Analytical SPLITT cell fractionation: Linearity and resolution study

In this paper the analytical SPLITT (split flow thin cell) procedure is used to characterize the percentage composition of micronic polydisperse particulate samples at a given cut‐off size. The linearity and resolution of the separation method have been tested using specifically prepared starch samples, in order to compare the analytical process with two continuous (preparative) SPLITT procedures. Linearity has been checked by injecting a series of suspensions (at different concentrations) under five different flow rate conditions. Retrieval factors F were evaluated to verify the relative amount of sample exiting the cell outlets. The effective resolution has been assessed by inspecting the SPLITT fractions with an optical microscope, counting the granules, and evaluating the percentage of granules of expected size. It has been found that the resolution is very good (around 90%) and independent of sample distribution. It is seen from the comparison that in the analytical SPLITT mode sample resolution is usually around 85–90% and it is significantly better than that of the continuous SPLITT modes, thus making the analytical mode valuable in characterizing polydisperse samples. The method was tested for the characterization of a commercial starch sample.     

Continuous split-flow thin cell and gravitational field-flow fractionation of wheat starch particles

The combined employment of the SPLITT (split-flow thin) cell--a relatively new system for fast, continuous binary separation--and of gravitational field-flow fractionation (GrFFF)--a fractionation technique suitable for micron particle size distribution determination--was investigated for starch separation and characterization. Emphasis is placed on the main advantages of both techniques: operating under gentle earth gravity field, low cost and ease of maintenance. The reproducibility of GrFFF is demonstrated. Both the SPLITT separation and GrFFF fractionation results were checked by optical microscopy. Application examples of typical starch fractionation experiments are reported and discussed.     

General theory for flow optimisation of split-flow thin fractionation

Recently, magnetic split-flow thin (SPLITT) fractionation has been developed to separate macromolecules, colloids, cells and particles. However, the previous theory, developed for an infinitely long channel, needs to be improved to consider the flow transit regimes at both inlet and outlet. In this paper, we describe a new approach to optimising flow-rates for particle separation which considers the effect of flow transit region. Surprisingly, the critical particle migration velocities derived by the present theory are identical to the previous simplified theory. Therefore, the previous simplified theory may have wider application than might have been expected. As a test of our theory, a numerical simulation based on solving Navier-Stokes equations has also been carried out for a magnetic SPLITT device. The trajectory of a particle with the critical migration velocity is exactly as expected by our theory. Following experimental validation, this work will facilitate the design of new SPLITT fractionation systems with smaller aspect ratio.     

Size-based analysis of incinerator fly ash using gravitational SPLITT fractionation, sedimentation field-flow fractionation, and inductively coupled plasma-atomic emission spectroscopy

Fly ash has been regarded as hazardous because of its high adsorption of toxic organic and/or inorganic pollutants. Fly ash is also known to have broad distributions of different chemical and physical properties, such as size and density. In this study, fly ash emitted from a solid waste incinerator was pre-fractionated into six sub-populations by use of gravitational SPLITT fractionation (GSF). The GSF fractions were then analyzed by sedimentation field-flow fractionation (SdFFF) and ICP–AES. SdFFF analysis showed the fly ash has a broad size distribution ranging from a few nanometers up to about 50 µm. SdFFF results were confirmed by electron microscopy. Inductively coupled plasma–atomic emission spectroscopy (ICP–AES) analysis of the GSF fractions showed the fly-ash particles contain a variety of inorganic elements including Ca, Si, Mg, Fe, and Pb. The most abundant in fly ash was Ca, followed by Si then Mg. No correlations were found between trace element concentration and particle size.     

Hollow-fiber flow/hyperlayer field-flow fractionation for the size characterization of airborne particle fractions obtained by SPLITT fractionation

Hollow-fiber flow field-flow fractionation (HF FlFFF) was applied for the separation and size characterization of airborne particles which were collected in a municipal area and prefractionated into four different-diameter intervals >5.0, 2.5-5.0, 1.5-2.5, <1.5 microm) by continuous split-flow thin (SPLIIT) fractionation. Experiments demonstrated the possibility of utilizing a hollow-fiber module for the high-performance separation of supramicron-sized airborne particles at steric/hyperlayer operating mode of HF FlFFF. Eluting particles during HF FlFFF separation were collected at short time intervals (approximately 10 s) for the microscopic examination. It showed that particle size and size distributions of all SPLITT fractions of airborne particles can be readily obtained using a calibration and that HF FlFFF can be utilized for the size confirmation of the sorted particle fraction during SPLITT fractionation.     

Pinched inlet gravitational split-flow thin fractionation of airborne particles and analysis of size dependent level of PCDD/Fs

Fine particles in air have a direct influence on human health because they carry toxic chemicals that can be deposited in the human lung when inhaled. Thus, particle size distribution and size dependent level of contamination of the airborne particles are important parameters for the study and assessment of environmental pollution. In this study, gravitational split-flow thin (SPLITT) fractionation (or GSF), a semi-preparative scale separation technique for particles, was applied for the continuous size sorting of airborne particles collected in urban area. About 2.0 g of airborne particles was fractionated into four different size intervals (<1.5, 1.5-2.5, 2.5-5.0, and >5.0 microm), and the collected fractions were examined by electron microscopy for particle size distribution and analyzed for the size dependent levels of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). It was found that more than 60% of particles including dissolved matters in weight were smaller than 5.0 microm and they contained more than 86% of the total PCDD/Fs amount in airborne particles.     

A microfabricated electrical SPLITT system

A growing need for methods to analyze and prepare monodisperse nanoparticles on an industrial scale exists and may be solved by the application of split flow thin fractionation (SPLITT) at the microscale. Microfluidic systems of this type have the ability to separate nanoparticles with high precision in a continuous manner. A miniaturized SPLITT system can be fabricated using standard microfabrication technologies, works in a continuous mode, and can be used as a sample preparation instrument in a micro-total-analysis-system (micro-TAS). In this paper, a miniaturized electrical SPLITT system, which separates particles continuously based on electrophoretic mobility, has been characterized. The advantages of miniaturization have been elucidated. The various aspects of the micro SPLITT system discussed in this paper can be broadly classified into: micro SPLITT system design, fluidics modeling to refine the splitter arrangements, and experimental characterization of the SPLITT system. The design of the micro SPLITT system has been elucidated focusing on the two designs that were implemented. Fluid modeling, used to arrive at a new SPLITT design, was done using a commercially available CFD package to investigate behavior of the fluid in the microchannel with various splitter arrangements. Testing was done with nanoparticles of varying diameter and electrophoretic mobilities to verify the modeling results and demonstrate functionality of the SPLITT system. Particles eluted from both outlets of the SPLITT system were characterized using AFM and SEM to verify the function of the system.     

Effect of flow development region and fringing magnetic force field on annular split-flow thin fractionation

Split-flow thin (SPLITT) fractionation devices have been widely used to separate macromolecules, colloids, cells and particles. Recently, the quadrupole magnetic flow sorter (QMS) has been reported in the literature as another family of SPLITT fractionation device. However, the separation performance observed in the experimental measurements is generally found to deviate from the ideal behaviour. Possible causes such as hydrodynamic lift force, high particle concentration and imperfect geometries have been extensively examined. However, the effects of flow development regions and fringing magnetic force field at the separation channel inlet and outlet, which are ignored by the theory, have not been investigated. The error introduced by ignoring these effects need to be rigorously studied so that the theory can be used to optimise operation flow rates with confidence. Indeed, we find in this paper that these ignored effects are responsible to the discrepancy between the experimental data and the theoretical predictions. A new theory has been proposed for optimisation of device operation.     

Assessment of the distribution of pesticides on soil particle fractions in simulated irrigation run-off using centrifugal SPLITT fractionation and ELISA

This study was designed to measure the distribution of pesticides within the mobile phase of simulated irrigation run-off water, using centrifugal split-flow thin-channel (SPLITT) fractionation, a novel technique providing a gentle separation of natural sediment and suspended particles. Particular attention is paid to the extraction of pesticide residues for enzyme-linked immunosorbent assay (ELISA) analysis; ELISA was used because of the limited sample size.Centrifugal SPLITT fractionation combined laminar flow hydrodynamics and centrifugal sedimentation to obtain a continuous binary separation of suspended particles. The non-destructive technique allowed an accurate separation of particles into fractions with divisions at 0.5, 2 and 10 μm, with those above 25 μm being performed by wet sieving. ELISA was used to analyse the concentration of endosulfan and diuron for each fraction generated by the SPLITT technique.This data can be used to determine the role that particulate fines and colloidal fractions play in the transport of bound organic pollutants within the environment and to examine prospects for remediation on farms.     

SPLITT Cell Analytical Separation of Silica Particles. Non-Specific Crossover Effects: Does the Shear-Induced Diffusion Play a Role?

The gravitational split-flow lateral transport thin fractionation is known to be a fast, simple, theoretically tractable and tunable tool for the binary separation of molecular or particulate samples into different dimensional fractions. This fractionation is performed in a so-called SPLITT cell and is due to the combined effect of the gravitational force field and the flow rates inside the separation channel. It is known that separation performance is strongly dependent on the flow rate conditions and feed flow concentration, however, to date, few studies have been conducted to investigate the effect non-specific crossover has on separation. The aim of this work is to establish whether diffusive processes stemming from hydrodynamic effects contribute in any way to the quality of separation. A silica sample of known granule size distribution was chosen for this study which has environmental applications.     

Magnetic split-flow thin fractionation of magnetically susceptible particles.

We recently built a magnetic separation system to extend the applications of split-flow thin (SPLITT) fractionation to magnetically susceptible particles. Here, we characterize the magnetic SPLITT system using magnetically susceptible particles and ion-labeled particles. The flow axis of separation channel was orientated parallel and perpendicular to gravitational forces to exclude and include, respectively, gravitational effects on separation. Both operating modes were used to test the theory experimentally, with emphasis on the parallel mode. The magnetic susceptibilities of carrier and ion-labeled particles were varied, and various ion-labeled and unlabeled particles were studied experimentally, resulting in successful separation of labeled particles, yeasts, and cells from unlabeled ones. The minimal difference in magnetic susceptibility (delta(chi)) required for complete particle separation was about 1.75 x 10(-5) [cgs], corresponding to about 10(9) labeling ions per particle in this study. The throughput was around 7.2 x 10(8) particles/h using the present setup. Magnetic SPLITT fractionation shows good potential for use in obtaining particles magnetic susceptibilities from a simple theoretical treatment.     

Study of magnetic particles pulse-injected into an annular SPLITT-like channel inside a quadrupole magnetic field

Advantages of the continuous magnetic flow sorting for biomedical applications over current, batch-wise magnetic separations include high throughput and a potential for scale-up operations. A continuous magnetic sorting process has been developed based on the quadrupole magnetic field centered on an annular flow channel. The performance of the sorter has been described using the conceptual framework of split-flow thin (SPLITT) fractionation, a derivative of field-flow fractionation (FFF). To eliminate the variability inherent in working with a heterogenous cell population, we developed a set of monodisperse magnetic microspheres of a characteristic magnetization, and a magnetophoretic mobility, similar to those of the cells labeled with a magnetic colloid. The theory of the magnetic sorting process has been tested by injecting a suspension of the magnetic beads into the carrier fluid flowing through the sorter and by comparing the theoretical and experimental recovery versus total flow-rate profiles. The position of the recovery maxima along the total flow-rate axis was a function of the average bead magnetophoretic mobility and the magnetic field intensity. The theory has correctly predicted the position of the peak maxima on the total flow-rate axis and the dependence on the bead mobility and the field intensity, but has not correctly predicted the peak heights. The differences between the calculated and the measured peak heights were a function of the total flow-rate through the system, indicating a fluid-mechanical origin of the deviations from the theory (such as expected of the lift force effects in the system). The well-controlled elution studies using the monodisperse magnetic beads, and the SPLITT theory, provided us with a firm basis for the future sorter evaluation using cell mixtures.     

Combination of gravitational SPLITT fractionation and field-flow fractionation for size-sorting and characterization of sea sediment

A combination of gravitational split-flow thin (SPLITT) fractionation and sedimentation/steric field-flow fractionation (Sd/StFFF) has been used for continuous size-sorting of a sediment sample and for size analysis of the collected fractions. An IAEA (International Atomic Energy Agency) sediment material was separated into four size fractions (with theoretical size ranges <1.0, 1.0–3.0, 3.0–5.0, and >5.0 m in diameter) by means of a three-step gravitational SPLITT fractionation (GSF) for which the same GSF channel was used throughout. The GSF fractions were collected and examined by optical microscopy (OM) and by Sd/St FFF. The mean diameters of the GSF fractions measured by OM were within the size interval predicted by GSF theory, despite the theory assuming that all particles are spherical, which is not true for the sediment particles. The Sd/St FFF results showed that retention shifted toward shorter elution time (or larger size) than expected, probably because of the shape effect. The results from GSF, OM, and Sd/StFFF are discussed in detail.     

Effect of hydrophilic comonomer and surfactant type on the colloidal stability and size distribution of carboxyl- and amino-functionalized polystyrene particles prepared by miniemulsion polymerization

Carboxyl and amino-functionalized polystyrene latex particles were synthesized by the miniemulsion copolymerization of styrene and acrylic acid or 2-aminoethyl methacrylate hydrochloride (AEMH). The reaction was started by using an oil-soluble initiator, such as 2,2'-azobis(2-methylbutyronitrile) (V-59). The effect of the functional monomer content and type of surfactant (non-ionic versus ionic) on the particle size and particle size distribution was investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). A bimodal particle size distribution was observed for functionalized latex particles prepared in the presence of the non-ionic surfactant (i.e., Lutensol AT-50) when 1 wt % of acrylic acid or 3 wt % of AEMH as a comonomer was employed. The copolymer particle nucleation was studied by using a highly hydrophobic fluorescent dye. From the obtained results, the formation of bimodal particle size distribution may be attributed to a budding-like effect, which takes place during the earlier stage of polymerization and is caused by the additional stabilizing energy originated from the ionic groups of a functional polymer. The reaction mechanism of particle formation in the presence of non-ionic and ionic surfactants has been proposed. The amount of the surface functional groups was determined from polyelectrolyte titration data.     

Dynamics of development of particle size distribution during styrene suspension polymerization

A variation of number particle size distribution during the suspension polymerization of styrene stabilized by poly(vinyl alcohol) has been studied. It has been disclosed that the dispersion of polymer-monomer particles plays a substantial role at the initial stage of the reaction up to a monomer conversion of ～60%. This phenomenon explains the occurrence of three peaks in the current and final distribution curves. This result provides an explanation for the previously observed polymodal particle size distribution. The typical S-shaped variation in the maximum particle diameter with time suggests a nonequilibrium dynamic character of the development of particle size distribution.     

Melting Refining Mechanisms in Supersonic Atmospheric Plasma Spraying

In recent years, Yttria-stabilized zirconia based thermal barrier coatings (TBCs) are deposited by newly-developed high-efficiency supersonic atmospheric plasma spraying (SAPS) technology. The final microstructure of the plasma-sprayed coatings is strongly dependent on the size distribution of spray particles. It has been corroborated through experiments that there is a special phenomenon of particle melting refining in SAPS, as compared with the conventional atmospheric plasma spraying (APS). This phenomenon greatly affects the final particle size and distribution, which has not been explained reasonably up to now. Therefore, it is necessary to investigate the melting refining behavior of in-flight particles to control the particle size and to analyze the coating properties. In this paper, the breakup of particle is presented to characterize the phenomenon of particle melting refining, and the peak of size distribution becomes bigger with increasing the spray distances, which is explained by collision-coalescence. Furthermore, based on the maximum entropy formalism, the particle-size distribution is calculated and the result is in good accordance with the plasma spraying experiment results, which verifies the mechanism analysis presented in this paper. This work could provide more efficient applications of the SAPS technology in high-performance TBCs.     

Preparation of PEGMA-functionalized latex particles. 2. System styrene/<Emphasis Type="Italic">N</Emphasis>-vinylcaprolactam

In a previous paper [Pich A, Lu Y, Adler H-J (2003) Colloid Polym Sci (submitted)], the synthesis of polystyrene-poly(ethylene glycol) methacrylate (PST/PEGMA) particles has been described. In the present paper polymeric particles have been prepared by emulsion co-polymerization of styrene/N-vinylcaprolactam (ST/VCL) or styrene/n-butylacrylate (ST/BA) mixtures in presence of poly(ethylene glycol) methacrylate (PEGMA). The influence of the monomer composition and PEGMA concentration on the particle size and particle size distribution was studied. Increase of VCL content in reaction mixture leads to dramatic increase of the final particle size. Particle size distribution becomes broader at higher VCL contents. Poly(ST/VCL) particles show dramatic change of the size with the temperature.     

Dimensional and elemental characterization of suspended particulate matter in natural waters: quantitative aspects in the integrated ultrafiltration, splitt-flow thin cell and inductively coupled plasma–atomic emission spectrometry approach

The present study investigates the quantitative aspects of an analytical procedure for the trace element characterization of suspended particulate matter (SPM) in natural waters. The procedure consists of the following steps: (1) ultrafiltration (UF) concentration; (2) splitt-flow thin (SPLITT) cell fractionation (SF) into different micronic–submicronic dimensional ranges; and (3) inductively coupled plasma–atomic emission spectrometry (ICP–AES) elemental determination on both the separated fractions and the bulk phase. One specific feature of the UF/SF steps is that they are gentle and thus preserve the complexity of the colloidal features of SPM samples as far as possible. The investigation was performed on a real SPM sample (Po River, Italy). Two SF modes were considered: the so called conventional SPLITT fractionation (CSF) mode and the full feed depletion SPLITT fractionation (FFDSF) mode. These differ in terms of resolution, time (both better in CSF as compared to FFDSF) and operating mode (FFDSF does not require a diluting carrier). Quantitative aspects of the UF step recovery and of the CSF and FFDSF modes were investigated in terms of total mass balance proving that only the FFDSF mode is currently satisfactory for quantitative purposes. Mass balance versus the following elements: Cd, Cr, Cu, Mn, Ni and Pb, was performed using ICP–AES over the 0.2–1.5 and 1.5–20 μm FFDSF SPM fractions, proving that the analytical procedure based on UF/FFDSF/ICP–AES is consistent and useful in the investigation of trace element distribution in different SPM dimensional ranges versus that of the bulk phase. The relevance of aggregation–solubility equilibria concerning colloids of SPM phase is emphasized and further improvement of the procedure is discussed.     

Correction to Microscopically Determined Particle Size According to Diffraction Correction Theory: II. Application to Aqueous Polystyrene Latex Particles of Varying Size

The theory of diffraction correction for transparent (phase) spherical particles under partially coherent illumination has been applied to the optical photomicrographic determination of particle size distribution for four different nearly monodisperse polystyrene latex samples. The thus corrected particle size distribution for each sample has been compared with the corresponding electron microscopic determination.     

Correction to Microscopically Determined Particle Size According to Diffraction Correction Theory

The theory of diffraction correction for transparent (phase) spherical particles under partially coherent illumination has been applied to the optical photomicrographic determination of particle size distribution for four different nearly monodisperse polystyrene latex samples. The thus corrected particle size distribution for each sample has been compared with the corresponding electron microscopic determination. Copyright 1999 Academic Press.