Graphene Flake Self-Assembly Enhancement via Stretchable Platforms and External Mechanical Stimuli

While the green production and application of 2D functional nanomaterials, such as graphene flakes, in films for stretchable and wearable technologies is a promising platform for advanced technologies, there are still challenges involved in the processing of the deposited material to improve properties such as electrical conductivity. In applications such as wearable biomedical and flexible energy devices, the widely used flexible and stretchable substrate materials are incompatible with high-temperature processing traditionally employed to improve the electrical properties, which necessitates alternative manufacturing approaches and new steps for enhancing the film functionality. We hypothesize that a mechanical stimulus, in the form of substrate straining, may provide such a low-energy approach for modifying deposited film properties through increased flake packing and reorientation. To this end, graphene flakes were exfoliated using an unexplored combination of ethanol and cellulose acetate butyrate for morphological and percolative electrical characterization prior to application on polydimethylsiloxane (PDMS) substrates as a flexible and stretchable electrically conductive platform. The deposited percolative free-standing films on PDMS were characterized via in situ resistance strain monitoring and surface morphology measurements over numerous strain cycles, with parameters extracted describing the dynamic modulation of the film’s electrical properties. A reduction in the film resistance and strain gauge factor was found to correlate with the surface roughness and densification of a sample’s (sub)­surface and the applied strain. High surface roughness samples exhibited enhanced reduction in resistance as well as increased sensitivity to strain compared to samples with low surface roughness, corresponding to surface smoothing, which is related to the dynamic settling of graphene flakes on the substrate surface. This procedure of incorporating strain as a mechanical stimulus may find application as a manufacturing tool/step for the routine fabrication of stretchable and wearable devices, as a low energy and compatible approach, for enhancing the properties of such devices for either high sensitivity or low sensitivity of electrical resistance to substrate strain

Direct Ink Writing of Graphene-Based Solutions for Gas Sensing

In the energy industry, there is a great need for novel low-cost gas-sensing solutions. This is particularly true for shale gas operations where there is a need to monitor both performance and compliance with environmental regulations. Specifically, there is a need to monitor the integrity of well casings as oil and gas producers try to understand and mitigate environmental issues, as well as avoid unfair claims against the industry. To address this need, we report studies on the additive fabrication and characterization of a graphene-based gas sensor through multilayer direct ink writing of graphene-based inks. An evaporation-assisted solvent exchange method allows tunability of graphene concentration while the addition of ethyl cellulose (EC) allows tuning of rheological properties in printable ink formulations. Robotically controlled direct ink writing enables the deposition of films with arbitrary size and shape. Printed films incorporated into sensor packages exhibit voltage dependent sensitivity to chemical effects of CH4 and H2 in an Ar environment. Surface analysis of the printed sensors suggests disordered layering and orientation of the graphene flakes because of distributed nondecomposed residues of EC from film processing. Capitalizing on the EC residues to form 3D scaffolding enables the spatial arrangement of graphene flakes. The disordered arrangement of flakes resulting from their interaction with the EC residue scaffolding contributes to increased surface area availability for gas sensing

Coaxial Ceramic Direct Ink Writing on Heterogenous and Rough Surfaces: Investigation of Core–Shell Interactions

In this work, coaxial conductor–ceramic direct ink writing enables the printing of sensitive or encapsulated materials onto heterogeneous and rough substrates. While encasing the core fluid within a stiff ceramic shell, continuity may be maintained, even while printing onto conventionally challenging substrates. Here, we report the development of a coaxial ceramic direct ink writing suite and explore coflow interrelationships based on microfluidic principles. A coaxial nozzle is designed to facilitate the coextrusion of an alumina shell, whereas indium–tin-oxide inks constitute the core. In this manner, a core–shell ceramic element may be printed onto rough substrates for future high-temperature applications. Colloidal inks are engineered to provide the required rheological and sintering performance. Moreover, flow simulations in conjunction with microfluidic coflow principles are used to explore the coaxial printing processing space, thus controlling the core–shell architectures. Physical modeling is further used to analyze core deformations and eccentricity. Simulations are validated experimentally, and the analyses are used to deposit coaxial ceramic features onto heterogeneous, high-temperature ceramic substrates

Robotic Deposition of TiO₂ Films on Flexible Substrates from Hybrid Inks: Investigation of Synthesis–Processing–Microstructure–Photocatalytic Relationships

TiO2 is an important material widely used in optoelectronic devices due to its semiconducting and photocatalytic properties, nontoxicity, and chemically inert nature. Some indicative applications include water purification systems and energy harvesting. The use of solution, water-based inks for the direct writing of TiO2 on flexible substrates is of paramount importance since it enables low-cost and low-energy intensive large-area manufacturing, compatible with roll-to-roll processing. In this work we study the effect of crystalline TiO2 and polymer addition on the rheological and direct writing properties of Ti-organic/TiO2 inks. We also report on the bridging crystallite formation from the Ti-organic precursor into the TiO2 crystalline phase, under ultraviolet (UV) exposure or mild heat treatments up to 150 °C. Such crystallite formation is found to be enhanced by polymers with strong polarity and pKα such as polyacrylic acid (PAA). X-ray diffraction (XRD) coupled with Raman and X-ray photoelectron (XPS) spectroscopy are used to investigate the crystalline-phase transformation dependence based on the initial TiO2 crystalline-phase concentration and polymer addition. Transmission electron microscopy imaging and selected area electron diffraction patterns confirm the crystalline nature of such bridging printed structures. The obtained inks are patterned on flexible substrates using nozzle-based robotic deposition, a lithography-free, additive manufacturing technique that allows the direct writing of material in specific, digitally predefined, substrate locations. Photocatalytic degradation of methylene blue solutions highlights the potential of the studied films for chemical degradation applications, from low-cost environmentally friendly materials systems

Direct Writing of a Titania Foam in Microgravity for Photocatalytic Applications

This work explores the potential for additive manufacturing to be used to fabricate ultraviolet light-blocking or photocatalytic materials with in situ resource utilization, using a titania foam as a model system. Direct foam writing was used to deposit titania-based foam lines in microgravity using parabolic flight. The wet foam was based on titania primary particles and a titania precursor (Ti (IV) bis(ammonium lactato) dihydroxide). Lines were also printed in Earth gravity and their resulting properties were compared with regard to average cross-sectional area, height, and width. The cross-sectional height was found to be higher when printing at low speeds in microgravity compared to Earth gravity, but lower when printing at high speeds in microgravity compared to Earth gravity. It was also observed that volumetric flow rate was generally higher when writing in Earth gravity compared to microgravity. Additionally, heterogeneous photocatalytic degradation of methylene blue was studied to characterize the foams for water purification and was found to generally increase as the foam heat treatment temperature increased. Optical and scanning electron microscopies were used to observe foam morphology. X-ray diffraction spectroscopy was used to study the change in crystallinity with respect to temperature. Contact angle of water was found to increase on the surface of the foam as ultraviolet light exposure time increased. Additionally, the foam blocked more ultraviolet light over time when exposed to ultraviolet radiation. Finally, bubble coarsening measurements were taken to observe bubble radius growth over time

User-Tailored Metal–Organic Frameworks as Supports for Carbonic Anhydrase

Carbonic anhydrase (CA) was previously proposed as a green alternative for biomineralization of carbon dioxide (CO2). However, enzyme’s fragile nature when in synthetic environment significantly limits such industrial application. Herein, we hypothesized that CA immobilization onto flexible and hydrated “bridges” that ensure proton-transfer at their interfaces leads to improved activity and kinetic behavior and potentially increases enzyme’s feasibility for industrial implementation. Our hypothesis was formulated considering that water plays a key role in the CO2 hydration process and acts as both the reactant as well as the rate-limiting step of the CO2 capture and transformation process. To demonstrate our hypothesis, two types of user-synthesized organic metallic frameworks [metal–organic frameworks (MOFs), one hydrophilic and one hydrophobic] were considered as model supports and their surface characteristics (i.e., charge, shape, curvature, size, etc.) and influence on the immobilized enzyme’s behavior were evaluated. Morphology, crystallinity and particle size, and surface area of the model supports were determined by scanning electron microscopy, dynamic light scattering, and nitrogen adsorption/desorption measurements, respectively. Enzyme activity, kinetics, and stability at the supports interfaces were determined using spectroscopical analyses. Analysis showed that enzyme functionality is dependent on the support used in the immobilization process, with the enzyme immobilized onto the hydrophilic support retaining 72% activity of the free CA, when compared with that immobilized onto the hydrophobic one that only retained about 28% activity. Both CA–MOF conjugates showed good storage stability relative to the free enzyme in solution, with CA immobilized at the hydrophilic support also revealing increased thermal stability and retention of almost all original enzyme activity even after heating treatment at 70 °C. In contrast, free CA lost almost half of its original activity when subject to the same conditions. This present work suggests that MOFs tunable hydration conditions allow high enzyme activity and stability retention. Such results are expected to impact CO2 storage and transformation strategies based on CA and potentially increase user-integration of enzyme-based green technologies in mitigating global warming

User-Tailored Metal–Organic Frameworks as Supports for Carbonic Anhydrase

Carbonic anhydrase (CA) was previously proposed as a green alternative for biomineralization of carbon dioxide (CO2). However, enzyme’s fragile nature when in synthetic environment significantly limits such industrial application. Herein, we hypothesized that CA immobilization onto flexible and hydrated “bridges” that ensure proton-transfer at their interfaces leads to improved activity and kinetic behavior and potentially increases enzyme’s feasibility for industrial implementation. Our hypothesis was formulated considering that water plays a key role in the CO2 hydration process and acts as both the reactant as well as the rate-limiting step of the CO2 capture and transformation process. To demonstrate our hypothesis, two types of user-synthesized organic metallic frameworks [metal–organic frameworks (MOFs), one hydrophilic and one hydrophobic] were considered as model supports and their surface characteristics (i.e., charge, shape, curvature, size, etc.) and influence on the immobilized enzyme’s behavior were evaluated. Morphology, crystallinity and particle size, and surface area of the model supports were determined by scanning electron microscopy, dynamic light scattering, and nitrogen adsorption/desorption measurements, respectively. Enzyme activity, kinetics, and stability at the supports interfaces were determined using spectroscopical analyses. Analysis showed that enzyme functionality is dependent on the support used in the immobilization process, with the enzyme immobilized onto the hydrophilic support retaining 72% activity of the free CA, when compared with that immobilized onto the hydrophobic one that only retained about 28% activity. Both CA–MOF conjugates showed good storage stability relative to the free enzyme in solution, with CA immobilized at the hydrophilic support also revealing increased thermal stability and retention of almost all original enzyme activity even after heating treatment at 70 °C. In contrast, free CA lost almost half of its original activity when subject to the same conditions. This present work suggests that MOFs tunable hydration conditions allow high enzyme activity and stability retention. Such results are expected to impact CO2 storage and transformation strategies based on CA and potentially increase user-integration of enzyme-based green technologies in mitigating global warming

Stabilizing Zn Anodes by Molecular Interface Engineering with Amphiphilic Triblock Copolymer

Aqueous Zn-based electrochemical technologies hold promise for large-scale energy storage applications, yet challenges persist in the unsatisfied Zn reversibility arising from an unstable Zn/electrolyte interface. Here, we employ molecular interface engineering using amphiphilic Pluronic triblock copolymers as electrolyte additives to stabilize the Zn anodes. With a balanced hydrophilic–hydrophobic nature, Pluronic F127 adsorbed on the Zn surface constructs a hydrodynamic interphase, where the hydrophobic PPO center shields the Zn surface from water-induced side reactions, while PEO side blocks guide the homogeneous Zn2+ redistribution. Additionally, F127 contributes to the Zn2+ solvation structure to weaken the water activity at the interfacial region. As a result, F127 additive enables cycling durability over 9300 and 3100 h at 1 and 5 mA cm–2, respectively, and considerable cyclability with high-capacity retention across a wide current density range in Zn||VO2 full cells. This study highlights the potential of amphiphilic block copolymers in stabilizing metallic anode interfaces in aqueous electrolytes

Short-Term Pulmonary Toxicity Assessment of Pre- and Post-incinerated Organomodified Nanoclay in Mice

Organomodified nanoclays (ONCs) are increasingly used as filler materials to improve nanocomposite strength, wettability, flammability, and durability. However, pulmonary risks associated with exposure along their chemical lifecycle are unknown. This study’s objective was to compare pre- and post-incinerated forms of uncoated and organomodified nanoclays for potential pulmonary inflammation, toxicity, and systemic blood response. Mice were exposed <i>via</i> aspiration to low (30 μg) and high (300 μg) doses of preincinerated uncoated montmorillonite nanoclay (CloisNa), ONC (Clois30B), their respective incinerated forms (I-CloisNa and I-Clois30B), and crystalline silica (CS). Lung and blood tissues were collected at days 1, 7, and 28 to compare toxicity and inflammation indices. Well-dispersed CloisNa caused a robust inflammatory response characterized by neutrophils, macrophages, and particle-laden granulomas. Alternatively, Clois30B, I-Clois30B, and CS high-dose exposures elicited a low grade, persistent inflammatory response. High-dose Clois30B exposure exhibited moderate increases in lung damage markers and a delayed macrophage recruitment cytokine signature peaking at day 7 followed by a fibrotic tissue signature at day 28, similar to CloisNa. I-CloisNa exhibited acute, transient inflammation with quick recovery. Conversely, high-dose I-Clois30B caused a weak initial inflammatory signal but showed comparable pro-inflammatory signaling to CS at day 28. The data demonstrate that ONC pulmonary toxicity and inflammatory potential relies on coating presence and incineration status in that coated and incinerated nanoclay exhibited less inflammation and granuloma formation than pristine montmorillonite. High doses of both pre- and post-incinerated ONC, with different surface morphologies, may harbor potential pulmonary health hazards over long-term occupational exposures