Toward an Electrolytic Micropump Actuator Design with Controlled Cyclic Bubble Growth and Recombination L. Hsu,a J. Ramunas,b J.

Gonzalez,b J. G. Santiago,b and D. G. Stricklanda Department of Mechanical Engineering, Santa Clara University, Santa Clara, CA 95126, USA b Department of Mechanical Engineering, Stanford University, Stanford, CA 95053, USA
a

We here show preliminary work developing a new micropump actuator design with controlled and cyclic electrolytic bubble growth and catalyst-driven recombination. We first present brief experimental data showing design feasibility. We then present an engineering model which predicts pump performance under two regimes: (1) fast bubble recombination, where pump performance is dominated by bubble generation rate and (2) finite bubble recombination, where bubble recombination time is significant. We identify a non-dimensional design parameter related to pump geometry and material-properties as critical to pump performance. In addition, we identify catalyst recombination rate as a key parameter which limits flow rate.

Introduction Micropump applications are numerous and include implantable drug delivery (1,2), micro total analysis systems (3), reagent delivery in fuel cells (4), microelectronics cooling (5), micro power systems (6), and fuel injection in internal combustion engines (7). Of these, in-vivo drug delivery may have the most stringent constraints, requiring precise drug dosing, low power consumption, operation against moderate back pressures, high reliability, and minimal control complexity. Laser and Santiago (8) classified micropumps into two categories: dynamic and displacement pumps. Dynamic pumps add energy to the working fluid in order to produce continuous fluid movement. Here, we focus on displacement pumps which employ actuators that leverage pressure and volume expansion to drive fluid flow. Actuator types include piezo-electric (9), phase change (10), bubble actuated, and electrostatic (11). Electrolysis-driven bubble actuation has several advantages to alternative actuators, including simple operation and few (if any) moving parts. Several groups have developed electrolytic bubble actuated pump designs. For example, Ateya et al. developed a pump design which sequentially generated multiple bubbles in order to drive fluid flow (12). This design achieved an optimized pump rate of 24 nl min-1. Cheng et al.s design leveraged a hydrophobic microchannel with a roughness gradient (13). By generating the bubble in a channel with varying roughness, the apparent contact angle on the leading meniscus is larger than that of the trailing meniscus. This results in a force imbalance which drives fluid flow. While electrolytic micropump designs show promise

for many applications, significant challenges remain regarding operation against moderate back pressures, complex flow rate control schemes, performance reproducibility, and closed-system operation. We here present preliminary work on a new micropump actuator design which uses electrolytic bubble growth and catalystdriven recombination of electrolysis gases to cyclically displace a membrane. We first detail pump design and present brief experimental data showing design feasibility. We then present an engineering model to predict pump performance under two operating regimes: (1) rapid bubble recombination and (2) finite bubble recombination times. Pump Actuator Design Figure 1 details pump design. In our design, we employ a bubble expansion channel to meter bubble growth. On one end, two platinum (Pt) electrodes embedded in a hydrophilic porous polymer generate electrolysis bubbles. On the far end, we introduce a catalyst to recombine electrolysis bubbles. During the expansion stroke, bubbles are generated and coalesce into a single bubble which expands in the channel toward the catalyst. The expansion stroke continues until the bubble comes in contact with the recombination catalyst. The catalyst initiates the retraction stroke via rapid recombination of the electrolysis gases into liquid water. Preliminary experiments have shown that a diverging channel geometry can be used to affect a capillary pressure gradient which insures most of the bubble is transferred to the catalyst region. Catalytic action reduces bubble touching catalyst, while a new bubble is formed and grows. These actions cause periodic increase and decrease of total bubble volume in the chamber, which can then be employed to actuate fluid flow via a membrane and flow rectification valves. We note that this design can be entirely closed, which is essential for some applications.

Figure 1. Overview of proposed bubble actuator design. The pump comprises four layers: a pump layer (magnified in center inset), a membrane layer, and two support layers on the top and bottom. We here focus on the pump layer. On one end of the bubble expansion channel, two platinum electrodes are embedded in a porous polymer. When a potential is applied, electrolysis reactions split water into hydrogen and oxygen gas. The electrolysis bubble expands into the bubble expansion chamber. This creates a high pressure in the bubble chamber, which pushes displaced fluid downstream through a hole connected to the backside of the membrane. The resulting membrane deformation is

used to drive liquid flow. We introduce a recombination catalyst at the far end of the expansion channel. At the end of the expansion stroke, the bubble comes into contact with the catalyst, which initiates electrolysis gas recombination and the pump retraction stroke. Right inset: Images from a preliminary experiment showing design feasibility. Pt electrodes are on left (upstream) and a gas diffusion electrode material (fuelcellstore.com) is used on right (downstream) for recombination catalyst. These preliminary experiments suggest that diverging channel geometry and interfacial forces can result in cyclic operation with (a,b) bubble growth from electrode to catalyst, (c) bubble detachment from electrode end and collapse toward recombination catalyst, and formation of a new electrolysis bubble on upstream end. As discussed below, catalyst recombination rate strongly affects pump performance. For finite bubble recombination times, continued electrolysis will initiate the formation of a new bubble upstream during the recombination step (shown in Figure 1c). This upstream bubble volume represents a reduction in the effective stroke volume. In the following sections, we therefore consider two pump operation regimes. In the first, we consider an ideal case where recombination is fast and upstream bubble formation is negligible. In this case, pump performance is governed by expansion channel size and bubble expansion time. In the second, we consider finite recombination times and analyze catalyst performance impact on overall pump performance. Pump performance for fast bubble recombination times We now develop a simplified model to predict ideal pump performance. In this initial development, we assume ideal flow rectification valves, ideal gas behavior, and fast recombination kinetics.

Figure 2. Schematic of pump design, highlighting important geometries. Membrane radius is r, membrane thickness is b, and bubble expansion channel volume is Vch. During operation, an electrolysis bubble is generated at the electrodes and expands downstream. Expansion stroke continues until bubble volume reaches Vch. Bubble recombination initiates retraction stroke as bubble boundary enters the catalyst structure. In this pump design, Vch sets displacement volume per cycle. During water electrolysis, molar generation rates of hydrogen and oxygen are described by Faradays law and are and , respectively. Here, F is Faradays constant and I is current. The total molar gas generation rate is the sum: . Assuming ideal gas, we determine bubble volume, Vb, as a function of time of electrolysis, t, as: [1]

where R is the universal gas constant, T is gas temperature, and Pwf is the working fluid pressure. In our pump design, bubble growth displaces fluid and deforms a membrane. This deformation exerts a force on the fluid and increases system pressure. For small displacements, membrane centerline displacement (y) is related to pressure as (14): ( ) [2]

where P is the pressure difference across the membrane, r is membrane radius, is Poissons ratio, E is Youngs modulus, and b is the membrane thickness. The membrane is assumed to behave as a fixed-edge circular diaphragm. Membrane deflection is integrated across area to relate P to total displaced volume: [3]

Here, P is the difference between the working fluid and pump operating backpressure (Pwf and Pb, respectively), and displaced volume is equal to Vb. Solving for working fluid pressure and substituting into equation [1] gives:

[4] ( )

Solving equation [4] for time and setting Vb = Vch, we obtain an expression for expansion stroke time: ( ) [5]

Here, exp represents the time for an electrolysis bubble to grow to fill the expansion channel. Average volumetric flow rate is the displaced volume per stroke, Vdisp, divided by pump period, p. For the simplified case of fast recombination times, Vdisp = Vch, and p = exp. Substituting and solving for flow rate per current:

)(

[6]

We note that the denominator of the last term on the right hand side is equal to the working fluid pressure at full membrane displacement. As such, elevated back pressure and large cross-membrane pressure differential both negatively impact overall pump

performance. Figure 3 plots flow rate per current as a function of the geometric parameter, r6/Vchb3, for various back pressures.

8 7
Qav/I [ L / min*mA ]

P b = 0 psi P b = 2 psi P b = 4 psi P b = 6 psi P b = 8 psi P b = 10 psi

6 5 4 3 2 1 0 2 10

10

10 6 r /Vchb3

10

10

10

Figure 3. Average flow rate per current, Qav/I, as a function of the geometric parameter r6/Vchb3. This parameter is key to pump design and is comprised of the bubble expansion chamber volume (Vch), membrane thickness (b), and membrane radius (r). Curves are plotted for a polyethylene terephthalate (Mylar) membrane (E = 4 GPa and = .44), for various backpressures. At low values of r6/Vchb3, net fluid displacement approaches zero. This is attributed to high pressures required for membrane displacement. For high r6/Vchb3, membrane pressure contribution become negligible and flow rate per current approaches a maximum value set by backpressure. Increased Pb results in decreased flow rate. As seen in Figure 3, pump performance varies significantly for r6/Vchb3 < ~107. For these lower values, the membrane is stiff and significantly increases the pressure of the working fluid during displacement. A single pump cycle therefore requires substantially greater molar production of electrolysis gases. Higher values of r6/Vchb3 correspond to a flexible membrane with minimal contribution toward working fluid pressure. As such, moles of gas generated per cycle reach a minimum value set only by operating backpressure. We therefore identify ideal pump performance as when the pressure contribution of the membrane is small compared to back pressure: ( )( ) [7]

Dividing through by backpressure, we define a non-dimensional parameter :

)(

[8]

When designing an electrolysis pump, geometric parameters and materials should therefore be chosen such that << 1. Figure 4a plots flow rate per current as a function of when operating at atmospheric pressure. As shown, small leads to a maximum flow rate per current of ~8 L/min mA. Figure 4b plots flow rate per current as a function of backpressure, for various . As expected, both increased and Pb result in increased working fluid pressure and decreased pump performance. We note that for low , pump performance is highly sensitive to backpressure. As such, increased may be advantageous for specialized applications requiring low backpressure sensitivity.

Qav/I [ L / min*mA ]

Qav/I [ L / min*mA ]

8 6 4 2 0 0 2 4 6 8 10

8 6 4 2 0 0 20 40 60 P b [psi]
(b)

= 0.0 = 0.1 = 1.0 = 10.0

80

100

(a)

Figure 4. (a) Calculated maximum flow rate as a function of , for atmospheric backpressure operation. As increases, increased membrane stiffness results in increased working fluid pressure and a corresponding reduction in pump performance. (b) Calculated maximum flow rate plotted as a function of backpressure, for = 0.0, 0.1, 1.0, and 10.0. Both increased and Pb result in increased working fluid pressure and decreased pump performance. Ideal pump performance for finite bubble recombination times Until now, we have assumed negligible bubble recombination time (rec 0). For finite bubble recombination times, continued electrolysis during the recombination stroke will initiate the formation of a new bubble upstream and negatively affect overall pump performance. This is illustrated in Figure 5, which shows pump operation at four time steps through one full pump cycle. At t = 0 (a), Vb = Vch and the electrolysis bubble has just reached the recombination catalyst. Catalyst initiates bubble collapse (for 0 < t < rec) (b). During recombination, continued electrolysis initiates a new bubble upstream. The retraction stroke ends upon complete recombination of the downstream bubble at t = rec (c). Subsequently, the expansion stroke begins with bubble growth from the bubble volume at the end of the retraction stroke, Vrec, to Vch at t = exp (d). The bubble volume at the end of recombination therefore represents a reduction in the pump displacement volume.

Figure 5. Expansion channel at various stages from t = 0 to t = rec. (a) At t = 0, an electrolysis bubble fills the expansion chamber and is in contact with the recombination catalyst. (b) Recombination begins and, simultaneously, a new electrolysis bubble is generated on the electrode end. (c) At t = rec, the original electrolysis bubble is fully recombined and the volume of the new upstream electrolysis bubble is Vrec. (d) Cycle is completed upon new bubble growth from Vrec to Vch at t = exp . For finite recombination times, the displacement volume is Vdisp = Vch Vrec. We therefore define the average volumetric flow rate for finite recombination as: [9] We now consider the effect of rec on otherwise ideal pump performance ( << 1). For small , Pwf = Pb and bubble volume is determined from the ideal gas law as: [10] Evaluating equation [10] for Vb = Vrec at t = rec , and Vb = Vch at t = exp, and substituting these volumes into equation [9] gives average flow rate per current as: [11] where N is: [12]

and is the molar recombination rate of the catalyst. We note that for short recombination times, N0 and we recover equation [6] for small . As N1 (rec = exp), there is no net displacement of fluid. This condition corresponds to an electrolysis bubble that is simultaneously generated upstream and recombined downstream at equivalent rates, resulting in a static bubble volume of Vch. For finite recombination time, an ideal current for maximum flow rate can be established. Physically, this is due to an inverse relationship between displacement

frequency and stroke volume. With increasing current, cycle period decreases. At the same time, because recombination time is fixed by catalyst performance, generated bubble volume during the recombination stroke increases, thus reducing effective stroke volume. Optimum pump performance is established by substituting equation [12] into [11] and solving for flow rate: ( ) [13]

We find the current which corresponds to maximum flow rate by taking the derivative of Qav with respect to I, and setting it equal to zero: Substituting back into equation [13], we find maximum pump flow rate as: ( ) [15] [14]

Equation [15] shows maximum flow rate is a linear function of molar catalyst recombination rate and equal to one fourth the volumetric recombination rate. As such, catalysts that minimize recombination time are critical to high flow rate performance. Summary and Future Work We presented an electrolytic micropump actuator design with bubble growth and catalyst-driven recombination, for cyclic displacement of a membrane. Our design leverages a bubble expansion channel for controlled bubble growth. This proposed actuator can be simply operated (by providing a constant current or voltage), is completely closed, and can operate over a wide range of pressures, making it well suited for in-vivo applications. We developed an engineering model to predict pump performance under two operating regimes: (1) fast bubble recombination time (ideal performance) and (2) finite recombination time. In the first regime, we derived a non-dimensional parameter, , which represents the pressure contribution of the membrane relative to backpressure, at full membrane displacement. We showed that for ideal performance, expansion channel geometry and diaphragm material should be chosen such that << 1. In the second regime, we showed that finite recombination times lead to reduced displacement volume per cycle. We identified the bubble recombination to generation time ratio as a parameter which should be minimized in order to maximize flow rate per current. In addition, we showed that maximum pump flow rate is proportional to bubble recombination rate. As such, high performance recombination catalyst structures are required for increased pump flow rates. Ongoing work includes pump fabrication and characterization. We are currently exploring contact liquid photopolymerization (15) for lithographic fabrication. This

technique shows potential for integration of both solid and porous (16) polymeric structures. In addition, we are exploring high performance recombination catalysts by employing high active surface area catalysts to enhance recombination rate. Active area is strongly affected by multiphase phenomena, as produced liquid water must be removed to allow transport of oxygen and hydrogen to catalyst sites. We seek to address this issue by embedding catalyst particles in a porous polymer matrix with mixed wettability. As such, hydrophilic pores allow liquid water transport paths, while hydrophobic pores remain open for electrolytic gas transport to recombination sites. Preliminary results have shown molar recombination rates of 6.0 M/min per L catalyst structure, corresponding to a maximum pump flow rate of 2.2 L/min (per L catalyst).

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