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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Direct and Inverse Photoelectron Spectroscopy Evidence for a Revised Picture of Electronic States of Negative Polarons in n‐Doped C 60

Abstract Determining the electronic levels associated with polarons, the fundamental charge carriers in organic semiconductors, is key to understanding the charge transport properties of these materials. Recent findings challenge the traditional view of these electronic levels by highlighting the importance of intra‐molecular Coulomb interactions in polarons. Experimental evidence was previously presented for a revised model of the negative polaron in the case of the polymer semiconductor poly(NDI2OD‐T 2 ); there, the addition of an excess electron was seen to lead to the emergence of a singly occupied state within the energy gap of the undoped material and an unoccupied state above the edge of the conduction states . Here, focus is on a small‐molecule semiconductor, C 60 , and spectral evidence is provided of a similar picture for the new states appearing upon polaron formation. Specifically, direct and inverse photoemission spectroscopy is used to investigate the density of states in C 60 films n‐doped with two dimeric dopants. The Coulomb interaction energy (Hubbard U ) of the C 60 anion is experimentally determined to be ≈1.1 eV, a value that aligns closely with theoretical predictions.

36 MATERIALS SCIENCE↗
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 OSTI2022

Efficient and mechanically-robust organic solar cells based on vertical stratification modulation through sequential blade-coating

Mechanically durable organic solar cells (OSCs) with high efficiency are deemed as the ideal candidate for the power source of the next generation wearable electronic devices. However, the brittle nature of small molecules in most high-efficiency OSCs consisting of polymer and small molecule encourages easy formation of cracks in the photoactive film under deformation. Here, the vertical composition distribution of the active layer has been well optimized through sequential blade coating to realize highly deformable while efficient OSC. The optimized morphology exhibits distinct donor-rich and homogenous region distributed along the vertical direction in the bulk. The donor-rich region provides sufficient chain entanglements and strong interfaces beneficial for mechanical robustness of film, while homogeneously mixed region offers continuous interpenetrating network to maintain high device through-put, resulting in superior efficiency of 14.4% with high crack-onset strain (COS) of 30.5%. This efficiency versus COS combination is much higher than the best combination reported in all polymer systems (COS of 15.9% and efficiency of 11.1%). To the best of our knowledge, it is the highest COS value achieved in polymer-small molecule systems. As a result, the rational control over vertical stratification demonstrated here would guide researchers in the development of innovative wearable electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

High-temperature 2D ferromagnetism in conjugated microporous porphyrin-type polymers

The need for magnetic 2D materials that are stable to the enviroment and have high Curie temperatures is very important for various electronic and spintronic applications. We have found that two-dimensional porphyrin-type aza-conjugated microporous polymer crystals are such a material (Fe-aza-CMPs). Fe-aza-CMPs are stable to CO, CO 2 , and O 2 atmospheres and show unusual adsorption, electronic, and magnetic properties. Indeed, they are semiconductors with small energy band gaps ranging from 0.27 eV to 0.626 eV. CO, CO 2 , and O 2 molecules can be attached in three different ways where single, double, or triple molecules are bound to iron atoms in Fe-aza-CMPs. For different attachment configurations we find that for CO and CO 2 a uniform distribution of the molecules is most energetically favorable while for O 2 molecules aggregation is most energetically preferable. The magnetic moments decrease from 4 to 2 to 0 for singly, doubly, triply occupied configurations for all gasses respectively. The most interesting magnetic properties are found for O 2 molecules attached to the Fe-aza-CMP. For a single attachment configuration we find that an antiferromagnetic state is favorable. When two O 2 molecules are attached, the calculations show the highest exchange integral with a value of J = 1071 μeV. This value has been verified by two independent methods where in the first method J is calculated by the energy difference between ferromagnetic and anitferromagnetic configurations. The second method is based on the frozen magnon approach where the magnon dispersion curve has been fitted by the Ising model. Finally, for the second method J has been estimated at J = 1100 μeV in excellent agreement with the first method.

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

Polyferrocenylsilane Semicrystalline Polymer Additive for Solution-Processed p-Channel Organic Thin Film Transistors

In this study, we demonstrated for the first time that a metal-containing semicrystalline polymer was used as an additive to mediate the thin film morphology of solution-grown, small-molecule organic semiconductors. By mixing polyferrocenylsilane (PFS) with an extensively-studied organic semiconductor 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene), PFS as a semicrystalline polymer independently forms nucleation and crystallization while simultaneously ameliorating diffusivity of the blend system and tuning the surface energies as a result of its partially amorphous property. We discovered that the resultant blend film exhibited a 6-fold reduction in crystal misorientation angle and a 3-fold enlargement in average grain width. Enhanced crystal orientation considerably reduces mobility variation, while minimized defects and trap centers located at grain boundaries lessen the adverse impact on the charge transport. Consequently, bottom-gate, top-contact organic thin film transistors (OTFTs) based on the TIPS pentacene/PFS mixture yielded a 40% increase in performance consistency (represented by the ratio of average mobility to the standard deviation of mobility). The PFS semicrystalline polymer-controlled crystallization can be used to regulate the thin film morphology of other high-performance organic semiconductors and shed light on applications in organic electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Designing Imidazolium Poly(amide-amide) and Poly(amide-imide) Ionenes and Their Interactions with Mono- and Tris(imidazolium) Ionic Liquids

Here we introduce the synthesis and thermal properties of a series of sophisticated imidazolium ionenes with alternating amide-amide or amide-imide backbone functionality, and investigate the structural effects of mono(imidazolium) and unprecedented tris(imidazolium) ionic liquids (ILs) in these ionenes. The new set of poly(amide-amide) (PAA) and poly(amide-imide) (PAI) ionenes represent the intersection of conventional high-performance polymers with the ionene archetype–presenting polymers with alternating functional and ionic elements precisely sequenced along the backbone. The effects of polymer composition on the thermal properties and morphology were analyzed. Five distinct polymer backbones were synthesized and combined with a stoichiometric equivalent of the IL 1-benzyl-3-methylimidazolium bistriflimide ([Bnmim][Tf 2 N]), which were studied to probe the self-assembly, structuring, and contributions of intermolecular forces when IL is added. Furthermore, three polyamide (PA) or polyimide (PI) ionenes with simpler xylyl linkages were interfaced with [Bnmim][Tf 2 N] as well as a novel amide-linked tris(imidazolium) IL, to demonstrate the structural changes imparted by the inclusion of functional, ionic additives dispersed within the ionene matrix. This work highlights the possibilities for utilizing concepts from small molecules which exhibit supramolecular self-assembly to guide creative design and manipulate the structuring of ionenes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A physics-informed multi-agents model to predict thermo-oxidative/hydrolytic aging of elastomers

This paper introduces a novel physics-informed multi-agents constitutive model to propose prediction in quasi-static constitutive behavior of cross-linked elastomer and the loss of mechanical performance during environmental aging. The presented model is used to simulate the effect of single-mechanism chemical aging (i.e. thermal-inducedor hydrolytic aging) on the behavior of the material in this hybrid framework. Those environmental single-mechanism damages change the polymer matrix over time due to massive chain scission, chain formations, and changing the arrangement of molecules in the polymer matrix. Here we propose a data-driven super-constrained machine-learned engine to represent damage in the polymer matrix and capture the changes in material behavior, including its inelastic features such as Mullins effect and permanent set in the course of aging. We have simplified the 3D stress–strain tensor mapping problem into a small number of super-constrained 1D mapping problems by means of a sequential order reduction. An assembly of multiple replicated conditional neural-network learning-agents (L-agents) is trained to systematically simplify the high-dimensional mapping problem into multiple 1D problems, each represented by a different type of agent. Our hybrid framework is designed to capture the effect of deformation history, aging time, and aging temperature. The model is validated with respect to a comprehensive set of experiments specifically designed to benchmark model capabilities and also against available data in the literature. Thermodynamic consistency and frame independency have been verified. Besides acceptable predictive abilities, a significant reduction of computational cost to predict behavior at multiple states of deformation is the most significant feature of this model.

42 ENGINEERING↗
DOE OSTI2021

Near-complete depolymerization of polyesters with nano-dispersed enzymes

Successfully interfacing enzymes and biomachinery with polymers affords on-demand modification and/or programmable degradation during the manufacture, utilization and disposal of plastics, but requires controlled biocatalysis in solid matrices with macromolecular substrates. Embedding enzyme microparticles speeds up polyester degradation, but compromises host properties and unintentionally accelerates the formation of microplastics with partial polymer degradation. Here we show that by nanoscopically dispersing enzymes with deep active sites, semi-crystalline polyesters can be degraded primarily via chain-end-mediated processive depolymerization with programmable latency and material integrity, akin to polyadenylation-induced messenger RNA decay. It is also feasible to achieve processivity with enzymes that have surface-exposed active sites by engineering enzyme-protectant-polymer complexes. Poly(caprolactone) and poly(lactic acid) containing less than 2 weight per cent enzymes are depolymerized in days, with up to 98 per cent polymer-to-small-molecule conversion in standard soil composts and household tap water, completely eliminating current needs to separate and landfill their products in compost facilities. Furthermore, oxidases embedded in polyolefins retain their activities. However, hydrocarbon polymers do not closely associate with enzymes, as their polyester counterparts do, and the reactive radicals that are generated cannot chemically modify the macromolecular host. This study provides molecular guidance towards enzyme-polymer pairing and the selection of enzyme protectants to modulate substrate selectivity and optimize biocatalytic pathways. Furthermore, the results also highlight the need for in-depth research in solid-state enzymology, especially in multi-step enzymatic cascades, to tackle chemically dormant substrates without creating secondary environmental contamination and/or biosafety concerns.

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

Transferring a Molecular Foundation Model for Polymer Property Predictions

Transformer-based large language models have remarkable potential to accelerate design optimization for applications such as drug development and material discovery. Self-supervised pretraining of transformer models requires large-scale data sets, which are often sparsely populated in topical areas such as polymer science. Further, state-of-the-art approaches for polymers conduct data augmentation to generate additional samples but unavoidably incur extra computational costs. In contrast, large-scale open-source data sets are available for small molecules and provide a potential solution to data scarcity through transfer learning. In this work, we show that using transformers pretrained on small molecules and fine-tuned on polymer properties achieves comparable accuracy to those trained on augmented polymer data sets for a series of benchmark prediction tasks.

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

Theoretical Pathway toward Improved Reverse Osmosis Membrane Selectivity for Neutral Solutes: Inspiration from Gas Separations

We report highly rigid membrane materials with tailored structures have exhibited permeabilities and selectivities that exceed the polymer upper bound in gaseous and organic solvent separations for challenging mixtures containing species that are similar in size and shape. One potential question is whether such membrane materials can maintain meaningful guest diffusivities in situations where the microporous spaces are essentially full of guest molecules. Here, we use a simplified transition state theory approach to estimate the diffusivity of water and small organics within a microporous membrane. The transition state theory model is parameterized using experimental values from zeolites and carbon molecular sieve materials found in the literature. We demonstrate the differences in transport and Maxwell–Stefan diffusivities based on guest species loading with different isotherm behaviors. These calculations theorize a path forward for highly selective reverse osmosis membranes for aqueous phase separations.

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

Catalytic Activation of Pyran Ethers in Self-Solvating Saccharides with Alkaline Earth Metals (Final Report)

Catalytic activation of cellulose ethers occurs via hydroxyl-stabilized cleavage of inter-monomer glycosidic bonds. Cooperativity between two hydroxyl groups lowers the ether cleavage transition state necessary to break apart long carbohydrate chains to initiate small molecule formation as fuel precursors. Metals existing with lignocellulosic materials including alkaline earth metals (Ca 2+ , Mg 2+ ) or alkali (Na + , K + ) also can catalyze ether scission cooperatively. By bonding with carbohydrate hydroxyl groups, a metal cation disrupt the hydrogen bonding network and free carbohydrate functional groups to react; a second metal cation stabilizes the carbohydrate ether transition state and enhances the rate of polymer scission. In this work, we expanded our initial understanding of metal-catalyzed glycoside ether scission. Within polysaccharides such as cellulose, two ether groups exist: one between monomers (glycosidic linkages) and one within a pyran ring. The hydroxyl-group hydrogen bonding network and bound metal ions form low energy binding states that interact with both ether oxygens simultaneously. Based on this interaction, our primary hypothesis was that the competition between stabilizing the two ether scission transition states determines the extent of the major pathways. Metals that disrupt the hydrogen bonding network of the C6 of sugars and stabilize the glycosidic ether promote transglycosylation to levoglucosan; in contrast, metals that stabilize the pyran ether oxygen promote sugar ring fragmentation to furans such as furfural. Varying characteristics of metal cation catalysts and configurations of bound polysaccharide chains dictate the relative rates of ether scission.

09 BIOMASS FUELS↗
DOE OSTI2021

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO 2 conversion integrated with CO 2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. We report our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 ($λ_{\text{SF}}$) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

25 ENERGY STORAGE↗
DOE OSTI2024

A General Approach to Activate Second‐Scale Room Temperature Photoluminescence in Organic Small Molecules

Organic small molecules that exhibit second‐scale phosphorescence at room temperature are of interest for potential applications in sensing, anticounterfeiting, and bioimaging. However, such materials systems are uncommon—requiring millisecond to second‐scale triplet lifetimes, efficient intersystem crossing, and slow rates of nonradiative recombination. Here, a simple and scalable approach is demonstrated to activate long‐lived phosphorescence in a wide variety of molecules by suspending them in rigid polymer hosts and annealing them above the polymer's glass transition temperature. This process produces submicron aggregates of the chromophore, which suppresses intramolecular motion that leads to nonradiative recombination and minimizes triplet–triplet annihilation that quenches phosphorescence in larger aggregates. In some cases, evidence of excimer‐mediated intersystem crossing that enhances triplet generation in aggregated chromophores is found. In short, this approach circumvents the current design rules for long‐lived phosphors, which will streamline their discovery and development.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Semiconducting Small Molecules as Active Materials for p-Type Accumulation Mode Organic Electrochemical Transistors

A series of semiconducting small molecules with bithiophene or bis-3,4-ethylenedioxythiophene cores are designed and synthesized. The molecules display stable reversible oxidation in solution and can be reversibly oxidized in the solid state with aqueous electrolyte when functionalized with polar triethylene glycol side chains. Evidence of promising ion injection properties observed with cyclic voltammetry is complemented by strong electrochromism probed by spectroelectrochemistry. Blending these molecules with high molecular weight polyethylene oxide (PEO) is found to improve both ion injection and thin film stability. The molecules and their corresponding PEO blends are investigated as active layers in organic electrochemical transistors (OECTs). For the most promising molecule:polymer blend (P4E4:PEO), p-type accumulation mode OECTs with µA drain currents, μS peak transconductances, and a µC* figure-of-merit value of 0.81 F V -1 cm -1 s -1 are obtained.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Achieving Balanced Crystallization Kinetics of Donor and Acceptor by Sequential-Blade Coated Double Bulk Heterojunction Organic Solar Cells

Sequential deposition has great potential to achieve high performance in organic solar cells due to the resulting well-controlled vertical phase separation. In this work, double bulk heterojunction organic solar cells are fabricated by sequential-blade cast in ambient conditions. Probed by the in situ grazing incidence X-ray diffraction and in situ UV–vis absorption measurements, the seq-blade system exhibits a different tendency from each of the binary films during the film formation process. Due to the extensive aggregation of FOIC, the binary PBDB-T:FOIC film displays a strong and large phase separation, resulting in low current density (J sc) and unsatisfactory power conversion efficiency. In the seq-blade cast system, the bottom layer PBDB-T:IT-M produces many crystal nuclei for the top layer PBDB-T:FOIC, so the PBDB-T molecules are able to crystallize easily and quickly. Balanced crystallization kinetics between polymer and small molecule and an ideal percolation network in the film are observed. In addition, the balanced crystallization kinetics are favorable toward realizing lower recombination loss through charge transport processes.

14 SOLAR ENERGY↗
DOE OSTI2021

A naphthalene diimide side-chain polymer as an electron-extraction layer for stable perovskite solar cells

Poly(N-(5-(5-norbornene-2-carbonyl)oxy)pentyl)-N'-n-hexyl-naphthalene-1,8:4,5-bis(dicarboximide) has been synthesized by esterification of (N-(5-hydroxypentyl)-N'-n-hexyl-naphthalene-1,8:4,5-bis(dicarboximide)) with exo-5-norbornene-2-carboxylic acid, and has been polymerized using the first-generation Grubbs initiator. This side-chain polymer exhibits good transparency throughout the visible (absorption onset at ca. 400 nm), good solubility in common low- and medium-polarity organic solvents, good resistance to dimethylformamide, and appropriate electron affinity for use as an electron-extraction layer in lead-halide perovskite solar cells. The performance of this polymer in n-i-p perovskite solar cells was compared to that of several small-molecule naphthalene-1,8:4,5-bis(dicarboximide) derivatives and of SnO 2 . Solar cells using the polymer exhibited open-circuit voltages of up to 1.02 V, short-circuit currents of over 21 mA cm –2 , and power conversion efficiencies (PCE) reaching 14% which stabilize at 13.8% upon 90 s of illumination. Meanwhile control SnO 2 devices exhibited a PCE of ca. 16%, and small-molecule devices gave PCE values of less than 10%. Here, the devices employing the polymer exhibited improved long-term stability relative to the SnO 2 control devices under continuous illumination.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A Review of Biodegradable Plastics: Chemistry, Applications, Properties, and Future Research Needs

Environmental concerns over waste plastics’ effect on the environment are leading to the creation of biodegradable plastics. Biodegradable plastics may serve as a promising approach to manage the issue of environmental accumulation of plastic waste in the ocean and soil. Biodegradable plastics are the type of polymers that can be degraded by microorganisms into small molecules (e.g., H 2 O, CO 2 , and CH 4 ). However, there are misconceptions surrounding biodegradable plastics. For example, the term “biodegradable” on product labeling can be misconstrued by the public to imply that the product will degrade under any environmental conditions. Such misleading information leads to consumer encouragement of excessive consumption of certain goods and increased littering of products labeled as “biodegradable”. Here this review not only provides a comprehensive overview of the state-of-the-art biodegradable plastics but also clarifies the definitions and various terms associated with biodegradable plastics, including oxo-degradable plastics, enzyme-mediated plastics, and biodegradation agents. Analytical techniques and standard test methods to evaluate the biodegradability of polymeric materials in alignment with international standards are summarized. The review summarizes the properties and industrial applications of previously developed biodegradable plastics and then discusses how biomass-derived monomers can create new types of biodegradable polymers by utilizing their unique chemical properties from oxygen-containing functional groups. The terminology and methodologies covered in the paper provide a perspective on directions for the design of new biodegradable polymers that possess not only advanced performance for practical applications but also environmental benefits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗