The Process of Particle Formation in the Flame Synthesis of Tin Oxide Nanoparticles

Tin oxide nanoparticles with sizes in the range 5-30 nm are generated within a low pressure flame reactor setup in the gas phase. We study the effect of preparation parameters such as precursor concentration, flame to substrate distance, and post-deposition annealing procedures on the morphology and crystal structure of the particles utilizing transmission electron microscopy and X-ray diffraction in order to characterize the particle formation process. The structural investigations indicate that monoxide particles form from SnO monomers within the flame. These primary particles need to be further oxidized and thermally annealed to transform into single phase rutile type SnO 2 nanoparticles.     

Workplace air measurements and likelihood of exposure to manufactured nano-objects,agglomerates, and aggregates

Workplace exposure to nanoparticles from gas metal arc welding (GMAW) process in an automobile manufacturing factory was investigated using a combination of multiple metrics and a comparison with background particles. The number concentration (NC), lung-deposited surface area concentration (SAC), estimated SAC and mass concentration (MC) of nanoparticles produced from the GMAW process were significantly higher than those of background particles before welding (P < 0.01). A bimodal size distribution by mass for welding particles with two peak values (i.e., 10,000–18,000 and 560–320 nm) and a unimodal size distribution by number with 190.7-nm mode size or 154.9-nm geometric size were observed. Nanoparticles by number comprised 60.7 % of particles, whereas nanoparticles by mass only accounted for 18.2 % of the total particles. The morphology of welding particles was dominated by the formation of chain-like agglomerates of primary particles. The metal composition of these welding particles consisted primarily of Fe, Mn, and Zn. The size distribution, morphology, and elemental compositions of welding particles were significantly different from background particles. Working activities, sampling distances from the source, air velocity, engineering control measures, and background particles in working places had significant influences on concentrations of airborne nanoparticle. In addition, SAC showed a high correlation with NC and a relatively low correlation with MC. These findings indicate that the GMAW process is able to generate significant levels of nanoparticles. It is recommended that a combination of multiple metrics is measured as part of a well-designed sampling strategy for airborne nanoparticles. Key exposure factors, such as particle agglomeration/aggregation, background particles, working activities, temporal and spatial distributions of the particles, air velocity, engineering control measures, should be investigated when measuring workplace exposure to nanoparticles.     

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.     

Thermodynamic-Controlled Gas Phase Process for the Synthesis of Nickel Nanoparticles of Adjustable Size and Morphology

Gas phase processes are a successful route for the synthesis of nano materials. Nickel particles are used in applications ranging from catalysis to nano electronics and energy storage. The application field defines the required particle size, morphology, crystallinity and purity. Nickel tetracarbonyl is the most promising precursor for the synthesis of high purity nickel particles. Due to the toxicity of this precursor and to obtain an optimal process control we developed a two-step flow type process. Nickel carbonyl and nickel particles are synthesized in a sequence of reactions. The particles are formed in a hot wall reactor at temperatures below 400°C in different gas compositions. Varying the process conditions enables the adjustment of the particle size in a range from 3 to 140 nm. The controllable crystalline habits are polycrystalline, single crystals or multiple twinned particles (MTP). Spectroscopic investigations show an excellent purity. We report about the process and first investigations of the properties of the synthesized nickel nanomaterial.     

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.     

Production of Monodisperse Nanoparticles and Application of Discrete-Monodisperse Model in Plasma Reactors

The particle growth in plasma reactor were investigated by using the discrete-monodisperse (D-M) model for various process conditions. The monodisperse large sized particle distribution predicted by the D-M model are in good agreement with the large sized particles by the discrete-sectional model and also in the experiments by Shiratani et al. (1996). Some fractions of the small size particles are in a neutral state or even charged positively, but most of the large sized monodisperse particles are charged negatively. As the mass generation rate of monomers increases, the large sized particles grow more quickly and the production rate of nanoparticles of 100nm by plasma reactor increases. As the initial electron concentration or the monomer diameter increases, it takes longer time for the large sized particles to grow up to 100nm, but the large sized particle concentration of 100nm increases and the resulting production rate of large sized particles of 100nm increases. As the residence time increases, the time for the large sized particles to grow up to 100nm decreases and the large sized particle concentration of 100nm increases and, as a result, the production rate of large sized particles of 100nm increases. We propose that the plasma reactor can be a good candidate to produce monodisperse nanoparticles.     

Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

Synthesis of carbon-encapsulated nickel nanoparticles

Carbon-encapsulated metal nanoparticles (CEMNs) were obtained by the catalytic decomposition of hydrocarbons (CH₄, C₂H₆, C₂H₄) on nanocrystalline nickel. Nanocrystalline nickel was obtained by precipitation from nickel nitrate solution, followed by calcination and reduction under hydrogen. A small amount of structural promoters (aluminium and calcium oxide) was added to avoid recrystallisation of fine nickel particles at elevated temperatures. Reduction and carburisation of the samples was carried out in a differential reactor with mass control. The rate of decomposition of methane, ethane and ethylene on nanocrystalline nickel was measured and the apparent activation energy of the process was determined. The obtained samples were characterised using the XRD, SEM and HRTEM methods.     

爆轰合成碳包覆钴、镍磁性纳米颗粒的探索

 介绍了爆轰法合成碳包覆钴、镍纳米磁性颗粒研究的初步结果。以黑索今炸药为主体,加入钴、镍金属硝酸盐与有机碳源材料,在爆炸容器中氮气保护下用导爆管雷管引爆,成功地合成了碳包覆钴、镍纳米磁性颗粒。为了探求爆轰固体产物的形貌特征及性能,分别采用了TEM、XRD、VSM等测试手段对其进行表征。实验结果表明,爆轰产物中主要含有碳包覆纳米钴、纳米镍磁性颗粒,成球体或者椭球体,具有完好的核壳结构形貌。合成的碳包覆钴颗粒分布在30~50 nm之间,碳包覆的镍颗粒分布在25~60 nm之间,外层碳壳层主要由无定形碳和石墨构成。磁性测试表明,所得碳包金属钴、镍颗粒在室温下具有良好的软磁特性。     

Preparation of magnetic nanoparticles by pulsed plasma chemical vapor synthesis

FePt nanoparticle is expected as a candidate for the magnetic material of the high density recording media. We attempted to synthesize FePt alloy nanoparticles using 13.56 MHz glow discharge plasma with the pulse operation of a square-wave on/off cycle of plasma discharge to control the size of nanoparticles. Vapors of metal organics, Biscyclopentadienyl iron (ferrocene) for Fe and (Methylcyclopentadienyl) trimethyl platinum for Pt, were introduced into the capacitively coupled flow-through plasma chamber, which consisted of shower head RF electrode and grounded mesh electrode. Synthesis experiments were conducted at room temperature under the conditions of pressure 0.27 Pa, source gas concentration 0.005 Pa, gas residence time 0.5 s and plasma powers 60 watts. Pulse width for plasma duration was chosen from 0.5 to 30 s and plasma off period was 4 s to each pulse operation. Visual observations during the particle growth showed plasma emission in the bulk region was increased with the particle growth. These were theoretically explained by using the model for both transient particle charging in the plasma and single particle behavior in the stationary plasma as well as assuming the similarity between the negative charged particle and negative gas containing plasma. Synthesized nanoparticles were directly collected onto TEM grid, which was placed just below the grounded mesh electrode in the plasma reactor downstream. TEM pictures showed two kinds of particles in size, one of which was nanometer size and isolated with crystal structures and the other appeared agglomerate of nanometer size particles. The size of agglomerated particle was controlled in the 10–120 nm range by varying the plasma-on time from 0.5 to 30 s, although the nanometer size particles did not change. The composition of FePt alloy particles could be altered by adjusting the source gas feed ratio. Also magnetization of FePt nanoparticles was measured by use of SQUID (superconducting quantum interference device) magnetometry measurements. As-synthesized FePt nanoparticles did not exhibit loop-shape characteristic, which indicated superpamagnetic property. Annealed nanoparticles with the composition of Fe₅₈Pt₄₂ at 650°C in atmospheric hydrogen showed clear hysterisis loop with the coercivity as large as 10 KOe.     

Silicon nanoparticles produced by spark discharge

On the example of silicon, the production of nanoparticles using spark discharge is shown to be feasible for semiconductors. The discharge circuit is modelled as a damped oscillator circuit. This analysis reveals that the electrode resistance should be kept low enough to limit energy loss by Joule heating and to enable effective nanoparticle production. The use of doped electrodes results in a thousand-fold increase in the mass production rate as compared to intrinsic silicon. Pure and oxidised uniformly sized silicon nanoparticles with a primary particle diameter of 3–5 nm are produced. It is shown that the colour of the particles can be used as a good indicator of the oxidation state. If oxygen and water are banned from the spark generation system by (a) gas purification, (b) outgassing and (c) by initially using the particles produced as getters, unoxidised Si particles are obtained. They exhibit pyrophoric behaviour. This continuous nanoparticle preparation method can be combined with other processing techniques, including surface functionalization or the immediate impaction of freshly prepared nanoparticles onto a substrate for applications in the field of batteries, hydrogen storage or sensors.     

Characterization of Nano‐Particles Using Laser‐Induced Incandescence

Laser‐induced incandescence (LII) is introduced as a valuable tool for the characterization of nanoparticles. This optical measurement technique is based on the heating of the particles by a short laser pulse and the subsequent detection of the thermal radiation. It has been applied successfully for the investigation of soot in different fields of application, which is described here in the form of an overview with a focus on work done at the LTT‐Erlangen during the last 10 years. In laboratory flames the soot primary particle size, volume concentration, and relative aggregate size have been determined in combination with the number density of primary particles. Furthermore, the primary particle sizes of carbon blacks have been measured in situ and online under laboratory conditions and also in production reactors. Measurements with different types of commercially available carbon black powders, which were dispersed in a measurement chamber yielded a good correlation between LII results and the specified product properties. Particle diameters determined by LII in a furnace black reactor correlate very well with the CTAB‐absorption number, which is a measure for the specific surface area. It turned out that the LII method is not affected by variations of the aggregate structure of the investigated carbon blacks. The LII signal also contains information on the primary particle size distribution, which can be reconstructed by the evaluation of the signal decay time at, at least, two different time intervals. Additionally, soot mass concentrations have been determined inside diesel engines and online measurements were performed in the exhaust gas of such engines for various engine conditions simultaneously providing information about primary particle size, soot volume, and number concentration. The LII results exhibit good correlation with traditional measurement techniques, e.g., filter smoke number measurements. In addition to the soot measurements, primarily tests with other nanoparticles like TiO₂ or metal particles are encouraging regarding the applicability of the technique for the characterization of such different types of nanoparticles.     

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.     

Characterization of TiO2 Smoke Prepared Using Gas‐Phase Hydrolysis of TiCl4

The formation of submicron TiO₂ smoke (a gas‐phase suspension) from titanium tetrachloride in a low‐pressure hydrolysis reaction in a simple reactor configuration has been studied. Particle size distribution, particle morphology and degree of crystallinity have been characterized as a function of reaction conditions. Highly crystalline anatase TiO₂ particles with narrow size distribution and smaller particle size were formed at high reactor temperature, while larger, amorphous particles were found at lower reactor temperatures. These results are consistent with literature studies. At 817 °C, small (450 nm), spherical, unagglomerated particles could be produced. A gas‐phase dispersion of these particles is intended for use as seeds in subsequent kinetic studies of titanium dioxide formation reactions involving a rapid compression methodology.     

Chemical vapor functionalization: a continuous production process for functionalized ZnO nanoparticles

The continuous functionalization of nanoparticles in the gas-phase directly after their generation, chemical vapor functionalization, is studied with ZnO and 1-hexanol as a model system using two reactors in series. In the first reactor ZnO nanoparticles are synthesized in the gas-phase from diethylzinc and oxygen at 1,073 K with grain sizes of 13 nm as determined by Rietveld refinement of X-ray diffractograms. The second reactor, connected at the exit of the first reactor and kept at lower temperatures (573, 673, and 773 K), is used as a functionalization chamber. At the connection point of the two reactors, the vapor of 1-hexanol is injected to react with the surface of ZnO nanoparticles in the gas phase. The process has been analyzed by quadrupole mass spectrometry to obtain information about optimal conditions for functionalization. Dynamic light scattering data show that the functionalized particles have substantially improved colloidal dispersibility with hydrodynamic diameters of 60 nm. Diffuse reflectance fourier transform infrared spectra and ¹H nuclear magnetic resonance spectra are consistent with 1-hexanol adsorbed at the particle surface acting as a functionalizing agent. The agglomerate size is substantially reduced owing to chemical vapor functionalization.     

脉冲激光气相沉积法制备钴纳米薄膜实验研究

 采用脉冲激光沉积技术制备了钴纳米薄膜，分析和讨论了不同背景气压和脉冲频率对钴纳米薄膜表面形貌的影响及纳米微粒的形成机理。实验结果表明：在低背景气压下，等离子体羽辉自身粒子之间的碰撞占主导作用，容易形成液滴；在较高背景气压下，等离子体羽辉边缘粒子和背景气体粒子之间的碰撞占主导作用，容易形成小岛并凝聚成微颗粒；在4Hz的脉冲重复频率和5Pa背景气压下生长出单分散性良好的钴纳米颗粒。     

Effect of ambient gas species on the formation of Cu nanoparticles in wire explosion process

In this paper, the effect of ambient gas species on the characteristics of the produced nanoparticles in wire explosion process is reported. Cu wires with a diameter of 125 μm and length of 6.1 cm were exploded in different ambiances of Ar and admixtures of Ar and N₂ at 500 mbar pressure. Immediate formation of arc plasma is observed for Ar ambiance. On the other hand, considerable delay in formation of arc plasma is observed for the admixtures of Ar and N₂. The arc plasma formation time is found to increase with increasing N₂ concentration in the admixture. Transmission electron microscope and X-ray diffraction were used to characterize the produced nanoparticles. Among the nanoparticles produced in different ambient gas species, the nanoparticles produced in Ar ambiance have higher particle size compared to admixtures of Ar and N₂. The particle size is found to reduce with increasing N₂ concentration in the ambiance. Difference in arc plasma formation time is probably the factor that gives rise to the difference in the particle sizes.     

Growth and morphology of carbon nanostructures on nickel oxide nanoparticles in catalytic chemical vapor deposition

The present study explores the conditions favorable for the growth of cylindrical carbon nanostructures such as multi-walled carbon nanotube (MWCNT) and carbon nanofiber by catalytic chemical vapor deposition (CCVD) method using nickel oxide-based catalyst nanoparticles of different average sizes as well as different levels of doping by copper oxide. The role of doping and the average size have been related to the observed melting behavior of nanoparticles of nickel oxide by thermal and diffraction analysis, and the importance of melting has been highlighted in the context of growth of cylindrical nanostructures. In the reducing environment prevailing in the CCVD chamber due to decomposition of flowing acetylene gas at elevated temperature, there is extensive reduction of oxide nanoparticles. Lack of melting and faster flow of carbon-bearing gases favor the formation of a carbon deposit cover over the catalyst nanoparticles giving rise to the formation of nanobeads. Melting allows rapid diffusion of carbon from the surface to inside catalyst particles, and reduced flow of gas lowers the rate of carbon deposit, both creating conditions favorable for the formation of cylindrical nanostructures, which grows around the catalyst particles. Smaller particle size and lower doping favor growth of MWCNT, while growth of fiber is commonly observed on larger particles having relatively higher level of doping.     

不同催化剂热解法制备硼碳氮纳米管过程中的影响

对以钴、镍、钴/镍、钴/二茂铁、镍/二茂铁和二茂铁为催化剂高温热解法制备的硼碳氮（BCN）纳米管的结构、产率等的影响进行了分析.实验中发现催化剂在BCN纳米管的生长过程中有重要作用.高分辨率透射电子显微镜图像显示在860℃时，以镍/二茂铁、钴/二茂铁为催化剂生成的BCN纳米管具有“竹节状”结构，且管壁较薄，镍、钴或镍/钴作催化剂生成的BCN纳米管不具有明显的“竹节状”结构，管壁较厚，且粗细不均匀，而以二茂铁作催化剂没有BCN纳米管生成.在所有生成的BCN纳米管中含有催化剂颗粒.通过对生成的BCN纳米管的结 关键词： BCN纳米管 热解 催化剂 拉曼光谱     

Gas-phase Crystallization of Titanium Dioxide Nanoparticles

We have investigated the development of crystal morphology and phase in ultrafine titanium dioxide particles. The particles were produced by a droplet-to-particle method starting from propanolic titanium tetraisopropoxide solution, and calcined in a vertical aerosol reactor in air. Mobility size classified 40-nm diameter particles were conveyed to the aerosol reactor to investigate particle size changes at 20–1200°C with 5–1-s residence time. In addition, polydisperse particles were used to study morphology and phase formation by electron microscopy. According to differential mobility analysis, the particle diameter was reduced to 21–23-nm at 600°C and above. Precursor decomposition occurred between 20°C and 500°C. The increased mobility particle size at 700°C and above was observed to coincide with irregular particles at 700°C and 800°C and faceted particles between 900°C and 1200°C, according to transmission electron microscopy. The faceted anatase particles were observed to approach a minimized surface energy by forming {101} and {001} crystallographic surfaces. Anatase phase was observed at 500–1200°C and above 600°C the particles were single crystals. Indications of minor rutile formation were observed at 1200°C. The relatively stable anatase phase vs. temperature is attributed to the defect free structure of the observed particles and a lack of crystal–crystal attachment points.