Advances in scalable gas-phase manufacturing and processing of nanostructured solids: A review

Although the gas-phase production of nanostructured solids has already been carried out in industry for decades, only in recent years has research interest in this topic begun to increase. Nevertheless, despite the remarkable scientific progress made recently, many long-established processes are still used in industry. Scientific advancements can potentially lead to the improvement of existing industrial processes, but also to the development of completely new routes. This paper aims to review state-of-the-art synthesis and processing technologies, as well as the recent developments in academic research. Flame reactors that produce inorganic nanoparticles on industrial- and lab-scales are described, alongside a detailed overview of the different systems used for the production of carbon nanotubes and graphene. We discuss the problems of agglomeration and mixing of nanoparticles, which are strongly related to synthesis and processing. Finally, we focus on two promising processing techniques, namely nanoparticle fluidization and atomic layer deposition.     

Influence of nanoparticle surface coating on pool boiling

The purpose of this work is to study the effects of nanostructured surface coatings on boiling heat transfer and CHF. Boiling experiments are performed on a 100 μm diameter platinum wire immersed in saturated water or pentane at 1 bar. Nanostructured surface coating is obtained by deposition of charged γ-Fe₂O₃ nanoparticles (average diameter of 10 nm) on the platinum wire. Two different processes are compared: vigorous boiling and electrophoresis.The deposition of nanoparticles onto the heated surface induces a significant increase of the boiling critical heat flux (CHF) related to the increase of wettability. It also induces a decrease of the heat transfer coefficient when the wire is entirely covered with nanoparticles. The critical heat flux enhancement depends on the wettability of the fluid compared with the bare heater. Different physical mechanisms are also studied to explain the evolution of the characteristic parameters of the boiling on nanostructured surfaces.     

Coating of finely dispersed particles by two-fluid nozzle

Particle coatings are used extensively to generate dispersed solids with well-defined properties, e.g., to protect active ingredients, with most coating processes using core particles of a diameter larger than 200 μm. This work contributes to the development of a coating process for fine dispersed particles (diameter less than 50 μm) by combining two particle-formulation processes, namely, coating and spray drying. The feasibility of the operation is based on and demonstrated by the innovative application of a two-fluid nozzle. Experiments were conducted by using glass particles as core particles and sodium benzoate as the coating agent. The coating of finely dispersed particles is achieved by the spraying of particles and coating solution as a homogeneous suspension. The aim is to create droplets with only one contained particle at the nozzle outlet. After evaporation of the water in the droplet, a thin solid film is built on the particle surface. The suspension viscosity was measured and compared with empirical equations from the literature. The liquid-film thickness on the particle surface was calculated to predict the building of a uniform coating layer or agglomerates. In this study, the feasibility of pneumatic transport through the nozzle and an investigation of the process were illustrated. The agglomeration fraction and degree of coating of the particle surface were analyzed optically by scanning electron microscopy. In this way, the influence of different processes and suspension parameters on the product quality were determined.     

INTERACTION-MEDIATED GROWTH OF CARBON NANOTUBES ON ACICULAR SILICA-COATED a-Fe CATALYST BY CHEMICAL VAPOR DEPOSITION BY CHEMICAL VAPOR DEPOSITION

1. Introduction Carbon nanotubes (CNTs), a kind of the most advanced nanomaterials with novel properties and promising for many applications, have aroused great interest of the world in a number of research fields (Iijima, 1991; Baughman et al., 2002; Iijima & Ichihashi, 1993; Rao & Govindaraj, 2002; Rueckes et al., 2000; Adrian et al., 2001; Javey et al., 2003). Catalytic chemical vapor deposition (CCVD) is re-garded as the most suitable method for the preparation of microstructured CN…     

INTERACTION-MEDIATED GROWTH OF CARBON NANOTUBES ON ACICULAR SILICA-COATED α-Fe CATALYST BY CHEMICAL VAPOR DEPOSITION

Multi-walled carbon nanotubes (MWNTs) with 20 nm outer diameter were prepared by chemical vapor deposition of ethylene using ultrafine surface-modified acicular α-Fe catalyst particles.The growth mechanism of MWNTs on the larger catalyst particles are attributed to the interaction between the Fe nanoparticles with the surface-modified silica layer.This interaction-mediated growth mechanism is illustrated by studying the electronic,atomic and crystal properties of surface-modified catalysts and MWNTs products by characterization with X-ray diffraction (XRD),transmission electron microscopy (TEM),high resolution transmission electron microscopy (HRTEM),thermal gravimetric analysis (TGA) and Raman spectra.     

纳米CeO2颗粒的制备及其化学机械抛光性能研究

以硝酸铈和六亚甲基四胺为原料制备出不同粒径的纳米CeO2粉体颗粒,将纳米CeO2粉体配制成抛光液并用于砷化镓晶片的化学机械抛光.结果表明,不同尺寸的纳米磨料具有不同的抛光效果,采用粒度8 nm的CeO2磨料抛光后微观表面粗糙度最低(0.740 nm),采用粒度小于或大于8 nm的CeO2磨料抛光后其表面粗糙度值均较高.通过简化的固-固接触模型分析,认为当粒度过小时,磨料难以穿透软质层,表现为化学抛光为主,表面凹坑较多,表面粗糙度较高;当粒度大于一定值时,随着磨料粒度增加,嵌入基体部分的深度加大,使得粗糙度出现上升趋势.提出当磨料嵌入晶片表面的最大深度等于或接近于软质层厚度时,在理论上应具有最佳的抛光效果.     

A REVIEW OF CURRENT KNOWLEDGE CONCERNING SIZE-DEPENDENT AEROSOL REMOVAL

The status of current knowledge on size-dependent aerosol removal by dry and wet processes, including dry deposition and impaction and nucleation scavenging, is reviewed. The largest discrepancies between theoretical estimations and measurement data on dry deposition and below-cloud scavenging are for submicron particles, Early dry deposition models, which developed based on chamber and wind tunnel measurements, tended to underestimate dry deposition velocity （Vσ） for submicron particles by around one order of magnitude compared to recent field measurements. Recently developed models are able to predict reasonable Vσ values for submicron particles but shift unrealistically the predicted minimum Vσ to larger particle sizes. Theoretical studies of impaction scavenging of aerosol particles by falling liquid drops also substantially underestimate the scavenging coefficients for submicron particles. Empirical formulas based on field measurements can serve as an alternative to the theoretical scavenging models. Future development of size-resolved impaction scavenging models needs to include more precipitation properties （e,g., droplet surface area） and to be evaluated by detailed cloud microphysical models and available measurements. Several recently developed nucleation scavenging parameterizations for in-cloud removal of interstitial aerosol give comparable results when evaluated against parcel models; however, they need to be verified once suitable field measurements are available. More theoretical and field studies are also needed in order to better understand the role of organic aerosols in the nucleation scavenging process.     

Rheological properties of suspensions of polyethylene-coated aluminum nanoparticles

Ultrafine aluminum powder was identified as very promising fuels for novel energetic materials formulations. However, the large specific surface area of this powder facilitates its oxidation and greatly reduces its shelf life. Therefore, different coating processes were proposed to solve this problem. The rheology of viscous suspensions of nanoparticles still remains poorly understood and the effect of the coating of such particles on the flow behavior is even more difficult to assess. We have studied the rheology of ultrafine aluminum suspensions in three low molecular weight polymers of different viscosities: a hydroxy-terminated polybutadiene, a polypropylene glycol, and a polysiloxane. The nanosize aluminum powder was previously coated by a thin layer of high-density polyethylene using an in situ polymerization process. The rheological characterization of the suspensions was conducted by the means of steady and oscillatory shear flow measurements for noncoated and coated particles. The effect of the coating process on the rheology of the suspensions is discussed in terms of the interactions between the particles and the suspending fluids.     

Determination of Hydrogen–Water Relative Permeability and Capillary Pressure in Sandstone: Application to Underground Hydrogen Injection in Sedimentary Formations

This paper presents fundamental analysis and micromechanical understanding of dense slurry behavior during settling in narrow smooth and rough slots. Particularly, this study seeks to contribute toward better understanding of dynamics of particle–particle and particle–wall interactions in viscous fluids using simple experiments. The findings of this study are applicable in a wide variety of problems, for example sediment transport, flow and transport of slurry in pipes, and industrial applications. However, the results interpretation focuses on better understanding of proppant flow and transport in narrow fractures. A sequence of experiments image frames captured by video camera is analyzed with particle image velocimetry (GeoPIV). The measurements include vertical velocities and displacement vectors of singular and agglomerated particles and larger area of formed slurry. Results present novel insights into the formation and effects of agglomerates on general slurry settling, and are supplemented with a comparison with previously published theoretical and empirical relationships. This work also emphasizes a role of particle–particle interactions in promoting agglomeration in viscous fluid. Particularly, a thin layer of viscous fluid between approaching particles dissipates particle kinetic energy due to lubrication effect. Lubrication effect is more pronounced when particles are constrained between two narrow walls and interact frequently with each other. Fluid tends to flow around agglomerated particles, and agglomerates remain stable for prolonged time periods gravitationally moving downward. The relative amount and size of agglomerated affects general settling of the slurry. It was found that fluid viscosity due to lubrication effect promotes agglomeration, and therefore, the overall slurry settling relatively increases at higher fluid viscosities. The results of the presented work have impact on various industrial and engineering processes, such as proppant flow and transport in hydraulic fractures, sand production in oil reservoirs, piping failure of dams and scour of foundation bridges.     

Using the DEM-CFD method to predict Brownian particle deposition in a constricted tube

Modelling of the agglomeration and deposition on a constricted tube collector of colloidal size particles immersed in a liquid is investigated using the discrete element method （DEM）. The ability of this method to represent surface interactions allows the simulation of agglomeration and deposition at the particle scale. The numerical model adopts a mechanistic approach to represent the forces involved in colloidal suspensions by including near-wall drag retardation, surface interaction and Brownian forces. The model is implemented using the commercially available DEM package EDEM 2.3~, so that results can be repli- cated in a standard and user-friendly framework. The effects of various particle-to-collector size ratios, inlet fluid flow-rates and particle concentrations are examined and it is found that deposition efficiency is strongly dependent on the inter-relation of these parameters. Particle deposition and re-suspension mechanisms have been identified and analyzed thanks to EDEM＇s post processing capability. One-way coupling with computational fluid dynamics （CFD） is considered and results are compared with a two- way coupling between EDEM 2.3 and FLUENT 12.1. It is found that two-way coupling requires circa 500% more time than one-way coupling for similar results.     

The role of several heat transfer mechanisms on the enhancement of thermal conductivity in nanofluids

A modelling of the thermal conductivity of nanofluids based on extended irreversible thermodynamics is proposed with emphasis on the role of several coupled heat transfer mechanisms: liquid interfacial layering between nanoparticles and base fluid, particles agglomeration and Brownian motion. The relative importance of each specific mechanism on the enhancement of the effective thermal conductivity is examined. It is shown that the size of the nanoparticles and the liquid boundary layer around the particles play a determining role. For nanoparticles close to molecular range, the Brownian effect is important. At nanoparticles of the order of 1–100 nm, both agglomeration and liquid layering are influent. Agglomeration becomes the most important mechanism at nanoparticle sizes of the order of 100 nm and higher. The theoretical considerations are illustrated by three case studies: suspensions of alumina rigid spherical nanoparticles in water, ethylene glycol and a 50/50w% water/ethylene glycol mixture, respectively, good agreement with experimental data is observed.     

A NOVEL METHOD FOR FABRICATING COMPOSITE MOSAIC MEMBRANE WITH UNIQUE NF SELECTIVITY

A novel method of fabricating composite mosaic membranes was studied on the basis of interracial polymerization （IP） by coating a thin selective layer onto the surface of a micro-porous hollow-fiber membrane, in which, 2,5-diaminobenzene sulfonic acid was used as one monomer of the IP reaction, and a mixture of trimesoyl chloride （TMCI） and 4-（chloromethyl） benzoyl chloride as the other monomer. Through the IP reaction a thin selective layer with negatively charged groups could be first formed on the polyethersulfone （PES） support membrane. Then trimethylamine solution was introduced to modify the IP layer through a quaternization reaction. Thus the selective layer of this composite membrane contained both negatively charged and positively charged groups to perform the mosaic functionality. Characterization of the composite mosaic membranes was carried out through permeation experiments using different inorganic salts and dyes. The experimental results showed that the membranes could permeate both mono- and bi-valent inorganic salts, but reject larger organic molecules. Such a mosaic membrane is potentially useful for the separation of salts from water-soluble organics, especially in dye and textile industries.     

Novel self assembly behavior for γ-alumina nanoparticles

In this study, self assembly behavior was induced for γ-alumina nanoparticles by adsorption of dimethyl disulfide. Following this trend, we have developed a chemical process to obtain γ-alumina in the nano scale. Scanning electron microscopy images of the prepared γ-alumina showed big and strong agglomeration of the nanoparticles indicating that these nanoparticles have strong surface forces. Transmission electron microscopy images confirmed that the γ-alumina nanoparticles 3–7 nm in size were converted to uniform spherical shape in the size range of 1–2 mm after shaking with dimethyl disulfide in the presence of n-hexane at room temperature. This phenomenon did not appear in the case of alumina in the micro scale. The surface properties of the prepared γ-alumina in the nano scale were characterized and compared with the γ-alumina in the micro scale by using low temperature nitrogen adsorption–desorption system, indicating that the specific surface area of the prepared γ-alumina nanoparticles is larger than that of the γ-alumina in the micro scale. Furthermore, micro- and meso-pores were observed for the γ-alumina nanoparticles while only mesoporous structure was detected for the γ-alumina in the micro scale. These experimental results suggested that the self assembly behavior of the γ-alumina nanoparticles may be due to the selective adsorption of dimethyl disulfide in the micropores of these nanoparticles to act as bridge linking the nanoparticles.     

Hierarchical structure observation and nanoindentation size effect characterization for a limnetic shell

In the present research, hierarchical structure observation and mechanical property characterization for a type of biomaterial are carried out. The investigated biomaterial is Hyriopsis cumingii, a typical limnetic shell, which consists of two different structural layers, a prismatic "pillar"structure and a nacreous "brick and mortar" structure. The prismatic layer looks like a "pillar forest" with variationsection pillars sized on the order of several tens of microns.The nacreous material looks like a "brick wall" with bricks sized on the order of several microns. Both pillars and bricks are composed of nanoparticles. The mechanical properties of the hierarchical biomaterial are measured by using the nanoindentation test. Hardness and modulus are measured for both the nacre layer and the prismatic layer, respectively.The nanoindentation size effects for the hierarchical structural materials are investigated experimentally. The results show that the prismatic nanostructured material has a higher stiffness and hardness than the nacre nanostructured material.In addition, the nanoindentation size effects for the hierarchical structural materials are described theoretically, by using the trans-scale mechanics theory considering both strain gradient effect and the surface/interface effect. The modeling results are consistent with experimental ones.     

Using the DEM-CFD method to predict Brownian particle deposition in a constricted tube

Modelling of the agglomeration and deposition on a constricted tube collector of colloidal size particles immersed in a liquid is investigated using the discrete element method (DEM). The ability of this method to represent surface interactions allows the simulation of agglomeration and deposition at the particle scale. The numerical model adopts a mechanistic approach to represent the forces involved in colloidal suspensions by including near-wall drag retardation, surface interaction and Brownian forces. The model is implemented using the commercially available DEM package EDEM 2.3^®, so that results can be replicated in a standard and user-friendly framework. The effects of various particle-to-collector size ratios, inlet fluid flow-rates and particle concentrations are examined and it is found that deposition efficiency is strongly dependent on the inter-relation of these parameters. Particle deposition and re-suspension mechanisms have been identified and analyzed thanks to EDEM's post processing capability. One-way coupling with computational fluid dynamics (CFD) is considered and results are compared with a two-way coupling between EDEM 2.3^® and FLUENT 12.1^®. It is found that two-way coupling requires circa 500% more time than one-way coupling for similar results.     

Equilibrium self-polarization of clay

A condition of equilibrium between charged clay particle surfaces and the solution contained in the pore space of the rock is derived using electrical double layer theory. This condition is the relation linking the cation concentration in the middle surface of the pores with the exchange capacity of the clay, the total ion charges, and the specific surface area of the particles. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 48, No. 5, pp. 96–103, September–October, 2007.     

In situ synthesis of Ag-SiO_2 Janus particles with epoxy functionality for textile applications

A facile method for the synthesis of silver-silica(Ag-SiO_2) Janus particles with functionalities suitable for textile applications is reported.Silica nanoparticles prepared by the Stober method were functionalized with epoxy,amine,and thiol groups,which were confirmed by Fourier transform infrared analysis.The functionalized silica nanoparticles were used to produce Pickering emulsions,and the exposed surface was used for the attachment of silver nanoparticles(AgNPs) via the low-temperature chemical reduction method.The morphology and structure of the Ag-SiO_2 Janus particles were characterized by scanning electron microscopy,scanning transmission electron microscopy,high-resolution transmission electron microscopy,energy-dispersive X-ray analysis,and UV-vis spectroscopy.Because of their specific functionalities,these Ag-SiO_2 Janus particles are proposed for applications on textile substrates,as they can overcome several drawbacks of direct application of AgNPs on textiles,such as leaching,agglomeration,and instability during storage.     

Numerische Berechnung des Partikeltransportes zu einer laminar angeströmten Kreisscheibe

Increasingly process steps become important, in which particles as product particles or contaminants are deposited on substrates out of the gas phase. In this paper the particles transport processes are investigated close to the surface of a circular plate surrounded by a laminar flow. The analogy between the governing equations of momentum, energy and mass is applied to the extended diffusion equation. In the nondimensional form the results of the numerical calculations give informations about velocity, temperature and particle concentration boundary layer thickness as well as their distributions. Especially the impact of external forces on particle concentration boundary layer thickness and profile is discussed. The transport of submicron particles to the surface due to convection, diffusion, gravity and thermophoretic forces acting independently is investigated. In the used normalized form the different forces are acting as one resulting force independently of their origin. Their resulting effect in comparison to the effect due to convective diffusive transport is important for particle deposition.     

Control of iron nanoparticle size by manipulating PEG–ethanol colloidal solutions and spin-coating parameters for the growth of single-walled carbon nanotubes

Iron catalyst nanoparticles were prepared on silicon wafers by spin-coating colloidal solutions containing iron nitrate, polyethylene glycol (PEG) and absolute ethanol. The effects of various spin-coating conditions were investigated. The findings showed that the size of the iron particles was governed by the composition of the colloidal solution used and that a high angular speed was responsible for the formation of a thin colloidal film. The effect of angular acceleration on the size and distribution of the iron particles were found to be insignificant. It was observed that a longer spin-coating duration provoked the agglomeration of iron particles, leading to the formation of large particles. We also showed that single-walled carbon nanotubes could be grown from the smallest iron catalyst nanoparticles after the chemical vapor deposition of methane.     

Factors influencing particle agglomeration during solid-state sintering

Discrete element method(DEM) is used to studythe factors affecting agglomeration in three-dimensionalcopper particle systems during solid-state sintering.A newparameter is proposed to characterize agglomeration.Theeffects of a series of factors are studied,including particlesize,size distribution,inter-particle tangential viscosity,temperature,initial density and initial distribution of particleson agglomeration.We find that the systems with smallerparticles,broader particle size distribution,smaller viscosity,higher sintering temperature and smaller initial densityhave stronger particle agglomeration and different distributions of particles induce different agglomerations.This studyshould be very useful for understanding the phenomenon ofagglomeration and the micro-structural evolution during sintering and guiding sintering routes to avoid detrimental agglomeration.