Toward High-Performance Piezoresistive Polymer Derived SiOC Ceramics through Masked Stereolithography 3D Printing with ß-Silicon Carbide Nanopowder Reinforcement.

Enhancing the piezoresistivity of polymer-derived silicon oxycarbide ceramics (SiOCPDC ) is of great interest in the advancement of highly sensitive pressure/load sensor technology for use in harsh and extreme working conditions. However, a facile, low cost, and scalable approach to fabricate highly piezoresistive SiOCPDC below 1400 °C still remains a great challenge. Here, the fabrication and enhancement of piezoresistive properties of SiOCPDC reinforced with ß-SiC nanopowders (SiCNP ) through masked stereolithography-based 3D-printing and subsequent pyrolysis at 1100 °C are demonstrated. The presence of free carbon in SiCNP augments high piezoresistivity in the fabricated SiCNP -SiOCPDC composites even at lower pyrolysis temperatures. A gauge factor (GF) in the range of 4385-5630 and 6129-8987 with 0.25 and 0.50 wt% of SiCNP , respectively is demonstrated, for an applied pressure range of 0.5-5 MPa at ambient working conditions. The reported GF is significantly higher compared to those of any existing SiOCPDC materials. This rapid and facile fabrication route with significantly enhanced piezoresistive properties makes the 3D-printed SiCNP -SiOCPDC composite a promising high-performance material for the detection of pressure/load in demanding applications. Also, the overall robustness in mechanical properties and load-bearing capability ensures its long-term stability and makes it suitable for challenging and severe environment applications.

Adsorption-coupled Fenton type reduction of bromate in water by high-yield polymer-derived ceramic-supported nano-zerovalent iron.

Nano-zerovalent iron (nZVI) is a promising material for the removal of both organic and inorganic pollutants from contaminated water. This study investigates the potential of a novel composite of nZVI on a polymer-derived supporting ceramic (nZVI-PDC) synthesized via the liquid-phase reduction method for the simultaneous adsorption and Fenton-type reduction of bromate anion (BrO3-) in water. The nZVI nanoparticles were effectively anchored onto the PDC by impregnating high-yield carbon in a ferrous sulfate solution. The PDC facilitated the uniform dispersion of nZVI nanoparticles due to its multiple active sites distributed within mesocarbon cavities. The developed nZVI-PDC composite exhibited a high specific surface area of 837 m2 g-1 and an ordered mesoporous structure with a pore volume of 0.37 cm3 g-1. As an adsorbent, the nZVI-PDC composite exhibited a maximum adsorption capacity (qe) of 842 mg g-1 and a partition coefficient (KH) of 10.2 mg g-1 µM-1, as calculated by the pseudo-second-order model. As a catalyst, the composite demonstrated a reaction kinetic rate of 43.5 µmol g-1 h-1 within 6 h at pH 4, using a dosage of 60 mg L-1 nZVI-PDC and a concentration of 0.8 mmol L-1 H2O2. Comparatively, PDC exhibited a qe of 408 mg g-1, KH of 1.67 mg g-1 µM-1, and a reaction rate of 20.8 µmol g-1 h-1, while nZVI showed a qe of 456 mg g-1, KH of 2.30 mg g-1 µM-1, and a reaction rate of 27.2 µmol g-1 h-1. The modelling indicated that the nZVI-PDC composite followed pseudo-second-order kinetics. The remarkable removal efficiency of the nZVI-PDC composite was attributed to the synergistic effects between PDC and nZVI, where PDC facilitated charge transfer, promoting Fe2+ generation and the Fe3+/Fe2+ cycle. Overall, this work introduces a promising adsorption technology for the efficient removal of BrO3- from contaminated aqueous solutions, highlighting the significant potential of the nZVI-PDC composite in water purification applications.

Novel Lewis Acid-Base Interactions in Polymer-Derived Sodium-Doped Amorphous Si-B-N Ceramic: Towards Main-Group-Mediated Hydrogen Activation.

Interest is growing in transition metal-free compounds for small molecule activation and catalysis. We discuss the opportunities arising from synthesizing sodium-doped amorphous silicon-boron-nitride (Na-doped a-SiBN). Na+ cations and 3-fold coordinated BIII moieties were incorporated into an amorphous silicon nitride network via chemical modification of a polysilazane followed by pyrolysis in ammonia (NH3) at 1000 °C. Emphasis is placed on the mechanisms of hydrogen (H2) activation within Na-doped a-SiBN structure. This material design approach allows the homogeneous distribution of Na+ and BIII moieties surrounded by SiN4 units contributing to the transformation of the BIII moieties into 4-fold coordinated geometry upon encountering H2, potentially serving as frustrated Lewis acid (FLA) sites. Exposure to H2 induced formation of frustrated Lewis base (FLB) N-= sites with Na+ as a charge-compensating cation, resulting in the in situ formation of a frustrated Lewis pair (FLP) motif (≡BFLA⋅⋅⋅Hδ-⋅⋅⋅Hδ+⋅⋅⋅:N-(Na+)=). Reversible H2 adsorption-desorption behavior with high activation energy for H2 desorption (124 kJ mol-1) suggested the H2 chemisorption on Na-doped a-SiBN. These findings highlight a future landscape full of possibilities within our reach, where we anticipate main-group-mediated small molecule activation will have an important impact on the design of more efficient catalytic processes and the discovery of new catalytic transformations.

Temperature and Pressure Wireless Ceramic Sensor (Distance = 0.5 Meter) for Extreme Environment Applications.

This paper presents a design for temperature and pressure wireless sensors made of polymer-derived ceramics for extreme environment applications. The wireless sensors were designed and fabricated with conductive carbon paste on an 18.24 mm diameter with 2.4 mm thickness polymer-derived ceramic silicon carbon nitride (PDC-SiCN) disk substrate for the temperature sensor and an 18 × 18 × 2.6 mm silicon carbide ceramic substrate for the pressure sensor. In the experiment, a horn antenna interrogated the patch antenna sensor on a standard muffle furnace and a Shimadzu AGS-J universal test machine (UTM) at a wireless sensing distance of 0.5 m. The monotonic relationship between the dielectric constant of the ceramic substrate and ambient temperature is the fundamental principle for wireless temperature sensing. The temperature measurement has been demonstrated from 600 °C to 900 °C. The result closely matches the thermocouple measurement with a mean absolute difference of 2.63 °C. For the pressure sensor, the patch antenna was designed to resonate at 4.7 GHz at the no-loading case. The sensing mechanism is based on the piezo-dielectric property of the silicon carbon nitride. The developed temperature/pressure sensing system provides a feasible solution for wireless measurement for extreme environment applications.

Combining Soft Polysilazanes with Melt-Shear Organization of Core-Shell Particles: On the Road to Polymer-Templated Porous Ceramics.

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%.

Rapid laser fabrication of indium tin oxide and polymer-derived ceramic composite thin films for high-temperature sensors.

Thin-film sensors are essential for real-time monitoring of components in high-temperature environments. Traditional fabrication methods often involve complicated fabrication steps or require prolonged high-temperature annealing, limiting their practical applicability. Here, we present an approach using direct ink writing and laser scanning (DIW-LS) to fabricate high-temperature functional thin films. An indium tin oxide (ITO)/preceramic polymer (PP) ink suitable for DIW was developed. Under LS, the ITO/PP thin film shrank in volume. Meanwhile, the rapid pyrolysis of PP into amorphous precursor-derived ceramic (PDC) facilitated the faster sintering of ITO nanoparticles and improved the densification of the thin film. This process realized the formation of a conductive network of interconnected ITO nanoparticles. The results show that the ITO/PDC thin film exhibits excellent stability, with a drift rate of 4.7 % at 1000 °C for 25 h, and withstands temperatures up to 1250 °C in the ambient atmosphere. It is also sensitive to strain, with a maximum gauge factor of -6.0. As a proof of concept, we have used DIW-LS technology to fabricate a thin-film heat flux sensor on the surface of the turbine blade, capable of measuring heat flux densities over 1 MW/m2. This DIW-LS process provides a viable approach for the integrated, rapid, and flexible fabrication of thin film sensors for harsh environments.

A Polymer-Based Metallurgical Route to Produce Aluminum Metal-Matrix Composite with High Strength and Ductility.

In this investigation, an attempt was made to develop a new high-strength and high-ductility aluminum metal-matrix composite. It was achieved by incorporating ceramic reinforcement into the metal which was formed in situ from a polymer by pyrolysis. A crosslinked PMHS polymer was introduced into commercially pure aluminum via friction stir processing (FSP). The distributed micro- and nano-sized polymer was then converted into ceramic particles by heating at 500 °C for 10 h and processed again via FSP. The produced composite showed a 2.5-fold increase in yield strength (to 119 MPa from 48 MPa) and 3.5-fold increase in tensile strength (to 286 MPa from 82 MPa) with respect to the base metal. The ductility was marginally reduced from 40% to 30%. The increase in strength is attributed to the grain refinement and the larger ceramic particles. High-temperature grain stability was obtained, with minimal loss to mechanical properties, up to 500 °C due to the Zenner pinning effect of the nano-sized ceramic particles at the grain boundaries. Fractures took place throughout the matrix up to 300 °C. Above 300 °C, the interfacial bonding between the particle and matrix became weak, and fractures took place at the particle-matrix interface.

SiOC Screens with Aligned and Adjustable Pore Structure for Screen Channel Liquid Acquisition Device.

The development of porous ceramic screens with high chemical stability, low density, and thermal conductivity can lead to promising screen channel liquid acquisition devices (SC-LADs) for propellant management under microgravity conditions in the future. Therefore, SiOC screens with aligned pores were fabricated via freeze-casting and applied as a SC-LAD. The pore window sizes and open porosity varied from 6 µm to 43 µm and 65% or 79%, depending on the freezing temperature or the solid loading, respectively. The pore window size distributions and bubble point tests indicate crack-free screens. On the one hand, SC-LADs with an open porosity of 79% removed gas-free liquid up to a volumetric flow rate of 4 mL s-1. On the other hand, SC-LADs with an open porosity of 65% were limited to 2 mL s-1 as the pressure drop across these screens was relatively higher. SC-LADs with the same open porosity but smaller pore window sizes showed a higher pressure drop across the screen and bubble ingestion at higher values of effective screen area when increasing the applied removal volumetric flow rate. The removed liquid from the SC-LADs was particle-free, thus representing a potential for applications in a harsh chemical environment or broad-range temperatures.

Rapid Printing of High-Temperature Polymer-Derived Ceramic Composite Thin-Film Thermistor with Laser Pyrolysis.

Polymer-derived ceramic (PDC)-based high-temperature thin-film sensors (HTTFSs) exhibit promising applications in the condition monitoring of critical components in aerospace. However, fabricating PDC-based HTTFS integrated with high-efficiency, high-temperature anti-oxidation, and customized patterns remains challenging. In this work, we introduce a rapid and flexible selecting laser pyrolysis combined with a direct ink writing process to print double-layer high-temperature antioxidant PDC composite thin-film thermistors under ambient conditions. The sensitive layer (SL) was directly written on an insulating substrate with excellent conductivity by laser-induced graphitization. Then, the antioxidant layer (AOL) was written on the surface of the SL to realize the integrated manufacturing of double-functional layers. Through characterization analysis, it was shown that B2O3 and SiO2 glass phases generated by the PDC composite AOL could effectively prevent oxygen intrusion. Therefore, the fabricated PDC composite thermistors exhibited a negative temperature coefficient in the temperature range from 100 to 1100 °C and high repeatability below 800 °C. Meanwhile, it has excellent high-temperature stability at 800 °C with a resistance change of only 2.4% in 2 h. Furthermore, the high-temperature electrical behavior of the thermistor was analyzed. The temperature dependence of the conductivity for this thermistor has shown an agreement with the Mott's variable range hopping mechanism. Additionally, the thermistor was fabricated on the surface of an aero-engine blade to verify its feasibility below 800 °C, showing the great potential of this work for state sensing on the surface of high-temperature components, especially for customized requirements.

High-Temperature Properties and Applications of Si-Based Polymer-Derived Ceramics: A Review.

Ceramics derived from organic polymer precursors, which have exceptional mechanical and chemical properties that are stable up to temperatures slightly below 2000 °C, are referred to as polymer-derived ceramics (PDCs). These molecularly designed amorphous ceramics have the same high mechanical and chemical properties as conventional powder-based ceramics, but they also demonstrate improved oxidation resistance and creep resistance and low pyrolysis temperature. Since the early 1970s, PDCs have attracted widespread attention due to their unique microstructures, and the benefits of polymeric precursors for advanced manufacturing techniques. Depending on various doping elements, molecular configurations, and microstructures, PDCs may also be beneficial for electrochemical applications at elevated temperatures that exceed the applicability of other materials. However, the microstructural evolution, or the conversion, segregation, and decomposition of amorphous nanodomain structures, decreases the reliability of PDC products at temperatures above 1400 °C. This review investigates structure-related properties of PDC products at elevated temperatures close to or higher than 1000 °C, including manufacturing production, and challenges of high-temperature PDCs. Analysis and future outlook of high-temperature structural and electrical applications, such as fibers, ceramic matrix composites (CMCs), microelectromechanical systems (MEMSs), and sensors, within high-temperature regimes are also discussed.

Characterization of thick and thin film SiCN for pressure sensing at high temperatures.

Pressure measurement in high temperature environments is important in many applications to provide valuable information for performance studies. Information on pressure patterns is highly desirable for improving performance, condition monitoring and accurate prediction of the remaining life of systems that operate in extremely high temperature environments, such as gas turbine engines. A number of technologies have been recently investigated, however these technologies target specific applications and they are limited by the maximum operating temperature. Thick and thin films of SiCN can withstand high temperatures. SiCN is a polymer-derived ceramic with liquid phase polymer as its starting material. This provides the advantage that it can be molded to any shape. CERASET™ also yields itself for photolithography, with the addition of photo initiator 2, 2-Dimethoxy-2-phenyl-acetophenone (DMPA), thereby enabling photolithographical patterning of the pre-ceramic polymer using UV lithography. SiCN fabrication includes thermosetting, crosslinking and pyrolysis. The technology is still under investigation for stability and improved performance. This work presents the preparation of SiCN films to be used as the body of a sensor for pressure measurements in high temperature environments. The sensor employs the phenomenon of drag effect. The pressure sensor consists of a slender sensitive element and a thick blocking element. The dimensions and thickness of the films depend on the intended application of the sensors. Fabrication methods of SiCN ceramics both as thin (about 40-60 µm) and thick (about 2-3 mm) films for high temperature applications are discussed. In addition, the influence of thermosetting and annealing processes on mechanical properties is investigated.

Ultrahigh-Temperature Ceramic-Polymer-Derived SiOC Ceramic Composites for High-Performance Electromagnetic Interference Shielding.

High-performance electromagnetic interference (EMI) shielding materials for a high-temperature harsh environment are highly required for electronics and aerospace applications. Here, a composite made of ultrahigh-temperature ceramic- and polymer-derived SiOC ceramic (PDC-SiOC) with high EMI shielding was reported for such applications. A total EMI shielding efficiency (SET) of 26.67 dB with a thickness of 0.6 mm at the Ka-band (26.5-40 GHz) was reported for ZrB2 fabricated by spark plasma sintering, which showed reflection-dominant shielding. A unique interface of t-ZrO2 was formed after the introduction of PDC-SiOC into ZrB2. This interface has better electrical conductivity than SiOC. The composites also displayed reflection-dominant shielding. Accordingly, the composite with a normalized ZrB2 fraction of 50% pyrolyzed at 1000 °C exhibited a significant SET of 72 dB (over 99.99999% shielded) with a thickness of 3 mm at the entire Ka-band. A maximum SET of 90.8 dB (over 99.9999999% shielded) was achieved with a thickness of 3 mm at around 39.7 GHz.

Multifunctional Ceramic Composite System for Simultaneous Thermal Protection and Electromagnetic Interference Shielding for Carbon Fiber-Reinforced Polymer Composites.

Achieving a high electrical conductivity while maintaining a good thermal insulation is often contradictory in the material design for the goal of simultaneous thermal protection and electromagnetic interference shielding. The reason is that materials with a high electrical conductivity often pertain a high thermal conductivity. To address this challenge, this study reports a multifunctional ceramic composite system for carbon fiber-reinforced polymer composites. The fabricated multifunctional ceramic composite system has a multilayer structure. The polymer-derived SiCN ceramic reinforced with yttria-stabilized zirconia fibers serves as the thermal protection and impedance-matching layer, while the yttria-stabilized zirconia fiber-reinforced SiCN ceramic with carbon nanotubes provides the electromagnetic interference shielding. The thermal conductance of the multilayered ceramic composite is about 22.5% lower compared to that of the carbon fiber-reinforced polymer composites. The thermal insulation test during the steady-state condition shows that the hybrid composite can be used up to 300 °C while keeping the temperature reaching the surface of carbon fiber-reinforced polymer composites at around 167.8 °C. The flame test was used to characterize the thermal protection capability under transient conditions. The hybrid composite showed temperature differences of 72.9 and 280.7 °C during the low- and high-temperature settings, respectively. The average total shielding efficiency per thickness of the fabricated four-layered ceramic composite system was 21.45 dB/mm, which showed a high reflection-dominant electromagnetic interference shielding. The average total shielding efficiency per thickness of the eight-layered composite system was 16.57 dB/mm, revealing a high absorption-dominant electromagnetic interference shielding. Typical carbon fiber-reinforced polymer composites reveal a reflection-dominant electromagnetic interference shielding. The electrons can freely move in the percolated carbon nanotubes within the inner layers of the composite material, which provide the improved electromagnetic interference shielding ability. The movement of electrons was impeded by the top and bottom layers whose thermal conduction relies on the lattice vibrations, resulting in a satisfactory thermal insulation of the composite materials and impedance matching with the free space. Results of this study showed that materials with a good thermal insulation and electromagnetic interference shielding can be obtained simultaneously by confining the electron movement inside the materials and refraining their movement at the skin surface.

Dielectric Properties and Electromagnetic Wave Absorbing Performance of Single-Source-Precursor Synthesized Mo4.8Si3C0.6/SiC/Cfree Nanocomposites with an In Situ Formed Nowotny Phase.

For the first time, dielectric properties and electromagnetic wave (EMW) absorbing performance of single-source-precursor derived Mo4.8Si3C0.6/SiC/Cfree ceramic nanocomposites with a highly electrically conductive intermetallic Nowotny phase (NP, i.e., Mo4.8Si3C0.6) are reported. High-temperature phase evolution of the nanocomposites reveals that free carbon (Cfree) plays a crucial role in the in situ formation of the NP, indicating that the microstructure of the nanocomposites can be tailored via molecular design of the single-source precursors. Compared with SiC/Cfree and MoSi2/SiC/Cfree nanocomposites obtained under the same conditions, the Mo4.8Si3C0.6/SiC/Cfree nanocomposites exhibit significantly enhanced EMW absorbing performance. A minimum reflection loss (RL) of -59 dB was achieved at 8 GHz for the thickness of 2.46 mm, proving the superiority of the Mo4.8Si3C0.6/SiC/Cfree nanocomposite as an outstanding EMW absorbing material. On the basis of our previous discovery that the Mo4.8Si3C0.6 embedded in a SiC-based matrix with high specific surface area exhibits excellent electrocatalytic properties suitable for the electrochemical hydrogen evolution reaction, the present results prove that Mo4.8Si3C0.6/SiC/Cfree nanocomposites have to be considered as novel multifunctional materials with tailorable microstructure and excellent performance in two different fields including electrochemical water splitting and EMW absorption.

Phase Evolution, Filler-Matrix Interactions, and Piezoelectric Properties in Lead Zirconate Titanate (PZT)-Filled Polymer-Derived Ceramics (PDCs).

PZT-silsesquioxane-based 0-3 hybrid materials are prepared by mixing lead zirconate titanate (Pb(Zr,Ti)O3; PZT) powder with a [R-SiO3/2]n (R = H, CH3, CH=CH2, C6H5) silsequioxane preceramic polymer. A PZT load up to 55 vol.% can be reached in the final composite. The piezoelectric and mechanical properties are investigated as a function of the filler content and are compared with theoretical models and reference samples made of the pure preceramic polymer or PZT filler. The piezoelectric response of the composites, as expressed by the relative permittivity and the piezoelectric coefficients d33 and g33, increases with an increasing PZT content. The bending strength of the composites ranges between 15 MPa and 31 MPa without a clear correlation to the filler content. The thermal conductivity increases significantly from 0.14 W∙m-1∙K-1 for the pure polymer-derived ceramic (PDC) matrix to 0.30 W∙m-1∙K-1 for a sample containing 55 vol.% PZT filler. From X-ray diffraction experiments (XRD), specific interactions between the filler and matrix are observed; the crystallization of the PDC matrix in the presence of the PZT filler is inhibited; conversely, the PDC matrix results in a pronounced decomposition of the filler compared to the pure PZT material.

Ultrasound-Assisted Hydroxyapatite-Decorated Breath-Figure Polymer-Derived Ceramic Coatings for Ti6Al4V Substrates.

The introduction of nanoparticles (NPs) into the breath-figure-templated self-assembly (BFTSA) process is an increasingly common method to selectively decorate a surface porous structure. In the field of prosthetic devices, besides controlling the morphology and roughness of the structure, NPs can enhance the osteointegration mechanism because of their specific ion release. Among the most widely used NPs, there are silica and hydroxyapatite (HAp). In this work, we propose a novel one-stage method to fabricate NP-decorated surface porous structures that are suitable for prosthetic coating applications. This technique combines the classical direct BFTSA process with the cavitation effect induced by an ultrasonic atomizer that generates a mist of water droplets with embedded NPs. Coatings were successfully obtained by combining a UV cross-linkable polymer precursor, alkoxy silicone, with synthesized HAp NPs, on Ti6Al4V alloy discs. The cross-linked polymeric surface porous structures at selected concentrations were then pyrolyzed in an ammonia atmosphere to obtain a silicon oxynitride (SiON) ceramic coating. Herein, we report the chemical and morphological analyses of both the polymeric and ceramic coatings as well as the effect of NPs at the interface.

Synthesis Based on a Preceramic Polymer and Alumina Nanoparticles via UV Lithography for High Temperature Applications.

Because of the increased demand for preceramic polymers in high-tech applications, there has been growing interest in the synthesis of preceramic polymers, including polysiloxanes and alumina. These polymers are preferred because of their low thermal expansion, conformability to surfaces over large areas, and flexibility. The primary objective was to evaluate the aspects of polymer-derived ceramic routs, focusing on the UV lithography process of preceramic polymers and the pyrolyzing properties of the final ceramics. We found that the p(DMS-co-AMS) copolymer was effective in scattering the hydrophilic Al2O3 nanoparticles into the exceedingly hydrophobic solvent. The physico-chemical behavior of characterized copolymers was explored during their pyrolytic transformation into amorphous silicon-based ceramics. The results indicate that an increase of the pyrolysis temperature degraded the Si-O network through the carbothermic reaction of silicon. We also found a rapid elimination of copolymer pores and densification when the temperature increased (1100 to 1200 °C). At different but specific temperature ranges, there are different distinct rearrangement reactions in the conversion of polymer to ceramic; reductions of the melting point (Tm) of the total heat of melting (ΔHm) of the pyrolysis process resulted in the crystallization of ceramic materials; hence, lithography based on pyrolysis properties of preceramic polymers is a critical method in the conversation of polymers.

Preparation and structure of SiOCN fibres derived from cyclic silazane/poly-acrylic acid hybrid precursor.

Ceramic matrix composite (CMC) materials have been considered a desired solution for lightweight and high-temperature applications. Simultaneously, among all different CMC reinforcements, polymer-derived ceramic (PDC) fibres have gained attention for the intrinsic thermal stability and mechanical strength with simple and cost-effective synthesis techniques. Here, carbon-rich SiOCN fibres were synthesized via hand-drawing and polymer pyrolysis of a hybrid precursor of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasilazane (TTCSZ) and poly-acrylic acid (PAA). The type of silazane reported in this work is considered as a major precursor for SiCN; however, it is unspinnable, due to its unfavourable physical properties (low viscosity) and chemical structure (cyclic rather than linear structure). The introduction of PAA to TTCSZ to create a hybrid precursor remarkably improved the spinnability of the silazane and should be widely applicable to other unspinnable PDC pre-ceramic polymers. Investigations on the structural and compositional development of the fibres were mainly conducted via Raman spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, nuclear magnetic resonance and thermo-gravimetric analysis to determine spinnability, free carbon content, cross-linking and pyrolysis behaviour of the fibres, respectively.

Microbial fuel cell performance of graphitic carbon functionalized porous polysiloxane based ceramic membranes.

Proton-conducting porous ceramic membranes were synthesized via a polymer-derived ceramic route and probed in a microbial fuel cell (MFC). Their chemical compositions were altered by adding carbon allotropes including graphene oxide (GO) and multiwall carbon nanotubes into a polysiloxane matrix as filler materials. Physical characteristics of the synthesized membranes such as porosity, hydrophilicity, mechanical stability, ion exchange capacity, and oxygen mass transfer coefficient were determined to investigate the best membrane material for further testing in MFCs. The ion exchange capacity of the membrane increased drastically after adding 0.5 wt% of GO at an increment of 9 fold with respect to that of the non-modified ceramic membrane, while the oxygen mass transfer coefficient of the membrane decreased by 52.6%. The MFC operated with this membrane exhibited a maximum power density of 7.23 W m-3 with a coulombic efficiency of 28.8%, which was significantly higher than the value obtained using polymeric Nafion membrane. Hence, out of all membranes tested in this study the GO-modified polysiloxane based ceramic membranes are found to have a potential to replace Nafion membranes in pilot scale MFCs.

Polymer-Derived Silicon Oxycarbide Ceramics as Promising Next-Generation Sustainable Thermoelectrics.

We demonstrate the potential of polymer-derived ceramics (PDC) as next-generation sustainable thermoelectrics. Thermoelectric behavior of polymer-derived silicon oxycarbide (SiOC) ceramics (containing hexagonal boron nitride (h-BN) as filler) was studied as a function of measurement temperature. SiOC, sintered at 1300 °C exhibited invariant low thermal conductivity (∼1.5 W/(m·K)) over 30-600 °C, coupled with a small increase in both Seebeck coefficient and electrical conductivity, with increase in measurement temperature (30-150 °C). SiOC ceramics containing 1 wt % h-BN showed the highest Seebeck coefficient (-33 µV/K) for any PDC thus far.