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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Multi-scale computer-aided design and photo-controlled macromolecular synthesis boosting uranium harvesting from seawater

By integrating multi-scale computational simulation with photo-regulated macromolecular synthesis, this study presents a new paradigm for smart design while customizing polymeric adsorbents for uranium harvesting from seawater. A dissipative particle dynamics (DPD) approach, combined with a molecular dynamics (MD) study, is performed to simulate the conformational dynamics and adsorption process of a model uranium grabber, i.e., PAO m -b-PPEGMA n , suggesting that the maximum adsorption capacity with atomic economy can be achieved with a preferred block ratio of 0.18. The designed polymers are synthesized using the PET-RAFT polymerization in a microfluidic platform, exhibiting a record high adsorption capacity of uranium (11.4 ± 1.2 mg/g) in real seawater within 28 days. This study offers an integrated perspective to quantitatively assess adsorption phenomena of polymers, bridging metal-ligand interactions at the molecular level with their spatial conformations at the mesoscopic level. The established protocol is generally adaptable for target-oriented development of more advanced polymers for broadened applications.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2025

Enabling Partnership between South Carolina and NREL for Advancing Opportunities in Plastics Recycling Research (EPSCOR for Plastics Recycling)

Proposal Objectives: 1. Utilize depolymerization/fractionation techniques to recover highly processable and reactive feedstocks for polymer synthesis from lignin. 2. Synthesize lignin‐derived non‐isocyanate polyurethane, epoxy, and polyamide using non‐ toxic, biobased route designed for chemical recycling. Characterize resulting materials. 3. Design a high‐yielding chemical recycling process for as‐synthesized materials yielding usable building blocks for many generations of polymer synthesis. 4. Optimize chemical recycling of PET waste for the synthesis of lignin‐based polymers. Compare properties to commercial materials. 5. Optimize reaction conditions and recycling steps to facilitate enhanced sustainability of the synthetic steps and final properties of materials. 6. Complete a lifecycle assessment of lignin utilization and chemical recycling to compare their environmental performance to that of materials produced from virgin material. Identify hot spots and benefits using the chemical recycling process.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Autonomous Synthesis and Inverse Design of Electrochromic Polymers with High Efficiency and Accuracy

Here, the design and synthesis of functional polymers, aimed at targeted properties through specific structures, have long been challenged by their complex and often nonlinear structure–property relationships. Key processes, including knowledge accumulation for predictive design and experimental refinement and validation, are traditionally labor-insensitive and time-consuming, making it difficult to balance accuracy and efficiency. Here, we introduce an accelerated, autonomous system for the on-demand synthesis of electronic polymers that achieves the desired electrochromic functionality with high accuracy and efficiency. Our approach leverages large language model-assisted data mining, a physics-informed copolymer machine learning model, and an AI-driven autonomous robotic workflow in the Polybot lab. Within 72 h, Polybot autonomously synthesized electrochromic polymers (ECPs) with targeted, previously-unreported color values, including green polymers with specific absorption profiles, precisely fine-tuning copolymer structures with a 5% step size in comonomer composition within a three-monomer system. A publicly accessible ECP informatics database has also been created to foster knowledge exchange.

AI-driven Robotic Lab↗

DOE OSTI2020

Design, Synthesis, and Characterization of Polymer Precursors to Li x PON and Li x SiPON Glasses: Materials That Enable All-Solid-State Batteries (ASBs)

LiPON-like glasses that form lithium dendrite impenetrable interfaces between lithium battery components are enabling materials that may replace liquid electrolytes permitting production of all-solid-state batteries (ASBs). Unfortunately, to date, such materials are introduced only via gas-phase deposition. Furthermore, we demonstrate the design and synthesis of easily scaled, lowtemperature, low-cost, solution-processable inorganic polymers containing LiPON/LiSiPON elements. OPCl 3 and hexachlorophosphazene [Cl 2 P=N] 3 provide starting points for elaboration using MNH 2 (M = Li/Na) or (Me 3 Si)NH followed by reaction with controlled amounts of LiNH 2 to produce oligomers/polymers with molecular weights (MWs) ≈1–2 kDa characterized by multinuclear NMR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and matrix-assisted laser desorption/ ionization (MALDI)-time-of-flight (ToF) offering stabilities to 150–200 °C and ceramic yields (800 °C) of 50–60%. 7 Li NMR suggests that precursor-bound Li + dissociates easily, beneficial for electrochemical applications. XPS shows higher N/P ratios (1–3) than via gas-phase methods (<1) correlating N/P ratios, 7 Li shifts, and Li + conductivities. Li 2 SiPHN offers the highest ambient conductivity of 3 × 10 –1 mS cm –1 at 400 °C/2 h/N 2 .

36 MATERIALS SCIENCE↗

NASA NTRS2003

Novel High Efficient Organic Photovoltaic Materials

Solar energy is a renewable, nonpolluting, and most abundant energy source for human exploration of a remote site or outer space. In order to generate appreciable electrical power in space or on the earth, it is necessary to collect sunlight from large areas and with high efficiency due to the low density of sunlight. Future organic or polymer (plastic) solar cells appear very attractive due to their unique features such as light weight, flexible shape, tunability of energy band-gaps via versatile molecular or supramolecular design, synthesis, processing and device fabrication schemes, and much lower cost on large scale industrial production. It has been predicted that supramolecular and nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration due to improved electronic ultrastructure and morphology in comparison to polymer composite system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel block copolymer system containing donor and acceptor blocks covalently attached. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (RO-PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (SF-PPV). The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block has a strong PL emission at around 560 nm, and acceptor block has a strong PL emission at around 520 nm, the PL emissions of final block copolymers are severely quenched. This verifies the expected electron transfer and charge separation due to interfaces of donor and acceptor nano phase separated blocks. The system therefore has potential for variety light harvesting applications, including high efficient photovoltaic applications.

Sun, Sam↗

NASA NTRS1995

Electro-Optically Active Monomers: Synthesis and Characterization of Thin Films of Liquid Crystalline Substituted Polyacetylenes

The overall objective of this study was the description of the behavior of mesogen substituted acetylene monomers and polymers in monolayer films at the air/water interface and as multilayer films including the formation of such films. Fundamental knowledge to be gained would include the effect of balancing hydrophilic and hydrophobic tendencies in a molecule more complex than the classical fatty acids or lipids. The effect of molecular shape on the packing and thus the ultimate stability of monolayers formed from these new molecules was explored. The work takes on the challenge of preorienting monomers in well-ordered arrays prior to attempting polymerization with the hope that order would be preserved in any resulting polymer. New knowledge gained with regard to the acetylenic monomers includes processing of the acetylene monomer into multi-layer films, followed by the design and synthesis of a second generation of improved monomer structure for superior LBK film transfer properties. A third generation of acetylenic monomer was synthesized which approaches more closely the goal of solid state polymerization of these materials. A parallel study took a different approach. The materials are pre-formed poly(phenylene-acetylene) polymers so questions about reactivity are mute. The materials are a variation on the well-known hairy-rod polymers with regard to their Langmuir film-forming properties. Overall, the goal was to demonstrate that these polymers could be processed into NLO materials with novel polar order.

Duran, R. S.↗

NASA NTRS1988

Electronic materials high-T(sub c) superconductivity polymers and composites structural materials surface science and catalysts industry participation

The fifth year of the Center for Advanced Materials was marked primarily by the significant scientific accomplishments of the research programs. The Electronics Materials program continued its work on the growth and characterization of gallium arsenide crystals, and the development of theories to understand the nature and distribution of defects in the crystals. The High Tc Superconductivity Program continued to make significant contributions to the field in theoretical and experimental work on both bulk materials and thin films and devices. The Ceramic Processing group developed a new technique for cladding YBCO superconductors for high current applications in work with the Electric Power Research Institute. The Polymers and Composites program published a number of important studies involving atomistic simulations of polymer surfaces with excellent correlations to experimental results. The new Enzymatic Synthesis of Materials project produced its first fluorinated polymers and successfully began engineering enzymes designed for materials synthesis. The structural Materials Program continued work on novel alloys, development of processing methods for advanced ceramics, and characterization of mechanical properties of these materials, including the newly documented characterization of cyclic fatigue crack propagation behavior in toughened ceramics. Finally, the Surface Science and Catalysis program made significant contributions to the understanding of microporous catalysts and the nature of surface structures and interface compounds.

Source record↗

DOE OSTI2020

Highly Catalytically Active High-spin Single-atom Iron Catalyst Supported by Catechol-containing Microporous 2D Polymer

Traditionally, Fe-SACs are prepared through energy-intense processes, which often lead to the loss of precision in structural features from the starting substrates and impeding rational design. In this work, we have described the synthesis of a unique catechol-containing porous polymer with designed features in the substrates maintained, affording atomically dispersed iron catalyst (Fe-SAC) through treatment of ferrous chloride (FeCl 2 ). An aberration-corrected scanning transmission electron microscope (AC-STEM) and synchrotron X-ray absorption spectroscopy (XAS) were employed to shed light on the local coordination geometry of the atomically dispersed iron catalyst. The resulting Fe-SAC exhibits excellent catalytic performance in reduction of nitroaromatics with highest molar K app among all Fe based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Selective Electrochemical End‐Group Removal Enhances Polymer Thermal Stability

Here we introduce an electrochemical strategy for the selective and quantitative removal of thiocarbonylthio end groups from polymers prepared by reversible addition–fragmentation chain transfer (RAFT) or photoiniferter polymerization. Our results indicate that applying a cathodic potential in an undivided cell promotes reductive cleavage of the thiocarbonylthio moiety, generating terminal polymer radicals that are efficiently capped with hydrogen atoms in the presence of benign donors. This transformation proceeds cleanly across diverse polymer backbones and end-group chemistries, including trithiocarbonates and dithiobenzoates, without chain coupling or degradation. Moreover, the applied potential can be tuned to enable chemoselective end-group removal in mixed-polymer systems, a level of control inaccessible by thermal, photochemical, or nucleophilic strategies. Beyond delivering colorless and optically transparent materials, electrochemical end-group removal significantly enhances polymer stability. Poly(methyl methacrylate) subjected to electrochemical end-group removal exhibited a T 95 of 342 °C, exceeding the stabilities of analogous polymers with end groups removed by aminolysis (T 95 = 260 °C) or radical-based methods (T 95 = 299 °C). These findings demonstrate redox-directed post-polymerization modification as a tool for designing robust, transparent, and thermally stable macromolecules and establish electrochemistry as a platform strategy in polymer synthesis and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Structural Effects on Solubility and Crystallinity in Polyamide Ionomers

Although polyamides have been an industrial staple for decades, their solubility and processability remain limited due to the strong hydrogen bonding between amide groups. Here, we report a family of polyamides in which aryl rings, alkyl spacers, sulfonate groups, and amide linkages are regularly spaced along the polymer backbone, allowing us to probe the structural elements that affect processability. We accessed these polymers through a synthetic route based on an expanded diamine monomer and characterized them through a range of physical and spectroscopic techniques. Our results show that the combination of sulfonate groups with increased amide content results in highly soluble polymers, which can dissolve in polar solvents such as water, methanol, and N,N-dimethylformamide. Infrared spectroscopy on the solid polymers shows that the aliphatic amides engage in hydrogen bonding with the sulfonate groups, thus inhibiting ion aggregation, crystallization, and microphase separation. These findings expand the avenue to sulfonate-containing polyamide chemistry and provide design rules for the synthesis of more processable ionic polyamides.

amides↗

DOE OSTI2023

Molecular Design of Functional Polymers for Silica Scale Inhibition

Silica polymerization, which involves the condensation reaction of silicic acid, is a fundamental process with wide-ranging implications in biological systems, material synthesis, and scale formation. The formation of a silica-based scale poses significant technological challenges to energy-efficient operations in various industrial processes, including heat exchangers and water treatment membranes. Despite the common strategy of applying functional polymers for inhibiting silica polymerization, the underlying mechanisms of inhibition remain elusive. In this study, we synthesized a series of nitrogen-containing polymers as silica inhibitors and elucidated the role of their molecular structures in stabilizing silicic acids. Polymers with both charged amine and uncharged amide groups in their backbones exhibit superior inhibition performance, retaining up to 430 ppm of reactive silica intact for 8 h under neutral pH conditions. In contrast, monomers of these amine/amide-containing polymers as well as polymers containing only amine or amide functionalities present insignificant inhibition. Molecular dynamics simulations reveal strong binding between the deprotonated silicic acid and a polymer when the amine groups in the polymer are protonated. Notably, an extended chain conformation of the polymer is crucial to prevent proximity between the interacting monomeric silica species, thereby facilitating effective silica inhibition. Furthermore, the hydrophobic nature of alkyl segments in polymer chains disrupts the hydration shell around the polymer, resulting in enhanced binding with ionized silicic acid precursors compared to monomers. Finally, our findings provide novel mechanistic insights into the stabilization of silicic acids with functional polymers, highlighting the molecular design principles of effective inhibitors for silica polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1983

New polymers for low-gravity purification of cells by phase partitioning

A potentially powerful technique for separating different biological cell types is based on the partitioning of these cells between the immiscible aqueous phases formed by solution of certain polymers in water. This process is gravity-limited because cells sediment rather than associate with the phase most favored on the basis of cell-phase interactions. In the present contract we have been involved in the synthesis of new polymers both to aid in understanding the partitioning process and to improve the quality of separations. The prime driving force behind the design of these polymers is to produce materials which will aid in space experiments to separate important cell types and to study the partitioning process in the absence of gravity (i.e., in an equilibrium state).

Harris, J. M.↗

DOE OSTI2020

Low-cost & Energy Dense Batteries for Transportation

The project sought to explore development of novel polymer separator materials and additives for Li-S and Li-ion batteries that would solve critical failure modes and performance bottlenecks for these chemistries. This technology presented significant advanced manufacturing challenges and opportunities in getting to scale, including materials synthesis scale-up, large-area polymer processing techniques, electrode formulation, and the development of coin and pouch cells for electrochemical energy storage. Specific accomplishments included synthesis of organic molecular and polymer materials designed to solve outstanding challenges in electrochemical cells. The primary focus of new materials design was aimed at improving longevity, power, cost reduction, and environmental sustainability of said electrochemical devices. The project also involved assembly and characterization of electrochemical devices with standard galvanostatic and potentiostatic techniques as well as electrochemical impedance spectroscopy.

25 ENERGY STORAGE↗

DOE OSTI2024

Aqueous Processed All-Polymer Solar Cells with High Open-Circuit Voltage Based on Low-Cost Thiophene–Quinoxaline Polymers

Eco-friendly solution processing and the low-cost synthesis of photoactive materials are important requirements for the commercialization of organic solar cells (OSCs). Although varieties of aqueous-soluble acceptors have been developed, the availability of aqueous-processable polymer donors remains quite limited. In particular, the generally shallow highest occupied molecular orbital (HOMO) energy levels of existing polymer donors limit further increases in the power conversion efficiency (PCE). Here, we design and synthesize two water/alcohol-processable polymer donors, poly[(thiophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-T)) and poly[(selenophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-Se)) with oligo(ethylene glycol) (OEG) side chains, having deep HOMO energy levels (~–5.4 eV). The synthesis of the polymers is achieved in a few synthetic and purification steps at reduced cost. The theoretical calculations uncover that the dielectric environmental variations are responsible for the observed band gap lowering in OEG-based polymers compared to their alkylated counterparts. Notably, the aqueous-processed all-polymer solar cells (aq-APSCs) based on P(Qx8O-T) and poly[(N,N'-bis(3-(2-(2-(2-methoxyethoxy)-ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-methyl)propyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-(2,5-thiophene)] (P(NDIDEG-T)) active layer exhibit a PCE of 2.27% and high open-circuit voltage (V OC ) approaching 0.8 V, which are among the highest values for aq-APSCs reported to date. This study provides important clues for the design of low-cost, aqueous-processable polymer donors and the fabrication of aqueous-processable OSCs with high V OC .

14 SOLAR ENERGY↗

DOE OSTI2026

Accurate Prediction of pKb in Amines: Validation of the CAM-B3LYP/6-311+G(d,p)/SMD Model

Amines play several key roles in chemistry and biology and are involved in numerous industrial processes, often with significant economic impacts. Recently, amines are also garnering interest as catalysts for polymer synthesis and for CO 2 fixation, incentivizing the need to rapidly design and screen new amino compounds. Hence, developing reliable methods to predict their physicochemical properties, e.g., the base dissociation constant (pKb), is pivotal. Here, a density functional theory (DFT)-based approach was employed to compute the pKb of substituted amines, exploring the impact of several key parameters, including (i) the number of explicit water molecules at the reaction center, (ii) the van der Waals (vdW) surface, and (iii) solvent polarizability. In previous work, it was determined that including two explicit water molecules at the reaction center resulted in highly accurate pKb estimates for primary amines. Here, we find that including a third water molecule at the reaction center is essential for accurate pKb for secondary and tertiary amines. The revised methodology was then applied to a wider selection of amines, obtaining a minimum average error (MAE) < 0.4. In conclusion, this result represents an extension of our “easy-to-use method,” a simple and direct DFT approach exploiting CAM-B3LYP/SMD/6-311G+(d,p) to compute pKb without post facto modifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Electronic Conductivity of Nanoporous Indium Oxide Derived from Sequential Infiltration Synthesis

Sequential infiltration synthesis (SIS) is a vapor phase synthetic method that enables the selective nucleation and growth of metal oxides within polymer volumes. The expanding palette of SIS materials and process designs enables tunability of the resulting material properties. We derive porous indium oxide thin films from the SIS of indium oxide using trimethyl indium and H 2 O 2 in polymethyl methacrylate films and observe the strong effect of SIS and post-deposition processing, which affords 7 orders of magnitude of tunability in electrical resistivity. While as-deposited hybrid nanocomposites show no measurable conductivity, high-temperature treatment in O 2 removes the polymer matrix and creates a porous nanocrystalline In 2 O 3 film with resistivities ranging from 10 3 to 10 5 Ω*cm, with lower resistivity correlated to larger grain sizes. Subsequent annealing in H 2 decreases the resistivity of films to less than 10 –2 Ω*cm. A clear correlation between increasing In 2 O 3 volume fraction, grain size, and carrier mobility is observed, which arises from increased percolation pathways, path length, and contact area in nanocrystalline In 2 O 3 films. Furthermore, this wide tunability demonstrates the importance of understanding growth mechanisms and processing conditions for functional materials development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Autonomous sputter synthesis of thin film nitrides with composition controlled by Bayesian optimization of optical plasma emission

Autonomous experimentation has emerged as an efficient approach to accelerate the pace of material discovery. Although instruments for autonomous synthesis have become popular in molecular and polymer science, solution processing of hybrid materials, and nanoparticles, examples of autonomous tools for physical vapor deposition are scarce yet important for the semiconductor industry. Here, we report the design and implementation of an autonomous workflow for sputter deposition of thin films with controlled composition, leveraging a highly automated sputtering reactor custom-controlled by Python, optical emission spectroscopy (OES), and a Bayesian optimization algorithm. We modeled film composition, measured by x-ray fluorescence, as a linear function of plasma emission lines monitored during co-sputtering from elemental Zn and Ti targets in an N 2 and Ar atmosphere. A Bayesian control algorithm, informed by OES, navigates the space of sputtering power to fabricate films with user-defined compositions by minimizing the absolute error between desired and measured optical emission signals. We validated our approach by autonomously fabricating Zn x Ti 1-x N y films that deviate from the targeted cation composition by a relative ±3.5%, even for 15 nm thin films, demonstrating that the proposed approach can reliably synthesize thin films with a specific composition and minimal human interference. Moreover, the proposed method can be extended to more difficult synthesis experiments where plasma intensity lines depend non-linearly on pressure, or the elemental sticking coefficients strongly depend on the substrate temperature.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Understanding Solvent-Induced Glass Transition in Polymer Thin Films Using Absorption–Desorption Isotherms

The fundamental thermodynamic and mechanical underpinnings of polymer thin films exposed to solvent vapor are critical for the development of advanced nanolithography and high-performance coatings. This work investigates the solvent− polymer interactions of glassy thin films by using the solvent absorption−desorption isotherms. An analogous relationship to the Flory−Fox equation was observed between solvent−induced glass transition, swelling, Flory−Huggins interaction parameter, and molecular weight. Isothermal swelling measurements revealed that the glass transition trends are more robust in the absorption curve compared to desorption, contrary to previous reports. Excess osmotic pressure analysis of the isotherm provides a measure of the degree of physical aging in thin films annealed below the glass transition. This is further validated in the ordering of block copolymer (BCP) films annealed at low solvent activity. In agreement with the thermal analysis, free-surface plasticization effects become the most prominent below 100 nm. However, solvent annealing is largely dependent on solvent mass transport, as made evident by the strong dependence on solvent viscosity. From these observations, four general types of isotherms are identified that graphically capture distinct solvent−polymer interaction regimes. More broadly, these results inform solvent vapor annealing-induced self-assembly, sequential infiltration synthesis, membrane-based separations, adsorptive processes, and swelling-based responsive materials design.

Hendeniya, Nayanathara [Iowa State Univ., Ames, IA↗