Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.     

Preparation of Pt-loaded TiO2 nanofibers by electrospinning and their application for WGS reactions

Preparation of Pt-loaded TiO₂ nanofibers and their catalytic performance for water gas shift (WGS) reactions have been explained in this work. The Pt-loaded TiO₂ nanofibers were obtained by electrospinning poly-ethylene oxide (PEO) aqueous solutions containing Ti(OH)_n slurry and Pt nanoparticles at room temperature, followed by calcination at 773 K for 4 h. The calcined nanofibers were rougher than the nanofibers of PEO/Ti(OH)_n/Pt due to the PEO degradation and oxidation of Ti(OH)_n to TiO₂. Diameters of the Pt-loaded TiO₂ nanofibers ranged between 200 and 900 nm. Catalytic activity of the Pt-loaded TiO₂ nanofibers for water gas shift (WGS) reactions was evaluated and it was observed that their activity was 5–7 times higher than that of a bulk catalyst. Such improvement is attributed to the larger surface area of the nanofiber catalyst compared to that of the bulk catalyst. To the best of our knowledge, this is the first demonstration of a synthesis of Pt-loaded TiO₂ nanofibers from a Ti(OH)_n nanoparticle slurry using electrospinning and its application to WGS reactions.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

Preparation and properties of B6O/TiB2-composites

B₆O/TiB₂ composites with varying compositions were produced by FAST/SPS at temperatures between 1850 and 1900 °C following a non-reactive or a reactive sintering route. The densification, phase and microstructure formation and the mechanical and thermal properties were investigated. The comparison to an also investigated pure B₆O material showed that the addition of TiB₂ in a non-reactive sintering route promotes the B₆O densification. Further improvement was obtained by sintering reactive B–TiO₂ mixtures which also results in materials with a finer grain size and thus in enhanced mechanical properties. The fracture toughness was significantly improved in all composites and is up to 4.0 MPa m^1/2 (SEVNB) and 2.6–5.0 MPa m^1/2 (IF method) while simultaneously a high hardness of up to 36 GPa (HV_0.4) and 28 GPa (HV₅) could be preserved. The high temperature properties at 1000 °C of hardness, thermal conductivity and CTE were up to 20 GPa, 18 W/mK and 6.63 × 10^?6/K, respectively.     

Pressureless sintering of boron carbide with Cr3C2 as sintering additive

In this study, chromium carbide (Cr₃C₂) was selected as the sintering additive for the densification of boron carbide (B₄C). Cr₃C₂ can react with B₄C and form graphite and CrB₂ in situ, which is considered to be effective for the sintering of B₄C composites. The sintering behavior, microstructure development and mechanical properties of B₄C composites were studied. The density of B₄C composite increased with the increase of Cr₃C₂ content and sintering temperature. The formation of liquid phase could effectively improve the densification of B₄C composites. The abnormal grains began to appear at 2080 °C. The bending strength could reach 440 MPa for the 25 wt% and 30 wt% Cr₃C₂ samples after sintering at 2070 °C.     

Effects of sintering temperature on mechanical properties of 3D mullite fiber (ALF FB3) reinforced mullite composites

A new method to weaken the interfacial bonding and increase the strength of 3D mullite fiber reinforced mullite matrix (Mu_f/Mu) composites is proposed and tested in this paper. Firstly, Mu_f/Mu composites were fabricated through sol–gel process with varied sintering temperature. Then, the effects of sintering temperature on mechanical properties of the composites were tested. As sintering temperature was raised from 1000 °C to 1300 °C, the three-point flexural strength of the composites firstly decreased from 66.17 MPa to 41.83 MPa, and then increased to 63.17 MPa. In order to explain the relationship between composite strength and sintering temperature, morphology and structure of the mullite fibers and mullite matrix after the same heat-treatment as in the fabrication conditions of the composites were also investigated. Finally, it is concluded that this strength variation results from the combined effects of matrix densification, interfacial bonding and fiber degradation under different sintering temperatures.     

Densification,microstructure and mechanical properties of ZrB2–SiCw ceramic composites

ZrB₂–SiCw composites were prepared through hot-pressing at a low temperature of 1800 °C, and Al₂O₃ plus Y₂O₃ were added as sintering aids. Analysis revealed that additives may react with impurities (i.e. surface oxygen impurities and residual metallic impurities) to form a transient liquid phase, thus promote the sintering and densification of ZrB₂–SiCw composites. The content of additives was found to have a significant influence on the sinterability, microstructure and mechanical properties of ZrB₂–SiCw composites. ZrB₂–SiCw composite prepared with a small amount of additives (3 vol.%) provided the optimal combination of microstructure (relative density of 98.3%) and excellent properties, including flexural strength of 783 MPa and fracture toughness of 6.7 MPa m^1/2. With further addition of additives, SiC whiskers were inclined to gather together and be enveloped by excessive liquids to form core-rim-like structures, which lead to little decrease in mechanical properties.     

Temperature-induced changes in morphology and microstructure of electrospun mullite nanofibers fabricated from a hybrid mullite sol

Mullite nanofibers with small diameter and high surface area are an ideal candidate as the reinforcements in composite materials, and have promising applications in the fields of catalysis, filtration, thermal storage and so forth. In this work, electrospun mullite nanofibers were successfully synthesized using a hybrid mullite sol. The morphology and microstructure of fibers calcined at different temperatures were investigated. The morphology of fibers synthesized at 900 °C is porous with coarse surface, and after crystallization it becomes compact with smooth surface. The densities of fibers increase with the increasing temperatures. At 1200 °C the surface of fibers becomes coarse again, as a result of the grain growth of mullite. The crystallization path of fibers was revealed that the Al-rich mullite (4Al₂O₃·SiO₂) together with amorphous silica formed at 1000 °C, changed into mullite with higher silica contents as temperature further increased, and finally transformed into a stable 3Al₂O₃·2SiO₂ phase at 1200 °C. During this crystallization process, the flow of amorphous silica phase and the formation of mullite crystal structure benefit the densification of fibers, leading to the resultant fibers with fine and compact microstructure. The present findings can provide a guideline for the preparation of the promising high-mechanical mullite nanofibers and the synthesized nanofibers display great potential as reinforcements in structural ceramic composites.     

Densification behavior and properties of alumina–chrome ceramics: Effect of TiO2

Highly dense alumina–chrome bodies with low porosity are usually used as corrosion and thermal resistant refractories. Alumina–chrome refractory with molar ratio 1:1 was developed using chemical grade hydrated alumina and chromium (III) oxide by conventional sintering route. Batch materials were attrition milled, isostatically pressed and sintered in the temperature range from 1000 °C to 1700 °C with 2 h soaking at peak temperature. Phase development of the sintered materials with temperature was studied by X-ray diffraction. Sintering temperature, sintering condition and addition of sintering aid (TiO₂) have immense effect on the densification of the alumina–chrome refractory. Highly dense alumina–chrome refractory with almost nil apparent porosity was developed at 1500 °C in reducing atmosphere. Flexural strength of the sintered materials at room temperature and at 1200 °C was also measured. 1 wt% TiO₂ gives the optimum result with respect to densification and flexural strength.     

Microstructure and mechanical properties of hot-pressed B4C/TiC/Mo ceramic composites

Boron carbide (B₄C)/TiC/Mo ceramic composites with different content of TiC were produced by hot pressing. The effect of TiC content on the microstructure and mechanical properties of the composites has been studied. Results showed that chemical reaction took place for this system during hot pressing sintering, and resulted in a B₄C/TiB₂/Mo composite with high density and improved mechanical properties compared to monolithic B₄C ceramic. Densification rates of the B₄C/TiC/Mo composites were found to be affected by additions of TiC. Increasing TiC content led to increase in the densification rates of the composites. The sintering temperature was lowered from 2150 °C for monolithic B₄C to 1950 °C for the B₄C/TiC/Mo composites. The fracture toughness, flexural strength, and hardness of the composites increased with increasing TiC content up to 10 wt.%. The maximum values of fracture toughness, flexural strength, and hardness are 4.3 MPa m^1/2, 695 MPa, and 25.0 GPa, respectively.     

Reactive hot pressing of SiC-ZrC composites at low temperature

SiC-ZrC composites with relative density in excess of 99% were prepared by reactive hot pressing (RHP) of SiC and ZrH₂ at 1800 °C for 1 h. The reaction between SiC and ZrH₂ resulted in the formation of ZrC_1-x. The formation process and densification behavior during RHP process were investigated. Low temperature densification of SiC-ZrC composites is attributed to the formed nonstoichiometric ZrC_1-x and the removal of SiO₂ impurity on the surface of SiC particles. As reinforced phase, ZrC_1-x has inhibiting effect on the abnormal grain growth of SiC, resulting in homogeneous microstructure of fine SiC grains. Adding 10 wt% ZrH₂ to SiC, the formed SiC-4.62 vol% ZrC composite exhibited better mechanical properties (Vickers hardness of 27.6 ± 0.7 GPa, flexure strength of 448 ± 38 MPa, fracture toughness of 6.0± 0.3 MPa·m^1/2, respectively) than monolithic SiC ceramic.     

Spark plasma sintering and characterization of ZrC-TiB2 composites

ZrC-based composites were consolidated from ZrC and TiB₂ powders by the Spark Plasma Sintering (SPS) technique at 1685 °C and 1700 °C for 300 s under 40-50-60 MPa. Densification, crystalline phases, microstructure, mechanical properties and oxidation behavior of the composites were investigated. The sintered bodies were composed of a (Zr,Ti)C solid solution and a ZrB phase. The densification behaviors of the composites were improved by increasing the TiB₂ content and applied pressure. The highest value of hardness, 21.64 GPa, was attained with the addition of 30 vol% TiB₂. Oxidation tests were performed at 900 °C for 2 h and the formation of ZrO₂, TiO₂ and B₂O₃ phases were identified by using XRD.     

Synthesis of TiO2(B)/SnO2 composite materials as an anode for lithium-ion batteries

A TiO₂(B) nanosheets/SnO₂ nanoparticles composite was prepared by the hydrothermal and chemical bath deposition (CBD) methods, and its electrochemical properties were investigated for use as the anode material of a lithium-ion battery. The as-prepared composites consisted of monoclinic-phase TiO₂(B) nanosheets and cassiterite structure SnO₂ nanoparticles, in which SnO₂ nanoparticles were uniformly decorated on the TiO₂(B) nanosheets. The TiO₂(B)/SnO₂ composites showed a higher reversible capacity and better durability than that of the pure TiO₂(B) for use as a battery anode. The composite electrodes exhibiting a high initial discharge capacity of 2239.1 mAh g⁻¹ and a discharge capacity of more than 868.7 mAh g⁻¹ could be maintained after 50 cycles at 0.1 C in a voltage range of 1.0–3.0 V at room temperature. The results suggest that TiO₂(B) nanosheets coated with SnO₂ could be suitable for use as a stable anode material for lithium-ion batteries. In addition, the coulombic efficiency of the nanosheets remains at an average of 93.1% for the 3rd–50th cycles.     

Hydrothermal synthesis and visible-light photocatalytic activity of α-Fe2O3/TiO2 composite hollow microspheres

Novel α-Fe₂O₃/TiO₂ composite hollow spheres were successfully synthesized by a template-assisted precipitation reaction using urea as a precipitating agent and carbon spheres as templates in a mixed solvent of water and ethanol, and then calcined at 400 °C for 4 h. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption–desorption isotherms, and vibrating sample magnetometer. The influence of calcination temperature and the molar ratio of titanium to iron (R) on the photocatalytic activity of the samples was investigated. The results indicated that the composite spheres show magnetic characteristics at room temperature and good photocatalytic activity under visible-light irradiation compare to the single-component α-Fe₂O₃ particles. This method can be further applied to synthesize nanocomposites of magnetic metal oxide and other metal oxide.     

Direct synthesis of carbon nanofibers on the surface of copper powder

A novel approach to synthesize carbon nanofibers (CNFs) directly on the surface of metal μm-sized particles to evenly disperse the carbon nanomaterials in a composite material was proposed. As a metal matrix, 5–10 μm copper particles were utilized. As a carbon source, C₂H₂, CH₄ and CO were examined. The best conditions were found to be in C₂H₂ (30 cm³/min) and H₂ (260 cm³/min) atmosphere at the temperature of 750 °C. The composites based on copper and CNFs prepared by vacuum hot pressing showed the increase in hardness from 35 to 60 kg/mm² almost retaining pure copper electrical properties.     

Electro-spinning Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3−δ nanofibers infiltrated with Gd0.2Ce0.8O1.9 nanoparticles as cathode for intermediate temperature solid oxide fuel cell

Pr_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3−δ (PSCFN) nanofibers and their corresponding Pr_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3−δ–Gd_0.2Ce_0.8O_1.9 (PSCFN–GDC) composites have been synthesized and applied as cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this paper, PSCFN nanofibers were obtained through electro-spinning and the following pyrolysis process. The resultant PSCFN nanofibers were infiltrated with GDC precursor to prepare nanofiber-structured PSCFN–GDC composite cathodes. The optimal PSCFN: GDC mass ratio of 1: 0.10 was identified to possess the lowest interfacial polarization resistances of 0.264, 0.155, 0.039 and 0.018 Ω cm² at 650, 700, 750 and 800 °C, respectively, lower than those of the PSCFN–GDC nanoparticle-structured composite cathode. The PSCFN–GDC (1: 0.10) shows an excellent stability of electrochemical activity under a current density of 200 mA cm⁻² for 100 h at 800 °C. All results proved that the nanofiber-structured PSCFN–GDC composite could act as a highly efficient cathode candidate for the IT-SOFCs.     

Pd-doped TiO2@polypyrrole core-shell composites as hydrogen-sensing materials

A core-shell composite consisting of polypyrrole (PPy) nanofibers and TiO₂ was synthesized by using PPy nanofibers as the core and TiO₂ as the shell. The TiO₂@PPy composite substrate was doped with Pd nanoparticles via chemical reduction. The resulting Pd–TiO₂@PPy nanocomposite was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller (BET) adsorption analysis before it was utilized to fabricate a hydrogen sensor. Compared with sensors based on TiO₂@PPy or PPy, the Pd–TiO₂@PPy sensor was highly sensitive and selective to hydrogen gas, exhibiting a fast response time in air at room temperature. The Pd–TiO₂@PPy-based sensor exhibited a sensitivity of 8.1% toward 1 vol% of H₂ gas, which is much larger than the sensitivities of sensors based on only TiO₂@PPy and PPy nanofibers. The excellent reproducibility, stability and selectivity of the Pd–TiO₂@PPy nanocomposite make it a high potential candidate for hydrogen sensors.     

Comparison of microstructure,toughness, mechanical properties and work hardening of titanium/TiO2 and titanium/SiC composites manufactured by accumulative roll bonding (ARB) process

In this study, the effects of TiO₂ ceramic nanoparticles and SiC microparticles on the microstructure, mechanical properties and toughness of titanium/TiO₂ nanocomposite and titanium/SiC composite were investigated. To achieve this goal, TiO₂ and SiC ceramic particles were incorporated as the reinforcement in titanium through the ARB (accumulative roll bonding) process. By adding SiC ceramic particles, the mechanical properties of the composite and the nanocomposite were enhanced, while their toughness was decreased, as compared to TiO₂ nanoparticles. After applying 8 cycles of the ARB process, UTS in Ti/5 vol% SiC composite reached to about 1200 (MPa), as compared to that in Ti/0.5 wt% TiO₂ nanocomposite, which was about 1100 (MPa). Furthermore, toughness in the Ti/5 vol% SiC composite and the Ti/0.5 wt% TiO₂ nanocomposite was 60 and 29 J/m³, respectively. Finally, SEM and TEM images showed SiC microparticles clustering in Ti/SiC composite samples and a suitable distribution of TiO₂ nanoparticles in the Ti/TiO₂ nanocomposite. By adding TiO₂ nanoparticles, mechanical properties and work hardening coefficient were found to be increased, as compared to those of the monolithic samples. TiO₂ nanoparticles, after being distributed in the titanium matrix through the ARB process, caused pin dislocations. As clearly shown in TEM images, dislocation tangles around TiO₂ nanoparticles acted as the main mechanism improving the work hardening coefficient.     

Stabilized tialite–mullite composites with low thermal expansion and high strength for catalytic converters

Aluminium titanate (AT) is a potential candidate material for use in demanding high temperature applications, because it exhibits an excellent thermal shock resistance due to its low thermal expansion coefficient and high refractoriness.However, industrial applications of this material are hindered by two major limitations. Its decomposition to α-Al₂O₃ and TiO₂ between 800 and 1280 °C and its low mechanical strength.The present work aims to stabilize aluminium titanate with the addition of Fe₂O₃. The decomposition of aluminium titanate–iron oxide solid solutions when heated at 1100 °C for up to 1000 h was studied. The effect of iron oxide addition on pure aluminium titanate properties was investigated. Additionally, strengthening of the iron stabilized AT with mullite was considered adding mullite (M), 3Al₂O₃·2SiO₂ to tialite body at various amounts (5–50%, w/w). Properties like four point bending strength, thermal expansion coefficient (TEC), and porosity of the composites, were evaluated. Finally, the effect of mullite on the mechanical properties of AT–mullite composites was investigated.It was found that aluminium titanate (iron oxide stabilized)–mullite composites exhibit very good mechanical strength combined with excellent thermal stability.     

Synergetic effects of SiC and Csf in ZrB2-based ceramic composites. Part I: Densification behavior

The effects of processing variables on densification behavior of hot pressed ZrB₂-based composites, reinforced with SiC particles and short carbon fibers (C_sf), were studied. A design of experiment approach, Taguchi methodology, was used to investigate the characteristics of ZrB₂–SiC–C_sf composites concentrated upon the hot pressing parameters (sintering temperature, dwell time and applied pressure) as well as the composition (vol% SiC/vol% C_sf). The analysis of variance recognized the sintering temperature and SiC/C_sf ratio as the most effective variables on the relative density of hot pressed composites. The microstructural investigations showed that C_sf can act as a sintering aid and eliminate the oxide impurities (e.g. B₂O₃, ZrO₂ and SiO₂) from the surfaces of raw materials. A fully dense composite was achieved by adding 10 vol% C_sf and 20 vol% SiC to the ZrB₂ matrix via hot pressing at 1850 °C for 30 min under a pressure of 16 MPa. Moreover, the in-situ formation of interfacial ZrC, which also improves the sinterability of ZrB₂-based composites, was studied by energy-dispersive X-ray spectroscopy analysis and verified thermodynamically.