Effect of surrounding gas temperature on the morphological evolution of TiO2 nanoparticles generated by laser ablation in tubular furnace

Titanium oxide nanoparticles are synthesized by laser ablation of Ti target in oxygen atmosphere under well-controlled temperature profiles in a tubular furnace. The size and the shape of generated nanoparticles are varied by changing the temperature of furnace. The mobility-based size distributions of generated air-borne nanoparticles are measured using a scanning mobility particle sizer, and the size distributions of primary particles are analyzed by a scanning electron microscope. When the particles are generated by laser ablation at the room temperature, the particles are agglomerates in gas phase with the average mobility diameter of 117 nm and the mean diameter of primary particles of 11 nm. The primary particle diameter increases from 11 to 24 nm by raising the furnace temperature up to 800 °C. Since the mass of Ti vapor ablated from a target is found to be constant regardless of the furnace temperature, this particle growth may be attributed to the reduction in nuclei number as a result of mild quenching at higher temperatures. As the temperature reaches higher than 1,000 °C, the mobility diameter suddenly drops and the primary particle diameter increases due to sintering, and at 1,200 °C the mobility diameter coincides with the primary particle diameter. Since the laser oven method offers an independent control of vapor concentration and the temperature of surrounding atmosphere, it is an effective tool to study the formation process of nanoparticles from primary particles with a given size.     

Structural properties of silver nanoparticle agglomerates based on transmission electron microscopy: relationship to particle mobility analysis

In this work, the structural properties of silver nanoparticle agglomerates generated using condensation and evaporation method in an electric tube furnace followed by a coagulation process are analyzed using Transmission Electron Microscopy (TEM). Agglomerates with mobility diameters of 80, 120, and 150 nm are sampled using the electrostatic method and then imaged by TEM. The primary particle diameter of silver agglomerates was 13.8 nm with a standard deviation of 2.5 nm. We obtained the relationship between the projected area equivalent diameter (d _pa) and the mobility diameter (d _m), i.e., d _pa = 0.92 ± 0.03 d _m for particles from 80 to 150 nm. We obtained fractal dimensions of silver agglomerates using three different methods: (1) D _f = 1.84 ± 0.03, 1.75 ± 0.06, and 1.74 ± 0.03 for d _m = 80, 120, and 150 nm, respectively from projected TEM images using a box counting algorithm; (2) fractal dimension (D _fL) = 1.47 based on maximum projected length from projected TEM images using an empirical equation proposed by Koylu et al. (1995) Combust Flame 100:621–633; and (3) mass fractal-like dimension (D _fm) = 1.71 theoretically derived from the mobility analysis proposed by Lall and Friedlander (2006) J Aerosol Sci 37:260–271. We also compared the number of primary particles in agglomerate and found that the number of primary particles obtained from the projected surface area using an empirical equation proposed by Koylu et al. (1995) Combust Flame 100:621–633 is larger than that from using the relationship, d _pa = 0.92 ± 0.03 d _m or from using the mobility analysis.     

Sintering kinetic measurement of nickel nanoparticle agglomerates by electrical mobility classification

The gas-phase sintering kinetics of nickel nanoparticle agglomerates was investigated by a two step electrical mobility classification. The first electrostatic classifier sorted the agglomerated mono-area nickel nanoparticles generated by pulsed laser ablation, and then the subsequent heating process created the sintered nickel nanostructures. The second electrostatic classifier combined with the condensation nucleus counter scanned the shrinkage of the agglomerated mono-area nickel nanoparticles due to the sintering process. The change in the mono-area particle mobility size measured by the electrical mobility classification technique was compared with the results of the existing coalescence model to extract the kinetic parameters for the sintering of nickel particles. The optimum activation energy found in this study was ∼63 kJ/mol, which falls between the diffusion of nickel atoms (∼49 kJ/mol) and the migration and coalescence of nickel particles (∼78 kJ/mol).     

Generation of nanoparticles by spark discharge

The production of nanoparticles by microsecond spark discharge evaporation in inert gas is studied systematically applying transmission electron microscopy, mobility analysis and BET surface area measurement. The method of spark discharge is of special interest, because it is continuous, clean, extremely flexible with respect to material, and scale-up is possible. The particle size distributions are narrow and the mean primary particle size can be controlled via the energy per spark. Separated, unagglomerated particles, 3–12 nm in size, or agglomerates can be obtained depending on the flow rate. The nanoparticulate mass produced is typically 5 g/kWh. A formula is given, which estimates the mass production rate via thermal conductivity, evaporation enthalpy and the boiling point of the material used. We showed that with gas purified at the spot, the method produced gold particles that were so clean that sintering of agglomerated particles occurred at room temperature. The influence of a number of parameters on the primary particle size and mass production rate was studied and qualitatively understood with a model of Lehtinen and Zachariah (J Aerosol Sci 33:357–368, 2002). Surprisingly high charging probabilities for one polarity were obtained. Spark generation is therefore of special interest for producing monodisperse aerosols or particles of uniform size via electrical mobility analysis. Qualitative observations in the present study include the phenomenon of material exchange between the electrodes by the spark, which opens the possibility of producing arbitrary mixtures of materials on a nanoscale. If spark generation of nanoparticles is performed in a standing or almost standing gas, an aerogel of a web-like structure forms between surfaces of different electrical potential.     

Emission measurement and safety assessment for the production process of silicon nanoparticles in a pilot-scale facility

Emission into the workplace was measured for the production process of silicon nanoparticles in a pilot-scale facility at the Institute of Energy and Environmental Technology e.V. (IUTA). The silicon nanoparticles were produced in a hot-wall reactor and consisted of primary particles around 60 nm in diameter. We employed real-time aerosol instruments to measure particle number and lung-deposited surface area concentrations and size distribution; airborne particles were also collected for off-line electron microscopic analysis. Emission of silicon nanoparticles was not detected during the processes of synthesis, collection, and bagging. This was attributed to the completely closed production system and other safety measures against particle release which will be discussed briefly. Emission of silicon nanoparticles significantly above the detection limit was only observed during the cleaning process when the production system was open and manually cleaned. The majority of the detected particles was in the size range of 100–400 nm and were silicon nanoparticle agglomerates first deposited in the tubing then re-suspended during the cleaning process. Appropriate personal protection equipment is recommended for safety protection of the workers during cleaning.     

煤燃烧过程中一次破碎的影响因素分析

本文从理论上分析了煤燃烧过程中的一次破碎过程,同时考虑热应力和内部压力积聚的作用,建立了简化的一次破碎模型,通过此模型分析了煤颗粒的粒径、炉膛温度、炉膛对煤颗粒的传热系数、煤颗粒的热扩散系数、煤颗粒脱挥发分的化学动力学参数、煤中对流孔直径、煤的孔隙率、挥发分的粘性系数以及挥发分含量这9个参数对燃烧过程中煤颗粒一次破碎的影响,分析所得结果与近年来报道的实验结论基本保持一致。     

随机取向烟尘团簇粒子的光学截面的数值计算

采用蒙特卡罗方法根据团簇—团簇凝聚（CCA）模型对由球形原始微粒凝聚而成的烟尘团簇粒子进行了模拟,利用离散偶极子近似（DDA）方法数值计算了不同原始微粒粒径和数目组成的随机取向的烟尘团簇粒子的总消光截面、吸收截面及散射截面等光学特性参数,研究了原始微粒粒径及数目对随机取向烟尘团簇粒子光学特性的影响。结果表明：当入射波长一定时,随机取向烟尘団簇粒子的光学特性主要取决于原始微粒的粒径和数目;烟尘团簇粒子对不同波段激光的吸收和散射存在差别,这种差别随原始微粒粒径及数目变化而变化。这一工作为研究电磁波在烟尘中的传输特性提供重要参考数据。     

Calibration and numerical simulation of Nanoparticle Surface Area Monitor (TSI Model 3550 NSAM)

TSI Nanoparticle Surface Area Monitor (NSAM) Model 3550 has been developed to measure the nanoparticle surface area deposited in different regions of the human lung. It makes use of an adjustable ion trap voltage to match the total surface area of particles, which are below 100 nm, deposited in tracheobronchial (TB) or alveolar (A) regions of the human lung. In this paper, calibration factors of NSAM were experimentally determined for particles of different materials. Tests were performed using monodisperse (Ag agglomerates and NaCl, 7–100 nm) and polydisperse particles (Ag agglomerates, number count mean diameter below 50 nm). Experimental data show that the currents in NSAM have a linear relation with a function of the total deposited nanoparticle surface area for the different compartments of the lung. No significant dependency of the calibration factors on particle materials and morphology was observed. Monodisperse nanoparticles in the size range where the response function is in the desirable range can be used for calibration. Calibration factors of monodisperse and polydisperse Ag particle agglomerates are in good agreement with each other, which indicates that polydisperse nanoparticles can be used to determine calibration factors. Using a CFD computer code (Fluent) numerical simulations of fluid flow and particle trajectories inside NSAM were performed to estimate response function of NSAM for different ion trap voltages. The numerical simulation results agreed well with experimental results.     

Size-controlled aerosol synthesis of silver nanoparticles for plasmonic materials

Aerosol techniques were used to synthesize spherical and monodisperse silver nanoparticles for plasmonic materials. The particles were generated with an evaporation-condensation technique followed by size selection and sintering with a differential mobility analyzer and a tube furnace, respectively. Finally, the nanoparticles were collected on a glass substrate with an electrostatic precipitator. The particle size distributions were measured with a scanning mobility particle sizer and verified with a transmission electron microscope. A spectrophotometer was used to measure the optical extinction spectra of the prepared samples, which contained particles with diameters of approximately 50, 90 and 130?nm. By controlling the particle size, the dipolar peak of the localized surface plasmon resonance was tuned between wavelengths of 398 and 448?nm. In addition, quadrupolar resonances were observed at shorter wavelengths as predicted by the simplified theoretical model used to characterize the measured spectra.     

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.     

Influence of the Particle Morphology on the Activity of Nanometer Platinum Aerosol Catalysts

For nanoparticle agglomerates, the catalytic activity may depend strongly on their structure. The influence of different parameters such as agglomerate structure, primary particle temperature history and surface preconditioning on the catalytic activity of nanoparticles was investigated. The fraction of agglomerate surface contributing to the reaction depends on the agglomerate structure and on the velocity of the reaction under investigation. For extremely fast reactions such as the oxidation of hydrogen on Pt nanoparticles, only the outermost surface (exposed surface) contributes substantially to the formation of water. For the system investigated here, the inner surface not substantially contributing to the reaction accounted for at least 70% of the total particle surface as determined from oxygen presaturation experiments of the agglomerate surface. A considerable activity loss of the platinum particles was observed on preheating the nanoparticle agglomerates. The preheating leads to an increase in the nanoparticle size by an order of magnitude due to sintering. It is unclear if this activity reduction is due to changes in the particle surface state or to a real size effect of the nanoparticles.     

Comparison of nanoparticle measurement instruments for occupational health applications

Nanoparticles are used in many applications because of their novel properties compared to bulk material. A growing number of employees are working with nanomaterials and their exposure to nanoparticles trough inhalation must be evaluated and monitored continuously. However, there is an ongoing debate in the scientific literature about what are the relevant parameters to measure to evaluate exposure to level. In this study, three types of nanoparticles (ammonium sulphate, synthesised TiO₂ agglomerates and aerosolised TiO₂ powder, modes in a range of 30–140 nm mobility size) were measured with commonly used aerosol measurement instruments: scanning and fast mobility particle sizers (SMPS, FMPS), electrical low pressure impactor (ELPI), condensation particle counter (CPC) together with nanoparticle surface area monitor (NSAM) to achieve information about the interrelations of the outputs of the instruments. In addition, the ease of use of these instruments was evaluated. Differences between the results of different instruments can mainly be attributed to the nature of test particles. For spherical ammonium sulphate nanoparticles, the data from the instruments were in good agreement while larger differences were observed for particles with more complex morphology, the TiO₂ agglomerates and powder. For instance, the FMPS showed a smaller particle size, a higher number concentration and a narrower size distribution compared with the SMPS for TiO₂ particles. Thus, the type of the nanoparticle was observed to influence the data obtained from these different instruments. Therefore, care and expertise are essential when interpreting results from aerosol measurement instruments to estimate nanoparticle concentrations and properties.     

A comparative study of nanoparticles in premixed flames by scanning mobility particle sizer, small angle neutron scattering, and transmission electron microscopy

Scanning mobility particle sizer (SMPS) and transmission electron microscopy (TEM) studies were conducted for TiO₂ and soot particles. The TiO₂ particles were produced from a premixed stagnation ethylene-oxygen-argon flame (? = 0.36) doped with titanium tetraisopropoxide. Soot was generated from a burner-stabilized premixed ethylene-oxygen-argon flame (? = 2.5). The close agreement among SMPS, TEM, and X-ray diffraction results for TiO₂ nanoparticles demonstrates that the probe sampling/mobility measurement technique is accurate for on-line analysis of the size distribution of particles as small as 3 nm in diameter. In the case of soot, notable disagreement between the SMPS and TEM sizes was found and attributable to the fact that the soot taken from the flame studied herein is liquid-like and that upon deposition on the TEM grid, the primary particles do not retain their sphericity. This interpretation is supported by measurements with photo ionization aerosol mass spectrometry, small angle neutron scattering, and thermocouple particle densitometry.     

Aerosol Catalysis on Nickel Nanoparticles

Nickel nanoparticles produced by spark discharges were used as aerosol catalyst for the formation of methane. The available surface area of the particles was determined using different methods. It was found that the surface area available for nitrogen adsorption and, therefore, for the methanation reaction remained virtually constant during restructuring of the agglomerates while the surface area based on the mobility was significantly reduced. In general, the reaction parameters such as activation energy and reaction rates agree well with the values for single nickel crystals and foils. At temperatures above 350°C the activation energy and the photoelectric activity of the particles decrease indicating the formation of graphite on the particle surface. Also the change of the work function points to the build up of multiple layers of graphite on the particle surface. The surprisingly low temperature for the surface deactivation may indicate an enhanced formation of carbon atoms at the surface.     

One-step synthesis of intrinsically functionalized fluorescent carbon nanoparticles by hydrothermal carbonization from different carbon sources

Nuclepore filter collection with subsequent electron microscopy analysis for nanosized agglomerates (20–500 nm in mobility diameter) was carried out to examine the feasibility of the method to assess the personal engineered nanoparticle exposure. The number distribution of the nanoparticles collected on the filter surface was obtained by visual counting and converted to the distribution in the air using validated capillary tube models. The model was validated by studying the overall penetrations of nanoparticles (Ag and soot) with different agglomeration degrees through 1 μm pore diameter Nuclepore filters at different face velocities (2–15 cm/s). In the model, the effects of the maximum length of agglomerates on interception deposition and the dynamic shape factor on impaction deposition were taken into account. Results showed that the data of the overall penetration were in very good agreement with the properly applied models. A good agreement of filter surface collection between the validated model and the SEM analysis of this study was obtained, indicating a correct particle number distribution in the air can be converted from the Nuclepore filter surface collection and this method can be applied for quantitative engineered nanoparticle exposure assessment.     

Surface science with aerosols

Experimental surface science with aerosol particles under atmospheric conditions is becoming a realistic possibility. The first part of this critical review focuses on nano-scopic aerosols generated in combustion of organic fuels at ambient pressures. The bizarre shape of soot agglomerates resists a simple definition of size and surface area. Yet a measure of the size known as the mobility diameter can be extracted from the mobility of the particles in their carrier gas. The total surface area must be divided into an active and a passive part. At the active surface, mass, energy, and momentum is exchanged with the molecules of the carrier gas. The active surface thus determines the dynamical properties of the particles. The passive surface is the surface enclosed in the interior as well as the surface in bays or cracks or, with larger particles, in the dead point of the laminar flow; it determines particle properties on a longer time scale. Simple automatic portable sensors measure the number density of airborne particles, their “size” and a characteristic fingerprint of the surface chemistry, making it possible to determine the source from which the particle was emitted. The response time of the sensors is ～1 s, hence one can monitor dynamical changes of the particles such as adsorption of water in the atmosphere. In the second part we examine a number of surface science techniques that have been used to characterize surfaces important to atmospheric chemistry in more detail, in particular the uptake of water and the influence of surfactants. We illustrate the application of these techniques to the investigation of alkali halide surfaces as a function of relative humidity. Finally we give first examples on how infrared spectroscopy and synchrotron-based ambient pressure X-ray photoelectron spectroscopy have been used to study more realistic aerosol particles, under conditions of ambient humidity. These examples show that in situ chemical analysis of the particles is possible with third generation synchrotron X-ray sources. In the near future, X-ray lasers might reveal the fast dynamics of chemical processes as well. Thus it is within reach to study aerosols under the conditions of the stratosphere. Stratospheric aerosols can reduce the insolation of the earth and may become one of the last resorts of humanity to counteract the effects of global warming.     

Catalytic soot oxidation in microscale experiments: Simulation of interactions between co-deposited graphitic nanoparticle agglomerates and platinum nanoparticles

Continuously regenerating catalytic soot traps are under development to reduce particulate emissions from diesel exhaust. A good understanding of the processes that take place during soot oxidation is needed to optimize diesel soot trap performance. To gain insight into these processes from the perspective of nanoparticle technology, the effects of catalyst particle size and the interparticle distance between soot and catalyst particles were measured. A model catalyst was prepared by depositing Pt nanoparticles on a SiO/SiO₂-coated transmission electron microscope (TEM) grid. A soot surrogate composed of graphitic nanoparticle agglomerates generated by laser ablation was deposited on the same surface. This system simulates, morphologically, catalytic soot traps used in practice. The reaction was carried out in a tubular flow reactor in which the gas phase simulated diesel exhaust gas, composed of a mixture of 10% O₂ and 1000 ppm NO with the remainder N₂. The progress of the carbon nanoparticle oxidation was monitored off-line by analysis of electron microscopy images of the agglomerates before and after reaction. This experimental method permitted the correlation of reaction rate with particle sizes and separation distances as well as catalyst surface area in the direct environs of the soot particles. The experimental results revealed no effect of Pt catalyst particle size in the range 7–31 nm on the rate of reaction. Also observed were a decrease in the rate of reaction with increasing distance between carbon agglomerates and catalyst particles and a linear dependence of the reaction rate on the fractional catalyst surface area coverage.     

Characterization of palmitic and lauric acid aerosols from rapid expansion of supercritical CO2 solutions

Palmitic acid aerosols and lauric acid aerosols were generated by rapid expansion of supercritical CO₂ solutions. The particle properties were analysed by rapid-scan infrared spectroscopy in situ, by X-ray powder diffraction, with a scanning mobility particle sizer, and by scanning electron microscopy. Particles with irregular elongated shapes were found. Most particles and agglomerates have sizes between 250 and 750 nm. Fewer agglomerates with sizes up to several microns are observed. Our investigation reveals that strong agglomeration takes place at the Mach disc. Palmitic and lauric acid particles are both crystalline and most particles crystallize in the C-form.     

Synthesis,forming and characterization of ceramic materials for the planar solid oxide fuel cell (SOFC)

Chemically-homogeneous and well-characterized ceramic powders have been used for the preparation and investigation of the SOFC components. The powders were synthesized by spray drying and subsequent calcination. The resulting powders were characterized with regard to the crystalline phases, chemical analysis, specific surface area, particle size and particle size distribution, morphology and particle agglomerates. These parameters are very important for forming thin, flat ceramic sheets and components by tape-casting and screen-printing technology. Forming process, sintering, electrical conductivity and compatibility are discussed. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

随机取向烟幕凝聚粒子的消光特性

采用蒙特卡罗方法根据团簇-团簇凝聚(CCA)模型对由球形原始微粒凝聚而成的烟幕凝聚粒子进行模拟,用离散偶极子近似(DDA)方法研究随机取向烟幕凝聚粒子的消光特性.结果表明,凝聚粒子的消光特性受到原始微粒数量以及粒径的影响,粒子的凝聚将减弱烟幕的消光性能;当凝聚结构中原始微粒的数目一定时,存在使烟幕消光性能达到最大的原始微粒粒径.