Control of the thermal conductivity of SiC by modifying the polymer precursor

Compared to other methods, the fabrication of SiC from precursors allows designing the microstructure and thus the properties of the ceramic material by adjusting the microstructure of the precursor materials. In this study, we used a divinylbenzene (DVB) isomer mixture to modify the polycarbosilane (PCS) precursor via the chemical modification method. The ceramics derived from the modified precursors showed different thermal conductivities. The SiC prepared from PCS without DVB exhibited a very low thermal conductivity at low and at high temperatures. A proper doping with DVB led to clean SiC grain boundaries, resulting in the typical thermal conductivity behaviour of coarse SiC ceramics. An excess doping with DVB led to the precipitation of free carbon around the SiC grains, resulting in a still suitable thermal conductivity which was between the other two values. The results clearly demonstrate that adjusting the thermal properties by modifying the microstructure is a promising approach.     

Electrical Conductivity of SiOCN Ceramics by the Powder‐Solution‐Composite Technique

SiOCN ceramics have been prepared by the polymer pyrolysis method. The preceramic polymers were synthesized from a polysiloxane cross‐linked with two different N‐containing compounds: a silazane or a ternary amine. The corresponding SiOCN ceramics were obtained by pyrolysis in nitrogen atmosphere at five different temperatures from 1000°C to 1400°C. The electrical conductivity of the powdered SiOCN ceramic samples was determined by the powder‐solution‐composite technique. The results show an increase in room temperature AC conductivity of three orders of magnitude, from ≈10^?5 (S/cm) to ≈10^?2 (S/cm), with increasing pyrolysis temperature from 1000°C to 1400°C. Furthermore, the electrical conductivity of the amine‐derived SiOCN is three to five times higher than that of the silazane‐derived ceramic at each pyrolysis temperature. The combined structural study by Raman spectroscopy and chemical analysis suggests that the increase of electrical conductivity with the pyrolysis temperature is due to the sp³‐to‐sp² transition of the amorphous carbon phase. The higher conductivity of the amine‐derived SiOCN is also discussed considering features like the volume% of the free‐carbon phase and its possible N‐doping.     

Electrically conductive and thermally stable SiC-TiC containing nanocomposites via flash pyrolysis

Flash pyrolysis, which combines conventional pyrolysis with flash sintering, was first conducted to produce polymer derived SiC-TiC nanocomposites. Pre-pyrolysis at 800℃ allows the conversion from titanium isopropoxide (TTIP) modified polysiloxane to an amorphous SiTiOC ceramic. The subsequent application of an electric field gives rise to the formation of turbostratic carbon and creates Joule heating to obtain a sample internal temperature of ~1400℃. The precipitation of β-SiC, TiC, as well as titanium oxides is realized upon carbothermal reduction of extensively phase separated SiO₂ and TiO₂ with carbon. Increasing TTIP content embodies the nanocomposites with prominent electrical percolation behaviors. The electrical transport of the synthesized ceramics follows an amorphous semiconductor mechanism. High thermal stability in air is guaranteed, thanks to the in-situ formed TiC nanocrystals and preferentially reduced amorphous carbon. Flash pyrolyzed nanocomposite with a Ti:Si molar ratio of 0.20 exhibits the highest electrical conductivity (0.696 S/cm) and minimum mass change (~2%) at 1000℃, serving as a competitive candidate for electro-discharge machining (EDM) applications or self-standing conducting devices that must withstand high temperature conditions.     

Polymer derived silicon oxycarbide ceramic monoliths: Microstructure development and associated materials properties

Polymer derived SiOC and SiCN ceramics (PDCs) are interesting candidates for additive manufacturing techniques to develop micro sized ceramics with the highest precision. PDCs are obtained by the pyrolysis of crosslinked polymer precursors at elevated temperatures. Within this work, we are investigating PDC SiOC ceramic monoliths synthesized from liquid polysiloxane precursor crosslinked with divinylbenzene for fabrication of conductive electromechanical devices. Microstructure of the final ceramics was found to be greatly influenced by the pyrolysis temperature. Crystallization in SiOC ceramics starts above 1200?°C due to the onset of carbothermal reduction leading to the formation of SiC and SiO₂ rich phases. Microstructural characterisation using ex-situ X-ray diffraction, FTIR, Raman spectra and microscopy imaging confirms the formation of nano crystalline SiC ceramics at 1400?°C. The electrical and mechanical properties of the ceramics are found to be significantly influenced by the phase separation with samples becoming more electrically conducting but with reduced strength at 1400?°C. A maximum electrical conductivity of 10¹ S?cm^?1 is observed for the 1400?°C samples due to enhancement in the ordering of the free carbon network. Mechanical testing using the ball on 3 balls (B3B) method revealed a characteristic flexural strength of 922?MPa for 1000?°C amorphous samples and at a higher pyrolysis temperature, materials become weaker with reduced strength.     

Porous SiC ceramics with dendritic pore structures by freeze casting from chemical cross-linked polycarbosilane

In this study, a commercial polycarbosilane (PCS) and divinylbenzene (DVB) were used as the preceramic polymer precursor and crosslinking agent, respectively to form porous silicon carbide (SiC) ceramics by freeze casting DVB/camphene/PCS solutions. Porous silicon carbide (SiC) with a dendritic pore structure and connecting bridges was obtained after pyrolysis at 1200 °C. The effects of DVB and PCS content on the rheological properties of the solution and the morphological characteristics and the compressive strengths of SiC ceramics were investigated. The use of DVB and the resulting chemical cross-linking yielded modified pore characteristics and much lower oxygen content in pyrolyzed SiC compared to the conventional thermal curing method. A compressive strength of 18.7 MPa was obtained for pyrolyzed SiC prepared with 20 wt% PCS and a 0.2 DVB/PCS mass ratio.     

The effect of B‐doping on the electrical conductivity of polymer‐derived Si(B)OC ceramics

In this work the room temperature electrical conductivity of Si(B)OC glasses made via polymer pyrolysis at 1200°C and 1400°C (maximum temperature) and having different amount of boron was measured. When B content is increased from zero (pure SiOC glass) up to B/Si=0.5 the electrical conductivity increases in 2 orders of magnitude from 4.09±0.64×10^?5 up to 2.93±1.91×10^?3 with a corresponding decrease in the activation energy from about 1.08 to 0.51 eV. This results shows for the first time that the electrical conductivity of Si‐based polymer‐derived ceramics can be controlled by the amount of the doping element. The structure of the Si(B)OC glasses has been studied with different techniques including FT‐IR, XRD and Raman spectroscopy. The Raman study indicates that B partially substitutes C into the sp² C planes of the free carbon phase forming trigonal BC₃ units. Accordingly, the evolution of the electrical properties with the B content has been correlated with the corresponding structural evolution and a hypothesis is presented to rationalize the role of boron on the electrical conductivity of SiOBC glasses.     

Microstructure,conductivity and mechanical properties of calcia stabilized zirconia ceramics obtained from nanosized precursor and reduced graphene oxide doped precursor powders

In the work 12CaO-88ZrO₂ (12CSZ, mol%) ceramics was manufactured both from nanopowder, obtained via cryochemical technique, and composite precursor 12CSZ?+?0.25?wt% rGO (reduced graphene oxide). Via SEM, XRD and Raman spectroscopy the detailed investigation of the effect of the precursor type and intermediate processing on the microstructure and electrical conductivity of ceramics was carried out. It was shown that rGO is completely removed during the annealing at 1550?°C for 3?h in air with no effect on the high ionic conductivity of ceramics. The use of nanosized powder and the additional processing step results in vacuum dense solid electrolytes characterized by well-formed cubic zirconia based solid solution, thin discontinuous grain boundaries and rather high ionic conductivity. The addition of rGO leads to slight microhardness (HV) decrease comparing to ceramics manufactured from the nanosized precursor. As a result, a new technique for zirconia based solid electrolytes having both high electrical conductivity at high temperatures and sufficient mechanical properties was suggested.     

SiAlCN型PDC陶瓷的研究进展

综述了SiAlCN型PDC（Polymer Derived Ceramics）陶瓷的制备、性能和应用。SiAlCN陶瓷有四类制备方法：粉末混合型：聚硅氮烷陶瓷前驱体与氧化铝粉末直接混合;粉末溶解型：含铝化合物粉末溶解于聚硅氮烷前驱体溶液中;单源前驱体型：铝原子通过适当的含铝化合物接枝在聚硅氮烷主链上,生成一种单源陶瓷前驱体聚铝硅氮烷;聚合物混合型：两种聚合物即聚硅氮烷与含铝聚合物共混;然后交联裂解制备陶瓷。与无Al的Si/C和Si/C/N体系相比,SiAlCN陶瓷具有优异的抗蠕变性、更好的抗氧化性和耐腐蚀性以及更好的导热性。因此,聚合物衍生的硅铝碳氮化物(SiAlCN)陶瓷是在高温和恶劣环境中应用很有潜力的材料。     

Influence of carbon enrichment on electrical conductivity and processing of polycarbosilane derived ceramic for MEMS applications

An analysis about the effect of carbon enrichment of allylhydridopolycarbosilane SMP10^® with divinylbenzene (DVB) as a promising material for electrical conductive micro-electrical mechanical systems (MEMS) is presented. The liquid precursors can be micropipetted and cured in polytetrafluoroethylene (PTFE) molds to produce 14 mm diameter disc shaped samples. The effect of pyrolysis temperature and carbon content on the electrical conductivity is discussed. The addition of 28.7 wt.% of DVB was found to be the optimum amount. Carbon was preserved in the microstructure during pyrolysis and the ceramic yield increased from 77.5 to 80.5 wt.%. The electrical conductivity increased from 10⁻⁶ to 1 S/cm depending on the annealing temperature. Furthermore, the ceramic samples obtained with this composition were found to be in many cases crack free or with minimal cracks in contrast with the behavior of pure SMP10. Using the same process we demonstrate that also microsized ceramic samples can be produced.     

Structure and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites

The incorporation of SiOC polymer‐derived ceramics into porous carbon materials could provide tailored shapeable, mechanical, electrical, and oxidation‐resistant properties for high‐temperature applications. Understanding the thermodynamic and kinetic stability of such materials is crucial for their practical application. We report here the dependence of structures and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites (CBCFs) on the pyrolysis temperature using spectroscopic methods and high‐temperature oxide melt solution calorimetry. The results indicate that a SiOC ceramic pyrolyzed at 1200°C and 1600°C is energetically stable with respect to an isocompositional mixture of cristobalite, silicon carbide, and graphite by 4.9 and 10.3 kJ/mol, respectively, and more energetically stable than that pyrolyzed at 1450°C. Their thermodynamic stability is related to their structural evolution. SiOC‐modified CBCFs become energetically less stable with increasing preparation temperature and concomitant increase in excess carbon content.     

Effect of hot-pressing sintering on thermal and electrical properties of AlN ceramics with impedance spectroscopy and dielectric relaxations analysis

The effects of hot-pressing sintering on the phase composition, microstructure, thermal and electrical properties of AlN ceramics with CeO₂–CeF₃ additives were studied. During hot-pressing sintering, high pressure reduced the grain boundary phase CeAlO₃ and decreased the concentration of oxygen in AlN ceramics. The hot-pressing sintered AlN samples had a much higher thermal conductivity of 191.9 W/m·K than pressureless sintered ones because of the great reduction of grain boundary phases and oxygen impurities in AlN ceramic. As the carbon content in hot-pressing sintered sample was very high, carbon contamination led to the decrease in electrical resistivity and changes in polarization mechanisms for AlN ceramics. The relaxation peak in the dielectric temperature spectrum with an activation energy of 0.64 eV for hot-pressing sintered samples was caused by electrons from free carbon at low temperature. Overall, hot-pressing sintering can effectively increase the thermal conductivity and change the electrical properties of AlN ceramics.     

Thermal and Electrical Conductivity of Amorphous and Graphitized Carbide‐Derived Carbon Monoliths

The influence of graphitization and composition of carbide‐derived carbon (CDC) monoliths on the electrical and thermal conductivity was investigated. Carbon monoliths with varying porosities were synthesized employing biomorphous macroporous TiC and SiC as precursors. Graphitization was carried out in situ during high‐temperature chlorination with and without addition of nickel, iron, and cobalt chloride to the carbide. The graphitized monoliths showed improved properties. The results demonstrate that despite graphitic carbon also glass‐like carbon, stemming from the carbide synthesis, increases the thermal and electrical conductivity significantly.     

Enhanced piezoresistivity of polymer-derived SiCN ceramics by regulating divinylbenzene-induced free carbon

In-situ formed free carbon nanodomain is an unique feature of polymer-derived ceramics (PDCs), which plays a significant role to affect the properties of PDCs, especially for the electoral property and piezoresistivity. In this study we report an enhanced piezoresistive properties of amorphous silicon carbonitrides (SiCN) ceramics derived by divinylbenzene (DVB)-modified polysilazane. Microstructure analysis indicated that the free carbon phase in SiCN ceramics is gradually increasing in order degree and concentration with increasing content of DVB. The average spacing between the conducting particles decreases with increasing concentration of free carbon, resulting in an enhanced internal electric field. The effects of DVB concentration on the piezoresistive properties of SiCN ceramics are also discussed, finding that the DVB has a significant effect on the piezoresistive properties.     

Thermophysical property and electrical conductivity of titanium isopropoxide – polysiloxane derived ceramics

In this study, high temperature resistant Si-O-C-Ti has been successfully prepared based on the pyrolysis of polysiloxane (PSO) and titanium (IV) isopropoxide (TTIP) at 1200–1400 °C. PSO can homogeneously mix with TTIP to enhance its conversion to TiC. The carbothermal reactions between TiO₂ (product of thermal decomposition of TTIP) and carbon result in the formation of TiC. All the Si-O-C-Ti composites pyrolyzed at 1200–1300 °C are stable up to 1000 °C in an oxidizing air atmosphere. TiC leads to high electrical conductivity at elevated temperatures; the maximum conductivity is 1176.55 S/m at 950 °C, which is the first reported value of >1000 S/m conductivity for Si-O-C-Ti ceramics. However, too high a pyrolysis temperature, such as 1400 °C, can potentially ‘destabilize’ the Si-O-C-Ti system by consuming the free carbon and result in lower conductivities.     

Hybrid carbon nanotubes/graphene modified acrylic coats

Water-borne one-component acrylic coating compositions and coats modified with carbon nanotubes (CNT), graphene (GN), as well as hybrid carbon nanofillers (CNT/GN mixtures) have been prepared and evaluated. These coating materials were successfully formulated on a basis of commercial components, i.e. acrylic resin aqueous dispersion, CNT and/or GN and auxiliary agents. Influence of a kind and ratio of incorporated carbon nanofillers on the following coats properties was investigated: electrical surface resistivity, transparency, gloss, mechanical (hardness and cross-cut adhesion) and thermal properties (glass transition temperature, storage modulus and thermal stability). The presence of carbon nanostructure significantly improved electrical conductivity, hardness, storage modulus and thermal stability of the coats. Moreover, the nanofillers did not negatively influence adhesion and glass transition temperature.     

Flash pyrolysis of polymer-derived SiOC ceramics

For the first time, flash pyrolysis was carried out to fabricate polymer derived silicon oxycarbide (SiOC) ceramics. With the application of a DC electric field at a furnace temperature of only 780?°C, the SiOC ceramics exhibit characteristics that usually have to be pyrolyzed at ～1300?°C. Both electric field and current density accelerate the SiOC microstructure development, causing carbon and SiC phases to form at >520?°C lower pyrolysis temperatures than conventional within the SiOC matrix. With higher electric fields, the samples experience greater mass loss and linear shrinkage, while also forming more SiC and a more ordered carbon phase. The SiC formation inversely impacts the carbon content, causing a decrease in electrical conductivity. Further, reducing current density results in significant carbon precipitation without SiC formation. The fundamentals can be explained based on increased nucleation rate by the electrical field, accompanied by Joule heating and electromigration. This work is the first to demonstrate the great potential of flash pyrolysis on accelerated phase separation of polymer derived SiOC.     

Pressureless sintering of multilayer graphene reinforced silicon carbide ceramics for mechanical seals

ABSTRACT

The silicon carbide (SiC) ceramics containing multilayer graphene derived from graphite exfoliation were successfully prepared by pressureless sintering, and the effect of graphene content on the sintering behaviours, microstructure, mechanical, tribological, electrical and thermal properties was investigated in detail. The bulk density, bending strength and hardness of the composite ceramics gradually decrease with the increase of graphene content, but the friction, conductance and thermal conductance properties are improved obviously. When the graphene content reaches 5?wt-%, the dry friction coefficient of 0.22, electrical conductivity of 2724.14 S?1?m?1 and thermal conductivity of 8.5?W?(m?1?K?1) can be obtained, indicating good comprehensive mechanical, tribological, electrical and thermal properties. This multilayer graphene reinforced silicon carbide ceramic is a promising seal material instead of SiC seal materials containing graphite to be applied in next-generation mechanical seals.     

The role of carbon in microstructure evolution of SiBCO ceramics

The composition of polymer derived ceramics could be readily tuned through controlling the structure and element content of the polymer precursors, and investigation on the effect of the element on microstructure evolution is important to the design of advanced ceramics. In this article, the effect of carbon content in SiBCO polymer precursors was systematically investigated. The polymer network and thermal stability of polymer precursors and the carbon content of pyrolyzed SiBCO ceramic could be readily tuned by controlling the DVB amount used. Carbon contributed to the formation of graphitic carbon in SiBC_xO ceramics and inhibited the growth of β–SiC and SiO₂ crystals at 1600 °C, but lead to an increase in the graphitic carbon phase at 1800 °C.     

Fabrication of dense polymer‐derived silicon carbonitride ceramic bulks by precursor infiltration and pyrolysis processes without losing piezoresistivity

Dense polymer‐derived silicon carbonitride (SiCN) ceramic bulks were fabricated by powder consolidation following precursor infiltration and pyrolysis (PIP) densification. The density and open porosity of the ceramics varied from 1.42 g/cm³ and 32.75% before the PIP to 2.29 g/cm³ and 3.64% after the PIP, respectively. The electrical conductivity of the ceramics sharply increased from 6.26 × 10^?10 S/cm before the PIP process to 3.20 × 10^?7 S/cm after the 1st cycle of PIP and then gradually increased to 6.89 × 10^?6 S/cm after four cycles of PIP. However, the piezoresistive coefficient did not change with the PIP. The Raman and electron paramagnetic resonance results show that the graphitization level of free carbon in ceramics derived from PIP was higher than the ceramics derived from powder consolidation. The high graphitization level of free carbon leads to a high conductivity, and thus the conductivity of ceramics increased significantly after the PIP process. The carbon cluster size, which is related to the gauge factor of piezoresistivity, did not change significantly after the PIP process; thus, the gauge factor did not change significantly. Dense, large‐scale polymer‐derived ceramics were fabricated by combined conventional powder consolidation and PIP without the loss of piezoresistivity. These ceramics have potential application as both structural and functional components that can bear loads as well as monitor variations in external stress.     

Polymer precursor‐derived HfC–SiC ultrahigh‐temperature ceramic nanocomposites

Due to poor mechanical properties and antioxidation properties, etc of single phase ultrahigh‐temperature ceramics (UHTCs), the second phase such as SiC was usually introduced for improving those properties. Herein, a novel stratagem for synthesis of binary HfC–SiC ceramics has been presented. A Hf–O–Hf polymer as a HfO₂ precursor has been synthesized for preparing soluble HfC–SiC precursors with high solid content and low viscosity solutions without additional organic solvents. The structure of PHO was characterized by FTIR and ¹H‐NMR, the crystalline behavior and morphologies of polymer‐derived ceramics were identified by XRD, SEM‐EDS, and TEM. It was shown that PHO firstly transformed into HfO₂, and then reacted with in situ carbon derived from DVB and PCS thus producing cubic HfC through carbothermal reduction. In addition, the obtained HfC–SiC nanopowders exhibited spherical morphology with a diameter less than 100 nm, while the Hf, Si, and C are homogeneously distributed.