Synthesis,characterization and ceramization of a novel vinyl-rich liquid precursor for Si(O)C ceramic

Polymethylsilane (PMS) was partially modified with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane ([CH₃(CH₂åCH)SiO]₄, D4Vi) via conventional hydrosilylation. The as-synthesized vinyl-rich liquid precursor (V-PMS) was characterized by the viscosity test, gel-permeation chromatography, Fourier-transform infrared spectroscopy, nuclear magnetic resonances spectroscopy. The results indicate that the obtained precursor is well soluble in common solvents and exhibits a controllable viscosity of 326.9–714.6 mPa s at room temperature. The thermal properties of V-PMS were investigated by differential scanning calorimetry and thermogravimetric analysis. The V-PMS can be cured readily at 150 °C in inert atomosphere. The ceramic yield of V-PMS reaches 81% at 1200 °C, 38% higher than that of PMS. The final pyrolytic residue is hard, dense monolithic up to 1400 °C under Ar atmospheres. The controllable viscosity, excellent thermal curability and high ceramic yield enable the liquid precursor a promising material to shape various Si(O)C ceramic materials for high-temperature application.     

Microstructure evolution of polycrystalline Ti2AlN MAX phase film during post-deposition annealing

Polycrystalline Ti₂AlN MAX phase films were fabricated by post-deposition annealing of Ti-Al-N film at annealing temperature in the range of 600?°C–800?°C in high vacuum. The temperature-dependent microstructure evolution from Ti-Al-N film to polycrystalline Ti₂AlN film has been investigated. It was found that after post-deposition annealing above 600?°C, the as-deposited amorphous Ti-Al-N film transformed to polycrystalline Ti₂AlN film. With the increase of annealing temperature from 600?°C to 700?°C, the crystallinity of polycrystalline Ti₂AlN film was improved. At 800?°C, the surface Ti₂AlN grains completely decomposed and transformed to TiN phase while inner grains was partial decomposed and surrounded by amorphous Al-rich phase. The polycrystalline Ti₂AlN film exhibited a highest hardness of 34.1?GPa while the hardness of amorphous Ti-Al-N film was only 24.2?GPa. The mechanism of texture changes and phase transformation as well as its effect on thermal stability was also discussed.     

Kr ion irradiation study of polymer-derived SiFeOC–C–SiC nanocomposite

This study focuses on the pyrolysis and ion irradiation behaviors of polymer-derived SiFeOC–C–SiC ceramic. The pyrolyzed material is composed of SiO₂ and SiOC (amorphous), carbon (amorphous and turbostratic), and Fe₃Si and β-SiC (nanocrystalline). Irradiation was carried out at both room temperature and 600°C using 400 keV Kr ions with fluences of 4 × 10¹⁵ and 1 × 10¹⁶ ions cm⁻², respectively. The Fe₃Si and SiC nanocrystals are stable against irradiation up to 3 displacement per atom (dpa) at room temperature and up to 12 dpa at 600°C. The SiOC tetrahedrals show phase separation and minor carbothermal reduction. The high irradiation resistance and the dense, defect-free amorphous microstructure of SiFeOC–C–SiC after prolonged irradiation demonstrate its great potential for advanced nuclear reactor applications.     

Effect of CH4/SiCl4 ratio on the composition and microstructure of 〈110〉-oriented β-SiC bulks by halide CVD

Halide chemical vapor deposition process was carried out for fast fabricating oriented stoichiometric β-SiC through controlling flow rate of precursors (SiCl₄ and CH₄). The effects of molar ratio of C and Si precursors (R_C/Si) on composition, preferred orientation, microstructure and deposition rate (R_dep) were investigated. The deposits transformed from silicon-rich to stoichiometric β-SiC to carbon-rich with increasing R_C/Si. 〈110〉-oriented stoichiometric β-SiC with lower density of defects were obtained at R_C/Si in the range of 0.86–1.00, where the maximum R_dep was 883 μm/h at R_C/Si = 1.00, leading to a thickness of 1.7 mm in 2 h deposition. Formation of ridge-like morphology has been discussed based on a twin plane propagation model.     

High temperature strength of silicon carbide sintered with 1 wt.% aluminum nitride and lutetium oxide

A heat-resistant SiC ceramic was developed from submicron β-SiC powders using a small amount (1 wt.%) of AlN–Lu₂O₃ additives at a molar ratio of 60:40. Observation of the ceramic using high-resolution transmission electron microscopy (HRTEM) showed a lack of amorphous films in both homophase (SiC–SiC) boundaries and junction areas. The junction phase consisted of Lu–Si–O elements, and the homophase boundaries contained Lu, Al, O, and N atoms as segregates. The ceramic maintained its room temperature (RT) strength up to 1600 °C. The flexural strength of the ceramic was 630 MPa and 633 MPa at RT and 1600 °C, respectively.     

Creep behaviour of an Al–Si–Al2O3 composite based on phase evolution at 1300oC

An Al–Si–Al₂O₃ composite was prepared with corundum, aluminium powder and silicon powder. A creep test was carried out at 1300°C under 0.2 MPa for 50 h in air. The results show that the Al–Si–Al₂O₃ composite performs a low constant creep rate and remain until the end of the 50-h test. This is attributed to the in-situ formation of the tough non-oxide reinforcements, whisker-like (AlN)_x(Al₂OC)_1-x solid solution and granular β-SiC, by reactions of Al and Si during creep test. The whisker-like (AlN)_x(Al₂OC)_1-x solid solution and granular β-SiC reinforcements are evenly filled in the pores, which play the role of bridging and pinning reinforcement, forming a strong network structure with corundum aggregates. Moreover, these non-oxide phases are not wetted by the liquid phases, which impel the liquid phase shrinks in the network structure in isolation during creep test. Thus, the adverse effect of the liquid phase on the high-temperature strength of the composites is eliminated, so the composites with strong network structure quickly get a stationary low-creep state. A creep mechanism model is established.     

Mechanism for the hydrolysis resistance of aluminum nitride powder modified by boric acid

Aluminum nitride (AlN) ceramics are becoming cutting-edge materials for electronic information and communication. However, raw AlN hydrolyzed rapidly, and the high storage costs of this material prevent widespread application. In this study, raw AlN was modified by boric acid (H₃BO₃) at 30 °C to enhance hydrolysis resistance. Transmission electron microscope (TEM), X-ray diffraction (XRD), the magic angle spinning nuclear magnetic resonance (²⁷Al-MAS-NMR and ¹¹B-MAS-NMR), and the fourier transform infrared spectrometer (FTIR) were used to characterize the powder before and after treatment, and the mechanism of hydrolysis resistance was determined. Modification with 0.1 M boric acid did not change the crystal phase of the AlN particles. The modified powder did not hydrolyse at 90% humidity and 70° Celsius. In the presence of boric acid, a network structure of B–O–B linkages ([BO_n], n = 3 or 4) formed that was connected to the AlN core via chemical bonds of B–N–Al and B–O–Al. The protective 6 – 10 nm-thick layer that formed on the surface of the AlN crystal, prevented attack by water molecules and hindered the hydrolysis of aluminium nitride. This study provides an alternative means of preparing anti-hydrolysis AlN powders.     

Reaction Synthesis and Mechanical Properties of TiB2–AlN–SiC Composites

TiB₂–AlN–SiC (TAS) ternary composites were prepared by reactive hot pressing at 2000°C for 60 min in an Ar atmosphere using TiH₂, Si, Al, B₄C, BN and C as raw powders. The phase composition was determined to be TiB₂, AlN and β-SiC by XRD. The distribution of elements Al and Si were not homogeneous, which shows that to obtain a homogeneous solid solution of AlN and SiC in the composites by the proposed reaction temperatures higher than 2000°C or time duration longer than 60 min are needed. The higher fracture toughness (6·35±0·74 MPa·m^1/2 and 6·49±0·73 MPa·m^1/2) was obtained in samples with equal molar contents of AlN and SiC (TAS-2 and TAS-5) in the TAS composites. The highest fracture strength (470±16 MPa) was obtained in TAS-3 sample, in which the volume ratio of TiB₂/(AlN+SiC) was the nearest to 1 and there was finer co-continuous microstructure. ©     

Effects of starting powder on microstructure and thermal conductivity of pressureless-sintered fully ceramic microencapsulated fuels

The effects of the starting SiC powder (α or β) with the addition of 5.67 wt% AlN–Y₂O₃–CeO₂–MgO additives on the residual porosity and thermal conductivity of fully ceramic microencapsulated (FCM) fuels were investigated. FCM fuels containing ～41 vol% and ～37 vol% tristructural isotropic (TRISO) particles could be sintered at 1870 °C using α-SiC and β-SiC powders, respectively, via a pressureless sintering route. The residual porosities of the SiC matrices in the FCM fuels prepared using the α-SiC and β-SiC powders were 1.1% and 2.3%, respectively. The thermal conductivities of FCM pellets with ～41 vol% and ～37 vol% TRISO particles (prepared using the α-SiC and β-SiC powders, respectively) were 59 and 41 Wm^?1K^?1, respectively. The lower porosity and higher thermal conductivity of FCM fuels prepared using the α-SiC powder were attributed to the higher sinterability of the α-SiC powder than that of the β-SiC powder.     

AC Impedance Spectroscopy of CaF2‐doped AlN Ceramics

The electrical conductivity of CaF₂‐doped aluminum nitride (AlN) ceramics was characterized at high temperatures, up to 500°C, by AC impedance spectroscopy. High thermal conductive CaF₂‐doped AlN ceramics were sintered with a second additive, Al₂O₃, added to control the electrical conductivity. The effects of calcium fluoride (CaF₂) on microstructure and related electrical conductivity of AlN ceramics were examined. Investigation into the microstructure of specimens by TEM analysis showed that AlN ceramics sintered with only CaF₂ additive have no secondary phases at grain boundaries. Addition of Al₂O₃ caused the formation of amorphous phases at grain boundaries. Addition of Al₂O₃ to CaF₂‐doped AlN ceramics at temperatures 200°C–500°C revealed a variation in electrical resistivity that was four orders of magnitude larger than for the specimen without Al₂O_3. The amorphous phase at the grain boundary greatly increases the electrical resistivity of AlN ceramics without causing a significant deterioration of thermal conductivity.     

Effects of oxidation cross-linking and sintering additives (TiN,B) on the formation and heat-resistant performance of polymer-derived SiC(Ti,B) films

Effects of oxidation cross-linking and sintering additives (TiN, B) on the microstructure formation and heat-resistant performance of freestanding SiC(Ti, B) films synthesized from Ti, B-containing polycarbosilane (TiB-PCS) precursor were investigated. TiB-PCS green films were first cross-linked for 1 h, 2 h, 3 h and 4 h, respectively, and then pre-sintered at 950 °C. Finally, they were sintered at 1800 °C to complete the conversion from organic films to inorganic SiC(Ti, B) films. The results reveal that curing time has a great impact on the uniformity and density of SiC(Ti, B) films. TiB-PCS films cured for 3 h yield the best quality SiC(Ti, B) films, which are composed of β-SiC crystals, C clusters, α-SiC nano-crystals, a small amount of TiB₂ and B₄C. TiB₂ and B₄C are both steady phases which can inhibit abnormal growth of β-SiC, effectively reduce sintering temperature and help consume excess C from decomposition of amorphous SiOxCy. After high temperature annealing at 1500 °C, 1600 °C and 1700 °C in argon, SiC(Ti, B) films still keep excellent mechanical properties, which makes them attractive candidate materials for microelectromechanical systems (MEMS) used at ultra-high temperatures (exceeding 1500 °C).     

Silicon oxycarbide-based composites produced from pyrolysis of polysiloxanes with active Ti filler

Phenyl (PPS) and methyl (PMS) containing polysiloxanes were pyrolyzed at elevated temperatures (900–1500 °C) under argon atmosphere to investigate the phase developments within the polymers. It was found that pyrolysis of the polymers under inert atmosphere up to 1300 °C leads to amorphous silicon oxycarbide (SiO_xC_y) ceramics. Conversions at higher temperatures results in the transformations into the crystalline β-SiC phases. Ceramic matrix composites (CMCs) were developed based on the active filler controlled pyrolysis (AFCOP) of polysiloxanes with active Ti filler additions. CMC monoliths were prepared with 60–80 wt.% of active Ti particulates blended into polymer precursors. Green bodies of the composites were made by warm pressing under 15 MPa pressure and ceramics were obtained by pyrolysis at elevated temperatures between 900 and 1500 °C under argon atmosphere. The results showed that due to the incorporation of active Ti fillers, formation of crystalline phases such as TiC, TiSi, and TiO occured within the amorphous matrix due to the reactions between the Ti and the polymer decomposition products. The microstructural and mechanical characterization results of the composites are presented within the paper.     

Structural Evolution of Silicon Carbide Phase from the Polycarbosilane Cured with Iodine: NMR Study

The structural evolution of silicon carbide phase from polycarbosilane fibers cured with iodine in air was investigated using nuclear magnetic resonance (NMR) together with in situ gas analysis up to 1400 °C by thermogravimetry coupled with mass spectroscopy (TG-MS). The investigation with solid-state ¹H, ¹³C, and ²⁹Si NMR analyses showed the influence of the oxygen affinity of Si atoms on the chemical structural changes of the SiOCH system during pyrolysis (up to 800 °C). In particular, the mechanism of phase segregation (SiOC?→?β-SiC?+?SiO₂?+?C) in amorphous SiOC structure at 800–1250 °C was determined. Carbon in the Si–O–C networks is replaced by silicon, forming the Si-O-Si network, while the cleaved carbon atoms, which have unpaired electrons, combine, forming C=C bonds. This mechanism accounts for the structural rearrangement from O₂SiC₂ to O₃SiC to SiO₄ (from the silicon-centered standpoint, i.e., SiO₂ phase), the growth of β-SiC crystallites, and the carbon clustering.     

Carbon-containing droplet combustion–carbothermal synthesis of well-distributed AlN nanometer powders

A novel three-step technique was employed to synthesize the well-distributed AlN nanopowders. First, the hollow spherical precursor particles with an average diameter of 2–5 μm, consisting of an amorphous structure mixture of Al₂O₃ and C, was prepared by carbon-containing droplet combustion method by using glucose, urea, and aluminum nitrate as starting materials. The carbothermal reduction and nitridation (CRN) was carried out at 1500°C under N₂ flow for 2 h and subsequently the CRN product was calcined at 700°C in air for 1 h to remove residual carbon and transform the CRN product to high-purity AlN powders consisting of nanostructured hollow spheres. The formation mechanism of precursor and AlN hollow spheres was discussed in detail. The AlN powder exhibited well-distributed spherical particles with a size of 30–50 nm and good sinterability. After additive-free and pressureless sintering at 1800°C for 2 h, the relative density of the sintered AlN sample was measured to be 99.02%.     

Effect of AlN-content on the microstructure and fracture toughness of hot-pressed and heat-treated LPS–SiC ceramics

The influence of additive content on the microstructural development of hot-pressed and heat-treated LPS–SiC has been investigated using AlN–Y₂O₃ mixtures at a molar ratio of 80:20, varying the total amount from 5, 10, 15 to 20 wt.%. Specimen were hot-pressed at 1900 °C for 1 h in nitrogen atmosphere under an applied pressure of 25 MPa and subsequently heat-treated at 2000 °C for 1, 2, 4 and 8 h.It has been found that the transformation rate of β- into α-SiC is retarded by higher AlN-contents and the formation of the 6H α-SiC polytype is favored. Furthermore, grain growth during annealing is also effectively inhibited. While hardness remained almost unchanged, fracture toughness varied with additive content and/or duration of the heat-treatment. Fracture toughness increased during the first 1 or 2 h of annealing,depending on the AlN-content, and diminishing for more prolonged treatments. The maximum fracture toughness has been determined for samples containing 10 wt.% of additives, hot-pressed and annealed during 1 h.     

Annealing effect on dielectric property of AlN ceramics

Effects of slow-cooling at high temperatures and annealing at intermediate temperatures on dielectric loss tangent of AlN ceramics were explored. Y₂O₃ was added as a sintering additive to AlN powders, and the powders were pressureless-sintered at 1900 °C for 2 h in a nitrogen flow atmosphere. In succession to the sintering, AlN samples were slow-cooled at a rate of 1 °C/min from 1900 to 1750 °C and/or annealed at 970 °C for 4 h. Al₅Y₃O₁₂ was detected in the AlN ceramics obtained by the slow-cooling and AlYO₃ was found in the ceramics cooled at a rate of 30 °C/min. AlN ceramics with a relative density of 0.986 were obtained by the slow-cooling method. On the other hand, very low tan δ values between 2.6 and 4.6 × 10⁻⁴ were obtained when the AlN ceramics were annealed at 970 °C for 4 h.     

Second-phase evolution and densification behavior of AlN with CaO–Y2O3–C multicomponent additive system

AlN compacts with different CaO–Y₂O₃–C mixtures were sintered between 1100 and 1850 °C to understand the effects of the in situ formed reducing atmosphere on the densification behavior and evolution of the second-phases. AlN with Y₂O₃ densified at 1750 °C, but the addition of C changed the second-phases evolution towards Y-rich phases that delayed the densification. For AlN containing CaO, the second-phases were little influenced by the reducing atmosphere, but the addition of C increased the evaporation of the second-phase compounds during sintering, limiting the densification due to the reduction of the liquid-phase fraction and the gas trapping inside the pores. AlN with CaO–Y₂O₃ mixtures could be completely densified at 1650 °C, but the addition of C inhibited the densification below this sintering temperature because liquid-phase had poor wetting and spreading characteristics and the second-phase a high melting point (>1800 °C).     

Two‐Step Carbothermal Synthesis of AlN–SiC Solid Solution Powder Using Combustion Synthesized Precursor

In the present work, a two‐step carbothermal reduction method is employed to prepare the AlN–SiC solid solution (AlN–SiCss) powders by using a combustion synthesized precursor. The precursor is prepared by low‐temperature combustion synthesis (LCS) method using a mixed solution of aluminum nitrate, silicic acid, polyacrylamide, glucose, and urea. The synthesized LCS precursor exhibits a porous and foamy uniform mixture of Al₂O₃ + SiO₂ + C consisting of flaky particles. The carbothermal reduction in the LCS precursor is carried out in two steps. First, the precursors are calcined at 1600°C in argon for 3 h. Subsequently, the precursors are further calcined at 1600°C–1900°C in nitrogen for 3 h. The results indicate that the precursor calcined at and above 1850°C in nitrogen for 3 h yields the single‐phase AlN–SiCss powders. The synthesized AlN–SiCss powder exhibits near‐spherical particles with diameter of 200–500 nm. The experimental and thermodynamical results reveal that the formation of AlN–SiCss occurs via the diffusion of AlN into SiC by virtue of formation of a highly defective β′ intermediate during the second step reaction.     

High pressure sintering of cubic boron nitride compacts with Al and AlN

Cubic boron nitride (cBN) compacts, using 15 wt.% Al and 20 wt.% AlN respectively as additives, were sintered in the temperature range of 1300–1700 °C for 20 min under high pressure of 5.0 GPa. The hardness, microstructure, phase composition and cutting performance of the high pressure sintered samples were investigated. A liquid phase sintering and reaction process was observed in the cBN–Al system, which leads to the formation of AlN and AlB₂ as confirmed by X-ray diffraction (XRD) in the sintered compacts. Scanning electron microscopy (SEM) analysis shows that the samples have a homogeneous microstructure. The hardness decreases with increase of sintering temperature and reaches the highest Vickers hardness of 32.1 GPa at 1350 °C. While in the cBN–AlN system, AlN grains agglomerate heavily at temperature below ~ 1500 °C. As the sintering temperature increasing, Al₂O₃ appeared and the AlN agglomeration disappeared gradually. A highest cBN–AlN composite hardness of 29 GPa was achieved when sintered at 1600 °C. Turning tests showed that cBN compacts with 15 wt.% Al as the additive has a longer tool life as compared to that with 20 wt.% AlN. Our results indicated that cBN–Al system is more favourable to obtain well-sintered cBN compacts comparing with the cBN–AlN system.     

Single-source-precursor synthesis of soft magnetic Fe3Si- and Fe5Si3-containing SiOC ceramic nanocomposites

We present here the single-source-precursor synthesis of Fe₃Si and Fe₅Si₃-containing SiOC ceramic nanocomposites and investigation of their magnetic properties. The materials were prepared upon chemical modification of a hydroxy- and ethoxy-substituted polymethylsilsesquioxane with iron (III) acetylacetonate (Fe(acac)₃) in different amounts (5, 15, 30 and 50 wt%), followed by cross-linking at 180 °C and pyrolysis in argon at temperatures ranging from 1000 °C to 1500 °C. The polymer-to-ceramic transformation of the iron-modified polysilsesquioxane and the evolution at high temperatures of the synthesized SiFeOC-based nanocomposite were studied by means of thermogravimetric analysis (TGA) coupled with evolved gas analysis (EGA) as well as X-ray diffraction (XRD). Upon pyrolysis at 1100 °C, the non-modified polysilsesquioxane converts into an amorphous SiOC ceramic; whereas the iron-modified precursors lead to Fe₃Si/SiOC nanocomposites. Annealing of Fe₃Si/SiOC at temperatures exceeding 1300 °C induced the crystallization of Fe₅Si₃ and β-SiC. The crystallization of the different iron-containing phases at different temperatures is considered to be a consequence of the in situ generation of a Fe–C–Si alloy within the materials during pyrolysis. Depending on the Fe and Si content in the alloy, either Fe₃Si and graphitic carbon (at 1000–1200 °C) or Fe₅Si₃ and β-SiC (at T > 1300 °C) crystallize. All SiFeOC-based ceramic samples were found to exhibit soft magnetic properties. Magnetization versus applied field measurements of the samples show a saturation magnetization up to 26.0 emu/g, depending on the Fe content within the SiFeOC-based samples as well as on the crystalline iron silicide phases formed during pyrolysis.