Effect of reaction atmosphere on particle morphology of TiO2 produced by thermal decomposition of titanium tetraisopropoxide

Thermal decomposition of titanium tetraisopropoxide (TTIP) was carried out in varying reaction atmospheres: nitrogen, oxygen, and nitrogen plus water vapor. The effect of reaction atmosphere on the morphology, size, and crystalline structure of produced TiO₂ particles was studied. The reactor used was similar to the microreactor proposed earlier by Park et al. (2001, J. Nanopart. Res., 3, 309–319), but for a modification in the precursor evaporator. The reactor temperature was varied from 300 to 700°C and the TTIP concentration in the evaporator from 1.0 to 7.0 mol%, holding the reactor residence time at 0.7 s. The primary-particle size was in the range 25–250 nm, varying with operating condition. The crystalline structure was amorphous in nitrogen, a mixture of rutile and anatase in nitrogen plus water vapor, and anatase in oxygen atmospheres. In nitrogen, agglomerates composed of very small particles whose individual boundaries are not clearly distinguished were produced. In oxygen, the particles composing an agglomerate became larger and were clearly spherical. As the atmosphere was varied to the nitrogen plus water vapor, the particle size increased further. The variation of primary particle size with reaction atmosphere was discussed in comparison with previous experimental data.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

Copper and Copper Oxide Nanoparticle Formation by Chemical Vapor Nucleation From Copper (II) Acetylacetonate

Crystalline nanometer-size copper and copper (I) oxide particle formation was studied by thermal decomposition of copper acetylacetonate Cu(acac)₂ vapor using a vertical flow reactor at ambient nitrogen pressure. The experiments were performed in the precursor vapor pressure range of P _prec = 0.06 to 44 Pa at furnace temperatures of 431.5°C, 596.0°C, and 705.0°C. Agglomerates of primary particles were formed at P _prec0.1 Pa at all temperatures. At 431.5°C the number mean size of the primary particles increased from D _p = 3.7 nm (with geometric standard deviation _g = 1.42) to D _p = 7.2 nm (_g = 1.33) with the increasing precursor vapor particle pressure from 1.8 to 16 Pa. At 705.0°C the primary particle size decreased from D _p = 24.0 nm (_g=1.57) to D _p = 7.6 nm (_g = 1.54), respectively.At furnace temperatures of 431.5°C and 596.0°C only crystalline copper particles were produced. At 705.0°C the crystalline product of the decomposition depended on the precursor vapor pressure: copper particles were formed at P _prec>10 Pa, copper (I) oxide at P _precleq 1 Pa, and a mixture of the metal and its oxide at intermediate vapor pressures. A kinetic restriction on copper particle growth was shown, which leads to the main role of Cu₂ molecule participation in the particle formation. The formation of copper (I) oxide particles occurs due to the surface reaction of the decomposition products (mainly carbon dioxide). For the explanation of the experimental results, a model is proposed to build a semiempirical phase diagram of the precursor decomposition products.     

Ultrafine anatase TiO2 nanoparticles produced in premixed ethylene stagnation flame at 1 atm

Nano-sized titanium oxide particles were synthesized in a stationary, laminar, premixed, stagnation flame burning an ethylene–oxygen–argon mixture at an equivalence ratio of 0.36 under the atmospheric pressure. The titanium precursor, titanium tetraisopropoxide (TTIP), was fed into the flame by a carrier argon flow through a heated TTIP bath. Particles synthesized in this flame were characterized for their size distribution, morphology, phase purity, and crystal structure, by scanning mobility particle sizer, transmission electron microscopy, and X-ray diffraction. It was found that the mean diameter of the particles was highly controllable and ranged from 3 to 6 nm depending on TTIP loading. The particle size was nearly uniform, and particles appeared to be single crystals without excessive aggregation. XRD analyses show that particles directly synthesized in the flame are pure anatase. Upon sintering and size growth on the flame stabilizer, a notable portion of particles transformed into rutile with much larger crystal sizes.     

Characteristics of Fe2O3 Nanoparticles from Doped Low-pressure H2/O2/Ar Flames

A burner stabilized premixed low-pressure flame has been used to generate iron-oxide (Fe₂O₃) nanoparticles with sizes in the range 7–20nm. The H₂/O₂/Ar flames were doped with different amounts of iron-pentacarbonyl (Fe(CO)₅) with concentrations in the range 524–2096ppm. The influence of precursor concentration on composition, structure, morphology, and size have been studied utilizing transmission electron microscopy (TEM), X-ray powder diffraction (XRD), measurements of the specific surface area (BET), and infrared spectroscopy (FT-IR). The product particles consist of both, the - and the -phase of Fe₂O₃. Average particle sizes were measured in the range 7.4–16nm depending on precursor concentration and flame conditions.     

Microflow reactor synthesis of palladium nanoparticles stabilized with poly(benzyl ether) dendron ligands

A simple glass capillary microflow reactor system has been applied for the synthesis of palladium nanoparticles by thermal decomposition of palladium acetate (Pd(OAc)₂) in diphenyl ether in the presence of poly(benzyl ether) dendron ligands (PBED Gn-NH₂, n = 1–3) as a stabilizer. Effect of hydrodynamic parameters (capillary diameter, linear flow rate, volume flow rate, and reaction temperature) and concentrations (precursor and stabilizer) on the particle size was investigated. The particle size can be controlled by varying linear flow rate and temperature as well as ligand/precursor concentration ratio. Volume flow rate does not affect the particle size when the linear flow rate is held constant for different capillary diameters (150–320 μm). Unlike batch systems, in this microreactor system, smaller particles are produced at low ligand concentrations when the molar ratio of the ligand to metal precursor ranged from 1 to 5. As another characteristic of the microreactor synthesis, the concentration of the Pd precursor can be increased (up to 27 mM) with maintaining a constant particle size (3.1 ± 0.2 nm) and a good monodispersity, while in the batch system a significant increase and broadening in the particle size are observed with increasing precursor concentration.     

The Ground State Energy of a Dilute Two-Dimensional Bose Gas

The ground state energy per particle of a dilute, homogeneous, two-dimensional Bose gas, in the thermodynamic limit is shown rigorously to be E₀/N=(2²/m)|ln(a²)|^–1, to leading order, with a relative error at most O(|ln(a²)|^–1/5). Here N is the number of particles, =N/V is the particle density and a is the scattering length of the two-body potential. We assume that the two-body potential is short range and nonnegative. The amusing feature of this result is that, in contrast to the three-dimensional case, the energy, E₀ is not simply N(N–1)/2 times the energy of two particles in a large box of volume (area, really) V. It is much larger.     

Surface reaction characteristics at low temperature synthesis BaTiO3 particles by barium hydroxide aqueous solution and titanium tetraisopropoxide

Well-crystallized cubic phase BaTiO₃ particles were prepared by heating the mixture of barium hydroxide aqueous solution and titania derived from the hydrolysis of titanium isopropoxide (TTIP) at 328 K, 348 K or 368 K for 24 h. The morphology and size of obtained particles depended on the reaction temperature and the Ba(OH)₂/TTIP molar ratio. By the direct hydrolytic reaction of titanium tetraisopropoxide, the high surface area titania (TiO₂) was obtained. The surface adsorption characteristics of the titania particles had been studied with different electric charges OH⁻ ions or H⁺ ions. The formation mechanism and kinetics of BaTiO₃ were examined by measuring the concentration of [Ba²⁺] ions in the solution during the heating process. The experimental results showed that the heterogeneous nucleation of BaTiO₃ occurred on the titania surface, according to the Avrami's equation.     

Growth of carbon nanotubes on Fe or Ni-coated Si substrate by feeding with carbon from a graphite ablation plume

By feeding with carbon clusters from the ArF excimer laser (=193 nm) ablation of graphite target, carbon nanotubes (CNTs) were grown on Fe and Ni films deposited on SiO₂/Si substrates, which were set inside a quartz tube with Ar gas pressure of 500 Torr operating at 1100 °C. Optical emission spectroscopic observation of the ablation plume of graphite and Ni/Y catalyst was performed in the Ar gas for a pressure range of 0–600 Torr at room temperature and 1000 °C. The emission band intensity of C₃ (ù_u) at the distance of 2 mm from the target increased with increasing Ar gas pressure. PACS 79.20.Ds; 81.07.De; 39.30.+w     

Kinetic limit of a conservative lattice gas dynamics showing long-range correlations

An anisotropic lattice gas dynamics is investigated for which particles on ^d jump to empty nearest neighbor sites with (fast) rate ^–2 in a specified direction and some particular configuration-dependent rates in the other directions. The model is translation and reflection invariant and is particle conserving. The space coordinate in the fast-rate direction is rescaled by ^–1. It follows that the density field converges in probability, as 0, to the corresponding solution of a nonlinear diffusion-type equation. The microscopic fluctuations about the deterministic macroscopic evolution are determined explicitly and it is found that the stationary fluctuations decay via a power law (1/r ^d ) with the direction dependence of a quadrupole field.     

Development of systems for the laser synthesis of nanoparticles starting from liquid precursors

The laser synthesis of nanoparticles starting from liquid precursors is particularly suitable as synthesis technique for obtaining nanoparticles. In the present work the laser pyrolysis is performed in a novel setup where the liquid precursor is brought with the aid of an original evaporator system to temperatures in excess of the boiling point and is finally fed into the reactor under the form of heated vapors.The process occurs in the gas phase and ensures the avoidance of the condensation. The temperature control system allows for the maintaining of the overall system temperature below the decomposition temperature and above the boiling. Temperatures up to 500 °C are assured for the mixed precursors. The control of the amount of the active substances is performed upstream, in the liquid phase. The set-up is able to offer safety conditions at the synthesis of substances with high toxicity. This experimental set-up was proposed in order to synthesize TiO₂ nanoparticles from TTIP because its boiling temperature is relatively high (239 °C grades). Different analytical techniques such as EDX, TEM, XRD and HRTEM were used in order to evaluate the structural characteristics of the produced nanopowders.     

Large time behaviour of someN-body systems

In this work we prove completeness forN-body systems that evolve asymptotically into eitherN free particles or a two cluster system with one of the clusters being a single particle. For the three body case our results imply completeness for a very general system with potentials decaying like |x|^–1– at .This work was done at the Indian Statistical Institute, New Delhi 110016, India     

Long time tails in stationary random media. I. Theory

Diffusion of moving particles in stationary disordered media is studied using a phenomenological mode-coupling theory. The presence of disorder leads to a generalized diffusion equation, with memory kernels having power law long time tails. The velocity autocorrelation function is found to decay like t^–(d/2+1), while the time correlation function associated with the super-Burnett coefficient decays liket ^–d/2 for long times. The theory is applicable to a wide variety of dynamical and stochastic systems including the Lorentz gas and hopping models. We find new, general expressions for the coefficients of the long time tails which agree with previous results for exactly solvable hopping models and with the low-density results obtained for the Lorentz gas. Finally we mention that if the moving particles are charged, then the long time tails imply that there is an ^d/2 contribution to the low-frequency part of the frequency-dependent electrical conductivity.     

Solid-precursor vaporizer for aerosol reactors: Synthesis of magnesium aluminate nanoparticles by thermal decomposition of magnesium aluminum tert-butoxide

A solid-precursor vaporizer for laboratory-scale aerosol reactors has been developed and successfully tested on the synthesis of magnesium aluminate (MgAl₂O₄) nanoparticles by thermal decomposition of magnesium aluminum tert-butoxide (Mg[Al(O^tBu)₄]₂), a single-source precursor, in a furnace aerosol reactor. The reactor temperature was varied from 600 to 1000°C with the precursor concentration at 6.4 × 10⁻⁶ mol/l. The atomic ratio of Al to Mg of produced particles was determined by XPS to be 2:1 and the primary particle size ranged from 28 to 55 nm. As-produced particles were all amorphous, but the particles further heated to 1000°C exhibited crystalline MgAl₂O₄ structures.     

Experimental Limit on the Probability of Neutral Pion Emission in Neutron-Induced Fission of 235U Nuclei

Results of an experiment on the search for the emission of ⁰ mesons in neutron-induced fission of ²³⁵U nuclei based on the detection in coincidence of two -quanta from the ⁰-meson decay performed with the nuclear reactor developed at the Scientific-Research Nuclear Physics Institute at Tomsk Polytechnic University are described. The experimental setup comprised two erenkov spectrometers of total absorption for the detection and measurement of -quantum energy placed in two coaxial horizontal channels of the nuclear reactor. Water filters placed in the channels were used to protect the detectors from -, -, and neutron fluxes. To reject the cosmic radiation, scintillation counters of large area, operating in anticoincidence mode, were placed above each spectrometer. The experimentally measured limitation on the probability of neutral pion emission in neutron-induced fission of nuclei was established 4.1·10^–11 with a 90% confidence level. The energy spectrum of -quanta from the active reactor zone was measured in the range 32–65 MeV. The parameters of the spectrum deviated from the results of theoretical calculations and from the experiment performed with the nuclear pulse reactor developed at the Joint Institute for Nuclear Research (Dubna).     

Production of ultrafine particles of high-temperature tetragonal WO<Subscript>3</Subscript> by dc arc discharge in Ar–O<Subscript>2</Subscript> gases

Ultrafine particles of WO₃ are successfully produced by dc arc discharge in Ar-O₂ gases. Particle sizes are distributed from 10 nm to 1 m depending on production conditions: gas pressure, collection position and discharge current. Observations of the cooled particles by electron microscopy indicate that the WO₃ particles are tetragonal, a phase that is usually only stable above 725 °C. The octahedral crystals are bounded by eight {1 0 1} faces and occasionally truncated by {1 0 0} and/or {0 0 1} faces. This method of producing WO₃ by dc arc discharge therefore affords a high-temperature phase that is preserved upon cooling to room temperature.     

Synthesis of nano-sized polycrystalline PZT powders using molecular building blocks by designed chemical route

Polycrystalline perovskite Pb(Zr _x Ti O₃ (PZT) powders in the form of particles with sizes in the range 2∼ ∼10 nm were obtained by hydrolysis of a mixed metal alkoxide precursor. The mixed metal alkoxide precursor was synthesized by refluxing Pb(OAc)₂, Zr(O– ⁿ Bu)₄ and Ti(O–ⁱPr)₄ in anhydrous ethanol. After it was hydrolyzed in a solution with a pH of 3 and dried at 423 K, nano-sized polycrystalline perovskite PZT was obtained. This temperature of formation of the PZT perovskite phase is noticeably lower than those reported elsewhere. The sizes of the freshly dried polycrystalline perovskite PZT particles are within the range of 2–5 nm.     

Gas phase electronic spectrum of propadienylidene C3H2

The rotationally resolved vibronic bands in the forbidden electronic transition of the cumulene carbene C₃H₂ have been observed in the gas phase by cavity ring down absorption spectroscopy through a supersonic planar plasma with allene as precursor. The band detected in the 16 223 cm⁻¹ region is a result of vibronic interaction and is assigned to a combination of a₁ and b₂ vibrations with a frequency around 2250 cm⁻¹. Another vibronic band near 15 810 cm⁻¹ has an unusual rotational structure because the K_a = 0-1 subband is absent. It is assigned to a combination of a₁ and b₁ vibrations, ∼1850 cm⁻¹, which borrow intensity from the near lying state due to a-type Coriolis coupling. A rotational analysis using a conventional Hamiltonian for an asymmetric top molecule yields molecular constants for the vibrational excited levels of the ùA₂ state, which were used for the determination of the geometry. The stronger transition of C₃H₂, measured in a neon matrix in the 16 161-24 802 cm⁻¹ range, was not detected. The reason for this is a short lifetime of the state, leading to line broadening.     

Synthesis and luminescence of CdS quantum dots capped with a silica precursor

A novel synthesis method for efficiently luminescing CdS nanocrystals is reported using (3-mercaptopropyl)-trimethoxysilane (MPS) as a capping agent in THF or MeOH. The synthesis yields particles capped with a precursor for coating the particle with a silica shell and offers control over a wide range of particle sizes (2-) by varying the MPS concentration. The temperature dependence of the luminescence and the luminescence life time was studied and explained in terms of a donor-acceptor recombination process in which both electron and hole are trapped at low temperature. In addition to varying the emission color by controlling the particle size, nanocrystals were doped with Zn or Cu resulting in a blue shift or a red shift of the emission.     

ArF laser CVD of hydrogenated amorphous silicon: The role of buffer gases

ArF laser-induced CVD has been employed to generate hydrogenated amorphous silicon (a-Si:H) from Si₂H₆ gas dilute with He, Ar, or H₂. The formation of amorphous films or powder is found to depend critically on the kind of buffer gas, the stationary total and partial gas pressures, and the substrate temperature. These dependences have been investigated in the 1–5 Torr pressure and 100–400 °C temperature ranges. They are semiquantitatively discussed in terms of ArF laser photolysis of disilane, gas heating by heat flow from the substrate and laser irradiation, diffusion, and gas phase polymerization. Furthermore, photo ionization has been observed but found irrelevant for the a-Si:H layer properties. The photo and dark conductivities ( _ph, _d) of the semiconductor layers are determined by the substrate temperature. The _ph values range between 10^–7 and 10^{–4 –1} cm^–1 and the _d values between 10^–11 and 10^{–8 –1} cm^–1. The maximum ratio _ph/ _d amounts to 4×10⁴. The layers are further characterized by their optical band gap and activation energy. The layer properties are compared to literature values of amorphous films prepared by various photo, HOMO, and plasma CVD methods.