Dielectric and EMW absorbing properties of PDCs-SiBCN annealed at different temperatures

Polymer derived SiBCN ceramics (PDCs-SiBCN) were prepared from polyborosilazane and then annealed at 1200–1800 °C in N₂. Effects of annealing temperature on the microstructure, phase composition, dielectric and wave-absorbing properties of ceramics were investigated. Results showed that nano-sized SiC grains were formed in amorphous SiBCN after annealing and the content and crystallization degree of SiC gradually intensified with annealing temperature increasing. The permittivity, dielectric loss and electrical conductivity of PDCs-SiBCN gradually increased as the temperature rose due to the formation of conductivity network of SiC grains and the increase of nano-grain boundary. The increased content of SiC (as the dipole) and interface between SiC nano-grains and amorphous SiBCN phase led to a higher polarization ability and higher dielectric loss. The RC gradually decreased with the annealing temperature increasing, demonstrating the annealed ceramics had the superior wave-absorbing ability and high annealing temperature was conducive to the improvement of wave-absorbing property.     

Effects of 1600 °C annealing atmosphere on the microstructures and mechanical properties of C/SiC composites fabricated by precursor infiltration and pyrolysis

Effects of 1600 °C annealing atmosphere on microstructures and mechanical properties of the C/SiC composites fabricated by PIP route were remarkable. Due to carbothermic reductions, the ratios of weight loss of the C/SiC composites were all above 7 wt% in 1 h. Consequently, the mechanical properties all had a significant drop during the first hour of annealing because of the bonding between the fibers and matrix remarkably weaken by cracks and pores. And then the flexural strengths gradually decreased with the annealing time increasing, when the flexural moduli slightly changed within the range of 44.2–49.7 GPa. However, the fracture behaviors of the C/SiC composites annealed under Ar faster became brittle than the C/SiC composites annealed under vacuum. The C/SiC composites annealed under Ar for 5 h and under vacuum for 10 h both became brittle mainly due to the sensitive to annealing of the weak carbon interphase, while the C/SiC composites annealed under Ar for 7 h became brittle mainly due to the chemical bonding between the fibers and matrix. And these phenomena were confirmed by the post densification and the stress-releasing annealing.     

Texture and Fracture Toughness Anisotropy in Silicon Carbide

Quantitative texture analysis, which included calculation of the orientation distribution function, was used to demonstrate textures in hot-pressed and subsequently annealed silicon carbide (SiC). The results indicated that the hot pressing and annealing could produce strong textures in SiC. Grain rotation during hot pressing and preferred grain growth of plate-shaped α-SiC grains during annealing both apparently contributed to texture development in the SiC materials. The {111} pole figure in hot-pressed material (mostly ß-SiC) and the (004) pole figure in annealed material (mostly α-SiC) were consistent with the microstructural observations. The fracture toughness of hot-pressed and annealed material measured parallel to the hot-pressing direction (5.7 MPam^1/2) was higher than that measured perpendicular to the hot-pressing direction (4.4 MPam^1/2), because of the texture and the microstructural anisotropy.     

Mechanical Characterization of Annealed ZrB2–SiC Composites

Composites consisting of 70 vol% ZrB₂ and 30 vol% α‐SiC particles were hot pressed to near full density and subsequently annealed at temperatures ranging from 1000°C to 2000°C. Strength, elastic modulus, and hardness were measured for as‐processed and annealed composites. Raman spectroscopy was employed to measure the thermal residual stresses within the silicon carbide (SiC) phase of the composites. Elastic modulus and hardness were unaffected by annealing conditions. Strength was not affected by annealing at 1400°C or above; however, strength increased for samples annealed below 1400°C. Annealing under uniaxial pressure was found to be more effective than annealing without applied pressure. The average strength of materials annealed at 1400°C or above was ~700 MPa, whereas that of materials annealed at 1000°C, under a 100 MPa applied pressure, averaged ~910 MPa. Raman stress measurements revealed that the distribution of stresses in the composites was altered for samples annealed below 1400°C resulting in increased strength.     

Microstructure evolution upon annealing of a ZrB2–SiC composite containing lanthana and magnesia

The purpose of this work was to produce a dense ZrB₂–SiC ceramic and to identify a suitable annealing cycle to crystallize the glassy phase and promote SiC growth along the c axis. The concept behind this work exploits the irreversible SiC β → α transformation occurring at temperature above 1900 °C, in such a way to have SiC platelets able to trigger effective toughening mechanisms. La₂O₃ and MgO were used as sintering additives. The as sintered and annealed materials were examined through X-ray diffraction (XRD), to identify the crystalline phases, scanning electron microscope (SEM), to study the distribution of the secondary phases, and transmission electron microscope (TEM), to analyze the microstructure at nanoscale level, with particular attention to new crystalline phases and to the interfaces in high resolution mode. A model for the microstructure evolution during densification and upon annealing is presented.     

Effect of annealing on SiC thin films prepared by pulsed laser deposition

Crystalline cubic SiC thin films were successfully fabricated on Si(100) substrates by using laser deposition combined with a vacuum annealing process. The effect of annealing conditions on the structure of the thin films was investigated by X-ray diffraction and Fourier transform infrared spectroscopy. It was demonstrated that amorphous SiC films deposited at 800°C could be transformed into crystalline phase after being annealed in a vacuum and that the annealing temperature played an important role in this transformation, with an optimum annealing temperature of 980°C. Results of X-ray photoelectron spectroscopy revealed the approximate stoichiometry of the SiC films. The characteristic microstructure displayed in a scanning electron microscope image of the films was indicative of epitaxial growth along the (100) plane.     

Spectroscopic characterization of thin SiC films

The electrical, structural and optical properties of thin SiC films were investigated. A new approach based on high temperature annealing of layered carbon–silicon structures was used for the formation of the films. The SiC films were prepared by deposition of 30 nm thick carbon films on crystalline silicon (c-Si) and on porous silicon layers grown on c-Si. The layers were annealed to temperatures between 800 and 1400°C for different annealing times ranging between 15 and 180 s. The structure of the resulting SiC films was analyzed by Raman spectroscopy. The Raman spectra of as-deposited films consist of two broad bands at 1350 and 1580 cm⁻¹ characteristic of the presence of amorphous carbon. These bands were shifted to lower frequencies in the spectra of annealed layers and were assigned to the hexagonal and cubic SiC phases. The photoluminescence spectra of the studied layers show a broad band at 550 nm. The most intense photoluminescence was observed from non-annealed porous silicon layers covered with thin carbon films. A degradation of the luminescence and a simultaneous increase of the conductivity of the layers with increasing annealing temperature and/or duration of annealing was observed. This behavior strongly suggests the creation of defect states which determine the conductivity of the layers and at the same time act as non-radiative centers. The increase of defect states was explained as originating from the dehydrogenation of the silicon carbide layers by annealing.     

Complex impedance spectra of polymer-derived SiC annealed at ultrahigh temperature

This study reports the complex impedance and alternative current conductivity of polymer-derived ceramic SiC (PDC-SiC) annealed at ultrahigh temperatures. The PDC-SiC shows an inductive response when annealed at temperatures of 1700°C-1900°C due to the percolation of turbostratic carbon. The material returns to a capacitive response at an annealing temperature of 2000°C due to the dissolution of carbon into the SiC lattice. The electrical resistance of the carbon phase decreases with the increase in annealing temperature. These results provide new insights into the effects of processing temperature on microstructure evolution and electrical and dielectric property development of the PDC-SiC ceramic system.     

Facile Synthesis of Calcium Borate Nanoparticles and the Annealing Effect on Their Structure and Size

Calcium borate nanoparticles have been synthesized by a thermal treatment method via facile co-precipitation. Differences of annealing temperature and annealing time and their effects on crystal structure, particle size, size distribution and thermal stability of nanoparticles were investigated. The formation of calcium borate compound was characterized by X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), and Thermogravimetry (TGA). The XRD patterns revealed that the co-precipitated samples annealed at 700 °C for 3 h annealing time formed an amorphous structure and the transformation into a crystalline structure only occurred after 5 h annealing time. It was found that the samples annealed at 900 °C are mostly metaborate (CaB₂O₄) nanoparticles and tetraborate (CaB₄O₇) nanoparticles only observed at 970 °C, which was confirmed by FTIR. The TEM images indicated that with increasing the annealing time and temperature, the average particle size increases. TGA analysis confirmed the thermal stability of the annealed samples at higher temperatures.     

Effect of crystallinity on enthalpy recovery peaks and cold‐crystallization peaks in PET via TMDSC and DMA studies

Poly(ethylene terephthalate) (PET) sheets of different crystallinity were obtained by annealing the amorphous PET (aPET) sheets at 110°C for various times. The peaks of enthalpy recovery and double cold‐crystallization in the annealed aPET samples with different crystallinity were investigated by a temperature‐modulated differential scanning calorimeter (TMDSC) and a dynamic mechanical analyzer (DMA). The enthalpy recovery peak around the glass transition temperature was pronounced in TMDSC nonreversing heat flow curves and was found to shift to higher temperatures with higher degrees of crystallinity. The magnitudes of the enthalpy recovery peaks were found to increase with annealing times for samples annealed ≤30 min but to decrease with annealing times for samples annealed ≥40 min. The nonreversing curves also found that the samples annealed short times (≤40 min) having low crystallinity exhibited double cold‐crystallization peaks (or a major peak with a shoulder) in the region of 108–130°C. For samples annealed long times (≥50 min), the cold‐crystallization peaks were reduced to one small peak or disappeared because of high crystallinity in these samples. The double cold‐crystallization exotherms in samples of low crystallinity could be attributed to the superposition of the melting of crystals, formed by the annealing pretreatments, and the cold‐crystallizations occurring during TMDSC heating. The ongoing crystallization after the cold crystallization was clearly seen in the TMDSC nonreversing heat flow curves. DMA data agreed with TMDSC data on the origin of the double cold‐crystallization peaks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of β-to-α Phase Transformation on the Microstructural Development and Mechanical Properties of Fine-Grained Silicon Carbide Ceramics

Ultrafine β-SiC powders mixed with 7 wt% Al₂O_3, 2 wt% Y₂O₃, and 1.785 wt% CaCO₃ were hot-pressed and subsequently annealed in either the absence or the presence of applied pressure. Because the β-SiC to α-SiC phase transformation is dependent on annealing conditions, the novel processing technique of annealing under pressure can control this phase transformation, and, hence, the microstructures and mechanical properties of fine-grained liquid-phase-sintered SiC ceramics. In comparison to annealing without pressure, the application of pressure during annealing greatly suppressed the phase transformation from β-SiC to α-SiC. Materials annealed with pressure exhibited a fine microstructure with equiaxed grains when the phase transformation from β-SiC to α-SiC was <30 vol%, whereas materials annealed without pressure developed microstructures with elongated grains when phase transformation was >30 vol%. These results suggested that the precise control of phase transformation in SiC ceramics and their mechanical properties could be achieved through annealing with or without pressure.     

Phase evolution and crystallization in Si–B–C–N ceramics derived from a polyborosilazane precursor: microstructural characterization

Amorphous Si–B–C–N ceramic powder samples obtained by thermolysis of polyborosilazane {B[C₂H₄Si(H)NH]₃}_n were isothermally annealed at different temperatures (1400–1800 °C) and hold-times (3, 10, 30, 100 h). Scanning electron microscopy (SEM) of annealed powders as well as polished cross sections of large powder particles from selected samples were carried out to study surface morphology, crystallization and associated microstructural changes. Microstructural and phase evolution were additionally investigated using high-resolution transmission electron microscopy (HRTEM) and energy filtering TEM (EFTEM). Higher surface areas of the powders were found to promote vapor-phase decomposition reactions resulting in SiC whisker growth. In coarser powders the influence of surface is manifested as a skin-core effect, where the ‘skin’ has undergone a higher degree of decomposition accompanied by an increased SiC crystal growth, compared to the ‘core.’ Crystallization of SiC occurs already at 1400 °C, although Si₃N₄ crystallization occurs only at 1700 °C, after more than 3 h of annealing.     

Recrystallization Kinetics of 3C Silicon Carbide Implanted with 400 keV Cesium Ions

Polycrystalline 3C silicon carbide (SiC) was implanted at room temperature with 400 keV cesium ions to a dose of 10¹⁶ ions/cm². The samples were annealed at 600°C–1000°C for times up to 48 h to observe changes in the implantation zone crystallinity and density. The implanted regions were characterized by transmission electron microscopy (TEM) and secondary ion mass spectroscopy (SIMS) before and after annealing. It is shown that the implantation resulted in a 217 ± 2 nm amorphous region with microstructural damage extending to ~250 nm below the surface. Recrystallization of the amorphous region was observed to begin at 725°C. Densification was determined indirectly through changes in the measured implantation zone thickness. Measurable thickness, or densification, of the implanted region was not observed until temperatures greater than ~800°C. The SiC recrystallization began at the interface between the amorphous, damaged region, and the underlying polycrystalline material. Image analysis was used to quantify the fraction of crystalline phase as a function of time and temperature. The recrystallization kinetics exhibited Arrhenius dependency with an apparent activation energy of 480 kJ/mol. SIMS demonstrated that 60%–70% of the cesium was retained within the recrystallized microstructure after thermal annealing.     

Effect of Annealing Conditions on Microstructural Development and Phase Transformation in Silicon Carbide

The effect of annealing with and without applied pressure on the microstructural development and phase transformation was investigated in fine-grained β-SiC ceramics containing α-SiC seeds. Materials annealed without pressure had a microstructure consisting of elongated grains, while materials annealed with pressure showed a duplex microstructure consisting of small matrix grains and some of elongated grains. However, annealing with pressure (25 MPa) was found to greatly retard phase transformation from β→α polytypes and inhibit grain growth. This change in lattice parameter suggests that the retardation of phase transformation and grain growth might be attributed to a reduced mass transport rate, which is the result of Al being introduced into the SiC by the annealing pressure.     

Opto-structural studies of well-dispersed silicon nano-crystals grown by atom beam sputtering

Synthesis and characterization of nano-crystalline silicon grown by atom beam sputtering technique are reported. Rapid thermal annealing of the deposited films is carried out in Ar + 5% H₂ atmosphere for 5 min at different temperatures for precipitation of silicon nano-crystals. The samples are characterized for their optical and structural properties using various techniques. Structural studies are carried out by micro-Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), high resolution transmission electron microscopy, and selected area electron diffraction. The optical properties are studied by photoluminescence and UV-vis absorption spectroscopy, and bandgaps are evaluated. The bandgaps are found to decrease after rapid thermal treatment. The micro-Raman studies show the formation of nano-crystalline silicon in as-deposited as well as annealed films. The shifting and broadening in Raman peak suggest formation of nano-phase in the samples. Results of micro-Raman, photoluminescence, and TEM studies suggest the presence of a bimodal crystallite size distribution for the films annealed at higher temperatures. The results show that atom beam sputtering is a suitable technique to synthesize nearly mono-dispersed silicon nano-crystals. The size of the nano-crystals may be controlled by varying annealing parameters.     

Raman spectroscopy studies of the high-temperature evolution of the free carbon phase in polycarbosilane derived SiC ceramics

The Raman spectra of a number of SiC ceramics synthesized from polycarbosilane at 1200 °C and annealed at 1400, 1600, 1800 and 2000 °C have been recorded using laser excitation wavelength of 532 nm. The peak positions, their intensities (I_D/I_G) and full width at half maximum (FWHM) were used to obtain information about the degree of disorder in the free carbon phases. The increasing ordering with annealing temperature was confirmed by lower FWHM values and G-peak positions obtained from the SiC ceramics annealed at higher temperature. However, the I_D/I_G has shown to be the highest point at 1600 °C, which illustrates that the temperature is one critical point of the microstructure evolution of the free carbon phase changing amorphous to turbostratic with increasing temperatures. Obviously, the oxidation behaviors of the SiC ceramics are significantly affected by the microstructures of the free carbon phases. In the SiC ceramics with above 1600 °C annealing, the oxidation temperatures of the SiC phases are postponed more than 100 °C, because they are surrounded by the free carbon phases.     

Effect of Processing Temperature on the Morphology of Silicon Carbide Whiskers

Two kinds of SiC whiskers were annealed at temperatures similar to those for the processing of ceramic matrix composites. The morphology and structure of the as-received and postannealed whiskers were investigated by SEM, TEM, and XRD, and the influence of processing temperature on the mechanical properties of ceramic matrix composites was discussed.     

Synthesize and crystallization behavior of SiOC/SiC nanocomposites derived from organosilane slurry residue

A route preparing SiOC/SiC nanocomposites directly by pyrolysis of organosilane slurry residue was investigated. Organosilane slurry residue's unique composition, containing both silicon and carbon, offers an intriguing platform for developing advanced ceramic materials. The pyrolysis process is examined comprehensively, revealing the chemical reactions and structural changes leading to SiC crystals formation. The phase evolution at various annealing temperatures was revealed. Crystallization behavior in the process were studied. The results reveal that SiOC matrix was generated at annealed temperature 800°C and SiC nanoparticles were formed at 1300°C. In comparison to phase separation of SiOC, carbothermal reduction of SiO₂ was domain in SiC formation. This research advances the understanding of SiOC/SiC nanocomposites, highlighting the value of repurposing industrial byproducts for sustainable and innovative materials development.     

Surface oxidation behavior in air and O2-H2O-Ar atmospheres of continuous freestanding SiC films derived from polycarbosilane

In this contribution, thermodynamic computational calculations firstly carried out on Ar-Si-C-O/Ar-Si-C-O-H database demonstrate that passive oxidation is main reaction of continuous freestanding SiC films in both air and 14%H₂O/8%O₂/78%Ar atmospheres. SiC films were subsequently annealed at 1300?°C, 1400?°C and 1500?°C for 1?h in air and O₂-H₂O-Ar atmospheres. Results suggest that modulus, hardness and resistivity decrease whereas crystallite size of β-SiC and α-cristobalite increase with elevated annealing temperature. In particular, hardness of wet oxidized samples is lower than that of air oxidized ones. Additionally, their oxidation kinetics models were also established and verified by annealing at 1200?°C in air and wet oxygen for different time from 1?h to 100?h. Oxidation of continuous freestanding SiC films is identified to follow parabolic oxidation kinetics, and water could effectively enhance the oxidation rates. It is revealed that SiO₂ layer can protect SiC films from further oxidation, and their thickness increases with prolonged annealing time. In this study, a dense and uniform SiO₂ layer with a thickness of 1.1–1.6?µm was produced for sacrificial and passivation layer based on suitable thermal oxidation process (annealing at 1000?°C for 5?h in O₂-H₂O-Ar environment). Interestingly, fast diffusion paths in this oxide layer could effectively accelerate oxidation process of SiC films. These obtained achievements would promote further applications of SiC films on microelectromechanical systems (MEMS) devices in harsh environments.     

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Study of Nonstoichiometric Silicon-Carbon-Oxygen Glasses

Crystallization behavior of Si-C-O glasses in the temperature range of 1000°–1400°C was investigated using transmission electron microscopy (TEM) in conjunction with electron energy-loss spectroscopy (EELS). Si-C-O glasses were prepared by pyrolysis of polysiloxane networks obtained from homogeneous mixtures of triethoxysilane, T^H, and methyldiethoxysilane, D^H. Si-C-O glass composition depended on the molar ratio of the precursors utilized. At a ratio of T^H/D^H= 1, the formation of a carbon-rich glass was observed, whereas a ratio of T^H/D^H= 9 yielded a Si-C-O glass with excess free silicon. Both materials were amorphous at 1000°C, but showed a distinct difference in crystallization behavior on annealing at high temperature. Although T^H/D^H= 1 revealed a small volume fraction of SiC precipitates in addition to a very small amount of residual free carbon at 1400°C, T^H/D^H= 9 showed, in addition to SiC crystallites, numerous larger silicon precipitates (20–50 nm), even at 1200°C. Both materials underwent a phase separation process, SiC _x O_2(1-x)→ x SiC + (1 - x )SiO₂, when annealed at temperatures exceeding 1200°C.