Post-transition elements, together with zinc-group metals and their alloys belong to an emerging class of materials with fascinating characteristics originating from their simultaneous metallic and liquid natures. These metals and alloys are characterised by having low melting points (i.e. between room temperature and 300 °C), making their liquid state accessible to practical applications in various fields of physical chemistry and synthesis. These materials can offer extraordinary capabilities in the synthesis of new materials, catalysis and can also enable novel applications including microfluidics, flexible electronics and drug delivery. However, surprisingly liquid metals have been somewhat neglected by the wider research community. In this review, we provide a comprehensive overview of the fundamentals underlying liquid metal research, including liquid metal synthesis, surface functionalisation and liquid metal enabled chemistry. Furthermore, we discuss phenomena that warrant further investigations in relevant fields and outline how liquid metals can contribute to exciting future applications.

Liquid metals: fundamentals and applications in chemistry

Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide “skin” enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects.

Emerging Applications of Liquid Metals Featuring Surface Oxides

Lab-on-a-chip devices

https://www.tandfonline.com/doi/pdf/10.1080/14686996.2018.1494493

Structure of graphene and its disorders: a review

Several gallium-based liquid metal alloys are liquid at room temperature. As 'liquid', such alloys have a low viscosity and a high surface tension while as 'metal', they have high thermal and electrical conductivities, similar to mercury. However, unlike mercury, these liquid metal alloys have low toxicity and a negligible vapor pressure, rendering them much safer. In comparison to mercury, the distinguishing feature of these alloys is the rapid formation of a self-limiting atomically thin layer of gallium oxide over their surface when exposed to oxygen. This oxide layer changes many physical and chemical properties of gallium alloys, including their interfacial and rheological properties, which can be employed and modulated for various applications in microfluidics. Injecting liquid metal into microfluidic structures has been extensively used to pattern and encapsulate highly deformable and reconfigurable electronic devices including electrodes, sensors, antennas, and interconnects. Likewise, the unique features of liquid metals have been employed for fabricating miniaturized microfluidic components including pumps, valves, heaters, and electrodes. In this review, we discuss liquid metal enabled microfluidic components, and highlight their desirable attributes including simple fabrication, facile integration, stretchability, reconfigurability, and low power consumption, with promising applications for highly integrated microfluidic systems.

Liquid metal enabled microfluidics

A room temperature liquid metal based electroosmotic flow (EOF) pump has been proposed in this work. This low-cost EOF pump is convenient for both fabrication and integration. It utilizes polydimethylsiloxane (PDMS) microchannels filled with the liquid-metal as non-contact pump electrodes. The electrode channels are fabricated symmetrically to both sides of the pumping channel, having no contact with the pumping channel. To test the pumping performance of the EOF pump, the mean flow velocities of the fluid (DI water) in the EOF pumps were experimentally measured by tracing the fluorescent microparticles in the flow. To provide guidance for designing a low voltage EOF pump, parametric studies on dimensions of the electrode and pumping channels were performed in this work. According to the experimental results, the pumping speed can reach 5.93 μm s−1 at a driving voltage of only 1.6 V, when the gap between the electrode and the pumping channel is 20 μm. Injecting a room temperature liquid metal into microchannels can provide a simple, rapid, low-cost but accurately self-aligned way to fabricate microelectrodes for EOF pumps, which is a promising method to achieve the miniaturization and integration of the EOF pump in microfluidic systems. The non-contact liquid electrodes have no influence on the fluid in the pumping channel when pumping, reducing Joule heat generation and preventing gas bubble formation at the surface of electrodes. The pump has great potential to drive a wide range of fluids, such as drug reagents, cell suspensions and biological macromolecule solutions.

A handy liquid metal based electroosmotic flow pump

Study on the nucleating agents for gallium to reduce its supercooling

A liquid metal based microfluidic system was proposed and demonstrated for the generation and sorting of liquid metal droplets. This micro system utilized silicon oil as the continuous phase and Ga66In20.5Sn13.5 (66.0 wt % Ga, 20.5 wt % In, 13.5 wt % Sn, melting point: 10.6 °C) as the dispersed phase to generate liquid metal droplets on a three-channel F-junction generator. The F-junction is an updated design similar to the classical T-junction, which has a special branch channel added to a T-junction for the supplement of 30 wt % aqueous NaOH solution. To perform active sorting of liquid metal droplets by dielectrophoresis (DEP), the micro system utilized liquid-metal-filled microchannels as noncontact electrodes to induce electrical fields through the droplet channel. The electrode channels were symmetrically located on both sides of the droplet channel in the same horizontal level. According to the results, the micro system can generate uniformly spherical liquid metal droplets, and control the flow direction of the liquid metal droplets. To better understand the control mechanism, a numerical simulation of the electrical field was performed in detail in this work.

A Microfluidic Chip for Liquid Metal Droplet Generation and Sorting

Nowadays, with the development of wearable devices, stretchable pressure sensors have been widely adopted in all kinds of areas. Most of the sensors aim to detect small pressure, such as fingertip tactile sensing, but only a few are focused on high-pressure sensing, such as foot pressure sensing during men’s walking. In this work, a liquid metal-based stretchable sensor for large-pressure measurement is investigated. This sensor is fully stretchable because it is made of soft materials. However, when the soft sensor is subjected to high pressure, the liquid metal easily leaks from microchannels because it maintains the liquid state at room temperature. We therefore propose to fabricate liquid metal-based leakage-free electrodes to handle the liquid-metal leak. Parametric studies are conducted to compare this sensor with liquid-metal-only electrodes and leakage-free electrodes. The leakage-free electrodes increase the measurement ranges from 0.18, 0.18, and 0.15 MPa to 0.44 MPa, with higher linearity and precision. The improvement in the liquid-metal electrode enables the sensors to work stably within 0.44 MPa pressure and 20% strain. In addition, we integrate two capacitors, namely, a working capacitor and a reference capacitor, into one sensor to reduce the influence of parasitic capacitance brought about by external interference. This stretchable capacitive sensor capable of working under a wide range of pressure with good repeatability, sensitivity, and linearity, exhibits great potential use for wearable electronics. Finally, the method for fabricating leakage-free electrodes shows great value for hyperelastic electronics manufacturing and micromachine technology.

Stretchable Pressure Sensor with Leakage-Free Liquid-Metal Electrodes.

A liquid-metal based capacitive soft pressure microsensor is proposed in this work for measuring pressure in microchannels. To measure the pressure of the target microchannel, a short detection channel is fabricated and connected to the target microchannel. Because the detection channel has only one outlet at the end which is connected to the target microchannel, the fluid in the detection channel will stay still during the measurement and the pressure remains constant inside the detection channel. A segment of reference fluid which is immiscible with the working fluid is sealed inside the detection channel. Because the chip material is soft, the pressure change will lead to the movement of the interface between the reference fluid and working fluid inside the detection channel. A pair of liquid metal electrodes are fabricated on both sides of the detection channel. By measuring the capacitance between these two liquid metal electrodes, the movement of the interface can be detected, and thus the pressure change can be detected as well. To minimize the influence from the environment, two liquid metal shield layers are placed on the top and the bottom of the microchannel layer separately. The microsensor was first tested in a microfluidic system and then utilized to measure the blood pressure of rabbit carotid artery in vivo. The experimental results showed excellent stability and linear correlation between capacitance and the value of fluid pressure. The pressure sensor can achieve a resolution of 7.5 mmHg within a pressure range of 20-300 mmHg. This work provides a promising approach to develop an implantable blood or intraocular pressure-monitoring device for clinical use.

Lin Gui

Papers

A handy liquid metal based electroosmotic flow pump

Study on the nucleating agents for gallium to reduce its supercooling

A Microfluidic Chip for Liquid Metal Droplet Generation and Sorting

Stretchable Pressure Sensor with Leakage-Free Liquid-Metal Electrodes.

A liquid metal based capacitive soft pressure microsensor