Spark plasma sintering and mechanical properties of compounds in TiB2-SiC pseudo-diagram

The influence of spark plasma sintering (SPS) parameters (temperature, time, pressure) and the role of particle size on densification, microstructure and mechanical properties of commercial additive-free TiB₂, SiC and composites thereof were studied by X-ray diffraction, scanning electron microscopy, the ultrasonic method and indentation. Three particle sizes of SiC and 2 of TiB₂ were processed. An optimal cycle was found for TiB₂ and SiC: 2000?°C, 3?min dwell time, and 100?MPa applied at 600?°C. The relative density of pure SiC increases linearly from 70% to 90% when the initial particle size decreases from 1.75?µm to 0.5?µm. Pure TiB₂ was densified up to 87%. Using 2.5?wt% SiC in TiB₂, the relative density increases to 97%. Young's modulus and the hardness of all samples were measured, with results discussed. The higher properties were obtained for additive-free TiB₂–5%SiC with a relative density of 97% and with the Young's modulus and Vickers hardness values being close to 378?GPa and 23?GPa, respectively.     

Effect of short carbon fiber content on the mechanical properties of TiB2-based composites prepared by spark plasma sintering

In this study, TiB₂-30 vol% SiC composites containing 0, 5, 10, and 15 vol% short carbon fibers (C_f) were produced by spark plasma sintering (SPS). The effect of carbon fiber content on microstructure, density, and mechanical properties (micro-hardness and flexural strength) of the fabricated composites was studied. Scanning electron microscopy (SEM) results indicated that the fibers were uniformly dispersed in the TiB₂–SiC matrix using wet ball milling before SPS process. Fully dense TiB₂–SiC–C_f composites were achieved by SPS process at 1900°C for 10 min under 30 MPa. With the addition of fibers, the relative density of the composites did not change considerably. Mechanical tests revealed that microhardness was reduced about 19% by the incorporation of carbon fibers, whereas the flexural strength improved significantly. However, the flexural strength diminished by adding carbon fibers above to critical value (5 vol%) due to residual thermal stresses, nonhomogeneous structure and graphitization of carbon fibers. It was found that the composite with 5 vol% C_f had the highest flexural strength (482 MPa), which was enhanced by 20% compared with the TiB₂–SiC composite.     

The interrelation among network structures,molecular transport of solvent,and creep behaviors of TiB2 ceramic containing butyl rubber composites

Swelling of polymer composites in solvents has become one of the major problems in the use of polymer composites exposed to petroleum products. As a possible solution to the problem, this experimental study was conducted to examine the potential application of TiB₂ ceramic in butyl rubber (IIR) composites. The effect of TiB₂ content on the curing kinetics of IIR composites was studied using a torque rheometer technique. The effect of TiB₂ on the network structure was investigated in terms of the crosslinking density, interparticle distance between conducting particles, surface tension, glass transition temperature, degree of crystallinity, scanning electron microscopy, and X‐ray analysis. Moreover, the effect of TiB₂ content on the molecular transport of solvent (kerosene) was examined by means of degree of swelling, solvent interaction parameters, volume fraction of rubber, interparticle distance after swelling, penetration rate of solvent, mean diffusion coefficient, cohesive energy density of polymer, standard entropy, standard enthalpy, and standard free energy of IIR composites. It was ascertained that with increasing TiB₂ content the degree of swelling shifts to a lower value. The main reason was interpreted as the introduction of good interface adhesion of TiB₂ with rubber matrix, which tends to block the diffusion of solvent molecules. The effect of TiB₂ content on hardness, tensile strength, Young's modules, and elongation at break is discussed. An apparent steady‐state creep of butyl rubber IIR/TiB₂ composites is evident under different constant stresses at room temperature. The strain rate of steady‐state creep showed a dependence on stress and TiB₂ volume fraction. The stress sensitivity parameter, viscosity coefficient, and activation volume for samples loaded with different content of TiB₂ were estimated. It is apparent that these new composites should be very useful for solvent permeation resistance at high TiB₂ loading level with good mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2226–2235, 2005     

Synthesis of fine dispersed titanium diboride from nanofibrous carbon

This paper presents the experimental data on the synthesis of titanium diboride (TiB₂) fine dispersed powder carried out in laboratory scale. TiB₂ powder was prepared by the reduction of titanium dioxide with boron carbide and nanofibrous carbon in an argon atmosphere. The powders of TiB₂ were characterized by X-ray diffraction (XRD), elemental analyses, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), low-temperature nitrogen adsorption, particle size analysis, simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC). The resulting material contains a single phase – titanium diboride. The particles of the powder were predominantly aggregated. The average size of the particles and the aggregates were 7.4–8.0 µm with a wide size of distribution. The specific surface values of samples obtained were 2.4–5.8 m²/g. The oxidation of titanium diboride began from the temperature of 450 °C. In this work, the optimal synthesis conditions were estimated: the molar ratio was TiO₂:B₄C:C=2:1:3 (according to stoichiometry), the temperature was 1600 °C, the process duration was 20–30 min.     

Production of TiB2 by SHS and HCl leaching at different temperatures: Characterization and investigation of sintering behavior by SPS

Sub-micron sized TiB₂ ceramic powders were prepared via self-propagating high-temperature synthesis (SHS) followed by HCl leaching at different temperatures. Purified powders obtained using optimum process parameters were consolidated by field assisted sintering technology/spark plasma sintering (FAST/SPS) technique. Phase and microstructural analyses of both the powder and sintered samples were carried out by X-ray diffractometer (XRD) and scanning electron microscope (SEM). The chemical analyses and particle size measurements of the specimen were conducted by inductively coupled plasma-mass spectrometry (ICP-MS) and dynamic light scattering (DLS) techniques. The final properties of the sintered sample were determined in terms of density and microhardness. The effects of different HCl leaching temperatures on the formation, microstructure, particle size, purity and sintering behavior of the SHS-produced TiB₂ powders were investigated. The SHS reaction of TiO₂-B₂O₃-Mg powders as a starting mixture yielded MgO, Mg₃(BO₃)₂ and Mg beside the desired phase TiB₂. All three magnesium containing by-products were completely removed by performing hot HCl leaching. TiB₂ powders after SHS reaction and leaching with 9.3 M HCl for 30 min at 80 °C revealed a minimum purity of 98.4% and a homogenous particle size distribution with an average particle size of 536 nm. In the ultimate SPS experiment which was conducted at 1500 °C for 5 min under a pressure of 50 MPa, a relative density of 94.9% and a micro-hardness value of 24.56 GPa were achieved.     

Synthesis of TiB2 from a carbon‐coated precursors method

This article deals with the synthesis of TiB₂ from carbon‐coated TiO₂ precursors with the addition of B₄C. The carbon‐coated precursors method alters the reaction process, compared with the conventional mixing of reactants, to produce high‐quality TiB₂ powders. The produced powders have a single phase, a submicron particle size (~0.3 to 0.8 μm), regular shape, loose agglomeration, and low level of contaminations (less than 0.5 wt% carbon and 0.6 wt% oxygen). The formation mechanism proposed is based on experimental results and thermodynamic evaluations. For comparison, the powders obtained from the mixture of reactants show higher agglomeration, a large particle size (>1 μm), high level of contaminations (0.7 wt% carbon and 1.1 wt% oxygen), and difficulty to control the reaction process (formation of TiBO₃ and Ti₂O₃ as the intermediate phases). The synthesized powders from the precursors method can be hot pressed to a relative density of ~94.5% with the formation of platelike grains at 1800°C under a pressure of 35 MPa without additives.     

Fracture toughness in some hetero-modulus composite carbides: carbon inclusions and voids

Structure and mechanical characteristics of dense ceramic composites synthesised by reactive hot pressing of TiC–B₄C powder mixtures at 1800–1950°C under 30?MPa were investigated by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM and EDX). The results show that during hot pressing solid-phase chemical reaction 2TiC?+?B₄C?=?2TiB₂?+?3C has occurred with final products like TiB₂–TiC–C, TiB₂–C or TiB₂–B₄C–C hetero-modulus composite formation with around one micrometer size carbon precipitates. The fracture toughness depends on the amount of graphite precipitation and has a distinct maximum K1C?=?10?MPa?m^1/2 at nearly 7?vol.-% of carbon precipitate. The fracture toughness behaviour is explained by the developed model of crack propagation. Within the model, it is shown that pores (voids) and low-modulus carbon inclusions blunt the cracks and can increase ceramic toughness in some cases.     

Effect of TiB2 particles on microstructure and mechanical properties of B4C–TiB2 ceramics prepared by hot pressing

B₄C-20 wt% TiB₂ ceramics were fabricated by hot pressing B₄C and ball-milled TiB₂ powder mixtures. The effects of the TiB₂ particle size on the microstructure and mechanical properties were investigated. The results showed that the TiB₂ particle size played an important role in the mechanical properties of the B₄C–TiB₂ ceramics. In addition, SiO₂ introduced by ball milling was beneficial for densification but detrimental to the mechanical properties of the B₄C–TiB₂ ceramics. The typical values of relative density, hardness, flexural strength, and fracture toughness of the ceramics were 99.20%, 35.22 GPa, 765 MPa, and 7.69 MPa m^1/2, respectively. The toughening mechanisms of the B₄C–TiB₂ ceramics were explained by crack deflection and crack branching. In this study, the effects of high pressure and temperature caused liquefying SiO₂ to migrate to the surface of B₄C–TiB₂ and react with diffused carbon source in the graphite foil to form a 30 μm thick SiC layered structure, which improved the high-temperature oxidation resistance of the material. The unique SiC layered structure overcame the insufficient oxidation resistance of B₄C and TiB₂, thereby improving the oxidation resistance of the ceramics under high-temperature service conditions.     

Microstructures and mechanical properties of high-performance nacre-inspired Al-Si/TiB2 composites prepared by freeze casting and pressure infiltration

The nacre-inspired Al-Si/TiB₂ composites were successfully prepared by freeze casting and pressure infiltration. The microstructures and mechanical properties of nacre-inspired Al-Si/TiB₂ composites were studied by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and mechanical testing. The results show that the high performance of Al-Si/TiB₂ composites can be attributed to the clean interfaces between TiB₂ and Al and several toughening mechanisms, such as crack blunting, crack branching, crack deflection, plastic deformation of Al layer, and bridging of the uncracked fracture process zone. Specifically, the compressive strength, three-point bending strength and K_IC of composites corresponding to LS were 640–710 MPa, 629 MPa, and 16.4 MPa m^1/2, respectively. The fracture behaviors of the Al-Si/TiB₂ composites have been discussed in detail in this work. It was found that single cracks were accompanied by the propagation of multiple micro-cracks in the layered composites. The precipitation of Si particles at the TiB₂/α-Al interface and the Al phases infiltrated in the TiB₂ layers play a great role in the formation of single crack fractures and multiple micro-cracks fractures, respectively, in the nacre-inspired Al-Si/TiB₂ composites.     

TiB2–ZrB2–SiC composite ceramic coating with the formation of solid-phase (TixZr1-x)B2 deposited by atmospheric plasma spraying as a barrier to molten cryolite-based salt

TiB₂, ZrB₂, and SiC powders with particles measuring several micrometers were first agglomerated and then deposited onto the substrate of a porous carbon block as a barrier to molten cryolite-based salt. Scanning electron microscopy, X-ray diffraction, and transmission electron microscopy were conducted to investigate the fine microstructure of the obtained ceramic coating and to elucidate the evolution of agglomerated powder from sprayed particles in plasma jet to splats on a substrate. Results indicated that a highly dense ceramic coating consisting of a solid solution (Ti_xZr_1-x)B₂, residual TiB₂, and ZrB₂ was obtained. The compactness of the coating and the formation of a solid solution phase was mainly caused by a SiC-rich liquid phase, as determined from a boride and silicon carbide pseudodiagram. After being submerged in molten cryolite-based salt for 8 h, the ceramic coating was firmly bonded to a carbon block. No molten slat permeated the ceramic coating.     

Synthesis and characterisation of nanocrystalline Ca–Al layered double hydroxide {[Ca2Al(OH)6]NO3.nH2O}: in vitro study

Abstract

Abstract

In this study, Ca–Al–NO₃ layered double hydroxide (LDH) nanoparticles of varying sizes were synthesised by a process involving co-precipitation under hydrothermal condition. This method produces stable homogeneous LDH suspensions under variable hydrothermal treatment conditions with particle size in the range of 7·5–2·5 μm. Layered double hydroxides were characterised by X-ray diffraction, Fourier transform infrared spectroscopy, thermal gravimetric/differential thermal analysis, scanning electron microscopy and transmission electron microscopy (TEM) and nanosizer analyses. By increasing the hydrothermal treatment time, the crystallinity and the particle size of obtained LDH increased. Scanning electron microscopy and TEM observations showed uniform hexagonal flake-like particles with high aspect ratio. Finally, Ca–Al–NO₃ LDH did not show any acute cytotoxic effect up to 100 μg mL^?1 as measured by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay.     

High-energy methods of creating a mesocomposite material with inclusions containing nanocrystalline particles

A thermally stable high-strength mesocomposite containing nano-sized particles of titanium diboride (TiB₂) is obtained by combining methods of self-propagating high-temperature synthesis and quasi-dynamic high-velocity pressing. The use of self-propagating high-temperature synthesis ensured obtaining a hardening component of the mesocomposite — nanocomposite with a TiB₂ particle size of ≈ 100 nm. The quasidynamic method of obtaining a material characterized by high deformations determines self-organization of the mesocomposite microstructure with an unchanged size of the hardening TiB₂ particles in the inclusion structure. Mechanical properties of the mesocomposite are substantially better than the properties of the composite matrix.     

Influence of mechanical activation on sphene based ceramic material synthesis

Sphene (CaTiSiO₅), a calcium titanosilicate ceramic has been prepared from a powder mixture of CaCO₃, TiO₂ and SiO₂ using vibro-milling for homogenization and activation of precursors. The mechanochemical process initially yielded amorphous powders, which on further calcination, crystallized to yield sphene ceramic. The evolution of the phase composition with thermal treatment was investigated by X-ray powder diffraction (XRPD). Powder morphology and particle size distribution were analyzed by scanning electron microscopy (SEM) and laser diffraction, respectively. Rietveld refinement was employed to get the structural information of the synthesized powder. Densification and microstructure evolution was determined by means of density and scanning electron microscopy (SEM). The most favorable conditions for mechanical activation and synthesis of sphene based ceramic material are reported.     

Effects of graphite nano-flakes on thermal and microstructural properties of TiB2–SiC composites

In the last decades, the production of ultra-high temperature composites with improved thermo-mechanical properties has attracted much attention. This study focuses on the effect of graphite nano-flakes addition on the microstructure, densification, and thermal characteristics of TiB₂–25 vol% SiC composite. The samples were manufactured through spark plasma sintering process under the sintering conditions of 1800 °C/7 min/40 MPa. Scanning electron microscopy images demonstrated a homogenous dispersion of graphite flakes within the TiB₂–SiC composite causing a betterment in the densification process. The thermal diffusivity of the specimens was gained via the laser flash technique. The addition of graphite nano-flakes as a dopant in TiB₂–SiC did not change the thermal diffusivity. Consequently, the remarkable thermal conductivity of TiB₂–SiC remained intact. It seems that the finer grains and more interfaces obstruct the heat flow in TiB₂–SiC–graphite composites. Adding a small amount of graphite nano-flakes enhances the densification of the mentioned composite by preventing the grain growth.     

TiB2 Powders Synthesis by Borothermal Reduction in TiO2 Under Vacuum

TiB₂ powders were synthesized by borothermal reduction in nanoscale TiO₂ with boron under vacuum. Reaction processes were investigated, and the effect of by‐product B₂O₃ was evaluated. Results showed that TiO₂ was firstly reduced by boron to form TiBO₃ and Ti₂O₃, and then to produce TiB₂ and B₂O₃ with increasing temperature. The reaction processes of TiB₂ powders synthesis included two‐step reduction in TiO₂ by boron and the removal of B₂O₃. The presence of B₂O₃, which was previously reported as the most important factor in promoting the coarsening of ZrB₂ and HfB₂ powders by borothermal reduction, did not lead to significant coarsening of TiB₂ powders. Due to the minor effect of B₂O₃, TiB₂ powders with small particle size and low oxygen content could be prepared by direct heat treatment of TiO₂ and boron at 1550°C under vacuum for 1 h. The particle size and oxygen content of synthesized TiB₂ powders were ~0.9 μm and ~1.7 wt%, respectively.     

Low‐temperature synthesis of ultrafine TiB2 nanopowders by molten‐salt assisted borothermal reduction

The synthesis of TiB₂ nanopowders arouses considerable interests due to its importance for implementing the extensive applications of TiB₂ ceramic. Herein, the high‐purity ultrafine TiB₂ nanopowders were successfully synthesized via a molten salt assisted borothermal reduction technique at a relatively low temperature of 1173 K using TiO₂ and B powders as precursors within a KCl/NaCl salt. The results showed that the as‐obtained TiB₂ nanopowders possessed a polycrystallinity structure, and their specific surface area and equivalent average particle size were 33.18 m²/g and 40 nm, respectively. This study provides a new low temperature synthesis technique of TiB₂ nanopowders.     

Effects of SiC amount and morphology on the properties of TiB2-based composites sintered by hot-pressing

This investigation intended to assess the influence of SiC morphology on the sinterability and physical-mechanical features of TiB₂-SiC composites. For this aim, different volume percentages of SiC particles and SiC whiskers were introduced to TiB₂ samples hot-pressed at 1950 °C for 2 h under an external pressure of 25 MPa. The characterization of as-sintered specimens was carried out using X-ray diffraction, optical microscopy, and scanning electron microscopy. The relative density studies revealed that SiC_w had a more significant impact on the sinterability of TiB₂-based composites. The XRD investigation confirmed the production of an in-situ TiC phase during the hot-pressing; however, some peaks related to the graphitized carbon also appeared in the patterns of SiC_w-doped ceramics. The addition of 25 vol% SiC_p halved the average grain size of TiB₂ while introducing the same content of SiC_w decreased this value by just around 20%. Finally, the highest Vickers hardness and fracture toughness were obtained for the sample reinforced with 25 vol% SiC_w, standing at 29.3 GPa and 6.1 MPa m^1/2, respectively.     

Microstructural and morphological analysis of pure and Ce-doped tin dioxide nanoparticles

Structural and morphological studies in pure and Ce-doped tin dioxide nanoparticles with high stability against particle growth were performed in samples, obtained using the polymeric precursor method and prepared at different annealing temperatures. A Ce-rich surface layer was used to control the particle size and stabilize SnO₂ against particle growth. The formation of this segregated layer can contribute to a decreased surface energy, acting in the driving force, or reducing the surface mobility. Only the cassiterite SnO₂ phase was observed below 1000 °C and a secondary phase (CeO₂) was observed for the Ce-doped SnO₂ at temperatures higher than 1000 °C, when de-mixing process occurs. The evolution of crystallite size, microstrain and morphology of the nanoparticles with annealing temperatures was investigated by X-ray diffraction (XRD), associated to Rietveld refinements, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

TEM characterization of a Supra-Nano-Dual-Phase binder phase in spark plasma sintered TiB2–5 wt%HEAs cermet

In our previous work, titanium diboride (TiB₂) with high relative density and excellent mechanical properties has been synthesized by spark plasma sintering (SPS) with CoCrFeNiAl high-entropy alloys (HEAs) as sintering aid. This present work mainly focuses on the detailed morphology and elemental distribution in the TiB₂–5?wt%HEAs cermet by transmission electron microscopy (TEM) with energy dispersive spectrometer (EDS) mapping analysis. The characterization of the HEAs binder phase proves a so-called “Supra-Nano-Dual-Phase (SNDP)” structure, which has near-ideal strength at room temperature. Therefore the high strength of the SNDP binder phase leads to the excellent mechanical properties of the TiB₂–5?wt%HEAs cermet.     

High-performance B4C–TiB2–SiC composites with tuneable properties fabricated by reactive hot pressing

In this work, we systematically studied the effects of powder characteristics (B₄C, TiC and Si powders) on the existential form of toughening phases (SiC and TiB₂) as well as the overall microstructure and properties of B₄C–TiB₂–SiC composites fabricated by reactive hot pressing. The particle size of the TiC powder plays a largely determining role in the development of novel toughening phases, the TiB₂–SiC composite structure, that are formed in the B₄C matrix, while the Si particle size affects the agglomerate level of the SiC phase. The TiB₂–SiC composite structure and SiC agglomerates enhance the fracture toughness, but decrease the flexural strength. Both the microstructure and mechanical properties of B₄C–TiB₂–SiC composites can be effectively tuned by regulating the combinations of the particle sizes of the starting powders. The B₄C–TiB₂–SiC composites demonstrate flexural strength, fracture toughness and Vickers hardness in the respective range of 567–632 MPa, 5.11–6.38 MPa m^1/2, and 34.8–35.6 GPa.