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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Seeing structural evolution of organic molecular nano-crystallites using 4D scanning confocal electron diffraction (4D-SCED)

Abstract Direct observation of organic molecular nanocrystals and their evolution using electron microscopy is extremely challenging, due to their radiation sensitivity and complex structure. Here, we introduce 4D-scanning confocal electron diffraction (4D-SCED), which enables direct in situ observation of bulk heterojunction (BHJ) thin films. 4D-SCED combines confocal electron optic setup with a pixelated detector to record focused spot-like diffraction patterns with high angular resolution, using an order of magnitude lower dose than previous methods. We apply it to study an active layer in organic solar cells, namely DRCN5T:PC 71 BM BHJ thin films. Structural details of DRCN5T nano-crystallites oriented both in- and out-of-plane are imaged at ~5 nm resolution and dose budget of ~5 e − /Å 2 . We use in situ annealing to observe the growth of the donor crystals, evolution of the crystal orientation, and progressive enrichment of PC 71 BM at interfaces. This highly dose-efficient method opens more possibilities for studying beam sensitive soft materials.

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

Directed self-assembly of chiral liquid crystals into biomimetic bouligand structures in thin film

The Bouligand structure, renowned for its helicoidal arrangement and enhanced mechanical properties, has attracted significant research interest for its ability to impart enhanced strength to intrinsically soft materials. Biomimetic approaches have centered on fibrous structures in bulk materials, but translating this architecture into thin-film regime for miniaturized-wearable devices with programmable functions remains challenging. Here, we direct the self-assembly of cholesteric liquid crystals (CLCs) into hierarchical helical structures using chemically patterned surfaces. Alternating surface anchoring regions align uniform lying-down helices at the nanoscale, guiding a secondary microscale helical structure exhibiting both left- and right-handed twists. This mimetic Bouligand structure in CLCs enables optical modulation under applied field and strain with enhanced mechanical response. Simulations reveal the structural evolution from initial Bouligand configuration in LC layers to alternating twist helices. This research provides a basis for designing and manufacturing miniaturized or wearable devices with nanometer-scale precision in regulating electro-optical and mechanical properties. Bouligand structures, which offer strength in natural materials, are of interest but difficult to obtain. Here, the authors report the development of such structures by directed self-assembly of cholesteric single crystals into hierarchical helical structures, with the secondary structure having right and left-handed twists.

Bouligand structure↗
DOE OSTI2021

Solid-state rigid-rod polymer composite electrolytes with nanocrystalline lithium ion pathways

A critical challenge for next-generation lithium-based batteries lies in development of electrolytes that enable thermal safety along with use of high-energy-density electrodes. We describe molecular ionic composite (MIC) electrolytes based on an aligned liquid crystalline polymer combined with ionic liquids and concentrated Li salt. This high strength (200 MPa) and non-flammable solid electrolyte possesses outstanding Li + conductivity (1 mS cm -1 at 25 °C) and electrochemical stability (5.6 V vs Li|Li + ) while suppressing dendrite growth and exhibiting low interfacial resistance (32 Ω cm 2 ) and overpotentials (≤ 120 mV @ 1 mA cm -2 ) during Li symmetric cell cycling. A heterogeneous salt doping process modifies a locally ordered polymer-ion assembly to incorporate an inter-grain network filled with defective LiFSI & LiBF 4 nanocrystals, strongly enhancing Li + conduction. Furthermore, this modular material fabrication platform shows promise for safe and high-energy-density energy storage and conversion applications, incorporating the fast transport of ceramic-like conductors with the superior flexibility of polymer electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2021

Diversity-oriented synthesis of polymer membranes with ion solvation cages

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells, and batteries. It remains a significant challenge to identify FVEs with analyte specificity, due to difficulties in generating microporous polymer libraries with sufficient diversity for screening their properties. Here, we describe a diversity-oriented synthetic (DOS) strategy for microporous polymer membranes from which we identified those whose FVEs serve as solid solvation cages for lithium ions (Li + ). Furthermore, key elements of our strategy included diversification of bis(catechol)-type monomers via multi-component Mannich reactions to introduce Li+-coordinating functionality within individual FVEs, topology-enforcing polymerizations for generating macromolecular skeletal diversity for networking FVEs into different pore architectures, and several classes of on-polymer reactions for diversifying pore geometries and dielectric properties. Lead candidate polymer membranes featuring explicit ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes where FVEs were aspecific, which indicates conventional bounds for membrane permeability and selectivity for ion transport can be overcome.4 These advantages are tied to enhanced Li + partitioning from the electrolyte when the cages are present, higher diffusion barriers for anions within the pores, and network-enforced restrictions on the number of solvent molecules bound to Li+ by comparison to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium-metal batteries for electric mobility.

42 ENGINEERING↗
DOE OSTI2023

Swelling characteristics of DNA polymerization gels

The development of biomolecular stimuli-responsive hydrogels is important for biomimetic structures, soft robots, tissue engineering, and drug delivery. DNA polymerization gels are a new class of soft materials composed of polymer gel backbones with DNA duplex crosslinks that can be swollen by sequential strand displacement using hairpin-shaped DNA strands. The extensive swelling can be tuned using physical parameters such as salt concentration and biomolecule design. Previously, DNA polymerization gels have been used to create shape-changing gel automata with a large design space and high programmability. Here we systematically investigate how the swelling response of DNA polymerization gels can be tuned by adjusting the design and concentration of DNA crosslinks in the hydrogels or DNA hairpin triggers, and the ionic strength of the solution in which swelling takes place. Finally, we also explore the effect hydrogel size and shape have on the swelling response. Tuning these variables can alter the swelling rate and extent across a broad range and provide a quantitative connection between biochemical reactions and macroscopic material behaviour.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Photoresponsive polymers for carbodiimide-fueled transient hydrogels

Light- and carbodiimide-responsive hydrogels were synthesized. An “AND” gate was developed using ortho-nitrobenzyl (ONB) protected carboxylic acids in the polymer backbone. Crosslinking was only realized in the presence of both UV stimulus to photocleave the ONB group and carbodiimide fuels to induce anhydride bonds. In the presence of water, the anhydride bonds eventually hydrolyze to carboxylic acids and the system returns to the solution state. The mechanical properties of the out-of-equilibrium hydrogels were investigated using oscillatory rheology to examine the effects of deprotection efficiency, carbodiimide concentration and chain architecture on the hydrogels’ moduli and decrosslinking time. Higher moduli and longer decrosslinking times were found with increased carbodiimide concentration and deprotection efficiency. These discoveries unveil new possibilities for photoresponsive chemically fueled soft materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Deciphering supramolecular and polymer-like behavior in metallogels: real-time insights into temperature-modulated gelation and rapid self-assembly dynamics

Bis(pyridyl) urea-based gelators, namely L2 and its isomeric mixture ( L1 + L2 ), are known to self-assemble into 1D architectures capable of inducing supramolecular gelation. Coordination with metal ions such as Ag( I ), Cu( II ), and Fe( III ) introduces structural reinforcement, enabling the formation of distinct 3D networks governed by metal-specific coordination geometries. Here, we present a comprehensive investigation into the temperature-responsive behavior (20–60 °C) of L2 and L1 + L2 , both in the absence and presence of Ag( I ), Dy( III ), Fe( III ), Cu( II ), and Ho( III ), using real-time small-angle neutron scattering (SANS). To probe long-term structural evolution/kinetics of self-assembly, real-time small-angle X-ray scattering (SAXS) was employed on L2 + Ag gels, complemented by differential scanning calorimetry (DSC) to evaluate thermal transitions. Our results reveal strikingly divergent gelation behaviors: L2 forms a highly rigid, covalent polymer-like network, while L1 + L2 exhibits remarkable thermal adaptability. Upon metal coordination, the assemblies exhibit pronounced crystallinity and exceptional thermal stability, as evidenced by persistent Bragg reflections and invariant d-spacings. Intriguingly, L2 : Fe (2 : 1) and L1 : L2 : Fe (0.5 : 0.5 : 1) in acetonitrile-d 3 (ACN-d 3 ) deviate from this trend, forming thermally labile amorphous gels. These systems show a complete loss of crystalline order, reduced Porod exponents—indicative of collapsed or branched fiber morphologies—and prominent melting and glass transition events in DSC. Fitting SANS and SAXS data to the correlation length model unveiled insightful nanostructural features. While most systems displayed minimal temperature-induced variation in mesh size or surface morphology, L2 : Ag in dimethyl sulfoxide-d 6 (DMSO-d 6 )/D 2 O and L2 : Fe (1 : 1) in ACN-d 3 exhibited a rare combination of thermally stable correlation lengths and increasing high- q exponents—strongly suggesting progressive fiber densification or surface smoothing within a robust gel framework. These findings highlight the tunability and structural resilience of supramolecular gels through precise control of ligand architecture, metal coordination, and temperature, offering valuable design principles for functional soft materials.

Pajoubpong, Jinnipha [Univ. of Cincinnati, OH (Uni↗
DOE OSTI2022

Single-beam plasma source deposition of carbon thin films

A single-beam plasma source was developed and used to deposit hydrogenated amorphous carbon (a-C:H) thin films at room temperature. The plasma source was excited by a combined radio frequency and direct current power, which resulted in tunable ion energy over a wide range. The plasma source could effectively dissociate the source hydrocarbon gas and simultaneously emit an ion beam to interact with the deposited film. Using this plasma source and a mixture of argon and C 2 H 2 gas, a-C:H films were deposited at a rate of ~26 nm/min. The resulting a-C:H film of 1.2 µm thick was still highly transparent with a transmittance of over 90% in the infrared range and an optical bandgap of 2.04 eV. Young’s modulus of the a-C:H film was ~80 GPa. The combination of the low-temperature high-rate deposition of transparent a-C:H films with moderately high Young’s modulus makes the single-beam plasma source attractive for many coatings applications, especially in which heat-sensitive and soft materials are involved. Here, the single-beam plasma source can be configured into a linear structure, which could be used for large-area coatings.

14 SOLAR ENERGY↗
DOE OSTI2024

Enhancing the dielectric constant of zwitterionic liquids via dipole moment and anion chemistry

The dielectric constant is a critical parameter in many energy-related applications. Typically, increasing the dielectric constant of soft materials involves adding high dielectric constant polar liquids or inorganic fillers, but there are limitations to this approach due to safety concerns with volatile and flammable solvents and the agglomeration of inorganic fillers. An alternative approach is to add zwitterionic liquids that exhibit exceptionally high dielectric constants with negligible volatility. Here, we report the synthesis of a series of zwitterionic liquids containing an imidazolium cation, exhibiting the highest dielectric constant among all organic molecules (∼350 at 293 K). The cation–anion linkage was tailored in a wide range between three and nine carbons, rendering the zwitterion dipole from 25 to 52 D. Comparing the dielectric constant for zwitterions with different anions (i.e., sulfonylimide, sulfonate, and carboxylate) reveals the beneficial impacts of the delocalized sulfonylimide anion vs the carboxylate anion due to the enlarged molecular dipole and more homogenous liquid morphology. Molecular dipole and liquid morphology are identified as the keys to developing high dielectric constant zwitterionic liquids. The extremely high dielectric constant accessible with the proposed molecular design paves new avenues for developing high dielectric constant zwitterions that act as dielectricizers.

Chemistry↗
DOE OSTI2020

Scaling relationships for the elastic moduli and viscosity of mixed lipid membranes

The elastic and viscous properties of biological membranes play a vital role in controlling cell functions that require local reorganization of the membrane components as well as dramatic shape changes such as endocytosis, vesicular trafficking, and cell division. These properties are widely acknowledged to depend on the unique composition of lipids within the membrane, yet the effects of lipid mixing on the membrane biophysical properties remain poorly understood. Here, we present a comprehensive characterization of the structural, elastic, and viscous properties of fluid membranes composed of binary mixtures of lipids with different tail lengths. We show that the mixed lipid membrane properties are not simply additive quantities of the single-component analogs. Instead, the mixed membranes are more dynamic than either of their constituents, quantified as a decrease in their bending modulus, area compressibility modulus, and viscosity. While the enhanced dynamics are seemingly unexpected, we show that the measured moduli and viscosity for both the mixed and single-component bilayers all scale with the area per lipid and collapse onto respective master curves. This scaling links the increase in dynamics to mixing-induced changes in the lipid packing and membrane structure. More importantly, the results show that the membrane properties can be manipulated through lipid composition the same way bimodal blends of surfactants, liquid crystals, and polymers are used to engineer the mechanical properties of soft materials, with broad implications for understanding how lipid diversity relates to biomembrane function.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Phase separation and ripening in a viscoelastic gel

The process of phase separation in elastic solids and viscous fluids is of fundamental importance to the stability and function of soft materials. We explore the dynamics of phase separation and domain growth in a viscoelastic material such as a polymer gel. Using analytical theory and Monte Carlo simulations, we report a domain growth regime in which the domain size increases algebraically with a ripening exponent α that depends on the viscoelastic properties of the material. For a prototypical Maxwell material, we obtain α = 1 , which is markedly different from the well-known Ostwald ripening process with α = 1 / 3 . We generalize our theory to systems with arbitrary power-law relaxation behavior and discuss our findings in the context of the long-term stability of materials as well as recent experimental results on phase separation in cross-linked networks and cytoskeleton.

Science & Technology - Other Topics↗
DOE OSTI2023

Scientific machine learning for modeling and simulating complex fluids

The formulation of rheological constitutive equations—models that relate internal stresses and deformations in complex fluids—is a critical step in the engineering of systems involving soft materials. While data-driven models provide accessible alternatives to expensive first-principles models and less accurate empirical models in many engineering disciplines, the development of similar models for complex fluids has lagged. The diversity of techniques for characterizing non-Newtonian fluid dynamics creates a challenge for classical machine learning approaches, which require uniformly structured training data. Consequently, early machine-learning based constitutive equations have not been portable between different deformation protocols or mechanical observables. Here, we present a data-driven framework that resolves such issues, allowing rheologists to construct learnable models that incorporate essential physical information, while remaining agnostic to details regarding particular experimental protocols or flow kinematics. These scientific machine learning models incorporate a universal approximator within a materially objective tensorial constitutive framework. By construction, these models respect physical constraints, such as frame-invariance and tensor symmetry, required by continuum mechanics. We demonstrate that this framework facilitates the rapid discovery of accurate constitutive equations from limited data and that the learned models may be used to describe more kinematically complex flows. This inherent flexibility admits the application of these “digital fluid twins” to a range of material systems and engineering problems. We illustrate this flexibility by deploying a trained model within a multidimensional computational fluid dynamics simulation—a task that is not achievable using any previously developed data-driven rheological equation of state.

Science & Technology - Other Topics↗
DOE OSTI2022

The 2022 Plasma Roadmap: low temperature plasma science and technology

Abstract The 2022 Roadmap is the next update in the series of Plasma Roadmaps published by Journal of Physics D with the intent to identify important outstanding challenges in the field of low-temperature plasma (LTP) physics and technology. The format of the Roadmap is the same as the previous Roadmaps representing the visions of 41 leading experts representing 21 countries and five continents in the various sub-fields of LTP science and technology. In recognition of the evolution in the field, several new topics have been introduced or given more prominence. These new topics and emphasis highlight increased interests in plasma-enabled additive manufacturing, soft materials, electrification of chemical conversions, plasma propulsion, extreme plasma regimes, plasmas in hypersonics, data-driven plasma science and technology and the contribution of LTP to combat COVID-19. In the last few decades, LTP science and technology has made a tremendously positive impact on our society. It is our hope that this roadmap will help continue this excellent track record over the next 5–10 years.

plasma diagnostics↗
DOE OSTI2023

Local structure, bonding, and asymmetry of $\mathrm{((NH_2)_2CH)PbBr_3}$, $\mathrm{CsPbBr_3}$, and $\mathrm{(CH_3MH_3)PbBr_3}$

Here we report local structure measurements for CsPbBr 3 and ((NH 2 ) 2 CH)PbBr 3 (FAPbBr 3 ) and compare them with recent results for (CH 3 NH 3 )PbBr 3 (MAPbBr 3 ). The Pb-Br bonding is similar for all three systems; the effective spring constants, κ, are comparable (ranging from 1.20 to 1.95 eV/Å 2 ), but small in magnitude indicating very soft materials. However, there are also important differences between the three systems. Static disorder is very small for CsPbBr3 but increases somewhat with the size of the organic molecular ions MA + and FA + . At room temperature, dynamic disorder dominates in all compounds. The thermal disorder of the Pb-Br pair distribution function (PDF), i.e., the Debye-Waller factor σ 2 follows a correlated Debye or Einstein model up to 300 K in CsPbBr 3 (orthorhombic phase), but for FAPbBr 3 and MAPbBr 3 , there is a break in the σ 2 (T) curve at the orthorhombic-tetragonal transition (o-t) near 150 K, indicating a small change in the spring constant κ. κ increases for MAPbBr 3 but decreases in FAPbBr 3 at this transition. These changes are attributed to changes in the H-bonding between Br - and MA + or FA + at this transition, as a result of librations or rotations of these molecular cations. In addition, the Pb-Br PDF becomes asymmetric at a relatively low temperature for FAPbBr 3 and MAPbBr 3 , while this effect is significantly smaller for CsPbBr 3 . Finally, we address the question of a model to explain the asymmetric PDF. Two main models are discussed in the literature, an anharmonic pair potential and a split-pair distribution, possibly driven by the presence of a lone pair on the Pb ion. We show that the fourth cumulant C 4 can differentiate between these two models and other possible models. Experimentally C 4 is positive at 250 K and above, for all three systems and that is inconsistent with a split-peak model, for which C 4 is negative for splittings larger than 0.12 Å.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Optical tweezer measurements of asymptotic nonlinearities in complex fluids

This article presents micro-medium-amplitude oscillatory shear (μMAOS), a method to measure the frequency-dependent micromechanical properties of soft materials in the asymptotically nonlinear regime using optical tweezers. For this work, we have developed a theoretical framework to extract these nonlinear mechanical properties of the material from experimental measurements and also proposed a physical interpretation of the third-order nonlinearities measured in single-tone oscillatory tests. We validate the method using a well-characterized surfactant solution of wormlike micelles, and subsequently employ this technique to demonstrate that the cytoplasm of a living cell undergoes strain softening and shear thinning when locally subjected to weakly nonlinear oscillatory deformations.

59 BASIC BIOLOGICAL SCIENCES↗