Hydrothermal synthesis of BaTiO3 from different Ti-precursors and microstructural and electrical properties of sintered samples with submicrometric grain size

Barium titanate submicrometric particles were synthesized at 180 °C in a closed PTFE-lined stainless steel reactor with continuous stirring. Precursors used for titanium were Degussa P25 TiO₂ or titanium isopropoxide (TIP). Barium hydroxide (Ba(OH)₂) was added in a Ba/Ti = 1.1 molar ratio and KOH was used as mineralizer. The obtained powders were characterized by XRD and Raman spectroscopy. Powders were uniaxially pressed into discs and sintered at 1250 °C. The resulting microstructures were characterized by XRD, SEM, and Raman spectroscopy. Electrical measurements were carried out in order to characterize the ferroelectric behavior. The Ti precursor determined the sample density and grain size distribution and, consequently, the electrical response.     

Direct synthesis of TiO2 nanoparticles by using the solid-state precursor TiH2 powder in a thermal plasma reactor

We attempt the direct synthesis of TiO₂ by using the solid state precursor TiH₂ powder with oxygen in a thermal plasma reactor. Nanocrystalline titanium dioxide powder has been synthesized by using thermal plasma synthesis in a non-transferred arc thermal plasma reactor. The thermal plasma-synthesized powder product consists of nano-sized particles of anatase and rutile phases of titanium dioxide. Particle compositions were observed on collecting powder from different positions of the reactor and varying the amount of flow rate of reactive gases (O₂). The characteristics of the powder such as particle size, size distribution and phases were analyzed using various techniques such as XRD, SEM, TEM, XPS, EDS and particle size analyzer. UV–visible reflection spectroscopy of the plasma-synthesized TiO₂ powders showed the absorbance in the visible region leading to effective photocatalytic activity, which is clearly confirmed from the XPS analysis. XPS analysis reveals the presence of –OH bonds on the surface of nanoparticles, which is the significant evidence of better quality of powders in comparison to other methods. Also, we have investigated the phase transformation phenomenon of anatase to rutile. At 1000 °C, complete transformation of the anatase to rutile occurs. Powders prepared in this procedure are white in colour and their diameter varies from 10 nm to 150 nm. Average particle size distributes in the range of 20–50 nm. The unique property about the plasma-synthesized powders is high resistance to heat treatment, with enhanced photocatalytic activity.     

Population Balance-Monte Carlo Simulation for Gas-to-Particle Synthesis of Nanoparticles

The process simulation of nanoparticle synthesis via the gas-phase method is essential to understanding the detailed dynamic evolution of nanoparticles within a very short time period under high temperature. The task is, however, very challengeable up to now as the conversion of the gaseous precursor to the end-use nanoparticle is a complex physicochemical process involving nucleation of the particulate phase, agglomeration between particles and sintering under industrial production conditions. In this article, we extended the differentially weighted Monte Carlo method for population balance to simulate the dynamic evolution of titania (TiO₂) nanoparticles synthesized by gas-to-particle conversion in a single aerosol reactor, considering simultaneous nucleation, agglomeration, and sintering. The simulated size distribution of TiO₂ agglomerate and primary particles produced by the thermal decomposition of titanium tetraisoproxide agreed well with the experimental data. In the simulation, the fast population balance-Monte Carlo method was utilized to accelerate the process simulation on a desktop PC. Results were obtained up to 178 times faster than that of a normal Monte Carlo method. The inhomogeneous internal structure of primary particles was considered through solving population balance of polydisperse primary particles within agglomerate. It was found the polydisperse model could predict the primary particle size distribution better. Simulation results revealed a complex competition relation among nucleation, agglomeration and sintering.

Copyright 2013 American Association for Aerosol Research     

Hydrothermal Synthesis of BaTiO3 Nanopowders Using TiO2 Nanoparticles

Anatase TiO₂ nanoparticles, obtained by hydrolyzing titanium isopropoxide in distilled water, were used to synthesize BaTiO₃ (BT) nanopowder by the hydrothermal method. When titanium isopropoxide was used, BT nanopowder with a low tetragonality of 1.0070 was formed because of the presence of OH^? ions in the oxygen sites and Ba vacancies. However, by changing the titanium source from titanium isopropoxide to TiO₂ nanoparticles, a homogeneous BT nanopowder with similar particle size and a high tetragonality of 1.0081 was synthesized. The size of the BT nanopowder particles was decreased by reducing the synthesis time. In particular, the BT nanopowder that was synthesized at 220°C for 16 h with a Ba/Ti molar ratio of 4.0 exhibited a high tetragonality of 1.0083 and a small particle size of 126.0 nm.     

Preparation of nanosized TiO2 particles via ultrasonic irradiation and their photocatalytic activity on the decomposition of 4-nitrophenol

TiO₂ nanoparticles were prepared by hydrolysis of TTIP (titanium tetraisopropoxide) using an ultrasonication technique coupled with a sol-gel method. The physical properties of nanosized TiO₂ were investigated. The photocatalytic degradation of 4-nitrophenol was studied by using a batch reactor in the presence of UV light. The crystallite size of the anatase phase is increased with an increase of R_EtOH ratio (EtOH/H₂O molar ratio). The particles’ crystallite size prepared with and without ultrasonic irradiation is marginally different. Those particles prepared with ultrasonic irradiation show a higher activity on the photocatalytic decomposition of 4-nitrophenol compared to those prepared without ultrasonic irradiation. The photocatalytic activity decreases with an increase of R_EtOH ratio. In addition, the photocatalytic activity shows the highest value on the titania particle calcined at 500 ‡C. This paper was presented at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4,2004.     

Continuous supercritical hydrothermal synthesis of controlled size and highly crystalline anatase TiO2 nanoparticles

The production of size-controlled and highly crystalline anatase titanium dioxide (TiO₂) nanoparticles was carried out under supercritical hydrothermal conditions (400 °C and 30 MPa) in a continuous flow apparatus with a residence time of 1.7 s. An industrially useful titanium sulfate (Ti(SO₄)₂) solution was used as the starting solution. KOH was used to change TiO₂ solubility and pH and thereby control the particle size. The apparatus comprised two micromixers operating at high temperature. The first mixer was configured to prepare a supercritical aqueous KOH solution from supercritical water (SC-H₂O) and KOH. The second mixer combined this KOH solution with aqueous Ti(SO₄)₂. In situ pH control and homogeneous nucleation were achieved in the second mixer. This two-step high-temperature micromixing process produced reasonably small and homogeneous particles. The particles were characterized by transmission electron microscopy (TEM) on the basis of morphology, average size, and size distribution, together with the coefficient of variation (CV). Powder X-ray diffraction (XRD) was used to determine the crystal structure and crystalline size. The weight loss of material was found through thermogravimetric (TG) measurement. The crystal structure of the product was assigned to the anatase single phase. The average particle size could be adjusted in the range 13–30 nm while maintaining a CV of 0.5 by changing the KOH concentration. At low pH, the powder XRD results for crystallite size were in good agreement with the average particle size measured by TEM, confirming that the products were single crystals of TiO₂ nanoparticles. When the reactor temperature was increased from 400 to 500 °C, the weight loss decreased from 4.5 to 2.5%, keeping the average particle size and high crystallinity of the TiO₂ particles unchanged.     

TiO2 nanopowders via radio-frequency thermal plasma oxidation of organic liquid precursors: Synthesis and characterization

TiO₂ nanopowders have been synthesized via Ar/O₂ thermal plasma oxidation of titanium butoxide (TBO) solutions stabilized with diethanolamine (DEA). Experiments were conducted by varying the O₂ input in the plasma sheath (10–90 L/min) and the DEA/TBO molar ratio (R), while keeping the plasma generation power at 25 kW and the reactor pressure at 500 Torr. The resultant powders are mixtures of the anatase and rutile polymorphs in the studied range, whose anatase content and crystallite size exhibit weak dependence on the O₂ input at a fixed R. Increasing R decreases the anatase content, signifying the role of CO gas, generated via oxidation of the organic precursor, on the phase structure. FE-SEM and TEM analysis show that the resultant powders contain majority of nanoparticles (<50 nm) and some large spheres (>100 nm), whose size and/or number tends to decrease at a higher O₂ input, leading to gradually increased specific surface area. Raman spectroscopy reveals no significant differences in the crystallite size and oxygen-vacancy concentration of the nanocrystals by varying the O₂ input.     

Synthesis of TiO<Subscript>2</Subscript> Nanoparticles by Microemulsion/Heat Treated Method and Photodegradation of Methylene Blue

In this work, TiO₂ nanoparticles were prepared by microemulsion (ME)/heat treated method and its photodecomposition property of methylene blue. Microemulsion (ME) consisted of water, cyclohexane and an anionic surfactant such as bis (2-ethylhexyl) sodium sulfosuccinate (AOT). Titanium tetraisopropoxide (TTIP) was dropped into the ME solution and then then TiO₂ nanoparticles were formed by the hydrolysis reaction between TTIP in the organic solvent and the water in the core of ME. The smallest diameter of the particles was 20 nm in the system of cyclohexane with surfactant when the molar ratio of water to surfactant was 2. The effect of the process parameters (water/surfactant ratio, different temperatures) on the final characteristics has been investigated, in terms of structural phase and particle size. The TiO₂ nanoparticles were characterized by means of X-ray diffraction, Transmission and scanning electron microscopy, Fourier-Transformed infrared and differential thermal analysis. TiO₂ nanoparticles prepared in this condition were collected as amorphous powder, and converted to anatase phase at less than 350 °C, which is lower than the ordinal phase transition temperature. The crystallite size and crystallinity increase with an increase of heat treated s temperature. The particles are shown to have a spherical shape and have a uniform size distribution. The size of nanoparticles raises with an increase of water/surfactant ratio. In the photocatalytic decomposition of methylene blue, the photocatalytic activity is mainly determined by the crystallinity of TiO₂. In addition, the TiO₂ heat treated at 350 °C shows the highest activity on the photocatalytic decomposition of methylene blue (k = 1.7 × 10⁻² min⁻¹).     

Physico-Chemical Effects on the Scale-Up of Ag Photodeposition on TiO2 Nanoparticles

We have previously demonstrated that TiO₂ nanoparticles can be functionalized by photodeposition with silver or gold particles in the 1?C2 nm range presumed to be desirable for catalysis applications. However, the preparation of these samples directly on microscope grids, while conducive to particle size determinations, did not produce sufficient materials for reaction studies. We report here scale-up techniques designed to produce greater quantities of material for testing, while maintaining characteristics that contribute to uniformity in the deposition process. For the scale-up process, an irradiation source with highly uniform intensity is necessary to generate Ag/TiO₂ samples with consistent Ag loading. In addition, control of the precursor concentration is also required to produce Ag/TiO₂ samples with high Ag loading and narrow Ag size distribution. The optimum conditions for the scale-up process found in this study involved Ag photodeposition from a 5 × 10^?3 M AgNO₃ solution using a high pressure Hg lamp at 366 nm for 60 s. Under these reaction conditions, the size of Ag particles determined by TEM and HAADF-STEM imaging was within 1?C2 nm and the Ag loading was ~3.2 wt%. Achievement of this level of uniformity required control of the uniformity of illumination, as well as of the solution concentration and irradiation conditions. Higher solution concentrations and higher power led to the growth of larger (ca. 10 nm) silver particles. In contrast, the loading and size distribution of the Ag particles photodeposited were remarkably insensitive to the source and morphology of the TiO₂ nanoparticles utilized. No Ag peak was resolved in the XRD patterns for Ag/TiO₂ samples obtained from the optimized scale-up process, corroborating the size range determination of the Ag nanoparticles. XPS showed that the Ag particles in all cases were metallic Ag.     

Synthesis of Titanium Dioxide Aerosol Gels in a Buoyancy-Opposed Flame Reactor

Aerosol gels are a novel class of materials with potential to serve in various energy and environmental applications. In this work, we demonstrate the synthesis of titanium dioxide (TiO₂) aerosol gels using a methane-oxygen coflow diffusion flame reactor operated in down-fired configuration (fuel flow in the direction opposite to buoyancy forces). Titanium tetraisopropoxide was fed as a precursor to the flame under different operating conditions. Control of the monomer size and crystalline phase of TiO₂ gel particles was achieved by adjusting the flame operating conditions, specifically the flame temperature, which was shown to significantly influence the phase transformation and rate of particle growth and sintering. The resulting materials were characterized for their physical and optical properties. Results showed that the TiO₂ aerosol gels had effective densities in the range 0.021–0.025 g/cm³, which is 2 orders of magnitude less than the theoretical mass density of TiO₂. The monomer size distribution, crystalline phase, and UV-Vis absorbance spectra of the gels showed distinct characteristics as a function of flame temperature.

Copyright © 2015 American Association for Aerosol Research     

Hydrothermal synthesis of titanium dioxide using acidic peptizing agents and their photocatalytic activity

We have prepared TiO₂ nanoparticles by the hydrolysis of titanium tetraisopropoxide (TTIP) using HNO₃ as a peptizing agent in the hydrothermal method. The physical properties of nanosized TiO₂ have been investigated by TEM, XRD and FT-IR. The photocatalytic degradation of orange II has been studied by using a batch reactor in the presence of UV light. When the molar ratio of HNO₃/TTIP was 1.0, the rutile phase appeared on the titania and the photocatalytic activity decreased with an increase of HNO₃ concentration. The crystallite size of the anatase phase increased from 6.6 to 24.2 nm as the calcination temperature increased from 300 °C to 600 °C. The highest activity on the photocatalytic decomposition of orange II was obtained with titania particles dried at 105 °C without a calcination and the photocatalytic activity decreased with increasing the calcination temperature. In addition, the titania particles prepared at 180 °C showed the highest activity on the photocatalytic decomposition of orange II. This paper was prepared at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4, 2004.     

Atomic layer deposition of TiO2 films on particles in a fluidized bed reactor

Atomic layer deposition (ALD) of controlled-thickness TiO₂ films was carried out on particle substrates in a fluidized bed reactor for the first time. Films were deposited on 550 nm SiO₂ spheres and 65 nm ZnO nanoparticles for enhanced optical properties. Nanoparticles were fluidized with the assistance of a magnetically-coupled stirring unit. The metalorganic precursor titanium tetraisopropoxide was used here followed by either H₂O or H₂O₂ to deposit TiO₂ at various substrate temperatures. Growth rates of 0.01 nm/cycle and 0.04 nm/cycle were achieved when using H₂O and H₂O₂ as the oxidizer, respectively. These conformal TiO₂ films were verified using HRTEM, ICP-AES, XPS and UV absorbance measurements. The specific surface area changed appropriately after the particle size increased by the deposition of films with a given density, which showed that primary particles were not agglomerated together due to the coating process. In situ mass spectrometry was used to monitor reaction progress throughout each ALD reaction cycle. Bulk quantities of powder were successfully functionalized by TiO₂ nanofilms without wasting excess precursor.     

Synthesis and Photocatalytic Activity of Anatase TiO2 Nanoparticles-coated Carbon Nanotubes

A simple and straightforward approach to prepare TiO₂-coated carbon nanotubes (CNTs) is presented. Anatase TiO₂ nanoparticles (NPs) with the average size ~8 nm were coated on CNTs from peroxo titanic acid (PTA) precursor even at low temperature of 100 °C. We demonstrate the effects of CNTs/TiO₂ molar ratio on the adsorption capability and photocatalytic efficiency under UV–visible irradiation. The samples showed not only good optical absorption in visible range, but also great adsorption capacity for methyl orange (MO) dye molecules. These properties facilitated the great enhancement of photocatalytic activity of TiO₂ NPs-coated CNTs photocatalysts. The TiO₂ NPs-coated CNTs exhibited 2.45 times higher photocatalytic activity for MO degradation than that of pure TiO₂.     

Parameter studies of the synthesis of titanium dioxide nanoparticles: Effect on particle formation and size

The large scale synthesis of TiO₂ nanoparticles in the nonaqueous benzyl alcohol route was investigated with respect to the influence of process parameters, like temperature, pressure, reactor filling ratio, agitator speed and precursor concentration, on the induction time of particle formation and particle size. A coherence of the varied process parameters and the molecular reaction mechanism was found that supports the suggested mechanism of particle formation, representing an important step toward a controllable and predictable particle synthesis.     

Emulsifier‐free miniemulsion polymerization of styrene and the investigation of encapsulation of nanoparticles with polystyrene via this procedure using an anionic initiator

Emulsifier‐free miniemulsion polymerization of styrene was investigated in the presence of potassium persulfate (KPS) as an anionic initiator and cetyl alcohol as a costabilizer using ultrasonic irradiation and comparison of this procedure with conventional emulsifier‐free emulsion polymerization showed that this method has a remarkably higher polymerization rate (R_p), smaller size of particles, and narrower molecular weight distribution via gravimetric measurement, transmission electron microscopy (TEM), and gel permeation chromatography techniques, respectively. Then, the encapsulation of magnetite (Fe₃O₄) and titanium dioxide (TiO₂) nanoparticles with polystyrene was investigated using this procedure. Attempt to encapsulate magnetite nanoparticles failed; however, the encapsulation of titanium dioxide nanoparticles was successfully carried out via this procedure using KPS in both cases. TEM proved the presence of TiO₂ nanoparticles in polymer particles, and thermogravimetric analysis was used to determine the percentage of TiO₂ in the products. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation of TiO2 thin films on glass beads by a rotating plasma reactor

We experimentally coated the TiO₂ thin films on the glass beads by a rotating cylindrical plasma chemical vapor deposition (PCVD) process. The precursors for the thin films were generated by the plasma reactions, and they deposited on the glass beads to become the grains on the films. The TiO₂ thin films grow more quickly on the glass beads by increasing the reactor pressure, or the rotation speed of the reactor. As the applied power increases, the thickness of the thin films on the glass beads decreases. As the thickness of the TiO₂ thin films increases, the uniformity of the TiO₂ thin films decreases due to the deposition of larger grains or due to the increase of crack size. The rotating cylindrical PCVD process can be a good method to prepare the particles coated with metal or organic-doped thin films for highly functionalized materials.     

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.     

Oval cuboid TiO2 particles with mesoporous structure fabricated by using fluorinated block copolymers as templates with photocatalytic performance

In this work, a poly(ethylene glycol)-b-poly(1H,1H,7H-dodecafluoroheptyl methacrylate) (PEG-b-PDFMA) block copolymer was first synthesized by the reversible addition−fragmentation chain transfer (RAFT) polymerization. Then a novel facile approach was developed to fabricate oval cuboid TiO₂ particles with mesoporous structure by using the PEG-b-PDFMA block copolymer as a template and titanium tetrabutoxide (TBOT) as a precursor, followed by evaporation-induced self-assembly (EISA) process and calcination process. The results show that the PEG-b-PDFMA block copolymer can control the oriented assembly of nanoparticles and act as templates for the formation of a mesopore. It is found that the mass ratio of TBOT/PEG-b-PDFMA and water content in the solution have a significant influence on the morphology of TiO₂ particles. When the mass ratio of TBOT/PEG-b-PDFMA is 0.25/1, oval cuboid TiO₂ particles with mesopores are obtained, which exhibits a high photocatalytic activity for the degradation of methylene blue (MB) dye under UV light irradiation.     

Preparation of titania/carbon nanotube composites using supercritical ethanol and their photocatalytic activity for phenol degradation under visible light irradiation

Titanium dioxide (anatase, TiO₂) nanoparticles have been successfully deposited onto multi-walled carbon nanotubes (MWCNTs) via hydrolysis of titanium isopropoxide in supercritical ethanol. The as-prepared composites were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. It was demonstrated that the MWCNTs were decorated with well-dispersed anatase nanoparticles less than 7 nm in diameter. The size and loading content of the nanoparticles on MWCNTs could be tuned by manipulating the ratio of precursor to MWCNTs, and the formation mechanism of the composites was also discussed. The absorbance spectrum of the resultant TiO₂/MWCNT composites extended to the whole UV-visible region due to the decoration of TiO₂ on MWCNTs. The TiO₂/MWCNT composites were used as photocatalyst for phenol degradation under irradiation of visible light, which showed higher efficiency compared to a mixture of TiO₂ and MWCNTs.     

Study of the process parameters in the synthesis of TiO2 nanospheres through reactive microemulsion precipitation

Spherical particles constituted by nanocrystals of titanium oxide TiO₂ have been prepared through reactive microemulsion precipitation. A water-in-oil microemulsion, added with a suitable emulsifier, has been used. The effect of the process parameters (water to oil ratio, type and amount of surfactant, concentration of precursor solution, mixing velocity) on the final characteristics has been investigated, in terms of structural phase and particle size. The titania nanopowders were characterized by means of X-ray diffraction, thermogravimetric and differential thermal analyses and scanning electron microscopy. The results obtained by different process conditions showed the development of both titania rutile and anatase spherical particles, with particle size ranging from tens to hundreds of nanometers.