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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Combining 3D printing of copper current collectors and electrophoretic deposition of electrode materials for structural lithium-ion batteries

Serving as a proof of concept, additive manufacturing and electrophoretic deposition are leveraged in this work to enable structural lithium-ion batteries with load-bearing and energy storage dual functionality. The preparation steps of a complex 3D printed copper current collector, involving the formulation of a photocurable resin formulation, as well as the vat photopolymerization process followed by a precursors-based solution soaking step and thermal post-processing are presented. Compression and microhardness testing onto the resulting 3D printed copper current collector are shown to demonstrate adequate mechanical performance. Electrophoretic deposition of graphite as a negative electrode active material and other additives was then performed onto the 3D printed copper collector, with the intention to demonstrate energy storage functionality. Half-cell electrochemical cycling of the 3D multi-material current collector/negative electrode versus lithium metal finally demonstrates that structural battery components can be successfully obtained through this approach.

25 ENERGY STORAGE↗
DOE OSTI2021

Visible-Light Photoinitiation of (Meth)acrylate Polymerization with Autonomous Post-Conversion

Conversion plateaus rapidly in radical photopolymerizations (RPPs) following discontinuation of irradiation due to rapid termination of reactive radicals, which restricts the wider use of RPPs in applications that involve nonuniform light access including those with attenuated light transmission or irregular surfaces. Based on our recent report of a radical dark-curing photoinitiator (DCPI) that continues polymerization beyond the cessation of irradiation by enabling latent redox initiation with photo-released amine in the presence of a suitable oxidant, we developed a new DCPI with an absorption spectrum that extends well into the visible range. Our design process involved a series of computational investigations of candidate molecules, including a systematic study of substituents and their position-dependent effects on absorption characteristics, electronic transitions, and the photochemical mechanism and its associated energetics. Our quantum chemical computations identified the target compound 5,7-dimethoxy-6-bromo-3-aroylcoumarin-DMPT/BPh4 and predicted that it would facilitate the dark-curing mechanism by concurrent photo-radical generation and photo-induced release of an efficient redox reductant under visible irradiation. This reductant-tethered chromophore was then synthesized and optically characterized with UV–vis spectroscopy that revealed its strong visible-light absorption with a molar absorptivity of 5710 M–1 cm–1 at 405 nm and 50 M–1 cm–1 at 455 nm. We then demonstrated extensive dark-curing of >35% additional conversion over 25 min following brief activation of the shelf-stable one-part system by irradiation with a 455 nm LED that was ceased at 20% conversion. In contrast, shuttering irradiation of the control formulation at that same point resulted in immediate cessation of conversion, which plateaued at 20%. We determined a remarkable initiator efficiency of 2.82 that results from the additional redox-generated radicals with a 77% photo-reductant generation quantum yield. The combination of superior photo- and dark-curing efficiencies of this new visible DCPI is expected to open new application opportunities in RPP, especially those involving resins that are highly light attenuating, surfaces that possess irregular features that produce uneven irradiance, and production lines where continued dark-curing downstream of the light activation step enhances line efficiencies.

absorption spectrum↗
DOE OSTI2023

Facile design of renewable lignin copolymers by photoinitiated RAFT polymerization as Pickering emulsion stabilizers

As the richest aromatic renewable resource, lignin has attracted significant attention for fabricating various materials. However, due to lignin's structural complexity, an effective and facile structural modification strategy remains a substantial challenge. Herein, we have successfully applied photoinitiated reversible addition–fragmentation chain transfer (RAFT) as a versatile tool to synthesize amphiphilic lignin copolymers with lignin derivatives as the macroinitiator. The experimental and density functional theory analysis systematically investigated the photopolymerization kinetics, proving excellent control over molecular weights. Additionally, 1 H NMR and FT-IR analyses confirmed the well-designed structures. Moreover, the structures of copolymers were tunable by simple variations of monomer structures. Finally, the self-assembly of the synthesized copolymers into nanoparticles was explored, together with the potential applications as Pickering emulsion stabilizers. Finally, we believe that this work will offer a facile and green approach to synthesize lignin-based novel copolymers and further expand its applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Tunable Work Functions in Plasmonic Metals

We have studied the effect of BITh molecules on the work functions of Ag and Au, with and without quartz lamp illumination. Silver and gold films coated with BITh molecules were fabricated and studied in reflection and Kelvin Probe experiments. The deposition of BITh films on Ag and Au reduced their work functions (in agreement with our recent study, wherein a similar reduction was caused by the deposition of a PMMA polymer). Illumination of the BITh-coated samples with a quartz lamp caused reductions in work functions by several tens of meV, which (almost) returned to their original values when the light was turned off. The characteristic time of this process (~15 min) was much shorter than that of photopolymerization (~180 min), suggesting that these two phenomena are nearly independent of each other. The effects of the Au substrates were qualitatively similar to those of the Ag substrates. Our findings pave the way to fundamental studies and applications of light–matter interactions.

BITh↗
DOE OSTI2023

Mechanical Actuation via Homeomorphic Transformations of Topological Solitons within Polymer Coatings

Abstract Topological solitons are currently under investigation for their exotic properties, especially in nonlinear physics, optics, and material sciences. However, challenges of robust generation and limited stability over time have hindered their practical uses. To address this issue, an approach is developed to form structured arrays of solitons in films of polymerizable liquid crystals. Their complex molecular architecture is preserved by in situ photopolymerization forming a stable liquid crystal network. Most excitingly, their properties are advanced to include responsiveness functions. When thermally actuated, these topological solitons mediate the reconfiguration of surface topographies. Complex shape changes occur depending on the intrinsic complex spatial distribution of the director, which may even lead to full shape inversion and topographical changes as high as ≈40% of the initial thickness. Conversely, the shape changes provide information on the initial director profile, which is consistent with the mathematical model. The soliton‐containing polymer coatings are applicable in multiple domains, ranging from tunable optics to haptics, and from shape‐coupled sensing systems to temperature‐coupled heat management.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Hybrid Additive and Subtractive Manufacturing of Dual‐Wavelength Photopolymer Thermosets

Additive manufacturing (AM) techniques such as digital light processing (DLP) AM and stereolithography enable the production of highly complex structures with speed and ease as not previously possible. However, many traditional thermosetting photopolymers used in these processes result in a permanently crosslinked structure incapable of being broken down or modified without the use of energy-intensive processes such as mechanical machining or ablation. To overcome this limitation, this production is described of thiol-ene photopolymer thermosets with dual-wavelength photopolymerization and photodegradation reaction pathways. The dual wavelength selectivity of the polymerization (405 nm) and degradation (365 nm) processes, combined with dual-wavelength DLP AM technology, enables hybrid manufacturing with the ability to add and sequentially subtract material with excellent spatiotemporal control. 2D lithographs and complex 3D architectures with soft elastomeric properties are produced with resolutions as small as 50 µm. Furthermore, the ability to selectively subtract supports from 3D printed structures with deliberate and accurate control is demonstrated. In conclusion, the ability to correct or modify existing structures enables a new paradigm of adaptable materials for corrective manufacturing techniques and temporary structures.

3D Printing↗
DOE OSTI2021

Polymer Stabilized Paraboloid Liquid Crystal Microlenses with Integrated Pancharatnam–Berry Phase

Aspheric lenses reduce aberration and provide sharper images with improved spot size compared to spherical lenses. Here this paper demonstrates that applying shear flow can produce plano-concave liquid crystal (LC) lens arrays with paraboloid aspheric profiles. The focal length of individual lenses, with a 0.2 mm aperture, decreases from 0.67 to 0.45 mm as the chiral dopant increases from 0 to 6 wt%. The focal length is also sensitive to the polarization state of the incoming light. The lenses are stabilized by photopolymerizing with 6 wt% of reactive monomer added to the LC. A qualitative explanation for the flow-induced lens formation and the optical properties of the lenses is provided. The potential tunability of the lenses in various fields and their use as paraboloid reflectors are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ability of x‐ray computed tomography to resolve critical flaw size in laser‐based, paste stereolithography ceramic printing of alumina

Abstract Complex alumina parts were printed using vat photopolymerization (VPP), which is a stereolithography‐based additive manufacturing (AM) technique used to shape ceramic preforms, or green parts. The critical flaw size was determined using classical fracture mechanics techniques. The strength and fracture toughness were measured and compared to flaws detected in x‐ray computed tomography (XCT or CT) distributions as well as the fracture surfaces. The strength was lower compared traditionally made alumina, and that is due to layering effects, slurry defects, and printing defects. The critical flaw size from fracture mechanics was 206 µm. XCT has high enough resolution to detect the critical flaw size and much smaller features, where the average flaw size observed in CT scans was around 80–100 µm. The fracture surfaces indicate that flaws causing failure are larger than that of the critical flaw size (∼300 µm), but fracture surfaces do not show definitive features compared to traditionally made ceramics. Since XCT can observe flaws smaller than the critical flaw size, this method can be used as a screening technique.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Cell alignment by smectic liquid crystal elastomer coatings with nanogrooves

Control of cells behavior through topography of substrates is a vital theme in biomedical applications. Among many materials used as substrates, polymers show advantages since they can be tailored by chemical functionalization. Fabrication of polymer substrates with nano- and microscale topography requires processing by lithography, microprinting, etching, etc. In this work, we present a different approach based on anisotropic elastic properties of polymerized smectic A (SmA) liquid crystal elastomer (LCE). When the SmA liquid crystal coating is deposited onto a substrate with planar alignment of the molecules, it develops nanogrooves at its free surface. After photopolymerization, these nanogrooves show an excellent ability to align human dermal fibroblasts (hDFs) over large areas. The alignment quality is good for both bare SmA LCE substrates and for substrates coated with fibronectin. The SmA LCE nano-topographies show a high potential for tissue engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Solventless Dual‐Cure Liquid Resins Via Circular Use of Phthalic Anhydride for Recyclable Composite Applications

Abstract Fiber‐reinforced composites (FRCs) possess a remarkable strength‐to‐weight ratio, making them ideal light‐weighing alternative materials of metals used in automotive, aerospace, and outdoor equipment applications, but their recycling is challenging. Chemically recyclable thermoset polymers can enable fiber recovery and reuse; however, challenges remain in the separation and purification of depolymerized small molecules for efficient polymer recycling. To this end, a series of liquid resins for chemically recyclable polymer networks is designed based on phthalic anhydride, a widely produced and inexpensive chemical. The straightforward sublimation of phthalic anhydride is leveraged to enable a simple and efficient separation process for polymer recycling. To liquefy phthalic anhydride, five mono‐acryloyl‐phthalates are synthesized to obtain stable liquid resins together with phthalic diglycidyl ester. These liquid resins undergo dual‐cure reactions that comprise photopolymerization of acrylate and, subsequently, heat‐mediated epoxy‐acid polymerization reactions. These liquid resins exhibit moderate viscosities (2600–6400 cP @ 22 °C), fast curing, and robust thermomechanical properties (T g s from 71 to 116 °C). It is demonstrated that hydrolysis of the dual‐cured polymers completes within 2 h at 80 °C, and direct sublimation produces phthalic anhydride with 82% yield. This resin system is expected to provide a cost‐competitive, highly efficient platform for recyclable FRCs.

Polymer Science↗
DOE OSTI2025

Zwitterionic Photocurable Resin for High‐Resolution 3D Printing of Ultralow‐Fouling Microstructures

High‐resolution 3D printing technologies are enabling a new generation of microstructured materials for applications where biocompatibility is critical. However, most conventional 3D‐printable resins yield materials that exhibit trade‐offs between antifouling properties and mechanical robustness, limiting their applicability in living systems. In nature, zwitterionic surface groups form tightly bound hydration layers that act as effective barriers against protein and cell attachment. Inspired by this strategy, a zwitterionic acrylamide‐based photoresist—carboxybetaine di‐methacrylamide (CBDA)—is developed for projection‐based vat photopolymerization, enabling the fabrication of complex microarchitectures with exceptional antifouling properties. The bifunctional monomer allows the formation of dense, cross‐linked networks that resist swelling while maintaining a high density of zwitterionic groups. Printed structures exhibit strong resistance to protein and cell adhesion, as confirmed by porcine blood assays, alongside robust mechanical performance. As a demonstration, a tubular structure featuring a negative Poisson's ratio lattice is printed to showcase structural fidelity and versatility. This resin formulation offers a broadly applicable strategy for fabricating microscale devices and surfaces where antifouling performance and structural integrity are both essential—spanning biomedical interfaces, soft robotics, and beyond.

3D printing↗
DOE OSTI2023

Rheology guiding the design and printability of aqueous colloidal composites for additive manufacturing

Vat photopolymerization (VP) and direct ink write (DIW) additive manufacturing (AM) provide complex geometries with precise spatial control employing a vast array of photo-reactive polymeric systems. Although VP is recognized for superior resolution and surface finish, DIW provides versatility for higher viscosity systems. However, each AM platform presents specific rheological requirements that are essential for successful 3D printing. First, viscosity requirements constrain VP polymeric materials to viscosities below 10 Pa s. Thus, this requirement presents a challenging paradox that must be overcome to attain the physical performance of high molecular weight polymers while maintaining suitable viscosities for VP polymeric materials. Second, the necessary rheological complexity that is required for DIW pastes requires additional rheological measurements to ensure desirable thixotropic behavior. Further, this manuscript describes the importance of rheological measurements when designing polymeric latexes for AM. Latexes effectively decouple the dependency of viscosity on molecular weight, thus enabling high molecular weight polymers with low viscosities. Photo-crosslinking of water-soluble monomers and telechelic oligomeric diacrylates in the presence of the latex enables the fabrication of a scaffold, which is restricted to the continuous aqueous phase and effectively surrounds the latex nanoparticles enabling the printing of otherwise inaccessible high molecular weight polymers. Rheological testing, including both steady and oscillatory shear experiments, provides insights into system properties and provides predictability for successful printing. This perspective article aims to provide an understanding of both chemical functionality (photo- and thermal-reactivity) and rheological response and their importance for the successful design and evaluation of VP and DIW processable latex formulations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Outcomes and Conclusions from the 2022 AM Bench Measurements, Challenge Problems, Modeling Submissions, and Conference

The Additive Manufacturing Benchmark Test Series (AM Bench) provides rigorous measurement data for validating additive manufacturing (AM) simulations for a broad range of AM technologies and material systems. AM Bench includes extensive in situ and ex situ measurements, simulation challenges for the AM modeling community, and a corresponding conference series. In 2022, the second round of AM Bench measurements, challenge problems, and conference were completed, focusing primarily upon laser powder bed fusion (LPBF) processing of metals, and both material extrusion processing and vat photopolymerization of polymers. In all, more than 100 people from 10 National Institute of Standards and Technology (NIST) divisions and 21 additional organizations were directly involved in the AM Bench 2022 measurements, data management, and conference organization. The international AM community submitted 138 sets of blind modeling simulations for comparison with the in situ and ex situ measurements, up from 46 submissions for the first round of AM Bench in 2018. Analysis of these submissions provides valuable insight into current AM modeling capabilities. The AM Bench data are permanently archived and freely accessible online. The AM Bench conference also hosted an embedded workshop on qualification and certification of AM materials and components.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reinforcement induced microcracking during the conversion of polymer-derived ceramics

This study investigates the role of discontinuous reinforcement on the microcracking of a preceramic polymer matrix during polymer to ceramic conversion. The material system comprised a carbosilane-based, preceramic polymer reinforced with mullite particles. The preceramic resin slurry was formulated for photopolymerization on a digital light projection 3D printer. Micro X-ray computed tomography, using a synchrotron light source, monitored a printed composite part during pyrolysis. The conversion of the carbosilane matrix into Si(O)C generated microcracks in the matrix that radially extended from particles. The likelihood of microcrack formation positively correlated with particle size. The largest particles (>10 4 µm 3 volume or >60 µm side length) always abutted microcracks, while the matrix surrounding smaller particles (<5 µm) was free of microcracks. Numerical calculations showed the particles resist the shrinking matrix during its conversion. This created tensile stresses within the matrix. The driving force for microcrack growth was also analyzed with regard to the influence of matrix material parameters, particle form-factor and crack length. These results reveal the need to consider the form factor of discontinuous reinforcements, with regard to the material properties of the polymer-derived ceramic, in order to reduce or eliminate defects in the final part.

36 MATERIALS SCIENCE↗
DOE OSTI2022

3D-printed electrically conductive silicon carbide

The development of electrically conductive ceramics could achieve robust mechanical strength as well as practically high conductivity, offering applications in structural electrodes, conductors, catalyst supports, etc. However, its operating temperature is limited due to the intrinsic dense structures inevitably hindering the thermal management capability, thus resulting in a temperature-dependent electrical behavior in high-temperature environments. In this work, we report an additive manufacturing protocol through vat photopolymerization 3D printing to fabricate the architectured conductive silicon carbide (SiC) ceramics that simultaneously possess high electrical conductivity as well as low thermal conductivity, and demonstrate electric reliability under high-temperature environments above 600°C. The percolation of graphene into the ceramic scaffold establishes a uniform conductive network, exhibiting its electrical conductivity up to 1000 S m –1 . The bulk density of the 3D-printed ceramic is measured from 0.366 g cm –3 to 0.897 g cm –3 , with thermal conductivity ranging from 62 mW m –1 K –1 to 88 mW m –1 K –1 . Furthermore, the mechanical performance of conductive ceramic can be effectively reinforced by densifying the microstructures via spark plasma sintering treatment. The proposed additive manufacturing strategy widens the potential of ceramics as a structural and functional material, offering a promising pathway toward high-temperature electronics applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Impact of hydrophobic pendant phenyl groups on transport and co-transport of methanol and acetate in PEGDA-SPMAK cation exchange membranes

CO 2 reduction cells are innovative devices that reduce CO 2 into valuable chemicals (i.e. methanol (MeOH) and acetate (OAc – )) on the cathode. A major challenge with such devices is to develop ion exchange membranes that allow ion-selective transport (i.e., protons for cation exchange membranes, CEM) and suppress the crossover of CO 2 reduction products. To design such membranes, it is important to understand multi-solute transport behavior of these solutes. Previously, our group reported acetate diffusivities in co-transport with MeOH increase in sulfonated CEMs, where we speculated charge screening of the electrostatic interactions by co-diffusing MeOH has an impact. Here, crosslinked membranes fabricated by photopolymerization of poly(ethylene glycol) diacrylate (PEGDA), 3-sulfopropyl methacrylate potassium (SPMAK, SO 3 – -containing ionomer), and a phenyl-containing comonomer either phenoxyethyl acrylate (PEA) or poly(ethylene glycol) phenyl ether acrylate (PEGPEA)) are investigated. We observe OAc – diffusivities to both (1) PEGDA-SPMAK and (2) PEGDA-PEGPEA increase in co-diffusion with MeOH and those to (3) PEGDA-SPMAK/PEGPEA decrease. To rationalize this emergent co-transport behavior, we speculate (1) electrostatic interactions are interfered with by co-diffusing MeOH, (2) chain mobility (segmental dynamics) increases in the presence of MeOH and (3) for films with both hydrophobic (PEGPEA) and hydrophilic (SPMAK) comonomers chain mobility (segmental dynamics) decrease due to interactions between the comonomer sidechains depressing overall solute diffusivities. Finally, while further investigations are needed, this work contributes to improving our fundamental understanding of the relationships between polymer film chemistry, solute chemistry, and emergent cotransport behavior observed and described in this work (and others) towards enabling the design of improved membrane materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Mechanically and thermally robust microporous copolymer separators for lithium ion batteries

Next generation, multifunctional separators can enhance energy storage, power, and safety performance of lithium ion batteries but must be simple to fabricate and incorporate with existing roll-to-roll manufacturing. Here, this study presents a strategy to facilely prepare these separators using UV-initiated polymerization-induced phase separation (PIPS), wherein microporous polymer separators are fabricated directly from constituent monomers and ethylene carbonate (EC) porogen. This enables a wide compositional design space as co-monomers with specific chemical functionality can be readily incorporated into the PIPS precursor mixture. Herein, 1,4-butanediol diacrylate (BDDA) was copolymerized with poly(ethylene glycol) diacrylate (PEGDA) to increase the acrylate conversion in the photopolymerization and improve mechanical properties. By tuning the ratio of PEGDA and EC, separators with high porosity (41.3%) and effective ionic conductivity (2.09 mS cm –1 ) were prepared. Inclusion of PEGDA was essential to increasing the elastic modulus to > 345 MPa, which is required for cell assembly by roll-to-roll manufacturing. All separators prepared were shown to enable reversible cycling of lithium metal/LiNi 0.5 Mn 0.3 Co 0.2 O 2 half-cells for 100 cycles. Unlike conventional polyolefin separators, which were shown to melt at 160 °C and shrink by up to 29.8% at elevated temperatures, the PIPS separators possess exceptional, safety-enhancing thermomechanical properties, undergoing no phase transitions or thermal shrinkage.

25 ENERGY STORAGE↗
DOE OSTI2025

3D printed polymer gaskets for custom-form batteries

Additive manufacturing (AM) processes, like 3D printing, help to facilitate complex and customizable battery geometries which can provide design freedom and enhance volumetric energy density within electronic devices. AM materials must have the thermal and mechanical properties that enable printability, and when used in batteries, AM materials must also be chemically and electrochemically compatible with the battery chemistry. The compatibility between AM materials and the battery is of particular importance for the cell packaging materials which must be inert and are often overlooked. This study systematically studies AM-compatible polymeric materials for use as gaskets in lithium-ion cells. The materials investigated include three thermoplastics suitable for material extrusion printing: polylactic acid (PLA), polycarbonate, and polypropylene/polyethylene copolymer (PPPEC); and two photoresins suitable for vat photopolymerization (VPP) printing: an acrylate-based photoresin and a polyethylene glycol diacrylate photoresin. The AM gasket materials were tested in comparison to a conventional commercial polypropylene gasket. Mechanical testing (swell measurements and material stiffness) and electrochemical testing (linear sweep voltammetry and galvanostatic cycling of full cells) demonstrated that PLA and the VPP polymers were the least compatible with the lithium-ion battery chemistry, despite their prevalent use in studies of AM batteries, and that PPPEC was the most compatible.

3D printing↗