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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 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Kinetically Controlled Formation of Semi-crystalline Conjugated Polymer Nanostructures

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. Furthermore, we demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tuning the Double Gyroid Phase Window in Block Copolymers via Polymer Chain Conformation Near the Interface

Block copolymer network morphologies have been proven interesting for applications ranging from mechanical to transport and optical properties. The shape of the polymer chain and its ability to stretch across an interface can be used as handles to target these network morphologies. Here, we show that the double gyroid phase window is broadened when there is a flexible segment near the interface and narrowed when a more constrained segment is placed there by using a series of poly(styrene-b-peptoid) block copolymers in which the polypeptoid block chain conformation can be tuned to adopt either a helical or a coil conformation (NRpe 6 vs Npe 6 ). The double gyroid phase is accessed in both block copolymer series, while the phase boundaries are shifted toward larger polypeptoid volume fractions in the helix-forming PS–(NRpe 6 Nmey) series, due to the more compact helix segment (i.e., the helix segment has the same chain volume as its random coil counterpart but occupies less space). The space-filling difference between the helix and coil segment is further confirmed by the smaller domain spacing of PS–(NRpe 6 Nme 39 ) compared to PS–(Npe 6 Nme 36 ) (13.9 nm vs 14.3 nm) despite the former having a longer polypeptoid block. Furthermore, a broadened double gyroid phase window is accessed in the PS–(Npe 6 Nme y ) series that has a flexible coil segment near the interface. These results demonstrate the possibility of tuning the double gyroid phase in linear block copolymers by chain conformation near the interface alone, highlighting chain conformation as a versatile handle in block copolymer design.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Nonlinear van der Waals Metasurfaces with Resonantly Enhanced Light Generation

Efficient nonlinear wave mixing is of paramount importance for a wide range of applications. However, weak optical nonlinearities pose significant challenges for accessing nonlinear light–matter interaction in compact systems. Here, we experimentally study second harmonic generation in deeply subwavelength 3R-MoS 2 metasurfaces (<λ/13 thick). Our measurements, supported by theoretical analysis, reveal a complex interplay and coupling between geometric resonances, optical extinction, and exciton-driven strong nonlinear susceptibility dispersion. We further demonstrate >150-fold enhancement in second harmonic signal at 740 nm mediated by the A exciton resonance. Additionally, our theoretical studies predict an enhancement of more than 10 6 in second harmonic generation in <100 nm thick structures exhibiting bound states in the continuum resonance. These findings provide insight into accessing and harnessing the unprecedented 3R-MoS 2 nonlinearities at a subwavelength scale, paving the way to ultracompact nonlinear photonic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Mechanism-Informed Breakdown: Understanding Degradation by Controlling Voltage-Hold Patterns in Proton Exchange Membrane Water Electrolyzers

Low catalyst loadings pose challenges to performance stability in proton exchange membrane (PEM) water electrolysis over extended operation. To study the impact of degradation mechanisms and voltage loss rates, different stress tests are applied to membrane electrode assemblies. Potential cycling conditions were observed to induce higher degrees of iridium (Ir) oxide crystallization, ionomer degradation, and catalyst layer (CL) thinning, which likely contributed to higher kinetic loss rates. On the other hand, while Ir migrating into the PEM (Ir band) generally impairs performance, the interconnected and more uniform Ir band formed under a constant 2 V hold may allow for Ir at the catalyst/membrane interface to remain electronically connected and kinetically accessible, as well as indicate greater Ir site access during the applied stressor. The 2 V hold also demonstrates improved kinetic durability through a lower Tafel slope, faster polarization kinetics, and reduced charge transfer resistance. In contrast, potential cycling caused the migration of disconnected Ir agglomerates into the membrane bulk and created a steady increase in charge transfer resistance, a more dramatic decrease in capacitance (46.7% loss), and significant damage to the surrounding ionomer, indicating a decline in both the quality and quantity of active sites in the anode CL. This work underscores the distinct degradation pathways associated with load holds versus cycling, highlighting the role of catalyst-ionomer interactions in kinetic performance and long-term stability. These insights can inform operational strategies for PEM electrolyzers powered by intermittent energy sources, aiming to minimize efficiency losses over extended operation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural Degradation of High Voltage Lithium Nickel Manganese Cobalt Oxide (NMC) Cathodes in Solid-State Batteries and Implications for Next Generation Energy Storage

In this study, we report the stability of the layered high voltage cathode NMC622 with respect to a standard liquid electrolyte and in an all solid-state configuration. NMC622 cathodes with a (104) orientation were found to suffer from degradation at high voltage (4.5 V vs Li/Li + ) due to electrolyte-promoted degradation of the layered structure in a carbonate electrolyte. The lithium phosphorus oxynitride (LiPON) electrolyte was able to suppress the extent of this decomposition in solid-state cells but not totally prevent it from occurring. In the solid-state cells the capacity decreased from 203 to 93 mAh/g in the first cycle and from 93 to 79 mAh/g over the subsequent 99 cycles, whereas, after 20 cycles, the liquid cell charge capacity was dominated by the irreversible electrolyte degradation. Furthermore, the interfacial resistances of the solid-state cells were stable with cycling, suggesting minimal degradation of the NMC622/LiPON interface and incumbent losses due to structural evolution associated with cathode orientation. This data indicates that accessing stable high voltage capacity in NMCs will not be enabled by simply stabilizing the cathode–electrolyte interface. Optimizing cathode crystallographic orientation may be the key to accessing this high voltage regime.

25 ENERGY STORAGE↗
DOE OSTI2020

Iridium-Doped Nanosized Zn–Al Layered Double Hydroxides as Efficient Water Oxidation Catalysts

Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. In this paper, we report the syntheses of three iridium-doped zinc–aluminum LDHs (Ir-LDHs) nanomaterials (1–3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO 4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (~0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO 4 , turnover number up to ~10,000). Nanomaterials 1–3 display the highest ever reported turnover frequency values (up to 402 min –1 ) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3–1 μm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1–3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir–Ir scattering from second-nearest neighbors, excluding the presence of IrO 2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Design of Graphene/Ionic Liquid Composites for Carbon Capture

Pore size is a crucial factor impacting gas separation in porous separation materials, but how to control the pore size to optimize the separation performance remains a challenge. Here, we propose a design of graphene/ionic liquid composites with tunable slit pore sizes, where cations and anions of ionic liquids are intercalated between graphene layers. By varying the sizes of the ions, we show from first-principles density functional theory calculations that the accessible pore size can be tuned from 3.4 to 6.0 Å. Grand canonical Monte Carlo simulations of gas sorption find that the composite materials possess high CO 2 uptake at room temperature and 1 bar (up to ~8.5 mmol/g). Further simulations of the sorption of gas mixtures reveal that high CO 2 /N 2 and CO 2 /CH 4 adsorption selectivities can be obtained when the accessible pore size is <5 Å. This work suggests a new strategy to achieve tunable pore sizes via the graphene/IL composites for highly selective CO 2 /N 2 and CO 2 /CH 4 adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Role of SnO2 Processing on Ionic Distribution in Double-Cation-Double Halide Perovskites

Moving toward a future of efficient, accessible, and less carbon-reliant energy devices has been at the forefront of energy research innovations for the past 30 years. Metal-halide perovskite (MHP) thin films have gained significant attention due to their flexibility of device applications and tunable capabilities for improving power conversion efficiency. Serving as a gateway to optimize device performance, consideration must be given to chemical synthesis processing techniques. Therefore, how does common substrate processing techniques influence the behavior of MHP phenomena such as ion migration and strain? Here, we demonstrate how a hybrid approach of chemical bath deposition (CBD) and nanoparticle SnO2 substrate processing significantly improves the performance of (FAPbI3)0.97(MAPbBr3)0.03 by reducing micro-strain in the SnO2 lattice, allowing distribution of K+ from K-Cl treatment of substrates to passivate defects formed at the interface and produce higher current in light and dark environments. X-ray diffraction reveals differences in lattice strain behavior with respect to SnO2 substrate processing methods. Through use of conductive atomic force microscopy (c-AFM), conductivity is measured spatially with MHP morphology, showing higher generation of current in both light and dark conditions for films with hybrid processing. Additionally, time-of-flight secondary ionization mass spectrometry (ToF-SIMS) observed the distribution of K+ at the perovskite/SnO2 interface, indicating K+ passivation of defects to improve the power conversion efficiency (PCE) and device stability. We show how understanding the role of ion distribution at the SnO2 and perovskite interface can help reduce the creating of defects and promote a more efficient MHP device.

conductive atomic force microscopy↗
DOE OSTI2023

Metal–Carbodithioate-Based 3D Semiconducting Metal–Organic Framework: Porous Optoelectronic Material for Energy Conversion

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate"(-CS 2 ) n M" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages-when combined with spirofluorene-derived organic struts and nickel-(II) ion-based nodes-provided a stable, semiconducting 3D-porous MOF, Spiro-CS 2 Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore"material recorded a Brunauer-Emmett-Teller area of similar to 400m 2 /g, where the "open pore" form possesses90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS 2 Ni possesses a band gap of 1.57 eV(sigma = 10 -7 S/cm at -1.3 V bias potential),which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst(upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τ CR = 6.5 mu s) capable of chemical transformation under a biased voltage. Spiro-CS 2 Ni can endure a compelling range of pH(1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous,light-energy-conversion materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Raising the Asymmetric Catalytic Efficiency of Chiral Covalent Organic Frameworks by Tuning the Pore Environment

Chiral covalent organic frameworks (COFs) hold considerable promise in the realm of heterogeneous asymmetric catalysis. However, fine-tuning the pore environment to enhance both the activity and stereoselectivity of chiral COFs in such applications remains a formidable challenge. In this study, we have successfully designed and synthesized a series of clover-shaped, hydrazone-linked chiral COFs, each with a varying number of accessible chiral pyrrolidine catalytic sites. Remarkably, the catalytic efficiencies of these COFs in the asymmetric aldol reaction between cyclohexanone and 4-nitrobenzaldehyde correlate well with the number of accessible pyrrolidine sites within the frameworks. Further, the COF featuring nearly one pyrrolidine moiety at each nodal point demonstrated excellent reaction yields and enantiomeric excess (ee) values, reaching up to 97 and 83%, respectively. The findings not only underscore the profound impact of a deliberately controlled chiral pore environment on the catalytic efficiencies of COFs but also offer a new perspective for the design and synthesis of advanced chiral COFs for efficient asymmetric catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Direct Laser Writing Crystal Polymorphs of Organic Semiconductors for Phase Change Electronics

The many diverse polymorphic behaviors observed in organic electronic materials offer opportunities to modulate electronic properties through reversibly switching crystal structures. Here, we access the prolific polymorphism observed in two-dimensional quinoidal terthiophene via laser writing to locally heat and direct the phase transitions. We access a metastable polymorph IV through rapid cooling and observe distinct symmetry as well as packing through grazing incidence X-ray diffraction (GIXD). Using our open-source PolyChemPrint patterning platform, we direct laser heating to initiate the IV-I transition, switching the conductance by >2 orders of magnitude. Here, this is confirmed via a combination of GIXD and Raman spectroscopy. Finally, we demonstrate switching of transistor devices as well as discrete tuning of conductance via laser writing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural Rearrangements of Subnanometer Cu Oxide Clusters Govern Catalytic Oxidation

Sub-nanometer metal oxide clusters are very important materials that are widely used, for example, in catalysis or electronic devices such as sensors. Hence, it is critical to understand the atomic structures and properties of sub-nanometer metal oxide clusters under a reactive gas environment, such as O 2 . We consider here experimentally accessible precise-size Cu clusters (Cu 4 ) supported on partially hydroxylated amorphous alumina and show that such clusters can access, in catalytic conditions at high temperature under a pressure of O 2 , a large ensemble of oxidized structures, representing a large variety of oxygen content, of geometries in link with the support, and of catalytic activities for oxidation reactions, as seen from their reducibilities. A grand canonical basin hopping method based on first-principles energy reveals an ensemble of 24 configurations for the Cu 4 O x cluster of low free energy, less than 0.8 eV above the global minimum. The low free energy ensemble consists of clusters of different stoichiometries, which are mainly Cu 4 O 3 and Cu 4 O 4 in the temperature range of 200–400 °C and under a pressure of 0.5 bar of O 2 . The presence of several competitive isomers at each composition implies that cluster fluxionality impacts the phase diagram, which should be ensemble-averaged. In terms of catalytic oxidation activity, Cu 4 O 3 isomers present highly variable O abstraction energy: the most stable isomers are inactive for alkane oxidative dehydrogenation, but isomerization to metastable isomers, that proceed with low barrier, enable to create active configurations with low O abstraction energy. O atoms with the lowest anionic character, and thus of more electrophilic nature, present the best oxidation capability. In contrast, all Cu 4 O 4 isomers show a low O abstraction energy and a high potential catalytic activity. Here, this manuscript demonstrates the unique structural and electronic properties of sub-nano Cu oxide clusters and illustrates the critical roles of configuration ensembles and rearrangement to highly reactive metastable cluster isomers in nanocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Bulk vs Intrinsic Activity of NiFeO x Electrocatalysts in the Oxygen Evolution Reaction: The Influence of Catalyst Loading, Morphology, and Support Material

We used a combination of ultrahigh vacuum surface science techniques, X-ray spectroscopy, electrochemistry, and density functional theory (DFT), to characterize the influence of catalyst morphology, loading/coverage, and substrate material on the bulk (all atoms) and intrinsic (electrochemically accessible atoms) activity of NiFeO x electrocatalysts in the oxygen evolution reaction (OER). NiFeO x catalysts were grown on both Au(111) and highly oriented pyrolytic graphite (HOPG) electrodes. DFT predicted Fe edge-site atoms at the NiFeO x /Au(111) interface to be the most thermodynamically favorable reaction center, and X-ray absorption spectroscopy data indicated small NiFeO x catalyst particles on Au(111) contained a high population of OER active Fe edge-site atoms. However, restructuring of the Au(111) surface due to repeated oxidation and reduction cycles of the OER CV measurements encapsulated small NiFeO x nanoparticles at catalyst loadings below ~1.5 nmol metal /cm 2 , passivated catalyst edges and reduced bulk OER activity of Au-supported NiFeO x compared with HOPG-supported ones. Analysis of intrinsic activity revealed that the Au(111) support strongly benefited electrochemically accessible NiFeO x atoms, and we observed a 2–3 fold activity enhancement compared with HOPG-supported catalysts for loadings above ~1 nmol metal /cm 2 . Overall, evaluating bulk vs intrinsic activity and identifying loading/coverage-dependent support effects is important for accurately probing fundamental interfacial chemistry, choosing suitable catalyst loadings and supports, and optimizing system parameters to maximize the performance of electrocatalyst systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hydrogen Evolution on Restructured B-Rich WB: Metastable Surface States and Isolated Active Sites

Borides have been recently identified to be a class of earth-abundant and low-cost materials that are surprisingly active toward oxidative dehydrogenation and hydrogen evolution reaction (HER) catalysis. Here, we explain from first-principles calculations the HER activity of WB, an industrial material known for its superior physical properties and chemical inertness. We find that, compared to bulk termination, a major surface reconstruction takes place, leading to the off-stoichiometric B-rich surface termination that contains the active sites. The hydrogen adsorbate configurations are further investigated under various adsorbate coverages. Many competing configurations appear to be accessible in reaction conditions, and thus, a grand canonical ensemble is established to describe the catalytic system. A phase diagram of adsorbate coverages is constructed as a function of pH and the applied potential. A complex reaction network is presented based on the ensemble-averaged reaction rates, and the electrocatalytic activities are evaluated under different overpotentials. Here, the major contributors to the activity are found to be a few metastable surface states with a distinct electronic structure that are only accessible at high adsorbate coverages in reaction conditions. In addition, while the activity of the dominant active site is nearly the same as that on the unreconstructed WB, the B-rich formations play an important role of isolating the active sites and preventing the passivation of the surface with H 2 bubble formation.

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

Role of Bimetallic Interactions in the Enhancement of Catalytic CO 2 Reduction by a Macrocyclic Cobalt Catalyst

The use of two metal centers in a CO 2 reduction catalyst that work together synergistically, with similar or complementary functions, can potentially lead to a significant reduction in overpotential, enhance catalytic activity and/or selectivity, and/or enable access to cascade strategies where each metal center catalyzes a different step in the conversion of CO 2 to a fuel. Here, the bimetallic reactivity of two metal centers has been identified as the primary route for the reduction of CO 2 to CO promoted by the macrocycle, [Co(HMD)] 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), based on the experimental characterization of all major steps of the proposed catalytic cycle using pulse radiolysis time-resolved IR (PR-TRIR) spectroscopy, corroborated by density functional theory (DFT) calculations and IR spectroelectrochemistry (IR-SEC). A bimetallic intermediate is formed in situ from two singly reduced [Co(HMD)] + species bridged by a CO 2 molecule, and the presence of a coordinating species, e.g., formate anion, appears to assist in the formation of such an intermediate. In this work, it has been demonstrated that this reactivity enables access to elementary steps with lower energy requirements, resulting in overall catalysis being kinetically more facile compared to the mononuclear pathway. A two-step approach that combines chemical reduction followed by PR-TRIR has been successfully used for probing the structure and reactivity of reactive intermediates involved in the advanced stages of a catalytic cycle, which are rarely interrogated using experimental techniques.

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

Carbonylative Co- and Terpolymerizations of 10-Undecen-1-ol: A Route to Polyketoesters with Tunable Compositions

A strategy to synthesize branched polyketoesters from the carbonylative polymerization of bifunctional α,ω-alkenols such as 10-undecen-1-ol is presented. This strategy hinges on the competitive application of two related catalytic manifolds, alternating alkene/CO copolymerization, and alkene hydroesterification, which share a common metal acyl intermediate. Small molecule model studies of cationic Pd-catalyzed alkene carbonylation in the presence of alcohols demonstrate that the relative rates of ketone formation (through alternating alkene/CO insertion) and ester formation (through metal acyl alcoholysis) can be tuned across a wide range through judicious bis(phosphine) ligand design. Carbonylative polymerization of 10-undecen-1-ol with a (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 catalyst (dppp(3,5-CF 3 ) 4 = 1,3-bis[bis[3,5-bis(trifluoromethyl)phenyl]-phosphino]propane) led to the formation of high molecular weight polyketoesters with intermediate dispersity (M n > 20,000 g/mol, D- = 2.6) and a ketone/ester microstructure ratio of approximately 1:2. In these polymerization reactions, deploying electron-deficient bis(phosphines) to suppress deleterious alkene isomerization was the key to accessing the high molecular weight polymer. Further, terpolymerization reactions of 1-hexene/10-undecen-1-ol/CO or 1-fluoro-10-undecene/10-undecen-1-ol/CO by (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 were also successful. Furthermore, this proof of concept polymerization unlocks access to tunable polymer microstructures without extensive postpolymerization treatment.

10-undecen-1-ol↗
DOE OSTI2025

Dual-Wavelength Simultaneous Patterning of Degradable Thermoset Supports for One-Pot Embedded 3D Printing

Vat photopolymerization (VP) techniques have enabled the fabrication of complex geometries while balancing high precision and fast processing times. 3D printed objects are traditionally built layer-by-layer with newly cured layers being structurally supported by previous ones. Fabricating unsupported features such as overhangs and arches risks misalignment and sagging, limiting the range of accessible designs. To overcome this issue, support structures are fabricated along with the primary object as temporary scaffolds that provide stability and conserve print fidelity. For VP specifically, patterning dissolvable sacrificial supports is attractive to avoid manual removal after printing. In this study, we demonstrate a base-degradable thermoset to pattern print supports in a one-pot formulation along with the primary structural material. Efficient printing is enabled using a dual-wavelength negative imaging (DWNI) DLP printer that patterns the degradable thermoset with visible light and the permanent network with UV light, which are simultaneously projected using a single digital micromirror device (DMD). Printed objects undergo thermal postprocessing to enhance the final conversion of the primary material, after which thermoset supports are degraded in a basic, aqueous solution. This approach provides a robust method for the dual-wavelength patterning of sacrificial thermoset supports, broadening the range of accessible 3D printable materials and geometries.

3D printing↗
DOE OSTI2022

Melt State Reinforcement of Polyisoprene by Silica Nanoparticles Grafted with Polyisoprene

Here, we systematically vary the nanoparticle (NP) dispersion state in composites formed by mixing polyisoprene homopolymers with polyisoprene grafted silica particles, and demonstrate how creep measurements allow us to overcome the limitations of small amplitude oscillatory shear (SAOS) experiments. This allows us to access nearly 13 orders in time in the mechanical response of the resulting composites. We find that a specific NP morphology, a percolating particle network achieved at intermediate graft densities, significantly reinforces the system and has a lower NP percolation loading threshold relative to other morphologies. These important effects of morphology only become apparent when we combine creep measurements with SAOS re-emphasizing the role of synergistically combining methods to access the mechanical properties of polymer nanocomposites over broad frequency ranges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗