The advantages of representing experimental plate height data as a plot of Kv/u0(2) or H2/Kv versus Kv/(Hu0) instead of as H versus u0 are discussed (Kv=column permeability). Multiplying the values on both axes by the ratio of a reference pressure drop and mobile-phase viscosity, the obtained plots directly yield the kinetic performance limits of the tested support structure, without any need for further numerical optimization. Directly showing the range of plate numbers or analysis times wherein the tested support geometry can yield faster separations or produce more plates than another support type, such kinetic plots are ideally suited to compare the performance of differently shaped or sized LC supports. The approach hence obviates the need for a common reference length, which is a clear problem if it is attempted to compare differently shaped supports on the basis of their flow resistance phi and reduced plate height h. It is also shown how an MS Excel template file, only requiring the user to paste the column permeability Kv and a series of experimental (u0, H) data, can be used to automatically establish a series of so-called kinetic performance (KP) numbers, which can be used to completely describe the performance characteristics of the considered support. The advantages of the proposed data representation methods are demonstrated by applying them to several recent literature plate height data sets, showing that the obtained kinetic plots directly visualize the range of plate numbers where new approaches such as ultra-high-pressure HPLC or the use of open-porous silica monoliths can be expected to provide a substantial gain and where not. The data analysis also showed that the most generally relevant KP numbers are N(opt) (the plate number for which the support achieves its best analysis time/pressure cost ratio), t(opt) (the time needed to obtain N(opt) plates), and t(1K) (the time needed to generate 1000 or 1 kilo of theoretical plates). These KP numbers are much more informative than the H(min), u(0,opt), and Kv data traditionally employed to quantify the performance of LC supports.

A series of theoretical calculations is presented to quantify the gain in LC separation efficiency that can be expected if the traditionally used packed bed columns were replaced by columns with a perfectly ordered flow-through pore network. It is shown that a perfectly ordered 2-D array of porous cylindrical pillars could yield reduced plate heights as small as h = 0.65 (for k' ' = 0.75) to h = 0.85 (for k' ' = 2) and separation impedances as small as E = 200 (for k' ' = 0.75) to E = 300 (for k' ' = 2) without having to compromise on the porosity (epsilon = 0.4) and the retention capacity of the packed bed of spheres. Fitting the calculated van Deemter plots with Knox's equation especially shows a strong decrease of the A-term contribution, hence confirming that the improved column performance indeed stems from the increased homogeneity of the packing. The presented results, hence, provide a clear quantitative support for Knox's recent argumentation that the use of more uniform beds could greatly enhance the efficiency of pressure-driven LC.

The present paper describes a method for the production of partly porous micro-pillars in columns suitable for use in liquid chromatography. These layers increase the available surface at least two orders of magnitude without destroying the huge benefits of the ordered nature of the system. A process flow was developed that enabled us to create a 550 nm thick porous layer on the pillar array in a sealed channel configuration, withstanding pressures up to at least 70 bar. Measuring band broadening under non-retained conditions, only a modest increase in plate height was observed in the porous pillar array as compared to that in a non-porous pillar array. The homogeneity of the layers was demonstrated using an optical microscope and SEM pictures and by monitoring peak velocities at constant pressures. The internal porosity was determined using particles with a diameter larger than the mesopores in combination with a dye that could penetrate into the pores.

We report on a computational study assessing the effect of the pillar shape in perfectly ordered porous chromatographic media. Using computational fluid dynamics to compare the band broadening and flow resistance characteristics of a large number of different pillar shapes, it is found that the most axially elongated shapes yield the best chromatographic performance and that diamonds are to be preferred over ellipsoids. The former pack into a more uniform pore space and display a smaller C(s) value, whereas the latter pack into a locally constricted pore space and therefore generate a considerably larger flow resistance. For the presently considered case of a densely packed array (epsilon = 0.4), changing the pillar shape from a cylinder to a more elongated diamond, for example, reduces the minimal plate heights from h(min) = 0.84 to h(min) = 0.72, the C factor from C = 0.062 to C = 0.050, and the separation impedance from E(min) = 330 to E(min) = 220, without affecting the number of interchannel coupling points.

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