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At least 811 records · Page 45

Interactions between nested sunspots. 1: The formation and breakup of a delta-type sunspot

We investigate a nest of sunspots in which three ordinary bipolar pairs of sunspots are aligned collinearly. The usual spreading action of the growing regions brings two spots of leading polarity together (p-p collision) and forces the leading and trailing spots of the two interior regions to overlap inot a single penumbra (p-f collision), thus forming a delta-spot. We examine digitally processed images from the Ottawa River Solar Observatory of two related events inside the delta-spot 5 days after the p-f collision begins: the violent disruption of the f-umbra, and the formation in less than a day of an hydrogen-alpha filament. The evolutionary changes in shape, area, relative motions, and brightness that we measure for each spot in the elongated nest are more compatible with Parker's (1979a) hypothesis of a sunspot as a cluster of flux tubes held together by downdrafts than with the notion of a sunspot as a monolithic plug of magnetic flux. From chromospheric developments over the delta-spot, we show that a shearing motion along a polarity inversion is more effective than convergence for creating a chromospheric filament. We invoke the release of an instability, triggered by a sequence of processes lasting 1 day or more, to explain the disruption of the f-umbra in this delta-spot. We show that the sequence is initiated when the colliding p-f umbrae reach a critical separation around 3200 +/- 200 km. We present a descriptive model in which the reconnected magnetic fields block vertical transport of convective heat flux just beneath the photosphere. We observe the formation of an unusual type of penumbra adjacent to the f-polarity portion of this delta-spot just before its disruption. A tangential penumbral band grows out of disordered matter connected to the f-umbra. We present this as evidence for the extrusion of umbral magnetic flux by thermal plumes rising through a loosely bound umbra.

Gaizauskas, V.↗

Porous Polymer Structures with Tunable Mechanical Properties Using a Water Emulsion Ink

Recently, the manufacturing of porous polydimethylsiloxane (PDMS) with engineered porosity has gained considerable interest due to its tunable material properties and diverse applications. An innovative approach to control the porosity of PDMS is to use transient liquid phase water to improve its mechanical properties, which has been explored in this work. Adjusting the ratios of deionized water to the PDMS precursor during blending and subsequent curing processes allows for controlled porosity, yielding water emulsion foam with tailored properties. The PDMS-to-water weight ratios were engineered ranging from 100:0 to 10:90, with the 65:35 specimen exhibiting the best mechanical properties with a Young’s Modulus of 1.17 MPa, energy absorption of 0.33 MPa, and compressive strength of 3.50 MPa. This led to a porous sample exhibiting a 31.46% increase in the modulus of elasticity over a bulk PDMS sample. Dowsil SE 1700 was then added, improving the storage capabilities of the precursor. The optimal storage temperature was probed, with -60 °C resulting in great pore stability throughout a three-week duration. The possibility of using these water emulsion foams for paste extrusion additive manufacturing (AM) was also analyzed by implementing a rheological modifier, fumed silica. Fumed silica’s impact on viscosity was examined, revealing that 9 wt% of silica demonstrates optimal rheological behaviors for AM, bearing a viscosity of 10,290 Pa·s while demonstrating shear-thinning and thixotropic behavior. This study suggests that water can be used as pore-formers for PDMS in conjunction with AM to produce engineered materials and structures for aerospace, medical, and defense industries as sensors, microfluidic devices, and lightweight structures.

36 MATERIALS SCIENCE↗

Development of Functionally Graded Material Capabilities in Large-scale Extrusion Deposition Additive Manufacturing

Additive manufacturing’s (AM) layer-by-layer nature is well-suited to the production of Functionally Graded Materials (FGM) with discrete material boundaries. Extrusion deposition is especially advantageous since multiple nozzles easily accommodate the inclusion of additional materials. However, discrete interfaces and sudden composition changes can limit the functionality of a printed part through inherently weak bonding. Furthermore, same-layer transitions are not only difficult to execute, but also further amplify structural weaknesses by creating multiple discrete interfaces. Therefore, successfully implementing a blended, continuous gradient will greatly advance the applicability of FGM in additive manufacturing. The pellet-fed nature and integrated screw design of the Big Area Additive Manufacturing system enables material mixing needed for development of this capability. Using constituent content analysis, this study evaluates the transition behavior of a neat ABS/CF-ABS material pair and characterizes the repeatability of the mixing and printing process, which ultimately leads to control of site-specific material deposition and properties.

Brackett, James↗

NASA-UVA Light Aerospace Alloy and Structures Technology program (LA2ST)

The objective of the LA2ST Program is to conduct interdisciplinary graduate student research on the performance of next generation, light-weight aerospace alloys, composites, and thermal gradient structures in collaboration with NASA-Langley researchers. The general aim is to produce relevant data and basic understanding of material mechanical response, environment/corrosion behavior, and microstructure; new monolithic and composite alloys; advanced processing methods; new solid and fluid mechanics analyses; measurement and modeling advances; and a pool of educated students for aerospace technologies. Specific technical objectives are presented for each of the following research projects: time-temperature dependent fracture in advanced wrought ingot metallurgy, and spray deposited aluminum alloys; cryogenic temperature effects on the deformation and fracture of Al-Li-Cu-In alloys; effects of aging and temperature on the ductile fracture of AA2095 and AA2195; mechanisms of localized corrosion in alloys 2090 and 2095; hydrogen interactions in aluminum-lithium alloys 2090 and selected model alloys; mechanisms of deformation and fracture in high strength titanium alloys (effects of temperature and hydrogen and effects of temperature and microstructure); evaluations of wide-panel aluminum alloy extrusions; Al-Si-Ge alloy development; effects of texture and precipitates on mechanical property anisotropy of Al-Cu-Mg-X alloys; damage evolution in polymeric composites; and environmental effects in fatigue life prediction - modeling crack propagation in light aerospace alloys.

Starke, Edgar A., Jr.↗

In Situ Monitoring of Direct Ink Write Process Using Electromagnetic Resonant Coupling

Additive manufacturing (AM) of multi-material objects enables the design of complex 3D architectures such as printed electronics and devices. The ability to detect the composition of multi-material printed inks in real time is an emerging need for a wide range of manufacturing applications. This study demonstrates the feasibility of using an in situ sensor to locally measure the composition of inks as they are being printed to facilitate greater control over the resulting properties and functionality of printed materials. Dielectric properties of microscale embedded metal particles in a dielectric matrix are measured and characterized as a function of particle size, shape, volume percentage and frequency. Results show that particle shape has a much greater influence on impedance measurements than the particle size. Measurements are found to agree with calculations based on an anisotropic Maxwell-Garnett dielectric function model. The resulting data can be used to generate a calibration curve correlating metal loading with impedance or capacitance and thus applied as an in situ sensor for compositional measurements during extrusion-based AM.

36 MATERIALS SCIENCE↗

Digital bead modeling for wire-arc directed energy deposition

Prediction of 2D cross-section and full 3D geometry for stacked weld beads is critical for the outcome of wire-arc directed energy deposition (DED) parts; however, most additive path planning software packages model beads as extrusions of a rectangle. Weld beads are not rectangular, and the resulting shape is dependent upon physics effects at the moment of deposition. Physics phenomena such as the geometry of the underlying surface, the heat input of the welding mode, and the direction of gravity contribute to bead shape. Here, this paper presents a novel implicit modeling method that discretizes a 2D area or 3D volume of space into pixels or voxels and constructs fields based on these physics phenomena. The fields are combined using a weighting scheme trained on 3D scan measurements of welds and wire-arc DED prints. Pixels or voxels are added until the known amount of deposited volume has been achieved. Thereby, a strong conservation of mass principle is applied to the process. Utilizing machine learning techniques, the present model can be trained on a database of scans allowing for the representation of a wide variety of prints. Results show that this method can produce predictions with realistic bead morphology and sub-millimeter form error.

Bead geometry modeling↗

Thermal Conductivity of Ultem(TradeMark)/Carbon Nanofiller Blends

In an effort to improve polymer thermal conductivity (TC), Ultem(TradeMark) 1000 was compounded with nano-fillers of carbon allotropes. Ultem(TradeMark) 1000 was selected since it is both solution and melt processable. As-received and modified multiwalled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNF) and expanded graphite (EG) were investigated. MWCNTs were modified by functionalizing the surface through oxidization with concentrated acids, mixing with an alkyl bromide, and addition of alkyl and phosphorus compounds after initial treatment with n-butyl lithium. Functionalization was performed to improve the TC compatibility between the resin and MWCNTs. It was postulated that this may provide an improved interface between the MWCNT and the polymer which would result in enhanced TC. The nano-fillers were mixed with Ultem(TradeMark) 1000 in the melt and in solution at concentrations ranging from 5 to 40 wt%. Ribbons were extruded from the blends to form samples where the nano-fillers were aligned to some degree in the extrusion direction. Samples were also fabricated by compression molding resulting in random orientation of the nano-fillers. Thermal properties of the samples were evaluated by Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analyzer (TGA). Tensile properties of aligned samples were determined at room temperature. The specimens were cut from the ribbons in the extrusion direction; hence the nano-fillers are somewhat aligned in the direction of stress. Typically it was observed that melt mixed samples exhibited superior mechanical properties compared to solution mixed samples. As expected, increased filler loading led to increased modulus and decreased elongation with respect to the neat polymer. The degree of dispersion and alignment of the nano-fillers was determined by high-resolution scanning electron microscopy (HRSEM). HRSEM of the ribbons revealed that the MWCNTs and CNFs were predominantly aligned in the flow direction. The TC of the samples was measured using a Nanoflash(TradeMark) instrument. Since the MWCNTs and CNF are anisotropic, the TC was expected to be different in the longitudinal (parallel to the nanotube and fiber axis) and transverse (perpendicular to the nanotube and fiber axis) directions. The extruded ribbons provided samples for transverse TC measurements. However, to determine the TC in the longitudinal direction, the ribbons needed to be stacked and molded under 1.7 MPa and 270 C. Samples were then obtained by cutting the molded block with a diamond saw. The largest TC improvement was achieved for aligned samples when the measurement was performed in the direction of MWCNT and CNF alignment (i.e. longitudinal axis). Unaligned samples also showed a significant improvement in TC and may be potentially useful in applications when it is not possible to align the nano-filler. The results of this study will be presented.

Ghose, S.↗

An Innovative Accident Tolerant LWR Fuel Rod Design Based on Uranium-Molybdenum Metal Alloy

The US Department of Energy is developing a uranium-molybdenum metal alloy Enhanced Accident Tolerant Fuel concept for Light Water Reactor applications that provides improved fuel performance during normal operation, anticipated operational occurrences, and postulated accidents. The high initial uranium atom density, the high thermal conductivity, and a low heat capacity permit a U-Mo-based fuel assembly to meet important design and safety requirements. These attributes also result in a fuel design that can satisfy increased fuel utilization demands and allow for improved accident tolerance in LWRs. This paper summarizes the results obtained from the on-going activities to; 1) evaluate the impact of the U-10wt%Mo thermal properties on operational and accident safety margins, 2) produce a triple extrusion of stainless steel cladding/niobium liner/U-10Mo fuel rod specimen and 3) test the high temperature water corrosion of rodlet samples containing a drilled hole in the cladding. Characterization of the cladding and liner thickness uniformity, microstructural features of the U-Mo gamma phase, and the metallurgical bond between the component materials will be presented. The results from corrosion testing will be discussed which yield insights into the resistance to attack by water ingress during high temperature water exposure for the triple extruded samples containing a drilled hole. These preliminary evaluations find that the U-10Mo fuel design concept has many beneficial features that can meet or improve conventional LWR fuel performance requirements under normal operation, AOOs, and postulated accidents. The viability of a deployable U-Mo fuel design hinges on demonstrating that fabrication processes and alloying additions can produce acceptable irradiation stability during normal operation and accident conditions and controlled metal-water reaction rates in the unlikely event of a cladding perforation. In the area of enhanced accident tolerance, a key objective is to establish that the lower stored energy of the U-Mo fuel design can provide the emergency core cooling systems the opportunity to maintain the reactor core in a coolable geometry following an accident.

Accident tolerance fuel↗

Highly oriented carbon fiber–polymer composites via additive manufacturing

Additive manufacturing, diverging from traditional manufacturing techniques, such as casting and machining materials, can handle complex shapes with great design flexibility without the typical waste. Although this technique has been mainly used for rapid prototyping, interest is growing in using this method to directly manufacture actual parts of complex shape. To use 3D-printing additive manufacturing in wide spread applications, the technique and the feedstock materials require improvements to meet the mechanical requirements of load-bearing components. Thus, we investigated the short fiber (0.2 mm to 0.4 mm) reinforced acrylonitrile-butadiene-styrene composites as a feedstock for 3D-printing in terms of their processibility, microstructure and mechanical performance; and also provided comparison with traditional compression molded composites. The tensile strength and modulus of 3D-printed samples increased ~115% and ~700%, respectively. 3D-printer yielded samples with very high fiber orientation in printing direction (up to 91.5 %), whereas, compression molding process yielded samples with significantly less fiber orientation. Microstructure-mechanical property relationships revealed that although the relatively high porosity is observed in the 3D-printed composites as compared to those produced by the conventional compression molding technique, they both exhibited comparable tensile strength and modulus. Furthermore, this phenomena is explained based on the changes in fiber orientation, dispersion and void formation.

36 MATERIALS SCIENCE↗

Multifunctional Polymers and Composites for Aerospace Applications

System needs and challenges for commercial aviation and space exploration are constantly changing. Multifunctional materials are ideal for aerospace applications because their integration into structural components has potential to not only improve efficiency, but it can also increase payload and mission capabilities without the burden of significant additions to mass and volume. Multi-constituent materials will play an important role in enabling structures with the potential to demonstrate true multi-functionality; however, modifications to many mature polymer processing methods may be necessary. This presentation will cover multifunctional materials development efforts underway at the NASA Glenn Research Center related to formulating and characterizing novel electrical insulation for high voltage aircraft. Incorporating functionality into the reinforcement material is another materials development technique that will be discussed, which includes braiding with hybrid fibers to enhance toughness in composite structures, stitching with carbon nanotube yarns to make durable electrically conductive textiles, and treating fabrics with shear thickening fluid suspensions to produce impact-resistant inflatable habitats.

multi-functional composites↗

Compositionally graded aluminum-silicon alloy fabricated via friction extrusion

Herein, a novel solid-phase gradient alloying technique was developed for a high throughput composition-microstructure-mechanical property assessment. Friction extrusion of a two-piece billet setup facilitated the formation of a seamless compositionally graded aluminum (Al)-silicon (Si) extrudate rod, with Si concentration in Al matrix gradually increasing from ~1 at% at one end to ~7 at% at the other end of the rod. We observed a strong dependence of the Al grain size, morphology, and texture on the Si concentration. The Si particles pinned the recrystallized grain boundaries resulting in refined (< 10 µm) and textured grains in the high Si content region, while the Al grains in the low Si region are equiaxed, randomly textured, and with a larger average size (~50 µm). The hardness of Al-Si gradient extrudate increases by ~50% percent with a 6 at% increase in Si content due to Hall Petch and particle strengthening effects. Our approach demonstrates the use of a solid phase processing technique to successfully produce a defect-free continuously compositionally graded bulk components thus overcoming the limitations of porosity and material heterogeneities commonly observed in other techniques such as by additive laser deposition.

36 MATERIALS SCIENCE↗

Using Digital Image Correlation for Material Testing at Cryogenic Temperatures

Recent efforts were made to parametrize an aluminum alloy at cryogenic temperatures to calibrate finite element models simulating material deformation. Digital image correlation (DIC) was used to measure material properties using front/back strains of specimens during tensile tests. Data acquired from DIC was compared to physical extensometer measurements. Two camera pairs (front and back) were mounted via aluminum extrusion to the exterior of an environmental chamber of a hydraulic test stand. Images were taken through single-pane optical glass windows of the environment chamber. Positive pressure bags encased the cameras, attaching to the perimeter of the glass to keep out moisture and prevent windows from frosting. Figure 1 shows the environmental setup and the camera setup during cryogenic testing. Some of the challenges during testing at cryogenic temperatures include the gaseous flow of liquid nitrogen in the optical path of the mounted cameras, frost buildup on the windows as seen in Figure 1b, and frost on the test coupon. The temperature gradient present during the introduction of liquid nitrogen into the chamber can increase the projection error of images captured of the specimen. Figure 2 shows the estimated projection error from DIC as a function of temperature during the cool down process. This presentation addresses some of the concerns and observations when using DIC for testing at cryogenic temperatures using methods of isolated camera system and techniques for maintaining the glass panel clear from frost.

Joseph Cochran↗

Constraining the Magmatic System at Mount St. Helens (2004-2008) Using Bayesian Inversion With Physics-Based Models Including Gas Escape and Crystallization

Physics-based models of volcanic eruptions track conduit processes as functions of depth and time. When used in inversions, these models permit integration of diverse geological and geophysical data sets to constrain important parameters of magmatic systems. We develop a 1-D steady state conduit model for effusive eruptions including equilibrium crystallization and gas transport through the conduit and compare with the quasi-steady dome growth phase of Mount St. Helens in 2005. Viscosity increase resulting from pressure-dependent crystallization leads to a natural transition from viscous flow to frictional sliding on the conduit margin. Erupted mass flux depends strongly on wall rock and magma permeabilities due to their impact on magma density. Including both lateral and vertical gas transport reveals competing effects that produce nonmonotonic behavior in the mass flux when increasing magma permeability. Using this physics-based model in a Bayesian inversion, we link data sets from Mount St. Helens such as extrusion flux and earthquake depths with petrological data to estimate unknown model parameters, including magma chamber pressure and water content, magma permeability constants, conduit radius, and friction along the conduit walls. Even with this relatively simple model and limited data, we obtain improved constraints on important model parameters. We find that the magma chamber had low (<5 wt %) total volatiles and that the magma permeability scale is well constrained at ~10 –11.4 m 2 to reproduce observed dome rock porosities. Here, compared with previous results, higher magma overpressure and lower wall friction are required to compensate for increased viscous resistance while keeping extrusion rate at the observed value.

58 GEOSCIENCES↗

Additive Manufacturing of Poly(phenylene Sulfide) Aerogels via Simultaneous Material Extrusion and Thermally Induced Phase Separation

Abstract Additive manufacturing (AM) of aerogels increases the achievable geometric complexity, and affords fabrication of hierarchically porous structures. In this work, a custom heated material extrusion (MEX) device prints aerogels of poly(phenylene sulfide) (PPS), an engineering thermoplastic, via in situ thermally induced phase separation (TIPS). First, pre‐prepared solid gel inks are dissolved at high temperatures in the heated extruder barrel to form a homogeneous polymer solution. Solutions are then extruded onto a room‐temperature substrate, where printed roads maintain their bead shape and rapidly solidify via TIPS, thus enabling layer‐wise MEX AM. Printed gels are converted to aerogels via postprocessing solvent exchange and freeze‐drying. This work explores the effect of ink composition on printed aerogel morphology and thermomechanical properties. Scanning electron microscopy micrographs reveal complex hierarchical microstructures that are compositionally dependent. Printed aerogels demonstrate tailorable porosities (50.0–74.8%) and densities (0.345–0.684 g cm −3 ), which align well with cast aerogel analogs. Differential scanning calorimetry thermograms indicate printed aerogels are highly crystalline (≈43%), suggesting that printing does not inhibit the solidification process occurring during TIPS (polymer crystallization). Uniaxial compression testing reveals that compositionally dependent microstructure governs aerogel mechanical behavior, with compressive moduli ranging from 33.0 to 106.5 MPa.

Chemistry↗

Magnesium Technology 2020

Magnesium and its alloys are being investigated widely for applications that require extraordinarily high strength-to-weight ratio, vibration damping, electromagnetic shielding, reduction in carbon footprint, sustainability improvements, and low toxicity. In the past decade or so, this drive has led to increased adoption of magnesium and its alloys in everyday products and it is no longer regarded as an esoteric material. The overarching goal of its widespread adoption and replacement of conventional materials such as steel and aluminum alloys has been restricted because of the cost of the material, limited sources of primary material, alloying constraints, high chemical reactivity, and challenges associated with its plasticity. Researchers, scientists, engineers, and economists from industry, government agencies and laboratories, and academic institutions alike are actively developing roadmaps for next-generation products and addressing these challenges as quickly as possible through unique and innovative methods. The TMS Magnesium Committee has been actively involved in providing a platform to these entities for disseminating the latest information, developments, and cutting-edge research and development, and showcasing the latest research and development trends related to magnesium and its alloys through the Magnesium Technology Symposium, which takes place every year at the TMS Annual Meeting. This proceedings volume retains the essence of this longstanding tradition. The twenty-first volume in the series, Magnesium Technology 2020, is the proceedings of the Magnesium Technology Symposium held during the 149th TMS Annual Meeting & Exhibition in San Diego, CA, February 23–27, 2020. The volume captures commentaries and papers from 15 different countries. The papers have been categorized systematically based on topics pertaining to magnesium production, casting and solidification, thermomechanical processing, deformation mechanisms, modeling, corrosion, and applications. The symposium began with keynote sessions that featured several distinguished invited speakers from government organizations and academia, who provided their perspectives on the state of the art, goals, and opportunities in magnesium alloy research and development. Dr. Carlos Tomé from Los Alamos National Laboratory, U.S. Department of Energy, discussed 3D characterization of mechanical twins across grain boundaries. This was followed by a talk on hierarchically structured ultrafine-grained magnesium alloys by Dr. Rajiv Mishra from the University of North Texas, USA, who presented an example of using friction stir additive manufacturing for implementing such microstructures at a component level. Dr. Mark Horstemeyer from Liberty University, USA, presented an overview of fatigue modeling to capture the corrosion-fatigue behavior of magnesium alloys. The final talk in this session was presented by Dr. Bin Jiang from Chongqing University, China, who presented a novel extrusion approach for achieving high-strength magnesium alloy plates.

Jordon, J. Brian↗

3D printing via ambient reactive extrusion

Here, Additive Manufacturing (AM) has the potential to offer many benefits over traditional manufacturing methods in the fabrication of complex parts with advantages such as low weight, complex geometry, and embedded functionality. In practice, today’s AM technologies are limited by their slow speed and highly directional properties. To address both issues, we have developed a reactive mixture deposition approach that can enable 3D printing of polymer materials at over 100X the volumetric deposition rate, enabled by a greater than 10X reduction in print head mass compared to existing large-scale thermoplastic deposition methods, with material chemistries that can be tuned for specific properties. Additionally, the reaction kinetics and transient rheological properties are specifically designed for the target deposition rates, enabling the synchronized development of increasing shear modulus and extensive cross linking across the printed layers. This ambient cure eliminates the internal stresses and bulk distortions that typically hamper AM of large parts, and yields a printed part with inter-layer covalent bonds that significantly improve the strength of the part along the build direction. The fast cure kinetics combined with the fine-tuned viscoelastic properties of the mixture enable rapid vertical builds that are not possible using other approaches. Through rheological characterization of mixtures that were capable of printing in this process as well as materials that have sufficient structural integrity for layer-on-layer printing, a “printability” rheological phase diagram has been developed, and is presented here. We envision this approach implemented as a deployable manufacturing system, where manufacturing is done on-site using the efficiently-shipped polymer, locally-sourced fillers, and a small, deployable print system. Unlike existing additive manufacturing approaches which require larger and slower print systems and complex thermal management strategies as scale increases, liquid reactive polymers decouple performance and print speed from the scale of the part, enabling a new class of cost-effective, fuel-efficient additive manufacturing.

36 MATERIALS SCIENCE↗

Custom-form iron trifluoride Li-batteries using material extrusion and electrolyte exchanged ionogels

Custom-form factor batteries fabricated in non-conventional shapes can maximize the overall energy density of the systems they power, particularly when used in conjunction with energy dense materials (e.g., Li metal anodes and conversion cathodes). Additive manufacturing (AM), and specifically material extrusion (ME), have been shown as effective methods for producing custom-form cell components, particularly electrodes. However, the AM of several promising energy dense materials (conversion electrodes such as iron trifluoride) have yet to be demonstrated or optimized. Furthermore, the integration of multiple AM produced cell components, such as electrodes and separators, along with a custom package remains largely unexplored. In this work, iron trifluoride (FeF 3 ) and ionogel (IG) separators are conformally printed using ME onto non-planar surfaces to enable the fabrication of custom-form Li-FeF 3 batteries. Further, to demonstrate printing on non-planar surfaces, cathodes and separators were deposited onto cylindrical rods using a 5-axis ME printer. ME printed FeF 3 was shown to have performance commensurate with FeF 3 cast using conventional means, both in coin cell and cylindrical rod formats, with capacities exceeding 700 mAh/g on the first cycle and ranging between 600 and 400 mAh/g over the next 50 cycles. Additionally, a ME process for printing polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) based IGs directly onto FeF 3 is developed and enabled using an electrolyte exchange process. In coin cells, this process is shown to produce cells with similar capacity to cells built with Celgard separators out to 50 cycles, with the exception that cycling instabilities are observed during cycles 8–20. When using printed and exchanged IGs in a custom cylindrical cell package, 6 stable high-capacity cycles are achieved. Overall, this work demonstrates approaches for producing high-energy-density Li-FeF 3 cells in coin and cylindrical rod formats, which are translatable to customized, arbitrary geometries compatible with ME printing and electrolyte exchange.

25 ENERGY STORAGE↗

Direct Functionalization of Established 3D-Printed Aza-Michael Liquid Crystal Elastomers with Donor–Acceptor Stenhouse Adducts

Extrusion 3D printing has advanced the manufacturing of complex liquid crystal elastomer (LCE) architectures. In parallel, donor–acceptor Stenhouse adducts (DASAs), a class of white-light-responsive photoswitches, have enabled both photochemical and photothermal LCE actuation. However, DASA–LCEs have yet to be extruded and 3D-printed. Two key challenges exist: DASA’s inherent sensitivity to heat and radicals can lead to degradation during ink preparation and printing, and small changes in the concentration of the added DASA component impact the properties of the extrudable ink, requiring reoptimization of well-established 3D-printing protocols. To overcome these challenges, we present a post-printing functionalization strategy that circumvents these limitations. Residual secondary amines, inherent to inks synthesized via standard aza-Michael addition, serve as active sites for covalent attachment of DASA photoresponsive groups following printing and cross-linking. Our method means that DASAs can be directly grafted onto 3D-printed aza-Michael LCEs without modifying the ink formulation or processing. The resulting DASA–LCEs exhibit wavelength tunability within the visible range and a variety of photothermal and photochemical responses. The post-functionalization can occur within 2 min and enables spatial control of the DASA concentration, producing films with tunable color gradients and locally varied photothermal and photochemical responses under visible light. In conclusion, this approach enables the rapid fabrication of DASA-based light-responsive LCEs using established ink formulations with the potential for the design of complex 3D architectures.

3D printing↗