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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Highly Emissive Semi-Ladder-Type Copolymers, Aggregation State, and Solution-Processed Organic Light-Emitting Transistor

An organic light-emitting transistor (OLET) integrates the logic function of a field-effect transistor (FET) with electroluminescence of a light-emitting diode (LED) into a single device. This has the potential to play an important role in smart displays, electrically pumped organic laser, and other flexible electronic devices. For achieving high-performance solution-processed OLET, three semiladder copolymers—TPTI-CC, TPTI-C, and TPTI-F—were developed in this study. It was found that variation in the chemical structure lead to significant differences in energy level, emission color, and intermolecular aggregation. High photoluminescence quantum yields (PLQY) was obtained in these three polymers. Solution-processed trilayered OLET devices were fabricated, which exhibited strong electroluminescence, balanced charge mobility, and external quantum efficiency (EQE) of 2.8%.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration Using Copolymer Grain Encapsulation

Thermal stability of organic–inorganic hybrid perovskites (OIHPs) remains as one of the critical challenges against the stable operation of perovskite solar cells (PSCs) in direct sunlight with elevated temperatures. Here, we show that the addition of a polystyrene-co-polyacrylonitrile (SAN) copolymer can significantly enhance thermal stability of OIHPs and improve the stability of the corresponding PSCs by suppressing the migration of organic cations in OHIP. The methylammonium lead iodide (MAPI) with SAN incorporated within the perovskite layer featured a superior thermal stability compared to pure MAPI without SAN, only displaying an average of 5–15% decrease in PCE even after continuous thermal aging for 24 h at 100 °C. The secondary ion mass spectrometry revealed that the thermal degradation of the pure MAPI was largely associated with MA+ out-migration. Conducting atomic force microscopy analysis further indicated that the incorporated SAN led to a suppression of ionic currents present at the grain boundaries of the perovskite film, which was understood by high immiscibility between SAN and MA+ components as confirmed by the experimentally estimated Flory–Huggins parameter between them. This study newly identifies a potential of using polymer grain encapsulation for enhancing thermal stability of OIHPs and their solar cell performance by suppressing the out-diffusion of cationic organic components.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t + 0 ) and a thermodynamic factor, T f . By systematically varying the volume fraction of the conducting phase, Φ c between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t + 0 and T f , we measure the current fraction, ρ + , and the open circuit potential, U, of concentration cells. We find that ρ + and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or Φ c , allowing us to calculate t + 0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. Finally, the framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.

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

Relaxation Dynamics and Ion Conduction of Poly(Ethylene Carbonate/Ethylene Oxide) Copolymer-Based Electrolytes

Poly(ethylene carbonate/ethylene oxide) P(EC/EO) copolymer was synthesized from EC monomer as a new matrix component of solid polymer electrolytes (SPEs), and the correlation between polymer dynamics and ionic conductivity in the P(EC/EO)-based SPEs at various lithium salt weight fractions (w Li ) was investigated by dielectric spectroscopy, rheology, and molecular dynamics (MD) simulations. With the addition of lithium salt, the molecular motions at various scales (i.e., from local to segmental and global motion scales) were found to change as follows: (i) the local motion of P(EC/EO) was slightly accelerated, and at w Li ≥ 0.22, it was separated into two relaxation modes, one faster and the other slower than that of P(EC/EO), (ii) the segmental motion of P(EC/EO) became significantly slower with the addition of lithium salt, and (iii) the global terminal relaxation became slightly slower with the increase of w Li . Thus, the motion of P(EC/EO) at various scales in SPEs changed with different trends with increasing lithium salt. It was also found that the temperature dependence of the ionic conductivity was described by a Vogel–Fulcher–Tammann-type function, which was correlated with the segmental motion, as is known in other SPE systems. Furthermore, from MD simulations, lithium ions are coordinated with the EC units more likely and with a closer distance than EO units in P(EC/EO), and the coordination number of oxygens around one lithium ion was estimated as 6–7 at the distance of 0.30 nm. Here, these results suggest that the coordination structure of the oxygens around the lithium ion is slightly disrupted due to the presence of EC units compared to the chelating structure of pure PEO electrolytes.

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

Complex pH-Dependent Interactions between Weak Polyelectrolyte Block Copolymer Micelles and Molecular Fluorophores

Amphiphilic block copolymers with weak polyelectrolyte blocks can assemble stimulus-responsive nanostructures and interfaces. Applications of these materials in drug delivery, biomimetics, and sensing largely rely on the well-understood swelling of polyelectrolyte chains upon deprotonation, often induced by changes in pH or ionic strength. This deprotonation can also tune interfacial interactions between the polyelectrolyte blocks and surrounding solution, an effect which is less studied than morphological swelling of polyelectrolytes but can be just as critical for intended function. Here, we investigate whether the pH-driven morphological response of polyelectrolyte-bearing nanostructures also affects the interactions of these nanostructures with molecules in solution, using micelles of a short-chain polybutadiene-block-poly(acrylic acid) (pBd–pAA) as a model system. Here we introduce a Förster resonance energy transfer (FRET) approach to probe interactions between micelles and fluorescent molecular solutes as a function of solution pH. As expected, the pAA corona of these pBd–pAA micelles increases in thickness monotonically as a function of pH. However, FRET efficiency, which provides a metric of the spatial proximity of fluorescently labeled micelles and freely diffusing fluorophores, exhibits complex nonmonotonic behavior as a function of pH, indicating that the average separation of micelles and acceptor fluorophores is not strictly correlated with micelle swelling. Dialysis experiments quantify the affinity of fluorophores for micelles as a function of pH, confirming that changes in FRET are driven almost entirely by the pH-dependent affinity of the pAA block for the investigated molecular fluorophores, not simply by a shape change of the pAA corona. This study provides key insights into the interfacial interactions between weak-polyelectrolyte-bearing nanostructures and molecular solutes, of importance for the development of their stimulus-responsive applications.

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

Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear

A simple strategy is presented to achieve well-ordered nanostructures in microphase-separated diblock bottlebrush copolymers (dbBB) for potential opportunities in nanotechnology that require large grain sizes and directed orientation. The unique architecture and relaxation processes of dbBBs offer a pathway to enhanced dynamic ordering and reorientation over macroscopic scales. Here, controlled shear is used to align lamellar domains. The high molecular mobility of dbBBs in the melt state, as shown by linear and nonlinear viscoelastic characterization, supports this alignment process. When subjected to large-amplitude oscillatory shear at controlled frequency (ω), strain amplitude (γ), and temperature (T shear ), microphase-separated lamellae transition into highly aligned states as determined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). High throughput synchrotron SAXS is used to rapidly characterize microphase separation and lamellar alignment across the entire bulk sample. Lamellae align parallel to shear planes with an orientation order parameter (S) approaching S = 0.8 over a large cubic volume (V ~ mm 3 ).

36 MATERIALS SCIENCE↗
DOE OSTI2020

Tailorable Micelle Morphology in Self-Assembling Block Copolymer Gels for Templating Nanoporous Ceramics

The self-assembly of block copolymers offers opportunities for the facile organization and templating of inorganic nanomaterials. Here, we describe a morphology map for a poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate) (PMMA-b-PnBA-b-PMMA) block copolymer/polycarbosilane system that allows for tunable control over nanoscale micelle geometry via manipulation of the preceramic polymer content. We produced gels with spherical, wormlike, and bicontinuous morphologies, which were processed to create silicon carbide-based ceramic structures with tunable nanoscale porosities. The role of the constituent polymers in influencing the structure and rheology of this system is discussed. The PMMA-b-PnBA-b-PMMA block copolymer/preceramic polymer system offers a number of advantages including: (i) commercial availability, (ii) rapid self-assembly kinetics, and (iii) successful conversion of the self-assembled nanostructure to ceramic via pyrolysis. Finally, this system may be useful for catalytic, structural, or thermal applications in both industrial and academic settings because of its ease of use and relatively inexpensive reagents.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Unraveling Ion Transport in Trifluoromethanesulfonimide Pentablock Copolymer Membranes in Nonaqueous Electrolytes

Cation exchange membranes provide a key function in various nonaqueous energy storage technologies. As such, understanding the role of a nonaqueous liquid electrolyte on ion transport through a membrane is imperative. This study unravels relationships between membrane ion transport and electrolyte salt concentration utilizing a trifluoromethanesulfonimide-based pentablock copolymer membrane with polar and nonpolar nonaqueous electrolyte solutions. Here, the membrane plasticized with propylene carbonate (PC) exhibits a single-ion conductivity of 9.3 × 10 –6 S/cm at 25 °C. Tailoring the nonaqueous electrolyte and electrolyte salt concentration enables the single-ion conducting membrane to maintain a high cation transport number, >0.75, and boost ion conductivity more than 10 times to 1.3 × 10 –4 S/cm at 25 °C for the PC-based electrolyte solution. The findings provide critically important design parameters for energy storage systems utilizing nonaqueous electrolytes, such as Li- and Na-ion batteries and nonaqueous flow battery technologies.

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

Effect of Tethering Anions in Block Copolymer Electrolytes via Molecular Dynamics Simulations

Ion-containing block copolymers (BCPs) are promising solid-state electrolytes as they can combine ion conduction and mechanical robustness via multiple microphases. However, salt-doped BCPs can have low ion conduction and transference number. One strategy to increase transference number is to tether anions to the polymer backbone (creating a single-ion conductor), though this may impact cation mobility. Leveraging coarse-grained molecular dynamics simulations, we compare the effects of ion concentration and polymer dielectric constant on BCPs with and without bonding anions to the chain (without changing any other chemical properties). We find that single-ion BCPs have higher cation conductivity than analogous salt-doped BCPs, especially at moderate ion concentrations. Furthermore, we also compare several structural features of these systems; notably, tethering anions causes the ions to spread more evenly throughout the conducting phase, which is related to improved cation conduction.

25 ENERGY STORAGE↗
DOE OSTI2023

Exponential vs Gaussian Correlation Functions in the Characterization of Block Copolymer Grain Structure by Depolarized Light Scattering

Block copolymer (BCP) grain structure affects the mechanical, optical, and electrical properties of BCP materials, making the accurate characterization of this grain structure an important goal. In this study, improved BCP grain parameters were obtained by employing an exponentially decaying correlation function within the ellipsoidal grain model, instead of the Gaussian correlation function that was used in previous work. The exponential correlation function provides a better fit to the experimental depolarized light scattering data, which outweighs the disadvantage that it requires numerical integration to obtain the model scattered intensity.

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

Correction to “Frank–Kasper Phases of Diblock Copolymer Melts Studied with the DPD Model: SCF Results”

In a recent study, (1) we performed the self-consistent field (SCF) calculations of a dissipative particle dynamics (DPD) model of conformationally asymmetric diblock copolymer A-B melts to study the stability of various Frank–Kasper (FK) phases formed by such A-B melts. While all the equations in ref (1) are correct, we did not calculate the dimensionless (mean-field) Helmholtz free energies per chain βf c = βu c,χ + βu c,κ – s c /k B and the dimensionless stresses dβf c /dθ of ordered phases accurately. For example, the dimensionless (nonbonded) internal energy per chain due to the system compressibility βu c,κ = (N/2κ)∑ q βû 0 (|q|)(ϕ̂ A (q) + ϕ̂ B (q) – δ q,0 )(ϕ̂ A (−q) + ϕ̂ B (−q) – δ– q,0 ) should be calculated in the reciprocal space as given (note that βû 0 (|q|) is obtained analytically, and that since ϕ A (r) is real 𝜙̂ A (−𝐪)= $\overline{𝜙̂ A}$(𝐪), i.e., the complex conjugate of ϕ̂ A (q)); this corresponds to numerically evaluating βu c,κ = (N/2κ)∫dr(ϕ A (r) + ϕ B (r) – 1)ψ(r) with ψ(r) ≡ (∫dr′βu 0 (|r–r′|)(ϕ A (r′) + ϕ B (r′) – 1)/V in the real space via the (composite) trapezoidal rule. While the trapezoidal rule is less accurate than the Romberg integration (2) in general, the opposite occurs when the integration domain is periodic; this was pointed out by Matsen in ref (3) and explained in detail in refs (4and5). With our ignorance of this exceptional convergence property of the trapezoidal rule for periodic functions, we calculated all convolutions having the form of ψ(r) in the reciprocal space via the fast Fourier transforms (6) but those having the form of βu c,κ in the real space via Romberg integration; the latter leads to inaccurate results and unfortunately incorrect phase diagrams reported in ref (1), which are corrected here.

He, Juntong↗
DOE OSTI2024

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide)

Here, bottlebrush statistical copolymers (BSCPs) with poly(ethylene oxide) (PEO) and polystyrene (PS) side chains grafted to a polynorbornene (PNB) backbone were synthesized by ring-opening metathesis polymerization (ROMP). The impact of the glassy PS side chains on the crystallization of the PEO side chains as a function of the backbone length, grafting densities, and fraction of the PS and PEO side chains is described. The bottlebrush architecture, where the side chains are anchored to the backbone, inherently constrains the mobility of PEO. Compared with the bulk crystallization temperature of PEO, the higher glass transition temperature of PS places further constraints on PEO crystallization. The limited mobility of PEO leads to cold crystallization behavior during heating. Reduced grafting densities, in turn, reduce side-chain crowding, leading to less extended pendant structures. The degree of crystallinity of PEO was found to decrease at lower grafting densities to a point where crystallization was not observed. The average distance between bottlebrush backbones increased linearly with the backbone length, suggesting that the backbone forms a distinct mesodomain. For BSCPs with asymmetric volume fractions of PS and PEO side chains, the degree of crystallinity of PEO increases with a change from cold crystallization to normal nucleation and growth during cooling, as a result of reduced constraints on PEO mobility by the glassy PS side chains.

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

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Backbone Stitching in Bottlebrush Copolymer Mesodomains and the Impact of Side Chain Crystallization

We synthesized bottlebrush statistical copolymers (BSCPs) having poly­(ethylene oxide) (PEO) and poly­(dimethylsiloxane) (PDMS) side chains attached to a polynorbornene backbone. Small-angle X-ray scattering analysis showed that for densely grafted BSCPs, the scattering length density gradually transitions between the PEO and PDMS domains. For loosely grafted BSCPs, the polymer backbone formed a distinct mesodomain, with a lower electron and mass density than both the PEO and PDMS domains. The bottlebrush backbone essentially “stitches” the PEO and PDMS side chains, looping back and forth from the PEO to PDMS domains with the backbone segments oriented normal to the domain interfaces. Self-consistent field theory (SCFT) calculations validated the stitching of the backbone driven by the microphase separation of PEO and PDMS, along with a strong segmental order of the side chains in the melt. The reduced birefringence upon PEO crystallization suggests the disruption of the strong segmental order by the crystallization. Both the static intrinsic and the form birefringences of the BSCPs decreased upon PEO crystallization. Solid-state NMR confirmed the rigidity of PEO crystallites and the bottlebrush backbone. Self-assembly of BSCPs containing polyhedral oligomeric silsesquioxane (POSS) pendent groups was also evaluated by X-ray scattering, showing the formation of lamellar microdomains that inhibited POSS crystallization.

Hu, Mingqiu↗
DOE OSTI2025

Designing a Block Copolymer Membrane for Selective Transport of Lactic Acid from Aqueous Mixtures

We report the design and synthesis of a triblock copolymer-based membrane for enabling selective transport of lactic acid from aqueous solutions. This is relevant to the production of polylactic acid, one of the few biodegradable and biobased polymers with sufficient mechanical strength for practical applications. The end blocks are positively charged with negatively charged lactate counterions. The middle block is polybutadiene (PBD). Due to microphase separation, the charged blocks form channels for transporting lactic acid. The mechanical integrity of the membrane is controlled by cross-linking the PBD block. Transport of lactic acid and water across the membrane was studied by placing the membrane between two chambers, a feed chamber containing aqueous lactic acid solutions, and a receiving chamber containing pure water. The lactic acid concentration in the receiving chamber was monitored as a function of time using conductivity, HPLC, and NMR. The corresponding flux of water from the receiving chamber to the feed chamber was measured using an NMR-based approach. The lactic acid and water permeabilities through our membrane were (1.12 ± 0.05) × 10–8 and (8.58 ± 0.75) × 10–9 cm2 s–1. To our knowledge, there are no reports of lactic acid permeabilities through any membrane in the literature. The separation factor of our membrane, αLA/water, 1.305 ± 0.123, is comparable to that of membranes used for selective transport of ethanol, despite the fact that lactic acid is a much larger molecule than ethanol. Selective transport of lactic acid in our membrane is governed mainly by differences in solubility; lactic acid is 18 times more soluble in the membrane than water.

Jana, Rounak↗
DOE OSTI2024

Adverse Effect of Polyelectrolyte Complexation on the CO 2 Permeability of Polyvinylamine Copolymers

Polyvinylamine (PVAm) is one of the most studied polymers for facilitated transport membranes (FTMs) in CO 2 separation applications. In this study, poly(N-vinylformamide) (PNVf) was hydrolyzed to prepare a range of PNVf-PVAm copolymer compositions and the effect of PVAm fraction on CO 2 permeability and CO 2 /N 2 selectivity these polymers examined. The most permeable film was the polymer containing 52 mol% PVAm units with a CO 2 permeability of 353 Barrer and CO 2 /N 2 selectivity of 96, when tested at 60°C with humidified 14/86 CO 2 /N 2 mixed gas. Despite containing a higher loading of amines to act as CO 2 carriers, higher PVAm contents yielded significantly lower CO 2 permeability, without a loss of selectivity. This trend was not due to polymer crystallization since none of the PVAm films exhibited crystallinity in X-ray diffraction analysis. The loss of gas permeability at high PVAm content was instead due to strong polyelectrolyte interactions between polymer chains formed when PVAm reacts with CO 2 . Since only the PVAm units are ionized upon reaction with CO 2 , with the PNVf units remaining neutral, the density of these ionic effects increased as PVAm content increased, leading to increased resistance to gas permeation.

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

Evolution of Protrusions on Lithium Metal Anodes Stabilized by a Solid Block Copolymer Electrolyte Studied Using Time-Resolved X-ray Tomography

The growing demand for rechargeable batteries with higher energy densities has motivated research focused on enabling the lithium metal anode. A prominent failure mechanism in such batteries is short circuiting due to the uncontrolled propagation of lithium protrusions that often have a dendritic morphology. In this paper, the electrodeposition of metallic lithium through a rigid polystyrene- b -poly(ethylene oxide) (PS- b -PEO or SEO) block copolymer electrolyte was studied using hard X-ray microtomography. In this system, protrusions were approximately ellipsoidal globules: we take advantage of this simple geometry to quantify their growth as a function of polarization time and electrolyte salt concentration. The growth of 47 different globules was tracked with time to obtain average velocities of globule growth into the electrolyte. The globule diameter was a linear function of globule height in the electrolyte with a slope of about 6, independent of time and electrolyte salt concentration.

25 ENERGY STORAGE↗