polysilsesquioxane Wacker-Belsil PMS MK (SiOCMK) and polysiloxane Polyramic RD-684a (SiOCRD) with tin(II)acetate and subsequent pyrolysis at 1000 °C. The obtained samples consist of an amorphous SiOC matrix and in-situ formed metallic Sn precipitates. Galvanostatic cycling of both composites demonstrate a first cycle reversible capacity of 566 mAhg−1 for SiOCMK/Sn and 651 mAhg−1 for SiOCRD/Sn. The superior cycling stability and rate capability of SiOCRD/Sn as compared to SiOCMK/Sn is attributed to the soft, carbon-rich SiOC matrix derived from the RD-684a polymer, which accommodates the Sn-related volume changes during Li-uptake and release. The poor cycling stability found for SiOCMK/Sn relates to mechanical failure of the rather stiff and fragile, carbon-poor matrix produced from PMS MK. Incremental capacity measurements outline different final Li-Sn alloy stages, depending on the matrix. For SiOCRD/Sn, alloying up to Li7Sn2 is registered, whereas for SiOCMK/Sn Li22Sn5 stoichiometry is reached. The suppression of Li22Sn5 phase in SiOCRD/Sn is rationalized by an expansion restriction of the matrix and thus prevention of a higher Li content in the alloy. For SiOCMK/Sn on the contrary, the matrix severely ruptures, providing an unlimited free volume for expansion and thus formation of Li22Sn5 phase. [ABSTRACT FROM AUTHOR]