The authors acknowledge support from Samsung, the NC State Chancellors Innovation Funds, NSF (CAREER CMMI-0954321 and Triangle MRSEC DMR-1121107), and Air Force Research Labs.

1. Manipulation of the Interfacial Tension of Liquid Metal in Electrolyte
<ol>
	<li>Oxidation
	<ol>
		<li>Pour an aqueous electrolyte (acidic or basic) into a Petri dish. To ensure that the oxide is completely removed, use an acid or base with a concentration greater than 0.1 M24 (e.g. 1 M NaOH or 1 M HCl). Use a volume that will fill the dish to a depth of approximately 1-3 mm. Avoid contacting the skin with these solutions.</li>
		<li>Use a syringe to place a drop (optimally between 10-500 &#181;l...

<ol>
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The authors have nothing to disclose.

This method controls the surface tension of gallium-based liquid metals using small voltages to drive the deposition and removal of a surface oxide. Although the method only works in electrolyte solutions, it is simple, and works in a wide variety of different conditions, but there are subtleties worth noting. In the absence of electrical potential, both acidic and basic solutions etch away the oxide27. The application of an oxidative potential drives the formation of surface oxide in all aqueous electrolytes,...

This method provides a simple way to control the surface tension of liquid metals containing gallium. The method uses modest voltages (~1 V) applied directly to the liquid metal (relative to a counter electrode in the presence of electrolyte) to achieve enormous and reversible changes to the surface tension of the metal1. 
Surface tension is a dominant force for liquids at small length scales and is important for a number of capillary phenomena including wetting, spreading, and surface-tension driven flow. Consequently, the ability to control surface tension is a sensible way to manipulate the shape, position, and flow of liquids at sub-mm length scales. The most common way to alter surface tension between two fluids is to use a surfactant, which is a molecule that spans the interface between the fluids. Surfactants lower surface tension, but in a way that is not easy to reverse since it is difficult to remove surfactants from the interface. Surface tension can also be altered using a variety of techniques, including temperature gradients2,3, light4, surface chemistry5-7,and voltage8. But most of these methods result in modest changes to surface tension, particularly for liquid metals, which have notably large surface tensions.
The ability to control the surface tension of liquid metal could enable new opportunities for creating shape reconfigurable structures with metallic properties for electronic, thermal, and optical applications9-14. The most common liquid metal is Hg, which is noted for its toxicity. The methods described here are relevant for liquid metals based on gallium. These metals have low viscosity, large surface tension, low volatility (low vapor pressure), and low toxicity15. Importantly, these metals form surface oxides composed of gallium oxide that are a few nm thick in air16. This oxide layer creates a physical skin that historically has been a nuisance for electrochemical and fluid dynamic applications17. The method here utilizes the oxide in new ways to control surface tension.
The most common way to manipulate liquid metals in electrolyte is to apply a potential to the metal relative to a counter electrode18. Oppositely charged ions from the electrolyte match the charges on the metal, causing the interfacial tension to drop. This phenomenon-termed electrocapillarity-has been known since the 1870s as described by Lippman19and has been utilized for alloys of gallium20. Typically, electrocapillarity achieves modest changes to surface tension, since undesirable electrochemical reactions limit the range of voltages applied to the metal. In contrast, the method described here utilizes the surface oxidation of the metal (or conversely, the reduction of the surface oxide) as a way to achieve enormous changes in surface tension above and beyond changes resulting from electrocapillarity. The leading explanation for this phenomenon is that the oxide is asymmetric; that is, the outer surface of the oxide terminates with hydroxyl groups (making a low interfacial tension interface with the aqueous electrolyte), and the interior surface of the oxide terminates with gallium atoms (making a low interfacial tension interface with the metal). In contrast, the removal of the oxide via electrochemical reduction results in a bare metal-electrolyte interface, which returns the metal back to a state of high surface tension. We characterize the interfacial tension of the metal by analyzing the shape of sessile droplets as a function of voltage while assuming that gravity and surface tension are the dominant forces that define the curvature of its surface. 
The advantage of this technique relative to classic electrocapillarity is that it can reversibly tune the tension of low toxicity liquid metals over enormous ranges (from ~500 mN/m to near zero). This delta change in surface tension may be the largest ever reported in literature for any fluid and it can be accomplished in a tunable and reversible manner. These large changes in surface tension are useful for manipulating the capillary behavior of metals; for example, it can induce the metal to spread on a surface, withdraw the metal from microchannels, fill microchannels with metal, and overcome the Rayleigh instabilities to form liquid metal fibers1,21. 
A drawback of this technique is that it requires electrolyte. It works best in acidic or basic conditions, because these electrolytes remove excess surface oxide that would otherwise contaminate the surface of the metal and mechanically restrict the movement of the metal. The simultaneous removal and deposition of the oxide layer complicates the analysis of the interfacial phenomena and it is our hope the methods described in this paper empowers additional analysis. Another disadvantage is that the electrochemical reactions at the surface of the metal must be matched by complimentary half-reactions at the counter electrode22,23. This can lead to hydrogen bubbles forming at the counter electrode.

<table>
	<tbody>
		<tr>
			<td>Eutectic Gallium Indium</td>
			<td>Indium Corporation</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium Hydroxide</td>
			<td>Fisher Scientific</td>
			<td>2318-3</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrochloric Acid</td>
			<td>Fisher Scientific</td>
			<td>A481-212</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium Fluoride</td>
			<td>Sigma-Aldrich</td>
			<td>201154</td>
			<td></td>
		</tr>
		<tr>
			<td>Optical Adhesive</td>
			<td>Norland</td>
			<td>NOA81</td>
			<td></td>
		</tr>
		<tr>
			<td>Polydimethylsiloxane (Sylgard-184)</td>
			<td>Dow Corning</td>
			<td></td>
			<td>Silicone Elastomer Kit</td>
		</tr>
		<tr>
			<td>Borosilicate Glass Capillaries</td>
			<td>Friedrich and Dimmoch</td>
			<td>B41972</td>
			<td></td>
		</tr>
		<tr>
			<td>Ag/AgCl Reference Electrode</td>
			<td>Microelectrodes Inc.</td>
			<td>MI-401F</td>
			<td></td>
		</tr>
		<tr>
			<td>Voltage Source</td>
			<td>Keithley</td>
			<td>3390</td>
			<td></td>
		</tr>
		<tr>
			<td>Potentiostat</td>
			<td>Gamry</td>
			<td>Ref 600</td>
			<td></td>
		</tr>
		<tr>
			<td>Laser Cutter</td>
			<td>Universal Laser Systems</td>
			<td>VLS 3.50</td>
			<td></td>
		</tr>
	</tbody>
</table>

a method to manipulate surface tension of a liquid metal via surface oxidation and reduction

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension.
Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries.
Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude ( &#820;500 mN/m to near zero). Furthermore, this method requires only a very modest potential (&#60; 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests.

Figure 1A shows an example of the simple two-electrode technique for oxidation and reduction. In this instance, a 70 &#181;l drop of the liquid metal placed in a 1 M NaOH solution contacts a copper wire to establish an electrical connection. The 1 M NaOH removes the surface oxide from the metal and allows the metal to bead up due to its interfacial tension. Applying a 2.5 V potential between the drop and a platinum mesh counter-elect...

Watch this Scientific Journal Video about A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction at JoVE.com

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

We present a method to control the interfacial energy of a liquid metal in an electrolyte via electrochemical deposition (or removal) of a surface oxide layer. This simple method can control the capillary behavior of gallium-based liquid metals by tuning the interfacial energy rapidly, significantly, and reversibly using modest voltages.

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where ...

The overall goal of this procedure is to demonstrate the manipulation of liquid metal under the influence of electrochemical potentials. This method tunes the interfacial tension of liquid metal over an enormous range while elucidating the role of oxides on interfacial tension. The main appeal of this technique is that it's simple, it's reversible, and it only requires very modest potentials.This thing has been utilized to make electronic devices that are reconfigurable and composed almost entirely of To perform oxidation, pour an aqueous electrolyte into a petri dish. Use a volume that will fill the dish to a depth of approximately one to three millimeters. Use a syringe to place a drop of a gallium based alloy in the electrolyte.Here, eutectic gallium indium is used. Place a copper wire with a diameter less than that of the drop into the liquid metal to establish the working electrode. In acid or base, the liquid metal will wet the copper and thereby form an excellent electrical contact.Place a conducting counter electrode in the solution, but not in contact with the liquid metal. If the counter electrode has a resistance of less than one ohm, its dimensions are irrelevant. Next, connect the wires to a voltage source and apply a positive potential to the liquid metal.For small shape deformation, apply positive voltages less than one volt. For larger shape deformation, apply greater than one volt. To perform reduction, dispense a drop of the liquid metal from a syringe into an empty petri dish.Then, poor a neutral aqueous electrolyte into the petri dish to a level that submerges the metal. Place a copper wire into the liquid metal to act as a working electrode, and place a conducting wire into the electrolyte to act as the counter electrode. Connect the wires to a voltage source and apply a negative potential to the liquid metal.Apply approximately minus one volt to remove the surface oxide and cause the metal to de-wet from the substrate. The metal should de-wet first on the side closest to the counter electrode. Apply more negative potentials to remove the oxide layer completely.Avoid applying excessively large negative voltages to prevent hydrogen bubbles from appearing on the liquid metal due to reduction of the electrolyte. Using a laser cutter, or milling tool, cut a direct path from the center to the edge of a piece of polymethylmethacrylate, or PMMA. Do not cut the path all the way through the thickness of the PMMA.This piece will serve as a substrate for the liquid metal. With the same tool, cut a one square millimeter hole through the center of the PMMA. Using the path as a guide, run an insulated copper wire with only the tip exposed, to the center of the PMMA.Position the wire so that it is protruding over the PMMA surface. Seal the wire in place with a leak proof adhesive. Cut the wire just above the surface of the PMMA, but do not let it extend too far or it will disturb the shape of the drop.Tape the PMMA piece down into a transparent container through which a clear image can be obtained. Place the container in a contact angle goniometer so that the surface profile of the drop is clearly visible. Fill the container with one molar sodium hydroxide.Then, place a 25 to 50 microliter drop of liquid metal on the protruding copper wire. This wire will serve as the working electrode and will wet the droplet. Connect all of the electrodes to a potentiostat.Next, place a platinum mesh counter electrode, and a saturated silver silver chloride reference electrode in the solution. Use the potentiostat to control the voltage with respect to the reference electrode, and use the goniometer to measure the shape and thereby the interfacial tension of the drop. Ensure that the goniometer is capable of measuring sessile drop interfacial tension.Fill a glass capillary with a solution of one molar sodium hydroxide. The capillary diameter should be approximately one millimeter. Place one end of the capillary flush against a drop of liquid metal.Align the capillary so that it is parallel with the surface of the table. Avoid air gaps between the liquid metal drop and the electrolyte filled capillary. Using a wipe, dab off any excess electrolyte that may have leaked during assembly.Place a copper wire in the liquid metal and a conductive counter electrode in the open end of the capillary so that it contacts the solution. Connect the wires to a voltage source and apply a positive potential to the liquid metal. The liquid metal should begin filling the capillary.Utilize soft lithographic and replica molding techniques to fabricate microfluidic channels composed of polydimethylsiloxane, or PDMS. Fabricate channels that are approximately 100 to 1, 000 microns wide, 100 microns tall, and 25 to 65 millimeters long. Inject liquid metal either manually, or using a syringe pump, to fill the channel completely.Using a cotton swab that has been dipped in one molar sodium hydroxide or one molar hydrogen chloride, remove excess amounts of liquid metal from the inlet of the channel so that the metal remains flush with the top surface of the PDMS. Submerge one end of the channel in electrolyte, and place the anode such that it touches the electrolyte but not the metal. At the other end of the channel, contact a separate electrode to the metal surface so that liquid metal itself acts as a cathode.Connect these wires to a voltage source, and complete the electric circuit. For a three-electrode system, place the reference electrode such that it barely submerges into the drop of electrolyte. Before applying a reducing voltage, mount a video camera on a tripod or in a microscope to record the experiments.Use the auto focus mode to get everything in focus. Utilize the manual focus to have better control over depth of field, white balance, and ISO. As necessary, use a higher f stop, a shutter speed of one one hundredth of a second, auto white balance, and auto ISO.Start recording the experiment. Apply approximately minus one volt to withdraw the liquid metal from the micro channels. Turn the voltage off to cause the metal to stop moving in neutral electrolyte.Shown here is a goniometer video of the liquid metal spreading under the influence of the electrochemical potential. A decrease in height signifies a more oxidative potential. The interfacial tension can be determined from the curvature of the droplet.The region to the left of the dotted line where the oxide layer is absent shows typical electro-capillary behavior. However, when the oxide layer is present, the interfacial tension shows a precipitous decline, further decreasing as larger voltages are applied. Applying a reducing potential to the metal removes the oxide and causes it to withdraw from microchannels.This graph shows the velocity profile of the capillary withdrawal at a constant voltage. As the liquid metal is replaced with electrolyte, the electrical resistance in the microchannel increases causing a drop in the velocity over time. Once mastered, this technique can be done in a matter of minutes and should allow scientists and engineers to further study this unique phenomenon.

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15.1K vistas.  North Carolina State University. The overall goal of this procedure is to demonstrate the manipulation of liquid metal under the influence of electrochemical potentials. This method tunes the interfacial tension of liquid metal over an enormous range while elucidating the role of oxides on interfacial tension. The main appeal of this technique is that it's simple, it's reversible, and it only requires very modest potentials.This thing has been utilized to make electronic devices that are reconfigurable and composed al...