High performance liquid chromatography column packings with deliberately broadened particle size distribution: relation between column performance and packing structure

The effect of the addition of 25%, 50% and 75% (weight percent, wt%) of larger particles (resp. 3 and 5 μm) to a commercial batch of 1.9 μm particles has been investigated as an academic exercise to study the effects of particle size distribution on the kinetic performance of packed bed columns in a magnified way. Comparing the performance of the different mixtures in a kinetic plot, it could be irrefutably shown that the addition of larger particles to a commercial batch of small particles cannot be expected to lead to an improved kinetic performance. Whereas the addition of 25 wt% of larger particles still only has a minor negative effect, a significantly deteriorated performance is obtained when 50 or 75 wt% of larger particles are added. In this case, separation impedance number increases up to 200% were observed. Studying the packing structure through computational packing simulations, together with the experimental determination of the external porosity, helped in understanding the obtained results. This showed that small particles tend to settle in the flow-through pores surrounding the larger particles, leading to very high packing densities (external porosities as low as 32% were observed) and also negatively influencing the column permeability as well as the band broadening (because of the broadened flow-through pore size range).     

Analytical and Numerical Methods for the Design of Maddock Mixers in Single Screw Plasticizing Technology

Summary: In single screw plasticizing technology dispersive mixing elements, i.e., axial and spiral Maddock shear heads, are often used to improve the melt quality. Mathematical models are necessary to efficiently design the mixing section. An analytical model for the design of Maddock mixers is presented in this work. In addition, a CFD-software package is employed to determine the flow and pressure field for different geometries and processing conditions. For the design and process analysis of fluted dispersive mixers the validity and potential of simplified analytical solutions are compared to more versatile and detailed CFD-simulations.     

Passive and Active Mixing in Microfluidic Devices

In microfluidics the Reynolds number is small, preventing turbulence as a tool for mixing, while diffusion is that slow that time does not yield an alternative. Mixing in microfluidics therefore must rely on chaotic advection, as well-known from polymer technology practice where on macroscale the high viscosity makes the Reynolds numbers low and diffusion slow. The mapping method is used to analyze and optimize mixing also in microfluidic devices. We investigate passive mixers like the staggered herringbone micromixer (SHM), the barrier embedded micromixer (BEM) and a three-dimensional serpentine channel (3D-SC). Active mixing is obtained via incorporating particles that introduce a hyperbolic flow in e.g. two dimensional serpentine channels. Magnetic beads chains-up in a flow after switching on a magnetic field. Rotating the field creates a physical rotor moving the flow field. The Mason number represents the ratio of viscous forces to the magnetic field strength and its value determines the fate of the rotor: a single, an alternating single and double, or a multiple part chain-rotor results. The type of rotor determines the mixing quality with best results in the alternating case where crossing streamlines introduce chaotic advection. Finally, an active mixing device is proposed that mimics the cilia in nature. The transverse flow induced by their motion indeed enhances mixing at the microscale.     

Preparation and use of packed capillary columns in chromatographic and related techniques

In this paper general considerations related to the various approaches and parameters influencing the preparation of highly efficient and stable capillary columns for use in liquid chromatography and related techniques are presented and the column production process is discussed in some detail. The different packing methods available for delivering a packing material into a capillary column are discussed from a practical viewpoint. Packing with a gas (dry packing), packing with a liquid solvent or a mixture of solvents (slurry packing), packing with supercritical carbon dioxide, electrokinetic packing, and sol-gel packing technologies are introduced and discussed throughout the paper. Practical recommendations for obtaining highly efficient (high plate numbers) and stable capillary packed columns are also addressed and discussed.     

The effects of engineering design on heterogeneous biocatalysis in microchannels

The results of a numerical study of the fundamental interactions of engineering design and micromixing on conversion in packed microchannels are presented. Previously, channel-based microreactors made of molded silicon plastic were designed, fabricated, and experimentally tested. These reactors have enzymes immobilized on the channel walls by various methods including layer-by-layer nano self-assembly techniques. They also contain molded packing features to add reactive surface area and to redistribute the fluid. An arbitrary but intuitively sensible packing arrangement was initially chosen and used in experimental studies. The current computer simulation study was undertaken to understand how static laminar mixing affects the conversion efficiency. The reactors previously used experimentally have been simulated using CFD-ACE+multiphysics software (ESI CFD Inc., Huntsville, AL). It is found that packing significantly increases conversion when compared with empty channels over the entire flow rate range of the study (0.25相似文献   

Dispersion and Coalescence in Fluid-Gas Jet Apparatus with Elongated Mixing Chamber

The problem of application of fluid-gas jet apparatus with elongated cylindrical mixing chamber as mixers is considered. Results obtained in studying the dispersion and coalescence of bubbles of the gas phase are presented. The obtained experimental data are processed in terms of Kolmogorov's theory of isotropic turbulence.     

Ligand close packing and the geometry of the fluorides of the nonmetals of periods 3, 4, and 5

This paper discusses the geometry of the fluorides of the nonmetals of periods 3, 4, and 5 in terms of the ligand close packing (LCP) model according to which molecular geometry is determined primarily by ligand-ligand repulsions (Pauli closed shell repulsions) rather than by the bonding and lone pair Pauli repulsions of the VSEPR model. The LCP model becomes the dominant factor in determing geometry when the ligands are sufficiently crowded that they may be regarded as essentially incompressible. Ligand close packing is a modification of the VSEPR model in which ligand-ligand repulsion (Pauli closed shell repulsion) is given more emphasis than bonding and nonbonding electron pair Pauli repulsion. The nonmetals of period 3 are large enough to form octahedral six coordinated molecules in which the ligands are close packed. The larger nonmetals of period 4 also have a maximum coordination number of six and an octahedral geometry although the ligands are not close packed. Ligand radii derived from the interligand distances in the molecules of period 3 depend only on the charge of the fluorine ligands and are consistent with the previously derived radii obtained from the fluorides of the close packed tetrahedral molecules of the period 2 elements. Although the ligands in the molecules of the period 4 nonmetals are not close packed, these elements are not large enough to form molecules with a higher coordination number. However, the larger period 5 nonmetals may have coordination numbers of seven and eight. The seven coordinated molecules have a pentagonal bipyramidal geometry in which the equatorial ligands are close packed. The eight coordinated molecules have a square antiprism geometry, which is not a close packed geometry although the fluorine interligand distances are only a little larger than expected for close packing. The difference between the axial and equatorial bond lengths in the trigonal bipyramidal pentafluorides and the pentagonal bipyramidal pentafluorides can be understood on the basis of ligand close packing. Ligand packing prevents the lone pair in AF(6)E molecules from fully entering the valence shell and thereby exerting its full stereochemical effect so that these molecules have a C(3)(v)() distorted octahedral geometry rather than a geometry based on pentagonal bipyramidal seven coordination.     

Quantitative relationship between the retention of peptides on a reversed-phase alumina support and their physicochemical parameters

Pack-in-place column packing methods were developed for Q Sepharose Big Beads at 40 cm I.D. and scaled up to 200 cm I.D. in Chromaflow columns. The efficiency and asymmetry of the packed bed were evaluated as a function of test velocity and sample volume. The performance of the packed beds at both scales approached the theoretical limits of column performance (Hred =2 and Af=1) expected in small analytical columns. The packing strategy was effective for scale up and the stability of the packed beds, the effectiveness of the column design with respect to the mobile phase distribution system and the stability of the media to the pack-in-place technology, are presented.     

Towards Integrated Continuous-Flow Chemical Reactors

 A device for rapid mixing of two solutions is presented. As the main mechanism for mixing is diffusional mass transport, the flow has to be split into several laminae which are narrower than the capillary width. Complete mixing is achieved within a few seconds in a flow-through device with a channel system that is 600 μm wide at its narrowest spot. Received July 14, 1998. Revision November 10, 1998.     

The art and science of forming packed analytical high-performance liquid chromatography columns

Columns of packed particles still are the most popular devices for high-performance liquid chromatography (HPLC) separations because of their great utility, excellent performance and wide variety. However, the forming of packed beds for efficient, stable columns traditionally has been an art where the basics of how to form optimum beds generally was not well understood. The recent development of monolith rods was introduced in part to overcome the difficulty of producing stable beds of packing particles. However, these materials are less versatile than packed particle columns. Technology developments in recent years have produced a better understanding among those skilled in the practice of how to form optimized packed beds, and this has led to widely available, high-quality commercial columns. This presentation discusses the developments that led to the present state of column packing technology. Important steps in the packing of efficient, stable beds are described. The key step of selecting the best solvent for the slurry packing method is emphasized. Factors affecting the mechanical stability of packed columns also are discussed. The early art of packing columns now has evolved into a more scientific approach that allows the packing of good columns with a minimum of effort and time.     

The Use of Contactless Conductivity for the On-Column Characterisation and Visualisation of Packing Homogeneity and Band Broadening in Capillary LC

Capacitively coupled contactless conductivity is presented as a simple non-invasive tool for the visualisation and evaluation of the axial homogeneity of packing density in capillary LC columns. Irregularities in frit structure and gross column voids were readily identified, the latter of which was confirmed with digital photography. Relative homogeneity of packing density was compared for two packed columns by measuring the variation in conductive response per unit length and varied from 1.1 to 4.2%. The on-column scanning methodology was applied to real-time visualisation of in-situ buffering effects arising from a packed poly-iminodiacetic acid bonded resin. Finally, the scanning detection technique was applied to the pre-elution visualisation of on-column band broadening.     

Chaotic micromixers using two-layer crossing channels to exhibit fast mixing at low Reynolds numbers

We report two chaotic micromixers that exhibit fast mixing at low Reynolds numbers in this paper. Passive mixers usually use the channel geometry to stir the fluids, and many previously reported designs rely on inertial effects which are only available at moderate Re. In this paper, we propose two chaotic micromixers using two-layer crossing channels. Both numerical and experimental studies show that the mixers are very efficient for fluid manipulation at low Reynolds numbers, such as stretching and splitting, folding and recombination, through which chaotic advection can be generated and the mixing is significantly promoted. More importantly, the generation of chaotic advection does not rely on the fluid inertial forces, so the mixers work well at very low Re. The mixers are benchmarked against a three-dimensional serpentine mixer. Results show that the latter is inefficient at Re = 0.2, while the new design exhibits rapid mixing at Re = 0.2 and at Re of O(10(-2)). The new mixer design will benefit various microfluidic systems.     

Lab on a chip packing of submicron particles for high performance EOF pumping

The packing of submicrometer sized silica beads inside a microchannel was enabled by a novel method which avoids the complication and limitations of generating a frit using conventional approaches and the restriction of flow using a submicrometer sized weir. A micrometer sized weir and two short columns of 5 μm and 800 nm silica beads packed in succession behind the weir together functioned as a high pressure frit to allow the construction of a primary packed bed of 390 nm silica beads. This packed bed microchannel was tested as an EOF pump, wherein it exhibited superior performance with regards to pressure tolerance, i.e., sustaining good flow rate under extremely high back pressure, and maximal pressure generation. Under a modest applied electric field strength of 150 V/cm, the flow rate against a back pressure of 1200 psi (～8.3 MPa) was 40 nL/min, and the maximal pressure reached 1470 psi (～10 MPa). This work has demonstrated that it is possible to create a high performance packed bed microchannel EOF pump using nanometer sized silica beads, as long as proper care is taken during the packing process to minimize the undesirable mixing of two different sized particles at the boundaries between particle segments and to maximize the packing density throughout the entire packed bed.     

Static micromixers based on large-scale industrial mixer geometry

Mixing liquids at the micro-scale is difficult because the low Reynolds numbers in microchannels and in microreactors prohibit the use of conventional mixing techniques based on mechanical actuators and induce turbulence. Static mixers can be used to solve this mixing problem. This paper presents micromixers with geometries very close to conventional large-scale static mixers used in the chemical and food-processing industry. Two kinds of geometries have been studied. The first type is composed of a series of stationary rigid elements that form intersecting channels to split, rearrange and combine component streams. The second type is composed of a series of short helix elements arranged in pairs, each pair comprised of a right-handed and left-handed element arranged alternately in a pipe. Micromixers of both types have been designed by CAD and manufactured with the integral microstereolithography process, a new microfabrication technique that allows the manufacturing of complex three-dimensional objects in polymers. The realized mixers have been tested experimentally. Numerical simulations of these micromixers using the computational fluid dynamics (CFD) program FLUENT are used to evaluate the mixing efficiency. With a low pressure drop and good mixing efficiency these truly three-dimensional micromixers can be used for mixing of reactants or liquids containing cells in many microTAS applications.     

Evidences of turbulent mixing in multi-pumping flow systems

Multi-pumping flow systems exploit pulsed flows delivered by solenoid pumps. Their improved performance rely on the enhanced radial mass transport inherent to the pulsed flow, which is a consequence of the establishment of vortices thus a tendency towards turbulent mixing.This paper presents several evidences of turbulent mixing in relation to pulsed flows, such as recorded peak shape, establishment of fluidized beds, exploitation of flow reversal, implementation of relatively slow chemical reactions and/or heating of the reaction medium. In addition, Reynolds number associated with the GO period of a pulsed flow is estimated and photographic images of dispersing samples flowing under laminar regime and pulsed flow conditions are presented.     

Inner wall coating of micro-LC columns. Wall effects in LC

An elastic inner wall coating in the fused silica capillaries used for Micro-LC (LC on packed fused silica capillary columns) stabilizes the packed bed and thus increases column efficiency and life expectancy. Probably the particles of packing material are partly forced into the elastic polymer layer which thus holds the packing in position. Bonded polymers of very different chemical polarity can be used with equally good results. Variation of the coating layer thickness shows that there is an optimum value around 0.3 μm. A discussion of various wall effects in LC columns is presented. The i.d. of the columns is a most important parameter in this respect.     

Estimating the maximum coordination number for spheres of different sizes

Eduljee, G.H. and McDermott, C., 1984. Estimating the maximum coordination number for spheres of different sizes. Fluid Phase Equilibria, 18: 103–108.The maximum coordination number is determined from a physical model in which the coordinatng spheres are packed on the surface of the central sphere to form a series of triangles. The efficiency of packing is given by a parameter α, which is 60° for the closest possible packing and greater than 60° for looser packing. The model is applied to computer-simulated coordination number data using the principles of spherical trigonometry to obtain a value of α that provides the best match. The results compare favourably with those of empirical fitting equations.     

T型微混合器混合特性的浓度分布评价法

提出一种微混合器混合性能的评价方法.在样品盒中注入不同浓度罗丹明B溶液并用体视显微镜观察捕获图像,通过Image J软件读取图像灰度值,建立不同深度下溶液的浓度-灰度值函数关系,运用此关系式将T型微混合器3种不同深度(0.1、 0.2和0.4 mm,质量浓度0.05 %的罗丹明B溶液和去离子水作为配对流体)混合实验中捕获的图像中各像素点上的灰度值转换为浓度值,绘制浓度等高线图及浓度频数分布图,分析各自混合情况,最后引入浓度混合指数概念及计算公式,分析3种深度混合器内不同截面上的混合程度.此方法从定性和定量两方面分析了微尺度下混合腔深度对微混合的影响程度,具有一定的应用价值.     

Effect of the Calorific Intensity of Combustion Chamber on Production of Synthesis Gas in Partial Oxidation of Methane–Oxygen Mixtures in the Combustion Mode

Optimal design of a flow-through chemical reactor with increased calorific intensity was experimentally sought for in partial oxidation of natural gas by oxygen at oxidant excess factors in the range 0.27 < α < 0.4. It was shown that this reactor with a chamber for additional turbulent mixing of the starting components, turbulizer, and supercritical pressure difference at the outlet from the combustion chamber can provide a combustion mode close to the process in the plug-flow reactor. The increase in the calorific intensity of the combustion chamber of the reactor as a result of a decrease in its volume leads to full conversion of the starting reagents and to lower carbon-black formation.     

An easily integrative and efficient micromixer and its application to the spectroscopic detection of glucose-catalyst reactions

The focus of this paper is on the fabrication of a PDMS-based passive efficient micromixer to be easily integrated into the other on-chip microfluidic system. The mixing is achieved by "strong stretching and folding," which employs a three-dimensional microchannel structure. By the simultaneously vertical and transversal dispersion of fluids, strong advection is developed. Owing to this powerful mixing performance (more than 70% of the mixing is accomplished within 2.3 mm over a wide range of Reynold number (Re)), the smaller integrative mixer can be realized. The feasibility and the potential usefulness of an integrative micromixer were evaluated by incorporating two mixers into the microchannel for the spectroscopic detection of a glucose-catalyst reaction. The results demonstrate a promising performance for diverse applications in the assay or synthesis of biological or chemical materials.