Multifunctional Quasi-Solid-State Zinc-Sulfur Battery.

The introduction of structural energy storage devices into emerging markets, such as electric vehicles, is predominately hindered by weak energy density, safety concerns, and immaturity of the field in materials. Herein, fabrication and testing of a freeze-resistant, multifunctional quasi-solid-state zinc-sulfur battery (ZnS) are reported. To this end, an electrostatic spray coating technique was used to deposit a thin layer of sulfur on the highly porous, unidirectional activated carbon nanofibers (A-CNFs) as a load-bearing cathode. This technique could fill micro- and mesopores, and microsized channels with sulfur, achieving an extensive sulfur loading of 60 wt %. Several drawbacks of structural energy storage devices (applicability under varied climate conditions, poor electrochemical performance and mechanical properties) are addressed by initiating an antifreezing hydrogel electrolyte with a failure strain of over 200%. This electrolyte possesses ethylene glycol and an I2 additive as an antifreezing agent and redox mediator, respectively. The as-assembled ZnS battery offers a high energy density of 283 Wh/kg based on the CNF-S cathode (149 Wh/kg based on the ZnS cell) and mechanical properties beyond state-of-the-art structural energy storage devices with a tensile strength of 377 MPa, Young's modulus of 16.7 GPa, and energy-to-failure of 4.5 MJ/m3. The electrochemomechanical properties of the ZnS battery were also investigated to elucidate the effects of electrochemical energy storage on mechanical properties and vice versa. Overall, the ZnS battery outperforms state-of-the-art structural energy storage devices in terms of energy storage and load-bearing capabilities.

Development of a controlled-atmosphere, rapid-cooling cryogenic chamber for tribological and mechanical testing.

Mechanical testing of seals, bearing materials, and mechanisms in cryogenic environments is a rapidly growing field of research, as it promises improvements in equipment performance and reliability for applications such as space exploration, liquid hydrocarbon storage, and superconducting devices. Cooling of test equipment is usually performed within a well-insulated test chamber, via direct or indirect evaporation of liquid cryogen. State-of-the-art equipment is frequently insufficient for rigorous testing, being expensive and cumbersome, cooling slowly, struggling to replicate relevant environmental conditions, and/or failing to reach the temperature of the cryogen. Herein, we employ a rapid prototyping approach using polymer 3D printing to iteratively refine cryogen-based cooling of a tribometer. The final design greatly exceeds the minimum temperature of state-of-the-art equipment, cooling a chamber to liquid nitrogen temperatures (-196 °C) while maintaining dry test conditions. When modified for use on a cryogenic tensile tester, the design cools to -150 °C in 149 s, significantly improving upon state-of-the-art performance. By utilizing this 3D-printed equipment, we find that components produced via Fused Deposition Modeling with unmodified, commodity polylactic acid have favorable mechanical properties in a cryogenic environment: tensile strength of 110 MPa, elongation at break of 10%, and specific wear of 5.6 × 10-5 mm3/Nm against stainless steel. By leveraging 3D printing for rapid manufacture of production-quality parts, highly refined cooling chamber designs have been experimentally developed for both a tribometer and a load frame in rapid succession, enabling significant improvements in cryogenic test capabilities.

Impact of Ionic Liquid Additives and Inorganic Fullerene-Like Tungsten Disulfide on Friction and Wear under Aqueous Environments.

Aqueous lubricants are gaining attention due to significant advantages such as being environmentally friendly, tunable, and thermally stable. The oil and gas industry can use such additives to utilize in water-based fluids for applications where small sliding velocities and large lateral forces require enhanced lubrication. This investigation aims to compare the effects of two different additives: (i) inorganic fullerene-like tungsten disulfide (IF-WS2) and (ii) an alkanolamine ionic liquid denoted as AA-IL. Both additives were paired with three different base fluids, deionized water (DIW), aqueous NaCl, and aqueous CaCl2, to measure the impact on fluids commonly utilized in the field. The addition of IF-WS2 to all three solutions resulted in a 30-60% decrease in the coefficient of friction (COF) and wear. Surface analysis by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDS) showed that the formation of a tribofilm (tungsten oxide layer) is primarily responsible for tribological improvements. The AA-IL did not show evidence of any chemical interaction. Instead, a physically bonded film of the AA-IL on the steel surface enabled the improved COF (40-50% reduction) and wear response. Both additives are effective in very small amounts and provide excellent wear and friction reduction properties.

Enabling Selectively Tunable Mechanical Properties of Graphene Oxide/Silk Fibroin/Cellulose Nanocrystal Bionanofilms.

Enhancing and manipulating the mechanical properties of graphene oxide (GO)-based structures are challenging because the GO assembly is easily delaminated. We develop nacre-like bionanofilms whose in-plane mechanical properties can be manipulated through water vapor annealing without influencing their mechanical properties in the thickness direction. These bionanofilms are prepared from GO, silk fibroin (SF), and cellulose nanocrystals (CNCs) via a spin-assisted layer-by-layer assembly. The postannealing mechanical properties of the films are determined with atomic force microscopy (AFM) bending and nanoindentation, and it is confirmed that the mechanical properties of the bionanofilms are altered only in the in-plane direction. While AFM bending shows Young's moduli of 26.9, 36.3, 24.3, and 41.4 GPa for 15, 15 annealed, 30, and 30 annealed GO/SF/CNC trilayers, nanoindentation shows reduced moduli of 19.5 ± 2.6 and 19.5 ± 2.5 GPa before and after annealing, respectively. The unaltered mechanical properties of the bionanofilms along the thickness direction after annealing can be attributed to the CNC frame in the SF matrix acting as a support against stress in the thickness direction, while annealing reorganizes the bionanofilm structure. The tunability of the bionanofilms' mechanical properties in only one direction through structure manipulation can lead to various applications, such as e-skin, wearable sensors, and human-machine interaction devices.

Development of Fluorine-Free Tantalum Carbide MXene Hybrid Structure as a Biocompatible Material for Supercapacitor Electrodes.

The application of nontoxic 2D transition-metal carbides (MXenes) has recently gained ground in bioelectronics. In group-4 transition metals, tantalum possesses enhanced biological and physical properties compared to other MXene counterparts. However, the application of tantalum carbide for bioelectrodes has not yet been explored. Here, fluorine-free exfoliation and functionalization of tantalum carbide MAX-phase to synthesize a novel Ta4C3Tx MXene-tantalum oxide (TTO) hybrid structure through an innovative, facile, and inexpensive protocol is demonstrated. Additionally, the application of TTO composite as an efficient biocompatible material for supercapacitor electrodes is reported. The TTO electrode displays long-term stability over 10 000 cycles with capacitance retention of over 90% and volumetric capacitance of 447 F cm-3 (194 F g-1) at 1 mV s-1. Furthermore, TTO shows excellent biocompatibility with human-induced pluripotent stem cells-derived cardiomyocytes, neural progenitor cells, fibroblasts, and mesenchymal stem cells. More importantly, the electrochemical data show that TTO outperforms most of the previously reported biomaterials-based supercapacitors in terms of gravimetric/volumetric energy and power densities. Therefore, TTO hybrid structure may open a gateway as a bioelectrode material with high energy-storage performance for size-sensitive applications.

Effects of SiO2 content on the nanomechanical properties of CoCrPt-SiO2 granular films.

CoCrPt material is used for perpendicular magnetic recording media due to its high magneto-crystalline anisotropy that brings good thermal stability on the media. The addition of SiO2 between the CoCrPt grains offers benefits including lower noise and better thermal stability. It has been reported that the SiO2 content has strong effects on the media's recording performance such as coercivity, anisotropy and noise. In this work, we focus on studying the effects of the SiO2 content on the nanomechanical properties of the media which are critical for the head-disk interface reliability. Variations of these properties with SiO2 content provide guidelines for optimum designs considering both recording and mechanical interface performance.

A microelectromechanical systems (MEMS) force-displacement transducer for sub-5 nm nanoindentation and adhesion measurements.

We present a highly sensitive force-displacement transducer capable of performing ultra-shallow nanoindentation and adhesion measurements. The transducer utilizes electrostatic actuation and capacitive sensing combined with microelectromechanical fabrication technologies. Air indentation experiments report a root-mean-square (RMS) force resolution of 1.8 nN and an RMS displacement resolution of 0.019 nm. Nanoindentation experiments on a standard fused quartz sample report a practical RMS force resolution of 5 nN and an RMS displacement resolution of 0.05 nm at sub-10 nm indentation depths, indicating that the system has a very low system noise for indentation experiments. The high sensitivity and low noise enables the transducer to obtain high-resolution nanoindentation data at sub-5 nm contact depths. The sensitive force transducer is used to successfully perform nanoindentation measurements on a 14 nm thin film. Adhesion measurements were also performed, clearly capturing the pull-on and pull-off forces during approach and separation of two contacting surfaces.

Fabrication and Deformation of 3D Multilayered Kirigami Microstructures.

Mechanically guided 3D microassembly with controlled compressive buckling represents a promising emerging route to 3D mesostructures in a broad range of advanced materials, including single-crystalline silicon (Si), of direct relevance to microelectronic devices. During practical applications, the assembled 3D mesostructures and microdevices usually undergo external mechanical loading such as out-of-plane compression, which can induce damage in or failure of the structures/devices. Here, the mechanical responses of a few mechanically assembled 3D kirigami mesostructures under flat-punch compression are studied through combined experiment and finite element analyses. These 3D kirigami mesostructures consisting of a bilayer of Si and SU-8 epoxy are formed through integration of patterned 2D precursors with a prestretched elastomeric substrate at predefined bonding sites to allow controlled buckling that transforms them into desired 3D configurations. In situ scanning electron microscopy measurement enables detailed studies of the mechanical behavior of these structures. Analysis of the load-displacement curves allows the measurement of the effective stiffness and elastic recovery of various 3D structures. The compression experiments indicate distinct regimes in the compressive force/displacement curves and reveals different geometry-dependent deformation for the structures. Complementary computational modeling supports the experimental findings and further explains the geometry-dependent deformation.

Fast Self-Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier.

A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m-2 d-1 atm-1 )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications.

Influence of Graphene Reduction and Polymer Cross-Linking on Improving the Interfacial Properties of Multilayer Thin Films.

Graphene is a versatile composite reinforcement candidate due to its strong mechanical, tunable electrical and optical properties, and chemical stability. However, one drawback is the weak interfacial bonding, which results in weak adhesion to substrates. This could be overcome by adding polymer layers to have stronger adherence to the substrate and between graphene sheets. These multilayer thin films were found to have lower resistance to lateral scratch forces when compared to other reinforcements such as polymer/clay nanocomposites. Two additional processing steps are suggested to improve the scratch resistance of these films: graphene reduction and polymer cross-linking. Graphene/polymer nanocomposites consisting of polyvinylamine (PVAm) and graphene oxide (GO) were fabricated using the layer-by-layer assembly (LbL) technique. The reduced elastic modulus and hardness of PVAm/GO films were measured using nanoindentation. Reducing GO enhances mechanical properties by 60-70% while polymer cross-linking maintains this enhancement. Both graphene reduction and polymer cross-linking show significant improvement to scratch resistance. Particularly, polymer cross-linking leads to films with higher elastic recovery, 50% lower adhesive and plowing friction coefficient, 140 and 50% higher adhesive and shear strength values, respectively, and lower material pileup and scratch width/depth.

Nanomechanical Behavior of High Gas Barrier Multilayer Thin Films.

Nanoindentation and nanoscratch experiments were performed on thin multilayer films manufactured using the layer-by-layer (LbL) assembly technique. These films are known to exhibit high gas barrier, but little is known about their durability, which is an important feature for various packaging applications (e.g., food and electronics). Films were prepared from bilayer and quadlayer sequences, with varying thickness and composition. In an effort to evaluate multilayer thin film surface and mechanical properties, and their resistance to failure and wear, a comprehensive range of experiments were conducted: low and high load indentation, low and high load scratch. Some of the thin films were found to have exceptional mechanical behavior and exhibit excellent scratch resistance. Specifically, nanobrick wall structures, comprising montmorillonite (MMT) clay and polyethylenimine (PEI) bilayers, are the most durable coatings. PEI/MMT films exhibit high hardness, large elastic modulus, high elastic recovery, low friction, low scratch depth, and a smooth surface. When combined with the low oxygen permeability and high optical transmission of these thin films, these excellent mechanical properties make them good candidates for hard coating surface-sensitive substrates, where polymers are required to sustain long-term surface aesthetics and quality.

Bacteria repelling on highly-ordered alumina-nanopore structures.

Bacteria introduce diseases and infections to humans by their adherence to biomaterials, such as implants and surgical tools. Cell desorption is an effective step to reduce such damage. Here, we report mechanisms of bacteria desorption. An alumina nanopore structure (ANS) with pore size of 35 nm, 55 nm, 70 nm, and 80 nm was used as substrate to grow Escherichia coli (E. coli) cells. A bacteria repelling experimental method was developed to quantitatively evaluate the area percentage of adherent bacterial cells that represent the nature of cell adhesion as well as desorption. Results showed that there were two crucial parameters: contact angle and contact area that affect the adhesion/desorption. The cells were found to be more easily repelled when the contact angle increased. The area percentage of adherent bacterial cells decreased with the decrease in the contact area of a cell on ANS. This means that cell accessibility on ANS depends on the contact area. This research reveals the effectiveness of the nanopored structures in repelling cells.

Dynamic adhesive force measurements under vertical and horizontal motions of interacting rough surfaces.

An instrument to measure dynamic adhesive forces between interacting rough surfaces has been developed. It consists of four parts, namely, main instrument body, vertical positioning system with both micrometer and nanometer positioning accuracies, horizontal positioning system with nanometer positioning accuracy, and custom-built high-resolution, and high dynamic bandwidth capacitive force transducer. The vertical piezoelectric actuator (PZT) controls the vertical (approaching and retracting) motion of the upper specimen, while the horizontal PZT controls the horizontal (reciprocal) motion of the lower specimen. The force transducer is placed in line with the upper specimen and vertical PZT, and directly measures the adhesive forces with a root-mean-square load resolution of 1.7 microN and a dynamic bandwidth of 1.7 kHz. The newly developed instrument enables reliable measurements of near-contact and contact adhesive forces for microscale devices under different dynamic conditions. Using the developed instrument, dynamic pull-in and pull-off force measurements were performed between an aluminum-titanium-carbide sphere and a 10 nm thick carbon film disk sample. Three different levels of contact force were investigated; where for each contact force level the vertical velocity of the upper sample was varied from 0.074 to 5.922 microms, while the lower sample was stationary. It was found that slower approaching and retracting velocities result in higher pull-in and pull-off forces. The noncontact attractive force was also measured during horizontal movement of the lower sample, and it was found that the periodic movements of the lower disk sample also affect the noncontact surface interactions.

An improved meniscus surface model for contacting rough surfaces.

Based on the Extended-Maugis-Dugdale (EMD) elastic theory, a single asperity capillary meniscus model considering asperity deformation due to both contact and adhesive forces was developed. Specifically included in the single asperity meniscus model was the solid surface interaction inside the contact area. Subsequently, the single asperity model was coupled with a statistical roughness surface model to develop an improved meniscus surface model applicable to a wide-range of humidity levels and adhesion parameter values. Simulations were performed using typical surfaces found in microelectromechanical systems (MEMS) and magnetic storage hard disk drives to examine the effects of surface roughness and relative humidity. It was found that smoother surfaces give rise to higher adhesive and pull-off forces, and at higher relative humidity levels, the capillary force governs the adhesive behavior. As the humidity decreases, the solid surface interaction increases and needs to be included in the total meniscus adhesion. By integrating the adhesive force-displacement curves, the adhesion energy per unit area was calculated for MEMS surfaces and favorably compared with reported experimental data.

An elastic-plastic hybrid adhesion model for contacting rough surfaces in the presence of molecularly thin lubricant.

The study of adhesion has received considerable attention in recent years, partly due to advances in the design and fabrication of micro/nano devices. Many adhesion investigations are centered on single-spherical-contact models, which include the classic Johnson-Kendall-Roberts (JKR), improved Derjaguin-Muller-Toporov (IDMT), and Maugis-Dugdale (MD) models. Based on the IDMT single-asperity model, adhesive rough surface contact models have also been developed, which are valid for elastic and elastic-plastic contact conditions. A limitation of the IDMT-based models is that they are only valid for application cases with low adhesion parameter values. In this research, a contacting rough surface adhesion model was developed by combining an extended Maugis-Dugdale (EMD) model (which is only valid for elastic contacts) with an IDMT-based elastic-plastic adhesion model. The proposed model, termed the elastic-plastic hybrid adhesion model, is valid for the entire adhesion parameter range and also for elastic-plastic contacts. The proposed model gives results similar to the EMD rough surface model when the contact is primarily elastic. Moreover, the proposed model was compared to an IDMT-based model (ISBL model) and both gave similar results for contacts with low adhesion parameter values. With high adhesion parameter values, the ISBL model fails, whereas the proposed model correctly predicts higher adhesion. Last, based on the stiffness of the external force, the instability for adhesive rough surfaces in contact was also discussed, and it was postulated that a high peak value of the external force stiffness directly relates to the unstable contact process.

Adhesive transition from noncontacting to contacting elastic spheres: extension of the Maugis-Dugdale model.

In this paper, an adhesion model for spherical noncontact is proposed based on the Maugis-Dugdale (MD) adhesive contact model. The proposed noncontact model is combined with the MD contact model, thus providing a full range adhesion model with analytical transition from noncontacting to contacting asperity geometry. The proposed model is favorably compared with the full range improved DMT model for low surface energy values. The transition process from noncontact to contact and the adhesion instability that occurs during this transition are also investigated. It is found that jump-off points are different for displacement control and force control. Moreover, under displacement control, jump-on and jump-off points are different when the adhesion parameter lambda is greater than 0.95, whereas they are identical for lambda<0.95. By curve fitting a relationship between the critical approach under displacement and force control separately and the adhesion parameter lambda, approach prediction equations for jump-on and jump-off under different adhesion levels were obtained.

Adhesive contact based on the Lennard-Jones potential: a correction to the value of the equilibrium distance as used in the potential.

A Lennard-Jones type surface law is commonly used in adhesive contact modeling; however, one of its parameters, namely the equilibrium distance z0, is not well defined. In this paper, a self-consistent method is used to derive the Lennard-Jones surface law from the interatomic Lennard-Jones potential. The parameters of the surface law are directly related to the material lattice parameter and surface energy, and the equilibrium distance z0 values are obtained for various materials. The effect of using the z0 proposed in the present work is demonstrated via the study of adhesive contact behavior for a single sphere and a flat surface, as well as the contact between planar rough surfaces. For pull-off force prediction of the contact between a single sphere and a flat surface, the error of using the z0 suggested in previous studies could be as large as 10% at intermediate ranges of a dimensionless adhesion parameter. For the contact between planar rough surfaces, the error of using the previously proposed z0 is larger for smoother cases, and the prediction of pull-off force could be different by as much as a factor of 5.

Measuring mechanical properties of fine-wire cross-sections used in medical devices.

In this study, it was demonstrated that the nanoindentation technique can be used to measure the elastic modulus and hardness of fine-wire cross-sections with diameters ranging from 100-200 microm. Using miniature optics and a specially developed micrometer positioning system, measurements were successfully performed on the wire cross-sections with an accuracy of 1 microm. Homogeneous wire cross-sections, such as MP35N (high-strength nickel-cobalt alloy), composite wires such as MP35N with a silver core (MP35N/Ag-core), and platinum-clad tantalum (Pt-clad Ta) were studied. From the nanoindentation measurements, the elastic modulus and hardness at different positions and depths were calculated. It was found that both elastic modulus and hardness reached a constant value below the hardened surface, which resulted from mechanical polishing. Material properties obtained from the measurements were compared with the literature values of bulk materials as well as available results on fine wires. The data from the wire cross-sections, especially the uniform material samples, showed that both the elastic modulus and hardness were significantly lower near the outer 10-15 microm of the wire as compared to the rest of the wire, which is due to surface weakening during manufacturing. In addition, both modulus and hardness showed a small but consistent "sawtooth" variation across the diameter of the wires, excluding the outer 10-15 microm, that is postulated to be induced by the distribution of residual stress.