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.

A Review on Progress, Challenges, and Prospects of Material Jetting of Copper and Tungsten.

Copper (Cu) and tungsten (W) possess exceptional electrical and thermal conductivity properties, making them suitable candidates for applications such as interconnects and thermal conductivity enhancements. Solution-based additive manufacturing (SBAM) offers unique advantages, including patterning capabilities, cost-effectiveness, and scalability among the various methods for manufacturing Cu and W-based films and structures. In particular, SBAM material jetting techniques, such as inkjet printing (IJP), direct ink writing (DIW), and aerosol jet printing (AJP), present a promising approach for design freedom, low material wastes, and versatility as either stand-alone printers or integrated with powder bed-based metal additive manufacturing (MAM). Thus, this review summarizes recent advancements in solution-processed Cu and W, focusing on IJP, DIW, and AJP techniques. The discussion encompasses general aspects, current status, challenges, and recent research highlights. Furthermore, this paper addresses integrating material jetting techniques with powder bed-based MAM to fabricate functional alloys and multi-material structures. Finally, the factors influencing large-scale fabrication and potential prospects in this area are explored.

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.

All-Ceramic Passive Wireless Temperature Sensor Realized by Tin-Doped Indium Oxide (ITO) Electrodes for Harsh Environment Applications.

In this work, an all-ceramic passive wireless inductor-capacitor (LC) resonator was presented for stable temperature sensing up to 1200 °C in air. Instead of using conventional metallic electrodes, the LC resonators are modeled and fabricated with thermally stable and highly electroconductive ceramic oxide. The LC resonator was modeled in ANSYS HFSS to operate in a low-frequency region (50 MHz) within 50 × 50 mm geometry using the actual material properties of the circuit elements. The LC resonator was composed of a parallel plate capacitor coupled with a planar inductor deposited on an Al2O3 substrate using screen-printing, and the ceramic pattern was sintered at 1250 °C for 4 h in an ambient atmosphere. The sensitivity (average change in resonant frequency with respect to temperature) from 200-1200 °C was ~170 kHz/°C. The temperature-dependent electrical conductivity of the tin-doped indium oxide (ITO, 10% SnO2 doping) on the quality factor showed an increase of Qf from 36 to 43 between 200 °C and 1200 °C. The proposed ITO electrodes displayed improved sensitivity and quality factor at elevated temperatures, proving them to be an excellent candidate for temperature sensing in harsh environments. The microstructural analysis of the co-sintered LC resonator was performed using a scanning electron microscope (SEM) which showed that there are no cross-sectional and topographical defects after several thermal treatments.

Direct foam writing in microgravity.

Herein we report 2D printing in microgravity of aqueous-based foams containing metal oxide nanoparticles. Such hierarchical foams have potential space applications, for example for in situ habitat repair work, or for UV shielding. Foam line patterns of a TiO2-containing foam have been printed onto glass substrates via Direct Foam Writing (DFW) under microgravity conditions through a parabolic aircraft flight. Initial characterization of the foam properties (printed foam line width, bubble size, etc.) are presented. It has been found that gravity plays a significant role in the process of direct foam writing. The foam spread less over the substrate when deposited in microgravity as compared to Earth gravity. This had a direct impact on the cross-sectional area and surface roughness of the printed lines. Additionally, the contact angle of deionized water on a film exposed to microgravity was higher than that of a film not exposed to microgravity, due to the increased surface roughness of films exposed to microgravity.

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.

On the unusual amber coloration of nanoporous sol-gel processed Al-doped silica glass: An experimental study.

Silica is the most abundant component on the earth's surface. It plays an important role in many natural processes. Silica is also a critical material for a wide range of technical applications such as in optics and electronics. In this work, we discuss our recent experimental observation of the unusual amber coloration of aluminum doped sol-gel glass that has not been reported in the past. We characterized Al-doped sol-gel glasses, prepared at different sintering temperature, using a plethora of techniques to investigate the origin of this unusual coloration and to understand their structural and chemical properties. We used these experimental results to test a number of possible coloring mechanisms. The results suggested this coloring is likely caused by temperature-dependent aluminum-associated defect centers associated with different amorphous-to-crystalline ratios of the annealed sol-gel silica glass structures.

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.

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 via 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.

Taking Professional Development From 2D to 3D: Design-Based Learning, 2D Modeling, and 3D Fabrication for Authentic Standards-Aligned Lesson Plans.

There is currently significant interest in 3D fabrication in middle school classrooms. At its best 3D printing can be utilized in authentic design projects that integrate math, science, and technology, which facilitate deep learning by students. In essence, students are able to tinker in a virtual world using 3D design software and then tinker in the real world using printed parts. We describe a professional development activity we designed to enable middle school teachers who had taken part in a three-year Math Science Partnership program to authentically integrate 3D printing into design-based lessons. We include some examples of successful design-based lesson plans.

Early Assessment and Correlations of Nanoclay's Toxicity to Their Physical and Chemical Properties.

Nanoclays' functionalization with organic modifiers increases their individual barrier properties, thermal stability, and mechanical properties and allows for ease of implementation in food packaging materials or medical devices. Previous reports have shown that, while organic modifiers integration between the layered mineral silicates leads to nanoclays with different degrees of hydrophobicity that become easily miscible in polymers, they could also pose possible effects at inhalation or ingestion routes of exposure. Through a systematic analysis of three organically modified and one pristine nanoclay, we aimed to relate for the first time the physical and chemical characteristics, determined via microscopical and spectroscopical techniques, with the potential of these nanoclays to induce deleterious effects in in vitro cellular systems, i.e. in immortalized and primary human lung epithelial cell lines. To derive information on how functionalization could lead to toxicological profiles throughout nanoclays' life cycle, both as-received and thermally degraded nanoclays were evaluated. Our analysis showed that the organic modifiers chemical composition influenced both the physical and chemical characteristics of the nanoclays as well as their toxicity. Overall, when cells were exposed to nanoclays with organic modifiers containing bioreactive groups, they displayed lower cellular numbers as well more elongated cellular morphologies relative to the pristine nanoclay and the nanoclay containing a modifier with long carbon chains. Additionally, thermal degradation caused loss of the organic modifiers as well as changes in size and shape of the nanoclays, which led to changes in toxicity upon exposure to our model cellular systems. Our study provides insight into the synergistic effects of chemical composition, size, and shape of the nanoclays and their toxicological profiles in conditions that mimic exposure in manufacturing and disposal environments, respectively, and can help aid in safe-by-design manufacturing of nanoclays with user-controlled functionalization and lower toxicity levels when food packaging applications are considered.

Toxicity evaluations of nanoclays and thermally degraded byproducts through spectroscopical and microscopical approaches.

BACKGROUND: Montmorillonite is a type of nanoclay that originates from the clay fraction of the soil and is incorporated into polymers to form nanocomposites with enhanced mechanical strength, barrier, and flammability properties used for food packaging, automotive, and medical devices. However, with implementation in such consumer applications, the interaction of montmorillonite-based composites or derived byproducts with biological systems needs to be investigated. METHODS: Herein we examined the potential of Cloisite Na+ (pristine) and Cloisite 30B (organically modified montmorillonite nanoclay) and their thermally degraded byproducts' to induce toxicity in model human lung epithelial cells. The experimental set-up mimicked biological exposure in manufacturing and disposal areas and employed cellular treatments with occupationally relevant doses of nanoclays previously characterized using spectroscopical and microscopical approaches. For nanoclay-cellular interactions and for cellular analyses respectively, biosensorial-based analytical platforms were used, with induced cellular changes being confirmed via live cell counts, viability assays, and cell imaging. RESULTS: Our analysis of byproducts' chemical and physical properties revealed both structural and functional changes. Real-time high throughput analyses of exposed cellular systems confirmed that nanoclay induced significant toxic effects, with Cloisite 30B showing time-dependent decreases in live cell count and cellular viability relative to control and pristine nanoclay, respectively. Byproducts produced less toxic effects; all treatments caused alterations in the cell morphology upon exposure. CONCLUSIONS: Our morphological, behavioral, and viability cellular changes show that nanoclays have the potential to produce toxic effects when used both in manufacturing or disposal environments. GENERAL SIGNIFICANCE: The reported toxicological mechanisms prove the extensibility of a biosensorial-based platform for cellular behavior analysis upon treatment with a variety of nanomaterials.

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.