Design and Performance Evaluation of a Fully Integrated Knitted Knee Brace for Knee Motion Sensing.

The use of e-textiles in wearable sensor design has recently received much interest in many applications, such as robotics, rehabilitation, personal wellness, and sports. Particularly in the rehabilitation domain, it has provided a potential alternative tool for telerehabilitation. In this paper, we designed and evaluated a knitted knee brace with interconnects, resistors, and sensors for real-time kinematic data acquisition. The real-time data acquisition is transmitted using a printed circuit board (PCB) connected to the knee brace through snap pins. The knitted knee brace was tested on three male and one female participant , aged between 30 and 50 years old. All participants were instructed to perform a walking activity at 1.5 km/h for a duration of 10 seconds on the Advanced Mechanical Technology, Inc (AMTI) treadmill over two sessions. The results demonstrated that the fully integrated knitted wearable knee brace could monitor and track human joint locomotion in real time with a standard deviation of 0.39V and 0.41V , respectively, for these two sessions. However, double peak signals were noticeable from the knitted knee brace at a mean of 80.54% during the gait cycles across the four subjects; this observation could be due to the coupled motion along the transverse and coronal planes during the activity.

All Knitted and Integrated Soft Wearable of High Stretchability and Sensitivity for Continuous Monitoring of Human Joint Motion.

E-textiles have recently gained significant traction in the development of soft wearables for healthcare applications. However, there have been limited works on wearable e-textiles with embedded stretchable circuits. Here, stretchable conductive knits with tuneable macroscopic electrical and mechanical properties are developed by varying the yarn combination and the arrangement of stitch types at the meso-scale. Highly extensible piezoresistive strain sensors are designed (>120% strain) with high sensitivity (gauge factor 8.47) and durability (>100,000 cycles), interconnects (>140% strain) and resistors (>250% strain), optimally arranged to form a highly stretchable sensing circuit. The wearable is knitted with a computer numerical control (CNC) knitting machine that offers a cost effective and scalable fabrication method with minimal post-processing. The real-time data from the wearable is transmitted wirelessly using a custom designed circuit board. In this work, an all knitted and fully integrated soft wearable is demonstrated for wireless and continuous real-time sensing of knee joint motion of multiple subjects performing various activities of daily living.

Triple and Quadruple Surface Pattern Memories in Nanoimprinted Polymer Blends.

Trigger-responsive surfaces with multiple surface properties have wide-ranging application potential from surfaces with trigger-responsive fluid flow to cell culture to optical effects; such surfaces can be achieved through surface morphological changes. Although multiple shape-memory effects are successful in bulk polymers, there is limited programing and recovery of multiple surface memories due to the challenges in fabricating multiple surface topographies with good controllability. Here, we report the synergy between the polymer blend formulation and the thermal nanoimprinting process to achieve multiple microtopography memories. A series of immiscible blends consisting of poly(caprolactone) (PCL) and polyethylene (PE) with distinct thermal transitions governed by distinct crystallization events were augmented with improved elasticity through preferential cross-linking in the polymer blend. The effect of preferential cross-linking by dicumyl peroxide on the elastic property of the PCL/PE has been found to be nonlinearly dependent on the blend composition. This approach enabled triple and quadruple surface pattern fixity and recovery in nanoimprinted PCL/PE blends. Specifically, we demonstrated the recovery of a micropillar structure (diameter: 20 µm and height: 10 µm) from a hierarchical micrograting topography (width: 2 µm and height: 2 µm) when exposed to a thermal stimulus at 60 °C for 180 s. Furthermore, we also demonstrated the recovery of a deformed micrograting followed by a secondary recovery of the micropillar structure.

Stiff Shape Memory Polymers for High-Resolution Reconfigurable Nanophotonics.

Reconfigurable metamaterials require constituent nanostructures to demonstrate switching of shapes with external stimuli. Yet, a longstanding challenge is in overcoming stiction caused by van der Waals forces in the deformed configuration, which impedes shape recovery. Here, we introduce stiff shape memory polymers. This designer material has a storage modulus of ∼5.2 GPa at room temperature and ∼90 MPa in the rubbery state at 150 °C, 1 order of magnitude higher than those in previous reports. Nanopillars with diameters of ∼400 nm and an aspect ratio as high as ∼10 were printed by two-photon lithography. Experimentally, we observe shape recovery as collapsed and touching structures overcome stiction to stand back up. We develop a theoretical model to explain the recoverability of these sub-micrometer structures. Reconfigurable structural color prints with a resolution of 21150 dots per inch and holograms are demonstrated, indicating potential applications of the stiff shape memory polymers in high-resolution reconfigurable nanophotonics.

Soft Wearable Knee Brace with Embedded Sensors for Knee Motion Monitoring.

E-textiles have shown great potential for development of soft sensors in applications such as rehabilitation and soft robotics. However, existing approaches require the textile sensors to be attached externally onto a substrate or the garment surface. This paper seeks to address the issue by embedding the sensor directly into the wearable using a computer numerical control (CNC) knitting machine. First, we proposed a design of the wearable knee brace. Next, we demonstrated the capability to knit a sensor with the stretchable surrounding fabric. Subsequently, we characterized the sensor and developed a model for the sensor's electromechanical property. Lastly, the fully knitted knee brace with embedded sensor is tested, by performing three different activities: a simple Flexion-extension exercise, walking, and jogging activity with a single test subject. Results show that the knitted knee brace sensor can track the subject's knee motion well, with a Spearman's coefficient (rs) value of 0.87 when compared to the reference standard.

Superhydrophobic Polymer Topography Design Assisted by Machine Learning Algorithms.

Superhydrophobic surfaces have been largely achieved through various surface topographies. Both empirical and numerical simulations have been reported to help understand and design superhydrophobic surfaces. Many such successful surfaces have also been achieved using bioinspired and biomimetic designs. Despite this, identifying the right surface texture to meet the requirements of specific applications is not a straightforward task. Here, we report a hybrid approach that includes experimental methods, numerical simulations, and machine learning (ML) algorithms to create design maps for superhydrophobic polymer topographies. Two design objectives to investigate superhydrophobic properties were the maximum water contact angle (WCA) and Laplace pressure. The design parameters were the geometries of an isotropic pillar structure in micrometer and sub-micrometer length scales. The finite element method (FEM) was validated by the experimental data and employed to generate a labeled dataset for ML training. Artificial neural network (ANN) models were then trained on the labeled database for the topographic parameters (width W, height H, and pitch P) with the corresponding WCA and Laplace pressure. The ANN models yielded a series of nonlinear relationships between the topographic design parameters and the WCA and Laplace pressure and substantial differences between the micrometer and sub-micrometer length scales. Design maps that span the topography design parameters provide optimal design or tradeoff parameters. This research demonstrates the potential of ANN as a rapid design tool for surface topography exploration.

Structural multi-colour invisible inks with submicron 4D printing of shape memory polymers.

Four-dimensional (4D) printing of shape memory polymer (SMP) imparts time responsive properties to 3D structures. Here, we explore 4D printing of a SMP in the submicron length scale, extending its applications to nanophononics. We report a new SMP photoresist based on Vero Clear achieving print features at a resolution of ~300 nm half pitch using two-photon polymerization lithography (TPL). Prints consisting of grids with size-tunable multi-colours enabled the study of shape memory effects to achieve large visual shifts through nanoscale structure deformation. As the nanostructures are flattened, the colours and printed information become invisible. Remarkably, the shape memory effect recovers the original surface morphology of the nanostructures along with its structural colour within seconds of heating above its glass transition temperature. The high-resolution printing and excellent reversibility in both microtopography and optical properties promises a platform for temperature-sensitive labels, information hiding for anti-counterfeiting, and tunable photonic devices.

Phototriggerable Transient Electronics via Fullerene-Mediated Degradation of Polymer:Fullerene Encapsulation Layer.

Transient electronics is an emerging class of electronics that has attracted a lot of attention because of its potential as an environmental-friendly alternative to the existing end-of-life product disposal or treatments. However, the controlled degradation of transient electronics under environmentally benign conditions remains a challenge. In this work, the tunable degradation of transient electronics including passive resistor devices and active memory devices was realized by photodegradable thin polymer films comprising fullerene derivatives, [6,6]-phenyl-C61-butyric acid methyl esters (PCBM). The photodegradation of polymer:PCBM under an aqueous environment is triggered by ultraviolet (UV) light. Experimental results demonstrate that the addition of PCBM in commodity polymers, including but not limited to polystyrene, results in a catalytic effect on polymer photodegradation when triggered by UV light. The degradation mechanism of transient electronics is ascribed to the photodegradation of polymer:PCBM encapsulation layers caused by the synergistic effect between UV and water exposure. The polymer:PCBM encapsulation system presented herein offers a simple way to achieve the realization of light-triggered device degradation for bioapplication and expands the material options for tailorable degradation of transient electronics.

Photoswitchable Solubility of Fullerene-Doped Polymer Thin Films.

Controlling polymer film solubility is of fundamental and practical interest and is typically achieved by synthetically modifying the polymer structure to insert reactive groups. Here, we demonstrate that the addition of fullerenes or its derivatives (C60 or phenyl-C61-butyric acid methyl ester, PCBM) to polymers, followed by ultraviolet (UV) illumination can change the film solubility. Contrary to most synthetic polymers, which dissolve in organic solvents but not in water, the fullerene-doped polymer films (such as polystyrene) can dissolve in water yet remain stable in organic solvents. This photoswitchable solubility effect is not observed in either film constituents individually and is derived from a synergy of photochemistries. First, polymer photooxidation generates macroradicals which cross-link with radical-scavenging PCBM, thereby contributing to the films' insolubility in organic solvents. Second, light exposure enhances polymer photooxidation in the presence of PCBM via the singlet oxygen pathway. This results in polymer backbone scission and formation of photooxidized products which can form hydrogen bonds with water, both contributing to water solubility. Nevertheless, the illuminated doped polymer thin films are mechanically robust, exhibiting significantly increased modulus and density compared to their pristine counterpart, such that they can remain intact even upon sonication in conventional organic solvents. We further demonstrate the application of this solubility-switching effect in dual tone photolithography, via a facile, economical, and environmentally benign solution-processing route made possible by the photoactive nature of polymer-PCBM thin films.

Massively Multiplexed Submicron Particle Patterning in Acoustically Driven Oscillating Nanocavities.

Nanoacoustic fields are a promising method for particle actuation at the nanoscale, though THz frequencies are typically required to create nanoscale wavelengths. In this work, the generation of robust nanoscale force gradients is demonstrated using MHz driving frequencies via acoustic-structure interactions. A structured elastic layer at the interface between a microfluidic channel and a traveling surface acoustic wave (SAW) device results in submicron acoustic traps, each of which can trap individual submicron particles. The acoustically driven deformation of nanocavities gives rise to time-averaged acoustic fields which direct suspended particles toward, and trap them within, the nanocavities. The use of SAWs permits massively multiplexed particle manipulation with deterministic patterning at the single-particle level. In this work, 300 nm diameter particles are acoustically trapped in 500 nm diameter cavities using traveling SAWs with wavelengths in the range of 20-80 µm with one particle per cavity. On-demand generation of nanoscale acoustic force gradients has wide applications in nanoparticle manipulation, including bioparticle enrichment and enhanced catalytic reactions for industrial applications.

The global rise of 3D printing during the COVID-19 pandemic.

3D printing enables on-demand solutions for a wide spectrum of needs ranging from personal protection equipment to medical devices and isolation wards. This versatile technology is suited to address supply-demand imbalances caused by socio-economic trends and disruptions in supply chains.

Nanostructured Free-Form Objects via a Synergy of 3D Printing and Thermal Nanoimprinting.

High-resolution surface patterning has garnered interests as a nonchemical-based surface engineering approach for creating functional surfaces. Applications in consumer products, parts for transportation vehicles, optics, and biomedical technologies demand topographic patterning on 3D net shape objects. Through a hybrid approach, high-resolution surface texture is incorporated onto 3D-printed polymers via direct thermal nanoimprinting process. The synergy of geometry design freedom in 3D printing and the high spatial resolution in nanoimprinting is demonstrated to be a versatile fabrication of high-fidelity surface pattern (from 2 µm to 200 nm resolution) on convex, concave semicylindrical, and hemispherical objects spanning a range of surface curvatures. The novel hybrid fabrication is further extended to achieve a high-resolution curved mold insert for rapid prototyping via injection molding. The versatility of the fabrication strategies reported here not only provides a post-3D printing process that enhances the surface properties of 3D-printed objects but also opens a new pathway to enable future study on the effects of combining microscale and nanoscale surface texture with macroscopic curvature. Both have been known, individually, as an effective approach to tune surface functionalities.

Gecko-Inspired Dry Adhesive Based on Micro-Nanoscale Hierarchical Arrays for Application in Climbing Devices.

The unusual ability of geckos to climb vertical walls underlies a unique combination of a hierarchical structural design and a stiffer material composition. While a dense array of microscopic hierarchical structures enables the gecko toe pads to adhere to various surfaces, a stiffer material (ß-keratin) composition enables them to maintain reliable adhesion over innumerable cycles. This unique strategy has been seldom implemented in engineered dry adhesives because fabrication of high-aspect-ratio hierarchical structures using a stiffer polymer is challenging. Herein, we report the fabrication of high-aspect-ratio hierarchical arrays on flexible polycarbonate sheets (stiffness comparable to that of ß-keratin) by a sacrificial-layer-mediated nanoimprinting technique. Dry-adhesive films comprising the hierarchical arrays showed a formidable shear adhesion of 11.91 ± 0.43 N/cm2. Cyclic adhesion tests also showed that the shear adhesion of the adhesive films reduced by only about 20% after 50 cycles and remained nearly constant until about 200 cycles. Most importantly, the high-aspect-ratio hierarchical arrays were integrated onto the feet of a miniature robot and the locomotion on a 30° inclined surface was demonstrated.

Physical Texturing for Superhydrophobic Polymeric Surfaces: A Design Perspective.

Surface wetting on the textured surface is classically explained by the theories of Cassie-Baxter or Wenzel. However, in recent years, an increasing number of complex surface topographies with superhydrophobic properties have been achieved without prediction or simulation using these theories. One example is biomimetic surfaces. In many instances, theories were used to explain surface properties found in nature but have not led to or predicted the complex topographies. Although new wetting theories continue to emerge, there is not yet a set of design rules to guide the selection of surface topographies to achieve superhydrophobicity. By grouping known surface topographies into common geometrical descriptions and length scale, this paper suggests a set of surface topography classifications to provide selection guidelines for engineering superhydrophobic surfaces. Two key outcomes emerged from the design analysis: first, categorization of frequently reported surface patterns shows that there exists a set of commonly used descriptions among diverse designs; second, the degree of hydrophobicity improvement within a class of topography design can be used to predict the limit of improvement in superhydrophobicity for a given material. The presentation of topography descriptors by categories of design and performance may serve as a prologue to an eventually complete set of design guidelines for superhydrophobic performance.

Geometry-dependent compressive responses in nanoimprinted submicron-structured shape memory polyurethane.

High resolution surface textures, when rationally designed, provide an attractive surface engineering approach to enhance surface functionalities. Designing smart surfaces by coupling surface texture with shape memory polymers has garnered attention in achieving tunable mechanical properties. We investigate the structure-mechanical property relationships for programmable, shape-memorizing submicron-scale pillar arrays subjected to flat-punch compression. The geometrically-dependent deformation of structured surfaces with two different aspect ratios (250 nm-pillars 1 : 1 and 550 nm-pillars 2.4 : 1) were investigated, and their moduli were found to be lower than that of non-patterned surface. From finite element analysis, the pillar deformation is correlated to a mechanistic transition from a discrete, unidirectional compression of 250 nm-pillars to lateral constraints caused by interpillar contact in 550 nm-pillars. This lateral pillar-pillar contact in the 550 nm-pillars resulted in an increased and maximum strain-dependent modulus but lower elastic recovery and energy dissipation as compared with the 250 nm-pillars. Furthermore, the compressive responses of temporarily shaped pillars (programmed by stretching) were compared with the permanently shaped pillars. The extent of lateral constraints controlled by pillar shape and spacing in 550 nm-pillars was responsible for the modulus differences between the original and stretched patterns, whereas the modulus of 250 nm-pillars remained as a constant value with different levels of stretching. This study provides mechanistic insights into how the mechanical behavior can be modulated by designing the aspect ratio of shape memory pillar arrays and by programming the surface geometry, thus revealing the potential of developing ingenious designs of responsive surfaces sensitive to mechanical deformation.

Geometry- and Length Scale-Dependent Deformation and Recovery on Micro- and Nanopatterned Shape Memory Polymer Surfaces.

Micro- and nanoscale surface textures, when optimally designed, present a unique approach to improve surface functionalities. Coupling surface texture with shape memory polymers may generate reversibly tuneable surface properties. A shape memory polyetherurethane is used to prepare various surface textures including 2 µm- and 200 nm-gratings, 250 nm-pillars and 200 nm-holes. The mechanical deformation via stretching and recovery of the surface texture are investigated as a function of length scales and shapes. Results show the 200 nm-grating exhibiting more deformation than 2 µm-grating. Grating imparts anisotropic and surface area-to-volume effects, causing different degree of deformation between gratings and pillars under the same applied macroscopic strain. Full distribution of stress within the film causes the holes to deform more substantially than the pillars. In the recovery study, unlike a nearly complete recovery for the gratings after 10 transformation cycles, the high contribution of surface energy impedes the recovery of holes and pillars. The surface textures are shown to perform a switchable wetting function. This study provides insights into how geometric features of shape memory surface patterns can be designed to modulate the shape programming and recovery, and how the control of reversibly deformable surface textures can be applied to transfer microdroplets.

Planar and tubular patterning of micro and nano-topographies on poly(vinyl alcohol) hydrogel for improved endothelial cell responses.

Poly(vinyl alcohol) hydrogel (PVA) is a widely used material for biomedical devices, yet there is a need to enhance its biological functionality for in vitro and in vivo vascular application. Significance of surface topography in modulating cellular behaviour is increasingly evident. However, hydrogel patterning remains challenging. Using a casting method, planar PVA were patterned with micro-sized features. To achieve higher patterning resolution, nanoimprint lithography with high pressure and temperature was used. In vitro experiment showed enhanced human endothelial cell (EC) density and adhesion on patterned PVA. Additional chemical modification via nitrogen gas plasma on patterned PVA further improved EC density and adhesion. Only EC monolayer grown on plasma modified PVA with 2 µm gratings and 1.8 µm concave lens exhibited expression of vascular endothelial cadherin, indicating EC functionality. Patterning of the luminal surface of tubular hydrogels is not widely explored. The study presents the first method for simultaneous tubular molding and luminal surface patterning of hydrogel. PVA graft with 2 µm gratings showed patency and endothelialization, while unpatterned grafts were occluded after 20 days in rat aorta. The reproducible, high yield and high-fidelity methods enable planar and tubular patterning of PVA and other hydrogels to be used for biomedical applications.

Highly sensitive reduced graphene oxide microelectrode array sensor.

Reduced graphene oxide (rGO) has been fabricated into a microelectrode array (MEA) using a modified nanoimprint lithography (NIL) technique. Through a modified NIL process, the rGO MEA was fabricated by a self-alignment of conducting Indium Tin Oxide (ITO) and rGO layer without etching of the rGO layer. The rGO MEA consists of an array of 10µm circular disks and microelectrode signature has been found at a pitch spacing of 60µm. The rGO MEA shows a sensitivity of 1.91nAµm(-1) to dopamine (DA) without the use of mediators or functionalization of the reduced graphene oxide (rGO) active layer. The performance of rGO MEA remains stable when tested under highly resistive media using a continuous flow set up, as well as when subjecting it to mechanical stress. The successful demonstration of NIL for fabricating rGO microelectrodes on flexible substrate presents a route for the large scale fabrication of highly sensitive, flexible and thin biosensing platform.

Atomic layer deposition of a MoS2 film.

A mono- to multilayer thick MoS2 film has been grown by using the atomic layer deposition (ALD) technique at 300 °C on a sapphire wafer. ALD provides precise control of the MoS2 film thickness due to pulsed introduction of the reactants and self-limiting reactions of MoCl5 and H2S. A post-deposition annealing of the ALD-deposited monolayer film improves the crystallinity of the film, which is evident from the presence of triangle-shaped crystals that exhibit strong photoluminescence in the visible range.

Substrate topography determines the fate of chondrogenesis from human mesenchymal stem cells resulting in specific cartilage phenotype formation.

To reproduce a complex and functional tissue, it is crucial to provide a biomimetic cellular microenvironment that not only incorporates biochemical cues, but also physical features including the nano-topographical patterning, for cell/matrix interaction. We developed spatially-controlled nano-topography in the form of nano-pillar, nano-hole and nano-grill on polycaprolactone surface via thermal nanoimprinting. The effects of chondroitin sulfate-coated nano-topographies on cell characteristics and chondrogenic differentiation of human mesenchymal stem cell (MSC) were investigated. Our results show that various nano-topographical patterns triggered changes in MSC morphology and cytoskeletal structure, affecting cell aggregation and differentiation. Compared to non-patterned surface, nano-pillar and nano-hole topography enhanced MSC chondrogenesis and facilitated hyaline cartilage formation. MSCs experienced delayed chondrogenesis on nano-grill topography and were induced to fibro/superficial zone cartilage formation. This study demonstrates the sensitivity of MSC differentiation to surface nano-topography and highlights the importance of incorporating topographical design in scaffolds for cartilage tissue engineering. From the clinical editor: These authors have developed spatially-controlled nano-topography in the form of nano-pillar, nano-hole and nano-grill on polycaprolactone surface via thermal nanoimprinting, and the effects of chondroitin sulfate-coated nano-topographies on cell characteristics and chondrogenic differentiation of human mesenchymal stem cells (MSC) were investigated. It has been concluded that MSC differentiation is sensitive to surface nano-topography, and certain nano-imprinted surfaces are more useful than others for cartilage tissue engineering.