Evaluating the performance of Russia in the research in nanotechnology

Many toxicology studies on insoluble and poorly soluble nanoparticles point out surface area as an indicator of inhalation exposure. Measuring this criterion thus constitutes an important challenge. Instruments exist which can measure particle surface area concentration in real-time, but it is not known how well they perform when faced with polydisperse nanostructured aerosols. In this study, the response functions of three commercially available instruments based on diffusion charging (LQ1-DC, Matter Engineering; NSAM, TSI model 3550; AeroTrak? 9000, TSI) were measured for monodisperse aerosols of four different chemical natures with particles ranging in size from 15 to 520?nm. Our results show good agreement between the experimental and theoretical response functions for the three instruments studied. In addition, no significant effect of the chemical nature, density or particle morphology was revealed. Instrument response was also tested with polydisperse aerosols. For these aerosols, discrepancies were observed between measurements and calculated concentrations based on response function and particle number size distribution. Relative differences varied between ?60 and +55?% with an average value of ?20?%. These differences may be explained by different factors; among them, the existence of a distribution of electrical charges on particles can lead to identical signals measured, and differential diffusion charging performance might lead to concentration-dependent response.     

Controllable synthesis, characterization, and magnetic properties of nanoscale zerovalent iron with specific high Brunauer–Emmett–Teller surface area

This article reports a novel approach for the controllable synthesis of nanoscale zerovalent iron (NZVI) particles with specific high Brunauer–Emmett–Teller (BET) surface areas. Borohydride reduction is a primary and effective liquid phase reduction method for the synthesis of zerovalent iron nanoparticles. However, previous methods for synthesizing NZVI did not suggest a standard technique for controlling the size of particles during the synthesis process; in addition, previous literature generally reported that NZVI had a BET surface area of <37 m²/g. In this communication, a novel approach for the controllable synthesis of NZVI particles with specific high BET surface areas is presented. As a result, the BET surface areas of the NZVI particles synthesized increased to 47.49 and 62.48 m²/g, and the particle sizes decreased to 5–40 and 3–30 nm. Additionally, the physical and chemical properties of the synthesized NZVI particles were investigated by a series of characterizations, and magnetic analysis indicated that the synthesized NZVI particles had super-paramagnetic properties.     

核磁共振技术在物质表面性质表征领域的新应用

核磁共振(nuclear magnetic resonance)技术具有快速、精确、分辨率高等优点,并已不断成熟成为土壤分析、物质结构鉴定、食品分析和医学成像等领域重要的研究分析手段。本文通过介绍利用NMR技术研究液相环境中高分子聚合物在颗粒表面(主要为SiO₂颗粒)的吸附、解吸及扩散等行为和利用NMR技术研究受污染土壤中水的摄取过程及土壤润湿性两大方面,综述了NMR技术在物质表面性质表征领域的重要应用,展现了NMR技术在高分子材料和环境领域中独特的重要作用。重点介绍基于NMR技术的Acorn比表面分析仪能够直接测定液相环境中物质的弛豫时间,反映物质的表面性质和结构特征,为解释污染物环境行为提供数据支持从而在环境领域发挥重要作用,展现出Acorn比表面分析仪相比于传统BET法在测量环境和测量时间等方面的优越性,尤其是Acorn比表面分析仪可以反映液相环境中物质的表面性质和结构特征的重要特性,解决了传统BET法无法直接获得液相环境中物质的比表面积信息的难题,是液相环境中NMR技术在物质表面性质表征领域的新突破。对Acorn比表面分析仪在制药、化妆品材料和电子产品等方面的应用进行了分析,并在土壤有机质、药物和天然产物检测等方面对NMR技术的应用进行了展望。     

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.     

The measurement of charging efficiencies and losses of aerosol nanoparticles in a corona charger

A methodology is proposed for the measurement of a number of parameters relevant to the performance evaluation of aerosol corona chargers. These parameters are intrinsic and extrinsic charging efficiencies, and diffusion and electrostatic particle losses. The methodology is essentially the same as that used in earlier works, except that free ions are removed just after the charger outlet in order to minimize the extent of possible after-charging effects which might lead to measurement errors. However, the experimental results show that after-charging is negligible and that, consequently, practically all the effective ion–particle collisions take place before the aerosol leaves the charger. Formation of new particles during corona discharge, which could in principle be an additional cause of measurement error, has not been observed in the working voltage range of the charger. Particle diffusion and electrostatic losses have been measured at varying values of the voltage applied to the charger: for a given particle size, diffusion loss decreases and electrostatic loss increases as the charger voltage is increased. The intrinsic charging efficiency increases with particle size and charger voltage. In contrast, the extrinsic charging efficiency, which is the parameter of importance in practice, attains a maximum value for a given charger voltage in such a manner that this optimum voltage depends on particle size.     

New technique for electrostatic charge measurement in gas–solid fluidized beds

Electrostatic charge generation within gas–solid fluidized bed reactors has been a concern to industry for many years. Over the years, numerous methods for measuring this phenomenon within a fluidization column have been proposed. This paper focuses on the design of a new method that minimizes effects such as extra charging due to particle handling and bed hydrodynamic disruption due to the location of the measurement device. In addition, the new method provides the bulk charge of the bed particles rather than a local measurement. The device is flexible and can be adapted to a range of fluidization columns. The new method developed consisted of a Faraday cup placed within the windbox of a fluidization column. The distributor plate was designed in such a way that it can be automatically opened to drop the charged fluidizing particles into the Faraday cup below. The new measurement technique was validated by conducting fluidization experiments in a system consisting of a 0.10 m in diameter carbon steel column with glass beads as the fluidizing particles. The technique was proven to be suitable for measuring the total net electrostatic charges in gas–solid fluidized beds.     

对利用动态光散射法测量颗粒粒径和液体黏度的改进

光散射技术通过测量悬浮液中布朗运动颗粒的平移扩散系数,得到颗粒流体力学直径或液体黏度.本文由单参数模型入手,建立了低颗粒浓度下,单颗粒平移扩散系数与颗粒集体平移扩散系数和颗粒浓度之间的线性依存关系并将其引入光散射法中,从而对现有的测量方法进行了改进.改进后的测量方法可实现纳米尺度球型颗粒标称直径的测量和液体黏度的绝对法测量.以聚苯乙烯颗粒+水和二氧化硅颗粒+乙醇两个分散系为参考样本,通过实验,验证了改进后方法的可行性.此外,还针对上述两个分散系,实验探讨了温度和颗粒浓度对颗粒集体平移扩散系数的影响规律,发现聚苯乙烯颗粒+水分散系中,颗粒间相互作用表现为引力;二氧化硅颗粒+乙醇分散系中,颗粒间相互作用表现为斥力.讨论了颗粒集体平移扩散系数随颗粒浓度变化规律与第二渗透维里系数的关系.     

水合金属氧化物对氟的吸附机理研究

通过碱沉淀法制备了Ce,Al,Ni,Cu的水合氧化物,研究了它们的Langmuir吸附等温线,并利用BET法通过吸附-脱附氮气测定了其比表面积,同时对其吸附氟离子前后的变化进行了IR谱图的表征.结果表明不同水合金属氧化物具有不同的比表面积,其孔径分布也不尽相同,吸附量与比表面积之间没有直接相关的正比关系.吸附等温线均符...     

Enhanced reactivity of nanoscale iron particles through a vacuum annealing process

A reactivity study was undertaken to compare and assess the rate of dechlorination of chlorinated aliphatic hydrocarbons (CAHs) by annealed and non-annealed nanoscale iron particles. The current study aims to resolve the uncertainties in recently published work studying the effect of the annealing process on the reduction capability of nanoscale Fe particles. Comparison of the normalized rate constants (m²/h/L) obtained for dechlorination reactions of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-1,2-DCE) indicated that annealing nanoscale Fe particles increases their reactivity ~30-fold. An electron transfer reaction mechanism for both types of nanoscale particles was found to be responsible for CAH dechlorination, rather than a reduction reaction by activated H₂ on the particle surface (i.e., hydrogenation, hydrogenolysis). Surface analysis of the particulate material using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with surface area measurement by Brunauer, Emmett, Teller (BET) indicate that the vacuum annealing process decreases the surface area and increases crystallinity. BET surface area analysis recorded a decrease in nanoscale Fe particle surface area from 19.0 to 4.8 m²/g and crystallite dimensions inside the particle increased from 8.7 to 18.2 nm as a result of annealing.     

Unipolar charging of nanoparticles by the Surface-discharge Microplasma Aerosol Charger (SMAC)

In this paper, we report the development of a novel unipolar charger for nanoparticles, a system that achieves low particle loss and high charging efficiency without the use of sheath air. The efficient unipolar charging of the system is realized mainly by the surface-discharge microplasma unit, a device previously applied with good success to the neutralization or charging of submicron particles [Kwon et al., 2005, Aerosol Sci. Technol., 39, 987–1001; 2006, J. Aerosol Sci., 37, 483–499]. The unipolar charger generates unipolar ions using the surface discharge of a single electrode with a DC pulse supply. This marks an advance from our previous method of generating bipolar ions with the use of dual electrodes in earlier studies. We evaluated the efficiency of the penetration (or loss) and charging of nanoparticles in the size range of 3–15 nm, then compared the charging efficiencies measured with those predicted by diffusion charging theory. More than 90% of inlet nanoparticles penetrated the charger (less than 10% of the particle were lost) without the use of sheath air. Other chargers have only realized this high penetration efficiency by relying on sheath air flow. Moreover, the measured charging efficiencies agreed well with those predicted by diffusion charging theory and were somewhat higher and more size-dependent than the charging efficiencies of other nanoparticle chargers.     

Influences of different powders on the characteristics of particle charging and deposition in powder coating processes

This experimental study investigated the influences of two different powder systems (coarse and ultrafine) on particle charging and deposition characteristics during electrostatic powder coating processes. Results disclosed that, despite their differences in particle sizes, the two powders behave similarly in deposition process, commonly resulting in a cone-shaped deposited pattern in the inner portion of the substrate and an increase of deposited particles in the fringe region. However, their different properties lead to the discrepancies in their deposition efficiencies, which account for a higher efficiency with the coarse powder. The study further revealed that the coarse powder is superior to the ultrafine powder in charging in-flight particles, which directly contributes to its higher deposition efficiencies. Furthermore, it was disclosed that the two powders exhibit distinct characteristics in charging deposited particles. Compared to the coarse powder, the ultrafine powder is more uniform in charging deposited particles, mainly owing to its greater particle number and higher specific surface area but less mass. In particular, the charging efficiency of overall deposited particles decreases for the ultrafine powder but increases for the coarse powder with increased charging voltage, closely related to their particle properties. However, both powders decrease in charging efficiency of deposited particles with extended spraying duration due to back corona intensifying with spraying.     

Ultrasonic-assisted sol-gel method of preparation of TiO2 nano-particles: characterization, properties and 4-chlorophenol removal application

Nano-size TiO2 photocatalysts were prepared by sol-gel and ultrasonic-assisted sol-gel methods using two different sources of ultrasonicator, i.e., a bath type and tip type. The physicochemical characteristics of the catalysts were investigated by BET, XRD and TEM analyses and the photocatalytic properties of the TiO2 catalysts prepared by three different methods were compared. The intrinsic and extrinsic properties of TiO2, such as the particle size, surface area, pore-volume, pore-diameter, crystallinity as well as anatase, rutile and brookite phase ratios, could be controlled by the ultrasonic-assisted sol-gel method. During this preparation method, the effect of such important operating variables as the ultrasonic irradiation time, power density, the ultrasonic sources (bath-type and tip-type), magnetic stirring during synthesis, initial temperatures and size of the reactors are discussed here. It was found that each of the parameters played a significant role in controlling the properties of the TiO2 nano-particles. Among the three different methods, TiO2 photocatalysts prepared by ultrasonic (tip-US) assisted sol-gel possessed the smallest particle size, highest surface area and highest pore-volume than the catalysts prepared by the other two methods. 4-Chlorophenol was used as a pollutant to observe the photocatalytic degradation ability of the prepared photocatalysts and the TiO2 catalysts prepared by the bath-US ultrasonic-assisted sol-gel method were shown to be the most highly active. This is due to their high surface area and high pore-diameter. This study clearly demonstrates the importance and advantages of ultrasonication in the modification and improvement of the photocatalytic properties of mesoporous nano-size TiO2 particles.     

BET surface area of carbonaceous adsorbents—Verification using geometric considerations and GCMC simulations on virtual porous carbon models

The applicability of BET model for calculation of surface area of activated carbons is checked by using molecular simulations. By calculation of geometric surface areas for the simple model carbon slit-like pore with the increasing width, and by comparison of the obtained values with those for the same systems from the VEGA ZZ package (adsorbate-accessible molecular surface), it is shown that the latter methods provide correct values. For the system where a monolayer inside a pore is created the ASA approach (GCMC, Ar, T = 87 K) underestimates the value of surface area for micropores (especially, where only one layer is observed and/or two layers of adsorbed Ar are formed). Therefore, we propose the modification of this method based on searching the relationship between the pore diameter and the number of layers in a pore. Finally BET; original and modified ASA; and A, B and C-point surface areas are calculated for a series of virtual porous carbons using simulated Ar adsorption isotherms (GCMC and T = 87 K). The comparison of results shows that the BET method underestimates and not, as it was usually postulated, overestimates the surface areas of microporous carbons.     

On-line Surface Area Measurement of Concentrated Slurries using low field spin-lattice relaxation NMR

A method for the rapid on-line determination of surface area and solids content in flowing concentrated slurries using low field NMR spin-lattice relaxation measurements has been developed and demonstrated. The relationship between flow and spin-lattice relaxation time (T₁) of protons in water at 20 MHz was examined using aqueous copper sulfate solutions. The ability to measure surface area and solids concentration in both stagnant (stopped flow) and flowing systems via NMR was demonstrated using several different concentrated aqueous titania and glass slurries (20 to 80 weight percent) for which the dried powder surface area was previously determined via nitrogen adsorption/BET analysis and the solids content determined gravimetrically. Surface areas were also calculated from particle size analysis and found to vary by up to an order of magnitude from the adsorption and NMR results.     

工业中粉体颗粒的荷电机理及数值模拟方法

工业过程中粉体颗粒不可避免地会相互摩擦碰撞而荷电. 荷电颗粒的存在可能会危害正常的工业生产过程, 也可能对工业过程起促进作用. 因此, 荷电粉体颗粒及其特性受到了广泛的关注, 但目前对粉体颗粒的荷电机理依然缺乏透彻的了解, 尤其是在气固两相流动中的粉体颗粒荷电现象. 事实上, 工业中存在的粉体颗粒的运动都受到流体的影响, 是典型的气固两相流系统, 流体对粉体颗粒的作用使粉体颗粒接触的荷电现象变得更为复杂, 因此从两相流动的观点来研究粉体颗粒荷电的物理本质就显得越来越重要. 本文介绍了工业过程中的几种不同类型的粉体颗粒荷电行为, 回顾了颗粒的荷电机理与描述颗粒荷电的数学模型. 对于工业过程中颗粒的荷电现象及颗粒在多相流体中的动力学行为, 介绍了研究颗粒受流体影响时荷电特性的数值模拟方法. 本文旨在对粉体颗粒的荷电机理、应用以及研究方法进行梳理与探讨, 为正确认识工业过程中粉体颗粒的荷电现象并加以控制利用提供理论借鉴.     

Preparation and hydrogen storage of activated rayon-based carbon fibers with high specific surface area

Activated carbon fibers were prepared from rayon-based carbon fibers by two step activations with steam and KOH treatments. Hydrogen storage properties of the activated rayon-based carbon fibers with high specific surface area and micropore volume have been investigated. SEM, XRD and Brunauer-Emmett-Teller (BET) were used to characterize the samples. The adsorption performance and porous structure were investigated by nitrogen adsorption isotherm at 77 K on the base of BET and density functional theory (DFT). The BET specific surface area and micropore volume of the activated rayon-based carbon fibers were 3144 m²/g and 0.744 m³/g, respectively. Hydrogen storage properties of the samples were measured at 77 and 298 K with pressure-composition isotherm (PCT) measuring system based on the volumetric method. The capacities of hydrogen storage of the activated rayon-based carbon fibers were 7.01 and 1.46 wt% at 77 and 298 K at 4 MPa, respectively. Possible mechanisms for hydrogen storage in the activated rayon-based carbon fibers are discussed.     

Coalbed methane adsorption and desorption characteristics related to coal particle size

Effects of particle size on CH_4 and CO_2adsorption and desorption characteristics of coals are investigated at 308 K and pressures up to 5.0 MPa.The gas adsorption and desorption isotherms of coals with particle sizes ranging from 250 μm to 840 μm are measured via the volumetric method,and the Langmuir model is used to analyse the experimental results.Coal particle size is found to have an obvious effect on the coal pore structure.With the decrease of coal particle size in the process of grinding,the pore accessibility of the coal,including the specific surface area and pore volume,increases.Hence,coal with smaller particle size has higher specific surface area and higher pore volume.The ability of adsorption was highly related to the pore structure of coal,and coal particle size has a significant influence on coal adsorption/desorption characteristics,including adsorption capacity and desorption hysteresis for CH_4 and CO_2,i.e.,coal with a smaller particle size achieves higher adsorption capacity,while the sample with a larger particle size has lower adsorption capacity.Further,coal with larger particle size is also found to have relatively large desorption hysteresis.In addition,dynamic adsorption performances of the samples are carried out at 298 K and at pressures of 0.1 MPa and 0.5 MPa,respectively,and the results indicate that with the increase of particle size,the difference between CO_2 and CH_4adsorption capacities of the samples decreases.     

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.     

Comparison of influence of fluidization time on electrostatic charge build-up in the bubbling vs. slugging flow regimes in gas–solid fluidized beds

Electrostatic charge generation poses significant problems in some commercial gas–solid fluidized bed reactors such as those in gas-phase polyolefin production. Understanding the contributing factors to charge generation is important in determining the charge generation mechanisms, leading to the development of methods to reduce or prevent this phenomenon. This work focused on determining the effect of fluidization time on particle charging and the amount of particle adhesion on the fluidization column wall in both the bubbling and slugging flow regimes. The charging effect was investigated for particles in three regions of the fluidized bed: elutriated fines, bulk particles inside the bed, and particles adhered to the column wall. The particles size distribution, mass and charge were measured for all three regions. Fluidization was carried out with polyethylene resins from an industrial reactor; times of 15, 30, 60, 120, 180, and 360 min were evaluated. Increased fluidization time decreased the amount of particles mass collected in the bulk region and increased those adhered to the column wall during the velocities tested in the bubbling flow regime. Whereas the quantity of particles in each region was not affected by fluidization time for the velocities examined in the slugging flow regime. Bipolar charging was observed with relatively smaller particles becoming predominately positively charged and larger particles becoming predominately negatively charged. Each region of the bed affected the magnitude of net q/m, with elutriated fines having the largest magnitude, followed by those adhered to the column wall, and finally those in the bulk of the bed. Charge saturation was attained for fluidization times greater than 60 min for particles in the bulk and along the column wall for all gas velocities. However, extended fluidization times were required with the entrained fines in bubbling flow; whereas charge saturation of fines in slugging flow occurred shortly after the onset of fluidization. Mean particle diameter for each measurement region was not impacted by the fluidization time for any of the gas velocities tested. The bed hydrodynamics was found to definitely have an impact on the particle–wall fouling where the particle layer continued to develop on the inner column wall as fluidization time increased for those velocities in the bubbling regime while comparatively less impact on particle layer growth was observed in the slugging flow regime. In addition, the bubbling flow regime resulted in particle layers formed on the column wall to be longer and thinner whereas those formed in the slugging flow regime were shorter and thicker.     

Effect of small particle sizes on the measured density of nanocrystalline powders of nonstoichiometric tantalum carbide TaC<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript>

Nanocrystalline powders of the nonstoichiometric tantalum carbide TaC_y (0.81 ≤ y ≤ 0.96) with an average particle size in the range from 45 to 20 nm have been prepared using high-energy ball milling of coarse-grained powders. The density of the initial coarse-grained and prepared nanocrystalline powders of TaC_y has been measured by helium pycnometry. The sizes of particles in tantalum carbide powders have been estimated using the X-ray diffraction analysis and the Brunauer–Emmett–Teller (BET) method. The density of TaC_y nanopowders measured by helium pycnometry is underestimated as compared to the true density due to the adsorption of helium by the highly developed surface of the nanocrystalline powders. It has been shown that the difference between the true and measured densities is proportional to the specific surface area or is inversely proportional to the average particle size of the nanopowders. The large difference between the true and measured pycnometric densities indicates a superhydrophobicity of the tantalum carbide nanopowders.