Preparation of microfiltration membrane supports using coarse alumina grains coated by nano TiO2 as raw materials

To increase the mixing uniformity of coarse alumina grains with a small amount of nano TiO₂ particles, TiO₂ particles were prepared on the surface of coarse Al₂O₃ grains by in-situ hydrolysis of TiCl₄. The coated coarse Al₂O₃ powder was used to prepare microfiltration membranes supports. The effects of TiO₂ content and sintering temperatures on the bending strength, porosity and pore size distribution of the obtained supports were studied. The results show that the melted nano TiO₂ grains locate mainly at the neck of Al₂O₃ grains, which increases the bending strength of the support by increases the neck area. However, the bending strength is weakened if the TiO₂ content is excessive. No aggregated nano TiO₂ grainsare found. The resulting supports sintered at 1650 °C for 2 h yields a bending strength of 55.4 MPa, a porosity of 38% with a mean pore size of 8.0 μm.     

Design and processing of Al2O3–Al2TiO5 layered structures

Al₂O₃–Al₂TiO₅ layered composites were manufactured by a colloidal route from aqueous Al₂O₃ and TiO₂ suspensions with 50 vol.% solids. The mechanical behaviours of individual monolithic composite materials were combined and taken as basis for the design of the layered structures. Residual stresses which are likely to occur due to processing and thermally introduced misfits were calculated and considered for the manufacture of the laminates.Monoliths with 10, 30 and 40 vol.% of second phase showed that increasing proportions of aluminium titanate decrease strength and increase the non-linear behaviour.In order to obtain the desired combination of mechanical behaviours of the layers, two laminate designs with external and central layers of one composition and the alternating internal layer of the other composition were chosen taking into account chemical compatibility and development of residual stresses. In the system AA10, external and central layers of monophase Al₂O₃ with high strength were combined with intermediate layers of Al₂O₃ with 10 vol.% of Al₂TiO₅. The system A10A40 was selected to combine low strength and energy absorbing intermediate layers of Al₂O₃ with 40 vol.% of Al₂TiO₅ and sufficient strength provided by external layers of Al₂O₃ with 10 vol.% of Al₂TiO₅.The stress–strain behaviour of the laminates was linear up to their failure stresses, with apparent strain for zero load after fracture larger than that corresponding to the monoliths of the same composition as that of the external layers. Moreover, the stress drop of the laminate samples occurred in step-like form thus suggesting the occurrence of additional energy consuming processes during fracture.     

Microstructures and material properties of fibrous HAp/Al2O3–ZrO2 composites fabricated by multi-pass extrusion process

Fibrous HAp/Al₂O₃–ZrO₂ composites were fabricated using the multi-pass extrusion process. In the 3rd and 4th passed extrusion bodies, fibrous microstructures were obtained. The 3rd and 4th passed Al₂O₃–ZrO₂ cores used as reinforcement, were about 35 and 4.5 μm in diameter, respectively. In the bodies sintered at over 1400 °C, the HAp decomposed and was transformed to β-TCP and TTCP, in which large numbers of pores were observed. The values of bending strength, Vickers hardness and fracture toughness of the 3rd passed HAp/Al₂O₃–ZrO₂ composites were 178 MPa, 325 Hv, and 3.4 MPa m^1/2, respectively while the values of the 4th passed bodies were 190 MPa, 405 Hv and 3.8 MPa m^1/2.     

Effects of additives on combustion synthesis of Al2O3–TiB2 ceramic composite

Al₂O₃, SiC and kaolin were employed as additives in combustion synthesizing Al₂O₃–TiB₂ ceramic composite. Effects of the additives on adiabatic temperature, combustion wave velocity, volume change and composite density were studied, and bending strength of the synthesized ceramics was evaluated. By theoretical calculation, the adiabatic temperature of Al–TiO₂–H₃BO₃ system is 2314.85 °C and decreases with increasing the additive addition. With Al₂O₃ addition, the phases presented in the ceramic composite are unchanged, and the phases of SiC and 3Al₂O₃·2SiO₂ emerges when SiC and kaolin are added. The addition of the additives results in a refined TiB₂ particulate size and reduces combustion wave velocity. The highest density is achieved with the addition of kaolin from 10 to 30 wt.% making the volume change from ?4.6 to ?1.2%. The bending strength of the TiB₂–Al₂O₃ composite is improved eight times with the addition of 30 wt.% kaolin.     

Colored films produced by electron beam deposition from nanometric TiO2 and Al2O3 pigment powders obtained by modified polymeric precursor method

Synthesis and the characterization of TiO₂:5%Co (green), TiO₃:5%Fe (brown-reddish), TiO₂:2%Cr (brown), Al₂O₃:5%Co (blue), Al₂O₃:5%Fe (brown-reddish) and Al₂O₃:2%Cr (light green) nanometric pigment powders using polymeric precursor (modified Pechini's method) is reported. Colored thick films were deposited on amorphous quartz substrates by electron beam physical vapor deposition (EB-PVD) using pellets of the pigment powders as target. The evaporation process was carried out in vacuum of 4 × 10⁻⁶ Torr and the amorphous quartz substrates were kept at 350 °C during deposition. The TiO₂-based pigment powders presented crystalline anatase phase and the Al₂O₃-based pigment powders showed corundum phase, investigated by X-ray diffraction (XRD). The average particle size of the pigment powders was about 20 nm, measured by scanning electron microscopy with field emission gun (SEM-FEG). Diffuse reflectance spectra and colorimetric coordinates L¹, a¹, b¹ using the CIE-L¹a¹b¹ method are shown for the pigment powders, in the 350–750 nm range. The colored thick films were characterized by transmittance (UV–Vis) and atomic force microscopy (AFM). The average film roughness was ∼5.5 nm and the average grain size obtained in the films was around 75 nm. Films with thickness from 400 nm to 690 nm were obtained, measured by talystep profiler. Transmission spectra envelop method has been used to obtain refractive index and thickness of the Al₂O₃ colored thick films.     

Microstructure and mechanical properties of Al2O3–20 wt%Al2TiO5 composite prepared from alumina and titania nanopowders

In the present work, Al₂O₃–20 wt%Al₂TiO₅ composite was prepared from reaction sintering of alumina and titania nanopowders. The nano-sized raw powders were reconstituted into nanostructured particles by ball milling. Then, the nanostructured reconstituted powders were pressed and pressureless-sintered into bulk ceramics at 1300, 1400, 1500 °C for 2 h. The phase composition and microstructures of reconstituted powders and as-prepared ceramic composites were characterized by using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope and energy-dispersive spectrometer (EDS). The microstructural analysis of the ceramic showed that the average grain size of the alumina–aluminium titanate composite increases with increasing the temperature. Also, SEM proved the existence of a proper interface between Al₂TiO₅ and Al₂O₃ grains and preferential distribution of aluminium titanate particles in the grain boundaries. XRD analysis indicated the absence of rutile titania in the sintered composite ensuring complete formation of aluminium titanate. The hardness of the samples sintered at 1300, 1400, 1500 °C were 4.8, 6.2 and 8.5 GPa, respectively.     

Solubility and microstructural development of TiO2-containing 3Al2O3·2SiO2 and 2Al2O3·SiO2 mullites obtained from single-phase gels

The interdependence of the titanium oxide amount and the anisotropic growth of mullites prepared from single-phase gels were investigated. Gels with stoichiometries 3(Al_2−xTi_xO₃)·2(SiO₂) and 2(Al_2−xTi_xO₃)·(SiO₂), with 0 ≤ x ≤ 0.15 were prepared by the semialkoxide method. Gels and specimens heated at temperatures between 1200 and 1600 °C were characterized by using infrared spectroscopy (IR), X-ray diffraction (XRD) and transmission and field emission scanning electron microscopies (TEM and FESEM). Al₂TiO₅ as minor impurity was detected in both series of mullites for gel precursor compositions x = 0.10 and x = 0.15, obtained at temperatures between 1200 and 1600 °C. Variations of lattice parameters of mullite, processed at temperatures from the range between 1400 and 1600 °C, with the starting nominal amount of titanium oxide indicated that the solubility limit of titanium oxide was in ranges 3.8–4.1 and 4.1–4.4 wt% TiO₂ for 3:2 and 2:1 mullites series, respectively. The anisotropic growth of titanium-doped mullite crystalline grains was significant only when the nominal amount of titanium oxide exceeded the limit of solubility into the mullite structure (for both mullite series). Stronger anisotropy occurred for the 3:2 series specimens, i.e. for the SiO₂-richer mullites. In both series of mullites, the anisotropic grain growth was observed for the process temperatures higher than 1400 °C; the crystalline grains of mullites processed at lower temperatures were equiaxials and of almost the same size.     

Effect of TiO2 addition on the properties of Ti3Si(Al)C2 based ceramics fabricated by reactive melt infiltration

In this paper, Ti₃Si(Al)C₂ based ceramics were fabricated by reactive melt infiltration (RMI) of TiC/TiO₂ preforms with liquid silicon. The microstructure, phase composition, and mechanical properties of the Ti₃Si(Al)C₂ based ceramics have been investigated to understand the effect of phase composition of the preforms on the formation mechanisms of Ti₃Si(Al)C₂. The preforms with different content of TiO₂ infiltrated at 1500 °C with liquid silicon for 1 h were composed of Ti₃Si(Al)C₂, Al₂O₃, TiC, TiSi_xAl_y and residual Al. The prior generated Al₂O₃ phases inhibited the dispersion of Ti₃Si(Al)C₂ phases, resulting in the drastically grain growth of Ti₃Si(Al)C₂. Subsequently, the microstructure with gradually increasing Ti₃Si(Al)C₂ grain size resulted in the decrease of the bending strength and fracture toughness of samples. When the content of TiO₂ reached 20 wt%, the bending strength reached the maximum, 326.6 MPa. The fracture toughness attained the maximum, 4.3 MPa m^1/2, when the content of TiO₂ was 10 wt%.     

Microwave dielectric properties and microstructures of Nb2O5-Zn0.95Mg0.05TiO3 + 0.25TiO2 ceramics with Bi2O3 addition

The effects of Bi₂O₃ addition on the microwave dielectric properties and the microstructures of Nb₂O₅-Zn_0.95Mg_0.05TiO₃ + 0.25TiO₂ (Nb-ZMT′) ceramics prepared by conventional solid-state routes have been investigated. The results of X-ray diffraction (XRD) indicate the presence of four crystalline phases, ZnTiO₃, TiO₂, Bi₂Ti₂O₇, and (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ in the sintered ceramics, depending upon the amount of Bi₂O₃ addition. In addition, in order to confirm the existence of (Bi_1.5Zn_0.5)(Ti_1.5Nb_0.5)O₇ phase in the samples, the microstructure of Nb-ZMT′ ceramic with 5 wt.% B₂O₃ addition was analyzed by using a transmission electron micrograph. The dielectric constant of Nb-ZMT′ samples was higher than ZMT′ ceramics. The Nb-ZMT′ ceramic with 5 wt.% Bi₂O₃ addition exhibits the optimum dielectric properties: Q × f = 12,000 GHz, ?_r = 30, and τ_f = ?12 ppm/°C. Unlike the ZMT′ ceramic sintered at 900 °C, the Nb-ZMT′ ceramics show higher Q value and dielectric constant. Moreover, there is no Zn₂TiO₄ existence at 960 °C sintering. To understand the co-sinterability between silver electrodes and the Nb-ZMT′ dielectrics, the multilayer samples are prepared by multilayer thick film processing. The co-sinterability (900 °C) between silver electrode and Nb-ZMT′ dielectric are well compatible, because there are no cracks, delaminations, and deformations in multilayer specimens.     

Role of the effective electrical conductivity of nanosuspensions in the generation of TiO2 agglomerates with electrospray

Suspensions with varying volume fraction of TiO₂ nanoparticles and ionic strength were electrosprayed to obtain agglomerates of different characteristics, which were then deposited to produce films with tailored morphology, thickness, and porosity. The role of the nanoparticle volume fraction in both the effective electrical conductivity of TiO₂ nanosuspensions and the control of the size of agglomerates produced by electrospray was investigated. A simple modified equation for the effective electrical conductivity of TiO₂ nanoparticle suspensions was derived. The equation, which accounted for nanoparticles' diffuse ionic layer and their agglomeration in a liquid, showed that the effective electrical conductivity is not only a function of the liquid and particle conductivities, and the particle volume fraction but also a function of both the thickness of the adsorbed ionic layer on the particles and the particle size. Gradual increase of particle volume fraction resulted in an increase in the suspension's effective electrical conductivity, when the initial liquid conductivity was in the range of 10^?4–10^?3 S m^?1. When the liquid conductivity was in the range of 10^?3–10^?2 S m^?1; however, addition of particles did not have any significant effect on the effective electrical conductivity. Control over the size of the TiO₂ nanoparticle agglomerates was achieved by electrospraying suspensions with liquid electrical conductivity of the order of 10^?3 S m^?1 and by varying the particle volume fraction. Electrospray deposition of suspensions with TiO₂ volume fraction=0.04% resulted in a more compact film with lower porosity and showed better water-splitting performance.     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Effect of Al2O3 on the microstructure and mechanical properties of Ti3AlC2/Al2O3 in situ composites synthesized by reactive hot pressing

Ti₃AlC₂/Al₂O₃ in situ composites with different Al₂O₃ contents were successfully synthesized from the powder mixture of Ti, TiC, Al and TiO₂ by a reactive hot-pressing method at 1350 °C. The effect of Al₂O₃ on the microstructure and mechanical properties of the composites was investigated in detail. The results indicate that the as-fabricated products mainly consist of Ti₃AlC₂, Al₂O₃ and a small amount of TiC. With increasing the Al₂O₃ content, the flexural strength of Ti₃AlC₂/Al₂O₃ composites increase gradually, the fracture toughness reaches the peak value of 8.21 MPa m^1/2 as the Al₂O₃ content increasing to 9 wt%, the hardness attains the maximum value of 10.16 GPa for 12 wt% Al₂O_3. The strengthening mechanism of the composites was also discussed.     

Fracture toughness of concentric Si3N4-based laminated structures

A new concentric rectangular laminated structure was designed and fabricated by slip-casting method and densified by pressureless sintering process. One class of laminates consists of layers of Si₃N₄ with 7 wt.% Y₂O₃ and 3 wt.% Al₂O₃ as sintering aids, and of interlayers consisting of 50 wt.% BN and 50 wt.% Al₂O₃ designated as SN-(BN + Al₂O₃). The other class of laminates has the same Si₃N₄ layer composition but different interlayer composition of 90 wt.% BN and 10 wt.% Si₃N₄ designated as SN-(BN + SN). The objective of this paper is to investigate the effects of the number of layers and their thickness on apparent fracture toughness of these laminates. The interfacial layer composition was discussed in terms of its role in toughening of the laminates. For the SN-(BN + Al₂O₃) laminates the highest apparent fracture toughness of 22 MPa m^1/2 was found in the samples with 7 Si₃N₄ layers and for the SN-(BN + SN) laminates the highest apparent fracture toughness of 19.5 MPa m^1/2 was found in the samples with 4 Si₃N₄ layers.     

Enhancing the sinterability and fracture toughness of Al2O3–TiN0.3 composites

We introduce a new and effective method for improving the fracture toughness of Al₂O₃-based composites through the addition of a nonstoichiometric material. Al₂O₃–TiN_0.3 composites were sintered by spark plasma sintering with different TiN_0.3 content at temperatures between 1300 and 1600 °C for 10 min and a micro-region diffusion phenomenon was observed at the Al₂O₃–TiN_0.3 interface. Ti atoms from TiN_0.3 diffused into Al₂O₃ to occupy Al sites, which led to the formation of Al vacancies that enabled the transport of aluminum by a vacancy mechanism. The optimal densification temperature of the Al₂O₃–30vol% TiN_0.3 composite was approximately 1400 °C. The maximum fracture toughness measured was 6.91 MPa m^1/2, from the composite with 30 vol% TiN_0.3 sintered at 1500 °C.     

Preparation and properties of high toughness RBAO macroporous membrane support

Reaction bonding of aluminum oxide (RBAO) is a novel technique for preparing porous alumina. By adapting this manufacturing route, macroporous Al₂O₃ supports with high fracture toughness are prepared for ceramic membrane. The effects of sintering temperatures and aluminum (Al) content on mechanical properties of macroporous Al₂O₃ supports are investigated, especially for the improvement of fracture toughness. When the sintering temperatures increase from 1200 °C to 1600 °C, increments of fracture toughness and bending strength are observed. Sintered at 1600 °C, when Al content is 16 wt%, the maximum value of fracture toughness and bending strength of macroporous Al₂O₃ supports are 2.0 MPa m^1/2 and 137 MPa, respectively, which are 2.0 and 2.6 times than that of the supports without adding any additives. By SEM analysis, many fine Al₂O₃ particles form a network which is beneficial to the improvements of fracture toughness and bending strength. After corroded in nitric acid and sodium hydroxide solutions of 1 mol L^?1 at 80 °C for 168 h, respectively, the mass loss percentage is lower than 1 wt%. And the bending strength keeps at the level of ～40 MPa which is strong enough to apply in industry. Simultaneously, the toughening mechanism of RBAO macroporous support is also discussed.     

TiO2–SnO2 nanomaterials for gas sensing and photocatalysis

Nanopowders of TiO₂–SnO₂ over a full composition range extending from 100 mol% TiO₂ to 100 mol% SnO₂ are obtained by the sol–gel method from TTIP and SnCl₂·5H₂O precursors of Ti and Sn, respectively followed by calcination at 400 °C. The samples are characterized by means of BET, XRD and TEM. Optical properties of the prepared nanomaterials are studied as well. TEM images indicate that the nanoparticles are regular in shape. The specific surface area, SSA of TiO₂ is 95 m²/g while that of SnO₂ amounts to 129 m²/g. The highest SSA of 156 m²/g is achieved at 20 mol% of TiO₂. Occurrence of rutile, anatase and brookite polymorphic forms depends on the chemical composition of nanopowders. Formation of rutile-type solid solution of TiO₂–SnO₂ over the range of 0–80 mol% TiO₂ is confirmed by Vegard rule applied to lattice constants. Electronic band gap decreases with Ti content from 3.84 eV (100 mol% SnO₂) to 3.18 eV (100 mol% TiO₂).     

Sintering,microstructure and mechanical properties of Al2O3–Y2O3–ZrO2 (AYZ) eutectic composition ceramic microcomposites

We report on how the mechanical properties of sintered ceramics (i.e., a random mixture of equiaxed grains) with the Al₂O₃–Y₂O₃–ZrO₂ eutectic composition compare with those of rapidly or directionally solidified Al₂O₃–Y₂O₃–ZrO₂ eutectic melts. Ceramic microcomposites with the Al₂O₃–Y₂O₃–ZrO₂ eutectic composition were fabricated by sintering in air at 1400–1500 °C, or hot pressing at 1300–1400 °C. Fully dense, three phase composites of Al₂O₃, Y₂O₃-stabilized ZrO₂ and YAG with grain sizes ranging from 0.4 to 0.8 μm were obtained. The grain size of the three phases was controlled by the size of the initial powders. Annealing at 1500 °C for 96 h resulted in grain sizes of 0.5–1.8 μm. The finest scale microcomposite had a maximum hardness of 19 GPa and a four-point bend strength of 282 MPa. The fracture toughness, as determined by Vickers indentation and indented four-point bending methods, ranged from 2.3 to 4.7 MPa m^1/2. Although strengths and fracture toughnesses are lower than some directionally or rapidly solidified eutectic composites, the intergranular fracture patterns in the sintered ceramic suggest that ceramic microcomposites have the potential to be tailored to yield stronger, tougher composites that may be comparable with melt solidified eutectic composites.     

Synthesis and electrochemical properties of TiO2/nanodiamond nanocomposite

Undoped nanodiamond (ND) powders were coated with TiO₂ through two steps: firstly Ti lay was deposited by cycled vacuum-feeding chemical vapour deposition from gaseous TiCl₄/H₂, and secondly an oxidation treatment was carried out in air. The structure and the morphology of the TiO₂/ND composite were characterized by Raman spectrum and transmission electron microscopy. The electrochemical properties of the TiO₂/ND powder electrode in a solution containing [Fe(CN)₆]^3?/4? or NO₂^? were investigated. The results showed that a continuous coating consisting of Ti nanoparticles covered on ND particle after the deposition. The following oxidation at 500 °C resulted in the formation of anatase phase TiO₂ nanoparticles of about 10 nm. The electrochemical results confirmed that the TiO₂/ND powder electrode exhibited higher electrochemical activity than the pristine ND electrode, especially higher catalytic ability toward the oxidation of nitrite anions. Moreover, the TiO₂/ND powder electrode presented fast response towards nitrite oxidation with a detection limit of 0.55 µM and a linear range of 0.05 to 1.0 mM.     

Zn2+ doped TiO2/C with enhanced sodium-ion storage properties

To improve the performance of anatase TiO₂ as an anode material for sodium-ion batteries, Zn²⁺-doped TiO₂/C composites are synthesized by a co-precipitation method. The results of XRD, EPR and XPS demonstrate that Zn²⁺ occupies at the Ti⁴⁺ site of TiO₂ to form a solid-solution, resulting in an expansion of lattice and an increase of Ti³⁺ content. The expansion of lattice can enhance the stability of the crystal structure of TiO₂. The increase of Ti³⁺ content can improve the conductivity of TiO₂. Therefore, Ti_0.94Zn_0.06O₂/C delivers a reversible capacity of 160 mA h g⁻¹ with a capacity retention of 96% after 100 cycles at 5 C. Even charged/discharged at 10 C, this sample still exhibits a reversible capacity of 117 mA h g⁻¹, comparing to 86 mA h g⁻¹ for TiO₂/C. The enhanced electrochemical performances can be ascribed to the improvement of the conductivity and the structural stability of TiO₂ due to Zn²⁺-doping. Therefore, Ti_0.94Zn_0.06O₂/C is an attractive anode material of sodium-ion batteries.     

Catalytic decomposition of CH2Cl2 over supported Ru catalysts

Ru/TiO₂ and Ru/Al₂O₃ were prepared by wet impregnation of TiO₂ and Al₂O₃, and tested in the catalytic decomposition of dichloromethane (DCM). Ru/TiO₂ catalyst presents the higher activity than Ru/Al₂O₃ catalyst, with 50% and 90% conversion occurring at 235 and 267 °C, respectively. Moreover, the higher stability on Ru/TiO₂ catalyst is observed, which can be related to ready removal of Cl species produced during DCM decomposition. The chlorine uptake on Ru/TiO₂ catalyst is estimated at 240 °C to be 0.36 mmol Cl/g_cat, while on Ru/Al₂O₃, the value is 1.46 mmol Cl/g_cat.