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At least 847 records · Page 47

CO2 interaction with geomaterials.

This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas No.3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or 'geopolymer') theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2 molecules may remain trapped for several months following several hours of exposure to high pressure (supercritical conditions), high temperature (above boiling point of water) or both. Such trapping is well preserved in either inert gas or the ambient environment and appears to eventually result in carbonate formation. We performed computer simulations of CO2 interaction with free cations (normal modes of CO2 and Na+CO2 were calculated using B3LYP / aug-cc-pVDZ and MP2 / aug-cc-pVDZ methods) and with clay structures containing interlayer cations (MD simulations with Clayff potentials for clay and a modified CO2 potential). Additionally, interaction of CO2 with hydrated Na-montmorillonite was studied using density functional theory with dispersion corrections. The sorption energies and the swelling behavior were investigated. Preliminary modeling results and experimental observations indicate that the presence of water molecules in the interlayer region is necessary for intercalation of CO2. Our preliminary conclusion is that CO2 molecules may intercalate into interlayer region of swelling clay and stay there via coordination to the interlayer cations.

01 COAL, LIGNITE, AND PEAT↗

Testing Protocol for Module Encapsulant Creep (Presentation)

Recently there has been an interest in the use of thermoplastic encapsulant materials in photovoltaic modules to replace chemically crosslinked materials, e.g., ethylene-vinyl acetate. The related motivations include the desire to: reduce lamination time or temperature; use less moisture-permeable materials; or use materials with better corrosion characteristics. However, the use of anythermoplastic material in a high-temperature environment raises safety and performance concerns, as the standardized tests currently do not expose the modules to temperatures in excess of 85C, yet modules may experience temperatures above 100C in operation. Here we constructed eight pairs of crystalline-silicon modules and eight pairs of glass/encapsulation/glass mock modules using differentencapsulation materials of which only two were designed to chemically crosslink. One module set was exposed outdoors with insulation on the back side in Arizona in the summer, and an identical set was exposed in environmental chambers. High precision creep measurements and performance measurements indicate that despite many of these polymeric materials being in the melt state at some of thehighest outdoor temperatures achievable, very little creep was seen because of their high viscosity, temperature heterogeneity across the modules, and in the case of the crystalline-silicon modules, the physical restraint of the backsheet. These findings have very important implications for the development of IEC and UL qualification and safety standards, and in regards to the necessary level ofcure during the processing of crosslinking encapsulants.

14 SOLAR ENERGY↗

Optical Thermal Characterization Enables High-Performance Electronics Applications

NREL developed a modeling and experimental strategy to characterize thermal performance of materials. The technique provides critical data on thermal properties with relevance for electronics packaging applications. Thermal contact resistance and bulk thermal conductivity were characterized for new high-performance materials such as thermoplastics, boron-nitride nanosheets, copper nanowires, and atomically bonded layers. The technique is an important tool for developing designs and materials that enable power electronics packaging with small footprint, high power density, and low cost for numerous applications.

30 DIRECT ENERGY CONVERSION↗

Toward the Advanced Manufacturing of Land-Based Wind Turbine Blades: Preprint

The National Renewable Energy Laboratory (NREL) and General Electric (GE) are partners within the Additive and Modular Enabled Rotor Blades and Integrated Composites Assembly (AMERICA) project. AMERICA aims to develop advanced manufacturing solutions to reduce labor and cycle time while increasing recyclability of wind turbine blades. The project is funded by the Advanced Manufacturing Office (AMO) of the U.S. Department of Energy (DOE). This paper describes the techno-economic analysis of the novel manufacturing process applied to the tip of the blade of a representative land-based wind turbine. A comparison to a standard manufacturing process is established, highlighting challenges and opportunities. Several uncertainties affect the analysis, but with the current set of assumptions, the tip adopting advanced manufacturing is predicted to lower labor by 21%, cycle time by 39%, and total blade tip costs by 15% while simultaneously increasing production quality and adopting recyclable thermoplastic resin.

3D printing↗

Additive Manufacturing of Thermal Energy Storage Composites with Microencapsulated Phase Change Materials Supported in a Multipolymer Matrix

Additive manufacturing (AM) techniques to directly integrate phase change materials (PCMs) are of interest for efficient thermal energy storage (TES) architectures. Complex, high surface-to-volume ratio composites embedded with PCM can improve thermal management with reduced material waste for customizable device fabrication. Reducing feature sizes of TES-integrated heat exchangers using AM can increase heat transfer without thermal conductivity enhancement. Here, composite AM materials containing 60 wt% microencapsulated phase change materials (MEPCM) are fabricated using off-the-shelf printers at common speeds and resolutions. High MEPCM loading in filaments is achieved with powder extrusion using two polymers, thermoplastic-polyurethane (TPU) and polycaprolactone (PCL), that mediate flexibility and rigidity for effective extrusion and printing without filament fracture or buckling. Furthermore, with PCL and TPU at 20 wt% each and 60 wt% MEPCM (P 20 T 20 M 60 ), smooth, form-stable filaments are consistently printed. Powder-based extrusion displays negligible damaging effects on the MEPCM. Printed P 20 T 20 M 60 demonstrates 105 J/g of energy storage with no degradation through 250 thermal cycles, within 5% of the theoretical storage enthalpy. Combining PCL/TPU shows good interfacial adhesion between print layers and produces high surface area objects, like 15% gyroids, and dense, 100% infilled pucks. Prints are also scalable to a 900 cm 3 honeycomb heat exchanger with an estimated 9 Wh energy storage.

25 ENERGY STORAGE↗

Diels–Alder Reversible Thermoset 3D Printing: Isotropic Thermoset Polymers via Fused Filament Fabrication

This study presents a new 3D printing process, the Diels–Alder reversible thermoset (DART) process, and a first generation of printable DART resins, which exhibit thermoset properties at use temperatures, ultralow melt viscosity at print temperatures, smooth part surface finish, and as‐printed isotropic mechanical properties. This study utilizes dynamic covalent chemistry based on reversible furan‐maleimide Diels–Alder linkages in the polymers, which can be decrosslinked and melt‐processed during printing between 90 and 150 °C, and recrosslinked at lower temperatures to their entropically favored state. This study compares the first generation of DART materials to commonly 3D printed high‐toughness thermoplastics. Parts printed from typical fused filament fabrication compatible materials exhibit anisotropy of more than 50% and sometimes upward of 98% in toughness when deformed along the build direction, while the first generation of DART materials exhibit less than 4% toughness reduction when deformed along the build direction. At room temperature, the toughest DART materials exhibit baseline toughness of 18.59 ± 0.91 and 18.36 ± 0.57 MJ m −3 perpendicular and parallel to the build direction, respectively. DART printing will enable chemists, polymer engineers, materials scientists, and industrial designers to translate new robust materials possessing targeted thermomechanical properties, multiaxial toughness, smooth surface finish, and low anisotropy.

Yang, Kejia↗

Additive Manufacturing of Biomechanically Tailored Meshes for Compliant Wearable and Implantable Devices

Abstract Additive manufacturing (AM) of medical devices such as orthopedic implants and hearing aids is highly attractive because of the potential of AM to match the complex form and mechanics of individual human bodies. Externally worn and implantable tissue‐support devices, such as ankle or knee braces, and hernia repair mesh, offer a new opportunity for AM to mimic tissue‐like mechanics and improve both patient outcomes and comfort. Here, it is demonstrated how explicit programming of the toolpath in an extrusion AM process can enable new, flexible mesh materials having digitally tailored mechanical properties and geometry. Meshes are fabricated by extrusion of thermoplastics, optionally with continuous fiber reinforcement, using a continuous toolpath that tailors the elasticity of unit cells of the mesh via incorporation of slack and modulation of filament–filament bonding. It is shown how the tensile mesh mechanics can be engineered to match the nonlinear response of muscle. An ankle brace with directionally specific inversion stiffness arising from embedded mesh is validated, and further concepts for 3D mesh devices are prototyped.

Pattinson, Sebastian W.↗

Low‐Volume Cores for Fabrication of Compact, Versatile, and Intelligent Soft Systems

Abstract This study introduces the low‐volume core (LVC) fabrication method, which enables the monolithic molding of compact, complex, versatile, and intelligent soft robotic systems. This method uses thin and flexible thermoplastic sheets to mold internal chambers in soft fluidic actuators, valves, and circuits. The LVC fabrication method creates low‐volume networks in soft actuators (LV‐net actuators) that can be made with compact and complex geometries, enabling both low actuation volume input and multi‐degree‐of‐freedom actuators. LVC fabrication can also be used for compact, completely soft, and monolithic logic components (valves with low‐volume core, also called as LV valves) to provide directional resistance as well as a switching mechanism that enables fluidic logic in soft systems. The compatibility of the fabrication methods for both soft actuators and valves facilitates the creation of compact, integrated, and versatile soft robotic systems with embodied intelligence. This study introduces two examples of such intelligent soft robotic systems that integrate both LV‐net actuators and LV valves to demonstrate capability for complex system fabrication.

Yu, Qifan↗

A Processable Shape Memory Polymer System for Biomedical Applications

Polyurethane shape memory polymers (SMPs) with tunable thermomechanical properties and advanced processing capabilities are synthesized, characterized, and implemented in the design of a microactuator medical device prototype. The ability to manipulate glass transition temperature ( T g ) and crosslink density in low-molecular weight aliphatic thermoplastic polyurethane SMPs is demonstrated using a synthetic approach that employs UV catalyzed thiol-ene “click” reactions to achieve postpolymerization crosslinking. Polyurethanes containing varying C=C functionalization are synthesized, solution blended with polythiol crosslinking agents and photoinitiator and subjected to UV irradiation, and the effects of number of synthetic parameters on crosslink density are reported. Thermomechanical properties are highly tunable, including glass transitions tailorable between 30 and 105 °C and rubbery moduli tailorable between 0.4 and 20 MPa. This new SMP system exhibits high toughness for many formulations, especially in the case of low crosslink density materials, for which toughness exceeds 90 MJ m –3 at select straining temperatures. To demonstrate the advanced processing capability and synthetic versatility of this new SMP system, a laser-actuated SMP microgripper device for minimally invasive delivery of endovascular devices is fabricated, shown to exhibit an average gripping force of 1.43 ± 0.37 N and successfully deployed in an in vitro experimental setup under simulated physiological conditions.

42 ENGINEERING↗

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↗

Reactive Processing of Furan‐Based Monomers via Frontal Ring‐Opening Metathesis Polymerization for High Performance Materials

Frontal ring-opening metathesis polymerization (FROMP) presents an energy-efficient approach to produce high-performance polymers, typically utilizing norbornene derivatives from Diels–Alder reactions. This study broadens the monomer repertoire for FROMP, incorporating the cycloaddition product of biosourced furan compounds and benzyne, namely 1,4-dihydro-1,4-epoxynaphthalene (HEN) derivatives. A computational screening of Diels–Alder products is conducted, selecting products with resistance to retro-Diels–Alder but also sufficient ring strain to facilitate FROMP. The experiments reveal that varying substituents both modulate the FROMP kinetics and enable the creation of thermoplastic materials characterized by different thermomechanical properties. Moreover, HEN-based crosslinkers are designed to enhance the resulting thermomechanical properties at high temperatures (>200 °C). The versatility of such materials is demonstrated through direct ink writing (DIW) to rapidly produce 3D structures without the need for printed supports. This research significantly extends the range of monomers suitable for FROMP, furthering efficient production of high-performance polymeric materials.

36 MATERIALS SCIENCE↗

Dynamic Diketoenamine Crosslinking Unlocks Vinyl Polymer Vitrimers From β ‐Triketone Chemistry

Covalent adaptable networks (CANs) offer a compelling strategy to unite the mechanical robustness of thermosets with the reprocessability of thermoplastics, yet achieving simultaneous durability, processability, and true recyclability remains challenging. We introduce diketoenamine (DKE) vitrimers derived from β-triketone methacrylate monomers and demonstrate how rational monomer design dictates network processability, viscoelasticity, and recyclability. By systematically varying the spacer length between the β-triketone (TK) moiety and the polymer backbone, we identify a key structure–property relationship that dictates vitrimer behavior. Networks bearing TK pendants minimally displaced from the backbone suppress creep but exhibit limited stress relaxation, whereas extended spacers yield lower glass transition temperatures, higher effective crosslink densities, and efficient stress dissipation, enabling optical transparency and reprocessability. Extending this platform to ultra-high molecular-weight prepolymers introduces physical entanglements as secondary crosslinks, further enhancing dimensional stability without compromising processability. Both mechanical and chemical recycling validate the closed-loop circularity of these materials. Furthermore, these results establish TK methacrylates as a versatile platform for designing high-performance vitrimers that integrate durability, reprocessability, and true closed-loop recyclability.

closed-loop recyclability↗

Solvent‐Templated Block Ionomers for Base‐ and Acid‐Gas Separations: Effect of Humidity on Ammonia and Carbon Dioxide Permeation

Abstract As energy needs continue to drive the development of biogas and fossil‐fuel technologies, methods by which to selectively remove basic (NH 3 ) and acidic (CO 2 ) gases are becoming increasingly important, especially in light of global climate change. Block copolymers are considered as suitable membrane candidates in gas separations due to the ability of such copolymers to microphase‐separate and spontaneously form nanoscale morphologies that exhibit spatially modulated chemical specificity. Incorporation of charged moieties along the midblock of a thermoplastic elastomeric multiblock copolymer yields an amphiphilic block ionomer possessing a flexible molecular network stabilized by rigid endblocks. The presence of hydrophilic microdomains introduces an important consideration regulating molecular transport: humidity. In this study, solvent‐templating paradigms are employed to control the morphologies of midblock‐sulfonated pentablock ionomers, as discerned by electron microscopy and X‐ray scattering. The effect of humidity on the permeation of NH 3 , CO 2 , and N 2 is then investigated through the resulting membranes. As expected, NH 3 permeates significantly faster than N 2 , especially under humid conditions. Although not as pronounced, similar behavior is observed for CO 2 , thereby establishing that this block ionomer is generally selective to humidified polar gases.

Ansaloni, Luca↗

3D Printing of Highly Porous Polypropylene Separators for Lithium‐Ion Batteries Using Fused Deposition Modeling and Thermally Induced Phase Separation

Appearing as one of the key-components of lithium-ion batteries (LIBs), this work specifically focuses on the additive manufacturing (AM) of custom-shape separators, facilitated by the filament material extrusion process, also called fused deposition modeling (FDM). The development and optimization of composite thermoplastic filament feedstocks combining polypropylene and paraffin wax, followed by the 3D printing of the separator membranes is shown. A post-processing step, based on thermal induced phase separation (TIPS), is introduced to promote porosity formation through removal of the paraffin wax sacrificial phase within the 3D printed items. Separators with different polypropylene/paraffin wax ratios are developed and the impact on printability, mechanical strength, porosity, and electrochemical performances, is thoroughly discussed. X-ray micro-computed tomography is employed to assess the geometric fidelity and to detect printing defects in a complex 3D lattice structure. The performance of the 3D printed porous separators is also compared to a commercial separator. This pioneering research establishes a foundation for the creation of porous separators that can adapt to and conform into 3D printed battery architectures with novel form factors, and also creates opportunities for the use of FDM and TIPS for a wide range of applications that employ porous structures beyond the energy storage field.

3D printing↗

Enhancing Composite Toughness Through Hierarchical Interphase Formation

High strength and ductility are highly desired in fiber-reinforced composites, yet achieving both simultaneously remains elusive. A hierarchical architecture is developed utilizing high aspect ratio chemically transformable thermoplastic nanofibers that form covalent bonding with the matrix to toughen the fiber-matrix interphase. The nanoscale fibers are electrospun on the micrometer-scale reinforcing carbon fiber, creating a physically intertwined, randomly oriented scaffold. Unlike conventional covalent bonding of matrix molecules with reinforcing fibers, here, the nanofiber scaffold is utilized - interacting non-covalently with core fiber but bridging covalently with polymer matrix - to create a high volume fraction of immobilized matrix or interphase around core reinforcing elements. This mechanism enables efficient fiber-matrix stress transfer and enhances composite toughness. Molecular dynamics simulation reveals enhancement of the fiber-matrix adhesion facilitated by nanofiber-aided hierarchical bonding with the matrix. The elastic modulus contours of interphase regions obtained from atomic force microscopy clearly indicate the formation of stiffer interphase. These nanoengineered composites exhibit a ≈60% and ≈100% improved in-plane shear strength and toughness, respectively. This approach opens a new avenue for manufacturing toughened high-performance composites.

36 MATERIALS SCIENCE↗

Interweaving 3D Network Binder for High-Areal-Capacity Si Anode through Combined Hard and Soft Polymers

We report that Si anodes suffer an inherent volume expansion problem. The consensus is that hydrogen bonds in these anodes are preferentially constructed between the binder and Si powder for enhanced adhesion and thus can improve cycling performance. There has been little research done in the field of understanding the contribution of the binder's mechanical properties to performance. Herein, a simple but effective strategy is proposed, combining hard/soft polymer systems, to exploit a robust binder with a 3D interpenetrating binding network (3D-IBN) via an in situ polymerization. The 3D-IBN structure is constructed by interweaving a hard poly(furfuryl alcohol) as the skeleton with a soft polyvinyl alcohol (PVA) as the filler, buffering the dramatic volume change of the Si anode. The resulting Si anode delivers an areal capacity of >10 mAh cm -2 and enables an energy density of >300 Wh kg -1 in a full lithium-ion battery (LIB) cell. The component of the interweaving binder can be switched to other polymers, such as replacing PVA by thermoplastic polyurethane and styrene butadiene styrene. Such a strategy is also effective for other high-capacity electroactive materials, e.g., Fe 2 O 3 and Sn. In conclusion, this finding offers an alternative approach in designing high-areal-capacity electrodes through combined hard and soft polymer binders for high-energy-density LIBs.

36 MATERIALS SCIENCE↗

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Synthetic polymers have found widespread use, but their ineffective end-of-life treatment is causing a significant environmental and human health crisis. Here, we demonstrate the upcycling of polynorbornene derivatives (pNBEs) through their deconstruction into distinct oligomeric buildings blocks that can be repolymerized into chemically recyclable pNBEs-like multiblock polymers via dehydrogenative polymerization. The resulting materials exhibit diverse mechanical properties, while integrating high melting temperatures (T m as high as 133 °C). Notably, this method could also enable the selective deconstruction of permanently cross-linked polydicyclopentadiene (pDCPD) thermosets into telechelic-OH functionalized oligomers, overcoming the significant challenges posed by their robust network structure in recycling and degradation. The resulting pDCPD oligomers can subsequently be repolymerized with macrodiols to create multiblock thermosets with tunable mechanical properties, including Young's modulus and tensile elongation. After use, upcycled plastics could be effectively deconstructed back to the oligomers for recovery and repolymerization. Overall, this work establishes an approach that can be utilized to upcycle pNBEs into previously inaccessible multiblock thermosets and thermoplastics with full recyclability, and may be generalizable to a range of polymers to shift their end-of-life waste disposal toward sustainable recovery and reuse.

36 MATERIALS SCIENCE↗