Porous glass electroosmotic pumps: theory

This paper presents an analytical study of electroosmotic (EO) pumps with porous pumping structures. We have developed an analytical model to solve for electroosmotic flow rate, pump current, and thermodynamic efficiency as a function of pump pressure load for porous-structure EO pumps. The model uses a symmetric electrolyte approximation valid for the high-zeta-potential regime and numerically solves the Poisson-Boltzmann equation for charge distribution in the idealized pore geometry. Generalized scaling of pumping performance is discussed in the context of a parameterization that includes porosity, tortuosity, pore size, bulk ionic density, and the nonuniform conductivity distribution over charge layers. The model also incorporates an approximate ionic-strength-dependent zeta potential formulation.     

An integrated micropump and electrospray emitter system based on porous silica monoliths

The work presents the design of an integrated system consisting of a high-pressure electroosmotic (EO) micropump and a microporous monolithic emitter, which together generate a stable and robust electrospray. Both the micropump and electrospray emitter are fabricated using a sol-gel process. Upon application of an electric potential of sufficient amplitude (>2 kV), the pump delivers fluids with an electroosmotically induced high pressure (>1 atm). The same potential is also harnessed to electrostatically generate a stable electrospray at the porous emitter. Electrokinetic coupling between pump and spray produces spray features different from sprays pressurized by independent mechanical pumps. Four typical spray modes, each with different drop sizes and charge-to-mass ratios, are observed and have been characterized. Since the monolith is silica-based, this integrated device can be used for a variety of fluids, especially organic solvents, without the swelling and shrinking problems that are commonly encountered for polymer monoliths. The maximum pressure generated by a 100 microm id monolithic pump is 3 atm at an applied voltage of 5 kV. The flow rate can be adjusted in the range of 100 nL/min to 1 microL/min by changing the voltage. For a given applied voltage across the pump and emitter system, it is seen that there exists one unique flow rate for which flow balance is achieved between the delivery of liquid to the emitter by the pump and the liquid ejection from the emitter. Under such a condition, a stable Taylor cone is obtained. The principles that lead to these results are also discussed.     

Low-voltage electroosmotic pumps fabricated from track-etched polymer membranes

Track-etched polymer membranes are used to realize low-voltage electroosmotic (EO) pumps. The nanopores in polycarbonate (PC) and polyethylene terephthalate (PET) membranes were fabricated by the track-etching technique, the pore diameter was controlled in the range of 100 to 250 nm by adjusting the etching time. The results show that these EO pumps can provide high flow rates at low applied voltages (2-5 V). The maximum normalized flow rate is as high as 0.12 ml min(-1) V(-1) cm(-2), which is comparable to the best values of previously demonstrated EO pumps. We attribute this high performance to the unique properties of the track-etched nanopores in the membranes.     

Application of a high-pressure electro-osmotic pump using nanometer silica in capillary liquid chromatography

A novel designed electro-osmotic pump (EOP) with simple structure was assembled using three 20 cm x 530 microm i.d. fused-silica capillaries packed with 20 +/- 5 nm silica grains for capillary liquid chromatography. It was found that the pump could generate pressures over 20 MPa and several microL/min flow rate for most of the liquids being delivered with the applied voltage less than 10 kV. By increasing the pressure, decreasing the applied voltage and the electrical current, the thermodynamic efficiency was about 1-4%. A practical application of the EOP in a 20cm x 150 microm i.d. 3 microm C18 fused-silica analytical capillary column demonstrated the applicability of the pump.     

A miniature, nongassing electroosmotic pump operating at 0.5 V

Electroosmotic pumps are arguably the simplest of all pumps, consisting merely of two flow-through electrodes separated by a porous membrane. Most use platinum electrodes and operate at high voltages, electrolyzing water. Because evolved gas bubbles adhere and block parts of the electrodes and the membrane, steady pumping rates are difficult to sustain. Here we show that when the platinum electrodes are replaced by consumed Ag/Ag(2)O electrodes, the pumps operate well below 1.23 V, the thermodynamic threshold for electrolysis of water at 25 °C, where neither H(2) nor O(2) is produced. The pumping of water is efficient: 13?000 water molecules are pumped per reacted electron and 4.8 mL of water are pumped per joule at a flow rate of 0.13 mL min(-1) V(-1) cm(-2), and a flow rate per unit of power is 290 mL min(-1) W(-1). The water is driven by protons produced in the anode reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-), traveling through the porous membrane, consumed by hydroxide ions generated in the cathode reaction Ag(2)O(s) + 2 H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). A pump of 2 mm thickness and 0.3 cm(2) cross-sectional area produces flow of 5-30 μL min(-1) when operating at 0.2-0.8 V and 0.04-0.2 mA. Its flow rate can be either voltage or current controlled. The flow rate suffices for the delivery of drugs, such as a meal-associated boli of insulin.     

A high current density DC magnetohydrodynamic (MHD) micropump

This paper describes the working principle of a DC magnetohydrodynamic (MHD) micropump that can be operated at high DC current densities (J) in 75-microm-deep microfluidic channels without introducing gas bubbles into the pumping channel. The main design feature for current generation is a micromachined frit-like structure that connects the pumping channel to side reservoirs, where platinum electrodes are located. Current densities up to 4000 A m(-2) could be obtained without noticeable Joule heating in the system. The pump performance was studied as a function of current density and magnetic field intensity, as well as buffer ionic strength and pH. Bead velocities of up to 1 mm s(-1) (0.5 microL min(-1)) were observed in buffered solutions using a 0.4 T NdFeB permanent magnet, at an applied current density of 4000 A m(-2). This pump is intended for transport of electrolyte solutions having a relatively high ionic strength (0.5-1 M) in a DC magnetic field environment. The application of this pump for the study of biological samples in a miniaturized total analysis system (microTAS) with integrated NMR detection is foreseen. In the 7 T NMR environment, a minimum 16-fold increase in volumetric flow rate for a given applied current density is expected.     

The effect of step height on the performance of three-dimensional ac electro-osmotic microfluidic pumps

Recent numerical and experimental studies have investigated the increase in efficiency of microfluidic ac electro-osmotic pumps by introducing nonplanar geometries with raised steps on the electrodes. In this study, we analyze the effect of the step height on ac electro-osmotic pump performance. AC electro-osmotic pumps with three-dimensional electroplated steps are fabricated on glass substrates and pumping velocities of low ionic strength electrolyte solutions are measured systematically using a custom microfluidic device. Numerical simulations predict an improvement in pump performance with increasing step height, at a given frequency and voltage, up to an optimal step height, which qualitatively matches the trend observed in experiment. For a broad range of step heights near the optimum, the observed flow is much faster than with existing planar pumps (at the same voltage and minimum feature size) and in the theoretically predicted direction of the "fluid conveyor belt" mechanism. For small step heights, the experiments also exhibit significant flow reversal at the optimal frequency, which cannot be explained by the theory, although the simulations predict weak flow reversal at higher frequencies due to incomplete charging. These results provide insight to an important parameter for the design of nonplanar electro-osmotic pumps and clues to improve the fundamental theory of ACEO.     

A photometric flow measurements method for characterisation of HPLC pumps

Summary The measurement of flow constancy and pulsation amplitudes of HPLC pump based on the photoconversion of malachite green leucocyanide is described. The irradiation time and hence the degree of conversion of the leucocyanide is correlated to flow fluctuations of piston driven HPLC pumps. It is possible to measure the amplitude of pulsations and determine the constancy of the flow rate. Most of the pumps show a flow stability better than ±1% measured as relative standard deviation of the flow rate under HPLC conditions (pressure drop 100 bar at 1 ml/min flow rate). The most expensive pump of those tested showed less than ±0.5% flow instability, however, this result was achieved by installation of a large-volume pulsation damper. The method described also allows flow rate measurements under FIA conditions where there is little or no pressure drop at the pump outlet.     

Steady flow generation in microcirculatory systems

In this paper we explore the mechanical generation of steady-non pulsatile-flow in microfluidic systems. The rationale of the paper is inspired in the example of cardiovascular systems where at the microscale (i.e. capillaries) the flow is steady rather than pulsatile to optimize performance. We present a solution to the generation of steady flow in engineered microfluidic systems either in open or closed loop configurations via the use of disc pumps. The disc pump consists of a flat rotating disc and utilizes both viscous drag and centrifugal force to achieve pumping. Experiments using single loop and double loop microfluidic systems are presented to characterize the disc pump. Continuous flow generated by the disc pumps can be used to separate particles based on size using recirculating loops and for extraction of small particles without disturbing the concentration of bigger particles. The potential impact of this technology includes sample separation and extraction techniques into portable microfluidic labs-on-a-chip, and long term culture systems for cells in suspension.     

A novel analytical low-cost flow system based on a 0.6 MPa (84 psi) diaphragm pump applied to on-line trace pre-concentration in flame AAS and ICP-OES

A novel inexpensive 0.6 MPa (84 psi) flow system based on a low-cost diaphragm pump has been developed. The unfavourable strong pulsation of the pump has been overcome by using highly flexible silicone tubing as a pulse suppression coil. This results in a smooth pulse-free continuous flow of 100 mL min(-1) in circulation. This flow rate is much too high for a flow-injection system; however, with a restrictor capillary the flow rate required can be tapped off down to a range of 0.1-50 mL min(-1). By employing diaphragm pumps in an analytical flow system the pressure gap between HPLC pumps (2-40 MPa) and peristaltic pumps (<0.2 MPa), mainly used in FIA systems, can be filled. Due to the higher pressure delivered by diaphragm pumps relative to peristaltic pumps, the new flow system can be applied to on-line sample pre-concentration and matrix separation in flame AAS and ICP-OES by using standard HPLC pre-columns or small ion-exchange columns, respectively. In this way, very low detection limits in flame AAS have been reached (Cd 0.07 micro g L(-1), Cu 0.05 micro g L(-1), Co 0.9 micro g L(-1), Ni 0.8 micro g L(-1), Mn 0.7 micro g L(-1), Pb 0.8 micro g L(-1) and Tl 0.2 micro g L(-1)).     

Low-voltage electroosmosis pump for stand-alone microfluidics devices

Two types of low-voltage electroosmosis pumps were developed using microfabrication technology for usage in handy or stand-alone applications of the micrototal analysis systems (micro-TAS) and the lab-on-a-chip. This was done by making a thin (< 1 microm) region in the flow path and by only applying voltages near this thin region using electrodes inserted into the flow path. The inserted electrodes must be free from bubble formation and be gas-tight in order to avoid pressure leakage. For these electrodes, Ag/AgCl or a gel salt bridge was used. For patterning the gel on the chip, a hydrophilic photopolymerization gel and a photolithographic technique were optimized for producing a gel with higher electric conductivity and higher mechanical strength. For high flow rate application, wide (33.2 mm) and thin (400 nm) pumping channels were compacted into a 1 mm x 6 mm area by folding. This pump achieves an 800 Pa static pressure and a flow of 415 nL/min at 10 V. For high-pressure application, a pump was designed with the thin and thick regions in series and positive and negative electrodes were inserted between them alternatively. This pump could increase the pumping pressure without increasing the supply voltage. A pump with 10-stage connections generated a pressure of 25 kPa at 10 V.     

An AC electroosmotic micropump for circular chromatographic applications

Flow rates of up to 50 microm s(-1) have been successfully achieved in a closed-loop channel using an AC electroosmotic pump. The AC electroosmotic pump is made of an interdigitated array of unequal width electrodes located at the bottom of a channel, with an AC voltage applied between the small and the large electrodes. The flow rate was found to increase linearly with the applied voltage and to decrease linearly with the applied frequency. The pump is expected to be suitable for circular chromatography for the following reasons: the driving forces are distributed over the channel length and the pumping direction is set by the direction of the interdigitated electrodes. Pumping in a closed-loop channel can be achieved by arranging the electrode pattern in a circle. In addition the inherent working principle of AC electroosmotic pumping enables the independent optimisation of the channel height or the flow velocity.     

Long-term stable electroosmotic pump with ion exchange membranes

We present the design, fabrication and test of a novel inline frit-based electroosmotic (EO) pump with ion exchange membranes. The pump is more stable than previous types due to a new flow component that ensures a controlled width of the diffusion layer close to the ion exchange membranes. The pump casing is constructed in polymers while the EO active part, the frit, is made in a nanoporous silica. The pressure capability of the pump is Deltapm/DeltaV = 0.15 bar V(-1). The flow rate to current ratio is Qm/I = 6 microL min(-1) mA(-1). This translates to Deltapm = 4.5 bar and Qm = 6 microL min(-1) at DeltaV = 30 V. The pump has been tested with four different buffer concentrations. In order to investigate day-to-day reproducibility each Q-p pump characteristic has been recorded several times during hour-long operation runs under realistic operating conditions.     

Electrically actuated, pressure-driven microfluidic pumps

In order to make the lab-on-a-chip concept a reality, it is desirable to have an integrated component capable of pumping fluids through microchannels. We have developed novel, electrically actuated micropumps and have integrated them with microfluidic systems. These devices utilize the build-up of electrolysis gases to achieve pressure-driven pumping, only require small voltages (approximately 10 V), and have approximate dimensions of 5 cm x 3 cm x 2 cm. Furthermore, these micropumps are composed of relatively inexpensive materials, and the reversible sealability of their poly(dimethylsiloxane) body to different microfluidic arrays enables repeated uses of the same pump. Under an applied potential of 10 V, three different micropumps had average flow rates of 8-13 microL min(-1) for water being pumped through five different 2 cm-long, 5500 microm(2) cross-sectional-area channels in poly(methyl methacrylate), in approximate agreement with predicted pump rates. We have also evaluated pump operation at the lower applied potential of 8 V and observed an average flow rate of 6.1 microL min(-1) for a pump-channel system. The current micropump design is capable of sustaining pumping pressures in the range of 300 kPa. The various advantages of these micropumps make them well suited for use in lab-on-a-chip analysis techniques.     

Bi-directional flow induced by an AC electroosmotic micropump with DC voltage bias

This paper discusses the principle of biased alternating current electroosmosis (ACEO) and its application to move the bulk fluid in a microchannel, as an alternative to mechanical pumping methods. Previous EO-driven flow research has looked at the effect of electrode asymmetry and transverse traveling wave forms on the performance of electroosmotic pumps. This paper presents an analysis that was conducted to assess the effect of combining an AC signal with a DC (direct current) bias when generating the electric field needed to impart electroosmosis (EO) within a microchannel. The results presented here are numerical and experimental. The numerical results were generated through simulations performed using COMSOL 3.5a. Currently available theoretical models for EO flows were embedded in the software and solved numerically to evaluate the effects of channel geometry, frequency of excitation, electrode array geometry, and AC signal with a DC bias on the flow imparted on an electrically conducting fluid. Simulations of the ACEO flow driven by a constant magnitude of AC voltage over symmetric electrodes did not indicate relevant net flows. However, superimposing a DC signal over the AC signal on the same symmetric electrode array leads to a noticeable net forward flow. Moreover, changing the polarity of electrical signal creates a bi-directional flow on symmetrical electrode array. Experimental flow measurements were performed on several electrode array configurations. The mismatch between the numerical and experimental results revealed the limitations of the currently available models for the biased EO. However, they confirm that using a symmetric electrode array excited by an AC signal with a DC bias leads to a significant improvement in flow rates in comparison to the flow rates obtained in an asymmetric electrode array configuration excited just with an AC signal.     

Optimal performance of a generalized irreversible four-reservoir isothermal chemical potential transformer

A new cyclic model of a four-reservoir isothermal chemical potential transformer with irreversible mass transfer, mass leakage and internal dissipation is put forward in this paper. The optimal relation be-tween the coefficient of performance (COP) and the rate of energy pumping of the generalized irre-versible four-reservoir isothermal chemical potential transformer has been derived by using finite-time thermodynamics or thermodynamic optimization. The maximum COP and the corresponding rate of energy pumping, as well as the maximum rate of energy pumping and the corresponding COP, have been obtained. Moreover, the influences of the irreversibility on the optimal performance of the iso-thermal chemical potential transformer have been revealed. It was found that the mass leakage affects the optimal performance both qualitatively and quantitatively, while the internal dissipation affects the optimal performance quantitatively. The results obtained herein can provide some new theoretical guidelines for the optimal design and development of a class of isothermal chemical potential trans-formers, such as mass exchangers, electrochemical, photochemical and solid state devices, fuel pumps, etc.     

Micro-flow injection analysis system: on-chip sample preconcentration, injection and delivery using coupled monolithic electroosmotic pumps

A micro-fluidic chip, within which two monolithic electroosmotic pumps are utilised for sample preconcentration, injection and delivery is presented. The monolithic pumps were capable of producing stable and bubble free flow rates at applied voltages below 2 kV, with a current <10 microA. Electrokinetic (EK) sample injection, down to low nano-litre volumes, was quantitatively controlled through applied voltage and injection times, whilst the sample pump delivered a carrier solution to indirectly dispense the sample. A nano-flow sensor (NFS) was used to continuously monitor the flow rate stability of each pump, showing response times of <5-10 s for changes in applied voltage. A capacitively coupled contactless conductivity detector (C(4)D), as an off-chip on-capillary detector, was used to complete the micro-flow injection analysis (FIA) system. A monolithic electroosmotic pump (EOP), modified with an anionic surfactant, was used to demonstrate a novel approach to on-chip cation preconcentration and elution.     

Analysis of electrokinetic pumping efficiency in capillary tubes

A mathematical model for predicting the maximum pumping efficiency and pressure difference generation by an electrokinetic-driven fluid pumping system through a capillary tube is presented in this study. Both the maximum pumping efficiency and optimum pressure difference generation are found to depend on a single variable. This single variable is termed as the figure of merit since it determines the performance of electrokinetic pumping. The figure of merit is found to depend on three dimensionless parameters, the normalized Debye length, zeta potential, and Levine number indicating the nominal ratio of convective current to conductive current. All three parameters can be related to the pH value and concentration of aqueous salt solution by the introduction of concentration-dependent electrical conductivity and pH-dependent zeta potential. By presenting the maximum pumping efficiency and optimum pressure difference generation as functions of pH value, salt concentration, and capillary tube radius, it is found that both maximum pumping efficiency and optimum pressure difference generation increase with the decrease in capillary radius and salt concentration. The optimum pH values at which the maximum pumping efficiency and optimum pressure difference generation occur are found to be in the range between 6 and 9. For the salt concentration of 10(-6) M, pH 6.9, and a capillary tube radius value of 0.5 micro m, the predicted maximum pumping efficiency is 5.4% which is close to the experimental measurement reported in the literature.     

Novel devices for solvent delivery and temperature programming designed for capillary liquid chromatography

Analyses in chromatographic systems able to save mobile and stationary phases without reducing efficiency and resolution are of current interest. These advantages regarding savings have challenged us to develop a system dedicated to miniaturized liquid chromatography. This paper reports on the development of a high‐pressure syringe‐type pump, an oven able to perform isothermal and temperature programming and a software program to control these chromatographic devices. The experimental results show that the miniaturized system can generate reproducible and accurate temperature and flow rate. The system was applied to the separation of statins and tetracylines and showed excellent performance.     

New approach to large-volume injection in reversed-phase high performance liquid chromatography: determination of atrazine and hydroxyatrazine in soil samples

A well established method of direct injection of larger than conventional sample volumes ranging from 0.1 mL to 10 mL in HPLC is the injection valve method in which a loop of tubing is totally or partially filled with sample. Recent HPLC pumps have a flow-rate setting accuracy of +/- 1-2% over a flow-rate range from 0.1 mL/min to 10 mL/min and the flow stability is 0.2% or less. Quarternary low pressure gradient pumps are widely available and used, but all their hydraulic lines are seldom utilised. The idea of using one line of a common commercial HPLC quaternary low-pressure pump for direct on-column injection (pumping) of large sample volumes ranging from 1 mL to 100 mL was tested. This approach was evaluated during practical work on the development of an RP-HPLC method of determination of residual atrazine and hydroxyatrazine. In lysimetric environmental experiments hydroxyatrazine was formed in situ in a soil column by hydrolysis of atrazine. The results proved the applicability of this approach not only in experiments with model mixtures of analytes at microg/L levels in solutions. Analysis of 20 mL of soil leachates and extracts of soil samples containing atrazine and hydroxyatrazine at the 10 microg/kg level (in dry soil) revealed that good figures-of-merit were preserved, even in the presence of a large excess of humic substances.