Search

Cubic silicon nitride (γ-Si3N4) is superhard and one of the hardest materials after diamond and cubic boron nitride (cBN), but has higher thermal stability in an oxidizing environment than diamond, making it a competitive candidate for technological applications in harsh conditions (e.g., drill head and abrasives). Here, we report the high-pressure synthesis and characterization of the structural and mechanical properties of a γ-Si3N4/Hf3N4 ceramic nanocomposite derived from single-phase amorphous silicon (Si)–hafnium (Hf)–nitrogen (N) precursor. The synthesis of the γ-Si3N4/Hf3N4 nanocomposite is performed at ~20 GPa and ca. 1500 ℃ in a large volume multi anvil press. The structural evolution of the amorphous precursor and its crystallization to γ-Si3N4/Hf3N4 nanocomposites under high pressures is assessed by the in situ synchrotron energy-dispersive X-ray diffraction (ED-XRD) measurements at ~19.5 GPa in the temperature range of ca. 1000–1900 ℃. The fracture toughness (KIC) of the two-phase nanocomposite amounts ~6/6.9 MPa·m1/2 and is about 2 times that of single-phase γ-Si3N4, while its hardness of ca. 30 GPa remains high. This work provides a reliable and feasible route for the synthesis of advanced hard and tough γ-Si3N4-based nanocomposites with excellent thermal stabililty.

In this study tin-functionalized silicon oxycarbide, Sn/SiOC, composite anode materials are synthesized using a carbon-rich polysiloxane as the preceramic polymer and nano-sized SnO2, which converts to metallic tin via carbothermal reduction at approximately 700 °C. The in-situ Sn formation leads to a uniform distribution of tin particles within a carbon-rich SiOC matrix. Raman spectra show no significant changes despite the carbothermal reduction of SnO2. The composite material provides a stable reversible capacity of 234 mAh g-1. By adjusting the composition and pyrolysis temperature a reversible capacity of 131 mAh g-1 at a high current rate of 2380 mA g-1 is achieved.

This article reports on the structure and electronic properties of carbon-rich polysilazane polymer-derived silicon carbonitride (C/SiCN) corresponding to pyrolysis temperatures between 1100 and 1600 °C in an argon atmosphere. Raman spectroscopy, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM) and Hall measurements were used to support the structural and electronic properties characterization of the prepared C/SiCN nanocomposites. A structural analysis using Raman spectroscopy showed the evolution of sp2 hybridized carbon phase that resulted from the growth in the lateral crystallite size (La), average continuous graphene length including tortuosity (Leq) and inter-defects distance (LD) with an increase in pyrolysis temperature. The prepared C/SiCN monoliths showed a record high room temperature (RT) electrical conductivity of 9.6 S/cm for the sample prepared at 1600 °C. The electronic properties of the nanocomposites determined using Hall measurement revealed an anomalous change in the predominant charge carriers from n-type in the samples pyrolyzed at 1100 °C to predominantly p-type in the samples prepared at 1400 and 1600 °C. According to this outcome, tailor-made carbon-rich SiCN polymer-derived ceramics could be developed to produce n-type and p-type semiconductors for development of the next generation of electronic systems for applications in extreme temperature environments.

In the last decade, Sodium-Ion-Batteries (SIB) started to gain interest as a possible complementary candidate to support the overburdened lithium technology, but the manufacturing of a proper anode material is one of the challenging factors for the development of performing SIB. Among others, porous polymer-derived ceramics have been widely explored as suitable anodes despite the production of such materials being time and energy-consuming. In this work, we investigate the feasibility of adopting a low-cost ultra-fast high-temperature pyrolysis for the ceramic conversion of a polymer-derived SiOC aerogel to be employed as anode material. A comprehensive study including N2 physisorption, 29Si MAS NMR and Raman spectroscopy provides the insights of the effect of ultra-fast and conventional heating rates (i.e., 200 °C·s−1 vs. 5 °C·min−1) on the microstructural features and ceramic yield of the SiOC aerogels. As a consequence of the ultra-fast heating rate, a compositional drift towards oxygen-rich SiOC is observed and discussed. The electrochemical performance of both ceramics has been tested and related to the observed compositional differences, revealing a stable capacity of 103 mAh·g−1 for the ultra-fast pyrolyzed SiOC anode, and 152 mAh·g−1 for SiOC ceramized at 5 °C·min−1.

In the present study, thin-film strain gauge element arrays were prepared based on large-area silicon oxycarbide thin films and lithographic deposition of structured electrodes. The individual strain gauge elements were systematically investigated concerning their piezoresistive behavior at ambient temperature and shown to possess giant piezoresistivity with gauge factors in the range of 3–5 × 103. This has been correlated with the large charge carrier mobility in the silicon oxycarbide thin films (i.e., 186 cm2 V−1 s−1) as well as with a unique phase composition and morphology thereof, consisting of high-conductivity carbon-rich segregations homogeneously dispersed within a silicon oxycarbide-based matrix. The studied strain gauge elements were evaluated in both cyclic tensile and compression load modes and showed excellent reversibility and short response times. The process capability of the strain gauge elements has been statistically assessed and revealed good robustness and replicability which may be further improved. The present work provides a robust and highly reproducible manufacturing process for an ultrasensitive strain gauge prototype and thus points towards a great potential concerning the use of silicon oxycarbides in MEMS-related applications.

In this work, the preparation of porous hybrid particle-based films by core-shell particle design and convenient film preparation is reported. Monodisperse core particles consisting of poly(methyl methacrylate‑co‑allyl methacrylate) (P(MMA‑co‑ALMA)) were synthesized by starved-feed emulsion polymerization followed by the introduction of an initiator-containing monomer (inimer) for subsequent atom transfer radical polymerization (ATRP). The inimer shell allowed for the introduction of allylhydrido polycarbosilane (SMP-10) under ATRP conditions by grafting to the core particles. The functionalization of the prepared core-shell particles was investigated by IR spectroscopy (FTIR), scanning transmission electron microscopy (STEM) and solid-state NMR combined with dynamic nuclear polarization (DNP). The obtained hard core/soft preceramic shell particles were subjected to the melt-shear organization technique, enabling a convenient alignment into a colloidal crystal structure in one single step without the presence of a dispersion medium or solvent for the designed particles. Moreover, the hybrid particle-based films were converted into a porous ceramic structure upon thermal treatment. As a result, freestanding ceramic porous films have been obtained after degradation of the organic template core particles. Noteworthy, the conversion of the matrix material consisting of SMP-10 into the ceramic occurred with preservation of the pristine colloidal crystal template structure. Herein, the first example of core-shell particle preparation by combining different polymerization methodologies and application of the convenient melt-shear organization technique is shown, paving a new way to ceramic materials with tailored morphology and porosity. Keywords: Hybrid film, Emulsion polymerization, ATRP, Self-assembly, Colloidal crystal, Particle processing

The present review introduces a class of ceramic nanocomposites that contain carbon as disperse phases and exhibit piezoresistive behavior. After a brief introduction in which the piezoresistive effect is described and selected principles for the design of piezoresistive sensing devices are highlighted, various carbon-containing ceramic nanocomposites are presented and discussed in the light of their preparative access as well as their piezoresistive behavior. Emphasis is put on carbon-containing ceramic nanocomposites in which the dispersed carbon phase is generated in situ during a thermal treatment process, which allows tunable carbon contents and crystallinities, along with a highly homogeneous dispersion of the carbon phase in the ceramic matrix. The piezoresistive carbon-containing ceramic nanocomposites presented here are furthermore critically discussed within the context of their potential use as force/strain/pressure sensing materials for applications at ultrahigh temperatures and in hostile environments.

The present work elaborates on the correlation between the amount and ordering of the free carbon phase in silicon oxycarbides and their charge carrier transport behavior. Thus, silicon oxycarbides possessing free carbon contents from 0 to ca. 58 vol.% (SiOC/C) were synthesized and exposed to temperatures from 1100 to 1800 °C. The prepared samples were extensively analyzed concerning the thermal evolution of the sp2 carbon phase by means of Raman spectroscopy. Additionally, electrical conductivity and Hall measurements were performed and correlated with the structural information obtained from the Raman spectroscopic investigation. It is shown that the percolation threshold in SiOC/C samples depends on the temperature of their thermal treatment, varying from ca. 20 vol.% in the samples prepared at 1100 °C to ca. 6 vol.% for the samples annealed at 1600 °C. Moreover, three different conduction regimes are identified in SiOC/C, depending on its sp2 carbon content: (i) at low carbon contents (i.e., 2 carbon precipitates appear to be responsible for the electrical conductivity; (iii) whereas above the percolation threshold, the charge carrier transport is only weakly activated (Ea = 0.03 eV) and is realized through the (continuous) carbon phase. Hall measurements on SiOC/C samples above the percolation threshold indicate p-type carriers mainly contributing to conduction. Their density is shown to vary with the sp2 carbon content in the range from 1014 to 1019 cm−3; whereas their mobility (ca. 3 cm2/V) seems to not depend on the sp2 carbon content.

There is an increasing clinical need to develop novel biomaterials that combine regenerative and biocidal properties. In this work, we present the preparation of silver/silica-based glassy bioactive (ABG) compositions via a facile, fast (20 h), and low temperature (80 °C) approach and their characterization. The fabrication process included the synthesis of the bioactive glass (BG) particles followed by the surface modification of the bioactive glass with silver nanoparticles. The microstructural features of ABG samples before and after exposure to simulated body fluid (SBF), as well as their ion release behavior during SBF test were evaluated using infrared spectrometry (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, X-ray diffraction (XRD), electron microscopies (TEM and SEM) and optical emission spectroscopy (OES). The antibacterial properties of the experimental compositions were tested against Escherichia coli (E. coli). The results indicated that the prepared ABG materials possess antibacterial activity against E. coli, which is directly correlated with the glass surface modification.

Solar hydrogen production via the photoelectrochemical water-splitting reaction is attractive as one of the environmental-friendly approaches for producing H2. Since the reaction simultaneously generates H2 and O2, this method requires immediate H2 recovery from the syngas including O2 under high-humidity conditions around 50 °C. In this study, a supported mesoporous γ-Al2O3 membrane was modified with allyl-hydrido-polycarbosilane as a preceramic polymer and subsequently heat-treated in Ar to deliver a ternary SiCH organic–inorganic hybrid/γ-Al2O3 composite membrane. Relations between the polymer/hybrid conversion temperature, hydrophobicity, and H2 affinity of the polymer-derived SiCH hybrids were studied to functionalize the composite membranes as H2-selective under saturated water vapor partial pressure at 50 °C. As a result, the composite membranes synthesized at temperatures as low as 300–500 °C showed a H2 permeance of 1.0–4.3 × 10−7 mol m−2 s−1 Pa−1 with a H2/N2 selectivity of 6.0–11.3 under a mixed H2-N2 (2:1) feed gas flow. Further modification by the 120 °C-melt impregnation of low molecular weight polycarbosilane successfully improved the H2-permselectivity of the 500 °C-synthesized composite membrane by maintaining the H2 permeance combined with improved H2/N2 selectivity as 3.5 × 10−7 mol m−2 s−1 Pa−1 with 36. These results revealed a great potential of the polymer-derived SiCH hybrids as novel hydrophobic membranes for purification of solar hydrogen.

The present Review addresses current developments related to polymer-derived ceramic nanocomposites (PDC-NCs). Different classes of preceramic polymers are briefly introduced and their conversion into ceramic materials with adjustable phase compositions and microstructures is presented. Emphasis is set on discussing the intimate relationship between the chemistry and structural architecture of the precursor and the structural features and properties of the resulting ceramic nanocomposites. Various structural and functional properties of silicon-containing ceramic nanocomposites as well as different preparative strategies to achieve nano-scaled PDC-NC-based ordered structures are highlighted, based on selected ceramic nanocomposite systems. Furthermore, prospective applications of the PDC-NCs such as high-temperature stable materials for thermal protection systems, membranes for hot gas separation purposes, materials for heterogeneous catalysis, nano-confinement materials for hydrogen storage applications as well as anode materials for secondary ion batteries are introduced and discussed in detail.

In the present work, Ca-containing silicon oxycarbides (SiCaOC) with varying Ca content have been synthesized via sol-gel processing and thermal treatment in inert gas atmosphere (pyrolysis). It has been shown that the as-prepared SiCaOC materials with low Ca loadings (Ca/Si molar ratios = 0.05 or 0.12) were X-ray amorphous; their glassy network contains Q3 sites, indicating the presence of Ca2+ at non-bridging-oxygen sites. SiCaOC with high Ca content (i.e., Ca/Si molar ratio = 0.50) exhibits the presence of crystalline calcium silicate (mainly pseudowollastonite). Furthermore, it has been shown that the incorporation of Ca into the SiOC glassy network has a significant effect on its porosity and specific surface area. Thus, the as-prepared Ca-free SiOC material is shown to be non-porous and having a specific surface area (SSA) of 22.5 m2/g; whereas SiCaOC with Ca/Si molar ratio of 0.05 exhibits mesoporosity and a SSA value of 123.4 m2/g. The further increase of Ca content leads to a decrease of the SSA and the generation of macroporosity in SiCaOC; thus, SiCaOC with Ca/Si molar ratio of 0.12 is macroporous and exhibits a SSA value of 39.5 m2/g. Bioactivity assessment in simulated body fluid (SBF) confirms the hydroxyapatite formation on all SiCaOC samples after seven days soaking, unlike the relatively inert ternary silicon oxycarbide reference. In particular, SiCaOC with a Ca/Si molar ratio of 0.05 shows an increased apatite forming ability compared to that of SiCaOC with Ca/Si molar ratio of 0.12; this difference is considered to be a direct consequence of the significantly higher SSA of the sample with the Ca/Si ratio of 0.05. The present work indicates two effects of Ca incorporation into the silicon oxycarbide glassy network on its bioactivity: Firstly, Ca2+ is shown to contribute to the slight depolymerization of the network, which clearly triggers the hydroxyapatite formation (compare the bioactive behavior of SiOC to that of SiCaOC with Ca/Si molar ratio 0.12 upon SBF exposure); secondly, the Ca2+ incorporation seems to strongly affect the porosity and SSA in the prepared SiCaOC materials. There is an optimum of Ca loading into the silicon oxycarbide glassy network (at a Ca/Si molar ration of 0.05), which provides mesoporosity and reaches maximum SSA, both highly beneficial for the bioactive behavior of the materials. An increase of the Ca loading leads, in addition to the crystallization of calcium silicates, to a coarsening of the pores (i.e., macroporosity) and a significant decrease of the SSA, both negatively affecting the bioactivity.

The preparation of ordered macroporous SiCN ceramics has attracted significant interest and is an attractive area for various applications, e.g., in the fields of catalysis, gas adsorption, or membranes. Non-oxidic ceramics, such as SiCN, own a great stability based on the covalent bonds between the containing elements, which leads to interesting properties concerning resistance and stability at high temperature. Their peculiar properties have become more and more important for a manifold of applications, like catalysis or separation processes, at high temperatures. Within this work, a feasible approach for the preparation of ordered porous materials by taking advantage of polymer-derived ceramics is presented. To gain access to free-standing films consisting of porous ceramic materials, the combination of monodisperse organic polymer-based colloids with diameters of 130 nm and 180 nm featuring a processable preceramic polymer is essential. For this purpose, the tailored design of hybrid organic/inorganic particles featuring anchoring sites for a preceramic polymer in the soft shell material is developed. Moreover, polymer-based core particles are used as sacrificial template for the generation of pores, while the preceramic shell polymer can be converted to the ceramic matrix after thermal treatment. Two different routes for the polymer particles, which can be obtained by emulsion polymerization, are followed for covalently linking the preceramic polysilazane Durazane1800 (Merck, Germany): (i) Free radical polymerization and (ii) atom transfer radical polymerization (ATRP) conditions. These hybrid hard core/soft shell particles can be processed via the so-called melt-shear organization for the one-step preparation of free-standing particle films. A major advantage of this technique is the absence of any solvent or dispersion medium, enabling the core particles to merge into ordered particle stacks based on the soft preceramic shell. Subsequent ceramization of the colloidal crystal films leads to core particle degradation and transformation into porous ceramics with ceramic yields of 18−54%.

Conductive nanotubes consisting of indium tin oxide (ITO) were fabricated by electroless deposition using ion track etched polycarbonate templates. To produce nanotubes (NTs) with thin walls and small surface roughness, the tubes were generated by a multi-step procedure under aqueous conditions. The approach reported below yields open end nanotubes with well defined outer diameter and wall thickness. In the past, zinc oxide films were mostly preferred and were synthesized using electroless deposition based on aqueous solutions. All these methods previously developed, are not adaptable in the case of ITO nanotubes, even with modifications. In the present work, therefore, we investigated the necessary conditions for the growth of ITO-NTs to achieve a wall thickness of around 10 nm. In addition, the effects of pH and reductive concentrations for the formation of ITO-NTs are also discussed.

In the present study, the effect of the chemical and phase composition on the thermal properties of silicon oxide carbides (SiOC) has been investigated. Dense monolithic SiOC materials with various carbon contents were prepared and characterized with respect to their thermal expansion, as well as thermal conductivity. SiOC glass has been shown to exhibit low thermal expansion (e.g., ca. 3.2 × 10−6 K−1 for a SiOC sample free of segregated carbon) and thermal conductivity (ca. 1.5 W/(m∙K)). Furthermore, it has been observed that the phase separation, which typically occurs in SiOC exposed to temperatures beyond 1000–1200 °C, leads to a decrease of the thermal expansion (i.e., to 1.83 × 10−6 K−1 for the sample above); whereas the thermal conductivity increases upon phase separation (i.e., to ca. 1.7 W/(m∙K) for the sample mentioned above). Upon adjusting the amount of segregated carbon content in SiOC, its thermal expansion can be tuned; thus, SiOC glass ceramics with carbon contents larger than 10–15 vol % exhibit similar coefficients of thermal expansion to that of the SiOC glass. Increasing the carbon and SiC content in the studied SiOC glass ceramics leads to an increase in their thermal conductivity: SiOC with relatively large carbon and silicon carbides (SiC) volume fractions (i.e., 12–15 and 20–30 vol %, respectively) were shown to possess thermal conductivities in the range from 1.8 to 2.7 W/(m∙K).

The microstructure of segregated carbon in silicon oxycarbide (SiOC), hot-pressed at T = 1600 °C and p = 50 MPa, has been investigated by VIS Raman spectroscopy (λ = 514 nm) within the temperature range 25–1000 °C in air. The occurrence of the G, D’ and D bands at 1590, 1620 and 1350 cm−1, together with a lateral crystal size La < 10 nm and an average distance between lattice defects LD ≈ 8 nm, provides evidence that carbon exists as nano-crystalline phase in SiOC containing 11 and 17 vol % carbon. Both samples show a linear red shift of the G band up to the highest temperature applied, which is in agreement with the description of the anharmonic contribution to the lattice potential by the modified Tersoff potential. The temperature coefficient χG = −0.024 ± 0.001 cm−1/°C is close to that of disordered carbon, e.g., carbon nanowalls or commercial activated graphite. The line width of the G band is independent of temperature with FWHM-values of 35 cm−1 (C-11) and 45 cm−1 (C-17), suggesting that scattering with defects and impurities outweighs the phonon-phonon and phonon-electron interactions. Analysis of the Raman line intensities indicates vacancies as dominating defects.

This study investigates the dissolution behavior as well as the surface biomineralization in simulated body fluid (SBF) of a paste composed of glycerol (gly) and a bioactive glass in the system CaO-MgO-SiO2-Na2O-P2O5-CaF2 (BG). The synthesis of the bioactive glass in an alumina crucible has been shown to significantly affect its bioactivity due to the incorporation of aluminum (ca. 1.3–1.4 wt %) into the glass network. Thus, the kinetics of the hydroxyapatite (HA) mineralization on the glass prepared in the alumina crucible was found to be slower than that reported for the same glass composition prepared in a Pt crucible. It is considered that the synthesis conditions lead to the incorporation of small amount of aluminum into the BG network and thus delay the HA mineralization. Interestingly, the BG-gly paste was shown to have significantly higher bioactivity than that of the as-prepared BG. Structural analysis of the paste indicate that glycerol chemically interacts with the glass surface and strongly alter the glass network architecture, thus generating a more depolymerized network, as well as an increased amount of silanol groups at the surface of the glass. In particular, BG-gly paste features early intermediate calcite precipitation during immersion in SBF, followed by hydroxyapatite formation after ca. seven days of SBF exposure; whereas the HA mineralization seems to be suppressed in BG, probably a consequence of the incorporation of aluminum into the glass network. The results obtained within the present study reveal the positive effect of using pastes based on bioactive glasses and organic carriers (here alcohols) which may be of interest not only due to their advantageous visco-elastic properties, but also due to the possibility of enhancing the glass bioactivity upon surface interactions with the organic carrier.

Novel bioactive glasses based on a Ca- and Mg-modified silicon oxycarbide (SiCaMgOC) were prepared from a polymeric single-source precursor, and their in vitro activity towards hydroxyapatite mineralization was investigated upon incubating the samples in simulated body fluid (SBF) at 37 °C. The as-prepared materials exhibit an outstanding resistance against devitrification processes and maintain their amorphous nature even after exposure to 1300 °C. The X-ray diffraction (XRD) analysis of the SiCaMgOC samples after the SBF test showed characteristic reflections of apatite after only three days, indicating a promising bioactivity. The release kinetics of the Ca2+ and Mg2+ and the adsorption of H+ after immersion of SiCaMgOC in simulated body fluid for different soaking times were analyzed via optical emission spectroscopy. The results show that the mechanism of formation of apatite on the surface of the SiCaMgOC powders is similar to that observed for standard (silicate) bioactive glasses. A preliminary cytotoxicity investigation of the SiOC-based bioactive glasses was performed in the presence of mouse embryonic fibroblasts (MEF) as well as human embryonic kidney cells (HEK-293). Due to their excellent high-temperature crystallization resistance in addition to bioactivity, the Ca- and Mg-modified SiOC glasses presented here might have high potential in applications related to bone repair and regeneration.