Microwave‐irradiated ring‐opening polymerization of D,L‐lactide under atmosphere

Poly(D ,L ‐lactide) (PDLLA) was synthesized by microwave‐irradiated ring‐opening polymerization catalyzed by stannous octoate (Sn(Oct)₂) under atmosphere. The effects of heating medium, monomer purity, catalyst concentration, microwave irradiation time, and vacuum level were discussed. Under the appropriate conditions such as carborundum (SiC) as heating‐medium, 0.15% catalyst, lactide with purity above 99.9%, 450 W microwave power, 30 min irradiation time, and atmosphere, PDLLA with a viscosity–average molecular weight (M_η) over 2.0 × 10⁵ and a yield over 85% was obtained. The dismission of vacuum to ring‐opening polymerization of D ,L ‐lactide (DLLA) under microwave irradiation simplified the process greatly. The temperature under microwave irradiation and conventional heating was compared. The largely enhanced ring‐opening polymerization rate of DLLA under microwave irradiation was the coeffect of thermal effects and microwave effects. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2244–2247, 2006     

Mechanical properties and sliding wear behaviour of Al2O3-SiC nanocomposites with 3–20 vol% SiC

Al₂O₃/SiC composites containing different volume fractions (3, 5, 10, 15, and 20 vol%) of SiC particles were produced by conventional mixing of alumina and silicon carbide powders, followed by hot pressing at 1740 °C for 1 h under the pressure of 30 MPa in the atmosphere of Ar. The influence of the volume fraction and size of SiC particles (two different powders with the mean size of SiC particles 40 and 200 nm were used), and final microstructure on mechanical properties and dry sliding wear behaviour in ball-on-disc arrangement were evaluated. The properties of the composites were related to a monolithic Al₂O₃ reference. Microstructure of the composites was significantly affected by the volume fraction of added SiC, with the mean size of alumina matrix grains decreasing with increasing content of SiC particles. The addition of SiC moderately improved the Vickers hardness. Fracture toughness was lower with respect to monolithic Al₂O₃, irrespective of the volume fraction and size of SiC particles. Al₂O₃/SiC nanocomposites conferred significant benefits in terms of wear behaviour under the conditions of mild dry sliding wear. Wear resistance of the alumina reference was poor, especially at the applied load of 50 N. The wear rates of composites markedly decreased with increasing volume fraction of SiC. Wear of the composites was also influenced by the material of counterparts, especially their hardness, with softer counterparts resulting in lower wear rates. All composites wore by a combination of grain pull-out with plastic deformation associated with grooving and small contribution of mechanical wear (micro-fracture). No influence of SiC particle size on wear rate or mechanism of wear was observed in the materials with identical volume fractions of SiC.     

Reaction-bonded B4C/SiC composites synthesized by microwave heating

The reaction-bonding technique was used to synthesize boron carbide (B₄C) - silicon carbide (SiC) composites by microwave heating. Preforms of porous B₄C were obtained by compaction followed or not by partial densification. Then, the material was infiltrated by molten silicon under a microwave heating. The influence of the thermal cycles (T: 1400-1500°C, t: 5-120 minutes) is low. The hardness of boron carbide is comparable to that of alumina (15-19 GPa) for a much lower density (≈2.5 g/cm³ for B₄C-based material instead of 3.95 g/cm³ for alumina). These properties make this composite, obtained by microwave heating, a good candidate for ballistic applications.     

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.     

Effect of sintering atmosphere on the grain growth and hardness of SiC/polysilazane ceramic composites

Silicon carbide (SiC) monoliths were synthesised using nano-size SiC powder mixed with/without polysilazane by hot pressing at 1750°C for 1?h under an applied pressure of 20?MPa in N₂ or Ar atmosphere. The effects of polysilazane and sintering atmosphere on the microstructure and hardness of SiC were examined. The grain sizes of the SiC ceramics sintered in N₂ atmosphere with and without the polysilazane were 161 and 605?nm, while the density for those samples were 96.5 and 98.1%, respectively. It was shown that Si₂N₂O was formed for the SiC/polysilazane composite and sintered in N₂. In addition, the sample mixed with polysilazane followed by sintering in N₂ atmosphere revealed a quite high hardness in spite of its relatively low density. It was suggested that Si₂N₂O phase played an important role for the inhibition of grain and subsequent high hardness.     

Replication of jute stem for porous cellular ceramics/composites in the SiO2–SiC–C System

The present work demonstrates that carbonaceous template preforms derived from jute stem by thermal and microwave processing can be infiltrated at room temperature under vacuum with silica sol, obtained by acid catalyzed hydrolysis of tetra ethyl orthosilicate (TEOS). The microwave processed carbon-preforms are better suited for exercising control of SiO₂ infiltration. The oven-dried hybrid C/SiO₂ material accumulates silica as SiO₂·nH₂O (n lying approximately between 1 and 3) and may be suitably converted, depending on the modes of processing, into macroporous cellular SiO₂ or SiC ceramics or SiC/SiO₂/C or SiC/C or SiC/SiO₂ composites with tailored composition and microstructures. The processes for synthesis of the specific products have been developed and their phase compositions and microstructures have been examined through characterization by bulk density measurements, X-ray diffraction and scanning electron microscopy.     

Effects of polycarbosilane infiltration processes on the microstructure and mechanical properties of 3D-Cf/SiC composites

Three-dimensional braided carbon fiber-reinforced silicon carbide (3D-C_f/SiC) composites were prepared through eight cycles of infiltration of polycarbosilane (PCS)/divinylbenzene (DVB) and subsequent pyrolysis under an inert atmosphere. The effects of infiltration processes on the microstructure and mechanical properties of the C_f/SiC composites were investigated. The results showed that increasing temperature could reduce the viscosity of the PCS/DVB solution, which was propitious to the infiltration processes. The density and flexural strength of 3D-C_f/SiC composites fabricated with vacuum infiltration were 1.794 g cm⁻³ and 557 MPa, respectively. Compared to vacuum infiltration, heating and pressure infiltration could improve the infiltration efficiency so that the composites exhibited higher density and flexural strength, i.e., 1.944 g cm⁻³ and 662 MPa. When tested at 1650 °C and 1800 °C in vacuum, the flexural strength reached 647 MPa and 602 MPa, respectively.     

Anisotropy of functional properties of SiC composites with GNPs,GO and in-situ formed graphene

This paper reports on anisotropy of functional properties of different silicon carbide-graphene composites due to preferential orientation of graphene layers during sintering. Dense silicon carbide/graphene nanoplatelets (SiC/GNPs) and silicon carbide/graphene oxide (SiC/GO) composites were sintered in the presence of yttria (Y₂O₃) and alumina (Al₂O₃) sintering additives at 1800 °C in vacuum by the rapid hot pressing (RHP) technique. It is found that electrical conductivity of SiC/GNPs and SiC/GO composites increases significantly in the perpendicular direction to the RHP pressing axis, reached up to 1775 S/m in the case of SiC/GO (for 3.15 wt.% of rGO). Also, thermal diffusivity was found to increase slightly by the addition of GNPs in the SiC/GNPs composites in the perpendicular direction to the RHP pressing axis. But, in the parallel direction, the addition of GNPs showed a negative effect. The formation of graphene domains was observed in reference sample SiC-Y₂O₃-Al₂O₃ sintered by RHP, without any addition of graphene. Their presence was confirmed indirectly by increasing electrical conductivity about three orders of magnitude in comparison to the reference sample sintered by conventional hot press (HP). Raman, SEM and TEM analysis were used for direct evidence of presence of graphene domains in RHP reference sample.     

Development of spark plasma sintered conductive SiC–TiB2 composites for electrical discharge machining applications

Highly dense electrically conductive silicon carbide (SiC)–(0, 10, 20, and 30 vol%) titanium boride (TiB₂) composites with 10 vol% of Y₂O₃–AlN additives were fabricated at a relatively low temperature of 1800°C by spark plasma sintering in nitrogen atmosphere. Phase analysis of sintered composites reveals suppressed β→α phase transformation due to low sintering temperature, nitride additives, and nitrogen sintering atmosphere. With increase in TiB₂ content, hardness increased from 20.6 to 23.7 GPa and fracture toughness increased from 3.6 to 5.5 MPa m^1/2. The electrical conductivity increased to a remarkable 2.72 × 10³ (Ω cm)^–1 for SiC–30 vol% TiB₂ composites due to large amount of conductive reinforcement, additive composition, and sintering in nitrogen atmosphere. The successful electrical discharge machining illustrates potential of the sintered SiC–TiB₂ composites toward extending the application regime of conventional SiC-based ceramics.     

Heat treatment of 6H-SiC under different gaseous environments

Silicon carbide is a useful material for the reactors in chemical processes. In recent years, microreactors have gained significant attentions due to the high demand for process miniaturization. As heat and mass-transfer are highly improved inside the gas flow channels in microreactors, any change on the surface of inner channels under heating becomes critical to the performance of microreactors. To investigate the surface changes of silicon carbide during the heat treatment, 6H-SiC coupons were processed in five different gases—Ar, N₂, air, 0.9% O₂ in Ar and 50% H₂O in air—that are commonly encountered in high temperature chemical processes. While the formation of oxide film was found to be dependent on the partial pressure of oxidizing gas, surface decomposition was found from the treatment in nitrogen environment. Characterization of the SiC surface by Raman spectroscopy and SEM–EDX revealed that a graphitic layer has formed at the oxide film/SiC interface. Crystallinity of graphitic layer at the interface seemed to be dependent on the partial pressure of oxidizing gas, which was revealed by the relationship between G peak position and R(I_D/I_G). The intensity ratio of FTO(0)/FTO(2/6) bands showed that stacking faults on the surface of SiC coupons were reduced after heat treatment.     

Development of microwave susceptors based on SiC composites and their application for a one-step synthesis of ZnO nanostructures

We report on the synthesis of silicon carbide (SiC)-based composites containing different proportions of aluminum and/or vanadium III oxides. These composites have been successfully tested as susceptors into a commercial microwave oven operating at 2.45?GHz frequency. After 120?s only of microwave irradiation, the generated temperature has reached a plateau of 1750?°C, which was obtained for SiC composite containing 10?wt% of Al₂O₃ and/or V₂O₃. Furthermore, the structural properties of these composites were investigated by means of X-ray diffraction and scanning electron microscopy before and after exposure to microwaves irradiation. These SiC-based susceptors were then used as a source of heat to synthesize a nanostructured ZnO material through two different processes, namely the zinc metal evaporation/condensation occurring under air, and through a rapid thermal decomposition of zinc acetates and nitrates precursors. The structural analysis supported the possibility to grow nanostructures of controlled morphologies via the control of the microwave power and the type of precursor employed. We believe that this proposed one-step microwave assisted method provides a simple and efficient alternative to synthesize various oxide nanostructures in a very short reaction-time.     

Carbon content and pyrolysis atmosphere effects on phase development in SiOC systems

In this study, bulk silicon oxycarbides (SiOCs) were fabricated from base polysiloxane (PSO) systems with different carbon content by using Ar or Ar + H₂O pyrolysis atmosphere. Compared to the Ar pyrolysis condition, the SiOC samples pyrolyzed with water vapor plus Ar generally show lower ceramic yield except for the Tospearl (polymethylsilsesquioxane) sample at 1400 °C. The SiOC ceramics contain significantly less SiC and carbon after pyrolysis under Ar + H₂O atmosphere compared to pure Ar atmosphere. The carbon-poor Tospearl sample shows a crystalline SiO₂ structure (cristobalite) after pyrolysis at 1400 °C in Ar + H₂O, which is also confirmed using TEM diffraction pattern analysis. TEM microstructures indicate little change in microstructures for the carbon-rich samples. The fundamentals, such as total Gibbs free energy, the driving force for crystallization, and phase contents at different pyrolysis temperatures can be calculated based on a Gibbs free energy minimization method. The phase content calculations predict considerable decrease in the amounts of SiC and C and significant increase in the percent of SiO₂ after pyrolysis in Ar + H₂O compared to Ar. The thermodynamic calculation results match with our experimental observations. This work provides a guided method to synthesize high temperature SiOCs with desired phases.     

Enhanced microwave-absorbing properties of FeCo magnetic film-functionalized silicon carbide fibers fabricated by a radio frequency magnetron method

Silicon carbide (SiC) fibers have potential application in microwave absorption materials in recent years. In this study, we provide a new method for improving the microwave-absorbing properties of SiC fibers. Magnetic FeCo films were fabricated on SiC fibers at low temperature and high vacuum by a radio frequency magnetron sputtering method. The properties of FeCo film/SiC fiber (FeCo/SiC_f) composites were investigated. When compared with SiC fiber, the FeCo/SiC_f composites exhibit excellent microwave-absorbing properties in the microwave range, with enhancements in the optimal reflectivity loss from −5.03 to −25.51 dB. This excellent performance may be because of the magnetic loss due to ferromagnetic resonance and interfacial polarization, thus inducing dielectric relaxation. In addition, the magnetic properties of FeCo/SiC_f composites are significantly improved: the value of saturation magnetization reaches up to 41.45 emu/g and the coercivity is 116.27 Oe. In addition, the strength of SiC fiber remains at 99.17% after the fabrication process. The method provided in this study for enhancing the microwave-absorbing properties of FeCo/SiC_f composites will pave a new way for the development of SiC microwave-absorbing materials.     

Influence of H2/NH3 mixtures on the composition of SiCNYO and SiCNAl(O) nanopowders

We performed pyrolysis of SiCNAlH and SiCNYOH nanopowder precursors under a reactive atmosphere (Ar/NH₃/H₂) with various compositions of ammonia (NH₃) and dihydrogen (H₂) to diminish C content, which is deleterious for thermal stability and sintering of the powders. This paper continues a previous work on the fabrication of an Si₃N₄/SiC composite without free C by studying the effect of H₂ on the C/N atomic ratio of the powder. We studied the influence of the nature of the gaseous mixture (Ar/NH₃/H₂) on the powder composition. Elemental analysis showed that the introduction of H₂ in the pyrolysis atmosphere limited the decomposition of NH₃ and allowed for control of the C/N ratio. This behaviour can be explained by the structural evolution observed by ²⁹Si NMR spectrometry but also by Fourier transform infrared and Raman spectroscopy. An Si₃N₄/SiC composite, with traces of free C, was obtained after post-pyrolysis heat treatment of the powders synthesized with 10 wt.% of H₂ and 25 wt.% NH₃.     

Processing of reaction-bonded B4C–SiC composites in a single-mode microwave cavity

In this study, the reaction sintering of boron carbide, which consists in doing reactive infiltration of molten silicon throughout a porous sample made of B₄C and carbon graphite was investigated. Thus, it has been shown that a single-mode microwave cavity can be successfully used to produce reaction-bonded B₄C–SiC composite. A specific package, consisting of a SiC based susceptor and a boron nitride based insulating container, was used to heat up the B₄C–Si system using a single-mode microwaves cavity under an Ar–H₂ atmosphere. Pore-free B₄C–SiC composite successfully produced consists of a mixture of B₄C and polygonal shaped β-SiC within a residual silicon matrix. The indentation technique permits to determine mechanical properties of the samples which are compared to those obtained conventionally. It appears that the average hardness (H≈22 GPa) value is quite constant all along the sample thickness which highlights good homogeneity of the samples obtained. Some aspects of the microstructure are also discussed and compared to those of samples conventionally obtained.     

Effects of Atmospheric Composition on the Molecular Structure of Synthesized Silicon Oxycarbides

The dependence of silicon oxycarbides' chemical composition and molecular structure on their reaction conditions was tested by varying the atmosphere under which pyrolysis was performed. To obtain the silicon oxycarbides, densely cross‐linked silicone resin particles with an averaged diameter of 2 μm were pyrolyzed in various atmospheres of H₂, Ar, and CO₂, in the temperature range 700°C–1100°C. The residual mass of resin after pyrolysis was almost constant at 700°C, although their apparent colors varied distinctly. The sample obtained from the H₂ atmosphere was white, whereas that obtained from the CO₂ atmosphere was dark brown. Fourier‐transform infrared (FT‐IR) spectra of the residues suggested that the Si–O–Si network evolution was accelerated in the CO₂ atmosphere. Beyond 800°C, the chemical compositions of the compounds obtained from a H₂ atmosphere increasingly approached near‐stoichiometric SiO₂–xSiC composition with increasing the pyrolysis temperature. Compounds from a CO₂ atmosphere approached a composition of SiO₂–xC with no free SiC as the pyrolysis temperature increased. In the products from an Ar atmosphere, SiO₂–xSiC–yC compositions were typically obtained. The observed effects of the pyrolysis atmosphere on the resulting chemical compositions were analyzed in terms of thermodynamic calculations. Electron spin resonance (ESR) spectra revealed broad and intense signals from products obtained from either Ar or CO₂. Estimating from the signal intensity, the residual spin concentrations were in the range 10¹⁸–10¹⁹ g^?1. Meanwhile, the spectra from the samples obtained in H₂ showed weak and sharp signals with estimated spin concentrations ranging from 10¹⁶–10¹⁷ g^?1. This signal attenuation may have been due to the hydrogen capping of dangling bond formed during pyrolysis.     

Phase formation in porous liquid phase sintered silicon carbide:: Part II Interaction between Y2O3 and SiC

During the sintering of porous liquid phase sintered silicon carbide (porous LPS-SiC) a strong interaction with the atmosphere takes place, influencing the composition and stability of porous LPS-SiC components. The present paper is focused on the interaction of Y₂O₃ with SiC, which is part of the common used sintering additives for LPS-SiC (Y₂O₃–Al₂O₃–SiC). The interaction of Al₂O₃ and SiC has been studied in a previous paper [J. Eur. Ceram. Soc. (in press)].The reaction products of the interaction of Y₂O₃ with SiC and the resulting microstructures were analysed using model experiments. The effects of the influence of different sintering atmospheres, namely Argon and Ar/CO, as well as vacuum and different temperatures have been investigated. The phase formation was determined by X-ray diffraction (XRD) and can be explained on the basis of thermodynamic calculations. Depending on the sintering conditions, silicides or yttrium carbides can be formed in addition to stable oxides, which can result in the decomposition of the samples after sintering. Reactions between SiC and Y₂O₃ during sintering can be suppressed successfully if an Ar/CO atmosphere is used.     

Combined role of SiC particles and SiC whiskers on the characteristics of spark plasma sintered ZrB2 ceramics

In this research work, the effects of silicon carbide (SiC) as the most important reinforcement phase on the densification percentage and mechanical characteristics of zirconium diboride (ZrB₂)-matrix composites were studied. In this way, a monolithic ZrB₂ ceramic (as the baseline) and three ZrB₂ matrix specimens each of which contains 25 vol% SiC as reinforcement in various morphologies (SiC particulates, SiC whiskers, and a mixture of SiC particulates/SiC whiskers), have been processed through spark plasma sintering (SPS) technology. The sintering parameters were 1900 °C as sintering temperature, 7 min as the dwell time, and 40 MPa as external pressure in vacuum conditions. After spark plasma sintering, a relative density of ~96% was obtained (using the Archimedes principles and mixture rule for evaluation of relative density) for the unreinforced ZrB₂ specimen, but the porosity of composites containing SiC approached zero. Also, the assessment of sintered materials mechanical properties has shown that the existence of silicon carbide in ZrB₂ matrix ceramics results in fracture toughness and microhardness improvement, compared to those measured for the monolithic one. The simultaneous addition of silicon carbide particulates (SiC_p) and whiskers (SiC_w) showed a synergistic effect on the enhancement of mechanical performance of ZrB₂-based composites.     

Computational characterisation of microwave heating of fibre preforms for CVI of SiCf/SiC composites

Silicon carbide fibre reinforced silicon carbide matrix composites (SiC_f/SiC) are known as materials with high-performance mechanical properties for the aerospace industry. Microwave-enhanced (ME) chemical vapour infiltration (CVI) heating of ceramic matrix composites is potentially an energy efficient production technique capable of yielding near fully dense SiC_f/SiC composites in a much shorter time span. This paper reports on the output of computational analysis of electromagnetic (EM) and thermal characteristics of the ME CVI process occurring with thin circular SiC fibre preform in a Labotron microwave system from SAIREM. Computer simulation is performed with the use of the finite-difference time-domain technique implemented in QuickWave computational environment. Multiple puzzling phenomena observed in the earlier experimental work are illuminated in the present study and the causes for the formation of microwave-induced temperature fields are clarified. With the use of the developed EM model, resonant and non-resonant frequencies of the Labotron system for different temperatures of the processed samples are analysed to explain the differences and variability in heating rates. This showed that when microwave processing of small SiC samples, energy coupling is extremely sensitive to frequency: a change of the reflection coefficient from 0.05 (absorbing) to 0.75 (reflective) could be made by a drift as small as 0.003–0.005 GHz, respectively, indicating the importance of scaling the microwave cavity to the sample size and the ability to precisely control the frequency of the microwave source. Moreover, energy coupling is temperature-dependent: low reflections produces very high heating rates (greater than 550 ℃ min^-1); the opposite is true for high reflections where heating rates are significantly slower. Temperature fields in the SiC fibre preforms are computed with the coupled EM-thermal model at different frequencies. It is shown that while being highly non-uniform in the beginning of the process, temperature patterns evolve to being fairly homogeneous by its end. Overall, the results suggest a means for better control of the equipment to pave the way to more efficient, controlled, and repeatable implementations of the ME CVI technology to produce high quality SiC_f/SiC composites.     

Influences of pre-forming on preparation of SiC by microwave heating

Silicon carbide (SiC) crystals were synthesized by microwave sintering using coal and tetraethoxysilane (TEOS) as raw materials. A sol-gel method was carried out to coat coal mineral particles with silicon dioxide (SiO₂). The mixed raw powders were pre-formed by uniaxial pressing into cylindrical pellets in dimension of ~ 30?×?3?mm². The pre-forming pressure was selected at 0?MPa, 1?MPa, 2?MPa, 3?MPa, 4?MPa and 5?MPa respectively, which led to different apparent density of the green pellets. The influence of apparent density of green pellets on microwave heating behavior was investigated. Different microwave thermal effects were analyzed. Techniques of XRD、SEM were carried out to characterize samples. It was found that pre-forming pressure showed crucial influences on microwave thermal effects and electric field (E-field) intensification. No SiC crystal could be formed without pre-forming pressure. Pre-forming pressure might be the prerequisite for synthesis of SiC by microwave heating. Five consecutive and indispensable heating stages including accumulation of residual air, microwave plasma generation, complex chemical reactions, nucleation and grain growth of SiC crystallites could be distinguished for samples under pre-forming pressure. Different pre-forming pressure leads to changes in heating behavior as well as morphologies of SiC crystals. ~ 4?MPa might be the optimized pre-forming pressure for both microwave plasma effects and E-field intensification.