The Effect of Si Substitution for SiC on SHS in the Ti–Si–C System

Investigated was the effect of Si substitution for SiC on SHS in the Ti–Si–C system. Starting powders were intermixed to obtain 3Ti–SiC–C and 3Ti–Si–2C green mixtures and then green compacts by uniaxial pressing. The influence of heating rate, reactor temperature, and replacement of SiC by Si was studied by XRD, SEM, and TEM. In combustion products obtained in optimized conditions, Ti₃SiC₂ was found to be predominant. In comparison with conventional methods, our products obtained in a one-step low-temperature process contained minimal amounts of undesired impurities and required no finishing processes such as chemical purification.     

Self-propagating high-temperature synthesis of advanced ceramics in the Mo–Si–B system: Kinetics and mechanism of combustion and structure formation

The goal of this work is to investigate the combustion mechanisms of reactions in the Mo–Si–B system and to obtain ceramic materials using the SHS method. It is concluded that the following processes are defined by the SHS for Si-rich Mo–Si–B compositions: silicon melting, its spreading over the surfaces of the solid Mo and B particles, followed by B dissolution in the melt, and formation of intermediate Mo₃Si-phase film. The subsequent diffusion of silicon into molybdenum results in the formation of MoSi₂ grains and molybdenum boride phase forms due to the diffusion of molybdenum into B-rich melt. The formation of MoB phase for B-rich compositions may occur via gas-phase mass transfer of MoO₃ gaseous species to boron particles. The stages of chemical interaction in the combustion wave are also investigated. The obtained results indicate the possibility of both parallel and consecutive reactions to form molybdenum silicide and molybdenum boride phases. Thus the progression of combustion process may occur through the merging reaction fronts regime and splitting reaction fronts regime. Molybdenum silicide formation leads the combustion wave propagation during the splitting regime, while the molybdenum boride phase appears later. Finally, targets for magnetron sputtering of promising multi-phase Mo–Si–B coatings are synthesised by forced SHS compaction method.     

Advanced modelling of self-propagating high-temperature synthesis: the case of the Ti–C system

A novel mathematical model to simulate SHS processes is proposed. Based on the so-called enthalpy approach to properly account for phase transitions, the model describes microstructural evolution using suitable population balances. For the case of the synthesis of TiC from pure Ti and C, the model quantitatively interprets that reactants are heated up to the Ti melting point. Once Ti melting occurs, the melt is redistributed within the porous system, thus increasing the contact area between reactants and favoring graphite dissolution. TiC grains are then modelled as nucleating in the melt and then growing until the final microstructure is reached. Model reliability is tested by comparison with experimental data.     

Microwave assisted combustion synthesis of coupled ZnO–ZrO2 nanoparticles and their role in the photocatalytic degradation of 2,4-dichlorophenol

Zinc oxide (ZnO), zirconium oxide (ZrO₂) and their coupled oxides in the molar ratio 1:1, 2:1 and 1:2 (labeled as ZnZr, Zn₂Zr, and ZnZr₂ respectively) were successfully prepared by a microwave assisted urea–nitrate combustion synthesis. The structure and morphology of the pure ZnO, ZrO₂ and coupled ZnZr, Zn₂Zr, and ZnZr₂ were characterized by powder X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), high resolution scanning electron microscopy (HRSEM), energy dispersive X-ray spectrometry (EDX) and Brunauer–Emmett–Teller (BET) methods. The results of the photocatalytic degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution indicated that the coupled metal oxide, Zn₂Zr is more effective towards the degradation of 2,4-DCP when compared to ZnO, ZrO₂, ZnZr and ZnZr₂.     

Microwave properties and structure of La–Ti–Si–B–O glass-ceramics for applications in GHz electronics

A dielectric bulk glass-ceramic of the La₂O₃–TiO₂–SiO₂–B₂O₃ system is developed which is able to fulfill the requirements for dielectric loading-based mobile communication technologies. It is shown that the given dielectric requirements can be fulfilled by glass-ceramic materials without being dependent on ceramic processing techniques. The material exhibited permittivity values of 20 < ɛ_r < 30, quality factor 2000 GHz < Qf < 10,000 GHz and a temperature coefficient of resonance frequency −100 < τ_f < +180 ppm/K. A zero τ_f material with a Qf value of 9500 GHz and ɛ_r = 21.4 could be achieved at a ceramming temperature T_cer = 870 °C. The material is aimed to provide an alternative to existing, commercially used sintered ceramic materials. Further focus is laid on the investigation of the dominant dielectric loss mechanisms in the GHz frequency range and how they are correlated with the microstructure.     

Experimental investigation and thermodynamic simulation of the uranium oxide–zirconium oxide–iron oxide system in air

The behavior of melts and the phase composition of crystallization products of six compositions in the uranium oxide-zirconium oxide-iron oxide system in air have been investigated. It has been revealed that crystallized samples containing 20–50 wt % uranium oxide and 25–80 wt % iron oxide (the rest is zirconium oxide) consist of five crystalline phases and involve two types of eutectic structures. The possible factors responsible for this phenomenon have been considered.     

Modelling and numerical simulation of liquid–solid circulating fluidized bed system for protein purification

A novel liquid–solid circulating fluidized bed (LSCFB) was modelled for protein recovery from the feed broth. A typical LSCFB system consists of downer and riser, integrating two different operations simultaneously. A general purpose, extensible, and dynamic model was written based on the tanks-in-series framework. The model allowed adjusting the degree of backmixing in each phase for both columns. The model was validated with previously published data on extraction of bovine serum albumin (BSA) as model protein. Detailed dynamic analysis was performed on the protein recovery operation. The interaction between the riser and downer were captured. Parametric studies on protein recovery in LSCFB system were carried out using the validated model to better understand the system behaviour. Simulation results have shown that both production rate and overall recovery increased with solids circulation rate, superficial liquid velocity in the downer and riser, and feed solution concentration. The model was flexible and could use various forms of ion exchange kinetics and could simulate different hydrodynamic behaviours. It was useful to gain insight into protein recovery processes. The general nature of the model made it useful to study other protein recovery operations for plant and animal proteins. It could also be useful for further multi-objective optimization studies to optimize the LSCFB system.     

Wetting and interfacial behavior of Al–Ti/4H–SiC system:A combined study of experiment and DFT simulation

Wetting and interfacial behavior of molten Al-(10, 20, 30, 40) at.%Ti alloys on C-terminated 4H–SiC at 1500 and 1550 °C were investigated experimentally, and theoretical bonding strength, structure stability and electronic structure of interfacial reaction products/C-terminated 4H–SiC interfaces were evaluated by first-principle calculations. The wetting experiments show that the Al–Ti/SiC systems present excellent wettability with contact angle of less than 15° except the Al–40Ti/SiC system performed at 1500 °C × 30 min. The SEM-EDS and TEM analyses demonstrate that the reaction products are mainly composed of Al₄C₃, TiC, Ti₃SiC₂, Ti₅Si₃C_X and τ phase, and their formation and evolution can be mainly affected by the Ti concentration in the Al–Ti alloys and wetting temperature. Moreover, the calculated results show that the SiC/C-terminated TiC interface presents the highest work of separation and its electronic property reveals that the localization of electrons and formation of covalent bond between interfacial C atoms lead to the excellent bonding strength of SiC/TiC interface.     

In situ synthesis and interfacial bonding mechanism of SiC in MgO–SiC–C refractories

Adding SiC directly to MgO–C refractories possesses the disadvantages of low dispersion and interfacial bonding strength. Herein, the in situ synthesized SiC was introduced into the MgO–SiC–C refractories to maintain the original excellent performance of MgO–C refractories and reduce the carbon dissolution in molten steel. With the increase of Si and C content in raw materials, the morphology of SiC changed from whisker to network, whose growth mechanism was vapor–solid and vapor–liquid–solid. The network structure and uniform distribution of SiC improved the thermal shock resistance of MgO–SiC–C refractories. According to the analysis of molecular dynamics simulation by Materials Studio software, SiC strengthened the relationship between periclase and graphite to enhance the structure of the compound.     

Plasma and Silane Surface Modification of SiC/Si: Adhesion and Durability for the Epoxy–SiC System

Gaseous plasma pretreatments and surface derivatization using silane coupling agents (SCA) have been used to enhance the adhesive bonding of an epoxy to SiC-coated Si wafers (SiC/Si). The surface modification approaches included 1) an SCA treatment using 3-aminopropyltriethoxysilane (APS) or 3-glycidoxypropyltrimethoxysilane (GPS) and 2) an oxygen plasma pretreatment followed by a silane treatment. Durability was evaluated by immersing epoxy-coated SiC/Si samples in aqueous solutions at various pHs at 60°C for selected times. Adhesion durability for the epoxy-coated SiC/Si systems was qualitatively evaluated by visual inspection to identify debonding and quantitatively evaluated with a probe test to determine the critical strain energy release rate, G _c . Durability via either test approach varied as a function of surface treatment in this manner: oxygen plasma treatment plus silane modification > silane treated > no treatment. X-ray photoelectron spectroscopic characterization of surfaces was carried out following the surface treatments and after complete adhesion failure in the durability tests. The XPS results suggested that improved performance was due to plasma cleaning and modification of the substrate surface, promotion of silane surface interaction, and the formation of a thicker oxide layer.     

Gas-solid displacement reactions in the Ti–W–C system

Displacement reactions between binary and ternary ceramics in the Ti–W–C system and reactive gaseous atmospheres are investigated in this work. Specifically, WC and 50:50 wt% TiC:WC solid solution powders were exposed to flowing hydrogen gas, or equilibrated against an excess of titanium in the presence of iodine, to form metallic tungsten and TiC solid products. In the case of pure WC reacting with hydrogen, transformation to metallic tungsten occurred as a result of removal of chemically bound carbon as gaseous hydrocarbons. In the case of pure WC reacting with titanium iodide vapors, transformation was accompanied by the appearance of TiC as a solid product formed at the gas-solid interface. In the case of 50:50 wt% TiC:WC solid solution powders, hydrogen was generally found to be an ineffective displacing reagent, whereas reaction with titanium iodide vapors was observed to proceed virtually to completion, resulting in a two phase product mixture comprising metallic tungsten and TiC. For the latter case, a variety of microstructures could be observed within a given batch, including tungsten platelets and/or lamellae in a TiC matrix, or coarse tungsten grains interspersed with TiC grains. These morphological variations are speculated to arise from compositional variation in the starting material and the occurrence of local rapid coarsening along fast diffusion pathways within reacting agglomerates and polycrystalline primary particles. The observed reaction products and relative efficacy of gaseous reagents to promote displacement reactions in the Ti–W–C system are rationalized on the basis of thermodynamic predictions. The reaction between 50:50 wt% TiC:WC solid solution powders and titanium iodide vapors constitutes the first known report of an internal displacement reaction proceeding via gaseous intermediates in a nonoxide ceramic system.     

Microwave assisted synthesis of Dy2Ti2O7 ultrafine powders by sol–gel method

Dy₂Ti₂O₇ ultrafine powders ranging from 100 to 300 nm were successfully synthesized by sol–gel method. Particularly, the dried gel precursor was treated at different temperatures (700–1000 °C) via microwave-heating, which contributed to decreasing the grain size and reaction time. The phase composition and structural evolution of the final products were examined by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). Furthermore, the resultant powders were selected to fabricate ceramics and rubber based absobers. Their sinterability, mechanical properties and neutron absorption ability were also studied. Results showed that the highest flexural strength of 99.0 MPa were obtained for Dy₂Ti₂O₇ samples when sintered at 1600 °C for 2 h in air atmosphere. Meanwhile, the neutron absorption rate of Dy₂Ti₂O₇ ceramics and rubber based absorbers could reach 97.39% and 80.00% respectively when the thickness of samples was set as 5.0 mm.     

SHS in the Nb–Si system: Influence of mechanical alloying

Influence of mechanical alloying (MA) on SHS in low-caloric Nb–2Si mixtures was explored as a function of MA time and Si content of green mixtures. The use of MA was found to extend the concentration limits for combustion synthesis in the Nb–Si system to the following range: between 43 wt % Si–57 wt % Nb and 10 wt % Si–90 wt % Nb. Due to MA, SHS in Nb–Si blends can be carried out in a mode of solid–solid or liquid–solid reaction.     

Experimental and numerical studies of the lower flammability limit of mixtures of C1–C5 hydrocarbons with air

The lower concentration limit of flammability of hydrocarbon-air mixtures has been studied experimentally and by numerical simulation. Simulation using a detailed mechanism of chemical reactions has shown that calculations results are in good agreement with experimental data on the effect of water vapor on the lean concentration limit of flammability of hydrocarbon mixtures with air. The presence of water vapor at low concentrations in the mixture does not affect the lower concentration limit of flammability, but, at the same time, significantly changes the flame propagation velocity. Key words: concentration limits of flammability, opposed-jet premixed flame, hydrocarbons.     

Sintering of powders in the CrSi2–Ti(Ta)Si2 systems depending on the methods for synthesis

Composite materials based on refractory silicides, in particular their solid solutions, are widely used in many areas of engineering for parts of heating elements and heat resistance protective coatings. This paper presents the findings obtained in the study of peculiarities of solid-phase interaction during synthesis of Cr_0.9Ta_0.1Si₂ and Cr_0.5Ti_0.5Si₂ solid solutions depending on the synthesis conditions. The effect of the powder dispersity on compaction of targets from Cr_0.9Ta_0.1Si₂ and Cr_0.5Ti_0.5Si₂ powders has been studied, and it has been established that the use of nanosized powders complicates the process of pressing. Also, sintering of targets from nanosized Cr_0.9Ta_0.1Si₂ and Cr_0.5Ti_0.5Si₂ powders was studied. The sintered targets were established to have a small grain size and uniform porosity all over the volume. Thanks to small closed porosity, the targets exhibit high heat resistance under thermal shock.     

Microstructure and joining strength evaluation of SiC/SiC joints brazed with SiCp/Ag–Cu–Ti hybrid tapes

SiC particulates were mixed with Ag–Cu–Ti powders to fabricate SiC_P/Ag–Cu–Ti (SICACT) sheets by tape casting process, which were used to braze the sintered SiC ceramics with the structure of SiC/Ag–Cu–Ti foil/SICACT sheet/Ag–Cu–Ti foil/SiC. Microstructure and joining strength both at room temperature and at high temperature were characterized by electron probe X-ray microanalyzer, electron dispersive spectroscopy, transmission electron microscopy, and flexural strength test. The SiC particulates from the SICACT sheets were randomly distributed in the filler alloy matrix and reacted with Ti from the filler alloy. Reaction products TiC and Ti₅Si₃ were found in the interfacial reaction layer. With the increase in SiC particulates volume fraction, the joining strength at room temperature first increased, and then decreased, which was affected by both CTE mismatch and the thickness of the reaction layer. In addition, the joining strength of joints brazed using SICACT sheets at 600?°C can reach 197 MPa, which was obviously higher than that brazed using Ag–Cu–Ti filler alloy.     

Study of molding structures and physicomechanical properties of carbon-ceramic composite materials of the SiC–C system

The microstructure of composite materials of the composition SiC–C is analyzed. It is established that they are a separate group of materials containing a ceramic matrix. The ceramic matrix experiences tensile stresses, as a result of which within the composite material a traditional internal stress field is distorted. The ceramic matrix increases strength at carbon phase boundaries of the composite material, and it reduces porosity. An excess of ceramic material reduces strength and thermal stress resistance. Requirements are provided for porosity of the structure that govern the optimum field of material composition.     

The influence of mechanical activation on the structure and phase formation of an electro-thermal explosion in the Ti–Zr–C system

The Ti_xZr_1-xC solid solutions were synthesized by electro-thermal explosion under pressure in the (Ti + Zr + C) blends mechanically activated in hexane (MA-ETE). The effect of mechanical activation (MA) duration on reaction blend characteristics, ETE parameters, phase composition, and microstructure formation in solid solutions was investigated. At MA, the Ti + Zr blend deforms metal crystal lattices for 20 min, complete amorphization occurs for 40 min, and the carbide grains form a cubic structure for 90 min. The single-phase Zr_0.50Ti_0.50C solid solution with a grain size of 3–5 μm and a submicron composite with a grain size of 0.1–0.2 μm containing the Ti_0.86Zr_0.14C and Zr_0.74Ti_0.26C solid solutions were synthesized in a one-stage process for the first time without any additional thermotreatment. The influence of mechanical activation on diffusional mass transfer of reactants, structure, and phase formation is discussed.     

Sol-Gel synthesis and characterization of SiC–B4C nano powder

In the present research, SiC–B₄C nano powders were synthesized through sol–gel process in water–solvent–catalyst–dispersant system. In order to evaluate the formation mechanism of the product during sol-gel process, TEM, SEM, DTA/TG, BET, XRD, FTIR and DLS analysis methods were employed. The nanometric size of precursor was controlled by dispersing agents and controlling pH inside the sol. DLS analysis revealed that the particles of the precursor inside the sol were below 10 nm. FTIR results indicated that the (Si–O–B) bonds were formed in the dried gel powder, due to hydrolysis and condensation reactions. DTA analysis confirmed that the synthesis temperature was lower than 1400 °C. XRD results implied the presence of cubic β-SiC and the rhombohedral B₄C phases, which were formed simultaneously in the SiC–B₄C nanopowder. BET analysis indicated a high surface area for the particles of about 171.42 m²/g, and that the surfaces of these particles were meso porous. SEM analysis exhibited that SiC– B₄C particle size was in the range of 20–40 nm with homogenous morphology. Ultimately, the TEM/EDS microstructural analysis showed that B₄C and SiC particles were formed simultaneously and uniformly in the final product.