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At least 19 records

Photo-Curing: UV Radiation curing of polymers

The Polymers Branch of the Materials Division is dedicated to the development of high-performance for a variety of applications. Areas of significant interest include high- temperature polymers, low density, and high strength insulating materials, conductive polymers, and high density polymer electrolytes. This summer our group is working diligently on a photo-curing project. There is interest in the medical community feel the need for a new and improved balloon that will be used for angioplasty (a form of heart surgery). This product should maintain flexibility but add many other properties. Like possibly further processability and resistance to infection. Our group intends on coming up with this product by using photo-enolization (or simply, photo-curing) by Diels-Alder trapping. The main objective was to synthesize a series of new polymers by Diels-Alder cycloaddition of photoenols with more elastomeric properties. Our group was responsible for performing the proper photo-curing techniques of the polymers with diacrylates and bismaleimides, synthesizing novel monomers, and evaluating experimental results. We attempted to use a diacrylate to synthesize the polymer because of previous research done within the Polymers Branch here at NASA. Most acrylates are commercially available, have more elastometric properties than a typical rigid aromatic structure has and they contain ethylene oxides in the middle of their structure that create extensive flexibility. The problem we encountered with the acrylates is that they photo chemically and thermally self polymerize and create diradicals at low temperatures; these constraints caused a lot of unnecessary side reactions. We want to promote solely, diketone polymerization because this type of polymerization has the ability to cause very elastic polymers. We chose to direct our attention towards the usage of maleimides because they are known for eliminating these unnecessary side reactions.

Inman, Christina A.↗

Unlocking Larger Scales and Aspect Ratios in 3D Printed Glass: Coupling Active Mixing and UV Curing for Advanced Printability and Crack Resistance

Recent developments in additive manufacturing (AM) of glass via silica-filled inks have facilitated fabrication of previously unattainable geometries and compositions. However, the maximum processable size of 15 mm limits the use of these prints in applications such as optics. A key limitation lies in the trade-off between material printability and green strength: increasing silica content in the feedstock improves crack resistance and reduces shrinkage but results in dramatic changes in viscoelastic properties that hinder flowability. Here, this paper presents a novel approach that offers expanded versatility in processable size, feedstock formulation, and printing. Described here is a direct ink writing (DIW) system coupled with an active high-shear micromixer and UV light source, capable of simultaneously printing multiple inks with a wide range of rheological properties. Choice of silica sourc, solvent, UV-curable binder, and dispersant is used to tune the ink rheology and improve printability and mechanical properties. Imparting high shear with the micromixer while UV-curing the extrudate allows for increased ink viscosities and reduced nozzle diameters, enabling printing finer feature sizes. With these advances, thin-walled high-aspect ratio structures and a crack-free glass disk measuring 44 mm in diameter are demonstrated, an increase of 3× in the greatest dimension compared to current state-of-the-art.

36 MATERIALS SCIENCE↗

UV Curing Polymers For Radiation Shielding Applications

The scope of the current research is to develop polymers that will be durable under space conditions. In space, polymers can undergo thermal, mechanical, and oxidative degradation depending on which direction in space they are rotated (ram, wake, zenith, or nadir). Polymers can also be synthesized using techniques such as UV-radiation curing1,2 and cross-linking. In the current project, three organic molecules, acrylamide, styrene-butadiene, and triethylene glycol divinyl ether, were studied using computational software called OLTARIS3 (On-Line Tool for the Assessment of Radiation In Space) developed by NASA Langley to predict the degree of radiation shielding. All three molecules showed shielding before 60 g/cm2 areal density.

UV Curing↗

Identifying Bounds of Inorganic Content in Solventless Processing of Hybrid Solid Electrolytes

Solid-state lithium batteries require safe, robust electrolytes to enable higher energy densities and improved safety over conventional cells. Hybrid polymer–ceramic electrolytes are a promising solution, combining the processability of polymers with the high ionic conductivity and mechanical strength of inorganic fillers. In this work, we demonstrate a solventless, UV-curing method to produce hybrid solid electrolytes using a poly(ethylene glycol) dimethyl ether (PEGDME)-based photocurable matrix incorporating Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) or Li 7 La 3 Zr 2 O 12 (LLZO) ceramic electrolyte. Inorganic filler loadings up to ∼55 wt.% could be successfully incorporated via this process which was the highest inorganic content at which the slurry remains processable and cured into a uniform film. The resulting UV-cured composite electrolytes remain flexible and exhibit room-temperature ionic conductivities on the order of 10 −4 S·cm −1 , along with notably improved lithium-ion transference numbers compared to conventional polymer electrolytes. Similar performance and processing limits were observed for both LAGP and LLZO, indicating that ceramic filler chemistry does not significantly affect the UV-curing process or the electrolyte's ion transport properties in this regime. Eliminating solvents from fabrication not only simplifies processing and mitigates environmental concerns but also enables higher solid contents that enhance mechanical strength and help suppress lithium dendrite formation. In conclusion, this scalable approach thus paves the way for manufacturing robust composite solid electrolytes for next-generation solid-state batteries (SSBs).

Batteries↗

Structure and dynamics of small polyimide oligomers with silicon as a function of aging

The effect of UV curing and shearing on the structure and behavior of a polyimide (PI) binder as it disperses silicon particles in a battery electrode slurry was investigated. PI dispersant effectiveness increases with UV curing time, which controls the overall binder molecular weight. Here, the shear force during electrode casting causes higher molecular weight PI to agglomerate, resulting in battery anodes with poorly dispersed Si particles that do not cycle well. It is hypothesized that when PI binder is added above a critical amount, it conformally coats the silicon particles and greatly impedes Li ion transport. There is an “interzonal region” for binder loading where it disperses silicon well and provides a coverage that facilitates Li transport through the anode material and into the silicon particles. These results have implications in ensuring reproducible electrode manufacturing and increasing cell performance by optimizing the PI structure and coordination with the silicon precursor.

36 MATERIALS SCIENCE↗

TuFF internal WRAP for Rapid Pipeline Repair (TuFF iWRAP)

The goal of “TuFF internal WRAP for Rapid Pipeline Repair” (TuFF iWRAP) program was to develop a novel material system and placement process to fabricate structural pipe within the existing deteriorated pipelines without disruption of gas delivery. The team (University of Delaware – Center for Composite Materials (UD-CCM) and Plitzie Inc.) addressed this challenge by developing a new material feedstock and pipe in pipe (PIP) repair strategy. This allows the potential for significant cost reduction and has minimum operational impact on gas customers. The new robotic based placement design allows discontinuous placement of pipe sections creating a stand-alone structural liner within the legacy pipeline without the need for pipe shutdown. Here, the material is supplied using a tethered material feeding system and is placed and UV cured with the internal Wound Rapid Automated Placement (iWRAP) system. This provides maximum placement efficiency capable of traversing 90 angle bends in 12-inch pipe and overall design customization to meet pipe repair requirements (e.g., variable wall thickness, bridging gaps, etc.). UV-curable fiber reinforced composite material has been optimized to meet structural performance and placement/cure times. Superior strength and fatigue life has been demonstrated by improving fiber-matrix adhesion using new fiber sizing for UV resins. Rapid cure approaches using new liner and resins have been evaluated with industry. The appropriate design of the section joints has been developed and tested. We estimate coating time to be ~100 hours per mile enabling typical pipe repair within 1 week.

03 NATURAL GAS↗

The Use of Solar Heating and Heat Cured Polymers for Lunar Surface Stabilization

Dust ejecta can affect visibility during a lunar landing, erode nearby coated surfaces and get into mechanical assemblies of in-place infrastructure. Regolith erosion was observed at many of the Apollo landing sites. This problem needs to be addressed at the beginning of the lunar base missions, as the amount of infrastructure susceptible to problems will increase with each landing. Protecting infrastructure from dust and debris is a crucial step in its long term functionality. A proposed way to mitigate these hazards is to build a lunar launch pad. Other areas of a lunar habitat will also need surface stabilization methods to help mitigate dust hazards. Roads would prevent dust from being lifted during movement and dust free zones might be required for certain areas critical to crew safety or to critical science missions. Work at NASA Kennedy Space Center (KSC) is investigating methods of stabilizing the lunar regolith including: sintering the regolith into a solid and using heat or UV cured polymers to stabilize the surface. Sintering, a method in which powders are heated until fusing into solids, has been proposed as one way of building a Lunar launch/landing pad. A solar concentrator has been built and used in the field to sinter JSC-1 Lunar stimulant. Polymer palliatives are used by the military to build helicopter landing pads and roads in dusty and sandy areas. Those polymers are dispersed in a solvent (water), making them unsuitable for lunar use. Commercially available, solvent free, polymer powders are being investigated to determine their viability to work in the same way as the solvent borne terrestrial analog. This presentation will describe the ongoing work at KSC in this field. Results from field testing will be presented. Physical testing results, including compression and abrasion, of field and laboratory prepared samples will be presented.

Hintze, Paul↗

Solvent Impregnated Polymers Loaded with Liquid-Like Nanoparticle Organic Hybrid Materials for Enhanced Kinetics of Direct Air Capture and Point Source CO 2 Capture

Hybrid CO 2 capture materials, solvent impregnated polymers (SIPs), are developed based on a simple and scalable encapsulation technique to enhance CO 2 capture kinetics of water-lean solvents with high viscosity. Liquid-like nanoparticle organic hybrid materials functionalized with polyethylenimine (NOHM-I-PEI) are incorporated into a shell material and UV-cured to produce gas-permeable solid sorbents with uniform NOHMs loading (NPEI-SIPs). The CO 2 capture kinetics of NPEI-SIPs show a remarkable 50-fold increase compared to that of neat NOHM-I-PEI due to a large increase in the NOHMs-CO 2 interfacial surface area provided by the SIP design. The optimum NOHM-I-PEI loading and sorption temperature are found to be ≈49 wt% and 50 °C, respectively, and NPEI-SIPs exhibit great thermal stability over 20 CO 2 capture/sorbent regeneration temperature swing cycles. The pseudoequilibrium CO 2 loadings of NPEI-SIPs under humid conditions are as high as 3.1 mmol CO 2 g -1 NPEI - SIPs for 15 vol% CO 2 (postcombustion capture) and 1.7 mmol CO 2 g -1 NPEI - SIPs for 400 ppm (direct air capture). Overall, these findings suggest that NPEI-SIPs can effectively capture CO 2 from a wide range of CO 2 concentrations including direct air capture while allowing the flexible design of CO 2 capture reactors by combining the benefits of liquid solvents and solid sorbents.

36 MATERIALS SCIENCE↗

Physics augmented machine learning discovery of composition-dependent constitutive laws for 3D printed digital materials

Multi-material 3D printing, particularly through polymer jetting, enables the fabrication of digital materials by mixing distinct photopolymers at the micron scale within a single build to create a composite with tunable mechanical properties. Here, this work presents an integrated experimental and computational investigation into the composition-dependent mechanical behavior of 3D printed digital materials. We experimentally characterize five formulations, combining soft and rigid UV-cured polymers under uniaxial tension and torsion across three strain and twist rates. The results reveal nonlinear and rate-dependent responses that strongly depend on composition. To model this behavior, we develop a physics-augmented neural network (PANN) that combines a partially input convex neural network (pICNN) for learning the composition-dependent hyperelastic strain energy function with a quasi-linear viscoelastic (QLV) formulation for time-dependent response. The pICNN ensures convexity with respect to strain invariants while allowing non-convex dependence on composition. To enhance interpretability, we apply $L_0$ sparsification. For the time-dependent response, we introduce a multilayer perceptron (MLP) to predict viscoelastic relaxation parameters from composition. The proposed model accurately captures the nonlinear, rate-dependent behavior of 3D printed digital materials in both uniaxial tension and torsion, achieving high predictive accuracy for interpolated material compositions. This approach provides a scalable framework for automated, composition-aware constitutive model discovery for multi-material 3D printing.

Constitutive modeling↗

Redox-homogeneous, gel electrolyte-embedded high-mass-loading cathodes for high-energy lithium metal batteries

Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi 0.8 Co 0.1 Mn 0.1 O 2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm -2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg -1 and 772 Wh L -1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm -2 ) and 25 °C.

25 ENERGY STORAGE↗

Additive manufacturing of LiCoO 2 electrodes via vat photopolymerization for lithium ion batteries

Additive manufacturing has the potential to revolutionize the fabrication of lithium-ion batteries for a diversity of applications including in portable, biomedical, aerospace, and the transportation fields. Standard commercial batteries consist of stacked layers of various components (current collectors, cathode, anode, separator and electrolyte) in a two-dimensional manner. By leveraging the latest advances in additive manufacturing and computer-aided design, an improved geometric and electrochemical configuration of these batteries can maximize energy efficiency while allowing design optimization to reduce dead space for a given application. In this work, a composite UV photosensitive resin was prepared and used as feedstock in a vat photopolymerization system. The resin was loaded with LiCoO 2 acting as electrochemically active material for the cathode of a lithium-ion battery, and was further improved with the addition of conductivity-enhancing carbonaceous additives. Challenges to additive manufacturing arise from the opacity and high viscosity of the composite nature of these electrochemically-active resins, which cause light refraction during selective UV curing. Subsequently, items were printed and subjected to a thermal post-processing step to obtain an adequate compromise between electrochemical performance and mechanical integrity. Both sintered and green state 3D printed cathodes were assembled into half-cell lithium-ion batteries using lithium metal as a reference and counter electrode. Electrochemical cycling of these batteries yielded satisfactory results approaching commercial LiCoO 2 cathodes’ performance, with the potential advantages of additive manufacturing – high surface area anode–cathode configurations for power performance as well as shape conformability.

25 ENERGY STORAGE↗

Elucidating Norrish type I reactive pathways by ultrafast X-ray absorption spectroscopy

Norrish type I reactions selectively cleave carbon–carbon bonds directly adjacent to carbonyl groups. Despite their broad use in combination with aromatic carbonyls for additive manufacturing and dental UV curing applications, the nature of the photochemically active state and its population mechanism remain insufficiently understood. Detailed mechanistic insight requires mapping of the photoexcited population flow involving internal conversion and intersystem crossing. We present a time-domain study of gas phase acetophenone as a prototypical aromatic carbonyl combining soft X-ray time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy at the oxygen K-edge with ab initio multiple spawning (AIMS) simulations. Exploiting the specific sensitivity of TR-NEXAFS spectroscopy to states with nπ* character, we observe population transfer from the initially excited 1 ππ* state to the 1 nπ* state with a time constant of (0.13 ± 0.02) ps after an initial induction period of (0.12 ± 0.02) ps without population transfer, in quantitative agreement with the AIMS simulations. The population in the 1 nπ* state subsequently decays via intersystem crossing, likely mediated by a 3 ππ* state, within (3.17 ± 0.66) ps to a long-lived 3 nπ* state, which is presumed to be active towards Norrish type I chemistry.

Graßl, Martin [SLAC National Accelerator Laborator↗

Plasticizer-Free Gradient-Crosslinked Polyurethane Electrolyte for Room-Temperature Solid-State Lithium Batteries

Polymer-based solid-state electrolytes are promising for next-generation lithium metal batteries, yet their limited ionic conductivity and mechanical stability at ambient conditions remain key challenges. Herein, we report a novel gradient crosslinked polymer electrolyte (PU/PUA/PU) synthesized via a sequential in situ UV-curing process that integrates a mechanically robust polyurethane acrylate (PUA) core with soft linear polyurethane (PU) interfaces. This all-solid membrane operates without any liquid plasticizer and the interfacial PU layers ensure low interfacial resistance and intimate electrode contact, while the PUA core provides enhanced dimensional stability and dendrite suppression. As a result, the gradient electrolyte delivers an impressive ∼2.6 × 10 −4 S cm −1 ionic conductivity at 25 °C (two orders of magnitude higher than conventional PEO) and remains electrochemically stable >5 V (vs Li + /Li). Structural analysis confirms the formation of a well-defined crosslinked network with suppressed crystallinity and expanded interchain spacing. Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) further validate these properties. When applied in a Li||NMC811 cell, the PU/PUA/PU electrolyte delivers stable cycling with high capacity at both 60 °C and 25 °C, demonstrating its potential for room-temperature solid-state battery applications without reliance on plasticizers or heating. In conclusion, this gradient design offers a practical path toward ambient-condition operation of solid-state lithium batteries, providing a paradigm for overcoming the traditional trade-off between ionic conductivity and mechanical robustness.

25 ENERGY STORAGE↗

Structural response of 3D-printed rubber lattice structures under compressive fatigue

In this work, a new direct UV curing, polyurethane-like, highly stretchable rubber, Elastic ToughRubber 90™ (ETR 90), is demonstrated for 3D printing via photocuring with Texas Instruments DLP® optical systems. An array of test specimens, comprising a sandwich structure with a body-centered cubic lattice core, are 3D printed from ETR 90. The compressive behavior of these specimens is characterized up to 10 k and up to 100 k fatigue-loading cycles. The internal, visually obstructed, structures under loads are visualized using in situ X-ray tomography. All lattice structures remain intact and full recovery is observed, indicating the cyclic durability of the 3D-printed rubber.

36 MATERIALS SCIENCE↗

Overview of the Fiber System for the Dark Energy Spectroscopic Instrument

The Dark Energy Spectroscopic Instrument (DESI) is a revolutionary instrument designed for precise measurements of cosmic distances and the investigation of dark energy. DESI utilizes 5000 optical fibers to simultaneously measure the spectra of distant objects and aims to measure 40 million galaxies and quasars in a 5 yr survey. One of the critical challenges to DESI's success was ensuring that the fiber system was not only highly efficient but also delivered a highly stable beam enabling more reliable sky subtraction for measurements of faint objects. We achieved this stability by minimizing the stress on the fiber system during the manufacture and operation of the telescope and fiber positioning robots. We installed the DESI fiber system on the 4 m Mayall telescope with ≥99% of fibers intact, and the instrument has delivered superb optical performance throughout the initial years of the DESI survey, including ≥90% average throughput when injected with a focal ratio of ~f/3.9 as delivered by the primary focus corrector, excluding fiber absorption losses. The design of DESI required multiple innovations to achieve these requirements, such as cleaved fibers bonded with a UV-curing epoxy to glass ferrules in the focal plane and fusion splicing instead of physical connectors. In this paper, we describe the development, delivery, and installation of the fiber system, the innovations that made the state-of-the-art performance possible, and the key lessons learned that could benefit future projects.

79 ASTRONOMY AND ASTROPHYSICS↗

Waveguides in Thin Film Polymeric Materials

Results on the fabrication of integrated optical components in polymeric materials using photo printing methods will be presented. Optical waveguides were fabricated by spin coating preoxidized silicon wafers with organic dye/polymer solution followed by soft baking. The waveguide modes were studied using prism coupling technique. Propagation losses were measured by collecting light scattered from the trace of a propagation mode by either scanning photodetector or CCD camera. We observed the formation of graded index waveguides in photosensitive polyimides after exposure of UV light from a mercury arc lamp. By using a theoretical model, an index profile was reconstructed which is in agreement with the profile reconstructed by the Wentzel-Kramers-Brillouin calculation technique using a modal spectrum of the waveguides. Proposed mechanism for the formation of the graded index includes photocrosslinking followed by UV curing accompanied with optical absorption increase. We also developed the prototype of a novel single-arm double-mode interferometric sensor based on our waveguides. It demonstrates high sensitivity to the chance of ambient temperature. The device can find possible applications in aeropropulsion control systems.

Sakisov, Sergey↗