Tungsten Oxide Coated Liquid Metal Electrodes via Galvanic Replacement as Heavy Metal Ion Sensors.

Gallium liquid metals (LMs) like Galinstan and eutectic Gallium-Indium (EGaIn) have seen increasing applications in heavy metal ion (HMI) sensing, because of their ability to amalgamate with HMIs like lead, their high hydrogen potential, and their stable electrochemical window. Furthermore, coating LM droplets with nanopowders of tungsten oxide (WO) has shown enhancement in HMI sensing owing to intense electrical fields at the nanopowder-liquid-metal interface. However, most LM HMI sensors are droplet based, which show limitations in scalability and the homogeneity of the surface. A scalable approach that can be extended to LM electrodes is therefore highly desirable. In this work, we present, for the first time, WO-Galinstan HMI sensors fabricated via photolithography of a negative cavity, Galinstan brushing inside the cavity, lift-off, and galvanic replacement (GR) in a tungsten salt solution. Successful GR of Galinstan was verified using optical microscopy, SEM, EDX, XPS, and surface roughness measurements of the Galinstan electrodes. The fabricated WO-Galinstan electrodes demonstrated enhanced sensitivity in comparison with electrodes structured from pure Galinstan and detected lead at concentrations down to 0.1 mmol·L-1. This work paves the way for a new class of HMI sensors using GR of WO-Galinstan electrodes, with applications in microfluidics and MEMS for a toxic-free environment.

Generation of precision microstructures based on reconfigurable photoresponsive hydrogels for high-resolution polymer replication and microoptics.

Microstructured molds are essential for fabricating various components ranging from precision optics and microstructured surfaces to microfluidics. However, conventional fabrication technology such as photolithography requires expensive equipment and a large number of processing steps. Here, we report a facile method to fabricate micromolds based on a reusable photoresponsive hydrogel: Uniform micropatterns are engraved into the hydrogel surface using photo masks under UV irradiation within a few minutes. Patterns are replicated using polydimethylsiloxane with minimum feature size of 40 µm and smoothness of Rq ~ 3.4 nm. After replication, the patterns can be fully erased by light thus allowing for reuse as a new mold without notable loss in performance. Utilizing greyscale lithography, patterns with different height levels can be produced within the same exposure step. We demonstrate the versatility of this method by fabricating diffractive optical elements devices and a microlens array and microfluidic device with 100 µm wide channels.

Fabrication of Multi-Material Pneumatic Actuators and Microactuators Using Stereolithography.

Pneumatic actuators are of great interest for device miniaturization, microactuators, soft robots, biomedical engineering, and complex control systems. Recently, multi-material actuators have become of high interest to researchers due to their comprehensive range of suitable applications. Three-dimensional (3D) printing of multi-material pneumatic actuators would be the ideal way to fabricate customized actuators, but so far, this is mostly limited to deposition-based methodologies, such as fused deposition modeling (FDM) or Polyjetting. Vat-based stereolithography is one of the most relevant high-resolution 3D printing methods but is only rarely utilized in the multi-material 3D printing of materials. This study demonstrated multi-material stereolithography using combinations of materials with different Young's moduli, i.e., 0.5 MPa and 1.1 GPa, for manufacturing pneumatic actuators and microactuators with a resolution as small as 200 µm. These multi-material actuators have advantages over single-material actuators in terms of their deformation controllability and ease of assembly.

Controllable Wetting Transitions on Photoswitchable Physical Gels.

Softness plays a key role in the deformation of soft elastic substrates at the three-phase contact line, and the acting forces lead to the formation of a wetting ridge due to elastocapillarity. The change in wetting ridge and surface profiles at different softness has a great impact on the droplet behavior in different phenomena. Commonly used materials to study soft wetting are swollen polymeric gels or polymer brushes. These materials offer no possibility to change the softness on demand. Therefore, adjustable surfaces with tunable softness are highly sought-after to achieve on-demand transition between wetting states on soft surfaces. Here, we present a photorheological physical soft gel with adjustable stiffness based on the spiropyran photoswitch that shows the formation of wetting ridges upon droplet deposition. The presented photoswitchable gels allow the creation of reversibly switchable softness patterns with microscale resolution using UV light-switching of the spiropyran molecule. Gels with varying softness are analyzed, showing a decrease in the wetting ridge height at higher gel stiffness. Furthermore, wetting ridges before and after photoswitching are visualized using confocal microscopy, showing the transition in the wetting properties from soft wetting to liquid/liquid wetting.

4D Printed Shape-Memory Elastomer for Thermally Programmable Soft Actuators.

Polymeric shape-memory elastomers can recover to a permeant shape from any programmed deformation under external stimuli. They are mostly cross-linked polymeric materials and can be shaped by three-dimensional (3D) printing. However, 3D printed shape-memory polymers so far only exhibit elasticity above their transition temperature, which results in their programmed shape being inelastic or brittle at lower temperatures. To date, 3D printed shape-memory elastomers with elasticity both below and above their transition temperature remain an elusive goal, which limits the application of shape-memory materials as elastic materials at low temperatures. In this paper, we printed, for the first time, a custom-developed shape-memory elastomer based on polyethylene glycol using digital light processing, which possesses elasticity and stretchability in a wide temperature range, below and above the transition temperature. Young's modulus in these two states can vary significantly, with a difference of up to 2 orders of magnitude. This marked difference in Young's modulus imparts excellent shape-memory properties to the material. The difference in Young's modulus at different temperatures allows for the programming of the pneumatic actuators by heating and softening specific areas. Consequently, a single actuator can exhibit distinct movement modes based on the programming process it undergoes.

Superrepellent Porous Polymer Surfaces by Replication from Wrinkled Polydimethylsiloxane/Parylene F.

Superrepellent surfaces, such as micro/nanostructured surfaces, are of key importance in both academia and industry for emerging applications in areas such as self-cleaning, drag reduction, and oil repellence. Engineering these surfaces is achieved through the combination of the required surface topography, such as porosity, with low-surface-energy materials. The surface topography is crucial for achieving high liquid repellence and low roll-off angles. In general, the combination of micro- and nanostructures is most promising in achieving high repellence. In this work, we report the enhancement of wetting properties of porous polymers by replication from wrinkled Parylene F (PF)-coated polydimethylsiloxane (PDMS). Fluorinated polymer foam "Fluoropor" serves as the low-surface-energy polymer. The wrinkled molds are achieved via the deposition of a thin PF layer onto the soft PDMS substrates. Through consecutive supercritical drying, superrepellent surfaces with a high surface porosity and a high water contact angle (CA) of >165° are achieved. The replicated surfaces show low roll-off angles (ROA) <10° for water and <21° for ethylene glycol. Moreover, the introduction of the micro-wrinkles to Fluoropor not only enhances its liquid repellence for water and ethylene glycol but also for liquids with low surface tension, such as n-hexadecane.

Skin-electrode iontronic interface for mechanosensing.

Electrodermal devices that capture the physiological response of skin are crucial for monitoring vital signals, but they often require convoluted layered designs with either electronic or ionic active materials relying on complicated synthesis procedures, encapsulation, and packaging techniques. Here, we report that the ionic transport in living systems can provide a simple mode of iontronic sensing and bypass the need of artificial ionic materials. A simple skin-electrode mechanosensing structure (SEMS) is constructed, exhibiting high pressure-resolution and spatial-resolution, being capable of feeling touch and detecting weak physiological signals such as fingertip pulse under different skin humidity. Our mechanical analysis reveals the critical role of instability in high-aspect-ratio microstructures on sensing. We further demonstrate pressure mapping with millimeter-spatial-resolution using a fully textile SEMS-based glove. The simplicity and reliability of SEMS hold great promise of diverse healthcare applications, such as pulse detection and recovering the sensory capability in patients with tactile dysfunction.

Iontronic pressure sensor with high sensitivity and linear response over a wide pressure range based on soft micropillared electrodes.

Electronic skins and flexible pressure sensors are important devices for advanced healthcare and intelligent robotics. Sensitivity is a key parameter of flexible pressure sensors. Whereas introducing surface microstructures in a capacitive-type sensor can significantly improve its sensitivity, the signal becomes nonlinear and the pressure response range gets much narrower, significantly limiting the applications of flexible pressure sensors. Here, we designed a pressure sensor that utilizes a nanoscale iontronic interface of an ionic gel layer and a micropillared electrode, for highly linear capacitance-to-pressure response and high sensitivity over a wide pressure range. The micropillars undergo three stages of deformation upon loading: initial contact (0-6 kPa) and structure buckling (6-12 kPa) that exhibit a low and nonlinear response, as well as a post-buckling stage that has a high signal linearity with high sensitivity (33.16 kPa-1) over a broad pressure range of 12-176 kPa. The high linearity lies in the subtle balance between the structure compression and mechanical matching of the two materials at the gel-electrode interface. Our sensor has been applied in pulse detection, plantar pressure mapping, and grasp task of an artificial limb. This work provides a physical insight in achieving linear response through the design of appropriate microstructures and selection of materials with suitable modulus in flexible pressure sensors, which are potentially useful in intelligent robots and health monitoring.

Highly Transparent and Flexible Iontronic Pressure Sensors Based on an Opaque to Transparent Transition.

Human-computer interfaces, smart glasses, touch screens, and some electronic skins require highly transparent and flexible pressure-sensing elements. Flexible pressure sensors often apply a microstructured or porous active material to improve their sensitivity and response speed. However, the microstructures or small pores will result in high haze and low transparency of the device, and thus it is challenging to balance the sensitivity and transparency simultaneously in flexible pressure sensors or electronic skins. Here, for a capacitive-type sensor that consists of a porous polyvinylidene fluoride (PVDF) film sandwiched between two transparent electrodes, the challenge is addressed by filling the pores with ionic liquid that has the same refractive index with PVDF, and the transmittance of the film dramatically boosts from 0 to 94.8% in the visible range. Apart from optical matching, the ionic liquid also significantly improves the signal intensity as well as the sensitivity due to the formation of an electric double layer at the dielectric-electrode interfaces, and improves the toughness and stretchability of the active material benefiting from a plasticization effect. Such transparent and flexible sensors will be useful in smart windows, invisible bands, and so forth.

Graphene/cyclodextrin-based nanocomposite hydrogel with enhanced strength and thermo-responsive ability.

Dual crosslinked system has been proved to be an efficient method to obtain tough and high strength hydrogels. Herein, we synthesized a novel graphene oxide/p(acrylamide-co-poly(ethylene glycol) methyl ether methacrylate)/α-cyclodextrin (GO/P(AM-co-PEGMA)/CD) physical dual crosslinked hydrogel via copolymerization of AM and PEGMA in the α-CD/GO solution. The polymer main chains adsorb onto the GO surface resulting in the first crosslinked system and multiple hydrogen bonds between α-CDs that thread on the PEGMA side chains establish the second crosslinked system. The GO/P(AM-co-PEGMA)/CD hydrogel exhibits favorable tensile properties with fracture strain of 1800% and high fracture stress of 660kPa; in addition, the hydrogel can bear large compressive stress (2.7MPa) at strain of 85% without rupture. Furthermore, physical dual crosslinked system endows the GO/P(AM-co-PEGMA)/CD hydrogel with thermoplastic ability and thermo-responsive shape memory behavior. This facial one-pot method will contribute to design and application of high performance hydrogel.