Synthesis,characterization, and properties of silylene–acetylene preceramic polymers

A series of silylene–acetylene preceramic polymers 3a–e were synthesized by polycondensation reaction of dilithioacetylene with dichlorosilane (H₂SiCl₂) or/and methyldichlorosilane (MeSiHCl₂). Their structures were confirmed by infrared spectra (IR), and ¹H and ²⁹Si NMR spectroscopies. Differential scanning calorimetry (DSC) diagrams show exotherms centered at 200 to 233°C temperature range, attributed to crosslinking reaction of the acetylene and Si? H groups. After thermal treatment, the obtained thermosets 4a–e possess excellent thermal stability. Thermogravimetric analysis (TGA) under nitrogen show the T_d5s (temperature of 5% weight loss) for all the thermosets are above 600°C, and the overall char yields are between 95.62% and 89.67% at 900°C. After pyrolysis at 1200°C, the obtained ceramic residues 5a–e exhibit good thermo‐oxidative stability with final weight retention between 98.76% and 91.66% at 900°C under air. In particular, perhydroploy(silylene)ethynylene 3a , which has the highest Si/C ratio in silylene–acetylene polymers, has the highest char yield, and the derived ceramic material 5a displays the best thermo‐oxidative stability. Based on Scanning electron microscopy and its associated energy‐dispersive X‐ray microanalysis (SEM EDX) and ¹³C magic angle spinning nuclear magnetic resonance (MAS NMR) analysis, ceramic 5a contains the highest SiC content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

ZrB2–SiC–G Composite Prepared by Spark Plasma Sintering of In‐Situ Synthesized ZrB2–SiC–C Composite Powders

To avoid introduction of milling media during ball‐milling process and ensure uniform distribution of SiC and graphite in ZrB₂ matrix, ultrafine ZrB₂–SiC–C composite powders were in‐situ synthesized using inorganic–organic hybrid precursors of Zr(OPr)₄, Si(OC₂H₅)₄, H₃BO₃, and excessive C₆H₁₄O₆ as source of zirconium, silicon, boron, and carbon, respectively. To inhabit grain growth, the ZrB₂–SiC–C composite powders were densified by spark plasma sintering (SPS) at 1950°C for 10 min with the heating rate of 100°C/min. The precursor powders were investigated by thermogravimetric analysis–differential scanning calorimetry and Fourier transform infrared spectroscopy. The ceramic powders were analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The lamellar substance was found and determined as graphite nanosheet by scanning electron microscopy, Raman spectrum, and X‐ray diffraction. The SiC grains and graphite nanosheets distributed in ZrB₂ matrix uniformly and the grain sizes of ZrB₂ and SiC were about 5 μm and 2 μm, respectively. The carbon converted into graphite nanosheets under high temperature during the process of SPS. The presence of graphite nanosheets alters the load‐displacement curves in the fracture process of ZrB₂–SiC–G composite. A novel way was explored to prepare ZrB₂–SiC–G composite by SPS of in‐situ synthesized ZrB₂–SiC–C composite powders.     

Synthesis,Characterization, and Microstructure of Hafnium Boride‐Based Composite Ceramics Via Preceramic Method

The ceramic precursor for HfB₂/HfC/SiC/C was prepared via solution‐based processing of polyhafnoxanesal, linear phenolic resin, boric acid and poly[(methylsilylene)acetylene)]. The obtained precursor could be cured at 250°C and subsequently heat treated at relative lower temperature (1500°C) to form HfB₂/HfC/SiC/C ceramic powders. The ceramic powders were characterized by element analysis, thermal gravimetric analysis, X‐ray diffraction, Raman spectroscopy, and Scanning electron microscopy. The results indicated that the ceramic powders with particle size of 200~500 nm were consisted of pure phase HfB₂, HfC, and SiC along with free carbon as fourth phase with low crystallinity.     

Microscopic and Spectroscopic Characterization of Stacking‐Sequence Disordered SiC

Nanometric silicon carbide (SiC) powder (~5 nm) with a stacking‐sequence disordered structure (SD‐SiC), synthesized from elemental powders of Si and C, was investigated by microscopic and several spectroscopic methods. The structure of SD‐SiC was characterized by transmission electron microscopy (TEM), ¹³C, and ²⁹Si‐NMR, and by infrared (IR), Raman, and X‐ray photoelectron spectroscopy (XPS) methods. TEM characterizations showed relatively large deviations of the lattice parameters in the as‐synthesized SiC, indicative of the presence of stacking‐sequence disorder. IR analysis showed a weaker Si‐C bond in the SD‐SiC than in the 3C‐SiC. XPS determinations showed that C and Si in SD‐SiC are similar to those in 3C‐SiC. Broader peaks of ²⁹Si and ¹³C MAS‐NMR also indicate that the structure of SD‐SiC is different from that of 3C‐SiC. Raman spectroscopy exhibited activities for the crystalline polytypes and the amorphous of SiC but lack of them for the SD‐SiC. The inactivity of Raman spectroscopy for the SD‐SiC along with large deviation of the lattice constant and the extremely broad X‐ray diffraction peaks would indicate that SD‐SiC is a possible intermediate state between conventional polytype SiC and amorphous SiC, that is, a possible new type of SiC.     

Highly Conductive p‐Type Zinc blende SiC Thin Films Fabricated on Silicon Substrates by Magnetron Sputtering

Polycrystalline silicon carbide (SiC) thin films were fabricated on Si(100) substrates using radio‐frequency magnetron sputtering followed by annealing at 1300°C in an Ar atmosphere. The SiC films exhibited a zinc blende structure with planar and point defects as detected by X‐ray diffraction and Raman spectroscopy. The SiC films were p‐type conductive with electrical resistivity as low as 2.8 × 10^?3 Ω·cm at room temperature. The p‐type character of the SiC films can be explained in terms of the Si vacancies in the C‐rich environment as evidenced by Raman spectroscopy.     

Resistance of 2ZrO2·Y2O3 top coat in thermal/environmental barrier coatings to calcia‐magnesia‐aluminosilicate attack at 1500°C

Internally cooled, hollow SiC‐based ceramic matrix composites (CMCs) components that may replace metallic components in the hot section of future high‐efficiency gas‐turbine engines will require multilayered thermal/environmental barrier coatings (T/EBCs) for insulation and protection. In the T/EBC system, the thermally insulating outermost (top coat) ceramic layer must also provide resistance to attack by molten calcia‐magnesia‐aluminosilicate (CMAS) deposits. The interactions between a potential candidate for top coat made of air‐plasma‐sprayed (APS) 2ZrO₂·Y₂O₃ solid‐solution (ss) ceramic and two different CMASs (sand and fly ash) are investigated at a relevant high temperature of 1500°C. APS 2ZrO₂·Y₂O₃(ss) top coat was found to resist CMAS penetration at 1500°C for 24 hours via reaction products that block CMAS penetration pathways. In situ X‐ray diffraction (XRD) studies have identified the main reaction product to be an Ca‐Y‐Si apatite, and have helped elucidate the proposed mechanism for CMAS attack mitigation. Ex situ electron microscopy and analytical spectroscopy studies have identified the advantageous characteristics of the reaction products in helping the CMAS attack mitigation in the APS 2ZrO₂·Y₂O₃(ss) coating at 1500°C. Finally, the Y³⁺ solubility limit and transport behavior are identified as potential comparative tools for assessing the CMAS resistance ability of top‐coat ceramics.     

Synthesis and Characterization of Silicon Carbide Powders Converted from Metakaolin‐Based Geopolymer

Silicon carbide (SiC) ceramic powders were synthesized by carbothermal reduction in specific geopolymers containing carbon nanopowders. Geopolymers containing carbon and having a composition M₂O·Al₂O₃·4.5SiO₂·12H₂O+18C, where M is an alkali metal cation (Na⁺, K⁺, and Cs⁺) were carbothermally reacted at 1400°C, 1500°C, and 1600°C, respectively, for 2 h under flowing argon. X‐ray diffraction and microstructural investigations by SEM/EDS and TEM were made. The geopolymers were gradually crystallized into SiC on heating above 1400°C and underwent significant weight loss. SiC was seen as the major phase resulting from Na‐based geopolymer heated to ≥1400°C, even though a minor amount of Al₂O₃ was also formed. However, phase pure SiC resulted with increasing temperature. While a slight increment of the Al₂O₃ amount was seen in potassium geopolymer, Al₂O₃ essentially replaced cesium geopolymer on heating to 1600°C. SEM revealed that SiC formation and a compositionally variable Al₂O₃ content depended on the alkaline composition. Sodium geopolymer produced high SiC conversion into fibrous and globular shapes ranging from ~5 μm to nanosize, as seen by X‐ray diffraction as well as SEM and TEM, respectively.     

In Situ Gas–Solid Reaction and Oxidation Resistance of Silicon Carbide Coating on Carbon Fibers

Silicon carbide (SiC) coating on carbon fibers was realized based on in situ low‐temperature gas–solid reaction processing in which carbon reacted with Si vapor at the temperature of 1200°C–1300°C. X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and energy‐dispersive spectroscopy (EDS) analysis showed that the SiC coating was uniform and crystallized by beta‐SiC. The oxidation resistant properties of the SiC‐coated carbon fibers were significantly improved according to isothermal oxidation measurement. The initial oxidation temperature of the SiC‐coated carbon fibers was about 200°C higher than that of the raw carbon fibers. The SiC‐coating carbon fibers treated at 1250°C possessed higher antioxidant property than the one treated at 1300°C.     

Structural evaluation and mechanical property of boron nitride fibers during melt‐drawn fabrication process

Boron nitride (BN) fibers were fabricated on a large scale through the melt‐drawn technique from low‐cost boric acid, NH₃, and N₂. Evolution of structure and properties of BN fibers during the fabrication process was studied by Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), scanning electron microscope (SEM), and X‐ray photoelectron spectroscopy (XPS). The mechanical properties of BN fibers were tested and analyzed. The results shown that both the mechanical properties and the crystallinity of BN fibers slightly increased with the temperature from 450 to 850°C, due to the combination of the fused‐B₃N₃. For BN fibers heat‐treated at 850 or 1000°C, the tensile strength (σ^R) and elastic modulus (E) were strongly increased because of the increase in crystallization of the BN phase. The meso‐hexagonal BN fibers with a diameter of 5.0 μm were fabricated at 1750°C, of which the tensile strength (σ^R) and elastic modulus (E) are 1200 MPa and 85 GPa, respectively. BN fibers with excellent mechanical properties and proper diameters were obtained by nitriding of green fibers during their conversion into ceramic.     

Synthesis,cure and pyrolysis behavior of heat‐resistant boron‐silicon hybrid polymer containing acetylene

The synthesis and characterization of a novel heat‐resistant boron‐silicon hybrid polymer containing acetylene (PBSA) and its conversion to a highly crosslinked thermoset were discussed. The polymer was synthesized from phenylboron dichloride using Grignard reagent method. The structure of PBSA was characterized by using Fourier transform infrared spectra, ¹H‐NMR, ¹³C‐NMR, and gel permeation chromatography. PBSA was thermosetting, highly heat‐resistant, high‐viscous, orange liquid at room temperature and good solubility in common organic solvents. Differential scanning calorimetry and thermogravimetric analysis analyses showed that the PBSA had excellent thermal and oxidative stability and the temperature of 5% weight loss (Td₅) were 650 and 638°C under nitrogen and air, respectively, and the residue at 1000°C were 93.3 and 91.3%, respectively, which indicated that the incorporation of boron and silicon into polymeric backbone was found to improve thermal and oxidative properties. X‐ray diffraction and scanning electron microscope were also used to analyze the formation of pyrolytic products. The results showed that the pyrolysis of PBSA resin was made up of β‐SiC and graphite. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The synthesis of SiCON ceramics through precursor method

A polymeric precursor, polysiloxazane (PSON), for SiCON ceramics has been synthesized by the partial hydrolysis of MeViSiCl₂, MeHSiCl₂, and MeSiCl₃ followed by ammonolysis reaction of the hydrolyzed intermediates with NH₃. The structure and thermal properties of the polymeric precursor were investigated by means of Fourier transfer infrared spectra (FTIR), ¹H‐NMR, ²⁹Si‐NMR, gel permeation chromatography, and thermogravimetric analysis. The structure of the SiCON ceramics derived from the pyrolysis of PSON was characterized by FTIR and X‐ray diffraction. The as‐synthesized PSON produced mainly α‐Si₃N₄ crystalline phase during pyrolysis at 1500°C under N₂ atmosphere, whereas when pyrolyzed at 1500°C under Ar atmosphere, crystalline phases of α/β‐SiC and/or α‐Si₃N₄ were detected. © 2012 Wiley Periodicals, Inc. J fAppl Polym Sci, 2012     

Structure and properties of polycarbosilane synthesized from polydimethylsilane under high pressure

The polycarbosilane (PCS), which is the precursor of SiC fiber, was synthesized under high pressure by thermal decomposition of polydimethylsilane. The composition, structure, and properties of the PCS were characterized by the measurements of softening point, elemental analysis, IR, GPC, NMR, TG‐DTG‐DTA, XRD, and oxidative reaction activity, respectively. Structure model of the PCS was therefore inferred. The results showed that the PCS was the polymer with a Si? C backbone with M_n about 1587. IR and NMR showed the presence of SiC₄ and SiC₃H structure units containing Si? CH₃, Si? CH₂? Si, and Si? H groups. The ratio between H in C? H bond and H in Si? H bond was about 8.84 with SiC₃H/SiC₄ and about 0.51 from ¹H NMR and ²⁹Si NMR, respectively. Elemental analysis gave an empirical formula of SiC_1.87H_7.13O_0.03. TG analysis showed that the ceramic yield of the PCS at 1200°C in a N₂ flow was about 78.9%. β‐SiC microcrystal could be obtained when PCS was pyrolyzed at 1250°C with the crystal size about 37.5 Å. Compared with the PCS with similar softening point synthesized under normal pressure, the PCS synthesized under high pressure had approximate elemental composition, higher Si? H bond content and reaction activity, higher molecular weight, and higher ceramic yield, but lower ratio of SiC₃H and SiC₄. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1188–1194, 2006     

Synthesis and Spark Plasma Sintering of Mg2Si Nanopowder by Mechanical Alloying and Heat Treatment

In this investigation, a two‐step method for the preparation of magnesium silicide (Mg₂Si) nanopowder was studied. This method is known as mechanical alloying followed by heat treatment. The results showed that the compositions of the combustion products depended on the milling time, heat treatment temperature, and starting mixtures. Pure Mg₂Si nanopowder was formed after short milling time and heat treatment, from Mg and Si powders with the mole ratio of 2.1:1 (Mg:Si) at 500°C in Ar atmosphere. Using the Mg₂Si nanopowder, Mg₂Si ceramic was produced by spark plasma sintering at 800°C under 50 MPa for 15 min. Composition and structure of reactants and products were examined by X‐ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM) and high‐resolution transmission electron microscopy (HR‐TEM).     

Thermal cure behavior and pyrolysis of methyl‐tri(phenylethynyl)silane resin

A polyfunctional organic–inorganic hybrid monomer, methyl‐tri(phenylethynyl)silane (MTPES) could be thermally polymerized by a free radical mechanism to a highly crosslinked structure of interest as a high temperature composite matrix resin. The structural changes during thermal cure process were characterized by fourier transform infrared spectrum and ¹³C‐CP‐MAS‐NMR spectrum. The disappearance of secondary acetylene stretching band at 2166 cm^?1 was used successfully to monitor cure reaction accompanied with the formation of cis‐polyene structure at 1600 and 754 cm^?1. The possible cure mechanism of MTPES was also proposed. The pyrolysis of cured MTPES under a stream of argon to 1450°C gave a ceramic in high yield (81%). Thermal conversion of polymer to ceramic was studied by means of X‐ray diffraction, Raman spectrum, and energy dispersive spectrometer analysis. The results showed that pyrolytic products were made up of β‐SiC, graphite, and glassy carbon. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

White Si–O–C Ceramic: Structure and Thermodynamic Stability

While pyrolysis of a polysiloxane precursor in argon typically produces a black amorphous Si–O–C ceramic containing “free” carbon (sp² carbon), pyrolyzing the same precursor in hydrogen leads to a white amorphous ceramic with a negligible amount of sp² carbon and a considerable hydrogen content. ²⁹Si magic‐angle‐spinning nuclear magnetic resonance (MAS NMR) spectroscopy confirms the existence of very similar bonding environments of Si atoms in the Si–O–C network for both samples. In addition, ¹H NMR spectroscopic measurements on both samples reveal that the hydrogen atoms are bonded mainly to carbon. For the thermodynamic analysis, the enthalpies of formation with respect to the most stable components (SiO₂, SiC, C) of the black‐and‐white Si–O–C samples obtained after the pyrolysis at 1100°C are determined using high‐temperature oxidative drop‐solution calorimetry in a molten oxide solvent. The white ceramic is 6 kJ/g‐atom more stable in enthalpy than the black one. Although the role of hydrogen in the thermodynamic stability of the white sample remains ambiguous, the thermodynamic findings and structural analysis suggest that the existence of sp²‐bonded carbon in the amorphous network of polymer derived Si–O–C ceramics does not provide additional thermodynamic stability to the ceramic.     

Nanocomposites based on copolymers of fluorinated imide and polyhedral oligomeric silsesquioxane macromonomer: microstructure and morphology studies

Towards the development of copolymeric nanocomposites, N‐3(trifluoromethyl)phenyl‐7‐oxanorbornene‐5,6‐dicarboximide (TFI) monomer and a macromonomer of polyhedral oligomeric silsesquioxane (POSS) were synthesized. Ring‐opening metathesis polymerization to copolymerization of specified proportions of the two co‐monomers was carried out. All the monomers and polymers were characterized using Fourier transform IR analysis and ¹H and ²⁹Si NMR. Gel permeation chromatography shows that copolymeric nanocomposites have a lower average molar mass than a homopolymer of TFI (HTFI). TGA shows that the thermal stability of the copolymer is inversely proportional to the proportion of POSS units. DSC studies have demonstrated that the glass transition temperature (T_g) of a nanocomposite possessing 25 wt% POSS is at a higher temperature (180 °C) than that of HTFI (175 °C). Transmission electron microscopy and AFM images of copolymers are consistent with the self‐assembled spherical aggregation of POSS units, while X‐ray diffraction studies have confirmed the homogeneous dispersion of the same units within the nanocomposites. © 2012 Society of Chemical Industry     

Synthesis,characterization, and properties of a polyhedral oligomeric octadiphenylsulfonylsilsesquioxane

A novel polyhedral oligomeric octadiphenylsulfonylsilsesquioxane (ODPSS) was synthesized from octaphenylsilsesquioxane and benzenesulfonyl chloride via a Friedel–Crafts reaction with a high yield. ODPSS was identified by Fourier transform infrared spectroscopy, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI–TOF MS), wide‐angle X‐ray diffraction, and elemental analysis to be a kind of polyhedral oligomeric silsesquioxane of a T₈R₈ structure. ODPSS exhibited superior thermal stability according to thermogravimetric analysis. Its initial thermal decomposition temperature (T_onset) was at 491°C in air and 515°C in nitrogen. Thermal and mechanical properties of epoxy resin (EP) composites with ODPSS added were studied by differential scanning calorimetry and tensile testing. The results show that the incorporation of ODPSS at a low loading content not only improved the glass‐transition temperature of the EP composites but also enhanced their tensile strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40892.     

The Manipulation and Alignment of Silicon Carbide Whiskers for Gallium Nitride Epitaxial Growth

As a substrate candidate for low‐cost III‐nitride thin film growth, 3C–SiC whiskers are employed and manipulated in this work. The alignment of the whiskers is achieved on a patterned 3M Vikuiti^? Brightness Enhancement Film surface. The degree of whisker alignment using this approach is higher than the whiskers lined up by extrusion methods according to X‐ray diffraction (XRD) analysis. The aligned whiskers are transferred from the 3M film and embedded into an alumina matrix by tape casting. A self‐regulating sintering technique for SiC whiskers is used to protect the whiskers from being oxidized in air during sintering at 1600°C. The aligned whiskers are rigidly embedded in the alumina matrix as shown in scanning electron microscopy (SEM) images and energy‐dispersive X‐ray spectrometry energy mapping images. GaN thin films grown by a low‐cost sputtering process on Alumina/SiC as well as Si and SiC as reference materials are characterized by XRD and SEM.     

Microwave Dielectric Properties of Scheelite Structured PbMoO4 Ceramic with Ultralow Sintering Temperature

In this work, a low‐firing microwave dielectric ceramic PbMoO₄ with tetragonal structure was prepared via a solid‐state reaction method. The sintering temperature ranges from 570°C to 670°C. Ceramic samples with relative densities above 97% were obtained when sintering temperature was around 600°C. The best microwave dielectric properties were obtained in the ceramic sintered at 650°C for 2 h with a permittivity ~26.7, a Q × f value about 42 830 GHz (at 6.2 GHz) and a temperature coefficient value of 6.2 ppm/°C. From the X‐ray diffraction, backscattered electron imaging results of the cofired sample with 30 wt% silver and aluminum additive, the PbMoO₄ ceramic was found not to react with Ag and Al at 630°C. The microwave dielectric properties and low sintering temperature of PbMoO₄ ceramic make it a candidate for low‐temperature cofired ceramic applications.     

Effects of starch addition on the characteristics of CoAl2O4 nano pigments

Nanocrystalline cobalt aluminate spinel, CoAl₂O₄, was prepared via a microwave‐assisted solution combustion process applying various mixtures of urea, glycine, and starch as a novel mixed fuel. The effects of starch addition (0, 10, 20, and 30 wt%) on the physical characteristics (e.g. crystallite size and colour) of the blue nano pigments were also investigated. The resultant powders were characterised by means of X‐ray diffraction, scanning electron microscopy, electron dispersive X‐ray analysis, and CIE L*a*b* colour measurements. The presence of a CoAl₂O₄ spinel lattice after calcination of precursors at 600 °C was confirmed by X‐ray diffraction patterns, and the crystallite sizes were ca. 10–39 nm. Colorimetric data pointed to the formation of bright‐blue pigments at low levels of starch addition. Scanning electron microscope images showed that starch enrichment reduced the agglomeration and size of synthesised nanoparticles.