Synergistic effects of the alternating application of low and high frequency ultrasound for particle synthesis in microreactors

Ultrasound (US) is a promising method to address clogging and mixing issues in microreactors (MR). So far, low frequency US (LFUS), pulsed LFUS and high frequency US (HFUS) have been used independently in MR for particle synthesis to achieve narrow particle size distributions (PSD). In this work, we critically assess the advantages and disadvantages of each US application method for the case study of calcium carbonate synthesis in an ultrasonic microreactor (USMR) setup operating at both LFUS (61.7 kHz, 8 W) and HFUS (1.24 MHz, 1.6 W). Furthermore, we have developed a novel approach to switch between LFUS and HFUS in an alternating manner, allowing us to quantify the synergistic effect of performing particle synthesis under two different US conditions. The reactor was fabricated by gluing a piezoelectric plate transducer to a silicon microfluidic chip. The results show that independently applying HFUS and LFUS produces a narrower PSD compared to silent conditions. However, at lower flow rates HFUS leads to agglomerate formation, while the reaction conversion is not enhanced due to weak mixing effects. LFUS on the other hand eliminates particle agglomerates and increases the conversion due to the strong cavitation effect. However, the required larger power input leads to a steep temperature rise in the reactor and the risk of reactor damage for long-term operation. While pulsed LFUS reduces the temperature rise, this application mode leads again to the formation of particle agglomerates, especially at low LFUS percentage. The proposed application mode of switching between LFUS and HFUS is proven to combine the advantages of both LFUS and HFUS, and results in particles with a unimodal narrow PSD (one order of magnitude reduction in the average size and span compared to silent conditions) and negligible rise of the reactor temperature.     

三维漏斗中颗粒物质堵塞问题的数值实验研究

对于工程和实验中使用漏斗颗粒流而言,连续稳定的流量是必要的.当漏斗口较小时,很容易发生堵塞行为.堵塞现象对于交通流、疏散问题等也具有重要的意义.前人主要使用扰动的方法破坏漏斗中已有的堵塞,以便引起下一次堵塞,加快实验进程.本文利用自主开发的基于GPU(graphics processing unit)的密集颗粒流模拟程序,主要研究当三维漏斗开口打开后的第一次堵塞行为,不再引入扰动.详细讨论了漏斗开口尺寸、漏斗锥角等几何参数对坍塌规模的影响.发现对于坍塌规模的概率分布符合前人的研究结果,可以分为两部分:峰的左边呈幂函数上升形式,峰的右边呈指数衰减趋势.对于漏斗开口尺寸和漏斗锥角而言,均存在一个临界值使得堵塞不再发生.     

非牛顿体不稳定流的研究

本文通过试验和分析研究了非牛顿体明渠不稳定流的机理,阐明了不稳定流的产生和发展是由于流体具有屈服应力,利用这一机理,解释了高含沙洪水的波动和“浆河”现象、冰川流和泥流的不稳定流和泥石流的阵流现象。     

A Directed Percolation Model for Clogging in a Porous Medium with Small Inhomogeneities

We propose a microscopic model based on directed percolation for the process of mechanical clogging of a porous medium by particles suspended in a fluid flow. Under appropriate conditions the deposited particles may form fractal clusters. A criterion for the occurrence of fractal clogging is presented. It links together the particle size and the pore size distribution. The effect of microscopic inhomogeneities is studied inside and outside the critical region using Monte Carlo calculations in two dimensions. The critical exponents remain unchanged because the perturbation induced by these inhomogeneities is irrelevant. The percolation threshold is found to shift to higher values almost linearly with increasing size of obstacles. For size distributed obstacles the arithmetic mean of the distribution is the only significant parameter which determines the shift. Type and broadness of the distribution have no influence. Also the percolation probability depends only on the mean even outside the critical region for all values of the occupation probability. Occupying the same fraction of the porous matrix, large obstacles cause more particles to deposit than small ones.     

Three-dimensional clogging structures of granular spheres near hopper orifice

The characteristic clogging structures of granular spheres blocking three-dimensional granular flow through hopper outlet are analyzed based on packing structures reconstructed using magnetic resonance imaging techniques.Spheres in clogging structures are arranged in a way with typical features of load-bearing,such as more contacting bonds close to the horizontal plane and more mutually-stabilized contact configurations than packing structures away from the orifice.The requirement of load-bearing inevitably leads to the cooperativity of clogging structures with a correlation length of several particle diameters.This correlation length being comparable with the orifice diameter suggests that a clogging structure is composed of several mutually-stabilized structural motifs to span the orifice perimeter,instead of a collection of independent individual spheres to cover the whole orifice area.Accordingly,we propose a simple geometric model to explain the unexpected linear dependence of the average size of three-dimensional clogging structures on orifice diameter.     

Asymmetric nozzle structure for particles converging into a highly confined region

Asymmetric nozzle inlet was suggested for particles to converge into a highly confined region. The physical properties from the nano-scaled volumetric difference at nozzle inlet were investigated using computational fluid dynamics and particle motion measurement with fluorescence beads and erythrocytes. The asymmetric nozzle structure made particles converge efficiently without clogging at nozzle inlet. It could be used as a micro/nanofluidic unit for cell based assay in a microchip such as chip-based flow cytometer.     

Erosion and deposition of solid particles in porous media: Homogenization analysis of a formation damage

The aim of the paper is to model at a large scale, the formation damage in porous media by erosion and deposition of solid particles. We start from the equations governing the pore-scale processes of erosion, deposition, convection and diffusion. The macroscopic equivalent behaviour is investigated by using a homogenization method. Four characteristic models with different dominating phenomena at the pore scale are determined. The main results are twofold: first dispersion-deposition and dispersion-erosion phenomena are shown at the macroscopic scale for peculiar values of the dimensionless numbers; furthermore, and contrarily to phenomenological models, erosion and deposition generally occur in regions of intense and slow flow, respectively.     

Modeling Biogeochemical Processes in Leachate-Contaminated Soils: A Review

During subsurface transport, reactive solutes are subject to a variety of hydrological, physical and biochemical processes. The major hydrological and physical processes include advection, diffusion and hydrodynamic dispersion, and key biochemical processes are aqueous complexation, precipitation/dissolution, adsorption/desorption, microbial reactions, and redox transformations. The addition of strongly reduced landfill leachate to an aquifer may lead to the development of different redox environments depending on factors such as the redox capacities and reactivities of the reduced and oxidised compounds in the leachate and the aquifer. The prevailing redox environment is key to understanding the fate of pollutants in the aquifer. The local hydrogeologic conditions such as hydraulic conductivity, ion exchange capacity, and buffering capacity of the soil are also important in assessing the potential for groundwater pollution. Attenuating processes such as bacterial growth and metal precipitation, which alter soil characteristics, must be considered to correctly assess environmental impact. A multicomponent reactive solute transport model coupled to kinetic biodegradation and precipitation/dissolution model, and geochemical equilibrium model can be used to assess the impact of contaminants leaking from landfills on groundwater quality. The fluid flow model can also be coupled to the transport model to simulate the clogging of soils using a relationship between permeability and change in soil porosity. This paper discusses the different biogeochemical processes occurring in leachate-contaminated soils and the modeling of the transport and fate of organic and inorganic contaminants under such conditions.     

Direct fabrication of copper patterns by reactive inkjet printing

Reactive inkjet printing (RIP) was applied to fabricate arbitrary copper (Cu) patterns. RIP prints reactive inks which can provide desired materials after the reaction on a substrate. Here, Cu precursors and reducing agents were dissolved together in one solution as a printable ink instead of conventional Cu nanoparticle inks. The prepared reactive ink was applied to the RIP method to provide dot arrays, lines, and films of Cu. The synthesis of Cu was confirmed to occur successfully by thorough analysis. The RIP method can reduce the process cost and resolve critical drawbacks of the conventional inkjet printing such as a nozzle clogging problem. Furthermore, utilizing reactive precursor inks broadens the choice of materials that can be processed by inkjet printing.     

Permeability evolution induced by the precipitation of an advected solute: Effect of the microscopic and the macroscopic scales competition on the clogging mechanism

A model is proposed for coupling the one-dimensional transport of solute with surface precipitation kinetics which induces the clogging of an initially homogeneous porous medium. The aim is to focus the non-linear feedback effect between the transport and the chemical reaction through the permeability of the medium. A Lagrangian formulation, used to solve the coupled differential equations, gives semi-analytical expressions of the hydrodynamic quantities. A detailed analysis reveals that the competition between the microscopic and macroscopic scales controls the clogging mechanism, which differs depends on whether short or long times are considered. In order to illustrate this analysis, more quantitative results were obtained in the case of a second and zeroth order kinetic. It was necessary to circumvent the semi-analytic character of the solutions problem by successive approximation. A comparison with results obtained by simulations displays a good agreement during the most part of the clogging time.Nomenclature a(x, t) Capillary tube radius (L) - A _(aq) Chemical species in the aqueous phase - A _n(s) Chemical species of the solid phase - C(x, t) Aqueous concentration in a capillary tube ([mole/L³] in the case of a permanent injection - [mole/L³/L] in the case of an instantaneous injection) - C(x, t) C(x, t)/C ₀ Dimensionless aqueous concentration in a capillary tube - C ₀ Aqueous concentration imposed at the inlet and also initial concentration in an elementary volume of fluid (mole/L³) - C _i(t) Concentration in a fluid element i (mole/L³) - C(_R) (t, C_o) Aqueous concentration in a stirred reactor (mole/L³) - d_ij (t) Length belonging to the volume, inside a fluid element i, which interacts with a precipitate element j (L) - dM _ij(t) Mass exchange between a fluid element i and a precipitate element j (M) - dN ₀ Number of molecules in an elementary volume of fluid injected at the inlet of a capillary tube during dt ₀ - dN(x, t, C₀) Number of molecules in an elementary volume of fluid - dt ₀ Time injection of an elementary volume of fluid (T) - D(x, t) Dispersion coefficient (L²/T) - Da(t, x) Damköhler number - D _m Molecular diffusion coefficient (L²/T) - F(x, t) Advective flux (mole/L²/T) - k ₁ Kinetic constant of dissolution (mole/L³/T) - k ₂ Kinetic constant of precipitation ([mole/L³]^{1 - n} /T) - k ₂ Kinetic constant of precipitation in the case of a zeroth order kinetics (mole/L³/T) - K(x, t) Permeability in a capillary tube (L²) - K(x, t) K (x, t)/K₀ Dimensionless permeability - k ₀ Permeability of a capillary tube at t = 0 (L²) - L Length of a capillary tube (L) - m Molecular weight of the reactive species (M/mole) - n Stochiometry of the chemical reaction and kinetic order of the precipitation reaction - P(x, t) Precipitate concentration in a capillary tube (mole/L³) - P _j(t) Concentration in a precipitate element j (mole/L³) - P(_r) (t, C_o) Precipitate concentration in a stirred reactor (mole/L³) - Pr(x, t) Local pressure in a capillary tube - (M/T²/L³) Pr(x, t) Pr(x, t)/Pr(x, 0) Dimensionless local pressure in a capillary tube - Q(t) Flow rate (L³/T) - Q(t) Q(t)U ₀/S₀ Dimensionless flow rate - R(x, t) Chemical flux between the aqueous and the solid phase in a capillary tube (mole/L³/T) - R _i(t) Chemical flux between an aqueous element i and the solid phase (mole/L³/T) - R _(R)[t, C₀] Chemical flux between the aqueous and the solid phase in a stirred reactor (mole/L³/T) - S(x, t) Cross sectional area of a capillary tube accessible to the aqueous phase (L²) - S(x, t) S(x, t)/S₀ Dimensionless cross-sectional area - S ₀ Cross-sectional area of a capillary tube at t = 0 (L²) - tlim(x) Time at which the precipitation front concentration vanishes in the case of zeroth order kinetics (T) - t _max Time of maximum propagation of the precipitation front in the case of zeroth order kinetics (T) - tmin(x) Time at which the precipitation front arrives at x (T) - t _p L/U ₀. Time necessary for an elementary volume of fluid, moving with the velocity U ₀, to reach the oulet of the medium - t _U max Time of maximum value of the velocity field in the case of zeroth order kinetics (T) - t ₀ Time at which an elementary volume of fluid has left the inlet of a capillary tube (T) - t _0m (x, t) Time at which the last elementary volume of fluid has left the inlet of a capillary tube to reach x at a time lower or equal to t (T) - U(x, t) Fluid velocity (L/T) - U(x, t) U(x, t)/U ₀. Dimensionless fluid velocity - U _j(x, t) Fluid velocity defined from the precipitate element j (L/T) - U _l (t₀, t) Lagrangian fluid velocity (L/T) - U _l (t ₀, t) U _l (x, t)/U ₀. Dimensionless lagrangian fluid velocity - U ₀ Velocity of the fluid at t = 0 (L/T) - V _ij(t) Volume, inside a fluid element i, which interacts with a precipitate element j (L³) - x _i(t) Front position of the fluid element i (L) - x _j Front position of the precipitate element j (L) - X _front(t) Position of the precipitation front (L) - x _lim(t) Position of the precipitation front when the value of its concentration is zero (L) - xmax Position of the maximum propagation of the precipitation front in the case of zeroth order kinetics and for high value of C ₀ (L) - Xmin (t) Position of the precipitation front (L) - x _inf* ^supmax Position of the maximum propagation of the precipitation front in the case of zeroth order kinetics and for small value of C_o (L) Greek Symbols t Time step used during the numerical computation (T) - Pro Imposed pressure drop (M/L/T²) - Injection time of reactive species (T) - Density of the precipitate (M/L³) - Dynamic viscosity (M/L/T) - <Ri(t)> _infi ^supj Mean chemical flux between a precipitate element j and all the fluid elements i susceptible to interact with the precipitate element j (mole/L³/T)